JPH0762161B2 - Method of manufacturing reinforced titanium - Google Patents
Method of manufacturing reinforced titaniumInfo
- Publication number
- JPH0762161B2 JPH0762161B2 JP3237782A JP23778291A JPH0762161B2 JP H0762161 B2 JPH0762161 B2 JP H0762161B2 JP 3237782 A JP3237782 A JP 3237782A JP 23778291 A JP23778291 A JP 23778291A JP H0762161 B2 JPH0762161 B2 JP H0762161B2
- Authority
- JP
- Japan
- Prior art keywords
- tib
- powder
- treatment
- temperature
- alloy
- 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.)
- Expired - Lifetime
Links
- 239000010936 titanium Substances 0.000 title claims description 30
- 229910052719 titanium Inorganic materials 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 4
- 239000000843 powder Substances 0.000 claims description 49
- 238000007731 hot pressing Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001513 hot isostatic pressing Methods 0.000 claims description 2
- 238000005551 mechanical alloying Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 description 40
- 239000000956 alloy Substances 0.000 description 40
- 239000002184 metal Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000000835 fiber Substances 0.000 description 15
- 238000012545 processing Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 238000005728 strengthening Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000010406 interfacial reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 208000010392 Bone Fractures Diseases 0.000 description 4
- 206010017076 Fracture Diseases 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 206010010214 Compression fracture Diseases 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、強化チタンの製造方法
に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing reinforced titanium.
【0002】[0002]
【従来の技術および背景ならびに発明が解決しようとす
る課題】Tiおよびその合金は比強度が高くしかも耐食
性に優れているため、α型、α+β型あるいはβ型など
多くの合金が開発され、化学プラント、ジェットエンジ
ン、航空機あるいは機械部品などに広範に利用されてい
る。しかし、Ti合金も他の合金と同様に、高温では結
晶粒の粗大化、熱処理による析出粒子の成長などの現象
により著しく強度が低下するため、最高使用温度はせい
ぜい573〜773K程度である。2. Description of the Related Art Since Ti and its alloys have high specific strength and excellent corrosion resistance, many alloys such as α type, α + β type or β type have been developed and chemical plants have been developed. Widely used in jet engines, aircraft or mechanical parts. However, the Ti alloy, like other alloys, has a marked decrease in strength at high temperatures due to phenomena such as coarsening of crystal grains and growth of precipitated particles due to heat treatment. Therefore, the maximum operating temperature is at most about 573 to 773K.
【0003】ところで、近年、Ti合金の耐熱性を改善
するために、CVD法で作製されたSiC繊維を複合化
した繊維強化チタン合金の開発が進められている。しか
し、CVD法で作製されたSiC繊維は非常に高価であ
り、なおかつ繊維強化金属基複合材料では高温での使用
時に強化繊維とマトリックス金属間に反応が生じるとい
う問題がある。この界面反応は高温では必然的に生じる
ため、反応を防止するためのコーティング法が種々検討
されているが充分でなく、そのため使用に際しては界面
反応の進行が問題にならない温度以下で使用するといっ
た方法が採用されている。このように、充分な高温特性
を有する繊維強化Ti合金は未だ提供されていない。By the way, in recent years, in order to improve the heat resistance of the Ti alloy, the development of a fiber-reinforced titanium alloy in which SiC fibers produced by the CVD method are compounded has been advanced. However, the SiC fiber produced by the CVD method is very expensive, and the fiber-reinforced metal matrix composite material has a problem that a reaction occurs between the reinforcing fiber and the matrix metal when used at high temperature. Since this interfacial reaction inevitably occurs at high temperatures, various coating methods for preventing the reaction have been studied, but it is not sufficient. Therefore, when used, the method is used at a temperature below the temperature at which the progress of the interfacial reaction does not matter. Has been adopted. Thus, a fiber reinforced Ti alloy having sufficient high temperature properties has not yet been provided.
【0004】そこで、界面反応が存在しないような母金
属と強化繊維の組合せが存在すれば、繊維をコーティン
グする必要もなく、界面反応を抑制するために低い温度
でしか使用できないという制約もなくなる。これに関
し、本発明者は以下のように考えた。すなわち、繊維あ
るいは粒子も含めて強化に寄与する物質は、「マトリッ
クス金属との溶解度積が小さいこと」または「マトリッ
クス金属に対して完全に平衡状態であること」のいずれ
かであれば、その複合材料は良好な特性を有すると考え
られる。本発明の目的の一つは後者の条件を満たすもの
を開発することにある。そのための物質としては、高温
でも安定である酸化物、炭化物、窒化物、ホウ化物が考
えられる。そこで、Ti−O系、Ti−C系、Ti−N
系、Ti−B系状態図を検討すると、NおよびOはTi
に対して非常に大きな固溶量を示し、Cも1193Kで
約0.5重量%固溶するため、これらの元素はTiマト
リックスの強化には寄与する。しかし、侵入型固溶体を
形成するため、同時に合金を脆化させるという一面を有
する。このため、酸化物、炭化物あるいは窒化物は、T
i基合金に対する強化物質として使用できない。一方、
Tiに対してBは殆ど固溶せず、図1に示す如く、Ti
−TiB共晶を形成する。従って、このTiBを微細化
できれば、TiB粒子の分散強化あるいは繊維強化によ
るTiの強化が期待できる。Therefore, if there is a combination of the mother metal and the reinforcing fiber such that the interfacial reaction does not exist, it is not necessary to coat the fiber, and there is no restriction that the fiber can be used only at a low temperature to suppress the interfacial reaction. In this regard, the present inventor considered the following. That is, a substance that contributes to strengthening, including fibers or particles, is either a "small solubility product with the matrix metal" or "complete equilibrium with the matrix metal" The material is believed to have good properties. One of the objects of the present invention is to develop a product that satisfies the latter condition. As a substance therefor, oxides, carbides, nitrides and borides which are stable even at high temperatures are considered. Therefore, Ti-O type, Ti-C type, Ti-N type
System and Ti-B system phase diagram, N and O are Ti
However, these elements also contribute to strengthening the Ti matrix, since C also forms a solid solution of about 0.5% by weight at 1193K. However, since it forms an interstitial solid solution, it has an aspect of simultaneously embrittlement the alloy. Therefore, oxides, carbides or nitrides are
It cannot be used as a strengthening material for i-based alloys. on the other hand,
B hardly dissolves in Ti, and as shown in FIG.
Form a TiB eutectic. Therefore, if the TiB can be made finer, it is expected that the TiB particles will be strengthened by dispersion strengthening or fiber strengthening.
【0005】本発明は、以上説明したような従来の技術
の有する問題点に鑑みてなされたものであって、その目
的は、TiBの分散強化あるいは繊維強化による充分な
高温で使用可能な強化Tiの製造方法を提供することに
ある。The present invention has been made in view of the problems of the prior art as described above, and its purpose is to strengthen the Ti which can be used at a sufficiently high temperature by dispersion strengthening of TiB or fiber strengthening. It is to provide a manufacturing method of.
【0006】[0006]
【課題を解決するための手段】上記目的を達成するため
に本発明の要旨は、Ti粉および非晶質ホウ素粉または
TiB2 粉をメカニカルアロイングした後、773K〜
1273Kの温度で高温静水圧成形またはホットプレス
を行うことを特徴とする強化チタンの製造方法にある。In order to achieve the above-mentioned object, the gist of the present invention is to mechanically alloy Ti powder and amorphous boron powder or TiB 2 powder, and thereafter 773K-
A method for producing a reinforced titanium is characterized in that hot isostatic pressing or hot pressing is performed at a temperature of 1273K.
【0007】[0007]
【実施例および作用】以下に、本発明の作用をその最適
実験例とともに説明する。EXAMPLES AND OPERATION The operation of the present invention will be described below together with its optimum experimental example.
【0008】〔実験概要〕まず、本発明を適用した実験
の概要について説明すると、本実験に用いた原料は、高
純度Ti粉、非晶質B粉およびTiB2 であり、それら
の走査型電子顕微鏡(SEM)像を図2(a) 〜(c) に示
す。図2(a) 、図2(b) 、図2(c) はそれぞれTi粉、
B粉、TiB2 粉のSEM像である。なお、TiB2 粉
は、図2(a) および図2(b) に示す高純度Ti粉および
非晶質B粉を所定の比に混合した後、自己燃焼合成法に
より得られたものを粉砕したものである。これらの粉末
を以下の表1に示すように、TiBの体積率が10.0
%、20.0%および30.0%となるように配合し、
高エネルギーボールミルによりアルゴン中で3.6×1
03 〜72.0×103 sec (以下「3.6ks〜7
2.0ks」という)間メカニカルアロイング(以下
「MA」という)し、得られたMA粉を673〜127
3Kの温度で3.6ks、高温静水圧成形(以下「HI
P」という)することにより固化成形した。[Outline of Experiment] First, an outline of an experiment to which the present invention is applied will be described. The raw materials used in this experiment are high-purity Ti powder, amorphous B powder, and TiB 2 , and their scanning electron Microscopic (SEM) images are shown in FIGS. 2 (a)-(c). 2 (a), 2 (b) and 2 (c) show Ti powder,
B powder, a SEM image of TiB 2 powder. The TiB 2 powder was obtained by mixing the high-purity Ti powder and the amorphous B powder shown in FIGS. 2 (a) and 2 (b) at a predetermined ratio and then pulverizing the powder obtained by the self-combustion synthesis method. It was done. These powders have a TiB volume ratio of 10.0 as shown in Table 1 below.
%, 20.0% and 30.0%,
3.6 × 1 in argon by high energy ball mill
0 3 to 72.0 × 10 3 sec (hereinafter “3.6 ks to 7
Mechanical alloying (hereinafter referred to as “MA”) for (2.0 ks)), and the resulting MA powder was 673 to 127.
High temperature isostatic molding at 3.6Ks at a temperature of 3K (hereinafter referred to as "HI
P)) to solidify and mold.
【0009】[0009]
【表1】 [Table 1]
【0010】以下に、実験工程順にその結果を説明す
る。The results will be described below in the order of the experimental steps.
【0011】〔MA処理による合金粉の変化〕図3は合
金粉No.3(Ti−B系、30体積%TiB)のMA
処理による形態の変化を示す。3.6ksのMA処理に
より粉末は細かく粉砕されると共にそれらが凝集して造
粒が開始されている様子が確認できる(図3(b) 参
照)。そして、18.0ksでは造粒が進行し、粉末形
状は丸みを帯びるようになり(図3(c) 参照)、72.
0ks後には100〜200μmとなった(図3(d) 参
照)。[Change of Alloy Powder by MA Treatment] FIG. MA of 3 (Ti-B system, 30% by volume TiB)
The change in morphology due to treatment is shown. It can be confirmed that the powder is finely pulverized by the MA treatment for 3.6 ks and that they are aggregated to start the granulation (see FIG. 3 (b)). Then, at 18.0 ks, granulation proceeds and the powder shape becomes rounded (see FIG. 3 (c)).
It became 100 to 200 μm after 0 ks (see FIG. 3 (d)).
【0012】図4(a) 、図4(b) はそれぞれ合金粉N
o.3(Ti−B系、30体積%TiB)、No.4
(Ti−TiB2 系、30体積%TiB)のMA処理に
よるX線回折図形の変化を示す。図4(a) においては、
MA処理の進行と共にTiの回折像はブロード化してい
る。これは歪みの蓄積と結晶粒の微細化に起因するもの
と思われる。また、図4(b) においても、Tiの回折像
はMA処理の進行と共にブロード化している。一方、T
iB2 の回折像は72.0ksのMA処理によって僅か
にブロード化しているが、Tiほど充分に粉砕されてい
ないものと思われる。というのは、TiB2 のビッカー
ス硬さは約3400と非常に硬いので、TiB2 を取り
囲む柔らかいTiのみが選択的に粉砕されたと考えられ
るからである。4 (a) and 4 (b) are alloy powder N, respectively.
o. 3 (Ti-B system, 30% by volume TiB), No. Four
(Ti-TiB 2 based, 30 vol% TiB) shows the change in X-ray diffraction pattern by MA process. In Figure 4 (a),
The Ti diffraction image is broadened with the progress of MA treatment. This seems to be due to the accumulation of strain and the refinement of crystal grains. Also in FIG. 4B, the Ti diffraction image is broadened with the progress of MA processing. On the other hand, T
The iB 2 diffraction image is slightly broadened by MA treatment for 72.0 ks, but it is considered that it is not pulverized sufficiently as Ti. This is because TiB 2 has a very high Vickers hardness of about 3400, and it is considered that only soft Ti surrounding TiB 2 was selectively crushed.
【0013】〔MA処理後の合金粉の熱処理による変
化〕図5(a) 、図5(b) はそれぞれ72.0ksMA処
理した合金粉No.3(Ti−B系、30体積%Ti
B)、No.4(Ti−TiB2 系、30体積%Ti
B)を真空中で3.6ks熱処理した場合のX線回折図
形の変化を示す。図5(a) では、773KですでにTi
Bの析出が認められ、平衡状態であるTi−TiB合金
となっている。TiBの回折像は熱処理温度の上昇によ
り僅かに鮮鋭化しているが、1273Kの熱処理でもか
なりブロードである。[Change of Alloy Powder after MA Treatment by Heat Treatment] FIGS. 5 (a) and 5 (b) show alloy powder No. 7 which has been treated with 72.0 ks MA. 3 (Ti-B system, 30 volume% Ti
B), No. 4 (Ti-TiB 2 system, 30 volume% Ti
The change of the X-ray-diffraction pattern when B) was heat-processed for 3.6 ks in vacuum is shown. In Fig. 5 (a), Ti is already at 773K.
Precipitation of B was observed, and the Ti-TiB alloy was in an equilibrium state. The diffraction image of TiB is slightly sharpened by the rise of the heat treatment temperature, but is considerably broad even by the heat treatment of 1273K.
【0014】一方、図5(b) に示すように、合金粉N
o.4では773Kの熱処理ではTiおよびTiB2 の
いずれもMA処理によって蓄積された歪みが開放され、
回折像は鮮鋭化したが、TiBの析出は認められなかっ
た。TiBの析出は873K以上の熱処理温度で認めら
れるようになり、処理温度の上昇と共に増大した。10
73K以上では完全に反応は終了し、平衡状態であるT
i−TiB合金となった。On the other hand, as shown in FIG. 5 (b), alloy powder N
o. In No. 4, in the heat treatment of 773 K, the strain accumulated by the MA treatment was released in both Ti and TiB 2 .
The diffraction image was sharpened, but precipitation of TiB was not observed. Precipitation of TiB became visible at a heat treatment temperature of 873 K or higher, and increased with an increase in the treatment temperature. 10
The reaction is completely completed at 73 K or higher, and the equilibrium T
It became an i-TiB alloy.
【0015】以上の結果、B源として非晶質B粉を使用
するほうが、TiB2 粉を使用するよりも、より低温で
平衡状態に達することが明らかとなった。From the above results, it was revealed that the use of the amorphous B powder as the B source reaches the equilibrium state at a lower temperature than the use of the TiB 2 powder.
【0016】 図6(a) 、(b) は、72.0ksMA処
理した合金粉No.1(Ti−B系、10体積%Ti
B)を1073K(図6(a))または1273K(図6
(b))で3.6ksHIP処理した場合の分析電子顕微鏡
(TEM)像を示す。析出するTiBはアスペクト比が
20〜30の針状あるいは棒状であり、低温の1073
Kのほうがより微細であるのが認められる。また、10
73Kの熱処理では、Tiの再結晶粒は部分的に認めら
れるのみであり、その平均粒径は300〜500nmで
あった。6 (a) and 6 (b) show alloy powder No. 7 processed by 72.0 ksMA. 1 (Ti-B system, 10 volume% Ti
B) is 1073K (Fig. 6 (a)) or 1273K (Fig. 6)
The analysis electron microscope (TEM) image at the time of 3.6ksHIP processing by (b)) is shown. The precipitated TiB is needle-shaped or rod-shaped with an aspect ratio of 20 to 30, and has a low temperature of 1073.
It can be seen that K is finer. Also, 10
In the heat treatment at 73K, the recrystallized grains of Ti were only partially recognized, and the average grain size was 300 to 500 nm.
【0017】図7(a) 、(b) は、72.0ksMA処理
した合金粉No.3(Ti−B系、30体積%TiB)
を873K(図7(a))または1073K(図7(b))で
3.6ksHIP処理した場合のTEM像を示す。87
3Kで析出するTiBは著しく微細であるのが明らかで
ある。一般にAl基、Cu基あるいはTiAl金属間化
合物などのMA合金の組織は非常に微細であることが報
告されているが、本実験でのTi−TiB合金も同様の
傾向を示した。7 (a) and 7 (b) show alloy powder No. 7 processed by 72.0 ksMA. 3 (Ti-B system, 30% by volume TiB)
Shows a TEM image of the case where the treatment was performed with 873K (Fig. 7 (a)) or 1073K (Fig. 7 (b)) for 3.6ksHIP. 87
It is clear that TiB precipitated at 3K is extremely fine. It is generally reported that the structure of an MA alloy such as an Al-based, Cu-based or TiAl intermetallic compound is very fine, but the Ti-TiB alloy in this experiment also showed the same tendency.
【0018】 以上の実験において、いずれのTiB濃
度およびHIP処理温度においても、析出するTiB繊
維はほとんどすべて単結晶であり、非常に大きなアスペ
クト比(20〜30)を有していた。本実験のように繊
維状に析出する例としては、Cu−Ti−B系の液相焼
結によって繊維状TiB2 が、またCu−Al合金の内
部酸化によってθ−Al2 O3 が析出することが報告さ
れているが、いずれも特定の処理温度あるいは濃度で繊
維状析出が認められるのみであるが、本実験では873
〜1273Kのすべての処理温度および10〜30体積
%の濃度範囲で繊維状析出が認められた。In the above experiments, at any TiB concentration and HIP treatment temperature, almost all TiB fibers precipitated were single crystals and had a very large aspect ratio (20 to 30). As an example of fibrous deposition as in the present experiment, fibrous TiB 2 is deposited by liquid phase sintering of Cu—Ti—B system, and θ-Al 2 O 3 is deposited by internal oxidation of Cu—Al alloy. Although it was reported that fibrous precipitation was only observed at a specific treatment temperature or concentration in all cases, in this experiment, 873
Fibrous deposits were observed at all treatment temperatures of ~ 1273K and in the concentration range of 10-30% by volume.
【0019】本実験による合金はTiとTiBの共晶を
利用しているため、両物質間のぬれ性は良好であると考
えられる。また、TiBの硬度はTiB2 のそれよりも
幾分低いが、分散強化材としては充分な硬さを有してい
る。Since the alloy according to the present experiment utilizes a eutectic of Ti and TiB, it is considered that the wettability between both substances is good. Although the hardness of TiB is somewhat lower than that of TiB 2 , it has sufficient hardness as a dispersion strengthening material.
【0020】一般に繊維強化金属基複合材料は、SiC
あるいはSi3 N4 などの繊維とマトリックス金属粉を
均一に混合し、ホットプレス、HIPあるいは熱間押出
しなどにより固化成形することにより製造されている。
しかしながら、混合時あるいは固化成形時に繊維が折損
したり、また繊維を充分均一に分散させることが困難で
あるといった問題が生じる。また、上記したようにSi
CあるいはSi3 N4 などの繊維は必ずといってよいほ
どマトリックス金属と界面反応を引き起こすため、複合
材料としての安定性に問題がある。しかしながら、本実
験で示した方法で作製したTi−TiB複合材料は、上
記したすべての問題を解決し得るものと考えられる。Generally, the fiber-reinforced metal matrix composite material is SiC.
Alternatively, it is manufactured by uniformly mixing fibers such as Si 3 N 4 and matrix metal powder and solidifying and molding by hot pressing, HIP or hot extrusion.
However, there are problems that the fibers are broken during mixing or solidification molding, and it is difficult to disperse the fibers sufficiently uniformly. In addition, as described above, Si
Since fibers such as C or Si 3 N 4 almost always cause an interfacial reaction with the matrix metal, there is a problem in stability as a composite material. However, it is considered that the Ti-TiB composite material produced by the method shown in this experiment can solve all the problems described above.
【0021】〔HIP処理材の常温機械的性質〕図8は
72.0ksMA処理した合金粉No.1(10体積%
TiB)およびNo.2(20体積%TiB)を、MA
処理状態のまま及びMA処理粉末を873〜1273K
の温度で3.6ksHIP処理した場合の常温硬さの変
化を示している。[Mechanical Properties of HIP Treated Material at Room Temperature] FIG. 8 shows alloy powder No. 7 treated with 72.0 ksMA. 1 (10% by volume
TiB) and No. 2 (20 volume% TiB), MA
As-treated and MA-treated powder 873-1273K
3 shows the change in room temperature hardness when the 3.6 ks HIP treatment was performed at the above temperature.
【0022】MA処理状態において、B添加量が多いN
o.2合金のほうが高い硬さを示している。これはMA
処理によるTi−B固溶体の形成による固溶強化に起因
すると考えられる。In the MA-treated state, N containing a large amount of B is added.
o. The two alloys have higher hardness. This is MA
It is considered to be due to solid solution strengthening due to the formation of a Ti-B solid solution by the treatment.
【0023】No.1合金またはNo.2合金のいずれ
においてもMA処理後に873KでHIP処理すること
により、硬さは著しく上昇している。MA処理により酸
素含有量は多少増大しているものと考えられるが、熱処
理によりこのように硬さが増大するのは、単繊維状Ti
Bの析出によるものと考えられる。さらにHIP処理温
度を上昇させると硬さは徐々に低下しているが、127
3KでのHIP後の硬さが依然MA処理状態の硬さより
も高い数値を示しており、TiB繊維強化が有効に作用
していることが顕著に示されている。No. 1 alloy or No. 1 In both of the two alloys, the hardness is remarkably increased by the HIP treatment at 873K after the MA treatment. It is considered that the oxygen content is slightly increased by the MA treatment, but the hardness is increased by the heat treatment in the single fiber Ti.
It is considered that this is due to the precipitation of B. When the HIP treatment temperature is further increased, the hardness gradually decreases.
The hardness after HIP at 3K still shows a higher value than the hardness in the MA-treated state, which clearly shows that the TiB fiber reinforcement effectively works.
【0024】図9は72.0ksMA処理した合金粉N
o.1(10体積%TiB)およびNo.2(20体積
%TiB)を、873〜1273Kの温度で3.6ks
HIP処理した試料の圧縮試験結果を示すもので、(a)
は0.2%耐力を、(b) は破壊に至るまでの歪み量を示
している。0.2%耐力はHIP処理温度が上昇するに
従って低下する傾向が認められる。なお、合金粉No.
2では、873Kの値が低いが、これはMA合金粉が硬
いため、HIP処理によってもなお焼結体に微細な空隙
が残留したことに起因するものと考えられる。FIG. 9 shows alloy powder N treated with 72.0 ks MA.
o. 1 (10% by volume TiB) and No. 2 (20% by volume TiB) at a temperature of 873-1273 K for 3.6 ks
The results of the compression test of the HIP-treated sample are shown in (a)
Indicates 0.2% proof stress, and (b) indicates the amount of strain until failure. The 0.2% proof stress tends to decrease as the HIP treatment temperature increases. In addition, alloy powder No.
In No. 2, the value of 873K is low, but it is considered that this is because the MA alloy powder is hard, and therefore fine voids remained in the sintered body even after the HIP treatment.
【0025】一方、破壊に至るまでの歪み量は、HIP
処理温度の上昇と共に増大している。これは処理温度の
上昇によるTi結晶粒の粗大化およびTiBの成長に起
因した強度低下によるものと考えられる。On the other hand, the amount of strain up to destruction is HIP
It increases as the processing temperature rises. It is considered that this is due to the coarsening of Ti crystal grains due to the increase in the processing temperature and the decrease in strength due to the growth of TiB.
【0026】図10(a) 、(b) は、72.0ksMA処
理した合金粉No.1(10体積%TiB)を1073
K(図10(a))または1273K(図10(b))で3.6
ksHIP処理した場合の圧縮破壊破面を示す。これら
の試料は、図9(b) に示す破壊に至るまでの歪み量が1
3%、22%の試料である。図10(a) の1073Kで
HIP処理した試料の破面は非常に脆性的であるが、
(b) の1273KでHIP処理した試料には微細なディ
ンプルパターンが認められ、この試料がより靱性に富ん
でいることを示している。10 (a) and 10 (b) show alloy powder No. 7 processed by 72.0 ksMA. 1 (10% by volume TiB) to 1073
K (Fig. 10 (a)) or 1273K (Fig. 10 (b)) is 3.6.
The compression fracture fracture surface at the time of ksHIP processing is shown. These samples have a strain amount of 1 up to the failure shown in Fig. 9 (b).
Samples of 3% and 22%. Although the fracture surface of the sample subjected to HIP treatment at 1073K in FIG. 10 (a) is very brittle,
A fine dimple pattern was observed in the sample subjected to HIP treatment at 1273K in (b), indicating that this sample is more tough.
【0027】[0027]
【発明の効果】 本発明によれば、Ti粉および非結質
B粉をMA処理した後、773K以上の温度で3.6k
sHIP処理することにより、アスペクト比が20〜3
0の針状または棒状の微細なTiBを析出させ、Tiの
強化を図ることができる。EFFECTS OF THE INVENTION According to the present invention, after Ti powder and non-bound B powder are subjected to MA treatment, 3.6 k at a temperature of 773 K or higher.
Aspect ratio of 20-3 by sHIP processing
The needle-like or rod-like fine TiB of 0 can be deposited to strengthen Ti.
【図1】Ti−B二元系の状態図である。FIG. 1 is a phase diagram of a Ti-B binary system.
【図2】供試材のSEM像を示す金属組織の写真で、
(a) はTiのSEM像を示す金属組織の写真、(b) は非
晶質BのSEM像を示す金属組織の写真、(c) はTiB
2のSEM像を示す金属組織の写真である。FIG. 2 is a photograph of a metal structure showing an SEM image of the test material,
(a) is a photograph of a metal structure showing a SEM image of Ti, (b) is a photograph of a metal structure showing a SEM image of amorphous B, and (c) is TiB.
2 is a photograph of a metal structure showing a SEM image of 2 .
【図3】合金粉No.3(Ti−B系、30体積%Ti
B)のMA処理による形態変化を示す金属組織の写真で
あり、(a) は初期状態(MA処理無し)、(b) は3.6
ksのMA処理後、(c) は18.0ksのMA処理後、
(d) は72.0ksのMA処理後の各形態を示す金属組
織の写真である。FIG. 3 Alloy powder No. 3 (Ti-B system, 30 volume% Ti
3B is a photograph of a metal structure showing a morphological change due to MA treatment in B), (a) is an initial state (without MA treatment), and (b) is 3.6.
After MA processing of ks, (c) after MA processing of 18.0ks,
(d) is a photograph of the metal structure showing each form after MA treatment for 72.0 ks.
【図4】(a) は合金粉No.3のMA処理に伴うX線回
折図形の変化を示す図、(b) は合金粉No.4のMA処
理に伴うX線回折図形の変化を示す図である。FIG. 4 (a) shows alloy powder No. 3 is a diagram showing a change in the X-ray diffraction pattern associated with the MA treatment of No. 3, FIG. 4 is a diagram showing a change in X-ray diffraction pattern associated with MA treatment of No. 4;
【図5】(a) は72.0ksMA処理した合金粉No.
3を真空中で773〜1273Kの温度で3.6ks熱
処理した場合のX線回折図形の変化を示す図、(b) は7
2.0ksMA処理した合金粉No.4を真空中で77
3〜1073Kの温度で3.6ks熱処理した場合のX
線回折図形の変化を示す図である。FIG. 5 (a) shows alloy powder No. 7 treated with 72.0 ksMA.
3 is a diagram showing a change in X-ray diffraction pattern when 3 is heat-treated in vacuum at a temperature of 773-1273 K for 3.6 ks, (b) shows 7
Alloy powder No. treated with 2.0 ksMA. 4 in vacuum 77
X when heat-treated at a temperature of 3 to 1073 K for 3.6 ks
It is a figure which shows the change of a line diffraction pattern.
【図6】(a) は72.0ksMA処理した合金粉No.
1を1073Kで3.6ksHIP処理した場合のTE
M像を示す金属組織の写真、(b) は72.0ksMA処
理した合金粉No.1を1273Kで3.6ksHIP
処理した場合のTEM像を示す金属組織の写真である。FIG. 6 (a) shows alloy powder No. 7 processed by 72.0 ksMA.
TE when 1 is subjected to 3.6 ks HIP processing at 1073K
A photograph of a metal structure showing an M image, (b) shows alloy powder No. 7 processed by 72.0 ksMA. 1 at 1273K for 3.6ksHIP
It is a photograph of a metal structure showing a TEM image when treated.
【図7】(a) は72.0ksMA処理した合金粉No.
3を873Kで3.6ksHIP処理した場合のTEM
像を示す金属組織の写真、(b) は72.0ksMA処理
した合金粉No.3を1073Kで3.6ksHIP処
理した場合のTEM像を示す金属組織の写真である。7 (a) is an alloy powder No. 7 processed by 72.0 ksMA.
TEM when 3 was treated with 873K for 3.6ksHIP
(B) shows alloy powder No. 7 processed by 72.0 ksMA. 3 is a photograph of a metal structure showing a TEM image in the case where 3 was subjected to 3.6 ks HIP treatment at 1073K.
【図8】72.0ksMA処理した合金粉No.1およ
びNo.2をMA処理状態のまま及びMA処理粉末を8
73〜1273Kの温度で3.6ksHIP処理した場
合の常温硬さの変化を示す図である。FIG. 8: Alloy powder No. treated with 72.0 ks MA 1 and No. 2 in the MA-treated state and MA-treated powder in 8
It is a figure which shows the change of normal temperature hardness at the time of 3.6ksHIP process at the temperature of 73-1273K.
【図9】(a) は72.0ksMA処理した合金粉No.
1およびNo.2を873〜1273Kの温度で3.6
ksHIP処理した場合の0.2%耐力の変化を示す図
で、(b) は72.0ksMA処理した合金粉No.1お
よびNo.2を873〜1273Kの温度で3.6ks
HIP処理した場合の破壊に至るまでの歪み量の変化を
示す図である。9 (a) is an alloy powder No. 7 processed by 72.0 ksMA.
1 and No. 2 at a temperature of 873-1273 K for 3.6.
It is a figure which shows the change of 0.2% yield strength at the time of ksHIP processing, (b) is the alloy powder No. 1 and No. 2 at a temperature of 873-1273K for 3.6ks
It is a figure which shows the change of the amount of strain until it becomes destruction when HIP-processed.
【図10】(a) は72.0ksMA処理した合金粉N
o.1を1073Kで3.6ksHIP処理した場合の
圧縮破壊破面を示す金属組織の写真で、(b) は72.0
ksMA処理した合金粉No.1を1273Kで3.6
ksHIP処理した場合の圧縮破壊破面を示す金属組織
の写真である。FIG. 10 (a) is alloy powder N treated with 72.0 ksMA.
o. No. 1 is a photograph of the metallographic structure showing the fracture surface under compression when treated with 1073 K for 3.6 ks HIP.
Alloy powder No. 1 at 1273K for 3.6
It is a photograph of a metal structure showing a compression fracture fracture surface in the case of ksHIP treatment.
Claims (1)
B2 粉をメカニカルアロイングした後、773K〜12
73Kの温度で高温静水圧成形またはホットプレスを行
うことを特徴とする強化チタンの製造方法1. Ti powder and amorphous boron powder or Ti
After the B 2 powder was mechanical alloying, 773K~12
Method for producing reinforced titanium, characterized by performing hot isostatic pressing or hot pressing at a temperature of 73K
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP3237782A JPH0762161B2 (en) | 1991-09-18 | 1991-09-18 | Method of manufacturing reinforced titanium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3237782A JPH0762161B2 (en) | 1991-09-18 | 1991-09-18 | Method of manufacturing reinforced titanium |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05171214A JPH05171214A (en) | 1993-07-09 |
JPH0762161B2 true JPH0762161B2 (en) | 1995-07-05 |
Family
ID=17020356
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JP3237782A Expired - Lifetime JPH0762161B2 (en) | 1991-09-18 | 1991-09-18 | Method of manufacturing reinforced titanium |
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US7416697B2 (en) | 2002-06-14 | 2008-08-26 | General Electric Company | Method for preparing a metallic article having an other additive constituent, without any melting |
US7531021B2 (en) | 2004-11-12 | 2009-05-12 | General Electric Company | Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix |
JP4796922B2 (en) * | 2006-09-05 | 2011-10-19 | 住友金属工業株式会社 | Titanium welded joint |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4639281A (en) | 1982-02-19 | 1987-01-27 | Mcdonnell Douglas Corporation | Advanced titanium composite |
US4673550A (en) | 1984-10-23 | 1987-06-16 | Serge Dallaire | TiB2 -based materials and process of producing the same |
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-
1991
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4639281A (en) | 1982-02-19 | 1987-01-27 | Mcdonnell Douglas Corporation | Advanced titanium composite |
US4673550A (en) | 1984-10-23 | 1987-06-16 | Serge Dallaire | TiB2 -based materials and process of producing the same |
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