JPS59159983A - Composite body of substrate coated with hard abrasion-resistant surface layer - Google Patents
Composite body of substrate coated with hard abrasion-resistant surface layerInfo
- Publication number
- JPS59159983A JPS59159983A JP59027365A JP2736584A JPS59159983A JP S59159983 A JPS59159983 A JP S59159983A JP 59027365 A JP59027365 A JP 59027365A JP 2736584 A JP2736584 A JP 2736584A JP S59159983 A JPS59159983 A JP S59159983A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- substrate
- layer
- drill
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims description 30
- 239000002344 surface layer Substances 0.000 title claims description 3
- 239000002131 composite material Substances 0.000 title claims 6
- 238000005299 abrasion Methods 0.000 title description 2
- 239000010410 layer Substances 0.000 claims description 39
- 238000005520 cutting process Methods 0.000 claims description 37
- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 9
- 238000005240 physical vapour deposition Methods 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 238000005553 drilling Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- -1 argon ions Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910010421 TiNx Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Drilling Tools (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
ａ、技術分野
本発明は、きわめて耐摩耗性のよい薄い弐面層でコーテ
ィングされた切削工具おるいは耐摩耗部品のような造形
体に関するものである。DETAILED DESCRIPTION OF THE INVENTION a. Technical Field The present invention relates to shaped bodies, such as cutting tools or wear-resistant parts, which are coated with a thin outer layer that is extremely wear-resistant.
ｂ、従来技術
超硬、セラミック、ｆ！ＩＪ６るいは他の材料からなる
、例えば、切削インサートような異なる種類の本体の摩
耗寿命を硬質堀面層の適用によってかなり伸ばすことが
できることは既に知られている。b. Conventional technology carbide, ceramic, f! It is already known that the wear life of bodies of different types, such as, for example, cutting inserts, made of IJ6 or other materials can be considerably increased by the application of a hard face layer.
耐摩耗性を高めるために耐火層を有する材料ようなコー
ティングは長い間広範曲に使用されていた。Such coatings have long been widely used in materials with fire-resistant layers to increase wear resistance.
前述の層は、普通、周期系の■〜■族に属する金属の炭
化物、窒化物および酸化物からなり、かつ非常な高硬度
および化学的安定性を特徴としている。The aforementioned layers usually consist of carbides, nitrides and oxides of metals belonging to groups 1 to 2 of the periodic system and are characterized by very high hardness and chemical stability.
上述したコーティング材料のなかで周期系の■〜■族に
属する金属の窒化物は、Ｔｉｅ又はＡＡ２（１３のよう
な他のコーティング材料と組合さって好ましい特性を示
す。しかしながら、窒化物の単層は、不満足な耐摩耗性
および不十分な基板への密着性のために、用途が限られ
ていた。Among the coating materials mentioned above, nitrides of metals belonging to groups 1 to 2 of the periodic system exhibit favorable properties in combination with other coating materials such as Tie or AA2 (13). had limited application due to unsatisfactory abrasion resistance and poor adhesion to substrates.
Ｃ０発明の概要
本発明によると、複数の窒化物層がコーティング材料と
して使用されるときにも優れた特性を得ることができる
とわかった。本発明に係る層は少なくとも２０個々の層
からなり、その内側層は亜化学量論的な（ｓｕｂｓｔｏ
ｉｃｈｉｏｍｅｔｒｉｃ ） ＭｅＮＸからなり（ここ
でＸは０．９よυ小さくかつ好ましくは０．５より大き
い）、そして外側層は化学量論的ないしほとんど化学量
論的なＭｅ Ｎｘからなる（ここでＸは０．９より大き
くかつ好ましくは０，９と１．０との間である）。Ｍｅ
は周期系の■〜■族に層する金属を衣す。窒化物層の総
厚さは一般的に１ないし１０μｍであシ、内側層は、普
通、４ないし６μｍ厚さでありそして外側層は１ないし
２μｍ厚さである。C0 SUMMARY OF THE INVENTION According to the present invention, it has been found that excellent properties can also be obtained when multiple nitride layers are used as coating materials. The layer according to the invention consists of at least 20 individual layers, the inner layer being substoichiometric.
ichiometric) MeNX, where X is less than 0.9 and preferably greater than 0.5, and the outer layer consists of stoichiometric to nearly stoichiometric MeNX, where X is less than 0.9 and preferably greater than 0.5. greater than 0.9 and preferably between 0.9 and 1.0). Me
covers the metals layered in the ■~■ groups of the periodic system. The total thickness of the nitride layer is typically 1 to 10 μm, the inner layer usually 4 to 6 μm thick and the outer layer 1 to 2 μm thick.
本発明は、ＰＶＤ（Ｐｙｓｉｃａｌ Ｖａｐｏｒ Ｄｅ
ｐｏｓｉｔｌｏｎ 。The present invention uses PVD (Physical Vapor De
positionlon.
物理的蒸着）技術による基板のコーティングに特に有益
である。以下、ＰＶＤ技術によるＴｉＮを有するねじれ
刃ドリルようなあるコーティング切削工具での本発明の
使用を述べることにする。It is particularly useful for coating substrates by physical vapor deposition (physical vapor deposition) techniques. In the following we will describe the use of the present invention in certain coated cutting tools, such as twisted-edge drills with TiN by PVD technology.
化学量論的含有量の窒素、炭素および酸素を有する硬質
窒化物、炭化物および酸化物の耐摩耗性コーティングは
既に知られており、例えば、スウェーデン特許第３７５
４７４号（これは亜化学童論的炭素含有量の炭化物、特
に、例えば、Ｔｉｃのコーティングを開示しており）お
よびフランス特許出願第８０１３０３０号（欧州特許出
願第００４３７８号、これはＴＩＮおよびＴｉＮｘのコ
ーティング、ただしＸは０．４ないし１の間で可変であ
る）参照。Hard nitride, carbide and oxide wear-resistant coatings with stoichiometric contents of nitrogen, carbon and oxygen are already known, for example from Swedish Patent No. 375
No. 474 (which discloses coatings of carbides with sub-chemical carbon content, in particular, e.g. coating, where X is variable between 0.4 and 1).
しかしながら、これらの場合において、これら層を本発
明程度まで詳しく明記していない。However, in these cases these layers are not specified in detail to the extent of the present invention.
言及したドリルが超硬付刃であシ（すなわち、超硬の切
削インサートを備えており）かつ本発明によるならば、
優れた孔直径許容差および表面仕上げをもたらして高送
り（浸入）速度（Ｐｅｎｅｔｒａｔｉｏｎｒａｔｅ）
、良好なチップ（切りくず）制御、および良好なニップ
（切り刃）安全性のような優れた特性を与え、これら特
性は好ましくは合金鋼又は低炭素鋼の穴あけにて高生産
性の結果になる。If the mentioned drill has a carbide cutting insert (i.e. is equipped with a carbide cutting insert) and according to the invention,
High penetration rates resulting in excellent hole diameter tolerances and surface finish
It provides excellent properties such as good chip control, and good nip safety, which results in high productivity, preferably in drilling alloy steels or low carbon steels. Become.
トリルのタイプは既に知られており、２つのらせん状切
れ刃を有する超硬付刃ねじれ刃ドリルであり、切れ刃は
ドリルの回転中心にて始まり力１つこの中心に対して対
称である。切れ刃はドリルの回転方向に外側ヘカーブし
ておりかつドリルの外側の周囲部よりも中央部にてよυ
大きくカーブしている。The type of trill is already known and is a carbide-tipped twisted-edge drill with two helical cutting edges, the cutting edges starting at the center of rotation of the drill and symmetrical about this center by one force. The cutting edge is curved outward in the direction of rotation of the drill, and is curved more towards the center than the outer periphery of the drill.
It has a large curve.
公知形状寸法を有するコーティングされていないドリル
を使用して、一般的に、相対的に高送り（浸入）速度と
、比較的に良好な孔直径許容差および表面仕上げと、適
度のチップ制御とが得られる。しかしながら、トリルの
全体的形状寸法設計およびドリルの切削速度がドリル中
央でのゼロに向かって常に減少していることのために、
並進は、切れ刃のある部分にいわゆる構成刃先が形成さ
れる。もしこの構成刃先が切れ刃へ密着しそれ−ａ−ら
剥れるならば、このことは失敗の頻度を高めることにな
る切れ刃への損傷となるであろう。構成刃先の形成は、
切れ刃の強くカーブしている部分からカーブのゆるい部
分への変化している領域にて特に決定的である。切れ刃
の強くカーブしている部分に泪ってチップが切れ刃から
切れ刃に対して直角に移動するだけでなく切れ刃にＧ
ってドリルの円周方向にも移動する。切れ刃のゆるいカ
ーブ部分にてチップの方向は切れ刃に対して実質的に直
角である。前述の事実は２つのチップ方向の間の遷移領
域にてチップの圧縮状態を引き起こし、このことは次に
高められた使用応力を切り刃のこの部分（領域）に与え
る。コーティングされていないドリルでの穴あけにおい
て、チッピング形慇の損傷が特に切れ刃のこの部分にし
ばしば見られる。この損傷は、並進、このタイプのドリ
ルの工具寿命内で大きく広がることになる。しかしなが
ら、この損傷は本発明に係るＴｉＮ層でドリルをコーテ
ィングすることによってほとんど解消されることを見出
した。この層は切れ刃に特に上述した危い部分にチップ
が密着するのを防ぐ・耐摩耗性ＴｉＮ ：ｌ−ティング
がＣＶＤ（ＣｈｅｍｉｃａｌＶａｐｏｒ Ｄｅｐｏｓｉ
ｔｉｏｎ、化学的蒸着）技術又はＰＶＤ技術のような方
法によって作られることは公知である。前者の方法は、
通例、比較的高い基板温度（７００〜１０１．０℃）を
必要とし、一方、ＰＶＤによるコーティングはそのよう
な高い基板温度を必要としない。したがって、後者の方
法は、ドリルおよび同様な製品（そのホルダ一部が鋼で
作られているもの）をコーティングするのに特に適して
いる。Using uncoated drills with known geometries, relatively high feed (penetration) rates, relatively good hole diameter tolerances and surface finishes, and reasonable chip control are generally achieved. can get. However, due to the overall geometry design of the drill and the fact that the cutting speed of the drill is constantly decreasing towards zero at the center of the drill;
The translation forms a so-called built-up edge in a certain part of the cutting edge. If this built-up edge were to adhere to the cutting edge and peel away from it, this would result in damage to the cutting edge which would increase the frequency of failures. The formation of the built-up cutting edge is
This is particularly critical in the area where the cutting edge changes from a strongly curved part to a less curved part. The strongly curved part of the cutting edge causes the chip not only to move from one cutting edge to the other at right angles to the cutting edge, but also to create a G force on the cutting edge.
It also moves in the circumferential direction of the drill. In the gently curved portion of the cutting edge, the direction of the chip is substantially perpendicular to the cutting edge. The aforementioned fact causes a compressive state of the chip in the transition region between the two chip directions, which in turn imparts an increased working stress to this part (area) of the cutting edge. When drilling with uncoated drills, chipping-type damage is often seen, especially in this area of the cutting edge. This damage will spread significantly over the translational tool life of this type of drill. However, it has been found that this damage is largely eliminated by coating the drill with a TiN layer according to the invention. This layer prevents the chip from adhering to the cutting edge, especially in the dangerous areas mentioned above.The wear-resistant TiN coating is made using CVD (Chemical Vapor Deposition).
It is known to be produced by methods such as chemical vapor deposition (chemical vapor deposition) or PVD techniques. The former method is
Typically, relatively high substrate temperatures (700-101.0° C.) are required, whereas PVD coatings do not require such high substrate temperatures. The latter method is therefore particularly suitable for coating drills and similar products whose holder part is made of steel.
本発明に従ってドリルをＰＶＤ技術によってＴｉＮ層（
その厚さが普通には１〜１０μｍで好ましくは５〜７μ
ｍである）でコーティングすることによって、切れ刃安
全性および耐摩耗性についての驚くほどの良い特性を得
ることができるとわかった。According to the invention, the drill is made with TiN layer (
Its thickness is usually 1 to 10 μm, preferably 5 to 7 μm.
It has been found that surprisingly good properties with respect to cutting edge safety and wear resistance can be obtained by coating with m).
これら特性は、基板に対するＴ’ｉＮ層のすぐれた密着
性およびチタンおよび窒素の含有量についてのＴｉＮ層
の特別な組成の結果である◎好ましくは５〜・７μｍ厚
さであるＴｉＮ層は２つのＴｉＮ層（ダブル層）からな
り、そのうちの基板に密着する内側層は通例４〜６μｍ
の厚さでありかつ亜化学量論的なＴｉＮＸからなる。な
お、Ｘは０．５と０．９との間で好ましくは０．６と０
．８との間で可変である。この内側層は薄い黄色を示し
、これは窒素が大きく不足しているＴｉＮの特質である
。もしＸが０．５より小さいと、第２相、すなわち、Ｔ
ｉ２Ｎが形成されるが、この相は摩耗層とし適していな
い。外側層は通例１〜２μｍの厚さでありかっＴｉＮｘ
からなり、ここで又は０．９より大きく好ましくは０．
９と１，０との間で可変である。この外側層の色はあざ
やかな黄色であり、これはほぼ化学量論的なＴｉＮの特
質である。These properties are the result of the excellent adhesion of the T'iN layer to the substrate and the special composition of the TiN layer in terms of titanium and nitrogen content. Consists of a TiN layer (double layer), of which the inner layer that adheres to the substrate is typically 4 to 6 μm thick.
thickness and is made of substoichiometric TiNX. Note that X is between 0.5 and 0.9, preferably between 0.6 and 0.
．． It is variable between 8 and 8. This inner layer exhibits a pale yellow color, which is characteristic of TiN, which is highly nitrogen deficient. If X is less than 0.5, the second phase, i.e., T
Although i2N is formed, this phase is not suitable as a wear layer. The outer layer is typically 1-2 μm thick.
or greater than 0.9, preferably 0.
It is variable between 9 and 1,0. The color of this outer layer is bright yellow, which is a near stoichiometric property of TiN.
顕著な切れ刃安全性は、前述したような切れ刃に密着す
る構成刃先をなくすことによって得られる。ドリル失敗
のだめの前述した理由はほとんど解消されてＴＩＮコー
ティングドリルは、工具寿命での非常に小さな広がりの
故に非常に大きな生産信頼性を示す。Significant cutting edge safety is obtained by eliminating the built-up edge that adheres to the cutting edge as described above. The aforementioned reasons for drill failure are largely eliminated and TIN coated drills exhibit much greater production reliability due to a much smaller spread in tool life.
本発明においてスパッタリングが超硬付刃ねじれ刃ドリ
ルをコーティングするのに用いられる。In the present invention, sputtering is used to coat the carbide tipped drill.
例えば、チタンのカソード材料４ ツタリングの原理は
公知である。チタンのターグツト材は水冷カソードに付
けられそして基板（工具）がカソードの反対であるアノ
ード（陽極）を構成している。カソードとアノードとの
間のグロー放電（プラズマ）を維持するのに使用される
ガスは、通常、減圧（１０−１００ＸＩＯｍｂａｒ）状
態のアルゴンであり、このことによってプラスのアルゴ
ンイオンが２〜５ｋＶのカソード電圧にてカソードの方
へ加速される。For example, the principle of titanium cathode material 4 is known. A titanium target material is attached to a water-cooled cathode and the substrate (tool) constitutes the anode (anode) opposite the cathode. The gas used to maintain the glow discharge (plasma) between the cathode and the anode is usually argon under reduced pressure (10-100XIO mbar), which allows positive argon ions to reach the cathode at 2-5 kV. It is accelerated towards the cathode by the voltage.
しかしながら、本発明に係るＴｉＮの堆積時に、池の方
法、いわゆる反応性マグネトロンスパッタリングが使用
できる。However, during the deposition of TiN according to the invention, the Pond method, so-called reactive magnetron sputtering, can be used.
マグネトロンスパッタリングの原理は、カソードの野面
に対して直角に入る環状磁界をスパッタリングシステム
に適用することである。この結果は、いわゆる二次電子
−カソード材料から出る電子−がいわゆるローレンツ力
のためにカソードの正面にて捕えられことである。この
ようにして、カソードの正面のプラズマの密度をさらに
高めることになる。強力に高められたイオン化の結果は
かなりコーティング速度が装着ることである。The principle of magnetron sputtering is to apply an annular magnetic field to the sputtering system that enters at right angles to the field of the cathode. The result of this is that so-called secondary electrons - electrons leaving the cathode material - are trapped in front of the cathode due to so-called Lorentz forces. In this way, the density of the plasma in front of the cathode will be further increased. The result of the strongly enhanced ionization is that coating speeds are significantly faster.
例えば、チタンのようなある金属の窒化物、炭化物およ
び酸化物を基板へ適用するときには、反応性カン−トス
バッタリンが用いられる。例えは炭化チタンをコーティ
ングするときは、真空室内のがスはアルコンおよび窒素
からなる。For example, when applying nitrides, carbides, and oxides of certain metals, such as titanium, to the substrate, reactive canthobatterins are used. For example, when coating titanium carbide, the gas in the vacuum chamber consists of alkones and nitrogen.
コーティングサイクル中は、チタンターゲットを備えた
２つの同じ組（ペアー）の間に対称的に配置された矩形
フレーム内に固定的に基板が装着されている。基板ホル
ダーフレームの両側にカソードのあるこの配列（両側か
らのスｉ’？ツタリング）は、ねじれ刃ドリルのような
円柱基板の壕わりの均一な層厚さの結果になる。During the coating cycle, the substrate is fixedly mounted in a rectangular frame symmetrically placed between two identical pairs with titanium targets. This arrangement with the cathode on both sides of the substrate holder frame (swivel from both sides) results in a uniform layer thickness of the trench of the cylindrical substrate like a twisted-blade drill.
コーティングプロセスは本質的には２つのステップ、す
なわチ、スパッタエツチングステップおよヒ被覆ステッ
プからなる。スパッタエツチングステップの前に、基板
を加熱することができる。スバツタエ、チング中は、基
板および基板ホルダーフレームが−１０００ないし一１
５００Ｖの負電圧にバイアスされ、すなわち、基板自身
およびフレームが同時にカソードでありターゲットであ
る。このステップ中に、グロー放電が５０Ｘ１０−５な
いし１００ＸＩ Ｏ−３ｍｂａｒの圧力にてかつ２ない
し４へのエツチング電流（基板電流）でアルゴン雰囲気
中で生じる。エツチング時間は５ないし２５分である。The coating process essentially consists of two steps: a sputter-etching step and a coating step. The substrate can be heated before the sputter etching step. During processing, the substrate and substrate holder frame are -1000 to 11
It is biased to a negative voltage of 500V, ie the substrate itself and the frame are cathode and target at the same time. During this step, a glow discharge occurs in an argon atmosphere at a pressure of 50.times.10@-5 to 100.times.I O@-3 mbar and an etching current (substrate current) of 2 to 4. Etching time is 5 to 25 minutes.
被覆ステップは５Ｘ１０ ないし２０Ｘ１０−３ｍｂ
ａｒの圧力にてアルゴンおよび窒素の混合ガス中で行な
われる。最適な層が１５〜２５チの窒素がス含有量にて
得られる。カソードのそれぞれに７０〜８０Ａの電流を
流して、グロー放電がカソードと−３００ないし一５０
０ｖの間で可変な電圧降下の他の表面との間に得られる
。負電圧（普通、−１００ないし一５００Ｖ）を基板に
印加する（基板バイアスする）こともでき、グラスのア
ルゴンイオンが基板の方へ加速されて成長層となる。こ
の方法はＡｎｇｌｏ−８ａｘｏｎ文献にて「パイアスー
スノぐツタ」と呼ばれており、コーティング層と基板と
の密着力を改善しかつ層のミクロ組織が本発明で考慮し
ている耐摩耗応用により適しているグラスの効果を有す
る。上述した条件下でのＴｉＮのコーティング速度は０
．０５ないし０．２０ μｍ／ｌＡ−である。Coating step is 5X10 to 20X10-3mb
It is carried out in a mixed gas of argon and nitrogen at a pressure of ar. Optimal layers are obtained with a nitrogen content between 15 and 25 inches. A current of 70 to 80 A is applied to each of the cathodes, and the glow discharge is between -300 and -150 A.
A variable voltage drop between 0v and other surfaces is obtained. A negative voltage (typically -100 to -500 V) can also be applied to the substrate (substrate biasing), causing the argon ions in the glass to be accelerated toward the substrate into the growth layer. This method is referred to as "pyre-snowing" in the Anglo-8axon literature and improves the adhesion between the coating layer and the substrate and makes the microstructure of the layer more suitable for the anti-wear applications considered in the present invention. It has the effect of a glass. The coating rate of TiN under the above conditions is 0.
．． 05 to 0.20 μm/lA-.
コーティングプロセス中は、基板（工具）の温度を３０
０へ３５０℃よシ低くしてはいけない。During the coating process, the temperature of the substrate (tool) should be kept at 30℃.
Do not lower the temperature lower than 350℃ to 0.
もし温度が前述の温度間隙より低いならば、吸着された
原子の表面上での拡散能力が低下して、多孔層の得らる
恐れが高まる。If the temperature is lower than the aforementioned temperature gap, the diffusion ability of the adsorbed atoms on the surface is reduced and the risk of obtaining a porous layer increases.
ｄ、実施例
下記実施例にて本発明に係る工具のコーティングを行な
う条件およびコーティングした工具とコーティングしな
い工具とでの切削試験の結果を示すＯ
去潰上巳
２本の超硬付刃ねじれ刃ドリル（＠径φ＝１４４覇）を
先行記載に係るコーティング装置内の基板ホルダフレー
ムのトップ列に配置した。コーティング前に、ドリルの
先端部、切削インサートおよびシャフトを研摩した。ド
リルは標準設計であったＯ
ドリルを５００℃まで加熱した（１０分間）。d. Examples The following examples show the conditions for coating a tool according to the present invention and the results of a cutting test with a coated tool and an uncoated tool. (@diameter φ=144 mm) was placed in the top row of the substrate holder frame in the coating apparatus according to the previous description. The drill tip, cutting insert and shaft were ground before coating. An O drill of standard design was heated to 500°C (for 10 minutes).
エツチングを１５分間、−１２００Ｖの基板電圧およＵ
５．８ Ｘ １０３ｍｂａｒの圧力にて行なった。エ
ツチング電流をＩＡから３Ａの間であった。エツチング
期間の後で、ターｆ、）を３０秒間閉じた穴でスパッタ
クリーニングした。ＴｉＮのコーティングを下記プロセ
スパラメータにて行なった。Etch for 15 minutes at -1200V substrate voltage and U
It was carried out at a pressure of 5.8 x 103 mbar. The etching current was between IA and 3A. After the etching period, the tar f,) was sputter cleaned with a closed hole for 30 seconds. TiN coating was performed using the following process parameters.
時間二６０分
Ｕバイアスニー２５０Ｖ
■バイアス：１２Ａ
圧カニ １．８ Ｘ １０２ｍｂａｒ
アルゴン流アルゴンイオン６ ＯＮｍＬ１分カンード電
流ニア５Ａ
始めの２７分間、窒素の一定流量（３４５Ｎｍｋ勿）に
て、カソード°電圧（カソード１）を３８２■ないし３
９８ｖの間であった。残りのスパッタリング時間（３３
分）間、同じ窒素流量（３４５Ｎｍ々分）にて、カソー
ド電圧（カソード１）を３８７ｖなｌｎｊ、３８９Ｖの
間であった。Time 260 minutes U bias knee 250V ■ Bias: 12A Pressure crab 1.8 Cathode 1) from 382■ to 3
It was between 98v. Remaining sputtering time (33
The cathode voltage (cathode 1) was between 387 V lnj and 389 V at the same nitrogen flow rate (345 N m min).
以下余白
医１上越
実施例１に従ってＴｉＮをコーティングした工具を下記
パラメータでの穴あけ試験にてテストした。A tool coated with TiN according to Joetsu Example 1 was tested in a drilling test with the following parameters.
機械： Ｐｅｄｅｒｓｅｎ Ｖｅｐｅｍａｔｉｃ乳濁液
： Ｃａ５ｔｒｏｌ ５ｙｎｔｔｌｏ ５Ｗ３０３０（
商品名）１０％材料：スウェーデン規格１６７２
（非合金鋼、０．４５％Ｃ）
穴あけデータ：穴あけ深さ４０嗣／穴
回転数ｎ ” １５３６ ｒｐｍ
外周切削速度τ＝７０ｍ／分
送り速度ｔ＜’＝ ４１５ ｗｎ／ｎ
回分当りの送り ｓ ＝ ０．２７ ｔｒｕｎ／ ｒｅ
ｖドリルで２８．２ｍの穴をあけ、そしてテストをやめ
た。１本のドリルをさらに別の材料（スウェーデン規格
１３１１．低炭素鋼）でテストし、もう２３．５７７Ｚ
の穴あけをした。したがって、このドリルの総穴あけ長
は５１．７７７Ｅであった。Machine: Pedersen Vepematic Emulsion: Ca5trol 5ynttlo 5W3030 (
Product name) 10% Material: Swedish standard 1672 (non-alloy steel, 0.45% C) Drilling data: Drilling depth 40cm/hole rotation speed n'' 1536 rpm Perimeter cutting speed τ = 70m/min Feed rate t<' = 415 wn/n feed per batch s = 0.27 trun/re
I drilled a 28.2m hole with a v-drill and then stopped testing. One drill was tested with yet another material (Swedish standard 1311. low carbon steel) and another 23.577Z
I drilled a hole. Therefore, the total drilling length of this drill was 51.777E.
表面層および切れ刃の金属顕微鏡断面から総厚さが約６
μｍであり、外側黄色ＴｉＮ層が１．５μｍ厚であるこ
とがわかった。内側層は外側層よりも窒素に対して亜化
学童論的であった。A cross section of the surface layer and cutting edge under a metallurgical microscope shows that the total thickness is approximately 6 mm.
The outer yellow TiN layer was found to be 1.5 μm thick. The inner layer was more sensitive to nitrogen than the outer layer.
ヌ１！目
本発明に係るＴｉＮでコーティングされた多数の（数百
の）ドリルを下記条件下でテストし、コーティングして
いないドリルと比較した。Nu1! A large number (hundreds) of drills coated with TiN according to the present invention were tested under the following conditions and compared to uncoated drills.
材料：スウェーデン規格１６７２（非合金鋼、０．４５
％Ｃ）外周切削速度ルーフ０ｍ／分
回転数ｎ ＝ １１１４ ｒｐｍ
送り速度ａ’ ＝ ３３４調／分
回転当りの送りＢ ” ０．３ ｒｕｎ／ ｒｅｖドリ
ル径φ＝２０調
結 果 工具寿命（分）
平均 最大
コーティングなし １０ ２０
コーテイングあり ４０−５０ ４０−５０且ｍ
実施例３と同様な穴あけテスト。Material: Swedish standard 1672 (non-alloy steel, 0.45
%C) Perimeter cutting speed Roof 0m/min Rotation speed n = 1114 rpm Feed rate a' = 334 adjustments/min Feed per revolution B ” 0.3 run/rev Drill diameter φ = 20 adjustments Results Tool life (minutes) Average Maximum Uncoated 10 20 With coating 40-50 40-50 and m Drilling test similar to Example 3.
材料：スウェーデン規格２５４１（強靭鋼、 ２８０−
３２０ＨＢ ）外周切削速度τ＝５５ｍ／分
回転数ｍ＝１１６７ｒｐｍ
送り速度ｓ’＝２９２調／分
回転当りの送りｓ ＝ ０．２５１ａ／ ｒｅｖドリル
径φ＝１５閣
結 果 工具寿命（分）
平均 最大
コーティングなし ０．５ ２０コーテイング
めり ３０−３５ ３０−３５去１上」
実施例３および４と同様な穴あけテスト・材料：スウェ
ーデン規格１３１１（低炭素鋼、０．１３チＣ）外周切
削速度υ＝８５ｍ／分
回転数ｎ ＝ １８０４ ｒｐｍ
送り速度ｓ’＝５４１閤／分
回転当りの送りＢ ＝０．３ ｍｍ／ ｒｅｖドリル径
φ二１５園
結 果 工具寿命（分）平均 最
大
コーティングなし ５−１０ ２５−３０コーテ
イングｂリ ５０−６０ ５０−６０実施３〜５
において、機械および乳濁液は実施例２と同じであった
。寿命の計算において、切れ刃損傷以外の理由によって
失敗したドリルは除外した。Material: Swedish standard 2541 (strong steel, 280-
320HB) Perimeter cutting speed τ = 55 m/min Rotation speed m = 1167 rpm Feed rate s' = 292 steps/min Feed per revolution s = 0.251 a/ rev Drill diameter φ = 15 Kaku Results Tool life (min) Average Maximum No coating 0.5 20 Coating cut 30-35 30-35 1 above" Drilling test similar to Examples 3 and 4 Material: Swedish standard 1311 (low carbon steel, 0.13 inch C) Perimeter cutting speed υ = 85 m/min Rotational speed n = 1804 rpm Feed speed s' = 541 Feed per min revolution B = 0.3 mm/ rev Drill diameter φ215 Result Tool life (minutes) Average Maximum without coating 5- 10 25-30 coating bri 50-60 50-60 implementation 3-5
In , the machine and emulsion were the same as in Example 2. In calculating life, drills that failed due to reasons other than cutting edge damage were excluded.
特許出願人 サントレード リミティド 特許出願代理人 弁理士 青 木 朗 弁理士 西舘和之 弁理士 内 １）幸 男 弁理士 山 口 昭 之 弁理士 西 山 雅 也patent applicant Suntrade Limited patent application agent Patent attorney Akira Aoki Patent Attorney Kazuyuki Nishitate Patent attorney 1) Yukio Patent attorney Akira Yamaguchi Patent Attorney Masaya Nishiyama
Claims (1)
んでなるコーティングとからなる複合体において、前記
基板の少なくとも一部を被覆している前記コーティング
は、厚さ工ないし１０μｍの２層コーティングからなる
層であり、この２層コーティングの内側コーティングが
亜化学量論的なＭｅＮｘ（ｘは０６９未満でかつ好まし
くは０．５より大きい）からなり、外側コーティングが
化学量論的又はほとんど化学量論的なＭｅＭＸ（ｘは０
．９を越えかつ好ましくは最大１である）からなり、Ｍ
ｅが周期系の■〜■族に属する金属であることを特徴と
する耐摩耗性表面層でコーティングされた基板からなる
複合体。 ２、前記内側層がＴ ｉ Ｎｘ （ｘは０．５と０．９
との間で可変である）からなり、そして前記外側層がＴ
ｉＮｘ （ｘは０．９を越えて好ましくは０．９とｏ
、ｉと間である）からなることを特徴とする特許請求の
範囲第１項記載の複合体。 ３、前記内側層の厚さが４ないし６μｍであり、そして
前記外側層の厚さが１ないし２μｍであることを特徴と
する特許請求の範囲第１項又は第２項記載の複合体。 ４、前記コーティング層が物理的蒸着（ＰＶＤ ）技術
によって形成されることを特徴とする特許請求の範囲第
１項から第３項までのいずれか１項に記載の複合体。 ５、前記基板がねじれ刃ドリルであり、その切れ刃は本
質的にカーブ部分で形づくられていることを特徴とする
特許請求の範囲第１項から第４項までのいずれか１項に
記載の複合体。 ６、前記基板が２つのらせん状切れ刃を有する超硬付刃
ねじれ刃ドリルであり、切れ刃がドリルの回転中心から
対称に始まってドリルの回転方向に外側ヘカープしてお
り、ドリルの外側の周囲部よりも中央部にてよシ大きく
カーブしていることを特徴とする特許請求の範囲第１項
から第５項までのいずれか１項に記載の複合体。Claims: 1. A composite comprising a substrate and a coating comprising at least one wear-resistant metal nitride, wherein the coating covering at least a portion of the substrate has a thickness of A layer consisting of a two-layer coating of 1 to 10 μm, the inner coating of which consists of substoichiometric MeNx (x less than 069 and preferably greater than 0.5) and the outer coating of chemical stoichiometric or nearly stoichiometric MeMX (x is 0
．． more than 9 and preferably at most 1), and M
A composite body comprising a substrate coated with a wear-resistant surface layer, characterized in that e is a metal belonging to groups 1 to 2 of the periodic system. 2. The inner layer is T i Nx (x is 0.5 and 0.9
), and the outer layer is T
iNx (x is greater than 0.9, preferably 0.9 and o
, i and between). 3. A composite according to claim 1 or 2, characterized in that the inner layer has a thickness of 4 to 6 μm, and the outer layer has a thickness of 1 to 2 μm. 4. Composite according to any one of claims 1 to 3, characterized in that the coating layer is formed by a physical vapor deposition (PVD) technique. 5. The substrate according to any one of claims 1 to 4, characterized in that the substrate is a twisted-blade drill, the cutting edge of which is essentially formed by a curved part. complex. 6. The substrate is a carbide-tipped twisted-edge drill with two spiral cutting edges, the cutting edges starting symmetrically from the rotation center of the drill and curve outward in the rotation direction of the drill, 6. The composite body according to any one of claims 1 to 5, characterized in that the central part is more curved than the peripheral part.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8300910A SE8300910L (en) | 1983-02-18 | 1983-02-18 | COMPOSITION BODY CONSISTS OF A SUBSTRATE COATED WITH HEART, Wear-resistant finish |
| SE83009100 | 1983-02-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59159983A true JPS59159983A (en) | 1984-09-10 |
Family
ID=20350098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59027365A Pending JPS59159983A (en) | 1983-02-18 | 1984-02-17 | Composite body of substrate coated with hard abrasion-resistant surface layer |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS59159983A (en) |
| DE (1) | DE3404944A1 (en) |
| FR (1) | FR2541154A1 (en) |
| GB (1) | GB2135337B (en) |
| IT (1) | IT1173805B (en) |
| SE (1) | SE8300910L (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03126861A (en) * | 1989-09-11 | 1991-05-30 | Union Carbide Coatings Services Technol Corp | Multilayer coating of a nitride-containing compound and method for |
| WO2020166466A1 (en) | 2019-02-12 | 2020-08-20 | 三菱マテリアル株式会社 | Hard coating cutting tool |
| JP2020127998A (en) * | 2019-02-12 | 2020-08-27 | 三菱マテリアル株式会社 | Hard coat cutting tool |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE453369C (en) * | 1986-05-28 | 1989-08-08 | Vni Instrument Inst | Durable Coating for Cutting Tools and Procedure for Coating |
| JPS634211U (en) * | 1986-06-23 | 1988-01-12 | ||
| DE3830525A1 (en) * | 1988-09-08 | 1990-03-22 | Beck August Gmbh Co | CARBIDE CUTTING PLATE COATED WITH HARD MATERIAL AND METHOD FOR THEIR PRODUCTION |
| US5123972A (en) * | 1990-04-30 | 1992-06-23 | Dana Corporation | Hardened insert and brake shoe for backstopping clutch |
| US5185211A (en) * | 1991-07-11 | 1993-02-09 | Praxair S.T. Technology, Inc. | Non-stoichiometric titanium nitride coating |
| US5242753A (en) * | 1991-07-11 | 1993-09-07 | Praxair S.T. Technology, Inc. | Substoichiometric zirconium nitride coating |
| AT401391B (en) * | 1993-09-09 | 1996-08-26 | Plansee Tizit Gmbh | CUTTING MATERIAL |
| DE69608027T2 (en) * | 1995-05-30 | 2000-09-28 | Praxair Technology Inc | Process for the production of a multilayer coating from a compound containing nitride |
| DE19602030B4 (en) * | 1996-01-20 | 2007-08-02 | Günther & Co. GmbH | drill |
| US7901799B2 (en) * | 2006-10-02 | 2011-03-08 | Praxair S.T. Technology, Inc. | Multilayer nitride-containing coatings |
| EP2222887B1 (en) | 2007-11-30 | 2013-11-06 | Anna University - Chennai | Non-stoichiometric titanium nitride films |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1190274A (en) * | 1958-01-20 | 1959-10-12 | Method for determining the profile of the cutting edge of a drill | |
| FR2123207B1 (en) * | 1971-01-29 | 1974-03-22 | Pompey Acieries | |
| DE2145254C3 (en) * | 1971-09-10 | 1974-04-25 | W.C. Heraeus Gmbh, 6450 Hanau | Process for the manufacture of spinning plates |
| DE2263210B2 (en) * | 1972-02-04 | 1977-03-17 | Metallwerk Plansee AG & Co. KG, Reutte, Tirol (Österreich) | WEAR PART MADE OF CARBIDE, ESPECIALLY FOR TOOLS |
| US3900592A (en) * | 1973-07-25 | 1975-08-19 | Airco Inc | Method for coating a substrate to provide a titanium or zirconium nitride or carbide deposit having a hardness gradient which increases outwardly from the substrate |
| GB1509912A (en) * | 1974-05-17 | 1978-05-04 | Osborn Mushet Tools Ltd | Twist drills |
| AT328254B (en) * | 1974-06-25 | 1976-03-10 | Plansee Metallwerk | HOBBING CUTTERS |
| JPS5594475A (en) * | 1979-01-09 | 1980-07-17 | Citizen Watch Co Ltd | Hard pinkish outer decoration part |
| FR2483848A1 (en) * | 1980-06-06 | 1981-12-11 | Stephanois Rech Mec | PROCESS FOR THE PRODUCTION OF A COMPOSITE LAYER RESISTING BOTH IN GRIPPING, ABRASION, CORROSION AND FATIGUE BY ALTERNATE STRESSES, AND COMPOSITE LAYER THUS OBTAINED |
| GB2102452B (en) * | 1981-07-03 | 1985-05-22 | Mo I Inzhenerov Zheleznodorozh | Titanium carbide or carbonitride coating of sintered hard alloys |
| US4645715A (en) * | 1981-09-23 | 1987-02-24 | Energy Conversion Devices, Inc. | Coating composition and method |
| AT381268B (en) * | 1982-05-05 | 1986-09-25 | Ver Edelstahlwerke Ag | TOOL AND METHOD FOR THE PRODUCTION THEREOF |
-
1983
- 1983-02-18 SE SE8300910A patent/SE8300910L/en unknown
-
1984
- 1984-02-11 DE DE19843404944 patent/DE3404944A1/en not_active Withdrawn
- 1984-02-15 IT IT19624/84A patent/IT1173805B/en active
- 1984-02-16 GB GB08404091A patent/GB2135337B/en not_active Expired
- 1984-02-16 FR FR8402343A patent/FR2541154A1/en not_active Withdrawn
- 1984-02-17 JP JP59027365A patent/JPS59159983A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03126861A (en) * | 1989-09-11 | 1991-05-30 | Union Carbide Coatings Services Technol Corp | Multilayer coating of a nitride-containing compound and method for |
| WO2020166466A1 (en) | 2019-02-12 | 2020-08-20 | 三菱マテリアル株式会社 | Hard coating cutting tool |
| JP2020127998A (en) * | 2019-02-12 | 2020-08-27 | 三菱マテリアル株式会社 | Hard coat cutting tool |
| KR20210118093A (en) | 2019-02-12 | 2021-09-29 | 미쓰비시 마테리알 가부시키가이샤 | hard film cutting tool |
Also Published As
| Publication number | Publication date |
|---|---|
| SE8300910L (en) | 1984-08-19 |
| GB2135337B (en) | 1986-01-08 |
| DE3404944A1 (en) | 1984-08-23 |
| IT1173805B (en) | 1987-06-24 |
| SE8300910D0 (en) | 1983-02-18 |
| IT8419624A0 (en) | 1984-02-15 |
| GB2135337A (en) | 1984-08-30 |
| GB8404091D0 (en) | 1984-03-21 |
| FR2541154A1 (en) | 1984-08-24 |
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