JPH09256138A - Titanium-base alloy member excellent in oxidation resistance and wear resistance - Google Patents
Titanium-base alloy member excellent in oxidation resistance and wear resistanceInfo
- Publication number
- JPH09256138A JPH09256138A JP8063429A JP6342996A JPH09256138A JP H09256138 A JPH09256138 A JP H09256138A JP 8063429 A JP8063429 A JP 8063429A JP 6342996 A JP6342996 A JP 6342996A JP H09256138 A JPH09256138 A JP H09256138A
- Authority
- JP
- Japan
- Prior art keywords
- film
- oxidation resistance
- group
- present
- resistance
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、自動車や航空機等
の如く高温使用下での耐熱性、耐酸化性や耐摩耗性等
（以下、単に高温特性と略記する場合がある）が要求さ
れる構造部材に有用なＴｉ基合金部材に関するものであ
る。TECHNICAL FIELD The present invention is required to have heat resistance, oxidation resistance, wear resistance and the like (hereinafter, may be simply referred to as high temperature characteristics) under high temperature use such as automobiles and aircrafts. The present invention relates to a Ti-based alloy member useful as a structural member.
【０００２】[0002]
【従来の技術】Ｔｉ基合金は、鋼等の従来合金に比べて
比強度が高いことから、自動車や航空宇宙分野等の様に
軽量化が要求される産業領域での使用が拡大している。
一般にＴｉ基合金は、比較的低温の酸化性雰囲気下で
は、その表面に形成される酸化物不動態皮膜によって優
れた耐酸化性を示すのに対し、５００℃を超えると該保
護皮膜の耐酸化性が低下し、酸化が進行するにつれ強度
等の機械的特性が著しく劣化する様になる。これは、Ｔ
ｉ基合金は酸素の固溶度が大きい為、該保護皮膜を透過
した酸素が母材中へ過度に固溶し、その結果、機械的特
性が劣化するものと考えられる。2. Description of the Related Art Ti-based alloys have a higher specific strength than conventional alloys such as steel, so that their use is expanding in industrial fields where weight reduction is required, such as in the fields of automobiles and aerospace. .
In general, Ti-based alloys show excellent oxidation resistance due to the oxide passivation film formed on the surface thereof in an oxidizing atmosphere at a relatively low temperature, whereas the oxidation resistance of the protective film exceeds 500 ° C. As a result, the mechanical properties such as strength are significantly deteriorated as the oxidation progresses. This is T
Since the i-based alloy has a high solid solubility of oxygen, it is considered that oxygen permeating the protective film excessively forms a solid solution in the base material, resulting in deterioration of mechanical properties.
【０００３】そこで、５００℃を超える高温使用下での
強度や耐酸化性等を改善することを目的として、表面に
適切な保護皮膜を施したＴｉ基合金部材が提案されてい
る。例えば、特開平４−２５４５６７号には、密着性
および耐酸化性の改善を目的として、ＭＣｒＡｌまたは
ＭＣｒ（Ｍ：Ｆｅ，Ｎｉ，Ｃｏ）で表される延性合金か
らなる皮膜が、特開平５−３４５９４２号には、高温
での更なる耐酸化性の改善を目的として、Ａｌ含有Ｔｉ
基合金にＰ等のＶｂ族、Ｓｅ等のVIｂ族を少なくとも１
種含有せしめた皮膜が、更に特開平５−１５６４２３
号および特開平６−９３４１２号には、耐酸化性や表面
性状の改善を目的としてＡｌ−Ｃｒ複合拡散皮膜が、夫
々記載されている。Therefore, for the purpose of improving strength and oxidation resistance under high temperature use exceeding 500 ° C., a Ti-base alloy member having a surface provided with an appropriate protective film has been proposed. For example, JP-A-4-254567 discloses a film made of a ductile alloy represented by MCrAl or MCr (M: Fe, Ni, Co) for the purpose of improving adhesion and oxidation resistance. 345942 discloses Al-containing Ti for the purpose of further improving the oxidation resistance at high temperatures.
At least 1 Vb group such as P and VIb group such as Se in the base alloy
A film containing a seed is further disclosed in JP-A-5-156423.
JP-A-6-93412 and JP-A-6-93412 respectively describe Al-Cr composite diffusion coatings for the purpose of improving oxidation resistance and surface properties.
【０００４】しかしながら、これらの皮膜はいずれも以
下の点で不十分である。即ち、上記の皮膜は或る程度
の耐酸化性を有するものの、近年における更なる耐酸化
性の要求特性を満足するには至っていない。また同公報
によれば、上記皮膜を形成するに当たりプラズマ溶射法
を推奨しているが、一般に、溶射法で形成された皮膜中
には気孔が存在する為、母材への酸素の拡散を抑制する
ことは非常に困難である。更に溶射法では、皮膜の均一
性および表面粗度の改善という点で不十分であり、この
Ｔｉ基合金部材をエンジンバルブ等の精密部材に適用し
ようとすると、溶射後に更に機械加工を施して再仕上を
行う必要がある。また、上記で得られる耐酸化性の程
度は、前記と同様、近年の過酷な要求レベルを満足す
るには至っていない。また、同公報ではイオン注入法に
より皮膜を形成しているが、この方法では、複雑な形状
への表面処理を施すことは原理的に困難であり、適用範
囲に限界があること、及びこの方法によって形成される
皮膜の膜厚は通常１μｍ以下であり、この程度の膜厚で
は、初期の酸化を抑制する程度の耐酸化性しか得られな
い等の問題がある。更に、上記では必然的に拡散被覆
処理を施すが、処理温度が約７００〜１３００℃と非常
に高温になる為、部品の寸法変化を回避することができ
ず、所望の部材が得られない。また、上記処理温度は、
Ｔｉ基合金の一般的なα−β変態点を大きく上回る場合
もあり、部材の機械的特性が著しく劣化するという問題
がある。更に、硬度に関しては上記〜の皮膜はいず
れもＨＶ：１０００未満であり、摺動下における耐摩耗
性は甚だ不十分である。However, all of these coatings are insufficient in the following points. That is, although the above-mentioned film has a certain degree of oxidation resistance, it has not yet satisfied the further required characteristics of oxidation resistance in recent years. Further, according to the same publication, plasma spraying is recommended for forming the above-mentioned coating, but since pores are generally present in the coating formed by the spraying method, diffusion of oxygen into the base material is suppressed. Very difficult to do. Furthermore, the thermal spraying method is insufficient in terms of improving the uniformity of the coating and the surface roughness, and when attempting to apply this Ti-based alloy member to precision parts such as engine valves, it is necessary to perform further machining after re-spraying. You need to finish it. Further, the degree of oxidation resistance obtained above does not satisfy the severe demand level in recent years, as in the above. Further, in the same publication, a film is formed by an ion implantation method, but in this method, it is theoretically difficult to apply a surface treatment to a complicated shape, and the applicable range is limited. The film thickness of the film formed by the method is usually 1 μm or less, and there is a problem that such a film thickness can only obtain oxidation resistance enough to suppress initial oxidation. Furthermore, in the above, the diffusion coating treatment is inevitably carried out, but since the treatment temperature is as high as about 700 to 1300 ° C., the dimensional change of the parts cannot be avoided and the desired member cannot be obtained. Further, the processing temperature is
In some cases, the temperature may exceed the general α-β transformation point of Ti-based alloys, and there is a problem in that the mechanical properties of the members are significantly degraded. Further, with respect to hardness, each of the above-mentioned coatings has an HV of less than 1000, and the abrasion resistance under sliding is extremely insufficient.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記事情に着
目してなされたものであり、その目的は５００℃を超え
る様な高温使用下での耐酸化性や耐摩耗性等の機械的特
性に優れた新規なＴｉ基合金部材を提供することにあ
る。The present invention has been made in view of the above circumstances, and its purpose is to provide mechanical properties such as oxidation resistance and wear resistance under high temperature use exceeding 500 ° C. It is to provide a novel Ti-based alloy member having excellent properties.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決し得た本
発明の耐酸化性および耐摩耗性に優れたＴｉ基合金部材
は、Ｔｉ基合金の表面に、Ａｌ及びＮを含有する皮膜が
存在するものであるところに要旨を有するものである。A Ti-based alloy member having excellent oxidation resistance and wear resistance according to the present invention, which has been able to solve the above problems, has a coating containing Al and N on the surface of the Ti-based alloy. Where it exists, it has a gist.
【０００７】ここで上記皮膜中に、更に４Ａ族、５Ａ族
および６Ａ族よりなる群から選択される少なくとも１種
の元素を含有するものは本発明の好ましい実施態様であ
り、特にＴｉ及び／又はＣｒを含有するものが推奨され
る。このＴｉ，Ｃｒは、（Ｔｉ及び／又はＣｒ）ｘ−Ａ
ｌｙ−Ｎｚの形で存在することが好ましい（式中、ｘ，
ｙ，ｚは夫々原子％を表し、５≦ｘ≦ｙ，２５≦ｙ≦９
０，１０≦ｚ≦５０である）。また、Ｔｉ基合金と皮膜
との間に、少なくとも一層以上の中間層が存在するもの
は、密着性を高めて耐酸化性を著しく向上し得るという
点で非常に有用である。It is a preferred embodiment of the present invention that the coating film further contains at least one element selected from the group consisting of 4A group, 5A group and 6A group, particularly Ti and / or Those containing Cr are recommended. The Ti and Cr are (Ti and / or Cr) x-A
It is preferably present in the form of ly-Nz, where x,
y and z respectively represent atomic%, 5 ≦ x ≦ y, 25 ≦ y ≦ 9
0,10 ≦ z ≦ 50). In addition, the presence of at least one or more intermediate layers between the Ti-based alloy and the coating is very useful in that the adhesion can be enhanced and the oxidation resistance can be significantly improved.
【０００８】[0008]
【発明の実施の形態】前述した様に、母材表面にＡｌ含
有皮膜を施すことによってＴｉ基合金部材の機械的特性
や耐酸化性が向上することは周知である。本発明者ら
は、この様なＡｌ含有皮膜における上記諸特性の更なる
改善、特に高温使用下での耐酸化性及び耐摩耗性の更な
る向上を目的として鋭意検討を重ねた結果、Ａｌ含有皮
膜にＮを含有することにより所期の目的を達成し得るこ
とを見出し、本発明を完成したのである。BEST MODE FOR CARRYING OUT THE INVENTION As described above, it is well known that the Ti-based alloy member is improved in mechanical properties and oxidation resistance by forming an Al-containing coating on the surface of the base material. The present inventors have conducted extensive studies for the purpose of further improving the above-mentioned various properties of such an Al-containing coating, particularly, further improving the oxidation resistance and the wear resistance under high temperature use. The inventors have found that the intended purpose can be achieved by containing N in the film, and have completed the present invention.
【０００９】即ち、本発明は、Ｔｉ基合金（単に母材と
呼ぶ場合がある）の表面に、Ａｌ及びＮを含有する皮膜
を存在させた点に最大の特徴を有するものである。この
様に本発明では、Ｎ含有Ａｌ皮膜を有するところにその
技術的思想を有するものであり、両元素のみを含有する
皮膜においても、従来のものに比べて硬度及び耐酸化性
を改善させることはできるが、更なる硬度及び耐酸化性
の向上を目的として、皮膜中に、更に４Ａ族（Ｔｉ，Ｚ
ｒ等）、５Ａ族（Ｖ，Ｎｂ，Ｔａ）および６Ａ族（Ｃ
ｒ，Ｍｏ，Ｗ）よりなる群から選択される少なくとも１
種の元素を含有することが好ましい。これらのなかで
も、特にＣｒ及び／又はＴｉを含有するものが最も推奨
される。即ち、Ｔｉは母材であるＴｉ基合金と同一元素
であり、従って皮膜と母材の密着性が向上して耐酸化性
を改善し得ること、及びＣｒは耐酸化性向上作用を有す
る元素であることから、これら元素の添加により上記作
用を有効に発揮させることができるのである。具体的に
は、これら元素はＴｉ及び／又はＣｒとＡｌの複合窒化
物の形態で存在することができ、（Ｔｉ及び／又はＣ
ｒ）ｘ−Ａｌｙ−Ｎｚで表すことができる（式中、ｘ，
ｙ，ｚは夫々原子％を表す）。好ましくは５≦ｘ≦ｙ，
２５≦ｙ≦９０，１０≦ｚ≦５０であり、より好ましく
は１０〜２０≦ｘ≦ｙ，２５≦ｙ≦４０，４０≦ｚ≦５
０である。尚、ｘ，ｙ及びｚは、ｘ＋ｙ＋ｚ＝１００の
関係を満足することが好ましいが、これに限定されず、
本発明の作用を損なわない範囲で、上記元素以外の他の
不可避的不純物を包含することができる。ここで、ｙ
（即ちＡｌ含有率）が２５未満では耐酸化性が低下し、
一方、９０を超えると硬度が低下する。また、ｚ（即ち
Ｎ含有率）が１０未満では硬度改善作用が得られず、上
限値：５０は皮膜中に含有し得る窒素量の限界値と考え
られる。ｘ（即ちＴｉ及び／又はＣｒの含有率）が５未
満では硬度が低く、一方、その上限値がｙを超えると耐
酸化性が損なわれる等の問題がある。このうちＣｒとＴ
ｉを両方含有するものは、Ｔｉ添加による密着性向上作
用と、Ｃｒ添加による耐酸化性向上作用を同時に具備し
得る点で非常に有用である。これらの添加元素は、上記
複合窒化物の形態で存在することができるが、皮膜中の
添加元素全てが、必ずしもこの様な形で存在する必要は
なく、本発明の作用を損なわない範囲であれば、窒素が
固溶した状態で存在していても良く、他の存在形態を排
除するものではない。That is, the present invention has the greatest feature in that a film containing Al and N is present on the surface of a Ti-based alloy (which may be simply referred to as a base material). As described above, the present invention has the technical idea of having the N-containing Al film, and improves the hardness and the oxidation resistance of the film containing only both elements as compared with the conventional one. However, in order to further improve hardness and oxidation resistance, a 4A group (Ti, Z
r etc.) 5A group (V, Nb, Ta) and 6A group (C
r, Mo, W) at least 1 selected from the group consisting of
It is preferred to contain seed elements. Among these, those containing Cr and / or Ti are most recommended. That is, Ti is the same element as the Ti-based alloy that is the base material, so that the adhesion between the coating and the base material can be improved to improve the oxidation resistance, and Cr is an element that has the effect of improving the oxidation resistance. Therefore, the addition of these elements makes it possible to exert the above effect effectively. Specifically, these elements may be present in the form of Ti and / or a composite nitride of Cr and Al, (Ti and / or C
r) x-Aly-Nz (where x,
y and z represent atomic% respectively). Preferably 5 ≦ x ≦ y,
25 ≦ y ≦ 90, 10 ≦ z ≦ 50, and more preferably 10-20 ≦ x ≦ y, 25 ≦ y ≦ 40, 40 ≦ z ≦ 5.
0. It is preferable that x, y, and z satisfy the relationship of x + y + z = 100, but not limited to this.
Other unavoidable impurities other than the above-mentioned elements can be included within a range not impairing the action of the present invention. Where y
If the (ie Al content) is less than 25, the oxidation resistance will decrease,
On the other hand, when it exceeds 90, the hardness decreases. Further, if z (that is, the N content) is less than 10, the hardness improving effect cannot be obtained, and the upper limit value: 50 is considered to be the limit value of the amount of nitrogen that can be contained in the film. If x (that is, the content ratio of Ti and / or Cr) is less than 5, the hardness is low, while if the upper limit exceeds y, there is a problem that the oxidation resistance is impaired. Of these, Cr and T
Those containing both i are very useful in that they can simultaneously have an adhesion improving effect by adding Ti and an oxidation resistance improving effect by adding Cr. These additional elements can be present in the form of the above composite nitride, but not all the additional elements in the coating need be present in such a form, as long as they do not impair the action of the present invention. For example, nitrogen may be present in a solid solution state, and other forms of existence are not excluded.
【００１０】尚、本発明皮膜には、上記元素の他にも、
更なる耐酸化性や耐密着性の向上を目的として、Ｙ等の
３Ａ族元素を少なくとも１種添加することができる。こ
れらの含有量は、添加する元素の種類によっても若干相
違するが、概して１０原子％以下とすることが好まし
く、より好ましくは５原子％以下である。In addition to the above elements, the film of the present invention also contains
At least one 3A group element such as Y can be added for the purpose of further improving oxidation resistance and adhesion resistance. The content of these elements is slightly different depending on the kind of the element to be added, but it is generally preferably 10 atomic% or less, and more preferably 5 atomic% or less.
【００１１】この様にＴｉ基合金の表面に上述したＮ含
有Ａｌ皮膜を存在させることにより該皮膜の硬度は２５
００〜３０００ＨＶとなり、Ｎを含有しないＡｌ含有皮
膜の硬度（通常１０００ＨＶ未満）に比べて飛躍的に向
上し、その結果、耐摩耗性を一段と改善させることがで
きる。この様にＮの添加により耐摩耗性を著しく向上し
得る理由については、詳細には不明であるが、皮膜中
に、硬度の大きい前記複合窒化物が多数形成されること
により、合金母材の硬度も飛躍的に上昇するのではない
かと考えられる。Thus, the presence of the above-described N-containing Al coating on the surface of the Ti-based alloy makes the hardness of the coating 25.
The hardness is from 00 to 3000 HV, which is dramatically higher than the hardness of an Al-containing coating containing no N (usually less than 1000 HV), and as a result, wear resistance can be further improved. The reason why the wear resistance can be remarkably improved by the addition of N is not clear in detail, but a large number of the composite nitrides having high hardness are formed in the coating film, which causes It is thought that the hardness will also increase dramatically.
【００１２】尚、Ａｌ含有皮膜の形成により高温特性が
向上する理由については、以下の様に考えられる。Ａｌ
酸化物の形成に必要な自由エネルギーは約−２４０ｋｃ
ａｌ／ｍｏｌと大きな負の値を有することから、高温酸
化性雰囲気中では、母材表面にＡｌ酸化物が優先的に形
成される。このＡｌ酸化物は緻密で且つ酸素を透過し難
いという性質を有している為、保護皮膜として優れた作
用を発揮し、更なる酸化の進行を抑制すると考えられ
る。この様に保護皮膜として非常に有用なＡｌ含有皮膜
を母材表面に形成させることにより、特に高温酸化雰囲
気下での使用時には、母材への酸素の拡散および皮膜表
面の酸化物形成を著しく抑制し、結果的に高温下での機
械的特性の低下を防ぐことができるのである。また、Ｃ
ｒもＡｌと同様、酸化物を形成し易い元素であり、緻密
な酸化皮膜の形成により該皮膜中への酸素拡散抑制効果
が高められ、耐酸化性を改善することができる。The reason why the high temperature characteristics are improved by forming the Al-containing coating is considered as follows. Al
Free energy required for oxide formation is approximately -240 kc
Since it has a large negative value of al / mol, Al oxide is preferentially formed on the surface of the base material in a high temperature oxidizing atmosphere. Since this Al oxide is dense and has a property of hardly permeating oxygen, it is considered that the Al oxide exerts an excellent function as a protective film and suppresses further progress of oxidation. By forming an Al-containing film, which is very useful as a protective film, on the surface of the base material, it is possible to significantly suppress the diffusion of oxygen into the base material and the formation of oxides on the surface of the base material, especially when used in a high temperature oxidizing atmosphere. As a result, it is possible to prevent deterioration of mechanical properties at high temperatures. Also, C
Similar to Al, r is an element that easily forms an oxide, and by forming a dense oxide film, the effect of suppressing oxygen diffusion into the film is enhanced, and the oxidation resistance can be improved.
【００１３】また、上記保護皮膜の膜厚は、薄過ぎると
皮膜がポーラスになり耐酸化性が低下するので、その下
限を０．１μｍとすることが好ましい。より好ましくは
０．５μｍである。一方、皮膜の膜厚を厚くすると、皮
膜欠陥の発生が少なく耐酸化性も良好になるが、膜厚増
加による皮膜欠陥の減少効果は約１０μｍで飽和するこ
と、更に厚膜化が進むと皮膜に過度の膜応力が発生し、
皮膜が剥離する原因となる等の点を勘案すれば、その上
限を２０μｍとするのが好ましい。より好ましくは１０
μｍである。If the protective film is too thin, the film becomes porous and the oxidation resistance is lowered, so the lower limit is preferably 0.1 μm. More preferably, it is 0.5 μm. On the other hand, when the film thickness is increased, the film defects are less likely to occur and the oxidation resistance is also improved, but the effect of reducing the film defects by increasing the film thickness is saturated at about 10 μm. Excessive film stress occurs,
Taking into consideration such factors as peeling of the film, the upper limit is preferably 20 μm. More preferably 10
μm.
【００１４】更に、上記皮膜と母材との間の密着力不足
や熱膨張率の著しい差に起因する熱サイクル下での剥離
を防止して耐酸化性を更に改善することを目的として、
皮膜と母材の間に、これら母材と保護皮膜の双方に親和
性を有する材料（例えばＡｌ，Ａｌ−Ｃｒ，Ａｌ−Ｔ
ｉ）や、母材と保護皮膜の間の熱膨張率を有する中間層
（例えばＡｌ，Ｎｉ，Ｃｏ，Ｆｅ等）を単層または複数
層存在させることも有効である。Further, for the purpose of further improving the oxidation resistance by preventing peeling under a thermal cycle due to insufficient adhesion between the film and the base material or a remarkable difference in thermal expansion coefficient,
Between the film and the base material, a material having an affinity for both the base material and the protective film (for example, Al, Al-Cr, Al-T).
It is also effective that i) or an intermediate layer (for example, Al, Ni, Co, Fe, etc.) having a coefficient of thermal expansion between the base material and the protective film is present in a single layer or a plurality of layers.
【００１５】Ｔｉ基合金表面に上記保護皮膜を形成する
方法としては特に限定されず、通常の皮膜形成手段を採
用することができ、例えばイオンプレーティング法、ス
パッタリング法、蒸着法、イオン注入法、ＣＶＤ法など
が挙げられる。このうちイオンプレーティング法は、成
膜速度が速く耐密着性に優れると共に、低温で緻密な皮
膜が得られるという点で実操業面に適した方法であり、
特に有用である。尚、前記「従来の技術」の項目で掲げ
た〜の保護皮膜を形成するには、夫々特定の皮膜形
成方法が採用／或いは推奨されていた（ＭＣｒＡｌ保
護膜：プラズマ溶射法，Ｔｉ3 Ａｌ系金属間化合物皮
膜：イオン注入法、Ａｌ−Ｃｒ複合拡散皮膜：拡散処
理法）が、採用した方法自体に種々の弊害がある為、作
製した保護皮膜も多くの問題を抱えるものであった。然
るに本発明の皮膜を用いれば、それ自体に弊害のある上
記方法を特に採用する必然性は全くなく、むしろこれら
の方法に比べて弊害の少ない方法（イオンプレーティン
グ法等）を好適に採用し得る点でも、非常に有用である
と言える。The method for forming the above-mentioned protective film on the surface of the Ti-based alloy is not particularly limited, and ordinary film forming means can be adopted, for example, ion plating method, sputtering method, vapor deposition method, ion implantation method, A CVD method and the like can be mentioned. Among them, the ion plating method is a method suitable for practical operation in that it has a high film forming speed and excellent adhesion resistance, and that a dense film can be obtained at low temperature.
Particularly useful. Incidentally, in order to form the protective coatings 1 to 3 listed in the above-mentioned "Prior Art", specific coating forming methods have been adopted / recommended (MCrAl protective coating: plasma spraying method, Ti 3 Al-based coating). Since the intermetallic compound film: ion implantation method, Al-Cr composite diffusion film: diffusion treatment method) has various harmful effects on the method itself, the prepared protective film also has many problems. However, if the coating film of the present invention is used, there is no need to particularly adopt the above-mentioned method, which has a harmful effect on itself, and rather, a method having less harmful effect (the ion plating method or the like) can be preferably adopted as compared with these methods. In terms of points, it can be said to be very useful.
【００１６】以下実施例に基づいて本発明を詳述する。
ただし、下記実施例は本発明を制限するものではなく、
前・後記の趣旨を逸脱しない範囲で変更実施することは
全て本発明の技術範囲に包含される。The present invention will be described in detail below based on examples.
However, the following examples do not limit the present invention,
All modifications and alterations without departing from the spirit of the preceding and following descriptions are included in the technical scope of the present invention.
【００１７】[0017]
【実施例】本実施例に使用した基材（Ｔｉ系合金または
純Ｔｉ）及び保護皮膜の種類、並びに成膜方法を表１に
示す。尚、表中「Ｔｉ−６２４２」とはＴｉ−６Ａｌ−
２Ｓｎ−４Ｚｒ−２Ｍｏを意味する。得られた各供試材
について、以下の評価項目を調査した。EXAMPLES Table 1 shows the types of base materials (Ti-based alloy or pure Ti) and protective films used in this example, and the film forming method. In the table, "Ti-6242" means Ti-6Al-
It means 2Sn-4Zr-2Mo. The following evaluation items were investigated for each of the obtained test materials.
【００１８】［耐摩耗性］各供試材の表面硬度をビッカ
ース硬度測定方法（荷重：５０ｇｆ）に準じて測定し、
耐摩耗性の指標とした。 ［耐酸化性］各供試材を大気中６５０℃で３０時間加熱
した場合の、加熱前後の単位面積当たりの増加量を算出
し、耐酸化性の指標とした。これらの結果を表１に併記
する。[Abrasion resistance] The surface hardness of each test material was measured according to the Vickers hardness measuring method (load: 50 gf),
Used as an index of wear resistance. [Oxidation resistance] The amount of increase per unit area before and after heating when each test material was heated in the air at 650 ° C for 30 hours was calculated and used as an index of oxidation resistance. These results are also shown in Table 1.
【００１９】[0019]
【表１】 [Table 1]
【００２０】Ｎo.１〜７は、種々の組成からなるＮ含有
Ａｌ含有皮膜を有する本発明例であり、Ｎo.８は、Ｔｉ
基合金とＮ含有皮膜の間に中間層（Ａｌ）が存在する本
発明例である。表１の結果から明らかな様に、本発明の
要件を満足する供試材は、成膜方法に拘わらず、いずれ
も極めて優れた耐摩耗性および耐酸化性を有すると共
に、中間層が存在する供試材は、耐酸化性が更に向上す
ることが分かる。Nos. 1 to 7 are examples of the present invention having N-containing Al-containing coatings of various compositions, and No. 8 is Ti.
It is an example of the present invention in which an intermediate layer (Al) exists between the base alloy and the N-containing coating. As is clear from the results in Table 1, all the test materials satisfying the requirements of the present invention have extremely excellent wear resistance and oxidation resistance regardless of the film forming method, and have an intermediate layer. It can be seen that the test material has further improved oxidation resistance.
【００２１】これに対して、Ｎo.９はＴｉ−Ｎ皮膜を施
した比較例であるが、硬度はやや高いものの、耐酸化性
が著しく低下する。Ｎo.１０，１１及び１５は、いずれ
も保護皮膜を施さない例であり、本発明例に比べて、硬
度及び耐酸化性の両方に劣るものである。On the other hand, No. 9 is a comparative example in which a Ti-N film is applied, but the hardness is slightly high, but the oxidation resistance is significantly reduced. Nos. 10, 11 and 15 are examples in which no protective film is applied, and are inferior in both hardness and oxidation resistance to the examples of the present invention.
【００２２】Ｎo.１２，１３及び１４は、夫々、従来の
技術で掲げた，及びの皮膜を施した従来例であ
り、いずれも、硬度及び耐酸化性の点で不十分である。
Ｎo.１６は、Ａｌのみ含有する皮膜を施した比較例であ
り、硬度及び耐酸化性が劣っている。Nos. 12, 13 and 14 are the conventional examples in which the coatings of and given in the prior art are applied, respectively, and all of them are insufficient in hardness and oxidation resistance.
No. 16 is a comparative example in which a film containing only Al is applied, and the hardness and the oxidation resistance are inferior.
【００２３】[0023]
【発明の効果】本発明は、上記の様に構成されているの
で、従来のＴｉ基合金部材に比べて、高温下での耐摩耗
性、耐酸化性等の機械的特性を飛躍的に改善することが
できる。EFFECTS OF THE INVENTION Since the present invention is constructed as described above, mechanical properties such as wear resistance and oxidation resistance at high temperatures are dramatically improved as compared with conventional Ti-based alloy members. can do.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大山 英人 兵庫県高砂市荒井町新浜２丁目３番１号 株式会社神戸製鋼所高砂製作所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideto Oyama 2-3-1, Niihama, Arai-cho, Takasago, Hyogo Prefecture Kobe Steel Works Takasago Works
Claims (5)
する皮膜が存在するものであることを特徴とする耐酸化
性および耐摩耗性に優れたＴｉ基合金部材。1. A Ti-based alloy member having excellent oxidation resistance and wear resistance, characterized in that a coating containing Al and N is present on the surface of the Ti-based alloy.
び６Ａ族よりなる群から選択される少なくとも１種の元
素を含有するものである請求項１に記載のＴｉ基合金部
材。2. The Ti-based alloy member according to claim 1, wherein the coating further contains at least one element selected from the group consisting of 4A group, 5A group and 6A group.
するものである請求項２に記載のＴｉ基合金部材。3. The Ti-based alloy member according to claim 2, wherein the film contains Ti and / or Cr.
−Ａｌｙ−Ｎｚが存在するものである請求項３に記載の
Ｔｉ基合金部材。式中、ｘ，ｙ，ｚは夫々原子％を表
し、 ５≦ｘ≦ｙ，２５≦ｙ≦９０，１０≦ｚ≦５０である。4. The film has (Ti and / or Cr) x
The Ti-based alloy member according to claim 3, wherein -Aly-Nz is present. In the formula, x, y, and z each represent atomic%, and 5 ≦ x ≦ y, 25 ≦ y ≦ 90, and 10 ≦ z ≦ 50.
とも一層以上の中間層が存在するものである請求項１〜
４のいずれかに記載のＴｉ基合金部材。5. The one or more intermediate layers are present between the Ti-based alloy and the film.
The Ti-based alloy member according to any one of 4 above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8063429A JPH09256138A (en) | 1996-03-19 | 1996-03-19 | Titanium-base alloy member excellent in oxidation resistance and wear resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8063429A JPH09256138A (en) | 1996-03-19 | 1996-03-19 | Titanium-base alloy member excellent in oxidation resistance and wear resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09256138A true JPH09256138A (en) | 1997-09-30 |
Family
ID=13229033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8063429A Pending JPH09256138A (en) | 1996-03-19 | 1996-03-19 | Titanium-base alloy member excellent in oxidation resistance and wear resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09256138A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000038653A (en) * | 1998-07-21 | 2000-02-08 | Sumitomo Electric Ind Ltd | Die or mold having surface film |
| US6309699B2 (en) | 1998-02-20 | 2001-10-30 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of producing a metallic part exhibiting excellent oxidation resistance |
| US6824601B2 (en) | 2000-12-28 | 2004-11-30 | Kobe Steel, Ltd. | Hard film for cutting tools, cutting tool coated with hard film, process for forming hard film, and target used to form hard film |
| US6906295B2 (en) * | 2003-02-20 | 2005-06-14 | National Material L.P. | Foodware with multilayer stick resistant ceramic coating and method of making |
| US6984457B2 (en) | 2003-06-27 | 2006-01-10 | Kobe Steel Ltd. | Titanium material, production thereof, and exhaust pipe |
| JP2006315173A (en) * | 2001-06-19 | 2006-11-24 | Kobe Steel Ltd | Hard coating film for cutting tool, and its manufacturing method |
| US7217466B2 (en) * | 2002-03-20 | 2007-05-15 | Joerg Guehring | Wear-resistant coating for metal-removing tools, particularly for rotary metal-cutting tools |
| JP2008150712A (en) * | 2008-02-12 | 2008-07-03 | Sumitomo Electric Ind Ltd | Die or mold having surface coating film |
| DE112007000544T5 (en) | 2006-03-30 | 2009-01-15 | Kabushiki Kaisha Kobe Seiko Sho, Kobe | Titanium material and exhaust pipe for engine |
| JP2010095800A (en) * | 2000-12-28 | 2010-04-30 | Kobe Steel Ltd | Method of producing hard film |
| JP2011025405A (en) * | 2001-06-19 | 2011-02-10 | Kobe Steel Ltd | Hard film having excellent wear resistance and method for manufacturing the same |
| US8021768B2 (en) | 2009-04-07 | 2011-09-20 | National Material, L.P. | Plain copper foodware and metal articles with durable and tarnish free multiplayer ceramic coating and method of making |
| US9011976B2 (en) | 2005-10-05 | 2015-04-21 | Nippon Steel & Sumitomo Metal Corporation | Titanium sheet covered with protective film superior in high temperature oxidation resistance and high temperature salt damage resistance, automobile exhaust system using same, and methods of production of same |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6309699B2 (en) | 1998-02-20 | 2001-10-30 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of producing a metallic part exhibiting excellent oxidation resistance |
| JP2000038653A (en) * | 1998-07-21 | 2000-02-08 | Sumitomo Electric Ind Ltd | Die or mold having surface film |
| JP2010095800A (en) * | 2000-12-28 | 2010-04-30 | Kobe Steel Ltd | Method of producing hard film |
| US6824601B2 (en) | 2000-12-28 | 2004-11-30 | Kobe Steel, Ltd. | Hard film for cutting tools, cutting tool coated with hard film, process for forming hard film, and target used to form hard film |
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| US7186324B2 (en) | 2000-12-28 | 2007-03-06 | Kabushiki Kaisha Kobe Seiko Sho | Hard film cutting tools, cutting tool coated with hard film, process for forming hard film and target used to form hard film |
| JP2006315173A (en) * | 2001-06-19 | 2006-11-24 | Kobe Steel Ltd | Hard coating film for cutting tool, and its manufacturing method |
| JP2012096353A (en) * | 2001-06-19 | 2012-05-24 | Kobe Steel Ltd | Hard film having superior wear resistance |
| JP2011025405A (en) * | 2001-06-19 | 2011-02-10 | Kobe Steel Ltd | Hard film having excellent wear resistance and method for manufacturing the same |
| US7217466B2 (en) * | 2002-03-20 | 2007-05-15 | Joerg Guehring | Wear-resistant coating for metal-removing tools, particularly for rotary metal-cutting tools |
| US6906295B2 (en) * | 2003-02-20 | 2005-06-14 | National Material L.P. | Foodware with multilayer stick resistant ceramic coating and method of making |
| US7462375B2 (en) | 2003-02-20 | 2008-12-09 | National Material L.P. | Method of making a stick resistant multi-layer ceramic coating |
| US6984457B2 (en) | 2003-06-27 | 2006-01-10 | Kobe Steel Ltd. | Titanium material, production thereof, and exhaust pipe |
| EP2014782A1 (en) | 2003-06-27 | 2009-01-14 | Kabushiki Kaisha Kobe Seiko Sho | Titanium material, production thereof, and exhaust pipe |
| US9011976B2 (en) | 2005-10-05 | 2015-04-21 | Nippon Steel & Sumitomo Metal Corporation | Titanium sheet covered with protective film superior in high temperature oxidation resistance and high temperature salt damage resistance, automobile exhaust system using same, and methods of production of same |
| DE112007000544T5 (en) | 2006-03-30 | 2009-01-15 | Kabushiki Kaisha Kobe Seiko Sho, Kobe | Titanium material and exhaust pipe for engine |
| US8431231B2 (en) | 2006-03-30 | 2013-04-30 | Kobe Steel, Ltd. | Titanium Material and Exhaust Pipe for Engine |
| DE112007000544B4 (en) | 2006-03-30 | 2018-04-05 | Kabushiki Kaisha Kobe Seiko Sho | Titanium material and exhaust pipe for engine |
| JP2008150712A (en) * | 2008-02-12 | 2008-07-03 | Sumitomo Electric Ind Ltd | Die or mold having surface coating film |
| US8021768B2 (en) | 2009-04-07 | 2011-09-20 | National Material, L.P. | Plain copper foodware and metal articles with durable and tarnish free multiplayer ceramic coating and method of making |
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