JPH04337064A - Boron nitride coating member - Google Patents

Boron nitride coating member

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Publication number
JPH04337064A
JPH04337064A JP11048191A JP11048191A JPH04337064A JP H04337064 A JPH04337064 A JP H04337064A JP 11048191 A JP11048191 A JP 11048191A JP 11048191 A JP11048191 A JP 11048191A JP H04337064 A JPH04337064 A JP H04337064A
Authority
JP
Japan
Prior art keywords
base material
boron nitride
layer
boundary layer
intermediate layer
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
Application number
JP11048191A
Other languages
Japanese (ja)
Other versions
JP2909248B2 (en
Inventor
Toshiya Watanabe
俊哉 渡辺
Tetsuyoshi Wada
哲義 和田
Nobuki Yamashita
信樹 山下
Makoto Ogawa
真 小川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Heavy Industries Ltd
Original Assignee
Mitsubishi Heavy Industries Ltd
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Filing date
Publication date
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Priority to JP11048191A priority Critical patent/JP2909248B2/en
Publication of JPH04337064A publication Critical patent/JPH04337064A/en
Application granted granted Critical
Publication of JP2909248B2 publication Critical patent/JP2909248B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To improve the adhesion of a member by providing the boundary part between a substrate or an intermediate layer and a baron nitride film with a boundary layer having an inclined compsn. CONSTITUTION:An intermediate layer 2 constituted of titanium nitride, a boundary layer 3 having an inclined compsn. and a CBN(cubic boron nitride) layer 4 are successively formed on a substrate 1. As for the compsn. in the boundary layer 3, the atomic ratio of baron continuously reduces from the side of the film to the side of the intermediate layer; and simultaneously, the atomic ratio of titanium continuously increases, and the boundary layer 3 takes on an inclined compsn. Furthermore, CBN is incorporated into the boundary layer 3, and its abundance is reduced successively from the side of the CBN layer 4 to the intermediate layer 2.

Description

【発明の詳細な説明】[Detailed description of the invention]

【0001】0001

【産業上の利用分野】本発明は、切削工具等に適用され
る立方晶窒化硼素皮膜あるいは、立方晶窒化硼素を含む
硬質窒化硼素皮膜を有する窒化硼素被覆部材に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a boron nitride-coated member having a cubic boron nitride coating or a hard boron nitride coating containing cubic boron nitride, which is applied to cutting tools and the like.

【0002】0002

【従来の技術】立方晶窒化硼素(Cubic Boro
n Nitride ;以下、CBNと記す)は、ダイ
ヤモンドに次ぐ硬さを有すると共に、反応性が低いため
、優れた耐摩耗性材料として知られている。このCBN
は、従来は高温・高圧法でしか作製できず、且つ粒状の
CBNしか合成できなかったため、その利用範囲は、焼
結品や砥粒等に限られていた。そこで、現在、利用範囲
を拡大する目的で、CBNを皮膜として合成する方法が
研究されており、イオンを利用するPVD(物理的蒸着
)法や、プラズマCVD(化学的蒸着)法による合成が
提案されている。
[Prior art] Cubic boron nitride (Cubic Boro nitride)
Nitride (hereinafter referred to as CBN) is known as an excellent wear-resistant material because it has a hardness second only to diamond and has low reactivity. This CBN
Conventionally, CBN could only be produced using a high temperature/high pressure method, and only granular CBN could be synthesized, so its use was limited to sintered products, abrasive grains, etc. Therefore, with the aim of expanding the scope of its use, research is currently being conducted into methods of synthesizing CBN as a film, and synthesis using PVD (physical vapor deposition) using ions and plasma CVD (chemical vapor deposition) have been proposed. has been done.

【0003】0003

【発明が解決しようとする課題】前述したPVD法やC
VD法により合成されるCBN皮膜は、いずれも基材上
あるいは基材上に形成された中間層上に直接形成された
ものであり、基材あるいは中間層と皮膜との間には明瞭
な境界が存在している。そのため、これらのCBN皮膜
はいずれも密着性が不良であり、未だ実用に耐え得る皮
膜は形成できていないのが現状である。CBN皮膜の密
着性が不良となる要因は、いずれの作製法も基本的には
非平衡反応を利用したものであり、合成されたCBN皮
膜が大きな内部応力を有し、基材あるいは中間層と皮膜
の境界部における密着力がこの内部応力に耐えきれずに
剥離するためである。また、CBN自身が反応性の低い
物質であるため、基材との密着力が他のセラミック皮膜
に比べて小さいことも原因である。本発明は上記状況に
鑑みなされたもので、密着性を向上させたCBN皮膜を
有する窒化硼素被覆部材を提供することを目的とする。
[Problem to be solved by the invention] The above-mentioned PVD method and C
All CBN films synthesized by the VD method are formed directly on a base material or an intermediate layer formed on a base material, and there is no clear boundary between the base material or intermediate layer and the film. exists. Therefore, all of these CBN films have poor adhesion, and at present, a film that can withstand practical use has not yet been formed. The reason why the adhesion of the CBN film is poor is that all the manufacturing methods basically utilize non-equilibrium reactions, and the synthesized CBN film has a large internal stress and does not bond well with the base material or intermediate layer. This is because the adhesion at the boundary of the film cannot withstand this internal stress and the film peels off. Another cause is that since CBN itself is a substance with low reactivity, its adhesion to the base material is smaller than that of other ceramic films. The present invention was made in view of the above situation, and an object of the present invention is to provide a boron nitride coated member having a CBN film with improved adhesion.

【0004】0004

【課題を解決するための手段】そこで、本発明ではCB
N皮膜の密着性を向上させる手段として、基材あるいは
基材上に形成された中間層上に窒化硼素皮膜を形成して
なる窒化硼素被覆部材において、基材あるいは中間層と
窒化硼素皮膜との境界部に基材あるいは中間層材料と窒
化硼素との混合組成である境界層を形成すると共に当該
境界層の組成を基材あるいは中間層成分が基材側から被
覆側へと順次減少していく傾斜組成とし、且つ当該境界
層中に立方晶窒化硼素を存在させると共に当該境界層中
における当該立方晶窒化硼素の存在量を窒化硼素皮膜側
から基材あるいは中間層側へ順次減少させるようにした
のである。
[Means for solving the problem] Therefore, in the present invention, CB
As a means to improve the adhesion of the N film, in a boron nitride coated member in which a boron nitride film is formed on a base material or an intermediate layer formed on the base material, the bond between the base material or intermediate layer and the boron nitride film is A boundary layer having a mixed composition of the base material or intermediate layer material and boron nitride is formed at the boundary part, and the composition of the boundary layer is gradually decreased from the base material side to the coating side. The composition is graded, and cubic boron nitride is present in the boundary layer, and the amount of cubic boron nitride in the boundary layer is gradually decreased from the boron nitride film side to the base material or intermediate layer side. It is.

【0005】[0005]

【作用】基材あるいは中間層とCBN皮膜間に傾斜組成
を有する境界層を形成させることにより密着性が向上す
る原因としては、以下のことが挙げられる。CBN皮膜
の密着性が不良である原因は、前述の通り、皮膜の内部
応力が大きいためである。そこで、傾斜組成を有する境
界層を形成させることにより、材料の組成及び構造が連
続的に変化することで、皮膜の内部応力を皮膜側から基
材側あるいは中間層側へと徐々に小さく移行していくこ
とが可能となる。つまり、基材あるいは中間層と皮膜と
の境界をなくすことにより、皮膜の内部応力を境界に集
中させず、境界層の厚さに分散させることで、内部応力
による皮膜の剥離を抑制することができる。また、境界
層中にCBNを含ませ、且つその存在量を皮膜側から基
材あるいは中間層へ順次減少させることで、境界層と皮
膜の構造的な結合が可能となり、これにより境界層自体
の機械的強度が向上し、両者の密着力が一層向上する。
[Operation] The reasons why adhesion is improved by forming a boundary layer having a gradient composition between the base material or intermediate layer and the CBN film are as follows. As mentioned above, the reason why the adhesion of the CBN film is poor is that the internal stress of the film is large. Therefore, by forming a boundary layer with a gradient composition, the composition and structure of the material change continuously, and the internal stress of the film is gradually reduced from the film side to the base material side or intermediate layer side. It becomes possible to go. In other words, by eliminating the boundary between the base material or intermediate layer and the film, the internal stress of the film is not concentrated at the boundary, but is dispersed over the thickness of the boundary layer, thereby suppressing the peeling of the film due to internal stress. can. In addition, by including CBN in the boundary layer and decreasing its abundance from the coating side to the base material or intermediate layer, it becomes possible to structurally bond the boundary layer and the coating, thereby increasing the strength of the boundary layer itself. The mechanical strength is improved and the adhesion between the two is further improved.

【0006】[0006]

【実施例】以下、本発明を実施例に基づいて説明する。 本実施例の窒化硼素被覆部材は、図1に示すように、高
速度工具鋼(JIS規格:SKH51)からなる基材1
上に、窒化チタンからなる中間層2、傾斜組成を有する
境界層3、及びCBN層4を順次形成させたものである
EXAMPLES The present invention will be explained below based on examples. As shown in FIG. 1, the boron nitride-coated member of this example has a base material 1 made of high-speed tool steel (JIS standard: SKH51).
An intermediate layer 2 made of titanium nitride, a boundary layer 3 having a graded composition, and a CBN layer 4 are sequentially formed thereon.

【0007】ここで中間層2は、例えばHCD(ホロカ
ソード)法によるイオンプレーティングによって、厚さ
3μmの窒化チタン皮膜を形成した。具体的には、基材
1に有機溶剤(例えばフロン)による超音波洗浄で前処
理を施した後、例えば0.1TorrAr中で1kv×
1Aで10分間イオンボンバードを行ない、その後、H
CDガン出力:45V×400A、基材温度:500℃
、反応ガス:N2 分圧5×10−4Torrの条件で
コーティングすることにより形成された。なお、中間層
は必ずしも形成させる必要はなく、基材1上に直に境界
層3を形成させても同様な効果を得ることができる。
For the intermediate layer 2, a titanium nitride film having a thickness of 3 μm was formed by, for example, ion plating using the HCD (holocathode) method. Specifically, after pre-treating the base material 1 by ultrasonic cleaning with an organic solvent (for example, CFC), for example, 1kV× in 0.1 TorrAr
Perform ion bombardment at 1A for 10 minutes, then
CD gun output: 45V x 400A, base material temperature: 500℃
, reaction gas: N2 partial pressure was formed by coating under conditions of 5 x 10-4 Torr. Note that the intermediate layer does not necessarily need to be formed, and the same effect can be obtained even if the boundary layer 3 is formed directly on the base material 1.

【0008】次に、中間層2又は基材1上へ境界層3を
作製する方法を説明する。尚、境界層の作製方法には種
々の方法があるが、その中ではイオン注入法やイオンビ
ームミキシング法等が適している。まず、イオン注入法
での作製法について述べる。この方法においては、イオ
ンの加速電圧を200kv、イオン種を窒素及び硼素と
し、これらのイオン種をそれぞれ8×1017ions
/cm2 の数で上記中間層2あるいは基材1に注入す
る。図1に中間層2を存在させたときの境界層3及びC
BN層4を形成させた結果を示すように、イオン注入法
により、中間層2中に窒素及び硼素がめり込む。これら
のめり込み量は深さ方向に自然と減少し、それに従い、
CBNの組成も深さ方向に自然と減少し、逆に中間層成
分は深さ方向に増加するという傾斜組成を有する境界層
3が形成された。
Next, a method for producing the boundary layer 3 on the intermediate layer 2 or the base material 1 will be explained. Note that there are various methods for producing the boundary layer, among which ion implantation method, ion beam mixing method, etc. are suitable. First, a manufacturing method using ion implantation will be described. In this method, the ion acceleration voltage is 200 kV, the ion species are nitrogen and boron, and each of these ion species is 8×1017 ions.
/cm2 into the intermediate layer 2 or base material 1. Boundary layer 3 and C when intermediate layer 2 is present in Figure 1
As shown in the results of forming the BN layer 4, nitrogen and boron sink into the intermediate layer 2 by the ion implantation method. The amount of these penetrations naturally decreases in the depth direction, and accordingly,
A boundary layer 3 was formed having a gradient composition in which the composition of CBN naturally decreased in the depth direction, and conversely, the intermediate layer component increased in the depth direction.

【0009】次に、イオンビームミキシングによる作製
法について述べる。この方法は、図2に示すような装置
を用いて行なう。同図に示す装置は、真空容器11内の
上部の基板ホルダー12に取り付けられた基材13に対
して、イオン源14から窒素イオン照射を行なうと同時
に、真空容器11内の下部に設置された蒸発源15内の
金属硼素16を電子ビーム17により蒸発させて、この
硼素蒸気18を基材13に蒸着させるものである。ここ
で、19は硼素蒸気18の基材への蒸着量を測定するモ
ニタである。
Next, a manufacturing method using ion beam mixing will be described. This method is carried out using an apparatus as shown in FIG. The apparatus shown in the figure irradiates nitrogen ions from an ion source 14 to a base material 13 attached to a substrate holder 12 at the upper part of a vacuum vessel 11, and at the same time irradiates nitrogen ions from an ion source 14. Metallic boron 16 in the evaporation source 15 is evaporated by an electron beam 17, and this boron vapor 18 is deposited on the base material 13. Here, 19 is a monitor that measures the amount of boron vapor 18 deposited on the base material.

【0010】作製手順としては、まず、基材13のとこ
ろへ中間層2を有する基材1あるいは基材1のみを設置
し、真空容器11内を2×10−6Torr以下に予備
排気する。次に、イオン源14に供給した窒素と希ガス
(例えばアルゴン)を、イオン源14内でイオン化して
、その混合イオン20を基材13へ照射すると共に、蒸
発源15より金属硼素16を蒸発させた硼素蒸気18を
基材13上に蒸着させる。このとき、混合イオン20の
エネルギーを70keV ,2keV ,1keV と
段階的に減少させ、そのときの硼素蒸気18の蒸発速度
を、それぞれ加速電圧7keV のとき3Å/sec 
、2keV のとき2Å/sec 、1keV のとき
1Å/sec とし、処理時間を各5分とすることによ
り、図1に示すような、CBNを含み且つ傾斜組成を有
する境界層3が形成された。ここで、境界層3中にCB
Nを含ませるためには、加速電圧を段階的に変化させる
ことが必要であり、特に2keV ,1keV の低い
加速電圧が重要となる。また、このときの真空度はおよ
そ1×10−4Torrである。
As for the manufacturing procedure, first, the base material 1 having the intermediate layer 2 or only the base material 1 is placed on the base material 13, and the inside of the vacuum container 11 is preliminarily evacuated to a pressure of 2.times.10@-6 Torr or less. Next, the nitrogen and rare gas (for example, argon) supplied to the ion source 14 are ionized in the ion source 14, and the mixed ions 20 are irradiated onto the base material 13, and metal boron 16 is evaporated from the evaporation source 15. The boron vapor 18 thus obtained is deposited on the base material 13. At this time, the energy of the mixed ions 20 is decreased stepwise to 70 keV, 2 keV, and 1 keV, and the evaporation rate of the boron vapor 18 at that time is 3 Å/sec when the acceleration voltage is 7 keV.
, 2 Å/sec at 2 keV, and 1 Å/sec at 1 keV, and the processing time was set to 5 minutes each, whereby a boundary layer 3 containing CBN and having a graded composition as shown in FIG. 1 was formed. Here, CB in the boundary layer 3
In order to include N, it is necessary to change the accelerating voltage stepwise, and in particular, low accelerating voltages of 2 keV and 1 keV are important. Further, the degree of vacuum at this time is approximately 1×10 −4 Torr.

【0011】また、境界層3上にCBN層4を形成させ
る方法は、基本的には境界層3を形成する手順と同様で
ある。具体的には、混合イオン20の照射エネルギーを
0.5keV 、硼素蒸気18の蒸発速度を0.4Å/
sec とすることで、CBN層4を形成することがで
きた。また、イオン注入法で得られた境界層上にも同様
な方法でCBN層4を形成することができる。
Furthermore, the method for forming the CBN layer 4 on the boundary layer 3 is basically the same as the procedure for forming the boundary layer 3. Specifically, the irradiation energy of the mixed ions 20 was set to 0.5 keV, and the evaporation rate of the boron vapor 18 was set to 0.4 Å/
sec, the CBN layer 4 could be formed. Furthermore, the CBN layer 4 can be formed by a similar method on the boundary layer obtained by the ion implantation method.

【0012】以上の実施例により製作した窒化チタンを
中間層に持つ窒化硼素被覆部材をオージュ電子分光分析
にて深さ方向の組成分析を行なった結果、境界層3中の
組成は皮膜側から中間層側へ硼素の原子比が連続的に減
少し、同時にチタンの原子比が連続的に増加しており、
境界層3は傾斜組成をとることが確認された。さらに光
電子分光分析により窒化硼素の構造分析を行なったとこ
ろ、境界層3中にCBNが存在することが確認された。 また、図3に、得られた窒化硼素被覆部材の密着力をス
クラッチ試験により評価した結果を示すが、境界層3を
形成させると、境界層3がないときと比べて8〜10倍
、密着力(スクラッチ試験で皮膜が剥離するときの荷重
)が増大しており、優れた密着性を有することが示され
た。また、比較のために、混合イオンの照射エネルギー
を70keV のみとして境界層を形成し、その後CB
N膜を合成したとき、オージェ電子分光分析により境界
層中は傾斜組成を有していることが確認されたが、光電
子分光分析によると、境界層中にはCBNが存在してい
なかった。さらに、これをスクラッチ試験により密着力
を評価した結果、図3に示すように、その密着力は境界
層がないときよりは大幅に向上しているが、境界層中に
CBNが存在しているときと比べると劣っている。これ
より、境界層中にCBNを存在させる効果が示された。
The composition of the boron nitride coated member having titanium nitride in the intermediate layer produced in accordance with the above embodiments was analyzed in the depth direction by Auger electron spectroscopy. As a result, the composition of the boundary layer 3 was found to vary from the film side to the intermediate layer. The atomic ratio of boron continuously decreases toward the layer side, and at the same time, the atomic ratio of titanium continuously increases.
It was confirmed that the boundary layer 3 has a gradient composition. Furthermore, when the structure of boron nitride was analyzed by photoelectron spectroscopy, it was confirmed that CBN was present in the boundary layer 3. In addition, Figure 3 shows the results of evaluating the adhesion of the obtained boron nitride coated member by a scratch test. When the boundary layer 3 is formed, the adhesion is 8 to 10 times higher than when there is no boundary layer 3. The force (load at which the film peels off in a scratch test) increased, indicating that it had excellent adhesion. For comparison, a boundary layer was formed by setting the mixed ion irradiation energy to only 70 keV, and then the CB
When the N film was synthesized, it was confirmed by Auger electron spectroscopy that the boundary layer had a gradient composition, but according to photoelectron spectroscopy, CBN was not present in the boundary layer. Furthermore, as a result of evaluating the adhesion force using a scratch test, as shown in Figure 3, the adhesion force was significantly improved compared to when there was no boundary layer, but CBN was present in the boundary layer. It's inferior compared to before. This demonstrated the effect of the presence of CBN in the boundary layer.

【0013】[0013]

【発明の効果】以上、説明したように、本発明による窒
化硼素被覆部材は、従来のものと比較して優れた密着性
を有しており、切削工具のみならず、各種回転機器の軸
受やスライド等の摺動部材など、他の耐摩耗部材として
実用に耐え得るものであり、工業的に利用価値の大きい
ものである。
Effects of the Invention As explained above, the boron nitride coated member according to the present invention has superior adhesion compared to conventional ones, and is useful not only for cutting tools but also for bearings of various rotating equipment. It can withstand practical use as other wear-resistant members such as sliding members such as slides, and has great industrial utility value.

【図面の簡単な説明】[Brief explanation of the drawing]

【図1】本発明の一実施例に係る窒化硼素被覆部材の断
面模式図。
FIG. 1 is a schematic cross-sectional view of a boron nitride-coated member according to an embodiment of the present invention.

【図2】本発明の一実施例に係る窒化硼素被覆部材形成
装置の概略図。
FIG. 2 is a schematic diagram of a boron nitride-coated member forming apparatus according to an embodiment of the present invention.

【図3】本発明に係る窒化硼素被覆部材に対して被覆の
スクラッチ試験を行って得た臨界荷重を示す図。
FIG. 3 is a diagram showing the critical load obtained by conducting a coating scratch test on the boron nitride coated member according to the present invention.

【符号の説明】[Explanation of symbols]

1  基材 2  中間層 3  境界層 4  CBN層 11  真空容器 12  基材ホルダ 13  基材 14  イオン源 15  蒸発源 16  金属硼素 17  電子ビーム 18  硼素蒸気 19  モニタ 20  窒素+希ガス混合イオン 1 Base material 2 Middle class 3 Boundary layer 4 CBN layer 11 Vacuum container 12 Base material holder 13 Base material 14 Ion source 15 Evaporation source 16 Metallic boron 17 Electron beam 18 Boron vapor 19 Monitor 20 Nitrogen + noble gas mixed ion

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】  基材あるいは基材上に形成された中間
層上に窒化硼素皮膜を形成してなる窒化硼素被覆部材に
おいて、基材あるいは中間層と窒化硼素皮膜との境界部
に基材あるいは中間層材料と窒化硼素との混合組成であ
る境界層を形成すると共に当該境界層の組成を基材ある
いは中間層成分が基材側から被覆側へと順次減少してい
く傾斜組成とし、且つ当該境界層中に立方晶窒化硼素を
存在させると共に当該境界層中における当該立方晶窒化
硼素の存在量を窒化硼素皮膜側から基材あるいは中間層
側へ順次減少させたことを特徴とする窒化硼素被覆部材
Claim 1: In a boron nitride-coated member in which a boron nitride film is formed on a base material or an intermediate layer formed on the base material, the interface between the base material or intermediate layer and the boron nitride film is coated with the base material or A boundary layer having a mixed composition of the intermediate layer material and boron nitride is formed, and the composition of the boundary layer is a gradient composition in which the base material or intermediate layer components sequentially decrease from the base material side to the coating side, and A boron nitride coating characterized in that cubic boron nitride is present in the boundary layer and the amount of cubic boron nitride in the boundary layer is gradually decreased from the boron nitride film side to the base material or intermediate layer side. Element.
JP11048191A 1991-05-15 1991-05-15 Boron nitride coated member Expired - Fee Related JP2909248B2 (en)

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JP11048191A JP2909248B2 (en) 1991-05-15 1991-05-15 Boron nitride coated member

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JP2909248B2 JP2909248B2 (en) 1999-06-23

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US5948541A (en) * 1996-04-04 1999-09-07 Kennametal Inc. Boron and nitrogen containing coating and method for making
US5976716A (en) * 1996-04-04 1999-11-02 Kennametal Inc. Substrate with a superhard coating containing boron and nitrogen and method of making the same
US6593015B1 (en) 1999-11-18 2003-07-15 Kennametal Pc Inc. Tool with a hard coating containing an aluminum-nitrogen compound and a boron-nitrogen compound and method of making the same
JP2005042146A (en) * 2003-07-25 2005-02-17 Mitsubishi Heavy Ind Ltd Coating with high abrasion resistance and high hardness
JP2005139515A (en) * 2003-11-07 2005-06-02 Mitsubishi Heavy Ind Ltd Wear resistant hard film
JP2014520204A (en) * 2011-05-27 2014-08-21 ナノメック、インコーポレイテッド Multilayer coating with cubic boron nitride particles
WO2023157466A1 (en) * 2022-02-15 2023-08-24 Seavac株式会社 Hard coating

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5948541A (en) * 1996-04-04 1999-09-07 Kennametal Inc. Boron and nitrogen containing coating and method for making
US5976716A (en) * 1996-04-04 1999-11-02 Kennametal Inc. Substrate with a superhard coating containing boron and nitrogen and method of making the same
US6054185A (en) * 1996-04-04 2000-04-25 Kennametal Inc. Substrate with superhard coating containing boron and nitrogen and method of making the same
US6086959A (en) * 1996-04-04 2000-07-11 Kennametal Inc. Boron and nitrogen containing coating and method for making
US6096436A (en) * 1996-04-04 2000-08-01 Kennametal Inc. Boron and nitrogen containing coating and method for making
US6117533A (en) * 1996-04-04 2000-09-12 Kennametal Inc. Substrate with a superhard coating containing boron and nitrogen and method of making the same
US6593015B1 (en) 1999-11-18 2003-07-15 Kennametal Pc Inc. Tool with a hard coating containing an aluminum-nitrogen compound and a boron-nitrogen compound and method of making the same
JP2005042146A (en) * 2003-07-25 2005-02-17 Mitsubishi Heavy Ind Ltd Coating with high abrasion resistance and high hardness
US7226659B2 (en) 2003-07-25 2007-06-05 Mitsubishi Heavy Industries, Ltd. High wear resistant hard film
US7449253B2 (en) 2003-07-25 2008-11-11 Mitsubishi Heavy Industries, Ltd. High wear resistant hard film
JP2005139515A (en) * 2003-11-07 2005-06-02 Mitsubishi Heavy Ind Ltd Wear resistant hard film
JP2014520204A (en) * 2011-05-27 2014-08-21 ナノメック、インコーポレイテッド Multilayer coating with cubic boron nitride particles
EP2714387B1 (en) * 2011-05-27 2019-10-16 Nanomech Inc. Method of making a multi-layer coating with cubic boron nitride particles
WO2023157466A1 (en) * 2022-02-15 2023-08-24 Seavac株式会社 Hard coating

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