JPH02194159A - Formation of wear resistant coating film - Google Patents
Formation of wear resistant coating filmInfo
- Publication number
- JPH02194159A JPH02194159A JP63278324A JP27832488A JPH02194159A JP H02194159 A JPH02194159 A JP H02194159A JP 63278324 A JP63278324 A JP 63278324A JP 27832488 A JP27832488 A JP 27832488A JP H02194159 A JPH02194159 A JP H02194159A
- Authority
- JP
- Japan
- Prior art keywords
- film
- composition
- cathode
- cutting tool
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title abstract description 7
- 239000011248 coating agent Substances 0.000 title abstract description 6
- 230000015572 biosynthetic process Effects 0.000 title description 11
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001241 arc-discharge method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 abstract description 25
- 229910045601 alloy Inorganic materials 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 8
- 239000012298 atmosphere Substances 0.000 abstract description 3
- 238000010891 electric arc Methods 0.000 abstract description 3
- 229910018575 Al—Ti Inorganic materials 0.000 abstract 3
- 229910009043 WC-Co Inorganic materials 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 abstract 1
- 238000007733 ion plating Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000758 substrate Substances 0.000 description 16
- 239000006104 solid solution Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000997 High-speed steel Inorganic materials 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001315 Tool steel Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 102220130791 rs886045975 Human genes 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、フライス加工工具等の表面に、密着性の優れ
た耐摩耗性皮膜を効率良く形成する方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for efficiently forming a wear-resistant film with excellent adhesion on the surface of a milling tool or the like.
［従来の技術］
高速度工具鋼や超硬合金工具鋼等を製作する場合は、耐
摩耗性等の性能をより優れたものとすることを目的とし
て、工具基材の表面にＴｉ等の窒化物や炭化物よりなる
耐摩耗性皮膜を形成することが行なわれている。[Prior art] When manufacturing high-speed tool steel, cemented carbide tool steel, etc., nitriding such as Ti is applied to the surface of the tool base material in order to improve performance such as wear resistance. Formation of a wear-resistant film made of carbide or carbide has been carried out.
基材表面に耐摩耗性皮膜を形成する方法としては、従来
よりＣＶＤ法（化学的蒸着法）及びＰＶＤ法（物理的蒸
着法）が知られている。しかし前者の方法では母材が高
温処理に曝される為母材特性が劣化するおそれがあり、
母材特性も重要視される工具の場合は後者の方法が好ま
れ、例えばＰＶＤ法によるＴｉＮ皮膜等が汎用されてい
た。ＴｉＮ皮膜は耐熱性が良好であって、切削時の加工
熱や摩擦熱による工具すくい面のクレータ摩耗を抑制す
る機能を発揮する。CVD (chemical vapor deposition) and PVD (physical vapor deposition) are conventionally known methods for forming a wear-resistant film on the surface of a base material. However, in the former method, the base material is exposed to high temperature treatment, which may cause the base material properties to deteriorate.
The latter method is preferred in the case of tools in which base material properties are also important, and for example, TiN coating by PVD method has been widely used. The TiN film has good heat resistance and exhibits the function of suppressing crater wear on the tool rake face due to machining heat and frictional heat during cutting.
しかしながら近年、切削速度の一層の高速化が要望され
ており、切削条件がより過酷化する傾向にある為、上記
した様な従来のＴｉＮ皮膜程度ではこの要請に応えきれ
なくなっている。However, in recent years, there has been a demand for higher cutting speeds, and cutting conditions have tended to become more severe, so the conventional TiN coatings described above are no longer able to meet this demand.
そこで耐熱性や硬度が更に優れた皮膜として、イオンブ
レーティング法やスパッタリング法によるＴ ｉ Ａ
Ｉ Ｎ、 Ｔ ｉ Ａ Ｉ Ｃ，或はＴｉＡｌＣＮ等の
皮膜が提案された［特開昭６２−５６５６５゜ジャーナ
ル・バキューム・ソサエティ・テクノロジー（Ｊ、 Ｖ
ａｃ、 Ｓｃｉ、 Ｔｅｃｈｎｏｌｙ）Ａ第４（６）巻
、Ｉｎ２年、第２７１７頁、 Ｊ、 ｏｆ ５ｏｌｉｄ
ＳｔａｔｅＣｈｅｍｉｓｔｒｙ、７０．１９８７年、
第３１８〜３２２頁］。Therefore, as a film with even better heat resistance and hardness, T i A using ion blating method or sputtering method was developed.
Films such as IN, TiAIC, or TiAlCN have been proposed [Japanese Patent Application Laid-Open No. 62-56565゜Journal Vacuum Society Technology (J, V
ac, Sci, Technology) Volume 4(6), In2, Page 2717, J, of 5olid
StateChemistry, 70.1987,
pp. 318-322].
［発明が解決しようとする課題］
しかしながらこの様な従来方法による皮膜の形成には、
次の様な問題があった。[Problems to be solved by the invention] However, in forming a film by such a conventional method,
There were the following problems.
（イ） イオンブレーティングの場合
従来のイオンブレーティング法は、蒸着金属をるつぼ内
で溶融・蒸発させる方式である為、蒸発源の設置位置が
制約される。この為複雑な形状の基材を被覆する場合は
生産性が低い、また複数の金属を蒸発させて基材表面上
で合金化させたい場合が多いにもかかわらず、個々の蒸
発金属には蒸気圧差があり、皮膜の合金組成を安定的に
コントロールすることが困難であった。(B) In the case of ion blating In the conventional ion blating method, the deposited metal is melted and evaporated in a crucible, so the installation position of the evaporation source is restricted. For this reason, productivity is low when coating a base material with a complex shape, and although it is often desired to evaporate multiple metals and alloy them on the surface of the base material, individual evaporated metals cannot be coated with steam. Because of the pressure difference, it was difficult to stably control the alloy composition of the film.
（０）スパッタリング法の場合
皮膜の密着性が必らずしも良好でなく、また複雑な形状
の基材を被覆する場合の生産性も低い。(0) In the case of the sputtering method, the adhesion of the film is not necessarily good, and the productivity is also low when coating a substrate with a complicated shape.
更にターゲットとしてＡ１．Ｔｉ、、や（ＡｌｘＴ ｉ
ｒ −ｘ ） Ｎ等を使用する場合は、スパッタ率が
経時的に変化し易いためこの変化を見込んだ組成のター
ゲットを要する。またスパッタ粒子のイオン化率が低い
ため、基板に突入するイオン量が少なく、従って十分な
膜密着性が得られないという欠点があった。しかも成膜
速度が遅く量産化が困難である。Furthermore, A1 as a target. Ti,,ya(AlxT i
When using N, etc., the sputtering rate tends to change over time, so a target with a composition that takes into account this change is required. Furthermore, since the ionization rate of the sputtered particles is low, the amount of ions that enter the substrate is small, resulting in a disadvantage that sufficient film adhesion cannot be obtained. Moreover, the film formation rate is slow and mass production is difficult.
次に組成に関する問題点について述べる。Next, problems related to composition will be discussed.
（Ａ）特開昭６２−５６５６５には（Ｔｉ、ＡＩ）Ｃ。(A) (Ti, AI)C in JP-A No. 62-56565.
（Ｔｉ、ＡＩ）Ｎおよび（Ｔｉ、Ａｌ）ｃＮと記述され
ているに止まり、ＴｉとＡＩの比率またＣとＮの比率に
ついて明確な記述がなく、すべての組成が適用できるも
のでない。It is only described as (Ti, AI)N and (Ti, Al)cN, but there is no clear description of the ratio of Ti to AI or the ratio of C to N, and not all compositions can be applied.
（ニ）さらにＪ、 Ｖａｃ、 Ｓｃ１． Ｔｅｃｈｎｏ
ｌ、、Ａ ４ （［ｉ）。(d) Furthermore, J, Vac, Sc1. Techno
l,, A 4 ([i).
１９８６年の論文には（Ｔｉ、ＡＩ）ＨにおいてＴｉ
：Ａ１＝７５：２５．Ｔｉ ：Ａ１冨５０：５０の組成
が記述されているにすぎない。これらの組成を固溶体成
分で記述すれば、ＴｉＮ−ＡＩＮ固溶体と表現でき、Ｔ
ｉＮを基本組成としてＡＩＮが最高５０モル％固溶した
ものと言える。In the 1986 paper, Ti in (Ti, AI)H
:A1=75:25. Only a composition of Ti:A1 concentration of 50:50 is described. If these compositions are described in terms of solid solution components, they can be expressed as TiN-AIN solid solutions, and T
It can be said that the basic composition is iN with a maximum of 50 mol% of AIN in solid solution.
（ネ） Ｊ、 ｏｆ ５ｏｌｉｄ ５ｔａｔｅ
Ｃｈｅｍｉｓｔｒｙ、７０ （１９ａ７年）の論
文には（Ｔｉ、ＡＩ）Ｈにおいて、全組成中ＡＩが３０
ａｔ％固溶できると記述されている。(ne) J, of 5olid 5tate
In the paper Chemistry, 70 (19a7), in (Ti, AI)H, AI is 30% in the total composition.
It is described that it can be dissolved in solid solution at %.
しかし上記（八）〜 （ネ）の組成では、ＡＩＮの高熱
伝導性、耐酸化性が十分発揮できるものとはいえないも
のである。However, the compositions (8) to (4) above cannot be said to fully exhibit the high thermal conductivity and oxidation resistance of AIN.
本発明は、ＡｌＮ−ＴｉＮ系全組成域について詳細に調
べ、ＡＩＮを基本組成としてＡＩＮ単組成の弱点をＴｉ
Ｎの固溶により改善し、その組成域を特定したものであ
って、耐摩耗性及び密着性に優れた皮膜を効率よく形成
することのできる様な皮膜形成方法を提供しようとする
ものである。In the present invention, the entire composition range of the AlN-TiN system was investigated in detail, and the weak points of the AIN single composition were investigated using AIN as the basic composition.
The objective is to provide a film forming method that can be improved by solid solution of N, and its composition range has been specified, and that can efficiently form a film with excellent wear resistance and adhesion. .
［課題を解決する為の手段］
本発明は基材表面に耐摩耗性皮膜を形成するに当たり、
化学組成が
（Ａ ｌｘ Ｔ ｉ ｌ−１１）（Ｎｙ Ｃｔ−ｙ ）
但し ０．５６≦ｘ≦０．７５
０．６ ≦ｙ≦１
膜厚：０．８〜１０μｍ
で示される耐摩耗性皮膜を、蒸発源としてカソードを用
いるアーク放電方式によって形成することを要旨とする
ものである。[Means for Solving the Problems] The present invention provides the following steps in forming a wear-resistant film on the surface of a base material:
The chemical composition is (A lx T i l-11) (Ny Ct-y)
However, 0.56≦x≦0.75 0.6≦y≦1 Film thickness: 0.8 to 10 μm The gist is to form a wear-resistant film using an arc discharge method using a cathode as an evaporation source. It is something to do.
［作用］
本発明においては、カソードを蒸発源とするアーク放電
によりて金属成分をイオン化するものであって、イオン
ブレーティング法やスパッタリング法等に代表されるＰ
ＶＤ法によって行なうことができるものである。これら
のうち例えばイオンブレーティング法で行なう場合を代
表的に取り上げて説明すると、前記の様にイオン化した
金属成分をＮ２雰囲気又はＮ２／ＣＨ４雰囲気中で反応
させる。カソードとしてはＴｉ及びＡＩをそれぞれ個別
に使用することもできるが、目的組成そのものからなる
ＡｌｘＴｉｔ−＋ｇをターゲットとすれば、皮膜組成の
コントロールが容易である。この場合の各合金成分の蒸
発は、数十アンペア以上の大電流域で行なわれるため、
カソード物質の組成ずれは殆んど生じない、しかもイオ
ン化効率が高く反応性に富み、基板にバイアス電圧を印
加することによって密着性の優れた皮膜が得られる。[Function] In the present invention, metal components are ionized by arc discharge using a cathode as an evaporation source, and the P
This can be done by the VD method. Among these methods, for example, the case where the ion blating method is used will be described as a representative example.The ionized metal components as described above are reacted in an N2 atmosphere or an N2/CH4 atmosphere. Although Ti and AI can be used individually as the cathode, the film composition can be easily controlled if AlxTit-+g, which has the desired composition itself, is targeted. In this case, each alloy component is evaporated in a large current range of several tens of amperes or more, so
The cathode material has almost no compositional deviation, has high ionization efficiency and high reactivity, and can obtain a film with excellent adhesion by applying a bias voltage to the substrate.
この様にして得られる皮膜の組成は
（Ａ Ｉ Ｘ ”ｒ ｉ １−Ｘ）（ＮｙＣｌ−ｙ ）
但し ０．５６≦ｘ≦０．７５
０．８≦ｙ≦１
であることが必要であり、好ましくは０．６≦ｘ≦０．
７である。The composition of the film obtained in this way is (A I X "r i 1-X) (NyCl-y)
However, it is necessary that 0.56≦x≦0.75, 0.8≦y≦1, and preferably 0.6≦x≦0.
It is 7.
上記皮膜組成からなる本発明の固溶体は、これを窒化物
系で代表して説明すると、ＡｌＮ−ＴｉＮを端組成とす
る固溶体であり、種々の成分範囲について調べた結果、
第１図（＾）及び（Ｂ）に示すような結晶構造を有する
ことが明らかとなった。第１図（Ａ）において（Ｐ）は
ＮａＣ１型（Ｂｌ構造）領域、（Ｑ）はＺｎＳ型（ウル
ツァイト型）領域である。即ち本発明の成分範囲は、第
１図（Ａ） 、 （Ｂ）から明らかなように、Ｂ１構造
を有する組成範囲内で、ＡＩＮにＴｉＮが２５〜４４モ
ル％固溶した固溶体である。この範囲に限定した理由を
以下に述べる。The solid solution of the present invention having the above-mentioned film composition is a solid solution having an end composition of AlN-TiN, as a representative example of a nitride system.As a result of investigating various component ranges,
It was revealed that it had a crystal structure as shown in FIGS. 1(^) and (B). In FIG. 1(A), (P) is a NaCl type (Bl structure) region, and (Q) is a ZnS type (wurtzite type) region. That is, as is clear from FIGS. 1(A) and 1(B), the component range of the present invention is a solid solution in which 25 to 44 mol % of TiN is dissolved in AIN within the composition range having the B1 structure. The reason for limiting to this range will be described below.
第１図（Ｂ）から明らかな様にＡＩ量（Ｘ）が０．７５
を超える場合は、皮膜組成がＡＩＮに近似してくる結果
、皮膜の軟質化を招き、十分な硬度が得られなくなり、
フランク摩耗を容易に引き起す、一方Ｘが０．７５以下
になると、皮膜は高硬度化し、フランク摩耗量は減少す
る。しかしＡＩＮの高耐酸化特性を有効に発揮する下限
として以下のように決めた。As is clear from Figure 1 (B), the AI amount (X) is 0.75
If it exceeds this, the film composition will approach AIN, resulting in softening of the film and insufficient hardness.
Flank wear is easily caused. On the other hand, when X is less than 0.75, the coating becomes highly hard and the amount of flank wear decreases. However, the lower limit for effectively exhibiting the high oxidation resistance properties of AIN was determined as follows.
即ち（ＡＩＩｌＴｉｔ−ｘ）Ｎ［但しｘ ＝ ０ 、０
．２５゜Ｑ、５ 、０．６ ］を大気中、昇温速度５℃
／分で昇温酸化した場合の温度変化に対する酸化量の変
化を測定したところ、第２図に示す結果が得られた。That is, (AIIlTit-x)N [where x = 0, 0
．． 25゜Q,5,0.6] in the atmosphere, heating rate 5℃
When the change in the amount of oxidation with respect to the temperature change was measured when the temperature was increased to oxidize at a rate of 1/min, the results shown in FIG. 2 were obtained.
第２図よりＡＩ量が増加するにつれて酸化開始温度が上
昇することがわかる。一方工具切削中の刃先温度の上昇
による皮膜の酸化を十分に抑制する為には、切削熱によ
るクレータ摩耗量を低下させる必要がある。この様な観
点から第２図を見ると、できる限りＡＩＮ成分に富んだ
組成範囲とすることが有効であることがわかる。したが
って、工具刃先温度が切削中にａＯＯ℃以上になること
を考慮して、酸化開始温度がａＯＯ℃以上の組成をｘ
＝ ０．５６と決めた。It can be seen from FIG. 2 that as the amount of AI increases, the oxidation initiation temperature increases. On the other hand, in order to sufficiently suppress the oxidation of the film due to the rise in the temperature of the cutting edge during tool cutting, it is necessary to reduce the amount of crater wear caused by cutting heat. Looking at FIG. 2 from this perspective, it can be seen that it is effective to have a composition range as rich in AIN components as possible. Therefore, taking into account that the tool edge temperature will become more than aOO℃ during cutting, the composition with an oxidation start temperature of aOO℃ or more will be x
= 0.56.
又本発明では炭窒化物を形成することによってＴｉｃの
高硬度性（常温硬度Ｈｖ：約３１００ｋｇ／ｍｍ’）を
発揮させるものである。即ち本発明の組成式においてｙ
の値が減少するにつれて硬度が大となり耐摩耗性は向上
する。第３図は、超硬チップ（ＷＣ−１０％Ｃｏを主成
分とする）に（Ａ １ ｏ、ａｓＴ ｔ ｏ、３ｓ）
（Ｎｙ Ｃｒ−ｙ ） ［但しｙ＝０．４ 、０．
６ 、０．８ 、０．９ 、 １ ］を３μｍ被覆し、
被剛材３５０Ｃを切削速度１７０ ｍ／ｍｉｎ 、送り
速度０．２５ｍｍ／ｒｅｖ 、切り込み０．１ｍｍで切
削した時の１５分後のクレータ摩耗量を測定した結果を
示す、この結果にみられるようにｙが０．６未満になる
と耐酸化性が低下してクレータ摩耗を起こし易くなる。Further, in the present invention, the high hardness of Tic (room temperature hardness Hv: about 3100 kg/mm') is exhibited by forming carbonitride. That is, in the composition formula of the present invention, y
As the value of decreases, the hardness increases and the wear resistance improves. Figure 3 shows a cemented carbide tip (WC-based on 10% Co) (A 1 o, asT to 3s).
(NyCr-y) [However, y=0.4, 0.
6, 0.8, 0.9, 1] to a thickness of 3 μm,
This shows the results of measuring the amount of crater wear after 15 minutes when cutting a 350C rigid material at a cutting speed of 170 m/min, a feed rate of 0.25 mm/rev, and a depth of cut of 0.1 mm. When y is less than 0.6, oxidation resistance decreases and crater wear tends to occur.
ｙ≧０．６の範囲では耐酸化性の顕著な低下はみられな
い。In the range of y≧0.6, no significant decrease in oxidation resistance is observed.
尚後述する実施例及び比較例から明らかな様に、膜厚が
０．８μｍ未満の場合は耐摩耗性が不十分となり、一方
１０μｍを超えると膜自体にクラックが入り易く、強度
が不十分となる。As is clear from the Examples and Comparative Examples described below, if the film thickness is less than 0.8 μm, the wear resistance will be insufficient, while if it exceeds 10 μm, the film itself will easily crack and the strength will be insufficient. Become.
以下実施例について説明するが１５本発明は下記の実施
例に限定されるものではなく、前・後記の趣旨に徴して
適宜設計変更することは本発明の技術的範囲に含まれる
。Examples will be described below, but the present invention is not limited to the following examples, and it is within the technical scope of the present invention to make appropriate design changes in accordance with the spirit described above and below.
［実施例］
実施例Ｉ
Ａ１゜６ Ｔ １ ｏ、４をカソード電極とするカソー
ドアーク方式イオンブレーティング装置の基板ホルダー
に超硬合金製チップ（ｗｃ−ｔｏ％Ｃｏを主成分とする
）を取付けた。尚本装置には、耐摩耗性皮膜形成状態の
均一性を確保する為の基材回転機構等及びヒータを設置
した。[Example] Example I A cemented carbide chip (mainly composed of wc-to%Co) was attached to the substrate holder of a cathode arc type ion blating device using A1゜6 T 1 o, 4 as the cathode electrode. Ta. This device was equipped with a base material rotation mechanism and a heater to ensure uniformity in the formation of the wear-resistant film.
成膜に当たっては、ヒータによって基材温度を４００℃
に加熱保持したまま、基材に一７０Ｖのバイアス電圧を
印加すると共に、装置内に高純度Ｎ２ガスをフＸ １Ｏ
−３Ｔｏｒｒまで導入し、アーク放電を開始して基材表
面に膜厚４μｍの皮膜を形成した。膜厚の測定は、基板
ホルダーに同時に取り付けた基材の内の１個を破断し、
膜断面を走査型電子顕微鏡で観察して測定したものであ
る。さらに膜組成の定量は、同じく同時に取り付けた基
材につきオージェ分光分析法により膜深さ方向の分析を
行なった。その結果ＡＩ、Ｔｉ、Ｎの膜厚さ方向には濃
度変化がなく一定で、各成分元素のピーク高さから、膜
組成は（Ａ Ｉ ０．ｌｌ２Ｔ ｉ ｏ３ａ）Ｎであっ
た。−膜中の金属成分比Ｔｉ／Ａｌはカソード成分比と
ずれがなく殆んど同一といえる。During film formation, the substrate temperature was kept at 400°C using a heater.
A bias voltage of -70V was applied to the substrate while heating and holding the substrate, and high purity N2 gas was blown into the apparatus at
-3 Torr was introduced, arc discharge was started, and a film with a thickness of 4 μm was formed on the surface of the base material. To measure the film thickness, break one of the substrates attached to the substrate holder at the same time,
The cross-section of the membrane was observed and measured using a scanning electron microscope. Furthermore, to quantify the film composition, the film depth direction was analyzed using Auger spectroscopy on the base material attached at the same time. As a result, the concentrations of AI, Ti, and N were constant with no change in the film thickness direction, and the film composition was (A I 0.ll2T io3a)N based on the peak height of each component element. - The metal component ratio Ti/Al in the film has no deviation from the cathode component ratio and can be said to be almost the same.
実施例２
Ａ１ｏｙＴｉｏｓカソードを用いた以外は、実施例１と
同一条件で成膜を行なった。成膜した膜厚は３．８μｍ
であり、膜組成は（Ａ１０．７７ ｉ ｏ、 ｓｓ）
Ｎであった。Example 2 Film formation was carried out under the same conditions as in Example 1, except that an A1oyTios cathode was used. The thickness of the film formed was 3.8μm
and the film composition is (A10.77 io, ss)
It was N.
実施例３
反応性ガスとしてＮ ｘ ／ ＣＨａ混合ガスを用いた
以外は実施例１と同一条件で成膜を行なった。成膜した
膜厚は４．３μｍであり、膜組成は（Ａ Ｉ ０．６１
Ｔ ｉ Ｏ，３９） （Ｎｏ）Ｃ８３）でありた。Example 3 Film formation was carried out under the same conditions as in Example 1 except that N x /CHa mixed gas was used as the reactive gas. The thickness of the formed film was 4.3 μm, and the film composition was (A I 0.61
T i O, 39) (No) C83).
（比較例） 比較の為次の試料を用意した。(Comparative example) The following samples were prepared for comparison.
比較例１
実施例１の基材に皮膜を形成しない試料比較例２
Ｔｉカソードを用いてＮ２ガスを７ Ｘ １０−’Ｔｏ
ｒｒまで導入し実施例１と同一条件でＴｉＮの成膜を行
なった。成膜した膜厚は４．３ μｍであった。Comparative Example 1 Sample in which a film is not formed on the base material of Example 1 Comparative Example 2 N2 gas was applied to the substrate using a Ti cathode at 7 x 10-'To
A TiN film was formed under the same conditions as in Example 1 by introducing up to rr. The thickness of the deposited film was 4.3 μm.
比較例３
蒸発器の加熱源として電子ビーム（Ｅ、Ｂｙ）を使用し
たイオンブレーティング装置を用いて、るつぼに実施例
１で使用したカソード物質と同一のＡ Ｉ （１，ａ
Ｔ ｉ Ｏ，４固溶体を装入し、基板ホルダーには超硬
合金製チップを取り付けた。膜の均−性及び膜の密着性
を確保するため、基板回転機構等を設置すると共にヒー
ターを設置した。成膜にあたってはヒーターにより基材
温度を４００℃に加熱保持したまま、基材に−ａｏｏｖ
のバイアス電圧を印加し、装置内に高純度Ｎ２を７×１
０−’ Ｔｏｒｒまで導入しイオンブレーティング法に
より基材に成膜を行なった。膜厚は４μｍとした。さら
に実施例１と同様の分析方法により皮膜を分析した結果
、ＡＩとＴｉの濃度比が膜厚方向に不均一で膜の成分比
は規定できなかった。Comparative Example 3 Using an ion brating device using an electron beam (E, By) as a heating source for the evaporator, a crucible was charged with A I (1, a
A T i O,4 solid solution was charged, and a cemented carbide chip was attached to the substrate holder. In order to ensure the uniformity of the film and the adhesion of the film, a heater was installed as well as a substrate rotation mechanism. During film formation, the substrate temperature was maintained at 400°C using a heater, and -aoov was applied to the substrate.
Apply a bias voltage of 7×1 high purity N2 into the device.
A film was formed on the substrate by the ion blating method with the introduction down to 0-' Torr. The film thickness was 4 μm. Furthermore, as a result of analyzing the film using the same analytical method as in Example 1, the concentration ratio of AI and Ti was non-uniform in the film thickness direction, and the component ratio of the film could not be defined.
特に基材と膜の界面にはＡＩの濃縮が観察され、Ｅ、Ｂ
、溶解の初期にＡ１が優先的に蒸発付着したものと考え
られる。In particular, concentration of AI was observed at the interface between the substrate and the membrane, and E, B
It is considered that A1 was preferentially evaporated and deposited at the early stage of dissolution.
比較例４
実施例１と同一のカソード物質であるＡｌｏ、５Ｔｉ（
、，４ターゲツトを製作し、スパッタリング装置を用い
てＡ ｒ ／ Ｎ ２混合ガスによる反応性スパッタリ
ング法にて超硬チップに成膜を行な〕た。得られた膜厚
は３μｍであった。膜を分析した結果、平均として（Ａ
１ ｏ、ｙａＴ ｉ Ｏ，２２） Ｎと判定された。Comparative Example 4 The same cathode materials as in Example 1, Alo, 5Ti (
, 4 targets were prepared, and a film was formed on a carbide tip by a reactive sputtering method using an Ar/N 2 mixed gas using a sputtering device. The obtained film thickness was 3 μm. As a result of analyzing the membrane, as an average (A
1 o, yaT i O, 22) It was determined to be N.
ＡＩ酸成分優先的にスパッタされたものと考えられる。It is thought that the AI acid component was preferentially sputtered.
比較例５
カソード物質としてＡ１゜４５Ｔ ｉ ｏ、 ｓｓツタ
−ットを製作し、実施例１と同一条件で成膜を行なった
。成膜した膜厚は４μｍであり、膜組成は（Ａ Ｉ ０
．４２Ｔ ｉ ｏ、ｓａ） Ｎであった。Comparative Example 5 As a cathode material, A1°45Tio, ss starter was manufactured, and film formation was performed under the same conditions as in Example 1. The thickness of the formed film was 4 μm, and the film composition was (A I 0
．． 42T io, sa) N.
比較例６
実施例１と同一のカソード、同一の条件で成膜を行なっ
た。膜厚は０．７μｍとし、膜組成は（Ａ １ ｏ、
ｅａＴ ｉ ｏ３ａ） Ｎであった。Comparative Example 6 Film formation was performed using the same cathode and under the same conditions as in Example 1. The film thickness was 0.7 μm, and the film composition was (A 1 o,
eaTio3a) N.
比較例７ 実施例１と同一カソード、同一条件で成膜を行なった。Comparative example 7 Film formation was performed using the same cathode and under the same conditions as in Example 1.
膜厚は１２μｍとし、膜組成は（ＡＩ。６４Ｔ ｉ ０
．３６） Ｎであった。The film thickness is 12 μm, and the film composition is (AI.64T i 0
．． 36) It was N.
実施例１〜３及び比較例１〜７によって得られた試料を
、下記切削条件により１０分間の切削試験に供したフラ
ンク摩耗幅及びクレータ摩耗深さを第１表に示す。The samples obtained in Examples 1 to 3 and Comparative Examples 1 to 7 were subjected to a cutting test for 10 minutes under the following cutting conditions, and the flank wear width and crater wear depth are shown in Table 1.
切削条件：
被削材 ５５０Ｃ
切削速度 １７０ ｍ ／ｗｉｎ
送り速度 ０．２５ ｍｍ／ｒｅｖ切り込み
０．１ ｆｆ１ｍ
矛
表
第１表より明らかな様に、比較例に比べて本発明例はい
ずれも耐摩耗性に優れていた。Cutting conditions: Work material 550C Cutting speed 170 m/win Feed speed 0.25 mm/rev depth of cut
0.1 ff1m As is clear from Table 1, the examples of the present invention were all superior in wear resistance compared to the comparative examples.
次に超硬ドリルへの適用例を以下に示す。An example of application to a carbide drill is shown below.
実施例４
６ｍａ＋φの（ＷＣ−８％ＣＯを主成分とする）超硬ド
リルに実施例１．と同一条件にて成膜を形成した。この
ときの膜組成は（Ａ １ ｏ、 ａｓＴ ｉ ０．３１
１） Ｎであり、膜厚は４．５μｍであった。Example 4 Example 1 was applied to a 6ma+φ (mainly composed of WC-8% CO) carbide drill. A film was formed under the same conditions. The film composition at this time is (A 1 o, asT i 0.31
1) N was used, and the film thickness was 4.5 μm.
比較例として次の試料を用意した。The following sample was prepared as a comparative example.
比較例８
６ｍａ＋φの超硬ドリルに比較例５と同一条件にて成膜
を形成した。このときの膜組成は（ＡＩｏ、４６７１０
、５４） Ｎであり、膜厚は４μｍであった。Comparative Example 8 A film was formed on a 6ma+φ carbide drill under the same conditions as Comparative Example 5. The film composition at this time was (AIo, 46710
, 54) N, and the film thickness was 4 μm.
比較例９
６ｍｍφの超硬ドリルに比較例２と同一条件でＴｉＮを
成膜した。膜厚は５μｍであった。Comparative Example 9 A TiN film was formed on a 6 mm diameter carbide drill under the same conditions as Comparative Example 2. The film thickness was 5 μm.
比較例１１
０６ＩＩ１φの超硬ドリルに実施例４と同一条件で成膜
を形成した。膜組成は（Ａ Ｉ Ｇ、 ６４Ｔ ｉ Ｑ
、 ３８） Ｎであり、膜厚を０．７ μｍとした。Comparative Example 11 A film was formed on a 06II 1φ carbide drill under the same conditions as in Example 4. The film composition is (A I G, 64T i Q
, 38) N, and the film thickness was 0.7 μm.
比較例１１
６ｍｍφの超硬ドリルに比較例１０と同一条件にて成膜
し、膜組成は（Ａ Ｉ ０．６４Ｔ ｉ ｏ、＊ｓ）
Ｎで膜厚は１２μｍとした。Comparative Example 11 A film was formed on a 6mmφ carbide drill under the same conditions as Comparative Example 10, and the film composition was (A I 0.64T io, *s)
The film thickness was 12 μm using N.
下記の切削条件で行なった穴明は個数の結果を第２表に
示す。Table 2 shows the results of the number of holes drilled under the following cutting conditions.
切削条件：
被削材 ５５０Ｃ，１３ｍｍｔ
切削速度 ５０ｍ／ｍｉｎ
送り速度 ０．２ ｍｍ／ｒｅｖ
潤滑 エマルジョンによる
第 ２ 表
第２表より明らかな様に本発明方法で得られた工具は、
比較例に比べて加工個数の大幅な増加が認められ、耐摩
耗性が良好であった。Cutting conditions: Work material 550C, 13mmt Cutting speed 50m/min Feed rate 0.2mm/rev Lubrication Emulsion Table 2 As is clear from Table 2, the tool obtained by the method of the present invention was
A significant increase in the number of processed pieces was observed compared to the comparative example, and the wear resistance was good.
次にハイスドリルへの適用例を以下に示す。An example of application to a high speed steel drill is shown below.
実施例５
６ＩＩＩｌＩｌφハイスドリルに実施例１と同一条件に
て成膜を形成した。膜組成は（Ａ １ ｏ、 ａｓＴ
ｉ ｏ３ｙ）Ｎであり、膜厚を５．５μｍとした。Example 5 A film was formed on a 6IIIlIlφ high-speed steel drill under the same conditions as in Example 1. The film composition is (A 1 o, asT
i o3y)N, and the film thickness was 5.5 μm.
比較例として次の試料を用意した。The following sample was prepared as a comparative example.
比較例１２
６ｍｍφハイスドリルに比較例２と同一条件でＴｉＮを
成膜した。膜厚は５μｍであった。Comparative Example 12 A TiN film was formed on a 6 mm diameter high speed steel drill under the same conditions as Comparative Example 2. The film thickness was 5 μm.
比較例１３
６■φハイスドリルに比較例５と同一条件にて成膜を形
成した。膜組成は（Ａ １ ｏ、 ａｓＴ ｉ ｏ、
ｓｙ）Ｎであり、膜厚を４．５ μｍとした。Comparative Example 13 A film was formed on a 6-inch diameter high-speed steel drill under the same conditions as Comparative Example 5. The film composition is (A 1 o, asT io,
sy)N, and the film thickness was 4.5 μm.
比較例１４
６■φハイスドリルに実施例４と同一条件で成膜を形成
した。膜組成は（Ａ １０．１１３Ｔ ｉ ０．３７）
Ｎであり、膜厚を１３μｍとした。Comparative Example 14 A film was formed on a 6-inch diameter high-speed steel drill under the same conditions as in Example 4. The film composition is (A 10.113T i 0.37)
N, and the film thickness was 13 μm.
下記の切削条件で行なった穴明は個数の結果を第３表に
示す。Table 3 shows the results of the number of holes drilled under the following cutting conditions.
切削条件：
被削材 ５５０Ｃ，１０ｍｍｔ
切削速度 ３０ｍ／ｗｉｎ
送り速度 ０．１５ｍｍ／ｒｅｖ
潤 滑 エマルジョンによる
第 ３ 表
第３表より明らかな様に本発明方法で得られた工具は、
比較例に比べて加工個数の大幅な増加がみられ、耐摩耗
性が良好であった。Cutting conditions: Work material 550C, 10mmt Cutting speed 30m/win Feed rate 0.15mm/rev Lubrication Emulsion Table 3 As is clear from Table 3, the tool obtained by the method of the present invention was
There was a significant increase in the number of processed pieces compared to the comparative example, and the wear resistance was good.
［発明の効果］
本発明は以上の様に構成されているので、ＴｉＮを基本
とした従来の（Ｔｉ、、ＡＩ）Ｎと異なり、ＩＩＩ ｂ
族の窒化物であるＡＩＮにＴｉが固溶した皮膜である為
、耐熱性、熱伝導性等に関し、ＡＩＮに近似した優れた
特性が発揮されるばかりか、従来のイオンブレーティン
グ法やスパッタリング法によって製造する場合よりも密
着性、膜組成の均−性及び生産効率の各面において優れ
た皮膜形成方法を提供することができる。[Effect of the invention] Since the present invention is configured as described above, unlike the conventional (Ti,, AI)N based on TiN, III b
Since the film is a solid solution of Ti in AIN, which is a nitride of the group, not only does it exhibit excellent properties similar to AIN in terms of heat resistance and thermal conductivity, but it also has excellent properties similar to AIN, and is also compatible with conventional ion blating and sputtering methods. It is possible to provide a method for forming a film that is superior in terms of adhesion, uniformity of film composition, and production efficiency compared to the case where the film is manufactured by the method.
第１図（Ａ）及び（Ｂ）は本発明における（Ａ１８Ｔ
ｉ Ｉ−Ｘ） Ｎ組成（窒化物で代表）と結晶構造の関
係を示す図であり、又第２図は（Ａ １ ｙ Ｔ ｉ
Ｉ−Ｘ）ＮにおいてＸを変化させた場合の温度変化に対
する酸化量の程度を示すグラフ、第３図は（Ａ １ ｏ
、ａｓＴ ｉ ｏ、ｓｓ） （Ｎｙ Ｃｌ−ｙ ）に
おいてｙを変化させた時の超硬チップの切削時のクレー
タ摩耗量を示す図である。
第１図（Ａ）
第１閃（Ｂ）FIGS. 1(A) and (B) show (A18T) in the present invention.
i I-X) A diagram showing the relationship between N composition (represented by nitride) and crystal structure, and FIG.
Figure 3 is a graph showing the degree of oxidation amount with respect to temperature change when X is changed in I-X)N.
, asTio,ss) (NyCl-y) is a diagram showing the amount of crater wear during cutting of a carbide tip when y is changed. Figure 1 (A) 1st flash (B)
Claims (1)
ｘＴｉ＿１＿−＿ｘ）（Ｎ＿ｙＣ＿１＿−＿ｙ）但し０
．５６≦ｘ≦０．７５ ０．６≦ｙ≦１ で示される化学組成からなり、膜厚が０．８〜１０μｍ
の耐摩耗性皮膜を、蒸発源としてカソードを用いるアー
ク放電方式によって形成することを特徴とする耐摩耗性
皮膜形成方法。[Claims] In forming a wear-resistant film on the surface of a base material, (Al_
xTi_1_-_x) (N_yC_1_-_y) However, 0
．． The film has a chemical composition of 56≦x≦0.75 0.6≦y≦1, and has a film thickness of 0.8 to 10 μm.
A method for forming a wear-resistant film, characterized in that the wear-resistant film is formed by an arc discharge method using a cathode as an evaporation source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278324A JPH02194159A (en) | 1988-03-24 | 1988-11-02 | Formation of wear resistant coating film |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7095688 | 1988-03-24 | ||
| JP25398088 | 1988-10-07 | ||
| JP63-253980 | 1988-10-07 | ||
| JP63-70956 | 1988-10-07 | ||
| JP63278324A JPH02194159A (en) | 1988-03-24 | 1988-11-02 | Formation of wear resistant coating film |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18613794A Division JPH07197235A (en) | 1994-08-08 | 1994-08-08 | Member coated with wear resistant film |
| JP30621295A Division JPH08209332A (en) | 1988-03-24 | 1995-11-24 | Production of tool excellent in wear resistance |
| JP7306213A Division JP2644710B2 (en) | 1988-03-24 | 1995-11-24 | Abrasion resistant coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02194159A true JPH02194159A (en) | 1990-07-31 |
| JPH0567705B2 JPH0567705B2 (en) | 1993-09-27 |
Family
ID=26412070
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63278324A Granted JPH02194159A (en) | 1988-03-24 | 1988-11-02 | Formation of wear resistant coating film |
| JP7306213A Expired - Lifetime JP2644710B2 (en) | 1988-03-24 | 1995-11-24 | Abrasion resistant coating |
| JP30621295A Pending JPH08209332A (en) | 1988-03-24 | 1995-11-24 | Production of tool excellent in wear resistance |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7306213A Expired - Lifetime JP2644710B2 (en) | 1988-03-24 | 1995-11-24 | Abrasion resistant coating |
| JP30621295A Pending JPH08209332A (en) | 1988-03-24 | 1995-11-24 | Production of tool excellent in wear resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (3) | JPH02194159A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JPS5240487A (en) * | 1975-09-26 | 1977-03-29 | Nobuo Nishida | Exterior parts for watch and its process for production |
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| JPS6411961A (en) * | 1987-07-06 | 1989-01-17 | Nippon Light Metal Co | Formation of thin composite nitride film by ion plating |
| JPH02194159A (en) * | 1988-03-24 | 1990-07-31 | Kobe Steel Ltd | Formation of wear resistant coating film |
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| JPS51151277A (en) * | 1975-06-20 | 1976-12-25 | Sumitomo Electric Ind Ltd | A coated super hard alloy |
| JPS5240487A (en) * | 1975-09-26 | 1977-03-29 | Nobuo Nishida | Exterior parts for watch and its process for production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08209332A (en) * | 1988-03-24 | 1996-08-13 | Kobe Steel Ltd | Production of tool excellent in wear resistance |
| JPH04103755A (en) * | 1990-08-23 | 1992-04-06 | Sumitomo Metal Mining Co Ltd | Surface coated steel product and its production |
| JPH05285215A (en) * | 1992-04-09 | 1993-11-02 | Masaru Yamaoka | Equipment coated with film of ti-al-n composition |
| US5679448A (en) * | 1993-07-12 | 1997-10-21 | Oriental Engineering Co., Ltd. | Method of coating the surface of a substrate and a coating material |
| DE19517120A1 (en) * | 1994-05-13 | 1995-11-16 | Kobe Steel Ltd | Coated part used as e.g. cutting tool |
| DE19517120C2 (en) * | 1994-05-13 | 1998-07-02 | Kobe Steel Ltd | Coated part with excellent hardness and adhesion, its use and manufacturing process |
| US6855405B2 (en) * | 2001-06-11 | 2005-02-15 | Mitsubishi Materials Corporation | Surface-coated carbide alloy tool |
| JP2007015106A (en) * | 2006-10-11 | 2007-01-25 | Hitachi Tool Engineering Ltd | Multilayered film coated tool and its coating method |
| JP4540120B2 (en) * | 2006-10-11 | 2010-09-08 | 日立ツール株式会社 | Multilayer coating tool and method for coating the same |
| EP2031090A2 (en) | 2007-08-31 | 2009-03-04 | Union Tool Co. | Hard covering film for cutting tool |
| JP2011504808A (en) | 2007-11-16 | 2011-02-17 | ベーレリト ゲーエムベーハー ウント コー． カーゲー． | Friction stir welding tool |
| EP2100985A1 (en) | 2008-01-31 | 2009-09-16 | Union Tool Co. | Hard film for cutting tool |
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| JP2013048210A (en) * | 2011-07-22 | 2013-03-07 | Toshiba Corp | Magnetic resistance element |
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| WO2013015004A1 (en) * | 2011-07-22 | 2013-01-31 | Kabushiki Kaisha Toshiba | Magnetoresistive element |
| WO2014208068A1 (en) * | 2013-06-24 | 2014-12-31 | 兼房株式会社 | Method for manufacturing circular saw with hard tip |
| EP3015206A4 (en) * | 2013-06-24 | 2017-01-25 | Kanefusa Kabushiki Kaisha | Method for manufacturing circular saw with hard tip |
| JPWO2014208068A1 (en) * | 2013-06-24 | 2017-02-23 | 兼房株式会社 | Manufacturing method of circular saw with tip |
| JP2015053357A (en) * | 2013-09-06 | 2015-03-19 | 三菱マテリアル株式会社 | Metal nitride material for thermistors, manufacturing method thereof, and thermistor sensor |
| RU2613837C1 (en) * | 2015-12-03 | 2017-03-21 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет" "МИСиС" | METHOD OF PRODUCING ION-PLASMA VACUUM-ARC CERAMETALLIC Ti-Ni COATING FOR CARBIDE CUTTING TOOL OF EXPANDED USE |
| KR20190043461A (en) | 2017-10-18 | 2019-04-26 | 유니온쓰루 가부시키가이샤 | Hard film for cutting tools and drill |
| CN109676179A (en) * | 2017-10-18 | 2019-04-26 | 佑能工具株式会社 | Cutting element hard coat and drill bit |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0567705B2 (en) | 1993-09-27 |
| JPH08209333A (en) | 1996-08-13 |
| JPH08209332A (en) | 1996-08-13 |
| JP2644710B2 (en) | 1997-08-25 |
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