JP5851772B2 - Titanium alloy hydride and method for producing the same - Google Patents
Titanium alloy hydride and method for producing the same Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims description 75
- 150000004678 hydrides Chemical class 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000956 alloy Substances 0.000 claims description 38
- 229910045601 alloy Inorganic materials 0.000 claims description 37
- 238000005984 hydrogenation reaction Methods 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 43
- 238000000034 method Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- -1 titanium hydride Chemical compound 0.000 description 17
- 229910000048 titanium hydride Inorganic materials 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000009703 powder rolling Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000005242 forging Methods 0.000 description 1
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Description
本発明は、チタン合金水素化物に係り、特に、チタン合金スクラップを出発原料としたチタン合金の水素化技術に関する。 The present invention relates to a titanium alloy hydride, and more particularly to a hydrogenation technology of a titanium alloy using titanium alloy scrap as a starting material.
金属チタンは、航空機に多く利用されてきているが、近年では、自動車や二輪車、建材やスポーツ用品等の民生用にも広く用いられている。民生用には、純チタン材が使用されているが、航空機に対してはチタン合金が主として使用されている。 Metallic titanium has been widely used for aircraft, but in recent years, it has been widely used for consumer use such as automobiles, motorcycles, building materials and sports equipment. Pure titanium materials are used for consumer use, but titanium alloys are mainly used for aircraft.
航空機用のチタン合金においては、溶解法で製造されたチタン合金インゴットを鍛造圧延により仕上げられた板材を加工して使用される場合がある。また、同チタン合金インゴットに対して削り出しにより製品として仕上げて製品とされる場合もある。また、要求される製品が複雑な場合には、粉末を原料としてこれを焼結体にしてから航空機の部品として使用される場合もある。 In a titanium alloy for aircraft, a titanium alloy ingot manufactured by a melting method may be used by processing a plate material finished by forging and rolling. In some cases, the titanium alloy ingot is cut into a finished product as a product. In addition, when the required product is complicated, it may be used as an aircraft part after making powder into a sintered body.
粉末法によるチタン合金を製造する方法として、いわゆる素粉末混合法という方法が知られている。素粉末混合法は、目的とするチタン合金を構成する金属の粉末を個別に準備してこれを均一に混合してから、成形体を製造した後、これを高温に加熱することにより、焼結体を得る方法である（例えば、特許文献１参照）。 As a method for producing a titanium alloy by a powder method, a so-called elementary powder mixing method is known. In the elementary powder mixing method, the powder of the metal that constitutes the target titanium alloy is individually prepared and mixed uniformly, and then a compact is produced and then heated to a high temperature for sintering. This is a method for obtaining a body (see, for example, Patent Document 1).
しかしながら、この方法においては、個別に準備した合金素粉を均一に混合することが難しく、よって均一な組成を有する焼結チタン合金を製造することが難しいという課題が残されている。また、たとえ均一に混合できたとしても、コストが嵩み、改善の余地が残されている。 However, in this method, there remains a problem that it is difficult to uniformly mix individually prepared alloy powders, and thus it is difficult to produce a sintered titanium alloy having a uniform composition. Moreover, even if it can mix uniformly, cost will increase and the room for improvement will be left.
このような点については、合金粉で構成した成形体をＶＡＲ溶解炉で溶解して均一な組成の合金を溶製する方法が知られている（例えば、特許文献２参照）。しかしながら、この方法では、粉末法と溶解法の長所を併せて利用する形のものであるが、粉末冶金の特徴であるニアネットシェイプ（最終製品に近い形状を一度で付与できる加工法）の製品にはこの技術を適用できないのみならず、溶解工程が新たに含まれてくるため、コスト面での検討の余地が残されている。 Regarding such a point, a method is known in which a compact formed of alloy powder is melted in a VAR melting furnace to melt an alloy having a uniform composition (see, for example, Patent Document 2). However, this method uses the advantages of both the powder method and the dissolution method, but it is a product of the near net shape (a processing method that can give a shape close to the final product), which is a feature of powder metallurgy. Not only can this technique not be applied, but it also includes a melting process, leaving room for cost consideration.
なお、６Ａｌ−４Ｖ合金の水素化処理については、水素化処理により製造された水素化チタンの粒度分布について記載されているが（例えば、特許文献３参照）、具体的な水素化方法に関する記載は見当たらない。 In addition, about the hydrogenation process of 6Al-4V alloy, although the particle size distribution of the titanium hydride manufactured by the hydrogenation process is described (for example, refer patent document 3), the description regarding the specific hydrogenation method is described. I can't find it.
更には、スポンジチタンの水素化物とアルミニウム粉からなる水素含有チタン−アルミニウム合金粉も知られている（例えば、特許文献４参照）。しかしながら、この技術はいわゆる前記した素粉末混合法に分類される方法であり、均一な組成の合金粉を製造し、合金組成の均一なチタン−アルミニウム合金を得るには、更なる改善が求められている。また、コストの点においても検討の余地が残されている。なお、この文献に開示されている粉末は、チタン合金が水素化されたものではなく、水素化チタンと、水素化アルミニウム合金というようにチタンと合金は別々の水素化物を構成している。 Furthermore, a hydrogen-containing titanium-aluminum alloy powder made of titanium hydride and aluminum powder is also known (see, for example, Patent Document 4). However, this technique is classified as the so-called elementary powder mixing method described above, and further improvement is required in order to produce an alloy powder having a uniform composition and obtain a titanium-aluminum alloy having a uniform alloy composition. ing. In addition, there is still room for consideration in terms of cost. The powder disclosed in this document is not a hydrogenated titanium alloy, but titanium and the alloy constitute separate hydrides such as titanium hydride and aluminum hydride alloy.
以上述べたように、均一な組成を有したチタン合金の製造に適した水素化チタン合金粉を効率よく製造することができる技術が求められている。 As described above, there is a need for a technique that can efficiently produce titanium hydride alloy powder suitable for producing a titanium alloy having a uniform composition.
本発明は、チタン合金の水素化において、特に、組成が均一で、しかもニアネットシェイプに好適であり、更に、チタン合金および同チタン合金を安価に製造しうる水素化チタン合金粉を提供することを目的としている。 The present invention provides a titanium hydride alloy powder having a uniform composition, suitable for near net shape, and capable of producing a titanium alloy and the titanium alloy at a low cost, particularly in hydrogenation of a titanium alloy. It is an object.
上述した課題に鑑み、鋭意検討を重ねてきた結果、本発明者は、チタン合金またはチタン合金スクラップを出発原料とし、この原料をある特定の条件下で水素化させることにより、同チタン合金の製造に好適な水素化チタン合金粉を安価に製造できることを見出し、本願発明を完成するに至った。 As a result of intensive studies in view of the above-mentioned problems, the present inventor made a titanium alloy or titanium alloy scrap as a starting material, and produced the titanium alloy by hydrogenating the raw material under a specific condition. The present inventors have found that titanium hydride alloy powder suitable for the above can be produced at low cost, and have completed the present invention.
即ち、本発明にかかるチタン合金水素化物は、３．９ｗｔ％以上の水素を含有し、かつ、粉末Ｘ線回折測定（以下、ＸＲＤと略称する場合がある）における２θ＝３５°近傍の半値幅が０．８５゜以下であることを特徴とするものである。 That is, the titanium alloy hydride according to the present invention contains 3.9 wt % or more of hydrogen and is a half of 2θ = 35 ° in the powder X-ray diffraction measurement (hereinafter sometimes abbreviated as XRD). The value range is 0.85 ° or less.
本発明のチタン合金水素化物の製造方法は、チタン合金に水素ガスを接触させ、１．２気圧（１２０ｋＰａ）以上、３．５気圧（３５０ｋＰａ）以下で、５００℃〜７７０℃の温度域にて反応させることを特徴としている。
なお、本願においては、圧力の単位を「ａｔｍ」と表記する場合もある。
また、本発明においては、水素化反応後、チタン合金水素化物を冷却する際に、炉内圧力を３．５気圧以上にすることを好ましい態様としている。
In the method for producing a titanium alloy hydride according to the present invention, a hydrogen gas is brought into contact with a titanium alloy, and the pressure is 1.2 atmospheres ( 120 kPa) or more and 3.5 atmospheres (350 kPa) or less in a temperature range of 500 ° C. to 770 ° C. It is characterized by Ru reacted Te.
In the present application, the unit of pressure may be expressed as “atm”.
Moreover, in this invention, when cooling titanium alloy hydride after hydrogenation reaction, it is set as the preferable aspect that the pressure in a furnace shall be 3.5 atmospheres or more.
本発明においては、前記チタン合金水素化物中の合金成分が、アルミニウム、シリコン、銅、マンガン、バナジウム、ジルコニウム、ニオブ、クロム、モリブデン、スズ、ルテニウム、レニウム、または鉄のうちから選択された少なくとも１種以上であることを好ましい態様としている。 In the present invention, the alloy component in the titanium alloy hydride is at least one selected from aluminum, silicon, copper, manganese, vanadium, zirconium, niobium, chromium, molybdenum, tin, ruthenium, rhenium, or iron. It is a preferred embodiment that it is a species or more.
本発明においては、前記チタン合金中の合金成分が、アルミニウム、シリコン、銅、マンガン、バナジウム、ジルコニウム、ニオブ、クロム、モリブデン、スズ、ルテニウム、レニウム、または鉄のうちから選択された少なくとも１種以上であることを好ましい態様としている。 In the present invention, the alloy component in the titanium alloy is at least one selected from aluminum, silicon, copper, manganese, vanadium, zirconium, niobium, chromium, molybdenum, tin, ruthenium, rhenium, or iron. This is a preferred embodiment.
本願発明によれば、安価なチタン合金スクラップを原料として使用することができ、これに水素ガスを接触させて水素化反応させることにより、良好な崩壊性を有する水素化チタン合金が安価に得られるという効果を奏するものである。さらに、本発明のチタン合金水素化物によれば、組成が均一で、しかもニアネットシェイプに好適であるチタン合金を製造することができる。 According to the present invention, an inexpensive titanium alloy scrap can be used as a raw material, and a hydrogenated titanium hydride alloy having good disintegration can be obtained at low cost by bringing this into contact with hydrogen gas to cause a hydrogenation reaction. This is an effect. Furthermore, according to the titanium alloy hydride of the present invention, it is possible to produce a titanium alloy having a uniform composition and suitable for near net shape.
本発明の好ましい態様につき、図面を用いながら以下に説明する。
本発明に係るチタン合金水素化物は、３．９％以上の水素を含有することを第一の特徴とするものであり、また、粉末Ｘ線回折測定における２θ＝３５°近傍のピークの半値幅が０．８５゜以下であることを第二の特徴とするものである。
Preferred embodiments of the present invention will be described below with reference to the drawings.
The titanium alloy hydride according to the present invention is characterized by containing 3.9% or more of hydrogen, and the half width of the peak in the vicinity of 2θ = 35 ° in powder X-ray diffraction measurement. The second characteristic is that the angle is 0.85 ° or less.
前記水素化物中の水素の含有率が３．９％未満である場合には、チタン合金製造用原料を水素化した後に行う粉砕工程においては、所定の大きさのチタン粉を製造するための粉砕時間が長時間に亘り、その結果、生産性の低下やコスト増、酸素含有量増を招き実用上、好ましくない。これに対して、チタン合金水素化物中の水素含有率を３．９％以上とした場合には、粉砕性が良好であり、目的とする水素化チタン粉の酸素含有量を増加させることなく、効率よく製造することができるという効果を奏するものである。 When the hydrogen content in the hydride is less than 3.9%, in the pulverization step performed after hydrogenating the raw material for titanium alloy production, pulverization for producing titanium powder of a predetermined size It takes a long time, and as a result, the productivity is lowered, the cost is increased, and the oxygen content is increased. On the other hand, when the hydrogen content in the titanium alloy hydride is 3.9% or more, the grindability is good, without increasing the oxygen content of the target titanium hydride powder, There is an effect that it can be manufactured efficiently.
前記のような組成の水素化物が含有されることにより、チタン合金水素化物の破砕整粒操作を効率的に進めることができるという効果を奏するものである。 By containing the hydride having the above composition, there is an effect that the crushing and sizing operation of the titanium alloy hydride can be efficiently advanced.
また、図１に「水素化６４合金」のチャート図として示すように、本願発明に係るチタン合金水素化物のＸＲＤ解析における２θ＝３５°近傍におけるＴｉＨ２の半値幅が０．８５゜以下であることを好ましい態様とするものである。 Further, as shown in FIG. 1 as a chart of “hydrogenated 64 alloy”, the half width of TiH 2 in the vicinity of 2θ = 35 ° in the XRD analysis of the titanium alloy hydride according to the present invention is 0.85 ° or less. This is a preferred embodiment.
前記ＴｉＨ２の半値幅が０．８５°以下の場合には、粉砕して得られた粉のうち粗粉の生成比率が少なくなり、製品歩留まりを高いレベルに維持することができる。一方、前記ＴｉＨ２の半値幅が０．８５°を超える場合には、粉砕して得られた粉のうち粗粉の生成比率が多くなり、製品歩留まりの低下を招き好ましくない。よって、本願発明においては、水素化６４合金粉末に対するＴｉＨ２の半値幅は、０．８５°以下が好ましいとされる。 When the half width of TiH 2 is 0.85 ° or less, the production ratio of coarse powder is reduced among the powder obtained by pulverization, and the product yield can be maintained at a high level. On the other hand, when the half width of TiH 2 exceeds 0.85 °, the ratio of coarse powder to increase in the powder obtained by pulverization increases, resulting in a decrease in product yield. Therefore, in the present invention, the half width of TiH 2 with respect to the hydrogenated 64 alloy powder is preferably 0.85 ° or less.
前記範囲にある水素化チタン粉とすることにより、粒度分布の狭いチタン合金水素化物を製造することができるという効果を奏するものである。また、原料のチタン合金に比べて脆化しているため、容易に所定の大きさまで粉砕することができるという効果を奏するものである。 By using titanium hydride powder in the above range, it is possible to produce a titanium alloy hydride having a narrow particle size distribution. In addition, since it is more brittle than the raw material titanium alloy, there is an effect that it can be easily pulverized to a predetermined size.
適度な大きさに粉砕されたチタン合金水素化物は、今度は、篩別により所定の大きさに整粒しておくことが好ましい。よって、本願発明においては、１０μｍ〜１５０μｍの間に整粒しておくことが好ましい。このような粒度範囲に整粒しておくことにより、焼結時の緻密化が促進されるという効果を奏するものである。 The titanium alloy hydride pulverized to an appropriate size is now preferably sized to a predetermined size by sieving. Therefore, in the present invention, it is preferable to size the particles between 10 μm and 150 μm. By adjusting the size within such a particle size range, there is an effect that densification during sintering is promoted.
前記水素化チタン合金粉の粒度が、１０μｍ未満の範囲では、脱水素化後のチタン合金粉での発火の問題が顕在化してくる。即ち、細かすぎるチタン合金粉は、安全性の点で問題があり、この点において、水素化チタン合金粉の段階でその最小粒度を１０μｍに調整することが望ましい。 When the particle size of the titanium hydride alloy powder is less than 10 μm, the problem of ignition in the titanium alloy powder after dehydrogenation becomes obvious. That is, titanium alloy powder that is too fine is problematic in terms of safety, and in this respect, it is desirable to adjust its minimum particle size to 10 μm at the stage of titanium hydride alloy powder.
一方、前記水素化チタン合金粉の粒度が、１５０μｍ超の範囲では、今度は焼結の際に高密度の焼結材を得にくいという問題が生じ、品質上の新たな課題に遭遇する。 On the other hand, when the particle size of the titanium hydride alloy powder exceeds 150 μm, there arises a problem that it is difficult to obtain a high-density sintered material at the time of sintering, and a new problem in quality is encountered.
前記した方法で製造された水素化チタン合金粉は、次なる脱水素工程により、水素含有率の低いチタン合金粉を製造することができるという効果を奏するものである。 The titanium hydride alloy powder produced by the above-described method has an effect that a titanium alloy powder having a low hydrogen content can be produced by the subsequent dehydrogenation step.
次に、本発明に係るチタン合金製造用原料の水素化方法について以下に説明する。
本発明に係るチタン合金製造用原料の水素化方法は、前記チタン合金製造用原料を、減圧下において高温に加熱後、水素ガスを炉内に導入し、炉内の水素分圧を１気圧（１００ｋＰａ）以上であって、３．５気圧（３５０ｋＰａ）以下の範囲で制御することを特徴とするものである。
Next, the method for hydrogenating a raw material for producing a titanium alloy according to the present invention will be described below.
In the method for hydrogenating a raw material for producing a titanium alloy according to the present invention, the raw material for producing a titanium alloy is heated to a high temperature under reduced pressure, hydrogen gas is introduced into the furnace, and the hydrogen partial pressure in the furnace is set to 1 atm ( 100 kPa) or more and 3.5 atmospheres (350 kPa) or less.
ここで、炉内の水素分圧が１００ｋＰａ（１気圧）未満の場合には、炉内を冷却する際に外部より空気が侵入する恐れがあり、空気による品質汚染を生じる場合があるので、これを下限値としている。一方、炉内の水素分圧は、高い方が水素化反応速度を高めることができて好ましい。しかしながら、反応時の炉内の水素分圧が、３５０ｋＰａ超の場合には、水素化反応速度の改善効果は飽和する傾向を示す。 Here, if the hydrogen partial pressure in the furnace is less than 100 kPa (1 atm), air may enter from the outside when cooling the furnace, which may cause quality contamination by air. Is the lower limit. On the other hand, a higher hydrogen partial pressure in the furnace is preferable because the hydrogenation reaction rate can be increased. However, when the hydrogen partial pressure in the furnace during the reaction exceeds 350 kPa, the effect of improving the hydrogenation reaction rate tends to be saturated.
よって、水素化処理における圧力の範囲は、１００ｋＰａ（１気圧）〜３５０ｋＰａ（３．５気圧）とされる。 Therefore, the pressure range in the hydrotreatment is 100 kPa (1 atm) to 350 kPa (3.5 atm).
次工程として、水素ガスを炉内に封じ込めつつ、反応炉の最大温度から室温まで炉内を冷却する。この場合には、炉内の圧力が１気圧（１００ｋＰａ)以下になると、空気が侵入する恐れがあるために、炉内の最高温度時の水素分圧を３．５気圧（３５０ｋＰａ）以上まで高めておくことが好ましい。３．５気圧まで炉内圧力を高めれば、冷却時に１気圧以下になることはなく、製品である水素化チタン合金の製品中の酸素が含有率を低いレベルに維持することができるという効果を奏するものである。 As the next step, the inside of the furnace is cooled from the maximum temperature of the reaction furnace to room temperature while containing hydrogen gas in the furnace. In this case, if the pressure in the furnace becomes 1 atm (100 kPa) or less, air may enter, so the hydrogen partial pressure at the maximum temperature in the furnace is increased to 3.5 atm (350 kPa) or more. It is preferable to keep it. If the pressure in the furnace is increased to 3.5 atm, it does not become 1 atm or less during cooling, and the oxygen content in the product of the titanium hydride alloy product can maintain the content rate at a low level. It is what you play.
よって、本願発明においては、炉内の水素分圧は、反応時に１００ｋＰａ以上であって、３５０ｋＰａまで、また、冷却前には、３５０ｋＰａ以上に高めておくことを好ましい態様とするものである。 Therefore, in the present invention, it is preferable that the hydrogen partial pressure in the furnace is 100 kPa or more at the time of reaction, to 350 kPa, and to 350 kPa or more before cooling.
また、チタン合金製造用原料の水素化の際の加熱温度は、５００〜７７０℃の温度範囲を意味するが、本願発明においては、特に、５００〜７００℃の範囲に加熱することが好ましい。水素化反応は、７７０℃以上では、Ｔｉ＋Ｈ２⇔ＴｉＨ２の反応式において左辺が安定相となり、一旦生成したＴｉＨ２相が乖離することになるため、炉内温度の上限を７７０℃とすることが重要である。実際の操業においては、水素化反応が発熱反応であることから、反応熱により炉内温度は高くなる傾向にあり、加熱を停止した後も温度の上昇がみられる。そのため、加熱によって炉内温度を上げる上限を７００℃とすれば、反応熱による温度上昇を加味して炉内温度が上限の７７０℃にコントロールできるというものである。 In addition, the heating temperature at the time of hydrogenation of the raw material for producing the titanium alloy means a temperature range of 500 to 770 ° C. In the present invention, it is particularly preferable to heat to a range of 500 to 700 ° C. When the hydrogenation reaction is at 770 ° C. or higher, the left side of the reaction formula of Ti + H 2 ⇔TiH 2 is a stable phase, and the once generated TiH 2 phase is separated, so the upper limit of the furnace temperature should be 770 ° C. is important. In actual operation, since the hydrogenation reaction is an exothermic reaction, the temperature in the furnace tends to increase due to the reaction heat, and the temperature rises even after the heating is stopped. Therefore, if the upper limit for raising the temperature in the furnace by heating is 700 ° C., the temperature in the furnace can be controlled to the upper limit of 770 ° C. in consideration of the temperature rise due to reaction heat.
以下により具体的な加熱方法を記載する。
まずは、内部にチタン材を挿入した後、減圧操作を開始後、ヒーターに通電して、炉内温度を５００℃まで加熱後、減圧操作を停止してから炉への水素ガス分圧が１気圧以上であって３．５気圧以下の範囲になるように炉内に水素ガスを導入する。
A specific heating method will be described below.
First, after inserting the titanium material inside, after starting the pressure reduction operation, the heater is energized, the furnace temperature is heated to 500 ° C., the pressure reduction operation is stopped, and then the hydrogen gas partial pressure to the furnace is 1 atm. Hydrogen gas is introduced into the furnace so that the pressure is in the range of 3.5 atmospheres or less.
炉内への水素ガスの導入開始に伴い、水素ガスとチタン合金との反応が開始する。前記水素ガスとチタン合金との反応は、発熱反応であるため、炉内温度は、次第に上昇する傾向を示すが、ヒーターの通電状態は維持したまま、５００〜７００℃付近まで加熱することが好ましいとされる。 As the introduction of hydrogen gas into the furnace begins, the reaction between the hydrogen gas and the titanium alloy starts. Since the reaction between the hydrogen gas and the titanium alloy is an exothermic reaction, the temperature in the furnace tends to gradually increase, but it is preferable to heat to around 500 to 700 ° C. while maintaining the energized state of the heater. It is said.
前記温度に達した時点で、ヒーターの通電を断つ。この後も、反応熱で温度が上昇するので、炉内温度が７７０℃を超えないように測温を継続し、７７０℃を超えそうな状況の場合には、炉内に導入する水素ガスの供給量を調整することが好ましい。一方、水素化反応における反応温度が５００℃以下では、水素化反応速度が遅く、生産性の観点から好ましくない。よって、本願発明に係るチタン合金水素化物を製造する際の反応温度は、５００〜７７０℃が好ましい範囲とされる。 When the temperature is reached, the heater is turned off. After this, since the temperature rises due to the reaction heat, the temperature measurement is continued so that the temperature in the furnace does not exceed 770 ° C. If the situation is likely to exceed 770 ° C., the hydrogen gas introduced into the furnace It is preferable to adjust the supply amount. On the other hand, when the reaction temperature in the hydrogenation reaction is 500 ° C. or lower, the hydrogenation reaction rate is slow, which is not preferable from the viewpoint of productivity. Therefore, 500-770 degreeC is made into the range with preferable reaction temperature at the time of manufacturing the titanium alloy hydride which concerns on this invention.
水素ガスとチタン合金原料との水素化反応が終了すると、次第に炉内温度も低下する傾向に転じ、また、炉内圧力も減少する傾向を示す。よって室温まで冷却しても１気圧以下とならないように、炉内圧力を３．５気圧まで高めてから炉内を封じ切るように構成することが好ましい。 When the hydrogenation reaction between the hydrogen gas and the titanium alloy raw material is completed, the temperature in the furnace gradually decreases and the pressure in the furnace also decreases. Therefore, it is preferable that the inside of the furnace is sealed after the pressure in the furnace is increased to 3.5 atm so that the pressure does not become 1 atm or less even when cooled to room temperature.
以上述べた方法に従うことにより、本願発明に係るチタン合金水素化物中の水素ガスの濃度を３．９ｗｔ％以上に維持することができるという効果を奏するものである。 By following the method described above, the concentration of hydrogen gas in the titanium alloy hydride according to the present invention can be maintained at 3.9 wt% or more.
本願発明に係るチタン合金の水素化物原料としては、チタン合金切粉、板材、または線材をも用いることができるが、これ以外には、チタン合金の加工工程で発生した切断片や打ち抜き時の残材等、いわゆるチタン合金スクラップも本発明のチタン合金製造用原料として好適に使用することができる。 As the hydride raw material of the titanium alloy according to the present invention, titanium alloy chips, plate material, or wire can be used, but in addition to this, a cut piece generated in the processing process of the titanium alloy or a residue at the time of punching is used. So-called titanium alloy scrap such as wood can also be suitably used as a raw material for producing the titanium alloy of the present invention.
前記原料に使用するチタン合金には、アルミニウム、シリコン、銅、マンガン、バナジウム、ジルコニウム、ニオブ、クロム、モリブデン、スズ、ルテニウム、レニウム、または鉄の中から少なくとも１種以上の元素が含まれていることを特徴とするものである。例えば、Ｔｉ−６Ａｌ−４Ｖ合金のみならず、Ｔｉ−１０Ｖ−２Ｆｅ−３Ａｌ合金、Ｔｉ−５Ａｌ−５Ｖ−５Ｍｏ−３Ｃｒ合金等に対しても好適に適用することができる。 The titanium alloy used for the raw material contains at least one element selected from aluminum, silicon, copper, manganese, vanadium, zirconium, niobium, chromium, molybdenum, tin, ruthenium, rhenium, or iron. It is characterized by this. For example, it can be suitably applied not only to Ti-6Al-4V alloy but also to Ti-10V-2Fe-3Al alloy, Ti-5Al-5V-5Mo-3Cr alloy, and the like.
前記方法で製造されたチタン粉は、ＨＩＰ、ＣＩＰあるいは粉末圧延、押出等の技術により、密度の高いチタン合金製品あるいは、チタン合金素材を製造することができるが、本願発明においては、特に、前記プロセスのうち、押出あるいは粉末圧延により、緻密なチタン合金を効率よく製造することができるという効果を奏するものである。 The titanium powder produced by the above method can produce a high-density titanium alloy product or a titanium alloy material by techniques such as HIP, CIP or powder rolling, extrusion, etc. In the present invention, Among the processes, there is an effect that a dense titanium alloy can be efficiently produced by extrusion or powder rolling.
以下、実施例および比較例により、本発明をより具体的かつ詳細に説明する。
［実施例１］
Ｔｉ−６Ａｌ−４Ｖ合金（以下、６４合金と称する場合がある）の切削切粉を原料として、水素化用の容器に充填して水素化炉に投入した。真空排気後、加熱を開始し、真空のまま５００℃まで昇温した。ここで、真空排気を停止し、水素ガスを炉内が１．２気圧になるまで導入した。水素ガス導入後も加熱を継続し、炉内温度が６５０℃になった時点で、加熱ヒーターを停止した。この時、炉内の圧力が３．５気圧になるまで水素ガスを炉内に導入し続けた。炉内は水素化による反応熱で７００℃まで上昇したが、その後冷却に転じた。６５０℃到達から７００℃到達まで１０分かかり、炉内温度が６５０℃以下になるまで１時間かかった。炉内温度が５０℃以下まで冷却後、真空排気、ベント処理で炉を開放し、水素化物を取り出した。
Hereinafter, the present invention will be described more specifically and in detail with reference to Examples and Comparative Examples.
[Example 1]
A cutting chip of Ti-6Al-4V alloy (hereinafter sometimes referred to as 64 alloy) was used as a raw material, filled in a hydrogenation vessel, and charged into a hydrogenation furnace. After evacuation, heating was started, and the temperature was raised to 500 ° C. in a vacuum. Here, the evacuation was stopped and hydrogen gas was introduced until the pressure in the furnace reached 1.2 atm. Heating was continued after the introduction of hydrogen gas, and the heater was stopped when the furnace temperature reached 650 ° C. At this time, hydrogen gas was continuously introduced into the furnace until the pressure in the furnace reached 3.5 atm. The temperature in the furnace rose to 700 ° C. due to the heat of reaction caused by hydrogenation, but then it turned to cooling. It took 10 minutes from 650 ° C. to 700 ° C., and it took 1 hour for the furnace temperature to reach 650 ° C. or lower. After the furnace temperature was cooled to 50 ° C. or lower, the furnace was opened by evacuation and venting, and the hydride was taken out.
取り出した水素化６４合金の水素含有量は３．９０ｗｔ％であった。ＡＣＭ粉砕・分級装置を用い、水素化物の粉砕・分級を行ったところ、１５０μｍ以下粉の製品率は９８％、４５μｍ以下粉の製品率は７０％であった。また、ＸＲＤ測定し、２θ＝３５°近傍のＴｉＨ２のピークの半値幅を測定したところ、０．７８であった。また、水素化物の粉砕処理に要した時間は、１０分／ｋｇであった。 The extracted hydrogenated 64 alloy had a hydrogen content of 3.90 wt %. When the hydride was pulverized and classified using an ACM pulverizer / classifier, the product ratio of the powder of 150 μm or less was 98%, and the product ratio of the powder of 45 μm or less was 70%. Further, XRD measurement was performed, and the half width of the peak of TiH 2 near 2θ = 35 ° was measured, and it was 0.78. The time required for the hydride pulverization was 10 minutes / kg .
［実施例２］
実施例１と同じ６４合金の切削切粉を実施例１と同様に水素化炉に投入した。真空のまま５５０℃まで昇温してから真空排気を停止し、水素ガスを炉内が１．２気圧になるまで導入した。水素ガス導入後も加熱を継続し、炉内温度が６５０℃になった時点で、加熱ヒーターを停止した。この時、炉内の圧力が３．５気圧になるまで水素ガスを炉内に導入し続けた。炉内は水素化による反応熱で７３０℃まで上昇したが、その後冷却に転じた。６５０℃到達から７３０℃到達まで１０分かかり、炉内温度が６５０℃以下になるまで１．５時間かかった。実施例１と同様の手段で、炉内の水素化物を取り出した。
[Example 2]
The same 64 alloy cutting chips as in Example 1 were put into a hydrogenation furnace in the same manner as in Example 1. After raising the temperature to 550 ° C. in a vacuum, evacuation was stopped and hydrogen gas was introduced until the pressure in the furnace reached 1.2 atmospheres. Heating was continued after the introduction of hydrogen gas, and the heater was stopped when the furnace temperature reached 650 ° C. At this time, hydrogen gas was continuously introduced into the furnace until the pressure in the furnace reached 3.5 atm. The temperature in the furnace rose to 730 ° C. due to the heat of reaction caused by hydrogenation, but then it turned to cooling. It took 10 minutes from 650 ° C. to 730 ° C., and 1.5 hours until the furnace temperature became 650 ° C. or lower. The hydride in the furnace was taken out by the same means as in Example 1.
取り出した水素化６４合金の水素含有量は４．０８ｗｔ％であった。ＡＣＭ粉砕・分級装置を用い、水素化物の粉砕・分級を行ったところ、１５０μｍ以下粉の製品率は９９％、４５μｍ以下の粉の製品率は８０％であった。また、ＸＲＤ測定し、２θ＝３５°近傍のＴｉＨ２のピークの半値幅を測定したところ、０．４５であった。また、水素化物の粉砕処理に要した時間は、１５分／ｋｇであった。 The extracted hydrogenated 64 alloy had a hydrogen content of 4.08 wt %. When the hydride was pulverized and classified using an ACM pulverizer / classifier, the product ratio of the powder of 150 μm or less was 99%, and the product ratio of the powder of 45 μm or less was 80%. Further, when the XRD measurement was performed and the half width of the peak of TiH 2 near 2θ = 35 ° was measured, it was 0.45. The time required for the hydride pulverization was 15 minutes / kg.
［水素化率と半値幅の検討］
実施例１〜２の方法により、６４合金の水素化率と半値幅に関する本願発明の数値的臨界意義につき試験で確認し、その結果を表２に整理した。
[Examination of hydrogenation rate and half width]
By the method of Examples 1-2, it confirmed by the test about the numerical critical significance of this invention regarding the hydrogenation rate and half value width of 64 alloys, and arranged the result in Table 2.
チタン合金水素化物の水素含有率が、３．８ｗｔ％の場合には、水素化されたチタン合金の粉砕性が好ましくなく、目的とする粒度まで微粉砕する場合には、３０〜５０分／ｋｇの時間を要した。しかしながら、チタン合金粉末の水素含有率が、４．０ｗｔ％以上である場合の粉砕時間は半値幅に関係なく１０〜１５分／ｋｇの範囲にあった。なお、前記粉砕時間のばらつきは半値幅の違いによるものである。 When the hydrogen content of the titanium alloy hydride is 3.8 wt%, the pulverization property of the hydrogenated titanium alloy is not preferable. When finely pulverizing to the target particle size, 30 to 50 minutes / kg. It took time. However, the pulverization time when the hydrogen content of the titanium alloy powder was 4.0 wt% or more was in the range of 10 to 15 minutes / kg regardless of the half width. In addition, the dispersion | variation in the said grinding | pulverization time is based on the difference in a half width.
また、チタン合金水素化物の半値幅が、０．９°の場合には、粉砕された粉に占める粗粉の比率が増加し、４５μｍ以下の粉末の製品歩留まりが４０〜４５％に留まった。しかしながら、チタン合金粉末の半値幅が０．８°および０．５°の場合には、４５μｍ以下の粉末の製品歩留まりが、それぞれ６０〜８０％および７０〜８０％の範囲にあった。 Moreover, when the half width of the titanium alloy hydride was 0.9 °, the ratio of the coarse powder to the pulverized powder increased, and the product yield of the powder of 45 μm or less remained at 40 to 45%. However, when the full width at half maximum of the titanium alloy powder was 0.8 ° and 0.5 °, the product yield of the powder of 45 μm or less was in the range of 60 to 80% and 70 to 80%, respectively.
以上の試験結果より、本願発明に係るチタン合金水素化物は、３．９重量％以上の水素を含有し、かつ、粉末Ｘ線回折測定における２θ＝３５°近傍のピークの半値幅が０．８５°以下が好ましい特徴であることが確認された。 From the above test results, the titanium alloy hydride according to the present invention contains 3.9% by weight or more of hydrogen, and the half width of the peak near 2θ = 35 ° in the powder X-ray diffraction measurement is 0.85. It has been confirmed that the preferred characteristics are below.
［温度と圧力の検討］
実施例１〜２の方法により、本願発明に係る６４合金の水素化の温度と圧力に関する数値的臨界意義について調査し、その結果を表３に示した。
[Examination of temperature and pressure]
The numerical critical significance regarding the temperature and pressure of hydrogenation of the 64 alloy according to the present invention was investigated by the methods of Examples 1 and 2, and the results are shown in Table 3.
本願発明の範囲にある反応温度が、５２０℃、６５０℃、および７５０℃であって、圧力が３．３ａｔｍ、２．０ａｔｍおよび１．２ａｔｍの場合には、水素化反応率は、９４〜９９％の範囲にあった。また、製品の酸素含有率は、１，０２０〜１，０８０ｐｐｍにあり、製品としての要求特性が満足された。しかしながら、水素化反応温度が、本願発明の範囲外にある７８０℃では水素化反応率が７５〜８０％に留まった。一方、水素化反応温度が４８０℃では、水素化反応率が７０〜７５％に留まった。なお、前記水素化反応率のバラツキは、圧力の違いによるものである。 When the reaction temperature within the range of the present invention is 520 ° C., 650 ° C., and 750 ° C. and the pressure is 3.3 atm, 2.0 atm, and 1.2 atm, the hydrogenation reaction rate is 94 to 99. % Range. Further, the oxygen content of the product was 1,020 to 1,080 ppm, and the required characteristics as the product were satisfied. However, at a hydrogenation reaction temperature of 780 ° C., which is outside the scope of the present invention, the hydrogenation reaction rate remained at 75-80%. On the other hand, when the hydrogenation reaction temperature was 480 ° C., the hydrogenation reaction rate remained at 70 to 75%. The variation in the hydrogenation reaction rate is due to the difference in pressure.
また、水素化処理圧力が、０．８ａｔｍでは、水素化処理炉内に外気が侵入し、その結果、水素化チタン合金粉中の酸素含有率が、４，２００〜４，６００ｐｐｍとなった。これに対して、炉内圧力を１ａｔｍ以上に保持した場合に得られた水素化チタンの酸素含有率は、１，０００〜１，１００ｐｐｍにあり品質の点で優れていることが確認された。なお、水素の圧力は、３．８ａｔｍ以上であっても製品品質に悪影響を及ぼすことは無い。しかし、水素の圧力が水素化反応率に効果的に作用する現象は、３．３ａｔｍ程度で飽和してしまい、これ以上高い水素圧力は、経済性の点で好ましくない。 In addition, when the hydrotreating pressure was 0.8 atm, outside air entered the hydrotreating furnace, and as a result, the oxygen content in the titanium hydride alloy powder was 4,200 to 4,600 ppm. On the other hand, it was confirmed that the oxygen content of titanium hydride obtained when the furnace pressure was maintained at 1 atm or higher was in the range of 1,000 to 1,100 ppm and was excellent in terms of quality. Even if the hydrogen pressure is 3.8 atm or higher, the product quality is not adversely affected. However, the phenomenon in which the hydrogen pressure effectively acts on the hydrogenation reaction rate is saturated at about 3.3 atm, and a hydrogen pressure higher than this is not preferable in terms of economy.
以上の試験結果より、本願発明に係るチタン合金水素化物を得るための好ましい圧力範囲は、１気圧〜３．５気圧であり、かつ、温度範囲は、５００〜７７０℃であることが確認された。 From the above test results, it was confirmed that the preferable pressure range for obtaining the titanium alloy hydride according to the present invention is 1 atm to 3.5 atm, and the temperature range is 500 to 770 ° C. .
［比較例］
実施例１と同じ６４合金の切削切粉を実施例１と同様に水素化炉に投入した。真空のまま６５０℃まで昇温してから真空排気を停止し、水素ガスを炉内が１．２気圧になるまで導入した。水素ガス導入後も加熱を継続し、炉内温度が７５０℃になった時点で、加熱ヒーターを停止した。この時、炉内の圧力が３．５気圧になるまで水素ガスを炉内に導入し続けた。炉内は水素化による反応熱で８２０℃まで上昇したが、その後冷却に転じた。６５０℃到達から８２０℃到達まで２５分かかり、炉内温度が最高温度から６５０℃以下になるまで２．５時間かかった。実施例１と同様の手段で、炉内の水素化物を取り出した。
[ Comparative example ]
The same 64 alloy cutting chips as in Example 1 were put into a hydrogenation furnace in the same manner as in Example 1. After raising the temperature to 650 ° C. in a vacuum, the evacuation was stopped and hydrogen gas was introduced until the pressure in the furnace reached 1.2 atm. Heating was continued after the introduction of hydrogen gas, and the heater was stopped when the furnace temperature reached 750 ° C. At this time, hydrogen gas was continuously introduced into the furnace until the pressure in the furnace reached 3.5 atm. The temperature in the furnace rose to 820 ° C. due to the heat of reaction caused by hydrogenation, but then it turned to cooling. It took 25 minutes from 650 ° C. to 820 ° C., and it took 2.5 hours for the furnace temperature to reach 650 ° C. or lower from the maximum temperature. The hydride in the furnace was taken out by the same means as in Example 1.
取り出した水素化６４合金の水素含有量は３．５５ｗｔ％であった。ＡＣＭ粉砕・分級装置を用い、水素化物の粉砕・分級を行ったところ、１５０μｍ以下粉の製品率は７０％、４５μｍ以下分の製品率は２０％であった。また、ＸＲＤ測定し、２θ＝３５°近傍のＴｉＨ２のピークの半値幅を測定したところ、１．０２であった。 The extracted hydrogenated 64 alloy had a hydrogen content of 3.55 wt %. When the hydride was pulverized and classified using an ACM pulverizer / classifier, the product ratio of the powder of 150 μm or less was 70%, and the product ratio of the powder of 45 μm or less was 20%. Further, the half width of the peak of TiH 2 near 2θ = 35 ° was measured by XRD and found to be 1.02.
本発明で製造されたチタン合金水素化物は、脱水素によりチタン合金粉を製造することができるのみならず、発泡金属製造用原料としても好適に用いることができ、有望である。
The titanium alloy hydride produced in the present invention can be used not only as a titanium alloy powder by dehydrogenation but also as a raw material for producing foam metal, which is promising.
Claims (4)
チタン合金に水素ガスを接触させ、１．２気圧（１２０ｋＰａ）以上、３．５気圧（３５０ｋＰａ）以下で、５００℃〜７７０℃の温度域にて反応させることを特徴とするチタン合金水素化物の製造方法。 A method for producing a titanium alloy hydride according to claim 1 or 2,
Titanium alloy is contacted with hydrogen gas, 1.2 atm (120 kPa) or more, at 3.5 atm (350 kPa) or less, a titanium alloy hydrogen, characterized in that Ru is reacted at a temperature range of 500 ℃ ~770 ℃ Method for producing chemicals .
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