JPH02138459A - Laminated hard material and production thereof - Google Patents
Laminated hard material and production thereofInfo
- Publication number
- JPH02138459A JPH02138459A JP28973588A JP28973588A JPH02138459A JP H02138459 A JPH02138459 A JP H02138459A JP 28973588 A JP28973588 A JP 28973588A JP 28973588 A JP28973588 A JP 28973588A JP H02138459 A JPH02138459 A JP H02138459A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- composite
- coating film
- hard material
- film
- 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
- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 nitrogen ions Chemical class 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000005520 cutting process Methods 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- 229910000997 High-speed steel Inorganic materials 0.000 description 7
- 230000001133 acceleration Effects 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000010884 ion-beam technique Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、複合硬質材料及びその製造方法に関し、特に
耐酸化性の優れた複合硬質材料及びその製造方法に係わ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hard composite material and a method for manufacturing the same, and particularly to a hard composite material with excellent oxidation resistance and a method for manufacturing the same.
［従来の技術及び課題］
耐熱性が高く、硬質であるＴｉＮは、従来より種々の基
材上に被覆してその特長である耐熱性、耐摩耗性を基材
に付与することが行われ、かつ各方面で実用化されてい
る。特に、高速度鋼、超硬合金にＴｉ Ｎ膜を被覆した
複合硬質材料は耐摩耗部品、切削工具等で長年に亙って
実績を上げてきている。しかしながら、工業的利用の面
から更に苛酷な使用条件に耐える複合硬質材料が要望さ
れている。[Prior Art and Problems] TiN, which has high heat resistance and is hard, has traditionally been coated on various base materials to impart its characteristics of heat resistance and wear resistance to the base materials. And it has been put into practical use in various fields. In particular, composite hard materials such as high-speed steel and cemented carbide coated with a TiN film have been used for many years as wear-resistant parts, cutting tools, and the like. However, from the standpoint of industrial use, there is a demand for composite hard materials that can withstand even more severe usage conditions.
上述した要望から、最近、Ｔｉ （Ｃ−Ｎ）、（Ｔｆ
、Ｈｆ）Ｎ、（Ｔｉ、Ｚｒ）Ｎ等の３元系の複合材料が
検討され、夫々の元素の特長を生かした特性を有する材
料の開発が行われている。Due to the above-mentioned demands, recently Ti (C-N), (Tf
, Hf)N, (Ti, Zr)N, and other ternary composite materials are being studied, and materials with characteristics that take advantage of the features of each element are being developed.
一方、（Ｔｉ 、ｌ）Ｎ系の複合材料はＡρ成分を含む
ため、高温での酸化条件下で保護膜であるＡｌ２０３を
生成することにより耐酸化性の向上が確認されており、
該複合材料を基材被覆した複合硬質材料は、従来の複合
硬質材料（例えば基材上にＴｉＮを被覆したもの）に比
べてクレータ及びフランク摩耗量が少ないため、有望な
切削工具用材料と考えられている。On the other hand, since (Ti, l)N-based composite materials contain Aρ components, it has been confirmed that they improve oxidation resistance by forming a protective film, Al203, under oxidizing conditions at high temperatures.
A hard composite material in which the composite material is coated on a base material is considered to be a promising material for cutting tools because it has less crater and flank wear than conventional hard composite materials (for example, a base material coated with TiN). It is being
しかしながら、（Ｔｉ 、ｌり Ｎの特定の組成、例え
ば（５０ａｔ％Ｔｌ−５０ａｔ％Ａｌ）Ｈの組成の複合
被膜を所望の基材上に直接被覆すると、基材と複合被膜
との化学組成、結晶構造の相違からそれらの界面での構
成ギャップにより密着性が不十分となったり、熱膨張係
数のギャップにより熱応力下で界面から複合被膜が剥離
する等の問題があった。However, when a composite film with a specific composition of (Ti, 1, 2, 2, 3, 3, 3, 4, 5, 4, 5, 4, 5, 4, 5, 5, 5, 5, 5, 5, 5, 5, 5, 4 There have been problems such as insufficient adhesion due to a structural gap at the interface due to the difference in crystal structure, and a composite coating peeling off from the interface under thermal stress due to a gap in thermal expansion coefficient.
本発明は、上記従来の課題を解決するためになされたも
ので、耐酸化性の優れた（Ｔｉ、Ａｎ））Ｎ組成を有す
る複合被膜を基材上にそれら界面でのクラックや剥離発
生等を招くことなく良好に密着させた複合硬質材料、並
びにかかる複合硬質材料を簡単な工程により製造し得る
方法を提供しようとするものである。The present invention was made in order to solve the above-mentioned conventional problems, and a composite coating having a (Ti, An))N composition with excellent oxidation resistance is coated on a base material, and cracks and peeling occur at the interface between them. It is an object of the present invention to provide a composite hard material that can be adhered well without causing problems, and a method for manufacturing such a composite hard material through simple steps.
［課題を解決するための手段］
本発明は、基材上に、該基材側からＡｌｆｆ１を段階的
もしくは連続的に増加させた（Ｔｌ、ｌりＮ系の組成構
造を有する複合被膜を被覆したことを特徴とする複合硬
質材料である。[Means for Solving the Problems] The present invention provides a method of coating a base material with a composite film having a composition structure of Tl, l and N, in which Alff1 is increased stepwise or continuously from the base material side. It is a composite hard material characterized by the following.
上記基材としては、例えば高速度鋼、超硬合金、サーメ
ット等からなるものを挙げることができる。Examples of the base material include those made of high-speed steel, cemented carbide, cermet, and the like.
また、本発明方法は基材上にＴ１及びＡｌ１を蒸着する
と同時にイオン源より窒素イオンを照射するイオンミキ
シング法により該基材側からＡｌｌ量を段階的もしくは
連続的に増加させた（Ｔｉ 。Furthermore, in the method of the present invention, the amount of Al is increased stepwise or continuously from the substrate side using an ion mixing method in which nitrogen ions are irradiated from an ion source at the same time as T1 and Al1 are deposited on the substrate (Ti.
Ａ１１））Ｎ系の組成構造を有する複合被膜を形成する
ことを特徴とする複合硬質材料の製造方法である。A11)) A method for producing a composite hard material characterized by forming a composite coating having an N-based composition structure.
上記Ｔｉ 、 Ａｌｔの蒸着手段としては、ターゲット
を利用したイオンビームスパッタ法と、電子ビームによ
る真空蒸着を挙げることができる。前者の方法では、所
定の化学組成を有するＴｉ −Ａ４７合金ターゲツトを
利用してもよく、或いはＴｉ及びＡＩ単体の金属ターゲ
ットに順次スパッタイオンビームを照射して合金膜を基
材表面に蒸着してもよい。この場合、スパッタイオンビ
ームの加速電圧、ビーム電流を調節したり、ターゲット
にイオンビームを照射する時間を調節することにより蒸
着組成を制御することが可能となる。また、電子ビーム
を用いる真空蒸着法の場合はダブルハース方式で電子ビ
ームによりＴｉと１を蒸着するがＴｉとＡｌとを連続的
に蒸着することも可能であり、適当な時間間隔をおいて
蒸着することも可能であり、組成制御も可能である。Examples of the means for depositing Ti and Alt include ion beam sputtering using a target and vacuum deposition using an electron beam. In the former method, a Ti-A47 alloy target having a predetermined chemical composition may be used, or a sputtering ion beam may be sequentially irradiated onto a single metal target of Ti and AI to deposit an alloy film on the surface of the substrate. Good too. In this case, it is possible to control the deposition composition by adjusting the accelerating voltage and beam current of the sputtering ion beam, or by adjusting the time for irradiating the target with the ion beam. In addition, in the case of the vacuum evaporation method using an electron beam, Ti and 1 are evaporated by the electron beam in a double hearth method, but it is also possible to evaporate Ti and Al continuously, and the evaporation can be performed at appropriate time intervals. It is also possible to control the composition.
前記イオン源より照射する窒素イオンは、蒸着と独立し
て操作することが可能である。このため、蒸着量と窒素
イオンの相対的な組成比率は自由に調節でき、目的とす
る所定比率の（Ｔｉ 、 ＡＩ ）Ｎの被膜を形成する
ことが可能であり、組成を段階的もしくは連続的に制御
することが可能である。The nitrogen ions irradiated from the ion source can be operated independently of the vapor deposition. Therefore, the amount of evaporation and the relative composition ratio of nitrogen ions can be freely adjusted, and it is possible to form a film of (Ti, AI)N with a desired predetermined ratio, and the composition can be changed stepwise or continuously. It is possible to control the
［作用］
本発明によれば、基材上に、該基材側からＡｆｌ量を段
階的もしくは連続的に増加させた（Ｔｉ 。[Function] According to the present invention, the amount of Afl is increased stepwise or continuously on the base material from the base material side (Ti.
Ａｌ）Ｎ系の組成構造を有する複合被膜を被覆すること
によって、基材と接する複合被膜の界面での極端な組成
の落差に起因する複合被膜のクラックや剥離等の発生を
防止できると共に基材に対する密着性を向上できる。ま
た、複合被膜中の１量を基材側から段階的もしくは連続
的に増加させることによって、最上層側の被膜部分中の
ＡＩのＴｉ リッチ層への拡散を抑制できるため、目的
とした耐酸化性及び切削性能を有する複合被膜を基材上
に被覆した複合硬質材料を得ることができる。By coating with a composite film having an Al)N-based composition structure, it is possible to prevent the occurrence of cracks and peeling of the composite film due to extreme compositional differences at the interface of the composite film in contact with the base material. can improve adhesion to In addition, by increasing the amount of Al in the composite coating stepwise or continuously from the base material side, it is possible to suppress the diffusion of AI in the uppermost coating part to the Ti-rich layer, thereby achieving the desired oxidation resistance. A composite hard material can be obtained by coating a base material with a composite film having excellent cutting performance and cutting performance.
更に、本発明によれば組成制御、組成の段階的もしくは
連続的な制御が容易なイオンミキシング法を採用してい
るため、既述したような耐酸化性及び切削性能を有する
複合被膜を基材上に対してクラック等を発生せずに良好
に密着、被覆した複合硬質材料を簡単に製造することが
できる。Furthermore, the present invention employs an ion mixing method that facilitates compositional control and stepwise or continuous control of the composition. It is possible to easily produce a hard composite material that is well adhered to and coated on the surface without causing cracks or the like.
［実施例］ 以下、本発明の実施例を詳細に説明する。[Example] Examples of the present invention will be described in detail below.
実施例１
まず、基材としてのａｏｘ ａｏｘ ２ ｍｍの寸法の
高速度鋼板を用意し、この板をイオン照射と蒸着機能を
備えた真空チャンバ内のホルダに保持した。つづいて、
このチャンバ内を５ Ｘ ｌｏ＝ ｔｏｒｒに真空引き
した後、イオン源から加速電圧５ｋＶのＡｒイオンを引
き出し、前記板に照射して表面清浄化のための前処理を
施した。次いで、Ｔｉ及びＡ、Ｑをダブルハース方式の
電子ビーム蒸着法で、まず前記高速度鋼板にＴｉを３．
０人／ｓｅｅの蒸着速度で蒸着しながら、Ａｌを０〜３
．０人／ ｓｅｅの蒸着速度で次第に蒸着速度を増大さ
せて、Ｔｉ−Ａｌの組成変化がなされた連続膜を形成す
ると同時にイオン源から窒素イオンを加速電圧１０ｋＶ
、イオン電流密度０．５ｍＡ／ｃｄの条件で引き出し、
該連続膜に照射して複合窒化物膜を形成し、最後に（５
０ａｔ％↑ｌ−５０ａｔ％Ａρ）Ｎの組成となるように
条件をコントロールして厚さが４μｍの複合被膜を形成
して複合硬質材料を製造した。Example 1 First, a high-speed steel plate having a size of aox aox 2 mm was prepared as a base material, and this plate was held in a holder in a vacuum chamber equipped with ion irradiation and vapor deposition functions. Continuing,
After the chamber was evacuated to 5×lo=torr, Ar ions were extracted from the ion source at an acceleration voltage of 5 kV, and the plate was irradiated with it to perform a pretreatment for surface cleaning. Next, Ti, A, and Q were first deposited on the high-speed steel plate in 3.5 seconds using a double-hearth electron beam evaporation method.
While depositing Al at a deposition rate of 0 people/see,
．． The deposition rate was gradually increased at a deposition rate of 0 people/see to form a continuous film with a Ti-Al composition change, and at the same time nitrogen ions were accelerated from the ion source at a voltage of 10 kV.
, extracted under the condition of ion current density 0.5 mA/cd,
The continuous film is irradiated to form a composite nitride film, and finally (5
A composite hard material was manufactured by controlling the conditions to have a composition of 0 at%↑l-50 at%Aρ)N to form a composite coating with a thickness of 4 μm.
比較例１
前記実施例１と同様な前処理を施した高速度鋼板にダブ
ルハース方式と窒素イオンの照射により厚さ４μｍの（
５０ａｔ％Ｔｉ−５０ａｔ％Ａｊ７）Ｎ（７）組成を持
つ複合被膜を直接形成して複合硬質材料を製造した。な
お、ＴｉとＡｌ１の蒸着速度は夫々３．０人／ｓｅｅ、
窒素イオンの照射を加速電圧１０ｋＶ、イオン電流密度
０．５ｍＡ／ｃ−の条件で行なった。Comparative Example 1 A high-speed steel plate pretreated in the same manner as in Example 1 was coated with a 4 μm thick (
A composite hard material was manufactured by directly forming a composite coating having a composition of 50 at% Ti-50 at% Aj7)N(7). In addition, the deposition rate of Ti and Al1 is 3.0 people/see, respectively.
Nitrogen ion irradiation was performed at an acceleration voltage of 10 kV and an ion current density of 0.5 mA/c.
しかして、真空チャンバから取出した本実施例１及び比
較例１の複合硬質材料を切断し、断面をＳＥＭで観察し
た。その結果、比較例１の複合硬質材料では高速度鋼と
複合被膜の界面に僅かであるがマイクロクラックの発生
が認められた。これに対し、本実施例１の複合硬質材料
では高速度鋼板と複合被膜との界面にも何等の欠陥も観
察されず良好な被覆構造を有することが確認された。The composite hard materials of Example 1 and Comparative Example 1 taken out from the vacuum chamber were cut, and the cross sections were observed using a SEM. As a result, in the composite hard material of Comparative Example 1, the occurrence of microcracks, although slight, was observed at the interface between the high-speed steel and the composite coating. In contrast, in the composite hard material of Example 1, no defects were observed at the interface between the high-speed steel plate and the composite coating, and it was confirmed that the composite hard material had a good coating structure.
実施例２
一般的なＣＶＤ法によりＴｉＮ膜が被覆された超硬合金
チップをイオン照射と蒸着機能を備えた真空チャンバ内
のホルダに保持した。つづいて、このチャンバ内を５
Ｘ １０＝ ｔｏｒｒに真空引きした後、イオン源から
加速電圧５ｋＶのＡｒイオンを引き出し、前記チップ表
面に５分間照射して表面清浄化のための前処理を施した
。ひきつづき、７５ａｔ％Ｔ１．−２５ａｔ％Ａｐのタ
ーゲットにスパッタイオン源より加速電圧３．５ｋＶ、
イオン電流２．ＯＡで弓出したＡｒイオンを照射して前
記チップにスパッタ蒸着すると同時に他のイオン源から
窒素イオンを加速電圧１０ｋＶ、イオン電流密度０．５
ｍＡ／ｃＪの条件で引き出し、該スパッタ蒸着膜に照射
して厚さ２μｍの（７５ａｔ％Ｔｉ ２５ａｔ％Ａｊ
７）Ｎ組成を有する複合窒化物膜を形成した。次いで、
この複合窒化物膜に別の５０ａｔ％Ｔｌ−５０ａｔ％Ａ
ｌのターゲットにスパッタイオン源より加速電圧２．５
ｋ Ｖ、イオン電流１，５Ａで引出したＡｒイオンを照
射して前記チップにスパッタ蒸着すると同時に他のイオ
ン源から窒素イオンを加速電圧１０ｋ Ｖ、イオン電流
密度０．５ｍＡ／ｃ−の条件で引き出し、該スパッタ蒸
着膜に照射して厚さ約２μｍの（５０ａｔ％Ｔｌ−５０
ａｔ％ＡΩ）Ｎ組成を有する複合窒化物膜を形成して複
合硬質材料を製造した。Example 2 A cemented carbide chip coated with a TiN film by a general CVD method was held in a holder in a vacuum chamber equipped with ion irradiation and vapor deposition functions. Next, go inside this chamber 5 times.
After evacuation to X 10 = torr, Ar ions were extracted from the ion source at an accelerating voltage of 5 kV, and the chip surface was irradiated for 5 minutes to perform pretreatment for surface cleaning. Continuing, 75at%T1. Acceleration voltage 3.5 kV from sputter ion source to -25 at% Ap target,
Ionic current2. At the same time, nitrogen ions from another ion source were irradiated with OA-produced Ar ions and sputter-deposited on the chip at an acceleration voltage of 10 kV and an ion current density of 0.5.
mA/cJ, and irradiated the sputter-deposited film to form a 2 μm thick film (75 at% Ti 25 at% Aj
7) A composite nitride film having a N composition was formed. Then,
This composite nitride film is coated with another 50 at% Tl-50 at% A.
An acceleration voltage of 2.5 from a sputter ion source to a target of
Ar ions extracted at kV and ion current of 1.5 A were irradiated and sputter-deposited on the chip, and at the same time nitrogen ions were extracted from another ion source at an acceleration voltage of 10 kV and an ion current density of 0.5 mA/c-. , the sputter-deposited film is irradiated to form a film with a thickness of about 2 μm (50 at% Tl-50
A composite hard material was manufactured by forming a composite nitride film having a composition of at%AΩ)N.
比較例２
前記実施例２と同様に表面清浄化処理されたＴｉ Ｎ膜
が被覆された超硬合金チップにスパッタ蒸着と窒素イオ
ンの照射により厚さ４μｍの（５０ａｔ％Ｔ１−５０ａ
ｔ％ＡＪ７）Ｎ組成を有する複合窒化物膜のみを形成し
て複合硬質材料を製造した。Comparative Example 2 A cemented carbide chip coated with a TiN film subjected to surface cleaning treatment in the same manner as in Example 2 was coated with a 4 μm thick (50 at% T1-50a) by sputter deposition and irradiation with nitrogen ions.
t%AJ7) A composite hard material was manufactured by forming only a composite nitride film having a N composition.
しかして、本実施例２及び比較例２の複合硬質材料ニヨ
リＨ，−２８０（７）ＳＮＣＭ８鋼をｖ −ｉｇ。Therefore, the composite hard material Niyori H, -280 (7) SNCM8 steel of Example 2 and Comparative Example 2 was v-ig.
ｍ／ｌｌ１ｎ Ｓｆ −０，２５ｍｍ／ｒｅｖ 、 ｔ
−１，５ｍｍ （１回の切削時での切り込み量）の条
件で切削した時の耐摩耗性を調べた。その結果、本実施
例２の複合硬質材料では１０分間テＶ Ｂ＝ ０．１５
Ｉｌ１ｍ テあったか、比較例２の複合硬質材料では１
０分間でＶＢ−０，２５■と劣っており、しかも基材で
あるＴｉＮ被覆超硬合金チップと複合窒化物膜との界面
で一部クラックの発生が認められた。m/ll1n Sf -0,25mm/rev, t
The wear resistance when cutting was conducted under the condition of -1.5 mm (depth of cut in one cutting) was investigated. As a result, in the composite hard material of Example 2, the TE V B = 0.15 for 10 minutes
Il1m Te was warm, 1 for the composite hard material of Comparative Example 2.
It was inferior to VB-0.25■ after 0 minutes, and cracks were partially observed at the interface between the TiN-coated cemented carbide chip as the base material and the composite nitride film.
実施例３
３０Ｘ ３０Ｘ ２ ｍｍのＴｉ板を実施例１と同様な
表面清浄化処理を施し、電子ビームによるダブルハース
方式によりＴｌ 、Ａｌの電子ビーム蒸着量をコントロ
ールしながら、同時に窒素イオンを照射して多層の複合
窒化物膜を形成した複合硬質材料を製造した。なお、各
膜の組成、Ｔ１及び八ρの蒸着速度、窒素イオンの照射
時の加速電圧、ビーム電流密度を下記第１表に示す。Example 3 A Ti plate of 30 x 30 x 2 mm was subjected to the same surface cleaning treatment as in Example 1, and was simultaneously irradiated with nitrogen ions while controlling the amount of electron beam evaporation of Tl and Al using a double hearth method using an electron beam. A composite hard material with a multilayered composite nitride film was manufactured using this method. The composition of each film, the deposition rate of T1 and 8ρ, the acceleration voltage during nitrogen ion irradiation, and the beam current density are shown in Table 1 below.
比較例３
ａｏｘ ３０Ｘ ２ ａｍのＴ１板を実施例１と同様な
表面清浄化処理を施した後、該Ｔｆ後板上上記第１表の
第３層目の膜形成と同様な方法により厚さ３ｕｍの（５
０ａｔ％Ｔｉ−５０ａｔ％ＡｊりＮ組成を有する複合窒
化物膜を直接形成して複合硬質材料を製造した。Comparative Example 3 A T1 plate of aox 30X 2 am was subjected to the same surface cleaning treatment as in Example 1, and then the thickness was reduced by the same method as the third layer film formation in Table 1 above on the Tf rear plate. 3um(5
A composite hard material was manufactured by directly forming a composite nitride film having a composition of 0 at% Ti-50 at% Aj and N.
しかして、本実施例３及び比較例３の複合硬質材料を夫
々空気中で１７００”ｃ、３００時間の酸化試験を行な
い、酸化増量を調べた。その結果を下記第２表に示した
。Therefore, the composite hard materials of Example 3 and Comparative Example 3 were each subjected to an oxidation test in air at 1700"C for 300 hours to examine the oxidation weight gain. The results are shown in Table 2 below.
第２表
上記第２表から明らがなように、本実施例３の複合硬質
材料は耐酸化性が極めて優れていることがわかる。Table 2 As is clear from Table 2 above, the hard composite material of Example 3 has extremely excellent oxidation resistance.
なお、上記実施例では基材上に該基材側がらＡＮ量を段
階的もしくは連続的に増大させた（Ｔｉ、ＡΩ）Ｎ系の
組成構造を有する複合被膜を被覆した複合硬質材料につ
いて説明したが、基材の種類や結晶構造等により該基材
側からＡｌ量を段階的もしくは連続的に減少させた（Ｔ
ｉ 。In addition, in the above example, a composite hard material was described in which a composite coating having a (Ti, AΩ)N composition structure in which the amount of AN was increased stepwise or continuously from the base material side was coated on the base material. However, depending on the type of base material, crystal structure, etc., the amount of Al was reduced stepwise or continuously from the base material side (T
i.
Ａｌ）Ｎ系の組成構造を有する複合被膜を基材上に被覆
したり、ＡｆＩ ｌを段階的もしくは連続的に増減させ
た複合被膜を基材上に被覆してもよい。A composite film having an Al)N-based composition structure may be coated on the base material, or a composite film may be coated on the base material in which the amount of AfIl is increased or decreased stepwise or continuously.
［発明の効果］
以上詳述した如く、本発明によれば耐酸化性の優れた（
Ｔｉ 、Ａｌ２）Ｎ組成を有する複合被膜を基材上にそ
れら界面でのクラックや剥離発生等を招くことなく良好
に密着させた耐摩耗部品や切削工具等に好適な複合硬質
材料、並びにかかる複合硬質材料を簡単な工程により製
造し得る方法を提供できる。[Effects of the Invention] As detailed above, according to the present invention, a material with excellent oxidation resistance (
A composite hard material suitable for wear-resistant parts, cutting tools, etc., in which a composite coating having a Ti, Al2)N composition is adhered well to a base material without causing cracks or peeling at the interface thereof, and such a composite It is possible to provide a method for manufacturing hard materials through simple steps.
出願人代理人 弁理士 鈴江武彦Applicant's agent: Patent attorney Takehiko Suzue
Claims (2)
は連続的に増加させた（Ｔｉ、Ａｌ）Ｎ系の組成構造を
有する複合被膜を被覆したことを特徴とする複合硬質材
料。(1) A composite hard material characterized by coating a base material with a composite film having a (Ti, Al)N composition structure in which the amount of Al is increased stepwise or continuously from the base material side. material.
ン源より窒素イオンを照射するイオンミキシング法によ
り該基材側からＡｌ量を段階的もしくは連続的に増加さ
せた（Ｔｉ、Ａｌ）Ｎ系の組成構造を有する複合被膜を
形成することを特徴とする複合硬質材料の製造方法。(2) The amount of Al was increased stepwise or continuously from the substrate side using an ion mixing method in which Ti and Al were vapor deposited on the substrate and nitrogen ions were irradiated from an ion source at the same time (Ti, Al)N. 1. A method for producing a composite hard material, which comprises forming a composite film having a compositional structure of a system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28973588A JPH02138459A (en) | 1988-11-16 | 1988-11-16 | Laminated hard material and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28973588A JPH02138459A (en) | 1988-11-16 | 1988-11-16 | Laminated hard material and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02138459A true JPH02138459A (en) | 1990-05-28 |
| JPH0588310B2 JPH0588310B2 (en) | 1993-12-21 |
Family
ID=17747075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28973588A Granted JPH02138459A (en) | 1988-11-16 | 1988-11-16 | Laminated hard material and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02138459A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02170965A (en) * | 1988-12-22 | 1990-07-02 | Sumitomo Metal Mining Co Ltd | Oxidation and wear resistant coated steel material |
| JPH04103755A (en) * | 1990-08-23 | 1992-04-06 | Sumitomo Metal Mining Co Ltd | Surface coated steel product and its production |
| JPH0592304A (en) * | 1991-05-21 | 1993-04-16 | Nachi Fujikoshi Corp | Multilayer coating tool |
| JPH05285215A (en) * | 1992-04-09 | 1993-11-02 | Masaru Yamaoka | Equipment coated with film of ti-al-n composition |
| DE4408250A1 (en) * | 1993-07-12 | 1995-01-19 | Oriental Engineering Co | Process for coating the surface of a substrate and coating material |
| US6071374A (en) * | 1996-06-26 | 2000-06-06 | Lg Electronics Inc. | Apparatus for etching glass substrate |
| US6197209B1 (en) | 1995-10-27 | 2001-03-06 | Lg. Philips Lcd Co., Ltd. | Method of fabricating a substrate |
| US6228211B1 (en) | 1998-09-08 | 2001-05-08 | Lg. Philips Lcd Co., Ltd. | Apparatus for etching a glass substrate |
| US6551443B2 (en) | 2000-12-30 | 2003-04-22 | Lg.Philips Lcd Co., Ltd. | Apparatus for etching glass substrate in fabrication of LCD |
| US6558776B1 (en) | 1998-10-22 | 2003-05-06 | Lg.Philips Lcd Co., Ltd. | Glass substrate for liquid crystal display device |
| US6824618B2 (en) | 2001-12-19 | 2004-11-30 | Lg.Philips Lcd., Ltd. | Substrate receiving apparatus and method thereof |
| US6836311B2 (en) | 2002-05-23 | 2004-12-28 | Lg. Philips Lcd Co., Ltd. | Seal pattern for liquid crystal display device including first, second and third dummy seal patterns in non-active area |
| US6930748B2 (en) | 2000-12-29 | 2005-08-16 | Lg.Philips Lcd Co., Ltd. | Liquid crystal display device and method for manufacturing the same |
| US6955840B2 (en) | 1997-10-20 | 2005-10-18 | Lg. Philips Lcd Co., Ltd. | Liquid crystal display device having thin glass substrate on which protective layer formed and method of making the same |
| US6958801B2 (en) | 2001-11-07 | 2005-10-25 | Lg.Philips Lcd Co., Ltd. | Seal pattern for ultra-thin liquid crystal display device |
| US7014732B2 (en) | 2001-12-29 | 2006-03-21 | Lg.Philips Lcd Co., Ltd. | Etching apparatus |
| US7016008B2 (en) | 2001-12-18 | 2006-03-21 | Lg.Philips Lcd Co., Ltd. | Method of fabricating liquid crystal display device having sealant patterns, dummy patterns, and substrate protective patterns |
| US7336334B2 (en) | 2001-12-06 | 2008-02-26 | Lg.Philips Lcd Co., Ltd. | Fabrication method of liquid crystal display device |
| US7361610B2 (en) | 2000-12-27 | 2008-04-22 | Lg.Philips Lcd Co., Ltd. | Method of etching a glass substrate |
| US7388642B2 (en) | 2000-11-30 | 2008-06-17 | Lg Display Co., Ltd. | Seal pattern for liquid crystal display device and forming method thereof |
| US7393431B2 (en) | 2001-09-25 | 2008-07-01 | Lg Display Co., Ltd. | Bubble plate for etching and etching apparatus using the same |
| US7736461B2 (en) | 2002-10-07 | 2010-06-15 | Lg Display Co., Ltd. | Cassette for preventing breakage of glass substrate |
| US8043466B1 (en) | 1997-03-21 | 2011-10-25 | Lg Display Co., Ltd | Etching apparatus |
| US8512580B2 (en) | 2001-09-21 | 2013-08-20 | Lg Display Co., Ltd. | Method of fabricating thin liquid crystal display device |
-
1988
- 1988-11-16 JP JP28973588A patent/JPH02138459A/en active Granted
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02170965A (en) * | 1988-12-22 | 1990-07-02 | Sumitomo Metal Mining Co Ltd | Oxidation and wear resistant coated steel material |
| JPH04103755A (en) * | 1990-08-23 | 1992-04-06 | Sumitomo Metal Mining Co Ltd | Surface coated steel product and its production |
| JPH0592304A (en) * | 1991-05-21 | 1993-04-16 | Nachi Fujikoshi Corp | Multilayer coating tool |
| JPH05285215A (en) * | 1992-04-09 | 1993-11-02 | Masaru Yamaoka | Equipment coated with film of ti-al-n composition |
| DE4408250C2 (en) * | 1993-07-12 | 2001-06-13 | Oriental Engineering Co | Surface layer system for substrates |
| DE4408250A1 (en) * | 1993-07-12 | 1995-01-19 | Oriental Engineering Co | Process for coating the surface of a substrate and coating material |
| US6197209B1 (en) | 1995-10-27 | 2001-03-06 | Lg. Philips Lcd Co., Ltd. | Method of fabricating a substrate |
| US6071374A (en) * | 1996-06-26 | 2000-06-06 | Lg Electronics Inc. | Apparatus for etching glass substrate |
| US8043466B1 (en) | 1997-03-21 | 2011-10-25 | Lg Display Co., Ltd | Etching apparatus |
| US6955840B2 (en) | 1997-10-20 | 2005-10-18 | Lg. Philips Lcd Co., Ltd. | Liquid crystal display device having thin glass substrate on which protective layer formed and method of making the same |
| US6228211B1 (en) | 1998-09-08 | 2001-05-08 | Lg. Philips Lcd Co., Ltd. | Apparatus for etching a glass substrate |
| US6558776B1 (en) | 1998-10-22 | 2003-05-06 | Lg.Philips Lcd Co., Ltd. | Glass substrate for liquid crystal display device |
| US7388642B2 (en) | 2000-11-30 | 2008-06-17 | Lg Display Co., Ltd. | Seal pattern for liquid crystal display device and forming method thereof |
| US7361610B2 (en) | 2000-12-27 | 2008-04-22 | Lg.Philips Lcd Co., Ltd. | Method of etching a glass substrate |
| US6930748B2 (en) | 2000-12-29 | 2005-08-16 | Lg.Philips Lcd Co., Ltd. | Liquid crystal display device and method for manufacturing the same |
| US6551443B2 (en) | 2000-12-30 | 2003-04-22 | Lg.Philips Lcd Co., Ltd. | Apparatus for etching glass substrate in fabrication of LCD |
| US8512580B2 (en) | 2001-09-21 | 2013-08-20 | Lg Display Co., Ltd. | Method of fabricating thin liquid crystal display device |
| US7393431B2 (en) | 2001-09-25 | 2008-07-01 | Lg Display Co., Ltd. | Bubble plate for etching and etching apparatus using the same |
| US6958801B2 (en) | 2001-11-07 | 2005-10-25 | Lg.Philips Lcd Co., Ltd. | Seal pattern for ultra-thin liquid crystal display device |
| US7068346B2 (en) | 2001-11-07 | 2006-06-27 | Lg.Philips Lcd Co., Ltd. | Seal pattern for ultra-thin liquid crystal display device |
| US7336334B2 (en) | 2001-12-06 | 2008-02-26 | Lg.Philips Lcd Co., Ltd. | Fabrication method of liquid crystal display device |
| US7016008B2 (en) | 2001-12-18 | 2006-03-21 | Lg.Philips Lcd Co., Ltd. | Method of fabricating liquid crystal display device having sealant patterns, dummy patterns, and substrate protective patterns |
| US6824618B2 (en) | 2001-12-19 | 2004-11-30 | Lg.Philips Lcd., Ltd. | Substrate receiving apparatus and method thereof |
| US7790052B2 (en) | 2001-12-19 | 2010-09-07 | Lg Display Co., Ltd. | Substrate receiving method |
| US7494595B2 (en) | 2001-12-29 | 2009-02-24 | Lg Display Co., Ltd. | Etching apparatus |
| US7014732B2 (en) | 2001-12-29 | 2006-03-21 | Lg.Philips Lcd Co., Ltd. | Etching apparatus |
| US6836311B2 (en) | 2002-05-23 | 2004-12-28 | Lg. Philips Lcd Co., Ltd. | Seal pattern for liquid crystal display device including first, second and third dummy seal patterns in non-active area |
| US6919949B2 (en) | 2002-05-23 | 2005-07-19 | Lg.Philips Lcd Co., Ltd. | Seal pattern for liquid crystal display device including inner seal with first and second openings |
| US7736461B2 (en) | 2002-10-07 | 2010-06-15 | Lg Display Co., Ltd. | Cassette for preventing breakage of glass substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0588310B2 (en) | 1993-12-21 |
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