JPH0633165A - Manufacture of sintered titanium alloy - Google Patents
Manufacture of sintered titanium alloyInfo
- Publication number
- JPH0633165A JPH0633165A JP4194319A JP19431992A JPH0633165A JP H0633165 A JPH0633165 A JP H0633165A JP 4194319 A JP4194319 A JP 4194319A JP 19431992 A JP19431992 A JP 19431992A JP H0633165 A JPH0633165 A JP H0633165A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- titanium
- alloy
- sintering
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 103
- 239000010936 titanium Substances 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 36
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- -1 titanium hydride Chemical compound 0.000 claims description 15
- 238000001513 hot isostatic pressing Methods 0.000 claims description 8
- 238000009694 cold isostatic pressing Methods 0.000 claims 4
- 230000002542 deteriorative effect Effects 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 14
- 238000005275 alloying Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 9
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 229910018084 Al-Fe Inorganic materials 0.000 description 2
- 229910018192 Al—Fe Inorganic materials 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012535 impurity Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 229910011212 Ti—Fe Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は焼結チタン合金の製造方
法に関する。さらに詳しくは、素粉末混合法による焼結
チタン合金の製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing a sintered titanium alloy. More specifically, the present invention relates to a method for producing a sintered titanium alloy by the elementary powder mixing method.
【０００２】[0002]
【従来の技術】粉末冶金法は、材料を最終形状に近い形
状にまで造形できるため、加工性や成形性あるいは被削
性の乏しいチタン合金等の製品を得るための製造法とし
て適している。とりわけ、純チタン粉末と合金化用添加
粉末を機械的に混合して、プレスもしくはＣＩＰ（冷間
等方圧成形）にて所定形状に成形し、真空もしくは不活
性ガス雰囲気中で焼結および合金化熱処理を同時に行
い、その後必要に応じてＨＩＰ（熱間等方圧成形）や鍛
造等の高密度化処理を行う素粉末混合法は、焼結以前
には軟質なチタン粉末が原料の大部分を占めるので良好
な成形性を有し、室温において精密な形状の圧粉体を製
造し得る。素材粉末の混合比を変えて、組成の異なる
各種の合金を製造することができる。などの利点を持っ
ている。2. Description of the Related Art The powder metallurgy method is suitable as a manufacturing method for obtaining a product such as a titanium alloy having poor workability, formability, or machinability, since the material can be formed into a shape close to the final shape. In particular, pure titanium powder and additive powder for alloying are mechanically mixed and formed into a predetermined shape by press or CIP (cold isotropic pressure forming), and sintered and alloyed in a vacuum or an inert gas atmosphere. The raw powder mixing method, in which the chemical heat treatment is performed at the same time, and then the densification treatment such as HIP (hot isostatic pressing) and forging is performed if necessary, is that soft titanium powder is used as a raw material in most of the raw materials before sintering. Since it has a good moldability, it is possible to produce a green compact having a precise shape at room temperature. Various alloys having different compositions can be manufactured by changing the mixing ratio of the raw material powders. Have such advantages.
【０００３】原料であるチタン粉末としては、廉価なも
のとして、ハンター法によるスポンジチタンの製造時に
発生する粉末である、いわゆるスポンジファインの使用
が考えられる。しかしスポンジファインは多量の塩素を
含有しており、真空熱処理工程では十分な塩素の除去が
できないため、製品中に残留する塩素に起因する多量の
空孔が発生し、その結果、焼結チタン合金の機械的特性
の劣化を招く。したがって素粉末混合法においてスポン
ジファイン粉末を原料粉末として使用することは、チタ
ン合金の優れた特性を活かしているとは言えない。この
ように、原料であるチタン粉末は塩素含有量が低いこと
が必須であり、現状ではチタン粉末は純チタンインゴッ
トの粉砕により得られている。As the titanium powder as a raw material, it is possible to use, as an inexpensive material, so-called sponge fine, which is a powder generated during the production of titanium sponge by the Hunter method. However, sponge fine contains a large amount of chlorine and cannot be removed sufficiently in the vacuum heat treatment process, so a large amount of vacancies are generated due to residual chlorine in the product. Causes deterioration of mechanical properties of the. Therefore, the use of sponge fine powder as a raw material powder in the elementary powder mixing method cannot be said to take advantage of the excellent properties of titanium alloys. As described above, it is essential that the titanium powder as a raw material has a low chlorine content, and at present, the titanium powder is obtained by crushing a pure titanium ingot.
【０００４】しかしながら、純チタンは延性が良好で、
通常の機械的な方法では粉砕が困難である。そこで、チ
タン粉末の製造には、チタンの脆化を目的として水素化
処理を行い、所定粒子径に粉砕を行った後、さらに脱水
素熱処理を行うというＨＤＨ処理を施す必要がある。こ
のＨＤＨ処理は、チタン粉末の水素量を通常のチタン合
金の水素含有量である、０．０２重量％以下にまで脱水
素するのに、６〜２０時間にわたる長時間の真空熱処理
が必要であり、非常に高価な原料となっている。However, pure titanium has good ductility,
Grinding is difficult with normal mechanical methods. Therefore, in the production of titanium powder, it is necessary to perform an HDH treatment in which hydrogenation treatment is performed for the purpose of embrittlement of titanium, pulverization is performed to a predetermined particle size, and then dehydrogenation heat treatment is further performed. This HDH treatment requires a long-time vacuum heat treatment for 6 to 20 hours in order to dehydrogenate the hydrogen content of the titanium powder to 0.02% by weight or less, which is the hydrogen content of a normal titanium alloy. , Is a very expensive raw material.
【０００５】したがって、このような原料粉末を使用し
ている素粉末混合法によるチタン合金の製造コストは極
めて高価であり、コストの低減が要請されている。Therefore, the production cost of the titanium alloy by the elementary powder mixing method using such raw material powder is extremely high, and it is required to reduce the cost.
【０００６】一方、「Powder Metallurgy Internationa
l 誌」（1974年発行）No.2、第６６頁に記載されている
ように、焼結純チタン材においては原料粉末に水素化チ
タン粉末や水素化チタン粉末とチタン粉末の混合粉末を
使用し、脱水素工程と焼結工程を同時に行う方法があ
る。この方法では、脱水素工程を行わない安価な水素化
チタン粉末を使用でき、なお熱処理工程が１工程省略で
きるのでチタン合金の特性に悪影響を及ぼす酸素による
汚染が軽減される利点がある。さらに、水素化チタン粉
末に含まれる多量の転位によりチタンの拡散が活性化さ
れ、チタン粉末のみを使用した場合より低温短時間で焼
結が進行する利点がある。On the other hand, "Powder Metallurgy Internationa
As described in “L Magazine” (issued in 1974), No. 2, p. 66, titanium hydride powder or mixed powder of titanium hydride powder and titanium powder is used as raw material powder in sintered pure titanium material. However, there is a method of simultaneously performing the dehydrogenation step and the sintering step. In this method, an inexpensive titanium hydride powder that does not undergo a dehydrogenation step can be used, and since one heat treatment step can be omitted, there is an advantage that contamination by oxygen that adversely affects the characteristics of the titanium alloy can be reduced. Further, there is an advantage that the diffusion of titanium is activated by a large amount of dislocations contained in the titanium hydride powder, and the sintering proceeds at a low temperature in a short time as compared with the case where only the titanium powder is used.
【０００７】しかしながら、この方法は、素粉末混合法
による焼結チタン合金の製造方法には直接的用はできな
い。その理由は以下に述べる通りである。まず、チタン
合金は、Ａｌ，Ｖ，Ｆｅ，ＭｏなどのＴｉ以外の元素を
多量に含み、これらの合金元素は水素と強く相互作用す
る。このため、水素を含む原料粉末を使用した焼結チタ
ン合金の製造は、焼結純チタンの製造に比べ、脱水素熱
処理に非常に長い時間が必要となる。この時一部の水素
は焼結の進行に従って、素材内部に残存する空孔にガス
として閉じ込められる。素材中に閉じ込められた水素ガ
スは、昇温および脱水素によるガス圧力の上昇に伴い、
再び素材に溶け込み、材料表面から抜け出るという過程
を経なくては素材の外部に排出されないため、脱水素に
さらに時間がかかることになる。同時に水素ガスの圧力
のため素材内部の空孔の消滅が遅れ、焼結の進行が阻害
される。さらに焼結時に抜けきれず素材中に残留した水
素は、チタン合金を脆化させるなど特性に悪影響を及ぼ
す。However, this method cannot be directly applied to the method for producing a sintered titanium alloy by the elementary powder mixing method. The reason is as described below. First, the titanium alloy contains a large amount of elements other than Ti such as Al, V, Fe and Mo, and these alloy elements interact strongly with hydrogen. Therefore, in the production of a sintered titanium alloy using a raw material powder containing hydrogen, the dehydrogenation heat treatment requires a very long time as compared with the production of sintered pure titanium. At this time, a part of hydrogen is confined as gas in the pores remaining inside the material as the sintering progresses. The hydrogen gas trapped in the material increases with increasing gas pressure due to temperature rise and dehydrogenation.
It takes more time to dehydrogenate because it is not discharged to the outside of the material unless it goes through the process of melting into the material again and escaping from the surface of the material. At the same time, the pressure of hydrogen gas delays the disappearance of pores inside the material, which hinders the progress of sintering. Further, hydrogen that cannot be completely removed during sintering and remains in the material has an adverse effect on properties such as embrittlement of the titanium alloy.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、素粉末混合
法により焼結チタン合金を製造するにあたり、本来チタ
ン合金の有する優れた特性を損なうことなく、なおかつ
安価な製造コストで製造するための方法を提供すること
を目的とする。DISCLOSURE OF THE INVENTION In producing a sintered titanium alloy by the elementary powder mixing method, the present invention is intended to produce it at a low production cost without deteriorating the excellent characteristics originally possessed by the titanium alloy. The purpose is to provide a method.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するため
に本発明は、 （１）素粉末混合法によって焼結チタン合金を製造する
方法において、チタン粉末の代わりに、チタン粉末及び
（Ｔｉ−Ｈ）合金粉末及び水素化チタン粉末を用いて水
素：チタンが質量比で０．００２以上で０．０３０未満
となるように配合した粉末を原料粉末として使用するこ
とを特徴とする。 （２）上記（１）の処理により配合された粉末を原料粉
末として使用し、圧粉体の成形を３００MPa 以上で６０
０MPa 以下の圧力でＣＩＰ（冷間等方圧成形）により行
うことを特徴とする。 （３）上記（２）の処理により作製された圧粉体を、焼
結後ＨＩＰ（熱間等方圧成形）処理を行うことを特徴と
するものである。In order to achieve the above object, the present invention provides (1) a method for producing a sintered titanium alloy by an elemental powder mixing method, wherein titanium powder and (Ti- H) An alloy powder and a titanium hydride powder are used as a raw material powder, which is a mixture of hydrogen and titanium in a mass ratio of 0.002 or more and less than 0.030. (2) Using the powder compounded by the above process (1) as the raw material powder, the green compact is molded at a pressure of 300 MPa or more at 60 MPa.
It is characterized by performing CIP (cold isotropic pressure forming) at a pressure of 0 MPa or less. (3) The method is characterized in that the green compact produced by the treatment of (2) above is subjected to HIP (hot isostatic pressing) treatment after sintering.
【００１０】本発明において、水素化チタン粉末とは、
チタン中に３．０重量％以上の水素を含有する粉末であ
り、この粉末の大部分はＴｉＨ2 が占める。また（Ｔｉ
−Ｈ）合金粉末とは、チタン中の水素含有量が０．２重
量％以上３．０重量％未満の粉末で、α−Ｔｉ相とＴｉ
Ｈ2 相の２相を主相とする粉末であり、例えばＴｉ−１
％Ｈ，Ｔｉ−２％Ｈ等の合金粉末をいう。配合した粉末
とはチタン粉末および水素化チタン粉末および（Ｔｉ−
Ｈ）合金粉末のうち１種類もしくは２種類以上を混合
し、チタン以外に水素を含んだ状態の混合粉末であり、
本発明中においては、（Ｔｉ−Ｈ）合金１種類のみを使
用した場合や、チタンと（Ｔｉ−Ｈ）合金、チタンと水
素化チタン粉末などの２種類の粉末を配合した場合や、
さらにチタンと（Ｔｉ−Ｈ）合金と水素化チタン粉末と
３種類以上の粉末を配合した場合など、いずれの配合を
使用しても良い。なお、水素：チタンの質量比０．００
２とは、水素量で換算した場合０．２重量％に相当し、
０．０３０とは２．６重量％に相当する。In the present invention, the titanium hydride powder means
It is a powder containing 3.0% by weight or more of hydrogen in titanium, and TiH 2 occupies most of this powder. Also (Ti
-H) alloy powder is a powder in which the hydrogen content in titanium is 0.2% by weight or more and less than 3.0% by weight, and the α-Ti phase and Ti
It is a powder having two phases of H 2 phase as a main phase, for example, Ti-1
% H, Ti-2% H, and other alloy powders. The blended powders are titanium powder, titanium hydride powder and (Ti-
H) a mixed powder in which hydrogen is contained in addition to titanium by mixing one kind or two or more kinds of the alloy powder,
In the present invention, when only one type of (Ti-H) alloy is used, when two types of powder such as titanium and (Ti-H) alloy, and titanium and titanium hydride powder are blended,
Further, any combination may be used, such as a case where three or more kinds of powders are mixed with titanium, (Ti-H) alloy, titanium hydride powder. The hydrogen: titanium mass ratio is 0.00
2 corresponds to 0.2% by weight when converted to the amount of hydrogen,
0.030 corresponds to 2.6% by weight.
【００１１】また、本発明において焼結チタン合金とは
Ｔｉと、Ａｌ，Ｖ，Ｆｅやこれら以外の合金成分および
０．７重量％未満のＯ，Ｎ，Ｃ，Ｈといった不純物から
なるチタン合金であり、例えばＴｉ−６Ａｌ−４Ｖ合
金，Ｔｉ−３Ａｌ−２．５Ｖ合金，Ｔｉ−５Ａｌ−２．
５Ｆｅ合金等の合金である。このような焼結チタン合金
を素粉末混合法により製造するに際して、Ａｌ，Ｖ，Ｆ
ｅその他の合金成分は、例えばＡｌ−Ｖ，Ａｌ−Ｆｅ，
Ｔｉ−Ａｌ，Ｔｉ−Ｆｅ，Ｔｉ−Ａｌ−Ｆｅ，などのよ
うな母合金粉末を混合することによって添加しても良い
し、Ａｌ粉末，Ｖ粉末，Ｆｅ粉末などの金属元素粉末を
それぞれ所定成分に混合しても良い。In the present invention, the sintered titanium alloy is a titanium alloy composed of Ti, Al, V, Fe and alloy components other than these and impurities such as O, N, C and H of less than 0.7% by weight. , Ti-6Al-4V alloy, Ti-3Al-2.5V alloy, Ti-5Al-2.
It is an alloy such as a 5Fe alloy. When manufacturing such a sintered titanium alloy by the elementary powder mixing method, Al, V, F
e Other alloy components include, for example, Al-V, Al-Fe,
It may be added by mixing master alloy powders such as Ti-Al, Ti-Fe, Ti-Al-Fe, etc., or metal element powders such as Al powder, V powder, Fe powder and the like may be added as predetermined components. You may mix in.
【００１２】[0012]
【作用】以下、本発明を詳細に説明する。本発明者ら
は、水素化チタン粉末の利用に関して研究を重ねた結
果、素粉末混合法において焼結チタン合金を製造するに
あたり、原料粉末に水素化チタン粉末および（Ｔｉ−
Ｈ）合金粉末とチタン粉末を特定量混合した粉末を使用
すると、合金元素の拡散が著しく速くなり、焼結時の合
金化が促進されることを見出した。本発明はこの新規知
見に基づくものである。すなわち、素粉末混合法の焼結
熱処理工程の２大目的である粉末の焼結と合金化におい
て、前者の遅延を後者で補おうとするものである。The present invention will be described in detail below. As a result of repeated studies on the use of titanium hydride powder, the present inventors have used titanium hydride powder and (Ti-
It has been found that the use of a powder obtained by mixing H) alloy powder and titanium powder in a specific amount makes the diffusion of alloying elements significantly faster and promotes alloying during sintering. The present invention is based on this new finding. That is, in the sintering and alloying of powders, which are the two main purposes of the sintering heat treatment step of the elementary powder mixing method, the latter delay is intended to be supplemented by the latter.
【００１３】原料粉末中に水素が含まれる場合、水素を
含まないチタン粉末を使用する場合と比べ、合金元素の
拡散が速くなるのは次の理由による。すなわち、水素は
β相安定化元素であるので、チタン中に水素を含有させ
ることにより、高温相であるβ相がより低温で出現す
る。このβ相中では、α相と比べＡｌ，Ｖ，Ｆｅ，Ｍｏ
等の金属合金元素は著しく速くなり、焼結の早期段階に
β相が低温から生じ、合金化が著しく加速される。When the raw material powder contains hydrogen, the diffusion of alloying elements becomes faster than when titanium powder containing no hydrogen is used for the following reason. That is, since hydrogen is a β-phase stabilizing element, the inclusion of hydrogen in titanium causes the β-phase, which is a high temperature phase, to appear at a lower temperature. In this β phase, Al, V, Fe, Mo are compared with the α phase.
Metal alloying elements such as, etc. become significantly faster, β-phase is generated from low temperature in the early stage of sintering, and alloying is significantly accelerated.
【００１４】この効果を十分活用するには、Ｈ：Ｔｉの
質量比で０．００２以上、０．０３０未満とする必要が
ある。すなわち、Ｈ：Ｔｉの質量比を０．００２以上に
限定したのは、これに満たない量しか添加しなかった場
合、水素添加による合金元素の拡散の活性化が十分でな
く、合金化促進効果が十分に現れないからである。ま
た、大部分の原料が既に脱水素工程を経たチタン粉末を
使用することになり、省工程による低コスト化の利点が
少ない。水素量の上限値をＨ：Ｔｉを質量比で０．０３
０未満としたのは、これ以上の水素含有量では合金化の
活性化よりも素材中の空孔内の水素ガス圧の増加による
焼結の遅延効果が勝り、本発明の効果が十分でなくなる
ためである。さらに、水素量を上限値より多くした場
合、急激に成形性が悪化し、成形体の密度が十分でな
く、さらには割れのために成形体が得られないこともあ
る。In order to fully utilize this effect, the H: Ti mass ratio must be 0.002 or more and less than 0.030. That is, the mass ratio of H: Ti is limited to 0.002 or more because when the amount added is less than this, activation of the diffusion of alloying elements by hydrogen addition is not sufficient and the alloying promoting effect is obtained. Is not enough to appear. In addition, most of the raw materials use titanium powder that has already undergone the dehydrogenation process, and there is little advantage of cost reduction due to process saving. The upper limit of the amount of hydrogen is 0.03 by mass ratio of H: Ti.
When the hydrogen content is more than 0, the effect of the present invention becomes insufficient because the effect of delaying the sintering due to the increase of the hydrogen gas pressure in the voids in the raw material is superior to the activation of the alloying. This is because. Further, when the amount of hydrogen is more than the upper limit value, the formability is rapidly deteriorated, the density of the molded body is insufficient, and further, the molded body may not be obtained due to cracking.
【００１５】本発明の請求項２の発明では、粉体の成形
をＣＩＰで行うこととした。ＣＩＰは、ダイプレス等の
１軸方向で圧縮成形する方法と異なり、素材に均一な圧
力を付与でき疎密の無い均質な成形体が得られるため、
脱水素がスムーズになり、有利な成形方法である。In the second aspect of the present invention, the powder is molded by CIP. Unlike the method of compression molding in a uniaxial direction such as die press, CIP can apply a uniform pressure to the material and can obtain a homogeneous molded body with no density.
Dehydrogenation becomes smooth, which is an advantageous molding method.
【００１６】本発明の請求項３では、真空焼結後にＨＩ
Ｐ処理を行う。これは焼結後わずかに残留する空孔を消
滅させ、さらにチタン合金の特性を向上させるためであ
り、焼結チタン合金の製造では通常９００℃から１００
０℃の間で行われる。According to claim 3 of the present invention, after vacuum sintering, the HI
P processing is performed. This is to eliminate slightly remaining holes after sintering and further improve the properties of the titanium alloy, and in the production of the sintered titanium alloy, it is usually from 900 ° C to 100 ° C.
It is carried out between 0 ° C.
【００１７】[0017]
【実施例】Ｔｉ−６Ａｌ−４Ｖ（Ａｌ：６重量％，Ｖ：
４重量％，残部：実質的にＴｉ、少量の不純物を含む）
に対して本発明を適用した場合を例に基づいて、さらに
詳しく説明する。EXAMPLES Ti-6Al-4V (Al: 6% by weight, V:
4% by weight, balance: substantially Ti, containing a small amount of impurities)
The present invention will be described in more detail based on an example.
【００１８】原料粉末は、平均粒径は７５μｍ、最大粒
径１５０μｍのＴｉ粉末および平均粒径７５μｍ、最大
粒径１５０μｍのＴｉＨ2 粉末（水素量４重量％）およ
び、平均粒径７５μｍ、最大粒径１５０μｍの（Ｈ−Ｔ
ｉ）合金粉末を使用した。添加合金成分であるＡｌおよ
びＶは、平均粒径３０μｍ、最大粒径４５μｍのＡｌＶ
母合金粉末（Ａｌ：６０重量％，Ｖ：４０重量％）を使
用し、Ｔｉ対母合金の重量比を９：１となるように混合
した。The raw material powder has an average particle size of 75 μm, a Ti powder having a maximum particle size of 150 μm and a TiH 2 powder having an average particle size of 75 μm and a maximum particle size of 150 μm (hydrogen content 4% by weight), and an average particle size of 75 μm and a maximum particle size. 150 μm diameter (HT
i) Alloy powder was used. Al and V as additive alloy components are AlV having an average particle size of 30 μm and a maximum particle size of 45 μm.
Mother alloy powders (Al: 60% by weight, V: 40% by weight) were used and mixed so that the weight ratio of Ti to the mother alloy was 9: 1.
【００１９】表１は、種々のチタン粉末混合体の圧粉体
を成形し、さらに毎分４０℃で昇温し、保持温度を１２
５０℃として真空焼結した場合、９５％以上の相対密度
を得るのに必要な焼結時間を測定した結果である。ここ
でいう相対密度とは、同じ組成の合金を溶解法により製
造した場合に得られる試料の密度を１００％とした場合
の比であり、粉末冶金法では経験的に９５％以上の相対
密度を有する焼結体は、その後のＨＩＰ処理により１０
０％相対密度になることが知られている。Table 1 shows that compacts of various titanium powder mixtures were molded, further heated at 40 ° C./min, and held at a temperature of 12.
This is the result of measuring the sintering time required to obtain a relative density of 95% or more when vacuum sintering is performed at 50 ° C. The relative density here is a ratio when the density of a sample obtained when an alloy having the same composition is manufactured by a melting method is set to 100%, and in the powder metallurgy method, a relative density of 95% or more is empirically determined. The sintered body has a HIP treatment of 10
It is known to be 0% relative density.
【００２０】[0020]
【表１】 [Table 1]
【００２１】表１にて試験番号１はＨＤＨ−Ｔｉ粉末と
６０Ａｌ−４０Ｖ母合金粉末を９：１の割合で混合した
粉末を原料とした場合で、従来法に相当する。この混合
粉末をＣＩＰにより４９０MPa で成形し、１２５０℃で
真空焼結を行うと、９５％以上の相対密度を得るには２
時間の焼結時間が必要である。In Table 1, Test No. 1 is a case where a powder obtained by mixing HDH-Ti powder and 60Al-40V mother alloy powder at a ratio of 9: 1 is used as a raw material and corresponds to the conventional method. When this mixed powder was molded by CIP at 490 MPa and vacuum-sintered at 1250 ° C., it was 2 to obtain a relative density of 95% or more.
Time sintering time is required.
【００２２】試験番号４は原料粉末を試験番号１で使用
したＨＤＨ−Ｔｉ粉末の代わりにＨＤＨ−Ｔｉ粉末とＴ
ｉＨ2 粉末を６：３の比率で配合し、Ｈ：Ｔｉの質量比
を０．０１４と本発明の請求範囲内の水素量を含む混合
粉末を用いた試験である。試験番号１と同様に成形をＣ
ＩＰにて４９０MPa で行い、１２５０℃で真空焼結し
た。この場合、９５％以上の相対密度を得るには１時間
４０分の焼結時間で可能であり、原料粉末への水素添加
効果のβ相の低温発生による合金元素拡散の活性化効果
が、水素ガスの発生による焼結の阻害する効果より勝る
ため、従来法より短時間での終結が可能となっている。Test No. 4 is the same as the HDH-Ti powder used in Test No. 1 except that the raw material powder was HDH-Ti powder and T.
In this test, iH 2 powder was mixed in a ratio of 6: 3, and a mixed powder containing H: Ti at a mass ratio of 0.014 and an amount of hydrogen within the scope of the present invention was used. Mold C as in Test No. 1.
It was performed at IP of 490 MPa and vacuum-sintered at 1250 ° C. In this case, it is possible to obtain a relative density of 95% or more with a sintering time of 1 hour and 40 minutes, and the activation effect of alloying element diffusion due to the low temperature generation of β phase of the hydrogen addition effect to the raw material powder is Since it outweighs the effect of inhibiting the sintering due to the generation of gas, it can be completed in a shorter time than the conventional method.
【００２３】試験番号３および５の原料チタン粉末の水
素量をそれぞれ本発明請求範囲内の下限値および上限値
近くに設定した配合粉末を使用している。これらの場合
９５％以上の相対密度に到達する焼結時間は従来法より
若干長めであるが、これは水素添加による合金拡散の活
性化の効果がガス発生による焼結阻害の効果を相殺した
ためであり、十分実用的な範囲にある。Blended powders were used in which the hydrogen contents of the raw material titanium powders of Test Nos. 3 and 5 were set close to the lower and upper limits, respectively, within the scope of the claims of the present invention. In these cases, the sintering time to reach the relative density of 95% or more is slightly longer than that of the conventional method, but this is because the effect of activation of alloy diffusion by hydrogen addition cancels the effect of sintering inhibition by gas generation. Yes, it is within a practical range.
【００２４】一方、本発明の比較例である、試験番号２
では、表１に示すように９５％以上の焼結密度を得るに
は３時間以上という長時間の熱処理が必要となる。この
理由は、Ｈ：Ｔｉの質量比が０．００１と本発明の請求
範囲の下限値より少ないため、水素添加による合金元素
拡散の活性化が十分でなく、焼結の促進効果が現れず、
ガス閉じ込めによる焼結の遅延が顕著になったためであ
る。また、試験番号６は本発明の請求範囲の水素量の上
限値の０．０３０以上であるため、合金化の活性化より
も素材中の空孔中の水素ガス圧の増加による焼結の遅延
効果が勝り、本発明の効果が十分でなくなるためであ
る。On the other hand, test number 2 which is a comparative example of the present invention
Then, as shown in Table 1, long-term heat treatment of 3 hours or more is required to obtain a sintered density of 95% or more. The reason for this is that the H: Ti mass ratio is 0.001, which is less than the lower limit of the claims of the present invention, so activation of alloying element diffusion by hydrogen addition is not sufficient, and the effect of promoting sintering does not appear.
This is because the sintering delay due to the gas confinement became remarkable. Further, since the test number 6 is 0.030 or more, which is the upper limit of the amount of hydrogen in the claims of the present invention, the sintering delay due to the increase of hydrogen gas pressure in the pores of the material rather than activation of alloying This is because the effect is superior and the effect of the present invention is not sufficient.
【００２５】試験番号７は（Ｔｉ−１％Ｈ）合金粉末を
試験番号８は（Ｔｉ−２％Ｈ）合金粉末をそれぞれ原料
粉末として使用した実施例である。これらの場合も９５
％以上の相対密度に到達するために必要な焼結時間は約
２時間程度あり、水素添加の効果が十分に現れている。
試験番号９は（Ｔｉ−２％Ｈ）粉末とＴｉＨ2 粉末の２
種類の粉末を配合した場合で試験番号１１は（Ｔｉ−２
％Ｈ）粉末とＴｉＨ2 粉末およびＴｉ粉末の３種類の粉
末を配合した場合の実施例である。両者とも十分実用的
な焼結時間内で９５％の相対密度に到達している。この
ように原料粉末中の水素の含有状態が異なる場合でも、
水素添加による合金拡散の活性化が脱水素反応の遅れや
水素ガス発生による焼結の遅延を補い、十分に本発明の
効果が達成される。Test number 7 is an example using (Ti-1% H) alloy powder and test number 8 is an example using (Ti-2% H) alloy powder as raw material powders. 95 in these cases
The sintering time required to reach the relative density of not less than about 2% is about 2 hours, and the effect of hydrogen addition is sufficiently exhibited.
Test number 9 is (Ti-2% H) powder and TiH 2 powder 2
Test No. 11 is (Ti-2
% H) powder, TiH 2 powder, and Ti powder. Both have reached a relative density of 95% within a sufficiently practical sintering time. In this way, even when the content of hydrogen in the raw material powder is different,
Activation of alloy diffusion by hydrogen addition compensates for delay of dehydrogenation reaction and sintering due to generation of hydrogen gas, and the effect of the present invention is sufficiently achieved.
【００２６】一方、試験番号１０は試験番号９と同様に
（Ｔｉ−２％Ｈ）粉末とＴｉＨ2 粉末の２種類の粉末を
配合した場合の比較例であるが、本発明の請求範囲の水
素量の上限値の０．０３０以上であるため、本発明の効
果が十分でなく、９５％の相対密度を得るために６時間
と長時間の焼結が必要である。On the other hand, Test No. 10 is a comparative example in which two kinds of powders (Ti-2% H) powder and TiH 2 powder are blended as in Test No. 9, but hydrogen in the claims of the present invention is used. Since the upper limit of the amount is 0.030 or more, the effect of the present invention is not sufficient, and sintering for 6 hours and a long time is required to obtain a relative density of 95%.
【００２７】試験番号１２は、原料粉末を試験番号４と
同様の配合比率にしたものを使用し、成形をＣＩＰの代
わりにダイプレスにて行った試料に対して真空焼結を施
した結果である。この場合では、焼結時間が２時間で９
５％以上の相対密度に到達しており、本発明の効果は十
分である。しかし、ＣＩＰ成形を行った試験番号４より
長時間の焼結が必要である。この理由は、ダイプレスが
１軸方向での圧縮成形であるため、成形された試料の位
置により密度に粗密ができるのと比べ、ＣＩＰは素材に
均一な圧力を付与し均質な成形体が得られるので、ＣＩ
Ｐで成形した試料の方が焼結時に発生した水素ガスを素
材外へよりスムーズに排出するためである。このように
ダイプレス法で成形を行っても、本発明の効果は期待で
きるが、ＣＩＰ法で成形を行うことにより効果は更なる
ものとなる。Test No. 12 is the result of vacuum sintering of a sample obtained by using a raw material powder having the same mixing ratio as in Test No. 4 and performing molding by a die press instead of CIP. . In this case, the sintering time is 2 hours and 9
The relative density of 5% or more is reached, and the effect of the present invention is sufficient. However, sintering for a longer time than that of test No. 4 in which CIP molding was performed is necessary. The reason for this is that since the die press is compression molding in the uniaxial direction, the density can be varied depending on the position of the molded sample, whereas CIP applies uniform pressure to the material to obtain a homogeneous molded body. So CI
This is because the sample molded with P discharges the hydrogen gas generated during sintering more smoothly to the outside of the material. Although the effects of the present invention can be expected even if the molding is carried out by the die press method as described above, the effects are further enhanced by carrying out the molding by the CIP method.
【００２８】表２において試験番号１３，試験番号１４
はそれぞれ従来法である試験番号１および本発明の実施
例である試験番号４で作製された焼結体に９００℃、１
２０MPa 、２時間のＨＩＰ処理を行い、引張試験を行っ
た結果である。表２に示すように原料粉末に水素を添加
した粉末を使用しても、従来法と同様に１００％の相対
密度が得られ、引張試験も遜色ない結果が得られてお
り、本発明の請求範囲内では残留水素による特性の劣化
は見られず、ＨＩＰ処理により、焼結チタン合金の特性
をさらに向上させることができる。In Table 2, test number 13 and test number 14
Is 900 ° C. for each of the sintered bodies prepared in Test No. 1 which is a conventional method and Test No. 4 which is an example of the present invention.
It is a result of performing a tensile test after performing HIP treatment for 20 hours at 20 MPa. As shown in Table 2, even if a powder obtained by adding hydrogen to the raw material powder was used, a relative density of 100% was obtained as in the conventional method, and a result comparable with the tensile test was obtained. Within the range, no characteristic deterioration due to residual hydrogen is observed, and the characteristics of the sintered titanium alloy can be further improved by the HIP treatment.
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【発明の効果】以上説明したように、本発明を適用する
ことにより、本来チタン合金の有する優れた特性を損な
うことなく、なおかつ安価な製造コストで製造するため
の方法を提供ことができる。As described above, by applying the present invention, it is possible to provide a method for producing a titanium alloy at a low production cost without deteriorating the excellent characteristics inherent in the titanium alloy.
フロントページの続き (72)発明者 田村 道夫 兵庫県姫路市広畑区富士町１番地 新日本 製鐵株式会社広畑製鐵所内Front page continued (72) Inventor Michio Tamura 1 Fuji-machi, Hirohata-ku, Himeji-shi, Hyogo Shin Nippon Steel Corp. Hirohata Works
Claims (3)
製造する方法において、チタン粉末の代わりに、チタン
粉末及び（Ｔｉ−Ｈ）合金粉末及び水素化チタン粉末を
水素：チタンが質量比で０．００２以上で０．０３０未
満となるように配合した粉末を原料粉末として使用する
ことを特徴とする焼結チタン合金の製造方法。1. A method for producing a sintered titanium alloy by an elementary powder mixing method, wherein titanium powder, (Ti—H) alloy powder and titanium hydride powder are replaced by titanium powder in place of titanium powder, and hydrogen: titanium is contained in a mass ratio of 0. A method for producing a sintered titanium alloy, which comprises using as a raw material powder a powder blended so as to be 0.002 or more and less than 0.030.
製造する方法において、チタン粉末の代わりに、チタン
粉末及び（Ｔｉ−Ｈ）合金粉末及び水素化チタン粉末を
水素：チタンが質量比で０．００２以上で０．０３０未
満となるように配合した粉末を原料粉末として使用し、
圧粉体の成形を３００MPa 以上で６００MPa 以下の圧力
でＣＩＰ（冷間等方圧成形）により行うことを特徴とす
る焼結チタン合金の製造方法。2. A method for producing a sintered titanium alloy by an elementary powder mixing method, wherein titanium powder, (Ti—H) alloy powder and titanium hydride powder are replaced by titanium powder in place of titanium powder and hydrogen: titanium in a mass ratio of 0. The powder blended so as to be 0.002 or more and less than 0.030 is used as a raw material powder,
A method for producing a sintered titanium alloy, characterized in that compacting is performed by CIP (cold isostatic pressing) at a pressure of 300 MPa or more and 600 MPa or less.
製造する方法において、チタン粉末の代わりに、チタン
粉末及び（Ｔｉ−Ｈ）合金粉末及び水素化チタン粉末を
水素：チタンが質量比で０．００２以上で０．０３０未
満となるように配合した粉末を原料粉末として使用し、
圧粉体の成形を３００MPa 以上で６００MPa 以下の圧力
でＣＩＰ（冷間等方圧成形）により行い、焼結後ＨＩＰ
（熱間等方圧成形）処理を行うことを特徴とする焼結チ
タン合金の製造方法。3. A method for producing a sintered titanium alloy by an elementary powder mixing method, wherein titanium powder, (Ti—H) alloy powder and titanium hydride powder are replaced by titanium powder in place of titanium powder and hydrogen: titanium in a mass ratio of 0. The powder blended so as to be 0.002 or more and less than 0.030 is used as a raw material powder,
The green compact is formed by CIP (cold isostatic pressing) at a pressure of 300 MPa or more and 600 MPa or less, and HIP after sintering
A method for producing a sintered titanium alloy, which comprises performing (hot isostatic pressing) treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4194319A JPH0633165A (en) | 1992-07-21 | 1992-07-21 | Manufacture of sintered titanium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4194319A JPH0633165A (en) | 1992-07-21 | 1992-07-21 | Manufacture of sintered titanium alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0633165A true JPH0633165A (en) | 1994-02-08 |
Family
ID=16322627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4194319A Withdrawn JPH0633165A (en) | 1992-07-21 | 1992-07-21 | Manufacture of sintered titanium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0633165A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010010993A1 (en) * | 2008-07-24 | 2010-01-28 | Mtig Co., Ltd. | Method of manufacturing powder injection-molded body |
| JP2020029598A (en) * | 2018-08-23 | 2020-02-27 | 東邦チタニウム株式会社 | Method for manufacturing green compact |
| WO2021060363A1 (en) | 2019-09-27 | 2021-04-01 | 東邦チタニウム株式会社 | Method for producing green compact and method for producing sintered body |
-
1992
- 1992-07-21 JP JP4194319A patent/JPH0633165A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010010993A1 (en) * | 2008-07-24 | 2010-01-28 | Mtig Co., Ltd. | Method of manufacturing powder injection-molded body |
| JP2020029598A (en) * | 2018-08-23 | 2020-02-27 | 東邦チタニウム株式会社 | Method for manufacturing green compact |
| WO2021060363A1 (en) | 2019-09-27 | 2021-04-01 | 東邦チタニウム株式会社 | Method for producing green compact and method for producing sintered body |
| US12103082B2 (en) | 2019-09-27 | 2024-10-01 | Toho Titanium Co., Ltd. | Method for producing green compact and method for producing sintered body |
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