JPH0741882A - Production of sintered titanium alloy - Google Patents
Production of sintered titanium alloyInfo
- Publication number
- JPH0741882A JPH0741882A JP5190613A JP19061393A JPH0741882A JP H0741882 A JPH0741882 A JP H0741882A JP 5190613 A JP5190613 A JP 5190613A JP 19061393 A JP19061393 A JP 19061393A JP H0741882 A JPH0741882 A JP H0741882A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- less
- alloy
- sintered
- weight
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、粉末冶金法による焼結
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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a sintered titanium alloy by powder metallurgy. More specifically, it relates to a method for producing a sintered titanium alloy by the elementary powder mixing method.
【０００２】[0002]
【従来の技術】粉末冶金法は材料から最終形状に近い形
の製品を直接製造する、いわゆるニアーネットシェイプ
技術の一つで、加工性や成形性あるいは被削性に乏しい
チタン合金製品を得るための製造方法として適してい
る。特に、素粉末混合法はチタン粉末と合金元素添加用
粉末を混合して容器に充填し、これを圧力３〜８ton/cm
2で成形して圧粉体とした後、真空中１１００〜１３０
０℃で１〜８時間の焼結と合金化熱処理を同時に行う方
法であり、焼結前に軟質のチタン粉末が大部分を占める
ことより良好な成形性を有しており室温において精密な
形状の圧粉体を得ることができるという利点を有してい
る。2. Description of the Related Art The powder metallurgy method is one of so-called near net shape technology for directly producing a product having a shape close to a final shape from a material, and for obtaining a titanium alloy product having poor workability, formability or machinability. Is suitable as a manufacturing method. Particularly, in the elementary powder mixing method, titanium powder and alloying element addition powder are mixed and filled in a container, and the pressure is 3 to 8 ton / cm.
After forming into a green compact by molding in 2 , it is 1100 to 130 in vacuum
This is a method in which sintering and alloying heat treatment are performed simultaneously at 0 ° C for 1 to 8 hours, and since soft titanium powder occupies the majority before sintering, it has good formability and a precise shape at room temperature. It has an advantage that a green compact of can be obtained.
【０００３】しかし、素粉末混合法は上記のような高温
・長時間の焼結を行っても焼結密度が不十分で内部ポア
が残存しているため疲労強度が低いという欠点がある。
これを解決する方法として、ＨＩＰ処理により高密度化
し内部ポアを完全に消滅させ疲労強度を向上させる方法
があるものの、製造コストが著しく高くなる。However, the elemental powder mixing method has a drawback that the fatigue strength is low because the sintering density is insufficient and the internal pores remain even after the above-mentioned sintering at high temperature for a long time.
As a method of solving this, there is a method of increasing the density by HIP treatment to completely eliminate the internal pores and improving the fatigue strength, but the manufacturing cost becomes significantly high.
【０００４】これに対して特公平２−５０１７２号公報
には、平均粒径４０〜１７７μｍのチタン粉末と、粉砕
により高エネルギーを付与した平均粒径０．５〜２０μ
ｍの合金形成粒子（本発明中の合金元素添加用粉末に相
当する）を使用し、粉末の表面エネルギーを高くするこ
とにより、焼結段階で理論値に対して９９．０％以上の
密度を得る方法が記載されている。On the other hand, Japanese Patent Publication No. 2-50172 discloses a titanium powder having an average particle size of 40 to 177 μm and an average particle size of 0.5 to 20 μm to which high energy is imparted by pulverization.
By using the alloy-forming particles of m (corresponding to the powder for alloying element addition in the present invention) and increasing the surface energy of the powder, a density of 99.0% or more with respect to the theoretical value is obtained at the sintering stage. The method of obtaining is described.
【０００５】しかしこの方法はハンタースポンジファイ
ン（ＨＳＦ）などの酸素を０．１重量％以下しか含有し
ない軟質のチタン粉末を使用した場合には、一般的な成
形・焼結条件で９９．０％以上の高密度化が可能である
が、製造工程上０．１重量％を超える酸素を不可避的に
含有するため、硬質で成形性に劣る水素化脱水素法によ
り製造したチタン粉末（ＨＤＨ粉末）を使用した場合に
は、上記の一般的な成形・焼結条件での高密度化は困難
であった。またＨＤＨ粉末は塩素を２０ppm 以下しか含
んでおらず、塩素による結晶粒粗大化の抑制効果がない
ため塩素を０．０５〜０．２重量％含むＨＳＦを使用し
た場合と異なり焼結時に組織が粗大化し機械的特性、特
に疲労特性の劣化をもたらすという欠点もあった。However, this method is 99.0% under general molding and sintering conditions when using a soft titanium powder such as Hunter Sponge Fine (HSF) containing less than 0.1% by weight of oxygen. Although the above densification is possible, titanium powder (HDH powder) produced by a hydrodehydrogenation method that is hard and inferior in moldability because it inevitably contains oxygen exceeding 0.1% by weight in the production process. However, it was difficult to increase the density under the above general molding and sintering conditions. Further, HDH powder contains less than 20 ppm of chlorine and has no effect of suppressing grain coarsening due to chlorine, so that the structure during sintering is different from that when HSF containing 0.05 to 0.2% by weight of chlorine is used. There is also a drawback that it coarsens and deteriorates mechanical properties, especially fatigue properties.
【０００６】一方、１９８０年 American Institute of
Mining, metallurgical, and Petroleum Engineers, I
nc. 発行の「Titanium '80 Science and Technology 」
１１８５頁に記載されているようにＴｉまたはＴｉ−６
Ａｌ−４Ｖ溶製材にＥｒあるいはＹを約１重量％以下添
加すると、これらの酸化物が合金中に生成し、これが粒
成長を抑制するため組織が微細化されるという知見があ
るが、この知見を素粉末混合法に応用しＹ，Ｅｒ，Ｙ2
Ｏ3 ，Ｅｒ2 Ｏ3 あるいはＴｉＢ2 ，Ｂ4 Ｃ，ＢＮなど
のＢ含有化合物を単独で直接添加、混合すると、チタン
粉末や合金元素添加用粉末の接触を阻害し、かつ粉末表
面の移動をピン止めするためＨＤＨ粉末の焼結特性をさ
らに劣化させ、その結果疲労強度がさらに低下するとい
う欠点があった。On the other hand, 1980 American Institute of
Mining, metallurgical, and Petroleum Engineers, I
"Titanium '80 Science and Technology" published by nc.
Ti or Ti-6 as described on page 1185.
It has been found that when Er or Y is added in an amount of about 1% by weight or less to an Al-4V ingot, these oxides are generated in the alloy, which suppresses grain growth, resulting in a finer structure. Is applied to the elementary powder mixing method, and Y, Er, Y 2
O 3, Er 2 O 3 or TiB 2, B 4 C, is added directly alone B-containing compound, such as BN, upon mixing, to inhibit contact of the powder additive titanium powder and alloying elements, and the movement of the powder surface The pinning causes a further deterioration of the sintering characteristics of the HDH powder, resulting in a further decrease in fatigue strength.
【０００７】[0007]
【発明が解決しようとする課題】そこで本発明は、水素
化脱水素法により製造した極低塩素チタン粉末を用いた
粉末混合法にて焼結チタン合金を製造する方法におい
て、従来と同様の一般的な成形・焼結条件で９９．５％
以上の高密度焼結チタン合金を、さらには結晶粒の粗大
化を抑制し従来より高い機械的特性を有する焼結チタン
合金を製造する方法を提供することを目的とする。SUMMARY OF THE INVENTION Therefore, the present invention is a method for producing a sintered titanium alloy by a powder mixing method using an ultra-low chlorine titanium powder produced by a hydrodehydrogenation method. 99.5% under typical molding and sintering conditions
It is an object of the present invention to provide a method for producing the above-described high-density sintered titanium alloy, and further, a sintered titanium alloy that suppresses coarsening of crystal grains and has higher mechanical properties than ever before.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
本発明は、（１）水素化脱水素法により製造した極低塩
素チタン粉末を用いた素粉末混合法で焼結チタン合金を
製造する方法において、使用粉末全重量の４０％以上７
０％以下が、粒径４５μｍ以上１５０μｍ以下で且つ
０．１重量％より多く０．２４重量％以下の酸素を含有
するチタン粉末であり、使用粉末全重量の５％以上２０
％以下が、平均粒径３μｍ以上１０μｍ以下の合金元素
添加用粉末であり、残部が粒径１０μｍ以上で４５μｍ
未満で且つ０．２重量％以上０．３７重量％以下の酸素
を含有するチタン粉末であることを特徴とする、焼結チ
タン合金の製造方法であり、（２）素粉末混合法にて焼
結チタン合金を製造する方法において、当該合金の０．
０３重量％以上０．５重量％以下に相当する量のＹ，Ｅ
ｒ，Ｂの少なくとも一種類を含有する合金元素添加用粉
末を使用することを特徴とする（１）記載の焼結チタン
合金の製造方法であり、（３）素粉末混合法にてＡｌを
含む焼結チタン合金を製造する方法において、合金元素
添加用粉末としてＴｉ，Ａｌの両元素とＹ，Ｅｒ，Ｂの
少なくとも一種類を当該合金の０．０３重量％以上０．
５重量％以下含有した粉末を使用することを特徴とする
（１）記載の焼結チタン合金の製造方法であり、（４）
素粉末混合法にてＡｌ，Ｖを含む焼結チタン合金を製造
する方法において、合金元素添加用粉末としてＡｌ，Ｖ
の両元素とＹ，Ｅｒ，Ｂの少なくとも一種類を当該合金
の０．０３重量％以上０．５重量％以下含有した粉末を
使用することを特徴とする（１）記載の焼結チタン合金
の製造方法であり、（５）素粉末混合法にてＦｅを含む
焼結チタン合金を製造する方法において、合金元素添加
用粉末としてＴｉ，Ｆｅの両元素とＹ，Ｅｒ，Ｂの少な
くとも一種類を当該合金の０．０３重量％以上０．５重
量％以下含有した粉末を使用することを特徴とする
（１）記載の焼結チタン合金の製造方法であり、（６）
素粉末混合法にてＡｌ，Ｆｅを含む焼結チタン合金を製
造する方法において、合金元素添加用粉末としてＴｉ，
Ａｌ，Ｆｅの３元素とＹ，Ｅｒ，Ｂの少なくとも一種類
を当該合金の０．０３重量％以上１．５重量％以下含有
した粉末を使用することを特徴とする（１）記載の焼結
チタン合金の製造方法である。In order to achieve the above object, the present invention provides (1) production of a sintered titanium alloy by an elementary powder mixing method using an ultra low chlorine titanium powder produced by a hydrodehydrogenation method. In the method, 40% or more of the total weight of the powder used 7
0% or less is a titanium powder having a particle size of 45 μm or more and 150 μm or less and containing oxygen in an amount of more than 0.1% by weight and 0.24% by weight or less, and 5% or more of the total weight of the used powder 20
% Or less is a powder for adding an alloy element having an average particle size of 3 μm or more and 10 μm or less, and the balance is 45 μm when the particle size is 10 μm or more.
A method for producing a sintered titanium alloy, characterized in that it is a titanium powder containing less than 0.2% by weight and 0.37% by weight or less of oxygen. In the method for producing a titanium-bound alloy, the alloy of 0.
Y, E in an amount corresponding to 03% by weight or more and 0.5% by weight or less
A method for producing a sintered titanium alloy according to (1), characterized in that a powder for adding an alloy element containing at least one of r and B is used, and (3) Al is included in the elementary powder mixing method. In the method for producing a sintered titanium alloy, both powders of Ti and Al and at least one of Y, Er and B are added as powders for addition of alloying elements in an amount of 0.03% by weight or more of the alloy.
(4) The method for producing a sintered titanium alloy according to (1), characterized in that a powder containing 5% by weight or less is used.
In a method for producing a sintered titanium alloy containing Al and V by an elementary powder mixing method, Al and V are used as alloy element addition powders.
Of the sintered titanium alloy according to (1), characterized in that a powder containing both of the above elements and at least one of Y, Er and B is contained in an amount of 0.03% by weight or more and 0.5% by weight or less of the alloy. (5) In the method of producing a sintered titanium alloy containing Fe by the elemental powder mixing method (5), both elements of Ti and Fe and at least one of Y, Er and B are used as the alloying element addition powder. A method for producing a sintered titanium alloy according to (1), characterized in that a powder containing 0.03% by weight or more and 0.5% by weight or less of the alloy is used.
In the method for producing a sintered titanium alloy containing Al and Fe by the elementary powder mixing method, Ti, Ti,
Sintering according to (1), characterized in that a powder containing three elements of Al and Fe and at least one of Y, Er and B in an amount of 0.03% by weight or more and 1.5% by weight or less of the alloy is used. It is a method for producing a titanium alloy.
【０００９】ここで、合金元素添加用粉末とはＴｉある
いは合金元素のうち２元素以上からなる母合金粉末ある
いは合金化元素の単一金属粉末である。また合金元素添
加用粉末に含有されるＹ，Ｅｒ，Ｂは単体でもよいし、
酸化物などの化合物、例えばＹ2 Ｏ3 ，Ｅｒ2 Ｏ3 ，Ｂ
4 Ｃなどでもよい。さらにＹ，Ｅｒ，Ｂのうち少なくと
も一種類を含有する合金元素添加用粉末を必要な合金元
素添加量の全部に使用してもよいし、一部に使用しても
よい。なお、本発明において、チタン合金中にはＴｉと
合金元素および０．４重量％以下の酸素の他、０．４重
量％未満のＦｅ（Ｆｅ非含有合金の場合）、Ｎ，Ｃ，Ｈ
などの不純物を不可避的に含んでもよい。Here, the alloying element-adding powder is a mother alloying powder of Ti or two or more of the alloying elements or a single metal powder of the alloying element. Further, Y, Er, B contained in the powder for adding the alloying element may be a single substance,
Compounds such as oxides such as Y 2 O 3 , Er 2 O 3 , B
4 C etc. may be used. Further, the powder for adding an alloying element containing at least one of Y, Er and B may be used for all of the required amount of the alloying element or a part thereof. In the present invention, in the titanium alloy, in addition to Ti and alloy elements and oxygen of 0.4 wt% or less, Fe of less than 0.4 wt% (in the case of Fe-free alloy), N, C, H
It may inevitably contain impurities such as.
【００１０】[0010]
【作用】以下、本発明を詳細に説明する。本発明者等
は、酸素を０．１重量％より多く含むためハンタースポ
ンジファインより成形性に劣るものの、安定供給が可能
な水素化脱水素法により製造した極低塩素チタン粉末
（ＨＤＨ粉末）を使用し、焼結段階で高密度で且つ高い
機械的特性を有する焼結チタン合金を得るため、粉末の
粒度分布、酸素量、組織制御などに関して研究を重ね
た。その結果、使用粉末の酸素含有量と粒度分布を最適
化することにより、さらには結晶粒成長を抑制する物質
の添加方法を工夫することにより、相対密度が９９．５
％以上で高い機械的特性を達成できることを見いだし
た。ここで相対密度とは、同一な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
た場合の密度である。The present invention will be described in detail below. The inventors of the present invention have an extremely low chlorine titanium powder (HDH powder) produced by the hydrodehydrogenation method, which can be stably supplied, though it is inferior in moldability to Hunter sponge fine because it contains more than 0.1% by weight of oxygen. In order to obtain a sintered titanium alloy which is used and has a high density and high mechanical properties in the sintering stage, studies have been conducted on the particle size distribution of powder, the amount of oxygen, the structure control, and the like. As a result, the relative density was 99.5 by optimizing the oxygen content and particle size distribution of the powder used, and further devising the method of adding a substance that suppresses crystal grain growth.
It has been found that a high mechanical property can be achieved at a rate of 100% or more. Here, the relative density is a density when the density of a sample obtained when alloys having the same composition are manufactured by a melting method is 100%.
【００１１】本発明１（請求項１の発明）では、０．１
重量％より多く０．２４重量％以下の酸素を含有し、粒
径が４５μｍ以上１５０μｍ以下のＨＤＨ粉末を使用粉
末全重量の４０％以上７０％以下使用し、平均粒径３μ
ｍ以上１０μｍ以下の合金元素添加用粉末を使用粉末全
重量の５％以上２０％以下使用し、残部が０．２重量％
以上０．３７重量％以下の酸素を含有し、粒径が１０μ
ｍ以上で４５μｍ未満のＨＤＨ粉末を使用することとし
た。このような特定の酸素含有量の粉末を特定の割合で
使用し、さらには特定の粒径の合金元素添加用粉末を特
定の割合で添加することにより、圧粉成形性や最終製品
の機械的特性を低下させる含有酸素量の大幅な上昇防止
と、粉末の充填率と焼結特性の向上による焼結密度上昇
の両者を同時に満たすことができる。In the present invention 1 (the invention of claim 1), 0.1
HDH powder containing more than 0.2% by weight and not more than 0.24% by weight and having a particle size of 45 μm or more and 150 μm or less is used.
A powder for adding an alloying element of m or more and 10 μm or less is used in an amount of 5% to 20% of the total weight of the powder, and the balance is 0.2% by weight.
Containing 0.37% by weight or less of oxygen and having a particle size of 10 μm
It was decided to use HDH powder of m or more and less than 45 μm. By using a powder with such a specific oxygen content in a specific ratio, and further adding a powder for adding an alloying element with a specific particle size in a specific ratio, the powder compactability and the mechanical properties of the final product can be improved. It is possible to simultaneously satisfy both a large increase in the amount of oxygen contained which deteriorates the characteristics and an increase in the sintering density due to the improvement of the powder filling rate and the sintering characteristics.
【００１２】ここで使用するチタン粉末の粒径を１０μ
ｍ以上１５０μｍ以下にしたのは、１５０μｍより粒径
が大きいと粉末の充填率が低下し十分な焼結密度が得ら
れないためであり、１０μｍ未満にすると活性なチタン
では安全上取扱いが困難となるためである。さらに、粒
径４５μｍ以上１５０μｍ以下のＨＤＨ粉末を使用粉末
全重量の４０％以上７０％以下としたのは、４０％未満
では粒径が４５μｍ未満のチタン粉末の割合が相対的に
増加し、製品の酸素量が上昇し機械的特性が急激に低下
するためであり、７０％より多いと粗大な粉末が多くな
り焼結密度が低下し機械的特性が劣化するためである。The particle size of the titanium powder used here is 10 μm.
The reason why the particle size is set to m or more and 150 μm or less is that if the particle size is larger than 150 μm, the powder filling rate decreases and a sufficient sintered density cannot be obtained. This is because Furthermore, the reason that the HDH powder having a particle size of 45 μm or more and 150 μm or less is set to 40% or more and 70% or less of the total weight of the powder used is that the ratio of titanium powder having a particle size of less than 45 μm is relatively increased when it is less than 40%. This is because the amount of oxygen increases and the mechanical properties sharply decrease, and when it is more than 70%, the coarse powder increases, the sintering density decreases, and the mechanical properties deteriorate.
【００１３】またチタン粉末の酸素量の下限値（１０〜
４５μｍ粉末で０．２％、４５〜１５０μｍ粉末で０．
１％）は、水素化脱水素法の製造工程上不可避的に含ま
れる値の下限値であり、上限値を粒径１０μｍ以上４５
μｍ未満の粉末で０．３７％、４５μｍ以上１５０μｍ
以下の粉末で０．２４％とした理由は、１０μｍ以上４
５μｍ未満の粉末では含有酸素量が０．３７重量％より
多いと本発明の粉末混合比では焼結後の製品の酸素量が
増加し機械的特性が低下するためであり、４５μｍ以上
１５０μｍ以下の粉末では含有酸素量が０．２４重量％
より多いと圧粉成形性が低下し十分な焼結密度が得られ
ないためである。The lower limit of the oxygen content of titanium powder (10 to 10
0.2% for 45 μm powder and 0.1% for 45-150 μm powder.
1%) is the lower limit of the value that is unavoidably included in the production process of the hydrodehydrogenation method, and the upper limit of the value is 10 μm or more and 45 μm or more.
0.37% for powder less than μm, 45 μm or more and 150 μm
The reason why the content of the following powder is 0.24% is 10 μm or more 4
This is because if the content of oxygen in the powder of less than 5 μm is more than 0.37% by weight, the oxygen content of the product after sintering will increase and the mechanical properties will decrease at the powder mixing ratio of the present invention. Oxygen content in powder is 0.24% by weight
This is because if the amount is larger than the above range, the powder compactability is lowered and a sufficient sintered density cannot be obtained.
【００１４】一方、合金元素添加用粉末の平均粒径を３
μｍ以上１０μｍ以下に制限したのは、３μｍ未満にす
ると粉末が凝集し均一に混合されないため成分偏析が起
きる理由による。また、１０μｍより大きくすると、チ
タン粉末間の空隙を埋めることによる充填密度向上効果
が小さくなるため、焼結密度が十分に向上しない。さら
に平均粒径を３μｍ以上１０μｍ以下の合金元素添加用
粉末を使用粉末全重量の５％以上２０％以下使用するこ
ととしたのは、５％未満だと、粉末が充填されていない
チタン粉末間の空隙の数が多くなり、充填密度が低下
し、さらには焼結密度が低下するためであり、２０％よ
り多くすると微細な粉末が多いため凝集し均一に混合さ
れず成分偏析が起きるためである。On the other hand, the average particle size of the alloying element addition powder is 3
The reason why the particle size is limited to 10 μm or more is that if the particle size is less than 3 μm, the powder agglomerates and is not mixed uniformly, so that segregation of components occurs. On the other hand, if it is larger than 10 μm, the effect of improving the packing density by filling the voids between the titanium powders becomes small, and the sintering density is not sufficiently improved. Further, the reason why the alloy element-adding powder having an average particle size of 3 μm or more and 10 μm or less is to be used in an amount of 5% or more and 20% or less of the total weight of the powder is that if the amount is less than 5%, This is because the number of voids increases, the packing density decreases, and further, the sintering density decreases. If it exceeds 20%, a large amount of fine powder agglomerates and is not uniformly mixed, resulting in segregation of components. is there.
【００１５】さて、本発明２（請求項２の発明）は、さ
らに当該合金の０．０３重量％以上０．５重量％以下に
相当するＹ，Ｅｒ，Ｂの少なくとも１種類を含有する合
金元素添加用粉末を使用することとした。これは焼結密
度向上に加え、組織を微細化することにより機械的特
性、特に疲労特性をさらに向上させることを目的とする
ものである。しかし、従来の技術の項で説明したよう
に、これらの粉末を直接添加すると焼結密度が著しく低
下する。そこで本発明では、焼結密度を低下することな
く結晶粒粗大化を抑制し組織を微細化にするため、予め
合金元素添加用粉末の内部に結晶粒を抑制する物質を含
有させて使用することとした。すなわちＹ，Ｅｒ，Ｂあ
るいはこれらの化合物の周囲を合金元素が被っている状
態の合金元素添加用粉末を使用することにより、Ｙ，Ｅ
ｒ，Ｂあるいはこれらを含む化合物がチタン粉末同士あ
るいはチタン粉末と合金元素の接触を阻害せず、且つ粉
末表面の移動を妨げることがなくなる。しかし、一方で
は焼結合金の結晶粒界移動を阻害し結晶粒成長を抑制す
る。その結果、従来と同様の条件での混合−充填−成形
−真空焼結の工程で、結晶粒微細化と９９．５％以上の
高い相対密度を有し、高い機械的性質を有する焼結チタ
ン合金が得られる。なお、Ｙ，Ｅｒ，Ｂの添加量につい
て、当該チタン合金の０．０３重量％未満では添加量が
少ないため組織微細化の効果が認められず、また０．５
重量％以下で既に十分な効果が得られており、０．５重
量％より多く添加するとＹ，Ｅｒ，Ｂの粗大な塊ができ
破壊の起点となり機械的特性を低下させる。The present invention 2 (the invention of claim 2) further comprises an alloy element containing at least one of Y, Er and B corresponding to 0.03% by weight or more and 0.5% by weight or less of the alloy. It was decided to use powder for addition. This is intended to further improve mechanical properties, particularly fatigue properties, by making the structure finer in addition to improving the sintering density. However, as described in the section of the prior art, when these powders are directly added, the sintered density is significantly reduced. Therefore, in the present invention, in order to suppress the crystal grain coarsening without reducing the sintered density and to make the structure finer, it is necessary to use a substance that suppresses the crystal grains in the powder for alloying element addition in advance. And That is, by using Y, Er, B or a powder for adding an alloy element in a state where the alloy element covers the periphery of these compounds, Y, E,
It does not occur that r, B or a compound containing these does not hinder the contact between titanium powders or between titanium powders and alloying elements, and does not hinder the movement of the powder surface. However, on the other hand, it inhibits the grain boundary migration of the sintered alloy and suppresses the grain growth. As a result, in the steps of mixing-filling-molding-vacuum sintering under the same conditions as conventional ones, sintered titanium having crystal grain refinement and a high relative density of 99.5% or more and high mechanical properties. An alloy is obtained. Regarding the addition amount of Y, Er, B, if the addition amount of the titanium alloy is less than 0.03% by weight, the effect of microstructure refinement is not recognized because the addition amount is small, and the addition amount is 0.5.
Sufficient effect has already been obtained at less than 0.5% by weight, and if more than 0.5% by weight is added, coarse Y, Er, and B lumps will be formed, which will cause fracture and deteriorate mechanical properties.
【００１６】本発明３（請求項３の発明）は、Ａｌを合
金元素として含む焼結チタン合金、例えばＴｉ−６Ａｌ
−４Ｖ、Ｔｉ−５Ａｌ−２．５Ｆｅ、Ｔｉ−５Ａｌ−
２．５Ｓｎなどに本発明２を適用した場合で、例えばＴ
ｉ−Ａｌ・２元母合金に予めＹ，Ｅｒ，Ｂを含有させた
母合金を合金元素添加用粉末として使用する。The present invention 3 (the invention of claim 3) is a sintered titanium alloy containing Al as an alloy element, for example, Ti-6Al.
-4V, Ti-5Al-2.5Fe, Ti-5Al-
When the present invention 2 is applied to 2.5Sn or the like, for example, T
A master alloy in which Y, Er, and B are contained in advance in an i-Al / binary master alloy is used as a powder for adding alloy elements.
【００１７】本発明４（請求項４の発明）は、Ａｌ，Ｖ
を合金元素として含む焼結チタン合金、例えばＴｉ−６
Ａｌ−４ＶやＴｉ−１０Ｖ−２Ｆｅ−３Ａｌなどに本発
明２を適用した場合で、例えばＡｌ−Ｖ・２元母合金に
予めＹ，Ｅｒ，Ｂを含有させた母合金を合金元素添加用
粉末として使用する。The present invention 4 (the invention of claim 4) is based on Al, V
Sintered titanium alloy containing Al as an alloy element, for example, Ti-6
When the present invention 2 is applied to Al-4V, Ti-10V-2Fe-3Al, etc., for example, a master alloy in which Y, Er, B is previously contained in an Al-V / binary master alloy is added as an alloy element powder. To use as.
【００１８】本発明５（請求項５の発明）は、Ｆｅを合
金元素として含む焼結チタン合金、例えばＴｉ−５Ａｌ
−２．５ＦｅやＴｉ−１０Ｖ−２Ｆｅ−３Ａｌなどに本
発明２を適用した場合で、例えばＴｉ−Ｆｅ・２元母合
金に予めＹ，Ｅｒ，Ｂを含有させた母合金を合金元素添
加用粉末として使用する。The present invention 5 (the invention of claim 5) is a sintered titanium alloy containing Fe as an alloy element, for example, Ti-5Al.
When the present invention 2 is applied to -2.5Fe, Ti-10V-2Fe-3Al, etc., for example, a master alloy in which Y, Er, B is previously contained in a Ti-Fe / binary master alloy is used for adding alloy elements. Used as a powder.
【００１９】本発明６（請求項６の発明）は、ＡｌとＦ
ｅを合金元素として含む焼結チタン合金、例えばＴｉ−
５Ａｌ−２．５ＦｅやＴｉ−１０Ｖ−２Ｆｅ−３Ａｌな
どに本発明２を適用した場合で、例えばＴｉ−Ａｌ−Ｆ
ｅ・３元母合金に、予めＹ，Ｅｒ，Ｂを含有させた母合
金を合金元素添加用粉末として使用する。The present invention 6 (the invention of claim 6) comprises Al and F
A sintered titanium alloy containing e as an alloying element, such as Ti-
In the case where the present invention 2 is applied to 5Al-2.5Fe or Ti-10V-2Fe-3Al, for example, Ti-Al-F
e. A ternary master alloy containing Y, Er, and B in advance is used as a powder for adding alloy elements.
【００２０】[0020]
【実施例】以下、実施例によって本発明をさらに詳しく
説明する。試験に供した試料は以下の工程で作製した。
すなわち、所定の割合の粉末を混合し、成形用容器に充
填し、４．９ton/cm2 の圧力で冷間静水圧成形（ＣＩ
Ｐ）を行い圧粉体を作製し、１×１０-3Paの真空中で１
２５０℃、２時間の焼結を行い、直径１５mmで長さ１５
０mmの円柱状試験片を作製した。この焼結合金に対し、
焼結密度（相対密度）測定、含有酸素量測定、β粒径測
定、引張試験による伸び測定、回転曲げ疲労試験を行っ
た。ここで、疲労強度は繰り返し数が１０7 回に達して
も破断しない負荷応力で評価した。The present invention will be described in more detail with reference to the following examples. The sample used for the test was prepared by the following steps.
That is, powders in a predetermined ratio are mixed and filled in a molding container, and cold isostatic pressing (CI) is performed at a pressure of 4.9 ton / cm 2.
P) to produce a green compact, and 1 in a vacuum of 1 × 10 −3 Pa
Sintering at 250 ℃ for 2 hours, diameter 15mm and length 15
A 0 mm columnar test piece was prepared. For this sintered alloy,
Sintered density (relative density) measurement, oxygen content measurement, β particle size measurement, elongation measurement by a tensile test, and rotary bending fatigue test were performed. Here, the fatigue strength was evaluated by a load stress that does not break even when the number of repetitions reaches 10 7 .
【００２１】まず最初に、本発明１について説明する。
粒径、含有酸素量の異なるＨＤＨ粉末、および合金元素
添加用粉末を、表１に示すように種々の割合で混合し、
圧粉成形、焼結を行った試料の焼結密度、含有酸素量、
β粒径、伸び、疲労強度を表２に示す。First, the present invention 1 will be described.
HDH powders having different particle sizes and oxygen contents, and alloy element addition powders are mixed in various proportions as shown in Table 1,
Sintered density, oxygen content, of the compacted and sintered sample
Table 2 shows β particle size, elongation, and fatigue strength.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】表１において、試験番号１は、粒径４５μ
ｍ以上１５０μｍ以下のチタン粉末９０％と平均粒径６
μｍの６０Ａｌ−４０Ｖ粉末１０％を使用した場合で、
従来法に相当する。従来の項で述べたように、ハンター
スポンジファインのような酸素含有量が０．１％以下の
チタン粉末を用いた場合には、この方法により高密度焼
結品が得られるが、表２に示すように、酸素含有量の高
いＨＤＨ粉末を用いた場合、９８％程度の焼結密度しか
得られず、伸び、疲労強度も低い値である。In Table 1, Test No. 1 has a particle size of 45 μm.
90% titanium powder with a particle size of m to 150 μm and an average particle size of 6
When using 10% of 60 Al-40V powder of μm,
It corresponds to the conventional method. As described in the conventional section, when titanium powder having an oxygen content of 0.1% or less such as Hunter Sponge Fine is used, a high density sintered product can be obtained by this method. As shown, when HDH powder having a high oxygen content is used, only a sintered density of about 98% is obtained, and the elongation and fatigue strength are also low values.
【００２５】これに対し、本発明１の実施例である試験
番号３，４，５，８，１０，１２，１５，１６，１９，
２０は、いずれも９９．５％以上の高い焼結密度が得ら
れており、焼結品の含有酸素量も０．３５％以下で、１
２％以上の高い伸び値、および３００MPa 以上の高い疲
労強度が得られている。これは、特定の酸素含有量の粉
末を特定の割合で、さらには特定の粒径の合金元素添加
用粉末を特定の割合で添加することにより、圧粉成形性
や最終製品の機械的特性を低下させる含有酸素量の大幅
な上昇防止と、粉末の充填率と焼結特性の向上による焼
結密度上昇の両者を同時に満たすことができた結果であ
る。On the other hand, the test numbers 3, 4, 5, 8, 10, 12, 15, 16, 19, which are the embodiments of the present invention 1,
No. 20 has a high sintered density of 99.5% or more, and the oxygen content of the sintered product is 0.35% or less.
A high elongation value of 2% or more and a high fatigue strength of 300 MPa or more are obtained. This is because the powder with a specific oxygen content is added in a specific ratio, and further, the powder for adding an alloy element with a specific particle size is added in a specific ratio to improve the powder compactability and the mechanical properties of the final product. This is the result of being able to simultaneously satisfy both a large increase in the contained oxygen content to be reduced and an increase in the sintering density due to the improvement of the powder filling rate and the sintering characteristics.
【００２６】一方、本発明１の比較例である試験番号
２，６，７，９，１１，１３，１４，１７，１８，２１
はいずれも、８％以下の低い伸び値と３００MPa 以下の
低い疲労強度しか得られなかった。特に、試験番号２１
はＴｉ−６Ａｌ−４Ｖよりも高強度の組成であるにもか
かわらず、例えば試験番号５のＴｉ−６Ａｌ−４Ｖより
も低い疲労強度しか得られていない。この理由は次の通
りである。試験番号２および７は、粒径４５μｍ以上１
５０μｍ以下のチタン粉末の割合が本発明１の範囲より
も多かったため、粗大なチタン粉末が多くなり焼結密度
が９９％にも達せず、そのため伸び、疲労強度が低下し
た。試験番号６および９は、粒径４５μｍ以上１５０μ
ｍ以下のチタン粉末の割合が本発明１の範囲よりも少な
かったため、粒径が４５μｍ未満のチタン粉末の割合が
相対的に増加し、製品の酸素量が０．３５％以上にまで
増加し、伸び、疲労強度が低下した。試験番号１１は、
４５μｍ以上１５０μｍ以下のチタン粉末の含有酸素量
が本発明１の上限値である０．２４重量％より多かった
ため、圧粉成形性が低下し十分な焼結密度が得られず、
伸び、疲労強度が低下した。試験番号１３は、粒径１０
μｍ以上４５μｍ未満のチタン粉末の含有酸素量が本発
明１の上限値である０．３７％を超えたため、焼結後の
製品の酸素量が０．３５％以上にまで増加し、伸び、疲
労強度が低下した。また、試験番号１４は合金元素添加
用粉末の平均粒径が本発明１の下限値以下であり、試験
番号２１はＴｉ−ＡｌとＴｉ−Ｆｅの添加量の総計が本
発明１の上限値である２０％を超えたため、いずれも成
分偏析を生じ、十分な伸び、疲労強度が得られなかっ
た。また、試験番号１７は、合金元素添加用粉末の平均
粒径が本発明１の上限値よりも大きかったため、チタン
粉末間の空隙を埋めることによる充填密度向上効果が小
さくなり、焼結密度が十分に向上せず、その結果、伸
び、疲労強度が低下した。試験番号１８は、合金元素添
加用粉末の使用割合が、５％未満であったため、粉末が
充填されていないチタン粉末間の空隙の数が多くなり、
充填密度および焼結密度が低下し、その結果、伸び、疲
労強度が低下した。On the other hand, test numbers 2, 6, 7, 9, 11, 13, 14, 17, 18, 21, which are comparative examples of the present invention 1.
In each case, only a low elongation value of 8% or less and a low fatigue strength of 300 MPa or less were obtained. In particular, test number 21
Despite having a higher strength composition than Ti-6Al-4V, for example, only a fatigue strength lower than that of Ti-6Al-4V of test number 5 was obtained. The reason for this is as follows. Test numbers 2 and 7 are particle sizes of 45 μm or more 1
Since the proportion of titanium powder having a particle size of 50 μm or less was higher than the range of the present invention 1, the amount of coarse titanium powder was large, and the sintered density did not reach 99%, so that the elongation and fatigue strength decreased. Test Nos. 6 and 9 have a particle size of 45 μm or more and 150 μm
Since the proportion of titanium powder of m or less was less than the range of the present invention 1, the proportion of titanium powder having a particle size of less than 45 μm was relatively increased, and the oxygen content of the product was increased to 0.35% or more. Elongation and fatigue strength decreased. Test number 11 is
Since the oxygen content of the titanium powder having a particle size of 45 μm or more and 150 μm or less was larger than 0.24% by weight, which is the upper limit of the present invention 1, the compacting property was reduced and a sufficient sintered density could not be obtained.
Elongation and fatigue strength decreased. Test number 13 is particle size 10
Since the oxygen content of the titanium powder having a size of μm or more and less than 45 μm exceeds 0.37%, which is the upper limit of the present invention 1, the oxygen content of the product after sintering increases to 0.35% or more, and elongation and fatigue The strength decreased. Further, Test No. 14 has an average particle size of the alloy element addition powder that is equal to or lower than the lower limit of Invention 1, and Test No. 21 has the total amount of Ti—Al and Ti—Fe added that is the upper limit of Invention 1. Since the content exceeds 20%, segregation of the components occurs in all cases, and sufficient elongation and fatigue strength cannot be obtained. Further, in Test No. 17, since the average particle diameter of the alloying element-adding powder was larger than the upper limit value of Invention 1, the effect of filling the voids between the titanium powders was small, and the effect of improving the packing density was small, and the sintering density was sufficient. As a result, the elongation and fatigue strength decreased. In Test No. 18, since the use ratio of the alloying element addition powder was less than 5%, the number of voids between the titanium powders not filled with the powder increased,
The packing density and the sintered density decreased, and as a result, the elongation and fatigue strength decreased.
【００２７】次に、本発明２〜６の実施例について説明
する。粒径が４５μｍ以上１５０μｍ以下で酸素を０．
１５重量％含有するＨＤＨ粉末を使用粉末全重量の５０
％、表３に示す合金元素添加用粉末、さらには粒径が４
５μｍ未満１０μｍ以上で酸素を０．３０重量％含有す
るＨＤＨ粉末を、母材の組成がＴｉ−６Ａｌ−４Ｖ（試
験番号２２〜３３および３７〜４０）またはＴｉ−５Ａ
ｌ−２．５Ｆｅで、Ｙ，Ｅｒ，Ｂの総量が母材に対して
表３に示すような値となるように混合し、成形、焼結を
行った。成形、焼結の条件、焼結品の寸法・形状、試験
方法・項目は先に述べた本発明１の説明と同じである。Next, examples of the present inventions 2 to 6 will be described. When the particle size is 45 μm or more and 150 μm or less, oxygen is less than 0.
Use HDH powder containing 15% by weight 50% of total weight of powder
%, The alloy element addition powder shown in Table 3, and further the particle size is 4
HDH powder containing less than 5 μm and 10 μm or more and containing 0.30% by weight of oxygen, the composition of the base material is Ti-6Al-4V (test numbers 22 to 33 and 37 to 40) or Ti-5A.
1-2.5Fe was mixed so that the total amount of Y, Er, and B would be the values shown in Table 3 with respect to the base material, followed by molding and sintering. The conditions of molding and sintering, the size and shape of the sintered product, and the test method and items are the same as those described in the first embodiment.
【００２８】[0028]
【表３】 [Table 3]
【００２９】表３において、試験番号２２〜２５は、
Ｙ，Ｙ2 Ｏ3 ，Ｅｒ2 Ｏ3 ，Ｂ4 Ｃの単体粉末をそのま
まチタン粉末および母材の合金元素添加用粉末（６０Ａ
ｌ−４０Ｖ）と混合した場合で、いずれも焼結密度が９
６％以下の低い値となっており、伸び、疲労強度は極端
に低い値となっている。これは、これらの粉末を直接添
加したため、チタン粉末や母材の合金元素添加用粉末の
接触を阻害し、且つ粉末表面の移動をピン止めし、水素
化脱水素により製造したチタン粉末の焼結特性をさらに
劣化させたことによる。In Table 3, the test numbers 22 to 25 are
A single powder of Y, Y 2 O 3 , Er 2 O 3 , and B 4 C is used as it is as a titanium powder and a powder for adding an alloy element to the base metal (60 A).
1-40 V), the sintered density was 9 in each case.
It is a low value of 6% or less, and the elongation and fatigue strength are extremely low values. Since these powders were added directly, the contact of titanium powder and the powder for alloying element addition of the base metal was inhibited, and the movement of the powder surface was pinned, and the sintering of titanium powder produced by hydrodehydrogenation was performed. This is because the characteristics are further deteriorated.
【００３０】一方、表３において、試験番号２６〜４０
では、母材の合金元素添加用物質（６０Ａｌ−４０Ｖ、
ＴｉＡｌ3 、ＴｉＦｅ、５Ｔｉ−５Ａｌ−２．５Ｆｅ）
の塊とＹ，Ｅｒ，Ｂ，Ｙ2 Ｏ3 ，Ｅｒ2 Ｏ3 ，Ｂ4 Ｃ粉
末を混合し、真空アーク溶解し、さらにこれを粉砕し、
Ｙ，Ｅｒ，Ｂあるいはこれらの化合物の周囲を合金元素
が被っている状態の合金元素添加用粉末を作製し使用し
た場合である。On the other hand, in Table 3, test numbers 26 to 40
Then, a substance for alloying element addition of the base material (60Al-40V,
TiAl 3 , TiFe, 5Ti-5Al-2.5Fe)
Mass and Y, Er, B, Y 2 O 3, Er 2 O 3, B 4 C powder were mixed, vacuum arc melting, and further pulverized into,
This is the case where a powder for alloying element addition in which Y, Er, B or the compound thereof is covered with the alloying element is prepared and used.
【００３１】本発明の実施例である試験番号２６〜３６
および３８，３９は、Ｙ，Ｅｒ，Ｂあるいはこれらの化
合物を添加しなかった場合、例えば試験番号４（表１，
表２）と比べて、平均β粒径は４分の１あるいはそれ以
下になっており、一方焼結密度は９９．５％以上の高い
値となっている。その結果、伸び、疲労強度は、Ｙ，Ｅ
ｒ，Ｂあるいはこれらの化合物を添加しなかった場合よ
りも高くなっており、特に疲労強度は３７０MPa 以上の
極めて高い値が得られた。これは、予め合金元素添加用
粉末の内部に結晶粒を抑制する物質を含有させて使用し
たことにより、チタン粉末同士あるいはチタン粉末と合
金元素の接触を阻害せず、且つ粉末表面の移動を妨げる
ことがなくなり、しかし、一方では焼結合金の結晶粒界
移動を阻害し結晶粒成長を抑制し、従来と同様の条件で
の混合−充填−成形−真空焼結の工程で、結晶粒微細化
と９９．５％以上の高い相対密度を有し、高い機械的性
質が得られたものである。Test Nos. 26 to 36, which are examples of the present invention
And 38 and 39, when Y, Er, B or these compounds are not added, for example, Test No. 4 (Table 1,
Compared with Table 2), the average β particle size is 1/4 or less, while the sintered density is a high value of 99.5% or more. As a result, the elongation and fatigue strength are Y, E
The values were higher than when r, B or these compounds were not added, and particularly, the fatigue strength was an extremely high value of 370 MPa or more. This is because the powder for alloying element addition contains a substance that suppresses crystal grains in advance, so that it does not hinder the contact between titanium powders or between titanium powders and alloying elements, and also prevents the movement of the powder surface. However, on the other hand, it inhibits the grain boundary movement of the sintered alloy and suppresses the grain growth, and in the process of mixing-filling-forming-vacuum sintering under the same conditions as the conventional one, the grain refinement is performed. It has a high relative density of 99.5% or more and high mechanical properties.
【００３２】これに対し、試験番号３７では、β粒径お
よび疲労強度は試験番号４と比較してほとんど変化して
おらず、Ｙ2 Ｏ3 の添加効果はほとんど見られなかっ
た。これは、Ｙ2 Ｏ3 の添加量が本発明の下限値である
０．０３重量％未満であったためである。また試験番号
４０では、β粒径は微細化したものの伸び、疲労強度は
低い値しか得られなかった。これは、Ｙ2 Ｏ3 の添加量
が、本発明の上限値を超えたため、Ｙ2 Ｏ3 の粗大な塊
が生成し、破壊の起点となり機械的特性を低下させたも
のである。On the other hand, in the test number 37, the β grain size and the fatigue strength were almost unchanged as compared with the test number 4, and the effect of adding Y 2 O 3 was hardly seen. This is because the amount of Y 2 O 3 added was less than 0.03% by weight, which is the lower limit of the present invention. In Test No. 40, the β particle size was refined, but the elongation and fatigue strength were low. This is because the amount of Y 2 O 3 added exceeded the upper limit of the present invention, so that a coarse lump of Y 2 O 3 was generated, which became the starting point of fracture and deteriorated the mechanical properties.
【００３３】[0033]
【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、水素化脱水素法により製造した極低塩素チタ
ン粉末を用いた素粉末混合法にて焼結チタン合金を製造
する方法において、従来と同様の一般的な成形・焼結条
件で９９．５％以上の高密度焼結チタン合金を、さらに
は結晶粒の粗大化を抑制し従来より高い機械的特性を有
する焼結チタン合金を製造することができる。By applying the present invention as described above, in a method for producing a sintered titanium alloy by an elementary powder mixing method using an ultra-low chlorine titanium powder produced by a hydrodehydrogenation method, Under the same general molding and sintering conditions as before, a high density sintered titanium alloy of 99.5% or more, and a sintered titanium alloy that suppresses the coarsening of crystal grains and has higher mechanical properties than before are used. It can be manufactured.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年２月１５日[Submission date] February 15, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項６[Name of item to be corrected] Claim 6
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】[0007]
【発明が解決しようとする課題】そこで本発明は、水素
化脱水素法により製造した極低塩素チタン粉末を用いた
素粉末混合法にて焼結チタン合金を製造する方法におい
て、従来と同様の一般的な成形・焼結条件で９９．５％
以上の高密度焼結チタン合金を、さらには結晶粒の粗大
化を抑制し従来より高い機械的特性を有する焼結チタン
合金を製造する方法を提供することを目的とする。Therefore, the present invention uses an ultra low chlorine titanium powder produced by the hydrodehydrogenation method.
In the method of producing a sintered titanium alloy by the elementary powder mixing method , 99.5% under the same general molding and sintering conditions as the conventional one.
It is an object of the present invention to provide a method for producing the above-described high-density sintered titanium alloy, and further, a sintered titanium alloy that suppresses coarsening of crystal grains and has higher mechanical properties than ever before.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するため
本発明は、（１）水素化脱水素法により製造した極低塩
素チタン粉末を用いた素粉末混合法で焼結チタン合金を
製造する方法において、使用粉末全重量の４０％以上７
０％以下が、粒径４５μｍ以上１５０μｍ以下で且つ
０．１重量％より多く０．２４重量％以下の酸素を含有
するチタン粉末であり、使用粉末全重量の５％以上２０
％以下が、平均粒径３μｍ以上１０μｍ以下の合金元素
添加用粉末であり、残部が粒径１０μｍ以上４５μｍ未
満で且つ０．２重量％以上０．３７重量％以下の酸素を
含有するチタン粉末であることを特徴とする、焼結チタ
ン合金の製造方法であり、（２）素粉末混合法にて焼結
チタン合金を製造する方法において、当該合金の０．０
３重量％以上０．５重量％以下に相当する量のＹ，Ｅ
ｒ，Ｂの少なくとも一種類を含有する合金元素添加用粉
末を使用することを特徴とする（１）記載の焼結チタン
合金の製造方法であり、（３）素粉末混合法にてＡｌを
含む焼結チタン合金を製造する方法において、合金元素
添加用粉末としてＴｉ，Ａｌの両元素とＹ，Ｅｒ，Ｂの
少なくとも一種類を当該合金の０．０３重量％以上０．
５重量％以下含有した粉末を使用することを特徴とする
（１）記載の焼結チタン合金の製造方法であり、（４）
素粉末混合法にてＡｌ，Ｖを含む焼結チタン合金を製造
する方法において、合金元素添加用粉末としてＡｌ，Ｖ
の両元素とＹ，Ｅｒ，Ｂの少なくとも一種類を当該合金
の０．０３重量％以上０．５重量％以下含有した粉末を
使用することを特徴とする（１）記載の焼結チタン合金
の製造方法であり、（５）素粉末混合法にてＦｅを含む
焼結チタン合金を製造する方法において、合金元素添加
用粉末としてＴｉ，Ｆｅの両元素とＹ，Ｅｒ，Ｂの少な
くとも一種類を当該合金の０．０３重量％以上０．５重
量％以下含有した粉末を使用することを特徴とする
（１）記載の焼結チタン合金の製造方法であり、（６）
素粉末混合法にてＡｌ，Ｆｅを含む焼結チタン合金を製
造する方法において、合金元素添加用粉末としてＴｉ，
Ａｌ，Ｆｅの３元素とＹ，Ｅｒ，Ｂの少なくとも一種類
を当該合金の０．０３重量％以上０．５重量％以下含有
した粉末を使用することを特徴とする（１）記載の焼結
チタン合金の製造方法である。In order to achieve the above object, the present invention provides (1) production of a sintered titanium alloy by an elementary powder mixing method using an ultra low chlorine titanium powder produced by a hydrodehydrogenation method. In the method, 40% or more of the total weight of the powder used 7
0% or less is a titanium powder having a particle size of 45 μm or more and 150 μm or less and containing oxygen in an amount of more than 0.1% by weight and 0.24% by weight or less, and 5% or more of the total weight of the used powder 20
% Or less is the powder for adding alloy elements having an average particle size of 3 μm or more and 10 μm or less, and the balance is 10 μm or more and 45 μm or less.
A method for producing a sintered titanium alloy, characterized in that it is a titanium powder containing oxygen in an amount of 0.2 wt% or more and 0.37 wt% or less. A method for producing a titanium-bound alloy, wherein the
An amount of Y, E equivalent to 3% by weight or more and 0.5% by weight or less
A method for producing a sintered titanium alloy according to (1), characterized in that a powder for adding an alloy element containing at least one of r and B is used, and (3) Al is included in the elementary powder mixing method. In the method for producing a sintered titanium alloy, both powders of Ti and Al and at least one of Y, Er and B are added as powders for addition of alloying elements in an amount of 0.03% by weight or more of the alloy.
(4) The method for producing a sintered titanium alloy according to (1), characterized in that a powder containing 5% by weight or less is used.
In a method for producing a sintered titanium alloy containing Al and V by an elementary powder mixing method, Al and V are used as alloy element addition powders.
Of the sintered titanium alloy according to (1), characterized in that a powder containing both of the above elements and at least one of Y, Er and B is contained in an amount of 0.03% by weight or more and 0.5% by weight or less of the alloy. (5) In the method of producing a sintered titanium alloy containing Fe by the elemental powder mixing method (5), both elements of Ti and Fe and at least one of Y, Er and B are used as the alloying element addition powder. A method for producing a sintered titanium alloy according to (1), characterized in that a powder containing 0.03% by weight or more and 0.5% by weight or less of the alloy is used.
In the method for producing a sintered titanium alloy containing Al and Fe by the elementary powder mixing method, Ti, Ti,
Sintering according to (1), characterized in that a powder containing three elements of Al and Fe and at least one of Y, Er and B in an amount of 0.03 wt% or more and 0.5 wt% or less of the alloy is used. It is a method for producing a titanium alloy.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１１】本発明１（請求項１の発明）では、０．１
重量％より多く０．２４重量％以下の酸素を含有し、粒
径が４５μｍ以上１５０μｍ以下のＨＤＨ粉末を使用粉
末全重量の４０％以上７０％以下使用し、平均粒径３μ
ｍ以上１０μｍ以下の合金元素添加用粉末を使用粉末全
重量の５％以上２０％以下使用し、残部が０．２重量％
以上０．３７重量％以下の酸素を含有し、粒径が１０μ
ｍ以上で４５μｍ未満のＨＤＨ粉末を使用することとし
た。このような特定の酸素含有量の粉末を特定の割合で
使用し、さらには特定の粒径の合金元素添加用粉末を特
定の割合で添加することにより、圧粉成形性や最終製品
の機械的特性を低下させる含有酸素量の大幅な上昇防止
と、粉末の充填率と焼結特性の向上による焼結密度上昇
の両者を同時に満たすことができる。In the present invention 1 (the invention of claim 1), 0.1
HDH powder containing more than 0.2% by weight and not more than 0.24% by weight and having a particle size of 45 μm or more and 150 μm or less is used.
A powder for adding an alloying element of m or more and 10 μm or less is used in an amount of 5% to 20% of the total weight of the powder, and the balance is 0.2% by weight.
Containing 0.37% by weight or less of oxygen and having a particle size of 10 μm
It was decided to use HDH powder of m or more and less than 45 μm. By using a powder with such a specific oxygen content in a specific ratio, and further adding a powder for adding an alloying element with a specific particle size in a specific ratio, the powder compactability and the mechanical properties of the final product can be improved. It is possible to simultaneously satisfy both a large increase in the amount of oxygen contained which deteriorates the characteristics and an increase in the sintering density due to the improvement of the powder filling rate and the sintering characteristics.
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２０】[0020]
【実施例】以下、実施例によって本発明をさらに詳しく
説明する。試験に供した試料は以下の工程で作製した。
すなわち、所定の割合の粉末を混合し、成形用容器に充
填し、４．９ton/cm2 の圧力で冷間静水圧成形（ＣＩ
Ｐ）を行い圧粉体を作製し、１×１０-3Paの真空中で１
２５０℃、２時間の焼結を行い、直径１５mmで長さ１５
０mmの円柱状試験片を作製した。この焼結チタン合金に
対し、焼結密度（相対密度）測定、含有酸素量測定、β
粒径測定、引張試験による伸び測定、回転曲げ疲労試験
を行った。ここで、疲労強度は繰り返し数が１０7 回に
達しても破断しない負荷応力で評価した。The present invention will be described in more detail with reference to the following examples. The sample used for the test was prepared by the following steps.
That is, powders in a predetermined ratio are mixed and filled in a molding container, and cold isostatic pressing (CI) is performed at a pressure of 4.9 ton / cm 2.
P) to produce a green compact, and 1 in a vacuum of 1 × 10 −3 Pa
Sintering at 250 ℃ for 2 hours, diameter 15mm and length 15
A 0 mm columnar test piece was prepared. For this sintered titanium alloy , sintered density (relative density) measurement, oxygen content measurement, β
Particle size measurement, elongation measurement by a tensile test, and rotary bending fatigue test were performed. Here, the fatigue strength was evaluated by a load stress that does not break even when the number of repetitions reaches 10 7 .
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２２[Name of item to be corrected] 0022
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２２】[0022]
【表１】 [Table 1]
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２６[Correction target item name] 0026
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２６】一方、本発明１の比較例である試験番号
２，６，７，９，１１，１３，１４，１７，１８，２１
はいずれも、８％以下の低い伸び値と３００MPa 以下の
低い疲労強度しか得られなかった。特に、試験番号２１
はＴｉ−６Ａｌ−４Ｖよりも高強度の組成であるにもか
かわらず、例えば試験番号５のＴｉ−６Ａｌ−４Ｖより
も低い疲労強度しか得られていない。この理由は次の通
りである。試験番号２および７は、粒径４５μｍ以上１
５０μｍ以下のチタン粉末の割合が本発明１の範囲より
も多かったため、粗大なチタン粉末が多くなり焼結密度
が９９％にも達せず、そのため伸び、疲労強度が低下し
た。試験番号６および９は、粒径４５μｍ以上１５０μ
ｍ以下のチタン粉末の割合が本発明１の範囲よりも少な
かったため、粒径が４５μｍ未満のチタン粉末の割合が
相対的に増加し、製品の酸素量が０．３５％以上にまで
増加し、伸び、疲労強度が低下した。試験番号１１は、
４５μｍ以上１５０μｍ以下のチタン粉末の含有酸素量
が本発明１の上限値である０．２４重量％より多かった
ため、圧粉成形性が低下し十分な焼結密度が得られず、
伸び、疲労強度が低下した。試験番号１３は、粒径１０
μｍ以上４５μｍ未満のチタン粉末の含有酸素量が本発
明１の上限値である０．３７％を超えたため、焼結後の
製品の酸素量が０．３５％以上にまで増加し、伸び、疲
労強度が低下した。また、試験番号１４は合金元素添加
用粉末の平均粒径が本発明１の下限値以下であり、試験
番号２１はＴｉＡｌとＴｉＦｅの添加量の総計が本発明
１の上限値である２０％を超えたため、いずれも成分偏
析を生じ、十分な伸び、疲労強度が得られなかった。ま
た、試験番号１７は、合金元素添加用粉末の平均粒径が
本発明１の上限値よりも大きかったため、チタン粉末間
の空隙を埋めることによる充填密度向上効果が小さくな
り、焼結密度が十分に向上せず、その結果、伸び、疲労
強度が低下した。試験番号１８は、合金元素添加用粉末
の使用割合が、５％未満であったため、粉末が充填され
ていないチタン粉末間の空隙の数が多くなり、充填密度
および焼結密度が低下し、その結果、伸び、疲労強度が
低下した。On the other hand, test numbers 2, 6, 7, 9, 11, 13, 14, 17, 18, 21, which are comparative examples of the present invention 1.
In each case, only a low elongation value of 8% or less and a low fatigue strength of 300 MPa or less were obtained. In particular, test number 21
Despite having a higher strength composition than Ti-6Al-4V, for example, only a fatigue strength lower than that of Ti-6Al-4V of test number 5 was obtained. The reason for this is as follows. Test numbers 2 and 7 are particle sizes of 45 μm or more 1
Since the proportion of titanium powder having a particle size of 50 μm or less was higher than the range of the present invention 1, the amount of coarse titanium powder was large, and the sintered density did not reach 99%, so that the elongation and fatigue strength decreased. Test Nos. 6 and 9 have a particle size of 45 μm or more and 150 μm
Since the proportion of titanium powder of m or less was less than the range of the present invention 1, the proportion of titanium powder having a particle size of less than 45 μm was relatively increased, and the oxygen content of the product was increased to 0.35% or more. Elongation and fatigue strength decreased. Test number 11 is
Since the oxygen content of the titanium powder having a particle size of 45 μm or more and 150 μm or less was larger than 0.24% by weight, which is the upper limit value of the present invention 1, the compacting property was reduced and a sufficient sintered density could not be obtained.
Elongation and fatigue strength decreased. Test number 13 is particle size 10
Since the oxygen content of the titanium powder having a size of μm or more and less than 45 μm exceeds 0.37%, which is the upper limit of the present invention 1, the oxygen content of the product after sintering increases to 0.35% or more, and elongation and fatigue The strength decreased. Further, in Test No. 14, the average particle diameter of the powder for alloying element addition is less than or equal to the lower limit value of Invention 1, and in Test No. 21 the total addition amount of TiAl and TiFe is 20% which is the upper limit value of Invention 1. Therefore, in all cases, segregation of components occurred, and sufficient elongation and fatigue strength could not be obtained. In Test No. 17, the average particle diameter of the alloying element-adding powder was larger than the upper limit value of Invention 1, so that the effect of filling the voids between the titanium powders was less effective to improve the packing density and the sintering density was sufficient. As a result, the elongation and fatigue strength decreased. In Test No. 18, since the use ratio of the alloying element addition powder was less than 5%, the number of voids between the titanium powders not filled with the powder was increased, and the packing density and the sintering density were decreased. As a result, elongation and fatigue strength decreased.
【手続補正９】[Procedure Amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２７[Name of item to be corrected] 0027
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２７】次に、本発明２〜６の実施例について説明
する。粒径が４５μｍ以上１５０μｍ以下で酸素を０．
１５重量％含有するＨＤＨ粉末を使用粉末全重量の５０
％、表３に示す合金元素添加用粉末、さらには粒径が１
０μｍ未満４５μｍ以上で酸素を０．３０重量％含有す
るＨＤＨ粉末を、母材の組成がＴｉ−６Ａｌ−４Ｖ（試
験番号２２〜３３および３７〜４０）またはＴｉ−５Ａ
ｌ−２．５Ｆｅで、Ｙ，Ｅｒ，Ｂの総量が母材に対して
表３に示すような値となるように混合し、成形、焼結を
行った。成形、焼結の条件、焼結品の寸法・形状、試験
方法・項目は先に述べた本発明１の説明と同じである。Next, examples of the present inventions 2 to 6 will be described. When the particle size is 45 μm or more and 150 μm or less, oxygen is less than 0.
Use HDH powder containing 15% by weight 50% of total weight of powder
%, Powder for alloying element addition shown in Table 3, and particle size of 1
An HDH powder containing less than 0 μm and 45 μm or more and containing 0.30% by weight of oxygen has a base material composition of Ti-6Al-4V (test numbers 22 to 33 and 37 to 40) or Ti-5A.
1-2.5Fe was mixed so that the total amount of Y, Er, and B would be the values shown in Table 3 with respect to the base material, followed by molding and sintering. The conditions of molding and sintering, the size and shape of the sintered product, and the test method and items are the same as those described in the first embodiment.
【手続補正１０】[Procedure Amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２８[Correction target item name] 0028
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２８】[0028]
【表３】 [Table 3]
【手続補正１１】[Procedure Amendment 11]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２９[Name of item to be corrected] 0029
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２９】表３において、試験番号２２〜２５は、
Ｙ，Ｙ2 Ｏ3 ，Ｅｒ2 Ｏ3 ，Ｂ4 Ｃの単体粉末をそのま
まチタン粉末および母材の合金元素添加用粉末（６０Ａ
ｌ−４０Ｖ）と混合した場合で、いずれも焼結密度が９
６％以下の低い値となっており、伸び、疲労強度は極端
に低い値となっている。これは、これらの粉末を直接添
加したため、チタン粉末や母材の合金元素添加用粉末の
接触を阻害し、且つ粉末表面の移動をピン止めし、水素
化脱水素法により製造したチタン粉末の焼結特性をさら
に劣化させたことによる。In Table 3, the test numbers 22 to 25 are
A single powder of Y, Y 2 O 3 , Er 2 O 3 , and B 4 C is used as it is as a titanium powder and a powder for adding an alloy element to the base metal (60 A).
1-40 V), the sintered density was 9 in each case.
It is a low value of 6% or less, and the elongation and fatigue strength are extremely low values. This is because these powders were added directly, so that they hinder the contact of the titanium powder and the alloying element addition powder of the base metal, and pin the movement of the powder surface to prevent hydrogen.
This is because the sintering characteristics of the titanium powder manufactured by the chemical dehydrogenation method were further deteriorated.
【手続補正１２】[Procedure Amendment 12]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３０[Name of item to be corrected] 0030
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３０】一方、表３において、試験番号２６〜４０
では、母材の合金元素添加用物質（６０Ａｌ−４０Ｖ、
ＴｉＡｌ3 、ＴｉＦｅ、５Ｔｉ−５Ａｌ−２．５Ｆｅ）
の塊とＹ，Ｅｒ，Ｂ，Ｙ2 Ｏ3 ，Ｅｒ2 Ｏ3 ，Ｂ4 Ｃ粉
末を混合し、真空アーク溶解し、さらにこれらを粉砕
し、Ｙ，Ｅｒ，Ｂあるいはこれらの化合物の周囲を合金
元素が被っている状態の合金元素添加用粉末を作製し使
用した場合である。On the other hand, in Table 3, test numbers 26 to 40
Then, a substance for alloying element addition of the base material (60Al-40V,
TiAl 3 , TiFe, 5Ti-5Al-2.5Fe)
Mass and Y, Er, B, Y 2 O 3, Er 2 O 3, B 4 C powder were mixed, vacuum arc melting, and further pulverized them, Y, Er, B or around these compounds This is a case where a powder for adding an alloy element in a state covered with the alloy element was prepared and used.
【手続補正１３】[Procedure Amendment 13]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３１[Correction target item name] 0031
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３１】本発明の実施例である試験番号２６〜３６
および３８，３９は、Ｙ，Ｅｒ，Ｂあるいはこれらの化
合物を添加しなかった場合、例えば試験番号４（表１，
表２）と比べて、平均β粒径は４分の１あるいはそれ以
下になっており、一方焼結密度は９９．５％以上の高い
値となっている。その結果、伸び、疲労強度は、Ｙ，Ｅ
ｒ，Ｂあるいはこれらの化合物を添加しなかった場合よ
りも高くなっており、特に疲労強度は３７０MPa 以上の
極めて高い値が得られた。これは、予め合金元素添加用
粉末の内部に結晶粒の成長を抑制する物質を含有させて
使用したことにより、チタン粉末同士あるいはチタン粉
末と合金元素の接触を阻害せず、且つ粉末表面の移動を
妨げることがなくなり、しかし、一方では焼結合金の結
晶粒界移動を阻害し結晶粒成長を抑制し、従来と同様の
条件での混合−充填−成形−真空焼結の工程で、結晶粒
微細化と９９．５％以上の高い相対密度を有し、高い機
械的性質が得られたものである。 ─────────────────────────────────────────────────────
Test Nos. 26 to 36, which are examples of the present invention
And 38 and 39, when Y, Er, B or these compounds are not added, for example, Test No. 4 (Table 1,
Compared with Table 2), the average β particle size is 1/4 or less, while the sintered density is a high value of 99.5% or more. As a result, the elongation and fatigue strength are Y, E
The values were higher than when r, B or these compounds were not added, and particularly, the fatigue strength was an extremely high value of 370 MPa or more. This is because the substance for suppressing the growth of crystal grains was previously contained in the alloying element addition powder, so that the titanium powders did not interfere with each other or the contact between the titanium powder and the alloying element, and the movement of the powder surface was prevented. However, on the other hand, on the other hand, it inhibits the grain boundary movement of the sintered alloy and suppresses the grain growth, and in the process of mixing-filling-molding-vacuum sintering under the same conditions as before, the crystal grains It has a fine structure and a high relative density of 99.5% or more, and has high mechanical properties. ─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年３月８日[Submission date] March 8, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１１】本発明１（請求項１の発明）では、０．１
重量％より多く０．２４重量％以下の酸素を含有し、粒
径が４５μｍ以上１５０μｍ以下のＨＤＨ粉末を使用粉
末全重量の４０％以上７０％以下使用し、平均粒径３μ
ｍ以上１０μｍ以下の合金元素添加用粉末を使用粉末全
重量の５％以上２０％以下使用し、残部が０．２重量％
以上０．３７重量％以下の酸素を含有し、粒径が１０μ
ｍ以上４５μｍ未満のＨＤＨ粉末を使用することとし
た。このような特定の酸素含有量の粉末を特定の割合で
使用し、さらには特定の粒径の合金元素添加用粉末を特
定の割合で添加することにより、圧粉成形性や最終製品
の機械的特性を低下させる含有酸素量の大幅な上昇防止
と、粉末の充填率と焼結特性の向上による焼結密度上昇
の両者を同時に満たすことができる。In the present invention 1 (the invention of claim 1), 0.1
HDH powder containing more than 0.2% by weight and not more than 0.24% by weight and having a particle size of 45 μm or more and 150 μm or less is used.
A powder for adding an alloying element of m or more and 10 μm or less is used in an amount of 5% to 20% of the total weight of the powder, and the balance is 0.2% by weight.
Containing 0.37% by weight or less of oxygen and having a particle size of 10 μm
It was decided to use HDH powder of m or more and less than 45 μm . By using a powder with such a specific oxygen content in a specific ratio, and further adding a powder for adding an alloying element with a specific particle size in a specific ratio, the powder compactability and the mechanical properties of the final product can be improved. It is possible to simultaneously satisfy both a large increase in the amount of oxygen contained which deteriorates the characteristics and an increase in the sintering density due to the improvement of the powder filling rate and the sintering characteristics.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堀谷 貴雄 千葉県富津市新富20−１ 新日本製鐵株式 会社技術開発本部内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takao Horiya 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Corporate Technology Development Division
Claims (6)
チタン粉末を用いた素粉末混合法で焼結チタン合金を製
造する方法において、使用粉末全重量の４０％以上７０
％以下が、粒径４５μｍ以上１５０μｍ以下で且つ０．
１重量％より多く０．２４重量％以下の酸素を含有する
チタン粉末であり、使用粉末全重量の５％以上２０％以
下が、平均粒径３μｍ以上１０μｍ以下の合金元素添加
用粉末であり、残部が粒径１０μｍ以上で４５μｍ未満
で且つ０．２重量％以上０．３７重量％以下の酸素を含
有するチタン粉末であることを特徴とする、焼結チタン
合金の製造方法。1. In a method for producing a sintered titanium alloy by an elementary powder mixing method using an ultra-low chlorine titanium powder produced by a hydrodehydrogenation method, 40% or more of the total weight of the powder used is 70.
% Or less is 45 μm or more and 150 μm or less, and 0.
A titanium powder containing oxygen in an amount of more than 1% by weight and 0.24% by weight or less, and 5% or more and 20% or less of the total weight of the powder used is a powder for adding an alloy element having an average particle size of 3 μm or more and 10 μm or less, A method for producing a sintered titanium alloy, wherein the balance is titanium powder having a particle size of 10 μm or more and less than 45 μm and containing 0.2% by weight or more and 0.37% by weight or less of oxygen.
する方法において、当該焼結チタン合金の０．０３重量
％以上０．５重量％以下に相当する量のＹ，Ｅｒ，Ｂの
少なくとも一種類を含有する合金元素添加用粉末を使用
することを特徴とする請求項１記載の焼結チタン合金の
製造方法。2. A method for producing a sintered titanium alloy by an elementary powder mixing method, wherein the amount of Y, Er, B is 0.03% by weight or more and 0.5% by weight or less of the sintered titanium alloy. The method for producing a sintered titanium alloy according to claim 1, wherein a powder for adding an alloy element containing at least one kind is used.
合金を製造する方法において、合金元素添加用粉末とし
てＴｉ，Ａｌの両元素とＹ，Ｅｒ，Ｂの少なくとも一種
類を当該焼結チタン合金の０．０３重量％以上０．５重
量％以下に相当する量を含有した粉末を使用することを
特徴とする請求項１記載の焼結チタン合金の製造方法。3. A method of producing a sintered titanium alloy containing Al by an elemental powder mixing method, wherein both elements of Ti and Al and at least one of Y, Er and B are sintered as alloying element addition powder. The method for producing a sintered titanium alloy according to claim 1, wherein a powder containing an amount corresponding to 0.03% by weight or more and 0.5% by weight or less of the titanium alloy is used.
タン合金を製造する方法において、合金元素添加用粉末
としてＡｌ，Ｖの両元素とＹ，Ｅｒ，Ｂの少なくとも一
種類を当該焼結チタン合金の０．０３重量％以上０．５
重量％以下含有した粉末を使用することを特徴とする請
求項１記載の焼結チタン合金の製造方法。4. A method for producing a sintered titanium alloy containing Al and V by an elementary powder mixing method, wherein both elements of Al and V and at least one of Y, Er and B are used as powders for adding alloy elements. 0.03% by weight or more of sintered titanium alloy 0.5
The method for producing a sintered titanium alloy according to claim 1, wherein a powder containing less than or equal to wt% is used.
合金を製造する方法において、合金元素添加用粉末とし
てＴｉ，Ｆｅの両元素とＹ，Ｅｒ，Ｂの少なくとも一種
類を当該焼結チタン合金の０．０３重量％以上０．５重
量％以下含有した粉末を使用することを特徴とする請求
項１記載の焼結チタン合金の製造方法。5. A method for producing a sintered titanium alloy containing Fe by the elementary powder mixing method, wherein both elements of Ti and Fe and at least one of Y, Er and B are sintered as the powder for adding alloy elements. The method for producing a sintered titanium alloy according to claim 1, wherein a powder containing 0.03% by weight or more and 0.5% by weight or less of the titanium alloy is used.
チタン合金を製造する方法において、合金元素添加用粉
末としてＴｉ，Ａｌ，Ｆｅの３元素とＹ，Ｅｒ，Ｂの少
なくとも一種類を当該焼結チタン合金の０．０３重量％
以上１．５重量％以下含有した粉末を使用することを特
徴とする請求項１記載の焼結チタン合金の製造方法。6. A method for producing a sintered titanium alloy containing Al and Fe by the elementary powder mixing method, wherein at least one of Ti, Al and Fe and Y, Er and B is used as a powder for adding alloy elements. 0.03% by weight of the sintered titanium alloy
The method for producing a sintered titanium alloy according to claim 1, characterized in that powder containing not less than 1.5% by weight is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5190613A JPH0741882A (en) | 1993-07-30 | 1993-07-30 | Production of sintered titanium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5190613A JPH0741882A (en) | 1993-07-30 | 1993-07-30 | Production of sintered titanium alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0741882A true JPH0741882A (en) | 1995-02-10 |
Family
ID=16260991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5190613A Withdrawn JPH0741882A (en) | 1993-07-30 | 1993-07-30 | Production of sintered titanium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0741882A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000005425A1 (en) * | 1998-07-21 | 2000-02-03 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Titanium-based composite material, method for producing the same and engine valve |
| CN102407337A (en) * | 2011-11-24 | 2012-04-11 | 李宝干 | Method for manufacturing titanium and titanium alloy powder metallurgy special-shaped pieces |
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-
1993
- 1993-07-30 JP JP5190613A patent/JPH0741882A/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000005425A1 (en) * | 1998-07-21 | 2000-02-03 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Titanium-based composite material, method for producing the same and engine valve |
| CN1097639C (en) * | 1998-07-21 | 2003-01-01 | 株式会社丰田中央研究所 | Titanium-based composition material, method for producing the same and engine valve |
| US6551371B1 (en) | 1998-07-21 | 2003-04-22 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Titanium-based composite material, method for producing the same and engine valve |
| US9977518B2 (en) | 2001-10-22 | 2018-05-22 | Apple Inc. | Scrolling based on rotational movement |
| US10353565B2 (en) | 2002-02-25 | 2019-07-16 | Apple Inc. | Input apparatus and button arrangement for handheld device |
| US10139870B2 (en) | 2006-07-06 | 2018-11-27 | Apple Inc. | Capacitance sensing electrode with integrated I/O mechanism |
| US10359813B2 (en) | 2006-07-06 | 2019-07-23 | Apple Inc. | Capacitance sensing electrode with integrated I/O mechanism |
| US10890953B2 (en) | 2006-07-06 | 2021-01-12 | Apple Inc. | Capacitance sensing electrode with integrated I/O mechanism |
| US10180732B2 (en) | 2006-10-11 | 2019-01-15 | Apple Inc. | Gimballed scroll wheel |
| US9654104B2 (en) | 2007-07-17 | 2017-05-16 | Apple Inc. | Resistive force sensor with capacitive discrimination |
| CN102407337A (en) * | 2011-11-24 | 2012-04-11 | 李宝干 | Method for manufacturing titanium and titanium alloy powder metallurgy special-shaped pieces |
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|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20001003 |