JPH03249147A - Intermetallic compound ti-al base alloy excellent in oxidation resistance and its manufacture - Google Patents
Intermetallic compound ti-al base alloy excellent in oxidation resistance and its manufactureInfo
- Publication number
- JPH03249147A JPH03249147A JP4642190A JP4642190A JPH03249147A JP H03249147 A JPH03249147 A JP H03249147A JP 4642190 A JP4642190 A JP 4642190A JP 4642190 A JP4642190 A JP 4642190A JP H03249147 A JPH03249147 A JP H03249147A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- oxidation resistance
- weight
- intermetallic compound
- grain size
- 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.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 63
- 239000000956 alloy Substances 0.000 title claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 60
- 230000003647 oxidation Effects 0.000 title claims abstract description 57
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000005096 rolling process Methods 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 33
- 229910010038 TiAl Inorganic materials 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 4
- 238000007670 refining Methods 0.000 abstract description 2
- 229910004349 Ti-Al Inorganic materials 0.000 abstract 3
- 229910004692 Ti—Al Inorganic materials 0.000 abstract 3
- 230000000694 effects Effects 0.000 description 21
- 238000000034 method Methods 0.000 description 12
- 230000001681 protective effect Effects 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、軽量で且つ高温強度に優れ、将来の航空機、
超音速旅客機、スペース・ブレーン等の部材として期待
されている金属間化合物ＴｉＡ４２基合金に係わり、詳
しくは高温での耐酸化性を改善した金属間化合物Ｔｉｌ
／！基合金とその製造方法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention is lightweight and has excellent high-temperature strength, and is useful for future aircraft,
The intermetallic compound TiA42-based alloy is expected to be used as a material for supersonic airliners, space brains, etc. In detail, the intermetallic compound TiA has improved oxidation resistance at high temperatures.
/! This article relates to base alloys and their manufacturing methods.
（従来の技術）
Ｔｉ−Ａｊ！２元系合金において、ｉ含有量が３５〜４
４％で、残部が実質Ｔｉである合金組成の範囲では、Ｔ
ｉＡｌの金属間化合物単相となることが知られている。(Prior art) Ti-Aj! In binary alloys, i content is 35 to 4
4% and the balance is substantially Ti.
It is known that the intermetallic compound of iAl becomes a single phase.
このＴｉＡｌ相は比重が約３．８でＴｉの比重４．５よ
りも小さく、非常に軽量である。また、８００℃程度の
温度まで室温の強度が低下せず、むしろ温度上昇ととも
に強度が高くなるといった特徴を有している。このこと
からＴｉＡｌ基合金は軽量、高強度で且つ耐酸化性の要
求されるジェットエンジン用部材等への応用が期待され
ている。This TiAl phase has a specific gravity of about 3.8, which is smaller than the specific gravity of Ti, which is 4.5, and is extremely lightweight. Moreover, the strength at room temperature does not decrease up to a temperature of about 800° C., but rather increases as the temperature rises. For this reason, TiAl-based alloys are expected to be applied to jet engine parts and the like that require light weight, high strength, and oxidation resistance.
ところが、ＴｉＡｌ基合金の欠点は常温延性および高温
での耐酸化性に乏しいことである。ＴｉＡｌ１基合金は
８００°Ｃ以下の温度での耐酸化性はＴｉ合金より優れ
るが、８００℃を超える温度領域では急速に耐酸化性が
劣化する０例えば、Ｍｎを添加したＴｉＡｆ基合金は、
常温延性が改善された合金であるが、第３元素無添加の
ＴｉＡ ｊ！基合金に比較して８００°Ｃ以上での高温
耐酸化性に劣る。However, the disadvantage of TiAl-based alloys is that they have poor room temperature ductility and poor oxidation resistance at high temperatures. TiAl single-based alloys have better oxidation resistance than Ti alloys at temperatures below 800°C, but oxidation resistance rapidly deteriorates at temperatures above 800°C. For example, TiAf-based alloys with Mn added are
Although it is an alloy with improved room temperature ductility, TiA j! without the addition of a third element! Poor high temperature oxidation resistance at temperatures above 800°C compared to base alloys.
ＴｉＡ ｌ基合金は、元来その基本組成であるＴｉおよ
びＡｌはそれぞれ単体では非常に酸化されやすい金属で
ある。これらがＴｉＡ ｊ！基合金となることで特別な
結晶構造（面心正方晶）を有する金属間化合物と呼ばれ
るものとなる。 ＴｉＡｌ基合金がこのような特別な
結晶構造を有する場合、その合金の耐酸化性を向上させ
るためには、合金表面に生成するＴｉおよびＡｌの酸化
物のうち、八ｌ ｔ’ｓの酸化皮膜が緻密にかつ長期間
安定に存在し、酸化反応の保護皮膜として働くことが必
要であるといわれている。緻密なＡ Ｉｌ ｔ（ｈの酸
化皮膜の生成には、ＴｉＡｆｆｉ２元系合金を２ Ｘ
１０−’Ｐａといった低酸素分圧下において熱処理する
のが有効であるとの報告がある（小林等、日本金属学会
誌、第５３巻（１９８９）Ｐ、２５１）、 Ｌかし、Ａ
１ ｔｏｉの酸化皮膜の保護性は酸化反応が進み、皮
膜層の増加によるクランクの発生とともに減少するので
、この方法で緻密なＡ ｊ！ ！０３の酸化皮膜を形成
しても、長期間安定に保護皮膜として保つのはむずかし
い。In the TiAl-based alloy, Ti and Al, which are the basic composition thereof, are metals that are easily oxidized when used alone. These are TiA j! When it becomes a base alloy, it becomes what is called an intermetallic compound with a special crystal structure (face-centered tetragonal). When a TiAl-based alloy has such a special crystal structure, in order to improve the oxidation resistance of the alloy, it is necessary to remove 8l t's oxide film from among the Ti and Al oxides that form on the alloy surface. It is said that it is necessary to exist in a dense and stable manner for a long period of time and to function as a protective film against oxidation reactions. To form a dense oxide film, a TiAffi binary alloy is used at 2X
There are reports that heat treatment under a low oxygen partial pressure of 10-'Pa is effective (Kobayashi et al., Journal of the Japan Institute of Metals, Vol. 53 (1989) P, 251), L. Kashi, A.
The protective properties of the oxide film of 1 toi decrease as the oxidation reaction progresses and cranks occur due to the increase in the film layer, so this method can be used to create a dense A j! ! Even if the oxide film of No. 03 is formed, it is difficult to maintain it as a stable protective film for a long period of time.
一方、特開昭６３−１１１１５２号公報には、ＴｉＡｌ
１基合金の耐酸化性の改善にはＳｔ添加が有効であると
記載されている。これはＳｉの添加により、合金表面に
Ｓｉｎｇの緻密な酸化皮膜が生成し、これが酸化時の保
護皮膜となり、耐酸化性向上効果を発揮するからである
。しかし、Ｓｔ単独では耐酸化性の向上に限りがある。On the other hand, in Japanese Patent Application Laid-Open No. 63-111152, TiAl
It is stated that the addition of St is effective in improving the oxidation resistance of single-base alloys. This is because the addition of Si forms a dense oxide film of Sing on the alloy surface, which becomes a protective film during oxidation and exhibits the effect of improving oxidation resistance. However, there is a limit to the improvement in oxidation resistance when using St alone.
（発明が解決しようとする課題）
ＴｉＡ ｊ！基合金は、軽量で且つ高温強度に優れるが
、航空機等の部材の材料として用いるためには良好な耐
酸化性も具備していることが必須である。(Problem to be solved by the invention) TiA j! The base alloy is lightweight and has excellent high-temperature strength, but it is essential that it also has good oxidation resistance in order to be used as a material for parts such as aircraft.
本発明の課題は、高温での耐酸化性、特に８００″Ｃ以
上での耐酸化性を改善したＴｉＡｌ基合金と、その製造
方法を提供することにある。An object of the present invention is to provide a TiAl-based alloy with improved oxidation resistance at high temperatures, particularly oxidation resistance at 800''C or higher, and a method for producing the same.
（課題を解決するための手段）
ＴｉＡｌ基合金の耐酸化性向上のためには、表面に生成
するＴｉおよび＾ｉの酸化物のうちＡ１．ｔ０３の酸化
皮膜が緻密にかつ長期間安定に存在し、酸化反応の保護
皮膜として働くことが必要である。(Means for Solving the Problems) In order to improve the oxidation resistance of TiAl-based alloys, A1. It is necessary for the t03 oxide film to exist densely and stably for a long period of time, and to function as a protective film against oxidation reactions.
本発明者らは、このＡｆｆｉ、０３の保護性を高めるこ
とを目的に検討を行い、下記の知見を得た。The present inventors conducted studies with the aim of increasing the protective properties of Affi, 03, and obtained the following knowledge.
■ ＴｉＡ ｊ！基合金に生成する酸化皮膜層は、Ａｆ
！、０．層とＴｉ（ｈ層であり、これらが混合している
。このためＡｌ！ＩＣｈ層の保護性が充分に発揮されな
い。■ TiA j! The oxide film layer formed on the base alloy is Af
! ,0. The Al!ICh layer is a mixture of the Al!ICh layer and the Ti(h layer).For this reason, the protective properties of the Al!ICh layer are not sufficiently exhibited.
■ へ１８０１層の保護性を充分に発揮させるには、Ｔ
ｉ０ｇ層よりも早期にＡ ｌ ｔＯｓ層を生成させる必
要がある。■ To fully demonstrate the protective properties of the 1801 layer, T
It is necessary to generate the Al tOs layer earlier than the i0g layer.
■ ＴｉＡ ｌ基合金の結晶粒を微細化すると、合金中
における＾！の表面への拡散速度が上がり、表面皮膜と
金属との界面においてＴｉ０１層よりもＡｊｊｇｏｓ層
の方が速く生成する。■ When the crystal grains of a TiAl-based alloy are made finer, the crystal grains in the alloy are reduced! The diffusion rate to the surface increases, and the Ajjgos layer is formed faster than the Ti01 layer at the interface between the surface film and the metal.
■ 上記■の結晶粒微細化はＴｉＡ−ｊ！基合金を熱間
加工して再結結晶させる方法が有効である。二〇〇と上
記■は常温延性改善のために添加したＭｎ、■を含むＴ
ｉＡｆｆｉ基合金においても有効である。■ The grain refinement mentioned in (■) above is TiA-j! An effective method is to hot work the base alloy and recrystallize it. 200 and the above ■ are T containing Mn and ■ added to improve room temperature ductility.
It is also effective for iAffi-based alloys.
■ ＴｉＡｌ基合金中にＭｏ、 Ｙの１種以上、または
／およびＳｉを添加すると、Ａ ｆ 、０２層が緻密化
し、且つ、皮膜中に生成する歪み量も減少して酸化進行
による皮膜中のクラック発生が減少する。その結果、結
晶粒微細化効果と相まってＡ Ｉｔ ｚＣｈ層の保護性
は一層高くなる。■ When one or more of Mo, Y, or/and Si is added to the TiAl-based alloy, the A f , 02 layer becomes denser, and the amount of strain generated in the film is also reduced, reducing the amount of strain in the film due to the progress of oxidation. Cracks are reduced. As a result, combined with the crystal grain refinement effect, the protective properties of the A It zCh layer become even higher.
上記知見に基づ（本発明は、下記の（１）〜（４）を要
旨とする。Based on the above findings (the gist of the present invention is (1) to (4) below).
（１） ３１〜４４重量％のＡｌを含育し、残りＴｉ
および不可避不純物からなり、結晶粒径が０．０５〜ｌ
Ｏμｍである耐酸化性に優れた金属間化合物ＴｉＡｌ基
合金。(1) Contains 31 to 44% by weight of Al, with the remainder being Ti
and unavoidable impurities, with a crystal grain size of 0.05 to 1
An intermetallic compound TiAl-based alloy with excellent oxidation resistance of 0 μm.
（２）３１〜４４重量％のＡｌとそれぞれ０．１〜７．
５重量％のＭｎおよび■の１種又は２種を合計量で０．
１〜７．５重量％含有し、残りＴｉおよび不可避不純物
がらなり、結晶粒径が０．０５〜ｌＯμ層である耐酸化
性に優れた金属間化合物ＴｉＡｆｆｉ基合金。(2) 31-44% by weight of Al and 0.1-7% by weight, respectively.
The total amount of 5% by weight of Mn and one or both of the following is 0.
An intermetallic compound TiAffi-based alloy containing 1 to 7.5% by weight, the remainder consisting of Ti and unavoidable impurities, and having a crystal grain size of 0.05 to 1Oμ layer and excellent in oxidation resistance.
（３）請求項（１１又は（２）に記載の成分に加えて、
さらに０．１〜７．５重量％のＭｏ、 ０．２〜１．０
重量％のＹおよび０．１〜１．２重量％のＳｉの１種又
は２種以上を含有し、結晶粒径が０．０５〜１０μ閣で
ある耐酸化性に優れた金属間化合物ＴｉＡ Ｉｌ基合金
。(3) In addition to the components described in claim (11 or (2)),
Further 0.1-7.5% by weight of Mo, 0.2-1.0
TiA Il is an intermetallic compound with excellent oxidation resistance that contains one or more of Y in weight% and Si in 0.1 to 1.2 weight%, and has a crystal grain size of 0.05 to 10 μm. Base alloy.
（４）請求項（］）、（２）又は（３）に記載の化学成
分のインゴットを、押出温度９００〜１４５０℃、押出
比１．３〜１５で押出加工するか又は圧延温度９００〜
１４５０℃、圧延比１０〜８０％で圧延加工を行い、結
晶粒径を０．０５〜ｌＯμｍに再結晶させることを特徴
とする金属間化合物ＴｉＡｌ４基合金の製造方法。(4) The ingot of the chemical component according to claim (]), (2) or (3) is extruded at an extrusion temperature of 900 to 1450°C and an extrusion ratio of 1.3 to 15, or rolled at a rolling temperature of 900 to 150°C.
A method for producing an intermetallic compound TiAl4-based alloy, which comprises rolling at 1450° C. and a rolling ratio of 10 to 80% to recrystallize the crystal grain size to 0.05 to 10 μm.
本発明において、結晶粒径とは平均粒径を意味する。平
均粒径の算出方法としては、例えば、試験片の組織を光
学顕微鏡にて５００倍に拡大して観察し、各結晶粒の長
径と短径からその結晶粒の平均粒径を求め、これを任意
の３視野の全ての結晶粒について行い、最終的に平均す
るという方法がある。In the present invention, the crystal grain size means the average grain size. To calculate the average grain size, for example, the structure of the test piece is observed under an optical microscope at 500 times magnification, and the average grain size of each crystal grain is determined from the major and minor axes. There is a method of performing this on all crystal grains in three arbitrary fields of view and finally averaging.
（作用） 以下、本発明について詳細に説明する。(effect) The present invention will be explained in detail below.
まず、前記（１）〜（３）のＴｉＡ ｊ！基合金に共通
する成分のＡｆと結晶粒度について述べる。First, TiA j! of (1) to (3) above! The common components Af and crystal grain size of the base alloy will be described.
Ｉ
Ａ２は本合金の根幹をなす元素である。へ！含有量を３
１〜４４重量％としたのは、ＴｉＡ ｌ金属間化合物の
結晶構造をとる必要性からである。この範囲を外れると
Ｔｉｓ＾ｌ相、ＴｉＡ １．相、ＴｉＡ １ ｓ相のい
ずれかが生成し、合金の延性が低下する。＾ｌは上記範
囲内で多口に含有させる方が望ましい、この方が耐酸化
性を発揮する保護皮膜である八１２０゜が効率よく生成
する。IA2 is the element that forms the basis of this alloy. fart! The content is 3
The reason why it is set at 1 to 44% by weight is because it is necessary to maintain the crystal structure of the TiAl intermetallic compound. Outside this range, Tis^l phase, TiA 1. phase, TiA 1 s phase is formed, and the ductility of the alloy decreases. It is preferable to contain a large amount of ^l within the above range, as this will more efficiently form a protective film exhibiting oxidation resistance.
結晶粒径：
合金の結晶粒径を制御することにより１．０３の早期生
成に必要なＡｆｆｉの拡散速度を制御することができる
。即ち、素材のインゴットは結晶粒が大きく、耐酸化性
に劣るが、この結晶粒を微細化することでＡｆの拡散速
度が増大し、八！□０．の生成が促進される結果、その
保護性によって耐酸化性は向上する。結晶粒の微細化は
後述する熱間加工と再結晶による方法で達成することが
できる。Grain size: By controlling the grain size of the alloy, the diffusion rate of Affi required for the early formation of 1.03 can be controlled. In other words, the raw material ingot has large crystal grains and poor oxidation resistance, but by making these crystal grains finer, the diffusion rate of Af increases, and 8! □0. As a result, the oxidation resistance is improved due to its protective properties. Refining of crystal grains can be achieved by hot working and recrystallization described below.
微細化による耐酸化性の向上効果は、結晶粒径が１０μ
ｍ以下から現れるが、０．０５μ園よりさらに微細化し
ても、それ以上の耐酸化性向上効果は得られない、また
、０．０５μｍ未満の微細結晶粒とするのは実生産上困
難である。望ましい結晶粒の大きさは０．２〜０．５μ
ｍである、この範囲が最も耐酸化性の改善効果が高い。The effect of improving oxidation resistance due to refinement is that the crystal grain size is 10 μm.
It appears from below 0.05 μm, but even if it becomes finer than 0.05 μm, no further improvement in oxidation resistance can be obtained, and it is difficult to achieve fine crystal grains of less than 0.05 μm in actual production. . Desirable grain size is 0.2-0.5μ
m, and this range has the highest effect of improving oxidation resistance.
本願（１）のＴｉＡｌ基合金は、前記範囲でＡ２を含み
、残部が実質的にＴｉからなる結晶粒径が０．０５〜１
０μ■の合金である。この合金にＭｎおよび■の１種又
は２種添加したものが、本願（２）のＴｉＡｆｆｉ基合
金である。The TiAl-based alloy of the present application (1) contains A2 in the above range, and the remainder is substantially Ti, and has a crystal grain size of 0.05 to 1.
It is an alloy of 0μ■. The TiAffi-based alloy of the present application (2) is obtained by adding one or both of Mn and (2) to this alloy.
Ｍｎおよび■：
ＭｎおよびＶはＴｉＡ１！基合金の常温延性を改善する
目的で１種又は２種添加される。常温延性の改善効果は
、ＭｎおよびＶともそれぞれ又は合計量で０．１重量％
の含有量から現れるが、それぞれ又は合計量で７．５重
量％を超えて含有すると寧ろ常温延性は低下する。なお
、Ｍｎは常温延性を改善する反面、耐酸化性に悪影響を
及ぼす元素であるや従って、Ｍｎを添加する場合は、常
温延性の確保できる範囲で低目の含を量とするのがよい
。或いは、Ｙと複合添加すればＭｎの悪影響を抑制する
ことができる。Mn and ■: Mn and V are TiA1! One or two elements are added for the purpose of improving the room temperature ductility of the base alloy. The effect of improving room temperature ductility is 0.1% by weight for both Mn and V individually or in total.
However, if each or the total amount exceeds 7.5% by weight, room temperature ductility deteriorates. Although Mn improves room-temperature ductility, it is an element that has a negative effect on oxidation resistance. Therefore, when adding Mn, it is preferable to use a low content within a range that can ensure room-temperature ductility. Alternatively, if Mn is added in combination with Y, the adverse effects of Mn can be suppressed.
（１）および（２）のＴｉＡｌ１基合金は、従来のＴｉ
Ａ４２基合金に比べて耐酸化性に優れる。これは結晶粒
が微細であるからである。これらのＴｉＡ ｌ基合金に
、Ｍｏ、 ＹおよびＳｉの１種又は２種以上添加し、耐
酸化性をさらに改善したのが（３）のＴｉＡｌ１基合金
である。The TiAl base alloys (1) and (2) are conventional TiAl
Excellent oxidation resistance compared to A42-based alloys. This is because the crystal grains are fine. The TiAl single-base alloy (3) is obtained by adding one or more of Mo, Y, and Si to these TiAl base alloys to further improve the oxidation resistance.
Ｍｏ、 ＹおよびＳｉ：
これらの元素はいずれも合金の耐酸化性を改善する効果
がある。即ち、ＭｏおよびＹは耐酸化性保護皮膜である
ＡＩ！ｔＯ，の安定化に効果を発揮する。Mo, Y and Si: All of these elements have the effect of improving the oxidation resistance of the alloy. That is, Mo and Y are oxidation-resistant protective coatings, such as AI! It is effective in stabilizing tO.
さらに、この他にＹはＭｎの添加による耐酸化性への悪
影響を抑制する効果があり、ガ０は常温延性を改善する
効果がある。Furthermore, in addition to this, Y has the effect of suppressing the adverse effect on oxidation resistance due to the addition of Mn, and Ga0 has the effect of improving room temperature ductility.
Ｍｏの場合、上記効果は０．１重量％の含有量から発揮
されるが、７．５重量％を超えて含有すると寧ろ耐酸化
性は低下する。Ｙの場合、０．２重量％の含有量から耐
酸化性保護皮膜であるＡｌ２．Ｏ，の安定化に効果を示
すが、１．０重量％を超えて含有するとＡｌ２ｚＯｓの
安定化効果は消失し、耐酸化性は向上しない。In the case of Mo, the above effects are exhibited from a content of 0.1% by weight, but if the content exceeds 7.5% by weight, the oxidation resistance is rather reduced. In the case of Y, the oxidation-resistant protective film Al2. It is effective in stabilizing Al2zOs, but if the content exceeds 1.0% by weight, the stabilizing effect of Al2zOs disappears and the oxidation resistance does not improve.
Ｓｉはへ〇、Ｏｓ皮膜の緻密化および安定化に効果を発
揮する。この効果はＭｏと複合添加されてさらに大きく
なり、Ｙの存在下ではさらに顕著となる。Si is effective in densifying and stabilizing the Os film. This effect becomes even greater when added in combination with Mo, and becomes even more pronounced in the presence of Y.
しかし、０．１重量％未満の含有量では上記のような効
果がなく、１．２重量％を超えて含有するとＡｌ！ｔ（
ｈの安定化効果が失われ、耐酸化性は低下する。However, if the content is less than 0.1% by weight, there is no effect as described above, and if the content exceeds 1.2% by weight, Al! t(
The stabilizing effect of h is lost and the oxidation resistance is reduced.
よって、ＭＯは０．１〜７．５重量％の含有量、Ｙは０
．２〜１．０重量％の含有量、Ｓｉは０．１〜１．２重
量％の含有量とした。望ましいＹの含有量は０．２５〜
０．７５重量％である。この範囲が最も耐酸化性改善効
果が高い。Therefore, MO has a content of 0.1 to 7.5% by weight, and Y has a content of 0.
．． The content was 2 to 1.0% by weight, and the content of Si was 0.1 to 1.2% by weight. Desirable Y content is 0.25~
It is 0.75% by weight. This range has the highest oxidation resistance improvement effect.
前記微細結晶組織は、次の方法で得ることができる。即
ち、前記化学組成のインゴットを溶解法又は粉末冶金法
のいずれかの方法で製造し、これに熱間押出加工または
熱間圧延のいずれかの熱間圧延を施し、再結晶させる方
法である０例えば、溶解法で製造したインゴットの場合
、針状組織をしており結晶粒径は大きく、これに均質化
熱処理を施しても結晶粒径は３０μ層以上の粗大組織で
あるが、熱間加工と再結晶で結晶粒径を１０μｍ以下に
することができる。The fine crystal structure can be obtained by the following method. That is, it is a method in which an ingot having the above chemical composition is produced by either a melting method or a powder metallurgy method, and then subjected to hot rolling, either hot extrusion or hot rolling, and then recrystallized. For example, ingots manufactured by the melting method have an acicular structure with large crystal grains, and even after homogenization heat treatment, the crystal grains remain coarse with a layer size of 30μ or more, but hot processing The crystal grain size can be reduced to 10 μm or less by recrystallization.
熱間加工としては押出加工又は圧延加工が有効である。Extrusion processing or rolling processing is effective as hot processing.
ＴｉＡｌ１基合金は変形抵抗が高く、加工が困難で
あるため、押出加工又は圧延加工のいずれの場合でも、
９００℃以上の温度で行うのがよい。TiAl mono-based alloy has high deformation resistance and is difficult to process, so whether it is extruded or rolled,
It is preferable to carry out the process at a temperature of 900°C or higher.
しかし、あまり高温で加工すると酸化や窒化の問題が生
じるため、上限は１４５０℃に止めるのがよい。However, if processed at too high a temperature, problems of oxidation and nitridation will occur, so the upper limit should be kept at 1450°C.
加工と再結晶による微細化効果が得られる最低の加工度
は、押出加工では押出比１．３、圧延加工では圧延比１
５％である。加工度を高くとるほど結晶粒はより微細化
され、耐酸化性の向上にとって有利であるが、丁ｊＡ
ｌ基合金は難加工性材料であるから高加工度の加工はむ
ずかしい、従って、上限はおのずと限定される。押出加
工の場合はこの上限は押出比１５程度であり、圧延加工
の場合には圧延比８０％程度である。The minimum working degree that can obtain the refinement effect through processing and recrystallization is an extrusion ratio of 1.3 for extrusion processing and a rolling ratio of 1 for rolling processing.
It is 5%. The higher the degree of processing, the finer the grains become, which is advantageous for improving oxidation resistance.
Since l-based alloys are difficult-to-work materials, it is difficult to process them to a high degree of workability, so the upper limit is naturally limited. In the case of extrusion processing, this upper limit is about an extrusion ratio of 15, and in the case of rolling processing, the upper limit is about 80% of the rolling ratio.
加工時における加熱雰囲気は、大気中でもよいが、＾ｒ
、 Ｈｅ等の不活性ガス雰囲気とする方が望ましい。The heating atmosphere during processing may be in the air, but
, It is preferable to use an inert gas atmosphere such as He.
熱間加工後は自己の保有熱で再結晶が進み、結晶粒径は
１０μｍ以下となる。再結晶は別途再結晶焼鈍工程を設
けて実施してもよい、この場合、８００〜１１００°Ｃ
の温度で行うのがよく、長時間加熱すると粒成長が起こ
るので加熱時間は３時間以下が望ましい。After hot working, recrystallization proceeds due to its own heat, and the crystal grain size becomes 10 μm or less. Recrystallization may be carried out by providing a separate recrystallization annealing step, in which case the temperature is 800 to 1100°C.
The heating time is preferably 3 hours or less since grain growth occurs if heated for a long time.
上記方法で熱間加工して再結晶すれば、溶製インゴット
では結晶粒径を０．１μｍ程度にまで微細化することが
できる。粉末から製造したインゴットを使用すれば、こ
れ以下の微細結晶粒とすることもできる。If hot worked and recrystallized using the above method, the crystal grain size of the melted ingot can be reduced to about 0.1 μm. If an ingot made from powder is used, it is possible to obtain finer grains than this.
（実施例）
第１表に示す化学成分の合金を製造した。素材インゴッ
トは、阻８および階１２を除いては非消耗電極式Ａｒア
ーク溶解炉により溶製し、ＮＯ，８および隘１２は、Ｔ
ｉとＡ２の粉末をＡｒガス雰囲気中で４００時間混合し
た混合物を１０００°Ｃでホットプレスして焼結体とし
た後、高密度化を目的に押出加工した。(Example) An alloy having the chemical composition shown in Table 1 was manufactured. The raw material ingots were melted in a non-consumable electrode type Ar arc melting furnace except for No. 8 and No. 12.
A mixture of powders i and A2 mixed for 400 hours in an Ar gas atmosphere was hot pressed at 1000°C to form a sintered body, which was then extruded for the purpose of high density.
前記溶製後のインゴットは、１２００℃で２４時間の真
空熱処理を施し、組織を均質化した。この時点での平均
結晶粒径は約３０μｍであり、粉末焼結材の平均結晶粒
径は１５μ糟であった。The ingot after the melting process was subjected to vacuum heat treatment at 1200° C. for 24 hours to homogenize the structure. The average crystal grain size at this point was about 30 μm, and the average crystal grain size of the powder sintered material was 15 μm.
次いで、これらのインゴットに第１表に示す条件で熱間
押出加工または熱間圧延加工を施し、再結晶させた。但
し、距３６は均質化の真空熱処理をしたままである。These ingots were then subjected to hot extrusion or hot rolling under the conditions shown in Table 1 to recrystallize them. However, the distance 36 is still subjected to the vacuum heat treatment for homogenization.
均質化処理熱処理のままのインゴットおよび加工材から
粒径測定用試験片と耐酸化試験用試験片（ｌａｍ’ Ｘ
１０ｍ５＋’ Ｘ４０ｍｍ’ ）を切り出し、結晶粒径
と耐酸化性を調べた。これらの結果を第１表に併記する
。A test piece for grain size measurement and a test piece for oxidation resistance test (lam'
A piece (10m5+' x 40mm') was cut out and the crystal grain size and oxidation resistance were examined. These results are also listed in Table 1.
耐酸化性は試験片の全表面をＳｉＣペーパー（１８００
）で研磨し、アセトン脱脂した後、下記の酸化試験して
調べた。For oxidation resistance, the entire surface of the test piece was coated with SiC paper (1800
) and degreased with acetone, the following oxidation test was performed.
酸化試験は大気酸化試験とし、電気抵抗式管状炉を用い
、炉心管端開放の条件で９３０℃で１００時間加熱し、
そのときの酸化による重量増加を測定することで評価し
た。なお、試験片は個々に高純度Ａｊｉｇｏｓ製のルツ
ボに入れ、酸化により生成した皮膜は残らず回収し、重
量測定に加えた。The oxidation test was an atmospheric oxidation test, using an electric resistance tube furnace and heating at 930°C for 100 hours with the furnace tube end open.
Evaluation was made by measuring the weight increase due to oxidation at that time. The test pieces were individually placed in a high-purity Ajigos crucible, and all the film produced by oxidation was collected and added to the weight measurement.
（以下、余白）
第１表から、本発明例はいずれも酸化増量が小さく、耐
酸化性に優れることがわかる。耐酸化性改善効果はＴｉ
Ａｊ！２元系の合金のみならず、第３元素を添加し
た合金においても発揮されている。(Hereinafter, blank space) Table 1 shows that all of the examples of the present invention have a small oxidation weight gain and are excellent in oxidation resistance. Ti improves oxidation resistance
Aj! This effect is exhibited not only in binary alloys but also in alloys to which a third element is added.
即ち、ＭＯ％ Ｙ％ ｓｉ添加合金では結晶粒微細化の
効果が顕著に発揮されており、耐酸化性は一段と優れて
いる。また、延性改善のために添加されるＭｎ、■を含
む合金についても同様の効果が認められる。That is, the MO% Y% Si-added alloy exhibits a remarkable effect of grain refinement, and its oxidation resistance is even more excellent. Similar effects are also observed for alloys containing Mn and (2) added to improve ductility.
（発明の効果）
実施例に示したように本発明のＴｉＡｆｆｉｌｉ合金は
、優れた耐酸化性を有しており、ＴｒＡ ｊ！基合金本
来の高い比強度特性と併せて航空機部材等への使用に適
するものである。(Effects of the Invention) As shown in the examples, the TiAffili alloy of the present invention has excellent oxidation resistance, and TrA j! Combined with the high specific strength characteristics inherent to base alloys, it is suitable for use in aircraft components, etc.
Claims (4)
び不可避不純物からなり、結晶粒径が０．０５〜１０μ
ｍである耐酸化性に優れた金属間化合物ＴｉＡｌ基合金
。(1) Contains 31-44% by weight of Al, remaining Ti and unavoidable impurities, and has a crystal grain size of 0.05-10μ
An intermetallic compound TiAl-based alloy with excellent oxidation resistance.
５重量％のＭｎおよびＶの１種又は２種を合計量で０．
１〜７．５重量％含有し、残りＴｉおよび不可避不純物
からなり、結晶粒径が０．０５〜１０μｍである耐酸化
性に優れた金属間化合物ＴｉＡｌ基合金。(2) 31-44% by weight of Al and 0.1-7% by weight, respectively.
5% by weight of one or both of Mn and V in a total amount of 0.
An intermetallic compound TiAl-based alloy containing 1 to 7.5% by weight, the remainder consisting of Ti and unavoidable impurities, and having a crystal grain size of 0.05 to 10 μm and excellent in oxidation resistance.
さらに０．１〜７．５重量％のＭｏ、０．２〜１．０重
量％のＹおよび０．１〜１．２重量％のＳｉの１種又は
２種以上を含有し、結晶粒径が０．０５〜１０μｍであ
る耐酸化性に優れた金属間化合物ＴｉＡｌ基合金。(3) In addition to the components described in claim (1) or (2),
Furthermore, it contains one or more of 0.1 to 7.5 wt% Mo, 0.2 to 1.0 wt% Y, and 0.1 to 1.2 wt% Si, and An intermetallic compound TiAl-based alloy having an excellent oxidation resistance of 0.05 to 10 μm.
分のインゴットを、押出温度９００〜１４５０℃、押出
比１．３〜１５で押出加工するか又は圧延温度９００〜
１４５０℃、圧延比１０〜８０％で圧延加工を行い、結
晶粒径を０．０５〜１０μｍに再結晶させることを特徴
とする金属間化合物ＴｉＡｌ基合金の製造方法。(4) The ingot of the chemical component according to claim (1), (2) or (3) is extruded at an extrusion temperature of 900 to 1450°C and an extrusion ratio of 1.3 to 15, or rolled at a rolling temperature of 900 to 1450°C.
A method for producing an intermetallic compound TiAl-based alloy, which comprises rolling at 1450°C and a rolling ratio of 10 to 80% to recrystallize the crystal grain size to 0.05 to 10 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4642190A JPH03249147A (en) | 1990-02-27 | 1990-02-27 | Intermetallic compound ti-al base alloy excellent in oxidation resistance and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4642190A JPH03249147A (en) | 1990-02-27 | 1990-02-27 | Intermetallic compound ti-al base alloy excellent in oxidation resistance and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03249147A true JPH03249147A (en) | 1991-11-07 |
Family
ID=12746689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4642190A Pending JPH03249147A (en) | 1990-02-27 | 1990-02-27 | Intermetallic compound ti-al base alloy excellent in oxidation resistance and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03249147A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05271830A (en) * | 1992-03-27 | 1993-10-19 | Sumitomo Metal Ind Ltd | Tial intermetallic compound based alloy member |
| US5562999A (en) * | 1992-07-07 | 1996-10-08 | Mtu Motoren-Und Turbinen-Union Muenchen Gmbh | Component made of an intermetallic compound with an aluminum diffusion coating |
| WO1998021375A1 (en) * | 1996-11-09 | 1998-05-22 | Georg Frommeyer | TiAl ALLOY AND ITS USE |
| KR100412426B1 (en) * | 2001-07-18 | 2003-12-31 | 학교법인 인하학원 | TiAl-based intermetallics compound comprising yttrium |
-
1990
- 1990-02-27 JP JP4642190A patent/JPH03249147A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05271830A (en) * | 1992-03-27 | 1993-10-19 | Sumitomo Metal Ind Ltd | Tial intermetallic compound based alloy member |
| US5562999A (en) * | 1992-07-07 | 1996-10-08 | Mtu Motoren-Und Turbinen-Union Muenchen Gmbh | Component made of an intermetallic compound with an aluminum diffusion coating |
| WO1998021375A1 (en) * | 1996-11-09 | 1998-05-22 | Georg Frommeyer | TiAl ALLOY AND ITS USE |
| KR100412426B1 (en) * | 2001-07-18 | 2003-12-31 | 학교법인 인하학원 | TiAl-based intermetallics compound comprising yttrium |
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