JP2000297365A - AlTi SERIES ALLOY SPUTTERING TARGET, WEAR RESISTANT AlTi SERIES ALLOY HARD FILM AND FORMATION OF THE FILM - Google Patents
AlTi SERIES ALLOY SPUTTERING TARGET, WEAR RESISTANT AlTi SERIES ALLOY HARD FILM AND FORMATION OF THE FILMInfo
- Publication number
- JP2000297365A JP2000297365A JP11106118A JP10611899A JP2000297365A JP 2000297365 A JP2000297365 A JP 2000297365A JP 11106118 A JP11106118 A JP 11106118A JP 10611899 A JP10611899 A JP 10611899A JP 2000297365 A JP2000297365 A JP 2000297365A
- Authority
- JP
- Japan
- Prior art keywords
- film
- alti
- sputtering target
- elements selected
- rare earth
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、切削、穿孔、フラ
イス加工等の切削工具、軸受け等の摺動部材、あるいは
金型等の成形加工具等に適用される耐摩耗性皮膜形成に
好適なＡｌＴｉ系合金スパッタリングターゲット及び耐
摩耗性ＡｌＴｉ系合金硬質皮膜並びに同皮膜の形成方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for forming a wear-resistant film applied to cutting tools such as cutting, drilling and milling, sliding members such as bearings, and molding tools such as dies. The present invention relates to an AlTi-based alloy sputtering target, a wear-resistant AlTi-based alloy hard coating, and a method for forming the same.
【０００２】[0002]
【従来の技術】従来、上記のような切削工具、摺動部
材、金属加工工具等の耐摩耗性表面硬化膜として、高硬
度の窒化チタン（ＴｉＣ）や炭窒化チタン（ＴｉＣＮ）
が使用されてきたが、最近では切削等の加工工具等の使
用コスト低減を目的としてこれらの皮膜の長寿命化及び
さらに特性を向上させた耐摩耗性表面硬化膜の開発が要
求されている。このため、従来の窒化チタンや炭窒化チ
タン膜に替わるものとしてＡｌＴｉ合金膜又はこの炭化
膜、窒化膜、あるいは炭窒化膜を耐摩耗性表面硬化膜と
して使用する提案がなされた。これらの膜は高温域にお
ける耐酸化性、耐摩耗性、さらには被覆される機材（母
材）との密着性が上記の窒化チタンや炭窒化チタン膜よ
りも一段と向上したので、それなりの評価を得たが、耐
酸化性や耐摩耗性の点で上記に要求される特性をまだ充
分に満足させるものとは言えなかった。2. Description of the Related Art Conventionally, high-hardness titanium nitride (TiC) or titanium carbonitride (TiCN) has been used as a wear-resistant surface-hardened film for cutting tools, sliding members, metal working tools and the like as described above.
In recent years, there has been a demand for the development of a wear-resistant surface-hardened film having a longer service life and further improved characteristics for the purpose of reducing the use cost of machining tools such as cutting. Therefore, it has been proposed to use an AlTi alloy film or a carbide film, a nitride film, or a carbonitride film as a wear-resistant surface-hardened film instead of the conventional titanium nitride or titanium carbonitride film. These films have much higher oxidation resistance and wear resistance in high temperature range and better adhesion to the equipment (base material) to be coated than the above-mentioned titanium nitride or titanium carbonitride films. However, it could not be said that the properties required above in terms of oxidation resistance and abrasion resistance were sufficiently satisfied.
【０００３】このようなことから、最近では炭窒化Ａｌ
Ｔｉ合金膜として、Ｓｉを０．１％以下添加して硬度を
高める提案がなされた（特許第０２７９３７７３号）。
しかし、切削工具、摺動部材、金属加工工具等に使用さ
れる特性は、皮膜の硬さ、耐酸化性、母材との密着性等
の総合評価で決まるもので、最終的にはその目的に応じ
た特性を発揮し、かつ持続する寿命の問題である。この
ような観点からみて、上記０．１％以下のＳｉを添加し
た炭窒化ＡｌＴｉ合金膜は、総合的な工具寿命の点でか
ならずしも満足できるものとは言えなかった。For these reasons, recently, carbonitride Al
It has been proposed to increase the hardness by adding 0.1% or less of Si as a Ti alloy film (Japanese Patent No. 02797733).
However, the properties used for cutting tools, sliding members, metalworking tools, etc. are determined by comprehensive evaluation of the hardness, oxidation resistance, adhesion to the base material, etc. of the film, and ultimately its purpose. This is a problem of exhibiting characteristics according to the above and maintaining the life. From such a viewpoint, the carbonitrided AlTi alloy film containing 0.1% or less of Si was not always satisfactory in terms of the overall tool life.
【０００４】[0004]
【発明が解決しようとする課題】以上から、本発明は切
削工具、摺動部材、金属加工工具等に形成する皮膜の硬
さ（耐摩耗性）、耐酸化性、母材との密着性等を向上さ
せるとともに、バランスの取れた特性を備え、安定した
皮膜の形成と該皮膜を形成した工具等の寿命を十分に向
上させることを課題とする。From the above, it can be seen that the present invention relates to the hardness (abrasion resistance), oxidation resistance, adhesion to the base material, etc. of the film formed on cutting tools, sliding members, metal working tools and the like. Another object of the present invention is to provide a stable film formation and a sufficiently long life of a tool or the like on which the film is formed, while having a well-balanced characteristic.
【０００５】[0005]
【課題を解決するための手段】本発明者は、皮膜の硬さ
及び耐酸化性を一段と向上させ、最終的に工具等の硬質
耐摩耗性皮膜の特性を維持しかつ寿命を延ばすことによ
り、上記問題点を解決できることの知見を得た。この知
見に基づき、本発明は（１）ＡｌＴｉ系合金スパッタリ
ングターゲットの組成が、ＡｌｘＴｉ１−ｘ−ｙ−ｚＭ
ｙＲｚ（但し、ＭはＳｉ、Ｃｒ、Ｗ、Ｍｏから選択した
元素の１種以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル
等の希土類元素から選択した元素の1種以上、０．０５
≦ｘ≦０．７、０．０２≦ｙ≦０．２５、０．０００５
≦ｚ≦０．０５）であることを特徴とするＡｌＴｉ系合
金スパッタリングターゲット、（２）Ｍ、すなわちＳ
ｉ、Ｃｒ、Ｗ、Ｍｏから選択した元素の１種以上の組成
範囲ｙが、０．１<ｙ≦０．２５であることを特徴とす
る上記（１）記載のＡｌＴｉ系合金スパッタリングター
ゲット、（３）硬質皮膜の組成が、ＡｌｘＴｉ
１−ｘ−ｙ−ｚＭｙＲｚ（但し、ＭはＳｉ、Ｃｒ、Ｗ、
Ｍｏから選択した元素の１種以上、ＲはＹ、Ｃｅ、Ｌ
ａ、ミッシュメタル等の希土類元素から選択した元素の
1種以上、０．０５≦ｘ≦０．７、０．０２≦ｙ≦０．
２５、０．０００５≦ｚ≦０．０５）であることを特徴
とする耐摩耗性ＡｌＴｉ系合金硬質皮膜、（４）Ｍ、す
なわちＳｉ、Ｃｒ、Ｗ、Ｍｏから選択した元素の１種以
上の組成範囲ｙが、０．１<ｙ≦０．２５であることを
特徴とする上記（３）記載の耐摩耗性ＡｌＴｉ系合金硬
質皮膜、（５）ＡｌＴｉ系合金スパッタリングターゲッ
トの組成が、ＡｌｘＴｉ１−ｘ−ｙ−ｚＭｙＲｚ（但
し、ＭはＳｉ、Ｃｒ、Ｗ、Ｍｏから選択した元素の１種
以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル等の希土類
元素から選択した元素の1種以上、０．０５≦ｘ≦０．
７、０．０２≦ｙ≦０．２５、０．０００５≦ｚ≦０．
０５）であるＡｌＴｉ系合金スパッタリングターゲット
を窒素雰囲気中でスパッタリングすることを特徴とす
る、硬質皮膜の組成が、ＡｌｘＴｉ１−ｘ−ｙ−ｚＭｙ
Ｒｚ（但し、ＭはＳｉ、Ｃｒ、Ｗ、Ｍｏから選択した元
素の１種以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル等
の希土類元素から選択した元素の1種以上、０．０５≦
ｘ≦０．７、０．０２≦ｙ≦０．２５、０．０００５≦
ｚ≦０．０５）である耐摩耗性ＡｌＴｉ系合金硬質皮膜
の形成方法、を提供するものである。SUMMARY OF THE INVENTION The present inventors have further improved the hardness and oxidation resistance of a film, and finally maintain the properties of a hard wear-resistant film such as a tool and extend the life of the film. We have found that the above problems can be solved. Based on this finding, the present invention is the composition of (1) AlTi alloy sputtering target, Al x Ti 1-x- y-z M
y R z (where M is at least one element selected from Si, Cr, W and Mo, R is at least one element selected from rare earth elements such as Y, Ce, La and misch metal, 0.05
≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.25, 0.0005
≦ z ≦ 0.05), (2) M, that is, S
(1) The AlTi-based alloy sputtering target according to (1), wherein one or more composition ranges y of elements selected from i, Cr, W, and Mo satisfy 0.1 <y ≦ 0.25. 3) The composition of the hard coating is Al x Ti
1-x-y-z M y R z ( where, M is Si, Cr, W,
One or more elements selected from Mo, R is Y, Ce, L
a, elements selected from rare earth elements such as misch metal
At least one kind, 0.05 ≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.
25, 0.0005 ≦ z ≦ 0.05), and (4) M, that is, at least one element selected from the group consisting of Si, Cr, W, and Mo. The composition range y is 0.1 <y ≦ 0.25, wherein the wear-resistant AlTi-based alloy hard coating according to (3) and (5) the composition of the AlTi-based alloy sputtering target are Al x Ti 1-x-y-z M y R z ( where, M is Si, Cr, W, 1 or more elements selected from Mo, R is selected Y, Ce, La, rare earth elements such as mischmetal At least one element, 0.05 ≦ x ≦ 0.
7, 0.02 ≦ y ≦ 0.25, 0.0005 ≦ z ≦ 0.
The AlTi alloy sputtering target is 05), characterized in that sputtering in a nitrogen atmosphere, the composition of the hard coating, Al x Ti 1-x- y-z M y
R z (where M is at least one element selected from Si, Cr, W, and Mo; R is at least one element selected from rare earth elements such as Y, Ce, La, and misch metal; 0.05 ≦
x ≦ 0.7, 0.02 ≦ y ≦ 0.25, 0.0005 ≦
z ≦ 0.05).
【０００６】[0006]
【発明の実施の形態】本発明のＡｌＴｉ系合金スパッタ
リングターゲットは、真空アーク溶解、プラズマ溶解、
電子ビーム溶解、誘導溶解等の溶製法によって製造でき
る。これらの溶解に際してはガス、特に酸素の混入が著
しく、また上記アルミニウム、チタン、シリコンはいず
れも酸素のと結合力が強いので、いずれの場合にも真空
中又は不活性中で溶解することが必要である。また、溶
解、凝固過程において偏析の発生や結晶粒が粗大化しな
いように、加工及び温度コントロールを実施して製造す
る。BEST MODE FOR CARRYING OUT THE INVENTION The AlTi-based alloy sputtering target of the present invention can be used for vacuum arc melting, plasma melting,
It can be manufactured by a melting method such as electron beam melting or induction melting. In dissolving these, gases, particularly oxygen, are remarkably mixed, and the above-mentioned aluminum, titanium, and silicon all have a strong bonding force with oxygen. In any case, it is necessary to dissolve in a vacuum or in an inert gas. It is. In addition, in order to prevent the occurrence of segregation and the coarsening of crystal grains during the melting and solidification processes, the production and the temperature control are carried out to manufacture.
【０００７】上記溶製法によるもの以外に粉末冶金法に
よって製造することもできる。この粉末冶金法によって
製造する場合、例えば、原料粉末としてそれぞれ平均粒
径１５０μｍ以下のＴｉ粉末、Ｓｉ粉末、同希土類元
素、Ａｌ粉末を本発明の組成となる所定の比率に配合
し、これらをボールミル混合し、乾燥して混合粉とす
る。原料粉としては、さらに微細なアトマイズ粉を使用
することができる。[0007] In addition to the above-mentioned melting method, it can be manufactured by powder metallurgy. When manufacturing by this powder metallurgy method, for example, Ti powder, Si powder, the same rare earth element and Al powder each having an average particle size of 150 μm or less are blended as raw material powders in a predetermined ratio to become the composition of the present invention, and these are mixed with a ball mill. Mix and dry to a mixed powder. As the raw material powder, finer atomized powder can be used.
【０００８】上記焼結用粉末は例えばメカニカルアロイ
ング法により所定の比率に予め合金化したＴｉＡｌ又は
ＴｉＡｌＳｉ（希土類）合金粉末を用いることができ
る。いずれの場合にも、微細かつ均一な混合粉末を使用
した場合には焼結体の密度が高く、その結果均一かつ緻
密なターゲットが得られ、またスパッタリングにより成
膜条件も安定し、均一微細な組織の皮膜が形成できると
いう利点がある。As the sintering powder, for example, TiAl or TiAlSi (rare earth) alloy powder alloyed in a predetermined ratio by a mechanical alloying method can be used. In any case, when a fine and uniform mixed powder is used, the density of the sintered body is high, and as a result, a uniform and dense target is obtained. There is an advantage that a tissue film can be formed.
【０００９】上記混合粉砕粉をモールドに入れ予備成形
した後、例えば冷間静水圧処理（ＣＩＰ処理）し、さら
に５００〜６００°Ｃ、圧力７００Ｋｇｆ／ｃｍ２以上
の条件でホットプレス処理（ＨＰ処理）するか、又はＣ
ＩＰ処理した後、同様に５００〜６００°Ｃ、圧力７０
０Ｋｇｆ／ｃｍ２以上の条件で熱間静水圧処理（ＨＩＰ
処理）して高密度（相対密度９９％以上であることが望
ましい）の焼結体とする。ＣＩＰ処理、ＨＰ処理、ＨＩ
Ｐ処理等の温度、圧力等の条件は上記に限らず、原料の
種類又は目的とする焼結体の密度等を考慮して他の条件
を設定してもよい。また、上記のようなＣＩＰ処理、Ｈ
Ｐ処理、ＨＩＰ処理等に替えて、黒鉛製のモールドに混
合粉末を充填し、これを上下ダイ（電極）間で圧縮しな
がらパルス通電を行い燃焼合成を行う、パルス通電燃焼
合成法により焼結体とすることもできる。この場合、特
に上記メカニカルアロイ粉を使用すると緻密かつ均一な
焼結体を得ることができる。After the above-mentioned mixed and ground powder is put into a mold and preliminarily formed, it is subjected to, for example, a cold isostatic pressure treatment (CIP treatment), and further a hot press treatment (HP treatment) at 500 to 600 ° C. and a pressure of 700 kgf / cm 2 or more. ) Or C
After IP treatment, similarly, at 500 to 600 ° C. and pressure 70
Hot isostatic pressure treatment (HIP) under the condition of 0 kgf / cm 2 or more
Treatment) to obtain a sintered body having a high density (preferably a relative density of 99% or more). CIP processing, HP processing, HI
The conditions such as the temperature and pressure of the P treatment are not limited to the above, and other conditions may be set in consideration of the type of the raw material or the density of the target sintered body. In addition, CIP processing as described above,
Instead of P treatment, HIP treatment, etc., the mixed powder is filled in a graphite mold, and pulse compression is performed between the upper and lower dies (electrodes) to perform pulse synthesis and combustion synthesis. It can also be a body. In this case, a dense and uniform sintered body can be obtained particularly when the mechanical alloy powder is used.
【００１０】上記の溶製法又は粉末冶金法によって得ら
れたインゴット又は焼結体からターゲット形状に切り出
し、組成がＡｌｘＴｉ１−ｘ−ｙ−ｚＭｙＲｚ（但し、
ＭはＳｉ、Ｃｒ、Ｗ、Ｍｏから選択した元素の１種以
上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル等の希土類元
素から選択した元素の1種以上、０．０５≦ｘ≦０．
７、０．０２≦ｙ≦０．２５、０．０００５≦ｚ≦０．
０５）であるＡｌＴｉ系合金ターゲット材を得る。該ス
パッタリングターゲットにおけるＡｌの量、すなわちｘ
は０．０５≦ｘ≦０．７とする。下限の０．０５未満で
はスパッタリングにより成膜（窒化膜）した場合に、該
膜の耐酸化性が不十分となり、又上限値０．７を超える
と、該皮膜の靭性が低下し母材から剥離し易くなるので
上記範囲とする。ＭすなわちＳｉ、Ｃｒ、Ｗ、Ｍｏから
選択した元素が下限値０．０２未満では耐酸化性と硬度
が不十分となり、上限値０．２５を超えると皮膜の密着
性が低下し剥離し易くなるので、上記の範囲とする。特
に、耐酸化性をより向上させるためには０．１<ｙ≦
０．２５の範囲とするのが望ましい。Ｒすなわち希土類
元素は、微量の添加で極めて効果的に耐酸化性を向上さ
せる。しかし、下限値０．０００５未満では添加による
効果がなく耐酸化性不十分となり、また上限値０．０５
を超えると希土類元素が偏析（濃縮）し、かえって耐酸
化性が劣化するので上記範囲とする。このターゲットは
さらに、銅製等のバッキングプレートにろう付け等の手
段により接合し、これをスパッタチャンバ内に挿入し、
窒素ガスとアルゴンガス等の希薄混合ガス雰囲気下にお
いて、反応性スパッタリングを実施する。これによっ
て、ＡｌｘＴｉ１−ｘ−ｙ−ｚＭｙＲｚ（但し、ＭはＳ
ｉ、Ｃｒ、Ｗ、Ｍｏから選択した元素の１種以上、Ｒは
Ｙ、Ｃｅ、Ｌａ、ミッシュメタル等の希土類元素から選
択した元素の1種以上、０．０５≦ｘ≦０．７、０．０
２≦ｙ≦０．２５、０．０００５≦ｚ≦０．０５）であ
る耐摩耗性ＡｌＴｉ系合金硬質皮膜を得ることができ
る。皮膜の厚みは剥離強度との兼ね合いから１〜１０μ
ｍとするのが良いが、製品に応じてそれ以上の膜厚とす
ることもできる。このようにして得た硬質皮膜は硬度が
高く、耐酸化性に優れ、母材との密着性が良好で、工具
等の寿命が大きく向上するという著しい特徴を有してい
る。[0010] cut into target shape from the smelting process or ingot or obtained by powder metallurgy sintered body composition Al x Ti 1-x-y -z M y R z ( where
M is at least one element selected from Si, Cr, W, and Mo; R is at least one element selected from rare earth elements such as Y, Ce, La, and misch metal;
7, 0.02 ≦ y ≦ 0.25, 0.0005 ≦ z ≦ 0.
05) is obtained. The amount of Al in the sputtering target, ie, x
Is set to 0.05 ≦ x ≦ 0.7. If the lower limit is less than 0.05, when formed by sputtering (nitride film), the oxidation resistance of the film becomes insufficient, and if it exceeds the upper limit of 0.7, the toughness of the film decreases, and Since it is easy to peel off, the above range is set. If the element selected from M, ie, Si, Cr, W, and Mo, is less than the lower limit of 0.02, the oxidation resistance and hardness are insufficient, and if it exceeds the upper limit of 0.25, the adhesion of the film is reduced and the film is easily peeled. Therefore, the above range is set. In particular, in order to further improve the oxidation resistance, 0.1 <y ≦
It is desirable to be in the range of 0.25. R, that is, a rare earth element, improves the oxidation resistance very effectively when added in a small amount. However, if the lower limit is less than 0.0005, there is no effect due to the addition and the oxidation resistance becomes insufficient.
If it exceeds, the rare earth element segregates (concentrates), and the oxidation resistance is rather deteriorated. This target is further joined to a backing plate made of copper or the like by brazing or the like, and inserted into a sputtering chamber,
Reactive sputtering is performed in a dilute mixed gas atmosphere such as a nitrogen gas and an argon gas. Thus, Al x Ti 1-x- y-z M y R z ( where, M is S
i is at least one element selected from i, Cr, W, and Mo; R is at least one element selected from rare earth elements such as Y, Ce, La, and misch metal; 0.05 ≦ x ≦ 0.7, 0 .0
2 ≦ y ≦ 0.25, 0.0005 ≦ z ≦ 0.05) can be obtained. The thickness of the film is 1 to 10μ in consideration of the peel strength.
The thickness is preferably m, but may be larger depending on the product. The hard coating thus obtained has the remarkable features of high hardness, excellent oxidation resistance, good adhesion to the base material, and greatly improved tool life.
【００１１】[0011]
【実施例および比較例】次に、本発明を実施例および比
較例に基づいて説明する。なお、本実施例は好適な例を
示し、かつ本発明の理解を容易にするためのものであ
り、これらの例によって本発明が制限されるものではな
い。すなわち、本発明の技術思想の範囲における他の態
様および例は、当然本発明に含まれるものである。Examples and Comparative Examples Next, the present invention will be described based on Examples and Comparative Examples. In addition, this Example shows a preferable example, and it is for making the understanding of this invention easy, and this invention is not limited by these examples. That is, other embodiments and examples within the technical idea of the present invention are naturally included in the present invention.
【００１２】（実施例１〜６）原料粉末として平均粒径
１５０μｍ以下のＴｉ粉末、平均粒径１５０μｍ以下の
Ｓｉ粉末、同各種希土類元素の粉末、平均粒径１５０μ
ｍ以下のＡｌ粉末を、それぞれ表１（実施例１〜６に相
当）に示す比率に配合し（表１では窒化物の配合を示す
が、ほぼこの配合率となるように調整する）、これらを
ボールミル混合し、乾燥して混合粉とした。次に、この
混合粉砕粉をモールドに入れ予備成形した後、冷間静水
圧処理（ＣＩＰ処理）した後、５００〜６００°Ｃ、圧
力７５０Ｋｇｆ／ｃｍ２の条件でホットプレス処理（Ｈ
Ｐ処理）した。これにより相対密度９９．８％の焼結体
が得られた。(Examples 1 to 6) Ti powder having an average particle size of 150 μm or less, Si powder having an average particle size of 150 μm or less, powders of various rare earth elements, and an average particle size of 150 μm were used as raw material powders.
m or less Al powders are blended in the proportions shown in Table 1 (corresponding to Examples 1 to 6) (Table 1 shows the blending of nitrides, but it is adjusted to be approximately this blending ratio). Was mixed in a ball mill and dried to obtain a mixed powder. Then, after preformed mixing was placed pulverized powder into a mold, after cold isostatic process (CIP process), 500 to 600 ° C, hot pressing under a pressure of 750Kgf / cm 2 (H
P treatment). As a result, a sintered body having a relative density of 99.8% was obtained.
【００１３】このようにして得た焼結体からターゲット
形状に切り出し、さらに銅製のバッキングプレートにろ
う付けにより接合してスパッタリング用ターゲットとし
た。このターゲットをスパッタチャンバ内に挿入し、窒
素ガスとアルゴンガスの希薄混合ガス雰囲気下におい
て、反応性スパッタリングを実施した。母材には切削工
具として使用されるタングステンカーバイド（ＷＣ）を
用いた。皮膜の厚みは５μｍとした。このようにして形
成した皮膜の組成をＭＡ（マイクロアナライザー）によ
り分析すると共に、皮膜を形成したタングステンカーバ
イド切削工具による切削試験を実施し、皮膜の硬さの測
定、耐酸化性試験、密着性の評価、及び寿命の判定（切
削試験）を行った。この結果を表１に示す。なお、表１
における希土類元素０．００１（４桁）の数値が含まれ
ることによって、合計量が１００を超えることを意味し
ない。すなわち、他成分（Ａｌ、Ｔｉ、Ｓｉ）の有効３
桁の数値の枠内にあり（に吸収され）、希土類元素０．
００１を含めて合計量は１００を意味する。耐酸化性試
験及び切削試験の条件は次の通りである。 （耐酸化性試験条件） ・温度：１０００°Ｃ ・時間：６０時間 ・雰囲気：大気 （切削試験条件） ・被削材：ＳＫＤ６１（ＨＲＣ５２） ・切削速度：３０ｍ／ｍｉｎ ・切り込み：半径方向 １ｍｍ、軸方向 ５ｍｍ ・送り：０．０５〜０．０７ｍｍ／刃 ・切削方式：ダウンカット ・潤滑：乾式 ブローなしThe sintered body thus obtained was cut into a target shape, and further joined to a copper backing plate by brazing to obtain a sputtering target. This target was inserted into a sputtering chamber, and reactive sputtering was performed in a dilute mixed gas atmosphere of nitrogen gas and argon gas. As a base material, tungsten carbide (WC) used as a cutting tool was used. The thickness of the film was 5 μm. The composition of the film formed in this way is analyzed by MA (microanalyzer), and a cutting test is performed with a tungsten carbide cutting tool on which the film is formed, and the hardness of the film is measured, an oxidation resistance test, and an adhesion test. Evaluation and life determination (cutting test) were performed. Table 1 shows the results. Table 1
Includes a value of 0.001 (four digits) for the rare earth element, does not mean that the total amount exceeds 100. That is, effective 3 of other components (Al, Ti, Si)
It is within (absorbed into) the figures of the digit and is rare earth element 0.1.
The total amount including 001 means 100. The conditions of the oxidation resistance test and the cutting test are as follows. (Oxidation resistance test conditions) Temperature: 1000 ° C Time: 60 hours Atmosphere: Air (Cutting test conditions) Work material: SKD61 (HRC52) Cutting speed: 30 m / min Cutting depth: 1 mm in radial direction Axial direction 5mm ・ Feed: 0.05 ~ 0.07mm / blade ・ Cutting method: Down cut ・ Lubrication: Dry type No blow
【００１４】[0014]
【表１】 [Table 1]
【００１５】表１から明らかなように、実施例１〜６の
硬質膜の硬さ（ＨμＶ）は、３０，６００〜３４，５０
０ＭＰａに達し、良好な硬さを有しており、密着性もい
ずれも良好であった。また、耐酸化性試験によると、Ｔ
Ｇ／ｍｇは０．０７から０．２２の範囲であり耐食性に
極めて優れていることが分かる。総合的な評価として、
切削寿命は６０〜８８Ｍに達し、極めて良好な結果が得
られた。As is apparent from Table 1, the hardness (HμV) of the hard films of Examples 1 to 6 was 30,600 to 34,50.
It reached 0 MPa, had good hardness, and had good adhesion. According to the oxidation resistance test, T
G / mg is in the range of 0.07 to 0.22, which indicates that the corrosion resistance is extremely excellent. As a comprehensive evaluation,
The cutting life reached 60-88M with very good results.
【００１６】（比較例１〜３）上記実施例と同条件で、
表１に示す組成のターゲットを作製し、タングステンカ
ーバイド切削工具に５μｍの皮膜を形成し、同条件で皮
膜の組成のマイクロアナライザーによる組成分析、皮膜
の硬さの測定、耐酸化性試験、密着性の評価、及び寿命
の判定（切削試験）を行った。この結果を実施例と対比
して表１に示す。比較例１は硬質膜の硬さ（ＨμＶ）が
２６，０００ＭＰａで、ある程度良好な硬さを有し、密
着性も良好であるが、耐酸化性試験によるＴＧ／ｍｇは
２．２０となり耐食性が極めて悪い。また総合的な評価
として、切削寿命は０．５Ｍであり極めて悪い結果とな
った。比較例２については密着性がやや良いが、硬質膜
の硬さ（ＨμＶ）は１０，０００ＭＰａ、耐酸化性試験
によるＴＧ／ｍｇは２．１２、切削寿命は０．８Ｍであ
り、いずれも極めて悪い結果となった。比較例３は、硬
質膜の硬さを増加させるために希土類を添加したもので
あるが、Ｓｉ量が低いため密着性に劣り、耐酸化性試験
によるＴＧ／ｍｇは１０．０で著しく悪い。そして切削
寿命は０．７Ｍであり極めて悪い結果となった。(Comparative Examples 1 to 3) Under the same conditions as in the above example,
A target having the composition shown in Table 1 was prepared, a 5 μm film was formed on a tungsten carbide cutting tool, and under the same conditions, the composition of the film was analyzed by a microanalyzer, the hardness of the film was measured, an oxidation resistance test, and adhesion were measured. Was evaluated and the life was determined (cutting test). The results are shown in Table 1 in comparison with the examples. In Comparative Example 1, the hardness (HμV) of the hard film was 26,000 MPa, the film had a somewhat good hardness and good adhesion, but the TG / mg in the oxidation resistance test was 2.20 and the corrosion resistance was low. Extremely bad. As a comprehensive evaluation, the cutting life was 0.5 M, which was an extremely bad result. Although the adhesiveness of Comparative Example 2 was slightly good, the hardness (HμV) of the hard film was 10,000 MPa, the TG / mg in the oxidation resistance test was 2.12, and the cutting life was 0.8 M. Bad result. In Comparative Example 3, a rare earth was added in order to increase the hardness of the hard film, but the adhesion was inferior due to the low Si content, and the TG / mg in the oxidation resistance test was 10.0, which was extremely poor. The cutting life was 0.7 M, which was extremely bad.
【００１７】[0017]
【発明の効果】以上、本発明はＡｌＴｉＮ系合金からな
る皮膜に、Ｓｉ、Ｃｒ、Ｗ、Ｍｏから選択した元素の１
種以上を０．０２〜０．２５％（トータル量として）含
有させ、またＹ、Ｃｅ、Ｌａ、ミッシュメタル等の希土
類元素から選択した元素の1種以上を０．０５〜０．７
％含有させることにより、母材との密着性等を良好に
し、特に皮膜の硬さ及び耐酸化性を大幅に向上させて、
バランスの取れた特性を備えた皮膜を形成することがで
きる。本発明は上記の通り、この皮膜の形成に使用する
ことのできるスパッタリングターゲット及び耐摩耗性Ａ
ｌＴｉ系合金硬質皮膜の形成方法を提供するものである
が、これによって、切削工具、摺動部材、金属加工工具
等の寿命を大きく延ばすことができるという優れた効果
を有する。As described above, according to the present invention, a film made of an AlTiN-based alloy is coated with one of the elements selected from Si, Cr, W and Mo.
At least one element selected from rare earth elements such as Y, Ce, La, and misch metal in an amount of 0.05 to 0.7%.
%, The adhesion to the base material is improved, and the hardness and oxidation resistance of the film are greatly improved,
A film having well-balanced properties can be formed. As described above, the present invention provides a sputtering target and an abrasion resistant A which can be used for forming this film.
An object of the present invention is to provide a method for forming a 1Ti-based alloy hard coating, which has an excellent effect of greatly extending the life of cutting tools, sliding members, metal working tools, and the like.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１２年４月１８日（２０００．４．１
８）[Submission date] April 18, 2000 (2004.1.
8)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【書類名】 明細書[Document Name] Statement
【発明の名称】 ＡｌＴｉ系合金スパッタリングターゲ
ット及び耐摩耗性ＡｌＴｉ系合金硬質皮膜並びに同皮膜
の形成方法Patent application title: AlTi-based alloy sputtering target, wear-resistant AlTi-based alloy hard coating and method for forming the same
【特許請求の範囲】[Claims]
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、切削、穿孔、フラ
イス加工等の切削工具、軸受け等の摺動部材、あるいは
金型等の成形加工具等に適用される耐摩耗性皮膜形成に
好適なＡｌＴｉ系合金スパッタリングターゲット及び耐
摩耗性ＡｌＴｉ系合金硬質皮膜並びに同皮膜の形成方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for forming a wear-resistant film applied to cutting tools such as cutting, drilling and milling, sliding members such as bearings, and molding tools such as dies. The present invention relates to an AlTi-based alloy sputtering target, a wear-resistant AlTi-based alloy hard coating, and a method for forming the same.
【０００２】[0002]
【従来の技術】従来、上記のような切削工具、摺動部
材、金属加工工具等の耐摩耗性表面硬化膜として、高硬
度の窒化チタン（ＴｉＮ）や炭窒化チタン（ＴｉＣＮ）
が使用されてきたが、最近では切削等の加工工具等の使
用コスト低減を目的としてこれらの皮膜の長寿命化及び
さらに特性を向上させた耐摩耗性表面硬化膜の開発が要
求されている。このため、従来の窒化チタンや炭窒化チ
タン膜に替わるものとしてＡｌＴｉ合金膜又はこの炭化
膜、窒化膜、あるいは炭窒化膜を耐摩耗性表面硬化膜と
して使用する提案がなされた。これらの膜は高温域にお
ける耐酸化性、耐摩耗性、さらには被覆される機材（母
材）との密着性が上記の窒化チタンや炭窒化チタン膜よ
りも一段と向上したので、それなりの評価を得たが、耐
酸化性や耐摩耗性の点で上記に要求される特性をまだ充
分に満足させるものとは言えなかった。2. Description of the Related Art Conventionally, high-hardness titanium nitride ( TiN ) or titanium carbonitride (TiCN) has been used as a wear-resistant surface-hardened film for cutting tools, sliding members, metal working tools and the like as described above.
In recent years, there has been a demand for the development of a wear-resistant surface-hardened film having a longer service life and further improved characteristics for the purpose of reducing the use cost of machining tools such as cutting. Therefore, it has been proposed to use an AlTi alloy film or a carbide film, a nitride film, or a carbonitride film as a wear-resistant surface-hardened film instead of the conventional titanium nitride or titanium carbonitride film. These films have much higher oxidation resistance and wear resistance in high temperature range and better adhesion to the equipment (base material) to be coated than the above-mentioned titanium nitride or titanium carbonitride films. However, it could not be said that the properties required above in terms of oxidation resistance and abrasion resistance were sufficiently satisfied.
【０００３】このようなことから、最近では炭窒化Ａｌ
Ｔｉ合金膜として、Ｓｉを０．１％以下添加して硬度を
高める提案がなされた（特許第０２７９３７７３号）。
しかし、切削工具、摺動部材、金属加工工具等に使用さ
れる特性は、皮膜の硬さ、耐酸化性、母材との密着性等
の総合評価で決まるもので、最終的にはその目的に応じ
た特性を発揮し、かつ持続する寿命の問題である。この
ような観点からみて、上記０．１％以下のＳｉを添加し
た炭窒化ＡｌＴｉ合金膜は、総合的な工具寿命の点でか
ならずしも満足できるものとは言えなかった。For these reasons, recently, carbonitride Al
It has been proposed to increase the hardness by adding 0.1% or less of Si as a Ti alloy film (Japanese Patent No. 02797733).
However, the properties used for cutting tools, sliding members, metalworking tools, etc. are determined by comprehensive evaluation of the hardness, oxidation resistance, adhesion to the base material, etc. of the film, and ultimately its purpose. This is a problem of exhibiting characteristics according to the above and maintaining the life. From such a viewpoint, the carbonitrided AlTi alloy film containing 0.1% or less of Si was not always satisfactory in terms of the overall tool life.
【０００４】[0004]
【発明が解決しようとする課題】以上から、本発明は切
削工具、摺動部材、金属加工工具等に形成する皮膜の硬
さ（耐摩耗性）、耐酸化性、母材との密着性等を向上さ
せるとともに、バランスの取れた特性を備え、安定した
皮膜の形成と該皮膜を形成した工具等の寿命を十分に向
上させることを課題とする。From the above, it can be seen that the present invention relates to the hardness (abrasion resistance), oxidation resistance, adhesion to the base material, etc. of the film formed on cutting tools, sliding members, metal working tools and the like. Another object of the present invention is to provide a stable film formation and a sufficiently long life of a tool or the like on which the film is formed, while having a well-balanced characteristic.
【０００５】[0005]
【課題を解決するための手段】本発明者は、皮膜の硬さ
及び耐酸化性を一段と向上させ、最終的に工具等の硬質
耐摩耗性皮膜の特性を維持しかつ寿命を延ばすことによ
り、上記問題点を解決できることの知見を得た。この知
見に基づき、本発明は（１）ＡｌＴｉ系合金スパッタリ
ングターゲットの組成が、ＡｌｘＴｉ１−ｘ−ｙ−ｚＭ
ｙＲｚ（但し、ＭはＷ又はＭｏから選択した元素の１種
以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル等の希土類
元素から選択した元素の1種以上、０．０５≦ｘ≦０．
７、０．０２≦ｙ≦０．２５、０．０００５≦ｚ≦０．
０５）であることを特徴とするＡｌＴｉ系合金スパッタ
リングターゲット、（２）上記Ｍがさらに、Ｓｉ又はＣ
ｒから選択した元素の１種以上を含有することを特徴と
する上記（１）記載のＡｌＴｉ系合金スパッタリングタ
ーゲット、（３）硬質皮膜の組成が、ＡｌｘＴｉ
１−ｘ−ｙ−ｚＭｙＲｚ（但し、Ｗ又はＭｏから選択し
た元素の１種以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタ
ル等の希土類元素から選択した元素の1種以上、０．０
５≦ｘ≦０．７、０．０２≦ｙ≦０．２５、０．０００
５≦ｚ≦０．０５）であることを特徴とする耐摩耗性Ａ
ｌＴｉ系合金硬質皮膜、（４）上記Ｍがさらに、Ｓｉ又
はＣｒから選択した元素の１種以上を含有することを特
徴とする上記（３）記載の耐摩耗性ＡｌＴｉ系合金硬質
皮膜、（５）ＡｌＴｉ系合金スパッタリングターゲット
の組成が、ＡｌｘＴｉ１−ｘ−ｙ−ｚＭｙＲｚ（但し、
ＭはＷ又はＭｏから選択した元素の１種以上、又はＷ若
しくはＭｏから選択した元素の１種以上及びＳｉ若しく
はＣｒから選択した元素の１種以上、ＲはＹ、Ｃｅ、Ｌ
ａ、ミッシュメタル等の希土類元素から選択した元素の
1種以上、０．０５≦ｘ≦０．７、０．０２≦ｙ≦０．
２５、０．０００５≦ｚ≦０．０５）であるＡｌＴｉ系
合金スパッタリングターゲットを窒素雰囲気中でスパッ
タリングすることを特徴とする、硬質皮膜の組成が、Ａ
ｌｘＴｉ１−ｘ−ｙ−ｚＭｙＲｚ（但し、ＭはＷ又はＭ
ｏから選択した元素の１種以上、又はＷ若しくはＭｏか
ら選択した元素の１種以上及びＳｉ若しくはＣｒから選
択した元素の１種以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュ
メタル等の希土類元素から選択した元素の1種以上、
０．０５≦ｘ≦０．７、０．０２≦ｙ≦０．２５、０．
０００５≦ｚ≦０．０５）の窒化物である耐摩耗性Ａｌ
Ｔｉ系合金硬質皮膜の形成方法、を提供するものであ
る。SUMMARY OF THE INVENTION The present inventors have further improved the hardness and oxidation resistance of a film, and finally maintain the properties of a hard wear-resistant film such as a tool and extend the life of the film. We have found that the above problems can be solved. Based on this finding, the present invention is the composition of (1) AlTi alloy sputtering target, Al x Ti 1-x- y-z M
y R z (where M is at least one element selected from W or Mo , R is at least one element selected from rare earth elements such as Y, Ce, La, and misch metal, 0.05 ≦ x ≦ 0 .
7, 0.02 ≦ y ≦ 0.25, 0.0005 ≦ z ≦ 0.
05) An AlTi-based alloy sputtering target, wherein (2) M is further Si or C
AlTi alloy sputtering target of the above (1), wherein the containing more than one kind of elements selected from r, the composition of (3) hard coating, Al x Ti
1-x-y-z M y R z ( where, W, or selected one or more elements from Mo, R is Y, Ce, La, one or more elements selected from rare earth elements such as misch metal, 0 .0
5 ≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.25, 0.000
5 ≦ z ≦ 0.05)
lTi-based alloy hard coating, (4) M is further
The above (3) Abrasion resistance AlTi alloy hard coating, wherein the containing one or more elements selected from Cr, the composition of (5) AlTi alloy sputtering target, Al x Ti 1- x-y-z M y R z ( However,
M is at least one element selected from W or Mo;
Or one or more elements selected from Mo and Si
Is at least one element selected from Cr , and R is Y, Ce, L
a, elements selected from rare earth elements such as misch metal
At least one kind, 0.05 ≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.
25, 0.0005 ≦ z ≦ 0.05), wherein the AlTi-based alloy sputtering target is sputtered in a nitrogen atmosphere.
l x Ti 1-x-y -z M y R z ( where, M is W or M
one or more elements selected from o, or W or Mo
Selected from one or more of the elements selected from
One or more selected elements , R is one or more elements selected from rare earth elements such as Y, Ce, La, and misch metal;
0.05 ≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.25, 0.
0005 ≦ z ≦ 0.05 abrasion resistance Al is a nitride of)
A method for forming a Ti-based alloy hard coating.
【０００６】[0006]
【発明の実施の形態】本発明のＡｌＴｉ系合金スパッタ
リングターゲットは、真空アーク溶解、プラズマ溶解、
電子ビーム溶解、誘導溶解等の溶製法によって製造でき
る。これらの溶解に際してはガス、特に酸素の混入が著
しく、また上記アルミニウム、チタン、シリコンはいず
れも酸素との結合力が強いので、いずれの場合にも真空
中又は不活性中で溶解することが必要である。また、溶
解、凝固過程において偏析の発生や結晶粒が粗大化しな
いように、加工及び温度コントロールを実施して製造す
る。BEST MODE FOR CARRYING OUT THE INVENTION The AlTi-based alloy sputtering target of the present invention can be used for vacuum arc melting, plasma melting,
It can be manufactured by a melting method such as electron beam melting or induction melting. In dissolving these, gases, particularly oxygen, are remarkably mixed, and the above-mentioned aluminum, titanium, and silicon all have a strong bonding force with oxygen, so that in any case, it is necessary to dissolve in a vacuum or in an inert gas. It is. In addition, in order to prevent the occurrence of segregation and the coarsening of crystal grains during the melting and solidification processes, the production and the temperature control are carried out to manufacture.
【０００７】上記溶製法によるもの以外に粉末冶金法に
よって製造することもできる。この粉末冶金法によって
製造する場合、例えば、原料粉末としてそれぞれ平均粒
径１５０μｍ以下のＴｉ粉末、Ｓｉ粉末、同希土類元
素、Ａｌ粉末を本発明の組成となる所定の比率に配合
し、これらをボールミル混合し、乾燥して混合粉とす
る。原料粉としては、さらに微細なアトマイズ粉を使用
することができる。[0007] In addition to the above-mentioned melting method, it can be manufactured by powder metallurgy. When manufacturing by this powder metallurgy method, for example, Ti powder, Si powder, the same rare earth element and Al powder each having an average particle size of 150 μm or less are blended as raw material powders in a predetermined ratio to become the composition of the present invention, and these are mixed with a ball mill. Mix and dry to a mixed powder. As the raw material powder, finer atomized powder can be used.
【０００８】上記焼結用粉末は例えばメカニカルアロイ
ング法により所定の比率に予め合金化したＴｉＡｌ又は
ＴｉＡｌＳｉ（希土類）合金粉末を用いることができ
る。いずれの場合にも、微細かつ均一な混合粉末を使用
した場合には焼結体の密度が高く、その結果均一かつ緻
密なターゲットが得られ、またスパッタリングにより成
膜条件も安定し、均一微細な組織の皮膜が形成できると
いう利点がある。As the sintering powder, for example, TiAl or TiAlSi (rare earth) alloy powder alloyed in a predetermined ratio by a mechanical alloying method can be used. In any case, when a fine and uniform mixed powder is used, the density of the sintered body is high, and as a result, a uniform and dense target is obtained. There is an advantage that a tissue film can be formed.
【０００９】上記混合粉砕粉をモールドに入れ予備成形
した後、例えば冷間静水圧処理（ＣＩＰ処理）し、さら
に５００〜６００°Ｃ、圧力７００Ｋｇｆ／ｃｍ２以上
の条件でホットプレス処理（ＨＰ処理）するか、又はＣ
ＩＰ処理した後、同様に５００〜６００°Ｃ、圧力７０
０Ｋｇｆ／ｃｍ２以上の条件で熱間静水圧処理（ＨＩＰ
処理）して高密度（相対密度９９％以上であることが望
ましい）の焼結体とする。ＣＩＰ処理、ＨＰ処理、ＨＩ
Ｐ処理等の温度、圧力等の条件は上記に限らず、原料の
種類又は目的とする焼結体の密度等を考慮して他の条件
を設定してもよい。また、上記のようなＣＩＰ処理、Ｈ
Ｐ処理、ＨＩＰ処理等に替えて、黒鉛製のモールドに混
合粉末を充填し、これを上下ダイ（電極）間で圧縮しな
がらパルス通電を行い燃焼合成を行う、パルス通電燃焼
合成法により焼結体とすることもできる。この場合、特
に上記メカニカルアロイ粉を使用すると緻密かつ均一な
焼結体を得ることができる。After the above-mentioned mixed and ground powder is put into a mold and preliminarily formed, it is subjected to, for example, a cold isostatic pressure treatment (CIP treatment), and further a hot press treatment (HP treatment) at 500 to 600 ° C. and a pressure of 700 kgf / cm 2 or more. ) Or C
After IP treatment, similarly, at 500 to 600 ° C. and pressure 70
Hot isostatic pressure treatment (HIP) under the condition of 0 kgf / cm 2 or more
Treatment) to obtain a sintered body having a high density (preferably a relative density of 99% or more). CIP processing, HP processing, HI
The conditions such as the temperature and the pressure of the P treatment are not limited to the above, and other conditions may be set in consideration of the type of the raw material or the density of the target sintered body. In addition, CIP processing as described above,
Instead of P treatment, HIP treatment, etc., the mixed powder is filled in a graphite mold, and pulse compression is performed between the upper and lower dies (electrodes) to perform pulse synthesis and combustion synthesis. It can also be a body. In this case, a dense and uniform sintered body can be obtained particularly when the mechanical alloy powder is used.
【００１０】上記の溶製法又は粉末冶金法によって得ら
れたインゴット又は焼結体からターゲット形状に切り出
し、組成がＡｌｘＴｉ１−ｘ−ｙ−ｚＭｙＲｚ（但し、
ＭはＷ又はＭｏから選択した元素の１種以上、又はＷ若
しくはＭｏから選択した元素の１種以上及びＳｉ若しく
はＣｒから選択した元素の１種以上、ＲはＹ、Ｃｅ、Ｌ
ａ、ミッシュメタル等の希土類元素から選択した元素の
1種以上、０．０５≦ｘ≦０．７、０．０２≦ｙ≦０．
２５、０．０００５≦ｚ≦０．０５）であるＡｌＴｉ系
合金ターゲット材を得る。該スパッタリングターゲット
におけるＡｌの量、すなわちｘは０．０５≦ｘ≦０．７
とする。下限の０．０５未満ではスパッタリングにより
成膜（窒化膜）した場合に、該膜の耐酸化性が不十分と
なり、又上限値０．７を超えると、該皮膜の靭性が低下
し母材から剥離し易くなるので上記範囲とする。Ｍすな
わちＷ又はＭｏから選択した元素の１種以上、又はＷ若
しくはＭｏから選択した元素の１種以上及びＳｉ若しく
はＣｒから選択した元素の１種以上の下限値０．０２未
満では耐酸化性と硬度が不十分となり、上限値０．２５
を超えると皮膜の密着性が低下し剥離し易くなるので、
上記の範囲とする。特に、耐酸化性をより向上させるた
めには０．１<ｙ≦０．２５の範囲とするのが望まし
い。Ｒすなわち希土類元素は、微量の添加で極めて効果
的に耐酸化性を向上させる。しかし、下限値０．０００
５未満では添加による効果がなく耐酸化性不十分とな
り、また上限値０．０５を超えると希土類元素が偏析
（濃縮）し、かえって耐酸化性が劣化するので上記範囲
とする。このターゲットはさらに、銅製等のバッキング
プレートにろう付け等の手段により接合し、これをスパ
ッタチャンバ内に挿入し、窒素ガスとアルゴンガス等の
希薄混合ガス雰囲気下において、反応性スパッタリング
を実施する。これによって、ＡｌｘＴｉ１−ｘ−ｙ−ｚ
ＭｙＲｚ（但し、ＭはＷ又はＭｏから選択した元素の１
種以上、又はＷ若しくはＭｏから選択した元素の１種以
上及びＳｉ若しくはＣｒから選択した元素の１種以上、
ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル等の希土類元素か
ら選択した元素の1種以上、０．０５≦ｘ≦０．７、
０．０２≦ｙ≦０．２５、０．０００５≦ｚ≦０．０
５）である耐摩耗性ＡｌＴｉ系合金硬質皮膜を得ること
ができる。皮膜の厚みは剥離強度との兼ね合いから１〜
１０μｍとするのが良いが、製品に応じてそれ以上の膜
厚とすることもできる。このようにして得た硬質皮膜は
硬度が高く、耐酸化性に優れ、母材との密着性が良好
で、工具等の寿命が大きく向上するという著しい特徴を
有している。[0010] cut into target shape from the smelting process or ingot or obtained by powder metallurgy sintered body composition Al x Ti 1-x-y -z M y R z ( where
M is at least one element selected from W or Mo;
Or one or more elements selected from Mo and Si
Is at least one element selected from Cr , and R is Y, Ce, L
a, elements selected from rare earth elements such as misch metal
At least one kind, 0.05 ≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.
25, 0.0005 ≦ z ≦ 0.05) is obtained. The amount of Al in the sputtering target, that is, x is 0.05 ≦ x ≦ 0.7
And If the lower limit is less than 0.05, when formed by sputtering (nitride film), the oxidation resistance of the film becomes insufficient, and if it exceeds the upper limit of 0.7, the toughness of the film decreases, and Since it is easy to peel off, the above range is set. M, that is, one or more elements selected from W or Mo, or W
Or one or more elements selected from Mo and Si
If the lower limit of at least one of the elements selected from Cr is less than 0.02, the oxidation resistance and hardness are insufficient, and the upper limit is 0.25.
If it exceeds, the adhesion of the film decreases and it becomes easy to peel off,
Within the above range. In particular, in order to further improve the oxidation resistance, it is desirable to set the range of 0.1 <y ≦ 0.25. R, that is, a rare earth element, improves the oxidation resistance very effectively when added in a small amount. However, the lower limit is 0.000
If it is less than 5, there is no effect due to the addition and the oxidation resistance becomes insufficient, and if it exceeds the upper limit of 0.05, the rare earth element segregates (concentrates) and the oxidation resistance is rather deteriorated. The target is further bonded to a backing plate made of copper or the like by brazing or the like, inserted into a sputtering chamber, and subjected to reactive sputtering in a dilute mixed gas atmosphere such as a nitrogen gas and an argon gas. Thereby, Al x Ti 1-x-y-z
M y R z (where, M represents one element selected from W, or Mo
Or more, or at least one element selected from W or Mo
One or more of the elements selected from above and Si or Cr ,
R is one or more elements selected from rare earth elements such as Y, Ce, La, and misch metal; 0.05 ≦ x ≦ 0.7;
0.02 ≦ y ≦ 0.25, 0.0005 ≦ z ≦ 0.0
5) It is possible to obtain an abrasion-resistant AlTi-based alloy hard coating. The thickness of the coating is 1 to 3 depending on the peel strength.
The thickness is preferably 10 μm, but may be greater than that depending on the product. The hard coating thus obtained has the remarkable features of high hardness, excellent oxidation resistance, good adhesion to the base material, and greatly improved tool life.
【００１１】[0011]
【実施例および比較例】次に、本発明を実施例および比
較例に基づいて説明する。なお、本実施例は好適な例を
示し、かつ本発明の理解を容易にするためのものであ
り、これらの例によって本発明が制限されるものではな
い。すなわち、本発明の技術思想の範囲における他の態
様および例は、当然本発明に含まれるものである。Examples and Comparative Examples Next, the present invention will be described based on Examples and Comparative Examples. In addition, this Example shows a preferable example, and it is for making the understanding of this invention easy, and this invention is not limited by these examples. That is, other embodiments and examples within the technical idea of the present invention are naturally included in the present invention.
【００１２】（実施例１及び２）原料粉末として平均粒
径１５０μｍ以下のＴｉ粉末、平均粒径１５０μｍ以下
の元素Ｍの粉末、同各種希土類元素の粉末、平均粒径１
５０μｍ以下のＡｌ粉末を、それぞれ表１（実施例１〜
６に相当）に示す比率に配合し（表１では窒化物の配合
を示すが、ほぼこの配合率となるように調整する）、こ
れらをボールミル混合し、乾燥して混合粉とした。次
に、この混合粉砕粉をモールドに入れ予備成形した後、
冷間静水圧処理（ＣＩＰ処理）した後、５００〜６００
°Ｃ、圧力７５０Ｋｇｆ／ｃｍ２の条件でホットプレス
処理（ＨＰ処理）した。これにより相対密度９９．８％
の焼結体が得られた。Examples 1 and 2 Ti powder having an average particle size of 150 μm or less , powder of element M having an average particle size of 150 μm or less, various rare earth element powders having the same
Table 1 (Examples 1 to 5)
(Corresponding to 6) (Table 1 shows the compounding of the nitride, but it is adjusted so as to have almost this compounding ratio). These were mixed in a ball mill and dried to obtain a mixed powder. Next, after putting this mixed and crushed powder into a mold and preforming,
After cold isostatic pressure treatment (CIP treatment), 500-600
Hot press processing (HP processing) was performed under the conditions of ° C and a pressure of 750 kgf / cm 2 . This gives a relative density of 99.8%
Was obtained.
【００１３】このようにして得た焼結体からターゲット
形状に切り出し、さらに銅製のバッキングプレートにろ
う付けにより接合してスパッタリング用ターゲットとし
た。このターゲットをスパッタチャンバ内に挿入し、窒
素ガスとアルゴンガスの希薄混合ガス雰囲気下におい
て、反応性スパッタリングを実施した。母材には切削工
具として使用されるタングステンカーバイド（ＷＣ）を
用いた。皮膜の厚みは５μｍとした。このようにして形
成した皮膜の組成をＭＡ（マイクロアナライザー）によ
り分析すると共に、皮膜を形成したタングステンカーバ
イド切削工具による切削試験を実施し、皮膜の硬さの測
定、耐酸化性試験、密着性の評価、及び寿命の判定（切
削試験）を行った。この結果を表１に示す。なお、表１
における希土類元素０．００１（４桁）の数値が含まれ
ることによって、合計量が１００を超えることを意味し
ない。すなわち、他成分（Ａｌ、Ｔｉ、Ｓｉ）の有効３
桁の数値の枠内にあり（に吸収され）、希土類元素０．
００１を含めて合計量は１００を意味する。耐酸化性試
験及び切削試験の条件は次の通りである。 （耐酸化性試験条件） ・温度：１０００°Ｃ・時間：６０時間 ・雰囲気：大気 （切削試験条件） ・被削材：ＳＫＤ６１（ＨＲＣ５２） ・切削速度：３０ｍ／ｍｉｎ ・切り込み：半径方向 １ｍｍ、軸方向 ５ｍｍ ・送り：０．０５〜０．０７ｍｍ／刃 ・切削方式：ダウンカット ・潤滑：乾式 ブローなしThe sintered body thus obtained was cut into a target shape, and further joined to a copper backing plate by brazing to obtain a sputtering target. This target was inserted into a sputtering chamber, and reactive sputtering was performed in a dilute mixed gas atmosphere of nitrogen gas and argon gas. As a base material, tungsten carbide (WC) used as a cutting tool was used. The thickness of the film was 5 μm. The composition of the film formed in this way is analyzed by MA (microanalyzer), and a cutting test is performed with a tungsten carbide cutting tool on which the film is formed, and the hardness of the film is measured, an oxidation resistance test, and an adhesion test. Evaluation and life determination (cutting test) were performed. Table 1 shows the results. Table 1
Includes a value of 0.001 (four digits) for the rare earth element, does not mean that the total amount exceeds 100. That is, effective 3 of other components (Al, Ti, Si)
It is within (absorbed into) the figures of the digit and is rare earth element 0.1.
The total amount including 001 means 100. The conditions of the oxidation resistance test and the cutting test are as follows. (Oxidation resistance test conditions) Temperature: 1000 ° C Time: 60 hours Atmosphere: Air (Cutting test conditions) Work material: SKD61 (HRC52) Cutting speed: 30 m / min Cutting depth: 1 mm in radial direction Axial direction 5mm ・ Feed: 0.05 ~ 0.07mm / blade ・ Cutting method: Down cut ・ Lubrication: Dry type No blow
【００１４】[0014]
【表１】 [Table 1]
【００１５】表１から明らかなように、実施例１及び２
の硬質膜の硬さ（ＨμＶ）は、３２，５００及び３１，
７００ＭＰａに達し、良好な硬さを有しており、密着性
もいずれも良好であった。また、耐酸化性試験による
と、ＴＧ／ｍｇはそれぞれ０．１５及び０．０８であり
耐食性に極めて優れていることが分かる。総合的な評価
として、切削寿命は６０Ｍ及び６３Ｍに達し、極めて良
好な結果が得られた。As is clear from Table 1, Examples 1 and 2
The hardness (HμV) of the hard film is 32,500 and 31,
It reached 700 MPa , had good hardness, and had good adhesion. In addition, according to the oxidation resistance test, TG / mg was 0.15 and 0.08, respectively, indicating that the TG / mg was extremely excellent in corrosion resistance. As a comprehensive evaluation, the cutting life reached 60M and 63M , and extremely good results were obtained.
【００１６】（比較例１〜３）上記実施例と同条件で、
表１に示す組成のターゲットを作製し、タングステンカ
ーバイド切削工具に５μｍの皮膜を形成し、同条件で皮
膜の組成のマイクロアナライザーによる組成分析、皮膜
の硬さの測定、耐酸化性試験、密着性の評価、及び寿命
の判定（切削試験）を行った。この結果を実施例と対比
して表１に示す。比較例１は硬質膜の硬さ（ＨμＶ）が
２６，０００ＭＰａで、ある程度良好な硬さを有し、密
着性も良好であるが、耐酸化性試験によるＴＧ／ｍｇは
２．２０となり耐食性が極めて悪い。また総合的な評価
として、切削寿命は０．５Ｍであり極めて悪い結果とな
った。比較例２については密着性がやや良いが、硬質膜
の硬さ（ＨμＶ）は１０，０００ＭＰａ、耐酸化性試験
によるＴＧ／ｍｇは２．１２、切削寿命は０．８Ｍであ
り、いずれも極めて悪い結果となった。比較例３は、硬
質膜の硬さを増加させるために希土類を添加したもので
あるが、Ｓｉ量が低いため密着性に劣り、耐酸化性試験
によるＴＧ／ｍｇは１０．０で著しく悪い。そして切削
寿命は０．７Ｍであり極めて悪い結果となった。(Comparative Examples 1 to 3) Under the same conditions as in the above example,
A target having the composition shown in Table 1 was prepared, a 5 μm film was formed on a tungsten carbide cutting tool, and under the same conditions, the composition of the film was analyzed by a microanalyzer, the hardness of the film was measured, an oxidation resistance test, and adhesion were measured. Was evaluated and the life was determined (cutting test). The results are shown in Table 1 in comparison with the examples. In Comparative Example 1, the hardness (HμV) of the hard film was 26,000 MPa, the film had a somewhat good hardness and good adhesion, but the TG / mg in the oxidation resistance test was 2.20 and the corrosion resistance was low. Extremely bad. As a comprehensive evaluation, the cutting life was 0.5 M, which was an extremely bad result. Although the adhesiveness of Comparative Example 2 was slightly good, the hardness (HμV) of the hard film was 10,000 MPa, the TG / mg in the oxidation resistance test was 2.12, and the cutting life was 0.8 M. Bad result. In Comparative Example 3, a rare earth was added in order to increase the hardness of the hard film, but the adhesion was inferior due to the low Si content, and the TG / mg in the oxidation resistance test was 10.0, which was extremely poor. The cutting life was 0.7 M, which was extremely bad.
【００１７】[0017]
【発明の効果】以上、本発明はＡｌＴｉＮ系合金からな
る皮膜に、Ｗ又はＭｏから選択した元素の１種以上、又
はＷ若しくはＭｏから選択した元素の１種以上及びＳｉ
若しくはＣｒから選択した元素の１種以上を０．０２〜
０．２５％（トータル量として）含有させ、またＹ、Ｃ
ｅ、Ｌａ、ミッシュメタル等の希土類元素から選択した
元素の1種以上を０．０５〜０．７％含有させることに
より、母材との密着性等を良好にし、特に皮膜の硬さ及
び耐酸化性を大幅に向上させて、バランスの取れた特性
を備えた皮膜を形成することができる。本発明は上記の
通り、この皮膜の形成に使用することのできるスパッタ
リングターゲット及び耐摩耗性ＡｌＴｉ系合金硬質皮膜
の形成方法を提供するものであるが、これによって、切
削工具、摺動部材、金属加工工具等の寿命を大きく延ば
すことができるという優れた効果を有する。As described above, according to the present invention, at least one element selected from W or Mo, and
Is at least one element selected from W or Mo and Si
Alternatively, one or more of elements selected from Cr
0.25% (as a total amount)
e, at least one element selected from the group consisting of rare earth elements such as La and Misch metal is contained in an amount of 0.05 to 0.7% to improve the adhesion to the base material and the like, and in particular, the hardness and acid resistance of the film. Thus, it is possible to form a film having well-balanced properties by greatly improving the chemical properties. As described above, the present invention provides a sputtering target and a method for forming an abrasion-resistant AlTi-based alloy hard film that can be used for forming this film. It has an excellent effect that the life of a working tool or the like can be greatly extended.
フロントページの続き (72)発明者 橋本 等 宮城県仙台市宮城野区苦竹４丁目２番１号 東北工業技術研究所内 (72)発明者 朴 容浩 宮城県仙台市宮城野区苦竹４丁目２番１号 東北工業技術研究所内 (72)発明者 齋藤 吉信 宮城県柴田郡村田町大字村田字西ケ丘23 東北特殊鋼株式会社内 (72)発明者 武田 裕正 宮城県柴田郡村田町大字村田字西ケ丘23 東北特殊鋼株式会社内 (72)発明者 及川 広勝 宮城県柴田郡村田町大字村田字西ケ丘23 東北特殊鋼株式会社内 Ｆターム(参考） 4K029 BA21 BA23 BC02 BD04 BD05 CA05 DC04 Continuation of the front page (72) Inventor Hashimoto et al. 4-2-1 Kutake, Miyagino-ku, Sendai City, Miyagi Prefecture Inside the Tohoku Institute of Industrial Technology (72) Inventor Yoko Hiroshi 4-2-1 Kutake, Miyagino-ku, Sendai City, Miyagi Prefecture Inside Tohoku Institute of Technology (72) Inventor Yoshinobu Saito 23 Nishigaoka, Murata-cho, Shibata-gun, Miyagi Prefecture, Japan 23 Inside Tohoku Special Steel Co., Ltd. 23 Tohoku Special Steel Co., Ltd. (72) Inventor Hirokatsu Oikawa Murata-cho, Shibata-gun, Miyagi Nishigaoka, 23 character F-term (reference) 4K029 BA21 BA23 BC02 BD04 BD05 CA05 DC04
Claims (5)
トの組成が、ＡｌｘＴｉ１−ｘ−ｙ−ｚＭｙＲｚ（但
し、ＭはＳｉ、Ｃｒ、Ｗ、Ｍｏから選択した元素の１種
以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル等の希土類
元素から選択した元素の1種以上、０．０５≦ｘ≦０．
７、０．０２≦ｙ≦０．２５、０．０００５≦ｚ≦０．
０５）であることを特徴とするＡｌＴｉ系合金スパッタ
リングターゲット。1. A composition of AlTi alloy sputtering target, Al x Ti 1-x- y-z M y R z ( where, M is Si, Cr, W, 1 or more elements selected from Mo, R Is at least one element selected from rare earth elements such as Y, Ce, La, and misch metal, and 0.05 ≦ x ≦ 0.
7, 0.02 ≦ y ≦ 0.25, 0.0005 ≦ z ≦ 0.
05), wherein the sputtering target is an AlTi alloy sputtering target.
選択した元素の１種以上の組成範囲ｙが、０．１<ｙ≦
０．２５であることを特徴とする請求項１記載のＡｌＴ
ｉ系合金スパッタリングターゲット。2. The composition range of at least one of M, that is, one or more elements selected from Si, Cr, W, and Mo is 0.1 <y ≦
2. The AlT according to claim 1, wherein the AlT is 0.25.
i-based alloy sputtering target.
１−ｘ−ｙ−ｚＭｙＲｚ（但し、ＭはＳｉ、Ｃｒ、Ｗ、
Ｍｏから選択した元素の１種以上、ＲはＹ、Ｃｅ、Ｌ
ａ、ミッシュメタル等の希土類元素から選択した元素の
1種以上、０．０５≦ｘ≦０．７、０．０２≦ｙ≦０．
２５、０．０００５≦ｚ≦０．０５）であることを特徴
とする耐摩耗性ＡｌＴｉ系合金硬質皮膜。3. The composition of the hard coating is Al x Ti
1-x-y-z M y R z ( where, M is Si, Cr, W,
One or more elements selected from Mo, R is Y, Ce, L
a, elements selected from rare earth elements such as misch metal
At least one kind, 0.05 ≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.
25, 0.0005 ≦ z ≦ 0.05), wherein the hard coating is a wear-resistant AlTi-based alloy.
選択した元素の１種以上の組成範囲ｙが、０．１<ｙ≦
０．２５であることを特徴とする請求項３記載の耐摩耗
性ＡｌＴｉ系合金硬質皮膜。4. The composition range of at least one of M, that is, one or more elements selected from Si, Cr, W, and Mo, is 0.1 <y ≦
The wear-resistant AlTi-based alloy hard coating according to claim 3, wherein the thickness is 0.25.
トの組成が、ＡｌｘＴｉ１−ｘ−ｙ−ｚＭｙＲｚ（但
し、ＭはＳｉ、Ｃｒ、Ｗ、Ｍｏから選択した元素の１種
以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル等の希土類
元素から選択した元素の1種以上、０．０５≦ｘ≦０．
７、０．０２≦ｙ≦０．２５、０．０００５≦ｚ≦０．
０５）であるＡｌＴｉ系合金スパッタリングターゲット
を窒素雰囲気中でスパッタリングすることを特徴とす
る、硬質皮膜の組成が、ＡｌｘＴｉ １−ｘ−ｙ−ｚＭｙ
Ｒｚ（但し、ＭはＳｉ、Ｃｒ、Ｗ、Ｍｏから選択した元
素の１種以上、ＲはＹ、Ｃｅ、Ｌａ、ミッシュメタル等
の希土類元素から選択した元素の1種以上、０．０５≦
ｘ≦０．７、０．０２≦ｙ≦０．２５、０．０００５≦
ｚ≦０．０５）である耐摩耗性ＡｌＴｉ系合金硬質皮膜
の形成方法。5. An AlTi alloy sputtering target.
The composition of AlxTi1-x-y-zMyRz(However
And M is one of the elements selected from Si, Cr, W and Mo
R is a rare earth element such as Y, Ce, La, misch metal, etc.
One or more elements selected from the elements, 0.05 ≦ x ≦ 0.
7, 0.02 ≦ y ≦ 0.25, 0.0005 ≦ z ≦ 0.
05) AlTi alloy sputtering target
Characterized by sputtering in a nitrogen atmosphere.
The composition of the hard coating is AlxTi 1-x-y-zMy
Rz(However, M is an element selected from Si, Cr, W and Mo
At least one element, R is Y, Ce, La, misch metal, etc.
At least one element selected from rare earth elements, 0.05 ≦
x ≦ 0.7, 0.02 ≦ y ≦ 0.25, 0.0005 ≦
z ≦ 0.05) wear-resistant AlTi alloy hard coating
Formation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11106118A JP3084402B1 (en) | 1999-04-14 | 1999-04-14 | AlTi-based alloy sputtering target, wear-resistant AlTi-based alloy hard coating, and method of forming the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11106118A JP3084402B1 (en) | 1999-04-14 | 1999-04-14 | AlTi-based alloy sputtering target, wear-resistant AlTi-based alloy hard coating, and method of forming the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP3084402B1 JP3084402B1 (en) | 2000-09-04 |
| JP2000297365A true JP2000297365A (en) | 2000-10-24 |
Family
ID=14425547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11106118A Expired - Lifetime JP3084402B1 (en) | 1999-04-14 | 1999-04-14 | AlTi-based alloy sputtering target, wear-resistant AlTi-based alloy hard coating, and method of forming the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3084402B1 (en) |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1219723A2 (en) * | 2000-12-28 | 2002-07-03 | Kabushiki Kaisha Kobe Seiko Sho | Hard film for cutting tools |
| EP1348776A1 (en) * | 2002-03-29 | 2003-10-01 | Kabushiki Kaisha Kobe Seiko Sho | Target for arc ion plating and method of manufacturing the same |
| JP2003286564A (en) * | 2002-03-29 | 2003-10-10 | Kobe Steel Ltd | Target for physical vapor deposition and manufacturing method therefor |
| EP1437388A1 (en) | 2003-01-08 | 2004-07-14 | Fuji Photo Film Co., Ltd. | Coloring composition and inkjet recording method |
| EP1463045A2 (en) * | 2003-03-24 | 2004-09-29 | TDK Corporation | Optical recording medium, method for manufacturing the same and target used for sputtering process |
| US6906295B2 (en) * | 2003-02-20 | 2005-06-14 | National Material L.P. | Foodware with multilayer stick resistant ceramic coating and method of making |
| KR100541322B1 (en) * | 2002-12-10 | 2006-01-11 | 공주대학교 산학협력단 | Hard Thin Film Coatings Having Oxidation Resistance in High Temperature and its Manufacturing Method |
| EP1783245A1 (en) * | 2005-11-04 | 2007-05-09 | METAPLAS IONON Oberflächenveredelungstechnik GmbH | Layer system to form a surface layer on the surface of a substrate, coating process and substrate with a layer system |
| US7217466B2 (en) * | 2002-03-20 | 2007-05-15 | Joerg Guehring | Wear-resistant coating for metal-removing tools, particularly for rotary metal-cutting tools |
| US20070231501A1 (en) * | 2003-03-28 | 2007-10-04 | Finley James J | Substrates coated with mixtures of titanium and aluminum materials, methods for making the substrates, and cathode targets of titanium and aluminum metal |
| US7410707B2 (en) * | 2003-12-05 | 2008-08-12 | Sumitomo Electric Hardmetal Corp. | Surface-coated cutting tool |
| JP2009001905A (en) * | 2007-06-25 | 2009-01-08 | Sulzer Metaplas Gmbh | Layer structure for creating surface layer on surface of substrate, and arc vapor deposition source for manufacturing layer structure |
| JP2009041106A (en) * | 2008-09-08 | 2009-02-26 | Toshiba Corp | Sputtering target |
| WO2009034971A1 (en) | 2007-09-12 | 2009-03-19 | Fujifilm Corporation | Process for production of desubstituted compounds, organic semiconductor film and process for production of the film |
| EP2116628A1 (en) | 2008-04-24 | 2009-11-11 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Hard coating film and target for formation thereof |
| EP2163586A1 (en) | 2005-02-07 | 2010-03-17 | Fujifilm Corporation | Coloring matter, ink, ink for ink jet, ink jet recording method, color toner, and color filter |
| US7781146B2 (en) | 2002-11-22 | 2010-08-24 | Tdk Corporation | Optical recording medium |
| EP2362004A1 (en) * | 2010-02-16 | 2011-08-31 | Kabushiki Kaisha Kobe Seiko Sho | Hard-coating-coated member, tool, and target |
| 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 |
| CN102280156A (en) * | 2011-06-21 | 2011-12-14 | 大连宝原核设备有限公司 | Method for preparing aluminum-based boron carbide neutron absorption board |
| WO2012090826A1 (en) | 2010-12-28 | 2012-07-05 | 富士フイルム株式会社 | Coloring composition and azo compound |
| US8309235B2 (en) * | 2008-07-31 | 2012-11-13 | Sulzer Metaplas Gmbh | Multilayer film-coated member and method for producing it |
| US8309234B2 (en) * | 2008-07-31 | 2012-11-13 | Sulzer Metaplas Gmbh | Multilayer film-coated member and method for producing it |
| WO2013031428A1 (en) | 2011-08-30 | 2013-03-07 | 富士フイルム株式会社 | Novel compound having triazine side chain, colored composition, inkjet ink, inkjet recording method, color filter, and color toner |
| WO2013069667A1 (en) | 2011-11-08 | 2013-05-16 | 富士フイルム株式会社 | Coloured composition and ink for inkjet recording |
| WO2013099677A1 (en) | 2011-12-26 | 2013-07-04 | 富士フイルム株式会社 | Compound having xanthene skeleton, coloring composition, ink for ink jet printing, and ink jet printing method |
| WO2013129265A1 (en) | 2012-02-29 | 2013-09-06 | 富士フイルム株式会社 | Colored composition, inkjet recording ink, and inkjet recording method |
| EP2669337A1 (en) | 2012-05-30 | 2013-12-04 | Fujifilm Corporation | Compound having xanthene structure, coloring composition, ink for inkjet recording and inkjet recording method |
| EP2669338A2 (en) | 2012-05-31 | 2013-12-04 | Fujifilm Corporation | Coloring composition, ink for inkjet recording and inkjet recording method |
| WO2014077291A1 (en) | 2012-11-15 | 2014-05-22 | 富士フイルム株式会社 | Coloring composition, ink jet recording ink, ink jet recording method, ink jet printer cartridge, and ink jet recording material |
| WO2014077223A1 (en) | 2012-11-15 | 2014-05-22 | 富士フイルム株式会社 | Coloring composition, ink jet recording ink using coloring composition, ink jet recording method using ink jet recording ink, ink cartridge, and ink jet recording material |
| WO2015105108A1 (en) | 2014-01-10 | 2015-07-16 | 富士フイルム株式会社 | Compound, coloring composition, inkjet recording ink, inkjet recording method, inkjet printer cartridge, inkjet recorded material, color filter, color toner, and transfer ink |
| WO2018061784A1 (en) | 2016-09-30 | 2018-04-05 | 富士フイルム株式会社 | Aqueous solution, colorant composition, inkjet recording ink, inkjet recording method, and ink cartridge |
| CN108018463A (en) * | 2016-10-31 | 2018-05-11 | 烟台南山学院 | A kind of aluminium titanium tungsten ternary alloy three-partalloy target that high-temperaure coating is obtained in metal material surface plated film and preparation method thereof |
| CN110257687A (en) * | 2019-05-31 | 2019-09-20 | 河北宏靶科技有限公司 | A kind of alloy target material and preparation method thereof containing rare earth element |
| US11767587B2 (en) | 2017-02-28 | 2023-09-26 | Plansee Composite Materials Gmbh | Sputter target and method for producing a sputter target |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112496333A (en) * | 2020-11-26 | 2021-03-16 | 大连理工大学 | Preparation method and application of Si-Ti alloy nano powder |
-
1999
- 1999-04-14 JP JP11106118A patent/JP3084402B1/en not_active Expired - Lifetime
Cited By (53)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1698714A2 (en) * | 2000-12-28 | 2006-09-06 | Kabushiki Kaisha Kobe Seiko Sho | Target used to form a hard film |
| EP1219723A3 (en) * | 2000-12-28 | 2002-09-04 | Kabushiki Kaisha Kobe Seiko Sho | Hard film for cutting tools |
| EP1992717A1 (en) * | 2000-12-28 | 2008-11-19 | Kabushiki Kaisha Kobe Seiko Sho | Target used to form a hard film |
| AU780899B2 (en) * | 2000-12-28 | 2005-04-21 | Kabushiki Kaisha Kobe Seiko Sho (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 |
| EP1698714A3 (en) * | 2000-12-28 | 2006-09-27 | Kabushiki Kaisha Kobe Seiko Sho | Target used to form a hard film |
| EP1219723A2 (en) * | 2000-12-28 | 2002-07-03 | Kabushiki Kaisha Kobe Seiko Sho | Hard film for cutting tools |
| US7217466B2 (en) * | 2002-03-20 | 2007-05-15 | Joerg Guehring | Wear-resistant coating for metal-removing tools, particularly for rotary metal-cutting tools |
| EP1348776A1 (en) * | 2002-03-29 | 2003-10-01 | Kabushiki Kaisha Kobe Seiko Sho | Target for arc ion plating and method of manufacturing the same |
| JP2003286564A (en) * | 2002-03-29 | 2003-10-10 | Kobe Steel Ltd | Target for physical vapor deposition and manufacturing method therefor |
| JP2003286566A (en) * | 2002-03-29 | 2003-10-10 | Kobe Steel Ltd | Target for arc ion plating of cathode discharge type and manufacturing method therefor |
| US7781146B2 (en) | 2002-11-22 | 2010-08-24 | Tdk Corporation | Optical recording medium |
| KR100541322B1 (en) * | 2002-12-10 | 2006-01-11 | 공주대학교 산학협력단 | Hard Thin Film Coatings Having Oxidation Resistance in High Temperature and its Manufacturing Method |
| EP1437388A1 (en) | 2003-01-08 | 2004-07-14 | Fuji Photo Film Co., Ltd. | Coloring composition and inkjet recording method |
| 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 |
| US7018694B2 (en) | 2003-03-24 | 2006-03-28 | Tdk Corporation | Optical recording medium, method for manufacturing the same and target used for sputtering process |
| EP1463045A3 (en) * | 2003-03-24 | 2005-06-01 | TDK Corporation | Optical recording medium, method for manufacturing the same and target used for sputtering process |
| CN1320542C (en) * | 2003-03-24 | 2007-06-06 | Tdk株式会社 | Optical recording medium, method for manufacturing the same and target used for sputtering process |
| EP1463045A2 (en) * | 2003-03-24 | 2004-09-29 | TDK Corporation | Optical recording medium, method for manufacturing the same and target used for sputtering process |
| US8597474B2 (en) * | 2003-03-28 | 2013-12-03 | Ppg Industries Ohio, Inc. | Substrates coated with mixtures of titanium and aluminum materials, methods for making the substrates, and cathode targets of titanium and aluminum metal |
| US20070231501A1 (en) * | 2003-03-28 | 2007-10-04 | Finley James J | Substrates coated with mixtures of titanium and aluminum materials, methods for making the substrates, and cathode targets of titanium and aluminum metal |
| US7410707B2 (en) * | 2003-12-05 | 2008-08-12 | Sumitomo Electric Hardmetal Corp. | Surface-coated cutting tool |
| EP2163586A1 (en) | 2005-02-07 | 2010-03-17 | Fujifilm Corporation | Coloring matter, ink, ink for ink jet, ink jet recording method, color toner, and color filter |
| EP1783245A1 (en) * | 2005-11-04 | 2007-05-09 | METAPLAS IONON Oberflächenveredelungstechnik GmbH | Layer system to form a surface layer on the surface of a substrate, coating process and substrate with a layer system |
| EP2256229A1 (en) * | 2005-11-04 | 2010-12-01 | Sulzer Metaplas GmbH | Layer system to form a surface layer on the surface of a substrate, coating process and substrate with a layer system |
| US7935426B2 (en) | 2005-11-04 | 2011-05-03 | Sulzer Metaplas Gmbh | Layer arrangement for the formation of a coating on a surface of a substrate, coating method, and substrate with a layer arrangement |
| JP2009001905A (en) * | 2007-06-25 | 2009-01-08 | Sulzer Metaplas Gmbh | Layer structure for creating surface layer on surface of substrate, and arc vapor deposition source for manufacturing layer structure |
| EP2009134A3 (en) * | 2007-06-25 | 2009-03-04 | Sulzer Metaplas GmbH | Layer system for creating a surface layer on a surface of a substrate, vaporisation source for manufacturing a layer system |
| WO2009034971A1 (en) | 2007-09-12 | 2009-03-19 | Fujifilm Corporation | Process for production of desubstituted compounds, organic semiconductor film and process for production of the film |
| US8025990B2 (en) | 2008-04-24 | 2011-09-27 | Kobe Steel, Ltd. | Hard coating film and target for formation thereof |
| EP2116628A1 (en) | 2008-04-24 | 2009-11-11 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Hard coating film and target for formation thereof |
| US8309235B2 (en) * | 2008-07-31 | 2012-11-13 | Sulzer Metaplas Gmbh | Multilayer film-coated member and method for producing it |
| US8309234B2 (en) * | 2008-07-31 | 2012-11-13 | Sulzer Metaplas Gmbh | Multilayer film-coated member and method for producing it |
| JP2009041106A (en) * | 2008-09-08 | 2009-02-26 | Toshiba Corp | Sputtering target |
| 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 |
| EP2362004A1 (en) * | 2010-02-16 | 2011-08-31 | Kabushiki Kaisha Kobe Seiko Sho | Hard-coating-coated member, tool, and target |
| US8475942B2 (en) | 2010-02-16 | 2013-07-02 | Kobe Steel, Ltd. | Hard-coating-coated member, tool, and target |
| WO2012090826A1 (en) | 2010-12-28 | 2012-07-05 | 富士フイルム株式会社 | Coloring composition and azo compound |
| CN102280156A (en) * | 2011-06-21 | 2011-12-14 | 大连宝原核设备有限公司 | Method for preparing aluminum-based boron carbide neutron absorption board |
| CN102280156B (en) * | 2011-06-21 | 2013-09-18 | 大连宝原核设备有限公司 | Method for preparing aluminum-based boron carbide neutron absorption board |
| WO2013031428A1 (en) | 2011-08-30 | 2013-03-07 | 富士フイルム株式会社 | Novel compound having triazine side chain, colored composition, inkjet ink, inkjet recording method, color filter, and color toner |
| WO2013069667A1 (en) | 2011-11-08 | 2013-05-16 | 富士フイルム株式会社 | Coloured composition and ink for inkjet recording |
| WO2013099677A1 (en) | 2011-12-26 | 2013-07-04 | 富士フイルム株式会社 | Compound having xanthene skeleton, coloring composition, ink for ink jet printing, and ink jet printing method |
| WO2013129265A1 (en) | 2012-02-29 | 2013-09-06 | 富士フイルム株式会社 | Colored composition, inkjet recording ink, and inkjet recording method |
| EP2669337A1 (en) | 2012-05-30 | 2013-12-04 | Fujifilm Corporation | Compound having xanthene structure, coloring composition, ink for inkjet recording and inkjet recording method |
| EP2669338A2 (en) | 2012-05-31 | 2013-12-04 | Fujifilm Corporation | Coloring composition, ink for inkjet recording and inkjet recording method |
| WO2014077291A1 (en) | 2012-11-15 | 2014-05-22 | 富士フイルム株式会社 | Coloring composition, ink jet recording ink, ink jet recording method, ink jet printer cartridge, and ink jet recording material |
| WO2014077223A1 (en) | 2012-11-15 | 2014-05-22 | 富士フイルム株式会社 | Coloring composition, ink jet recording ink using coloring composition, ink jet recording method using ink jet recording ink, ink cartridge, and ink jet recording material |
| WO2015105108A1 (en) | 2014-01-10 | 2015-07-16 | 富士フイルム株式会社 | Compound, coloring composition, inkjet recording ink, inkjet recording method, inkjet printer cartridge, inkjet recorded material, color filter, color toner, and transfer ink |
| WO2018061784A1 (en) | 2016-09-30 | 2018-04-05 | 富士フイルム株式会社 | Aqueous solution, colorant composition, inkjet recording ink, inkjet recording method, and ink cartridge |
| CN108018463A (en) * | 2016-10-31 | 2018-05-11 | 烟台南山学院 | A kind of aluminium titanium tungsten ternary alloy three-partalloy target that high-temperaure coating is obtained in metal material surface plated film and preparation method thereof |
| US11767587B2 (en) | 2017-02-28 | 2023-09-26 | Plansee Composite Materials Gmbh | Sputter target and method for producing a sputter target |
| CN110257687A (en) * | 2019-05-31 | 2019-09-20 | 河北宏靶科技有限公司 | A kind of alloy target material and preparation method thereof containing rare earth element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3084402B1 (en) | 2000-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3084402B1 (en) | AlTi-based alloy sputtering target, wear-resistant AlTi-based alloy hard coating, and method of forming the same | |
| US7070643B2 (en) | Compositionally graded sintered alloy and method of producing the same | |
| JP2622131B2 (en) | Alloys for cutting tools | |
| US4973356A (en) | Method of making a hard material with properties between cemented carbide and high speed steel and the resulting material | |
| EP0646186B1 (en) | Sintered extremely fine-grained titanium based carbonitride alloy with improved toughness and/or wear resistance | |
| JP3080983B2 (en) | Hard sintered alloy having gradient composition structure and method for producing the same | |
| JPS6112847A (en) | Sintered hard alloy containing fine tungsten carbide particles | |
| JP3089262B1 (en) | AlTi-based alloy sputtering target, wear-resistant AlTi-based alloy hard coating, and method of forming the same | |
| JP2000328170A (en) | Cubic boron nitride-containing hard member and its production | |
| JP2893886B2 (en) | Composite hard alloy material | |
| JP3366659B2 (en) | Heterogeneous layer surface-finished sintered alloy and method for producing the same | |
| JP4069749B2 (en) | Cutting tool for roughing | |
| JPH0681072A (en) | Tungsten carbide base sintered hard alloy | |
| JP2796011B2 (en) | Whisker reinforced cemented carbide | |
| JPS6256944B2 (en) | ||
| JP2819648B2 (en) | Coated cemented carbide for wear-resistant tools | |
| JPH10324943A (en) | Ultra-fine cemented carbide, and its manufacture | |
| JP3762278B2 (en) | Cemented carbide and method for producing the same | |
| JP2932658B2 (en) | Powder sintered titanium and method for producing powder sintered titanium base alloy | |
| JP2003094207A (en) | Cutting tool | |
| RU2133296C1 (en) | Solid alloy (variants) and method of preparing thereof | |
| JP2893887B2 (en) | Composite hard alloy material | |
| JP2023048855A (en) | Hard sintered body, method for producing hard sintered body, cutting tool, wear-resistant tool and high-temperature member | |
| JPH11172364A (en) | Production of sintered tool steel | |
| JPS6335706B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20000530 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070707 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080707 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080707 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080707 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090707 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090707 Year of fee payment: 9 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090707 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100707 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110707 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110707 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120707 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130707 Year of fee payment: 13 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |