JPH0466659A - Object having ti2n coating layer and its manufacture - Google Patents
Object having ti2n coating layer and its manufactureInfo
- Publication number
- JPH0466659A JPH0466659A JP17684390A JP17684390A JPH0466659A JP H0466659 A JPH0466659 A JP H0466659A JP 17684390 A JP17684390 A JP 17684390A JP 17684390 A JP17684390 A JP 17684390A JP H0466659 A JPH0466659 A JP H0466659A
- Authority
- JP
- Japan
- Prior art keywords
- coating layer
- ti2n
- titanium nitride
- nitride coating
- mainly composed
- 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
- 239000011247 coating layer Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000010410 layer Substances 0.000 claims abstract description 4
- 238000005240 physical vapour deposition Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 19
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 239000008246 gaseous mixture Substances 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000007740 vapor deposition Methods 0.000 abstract 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 13
- 229910001369 Brass Inorganic materials 0.000 description 7
- 239000010951 brass Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009958 sewing Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、Ｔｉ２Ｎ被覆層を有する物体およびその製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an object having a Ti2N coating layer and a method for producing the same.
従来から各種の材料および物品の耐磨耗性、耐蝕性など
を改善するとともに、装飾性を高めるために、窒化チタ
ンによりこれら材料および物品を被覆することが行なわ
れている。この際、被覆層の形成には、化学的蒸着法（
ＣＶＤ法）および物理的蒸着法（ＰＶＤ法）が採用され
ている。BACKGROUND OF THE INVENTION Conventionally, various materials and articles have been coated with titanium nitride in order to improve their abrasion resistance, corrosion resistance, etc., and to enhance their decorative properties. At this time, the chemical vapor deposition method (
CVD method) and physical vapor deposition method (PVD method) are employed.
窒化チタンには、ＴｉＮとＴｉ２Ｎとがあるが、被覆層
としては、ＴｉＮがもっばら使用されている。Ｔｉ２
ＮがＴｉＮ中又はＴｉ中に混合相として形成されたとの
報告は存在するが（日本金属学会秋期大会シンポジウム
講演概要（１９８９）第１７３〜１７４頁；神戸製鋼技
報（１９８９）、第３９巻、１号、第３２〜３５頁）
、Ｔｉ２ Ｎそのものが被覆層として使用されている実
例乃至そのための研究例は、無い。従って、従来は、Ｔ
ｉＮ被覆層形成のためのより良い条件についての研究が
主に進められている。しかしながら、ＴｉＮ被覆層の形
成は、高温で行なう必要があり、ＣＶＤ法では８００℃
以上、ＰＶＤ法でも、特殊な場合を除いては、３００℃
以上で行なわれている。Titanium nitride includes TiN and Ti2N, and TiN is most often used as a coating layer. Ti2
There are reports that N is formed as a mixed phase in TiN or Ti (Japan Institute of Metals Autumn Symposium Lecture Summary (1989), pp. 173-174; Kobe Steel Technical Report (1989), Vol. 39, No. 1, pp. 32-35)
There are no actual examples or research examples of Ti2N itself being used as a coating layer. Therefore, conventionally, T
Research is mainly underway on better conditions for forming an iN coating layer. However, the formation of the TiN coating layer needs to be performed at a high temperature, and in the CVD method, the temperature is 800°C.
As mentioned above, even with the PVD method, the temperature is 300℃ except in special cases.
This is done above.
この様な高温でのＴｉＮ被覆層の形成は、被処理物の材
質によっては、硬度の低下、脱元素による材質の劣化乃
至変質などを引き起こす危険性がある。Formation of the TiN coating layer at such a high temperature may cause a decrease in hardness or deterioration or alteration of the material due to element removal, depending on the material of the object to be treated.
ＰＶＤ法によるＴｉＮ被覆層の形成を２００℃以下の比
較的低温領域で行なう試みもなされているが、この場合
には、本来黄金色を呈すべきＴｉＮ被覆層が茶褐色など
に変色して装飾的価値を失ったり、被覆層に多数の亀裂
を生じて耐磨耗性、耐蝕性などの特性も大幅に低下する
。さらに、黒褐色の微粉末が大量に発生して、ＰＶＤ処
理装置の保守にも大きな障害となっている。Attempts have also been made to form a TiN coating layer using the PVD method at a relatively low temperature of 200°C or less, but in this case, the TiN coating layer, which should normally have a golden color, turns brown or other colors and loses its decorative value. The coating layer may lose its properties, or many cracks may occur in the coating layer, resulting in a significant decline in properties such as abrasion resistance and corrosion resistance. Furthermore, a large amount of blackish brown fine powder is generated, which poses a major problem in the maintenance of PVD processing equipment.
問題点を解決するための手段
本発明者は、この様な技術の現状に鑑みて研究を重ねた
結果、ＰＶＤ法の一例である中空陰極放電（ｈｏｔ ｌ
ｏｗ ｃａｔｈｏｄｅ ｄｉｓｃｈａｒｇｅ ： ＨＣ
Ｄ ）方式により、被覆すべき基材となる各種の材料乃
至物体（以下特に必要でない限り、単に基材という）に
対して特定の条件下でイオンブレーティングを行なう場
合には、Ｔ１２Ｎ単独若しくは主としてＴｉ２ Ｎから
なる窒化チタン被覆層を形成し得ることを見出した。そ
して、引き続く研究により、このＴｉ２ Ｎ単独若しく
は主としてＴｉ２ Ｎからなる窒化チタンからなる被覆
層が、ＴｉＮ層からは予測し得ない程度に極めて優れた
特性を備えていることをも見出した。Means for Solving the Problems As a result of repeated research in view of the current state of technology, the present inventor has developed a hollow cathode discharge (hot l discharge) method, which is an example of the PVD method.
ow cathode discharge: HC
D) When performing ion blasting under specific conditions on various materials or objects (hereinafter simply referred to as the base material unless otherwise required) that serve as the base material to be coated, use T12N alone or primarily. It has been found that it is possible to form a titanium nitride coating layer consisting of Ti2N. Further, through subsequent research, it was discovered that this coating layer made of titanium nitride consisting solely of Ti2N or mainly Ti2N has extremely excellent properties to a degree that could not be expected from a TiN layer.
すなわち、本発明は、この様な新たな知見に基いて完成
されたものであり、下記の物体およびその製造方法を提
供するものである：
（１）Ｔｉ２Ｎを主体とする窒化チタン被覆層を有する
物体。That is, the present invention was completed based on such new knowledge, and provides the following object and method for manufacturing the same: (1) Having a titanium nitride coating layer mainly composed of Ti2N. object.
■温度＝室温乃至６００℃およびガス圧力＝Ｉ Ｘ １
０−１〜１ ｘ １０−４Ｔｏｒｒの条件下且つＡｒ／
ｒ’ｈ ＝１／１５〜１／３ （モル比）の混合ガス雰
囲気中で被覆層を形成すべき物体を物理的蒸着法に供し
、Ｔｉ２ Ｎ層を形成させることを特徴とするＴｉ２Ｎ
を主体とする窒化チタン被覆層を有する物体の製造方法
。■Temperature = room temperature to 600°C and gas pressure = I x 1
Under conditions of 0-1 to 1 x 10-4 Torr and Ar/
Ti2N characterized by subjecting the object on which the coating layer is to be formed to a physical vapor deposition method in a mixed gas atmosphere of r'h = 1/15 to 1/3 (molar ratio) to form a Ti2N layer.
A method for manufacturing an object having a titanium nitride coating layer mainly composed of.
本明細書において、“Ｔｉ２ Ｎを主体とする窒化チタ
ン被覆層”とは、Ｔｉ２ Ｎ単独からなる窒化チタン被
覆層のみならず、主としてＴｉ２ Ｎからなり少量のＴ
ｉ２−エＮｙ （０＜ｘ≦１．０≦ｙ≦１）を含む窒
化チタン被覆層をも包含するものである。In this specification, "a titanium nitride coating layer mainly composed of Ti2N" refers to not only a titanium nitride coating layer consisting of Ti2N alone, but also a titanium nitride coating layer mainly composed of Ti2N and containing a small amount of T.
It also includes a titanium nitride coating layer containing i2-ENy (0<x≦1.0≦y≦1).
本発明方法においては、ＰＶＤ法により、窒化チタン被
覆層を形成することを必須とするが、以下においては、
ＨＣＤ方式をＰＶＤ法の代表例として、説明を行なう。In the method of the present invention, it is essential to form a titanium nitride coating layer by the PVD method, but in the following,
An explanation will be given using the HCD method as a representative example of the PVD method.
ＨＣＤ方式における制御パラメータとしては、主に下記
のようなものが挙げられる。Control parameters in the HCD method mainly include the following.
（１）処理温度
（２）処理時間
（３）ビーム電流
（４）バイアス電圧
（５）雰囲気ガス圧力および流量
（６）雰囲気ガス混合比（Ａｒ／Ｎ２）（７）蒸発源と
基板との距離
（８）基板の傾斜角（基板と蒸発源とを結ぶ線分と基板
の法線とのなす角）
本発明者の研究によれば、基材表面にＴｉ２Ｎを主体と
する窒化チタン被覆層を形成するために特に重要なパラ
メータは、処理温度、雰囲気ガス圧力および雰囲気ガス
混合比（Ａｒ／Ｎ２）であることが明らかとなった。そ
の具体的条件は、下記の通りである。(1) Processing temperature (2) Processing time (3) Beam current (4) Bias voltage (5) Atmospheric gas pressure and flow rate (6) Atmospheric gas mixing ratio (Ar/N2) (7) Distance between evaporation source and substrate (8) Inclination angle of the substrate (angle between the line segment connecting the substrate and the evaporation source and the normal line of the substrate) According to the research of the present inventor, a titanium nitride coating layer mainly composed of Ti2N is coated on the surface of the substrate. It has become clear that the particularly important parameters for formation are processing temperature, atmospheric gas pressure, and atmospheric gas mixing ratio (Ar/N2). The specific conditions are as follows.
■、処理温度＝室温乃至６００°Ｃ：
本発明方法では、処理温度が室温という低温であっても
、基材表面にＴｉ２Ｎを主体とする窒化チタン被覆層を
形成することができる点が、太きな特徴である。このこ
とは、ＴｉＮからなる窒化チタン被覆層の形成に関する
従来技術からは、全（予測し得なかったところである。(2) Processing temperature = room temperature to 600°C: The method of the present invention has the advantage that a titanium nitride coating layer mainly composed of TiN can be formed on the surface of the substrate even when the processing temperature is as low as room temperature. This is a great feature. This could not have been predicted from the prior art regarding the formation of a titanium nitride coating layer made of TiN.
その結果、本発明によれば、従来窒化チタン被覆層の形
成か全く不可能であった耐熱性の低いプラスチックス、
蒸気圧の高い金属類、軟化点の低い合金鋼類および非鉄
金属類などに対する窒化チタン被覆層の形成が可能とな
った。As a result, according to the present invention, it is possible to form a titanium nitride coating layer on plastics with low heat resistance, which was previously impossible to form.
It has become possible to form titanium nitride coating layers on metals with high vapor pressure, alloy steels with low softening points, non-ferrous metals, etc.
勿論、本発明方法は、６００℃程度までの耐熱性を有す
る基材に対しても適用し得ることは、言うまでもない。Of course, it goes without saying that the method of the present invention can also be applied to base materials having heat resistance up to about 600°C.
■、雰囲気ガス圧力＝ ｌＸｌ０−１〜ｌＸｌ０−４Ｔ
ｏｒｒ ：雰囲気ガス圧力が高すぎる場合及び低すぎる
場合には、Ｔｉ２ Ｎを主体とする窒化チタン被覆層の
形成が良好に行なわれない
■、雰囲気ガス混合比（Ａ ｒ ／ Ｎ ２モル比）＝
１／１５〜１／３：
Ａｒの量が少なすぎる場合には、相当量のＴｉＮが、ま
た、Ａｒの量が過剰となる場合には、相当量のＴｉが混
入して、本発明方法の特徴であるＴｉ２ Ｎ単独または
これを主体とする被覆層の形成が良好に行われない。■, Atmospheric gas pressure = lXl0-1 ~ lXl0-4T
orr: When the atmospheric gas pressure is too high or too low, the formation of a titanium nitride coating layer mainly composed of Ti2N is not performed well.■, Atmospheric gas mixing ratio (Ar / N2 molar ratio) =
1/15 to 1/3: If the amount of Ar is too small, a considerable amount of TiN will be mixed in, and if the amount of Ar is excessive, a considerable amount of Ti will be mixed in, and the method of the present invention will be The characteristic feature of forming a coating layer consisting solely of Ti2N or mainly consisting of Ti2N is not well achieved.
本発明方法の対象となる基材には、殆ど制限はない。す
なわち、従来法によりＴｉＮからなる窒化チタン被覆層
形成の対象となっていた耐熱性の材料のみならず、従来
ＴｉＮからなる窒化チタン被覆層形成の対象とはなり得
なかった材料、例えば、プラスチックスなどの有機材料
；２００℃以上では急速に軟化する炭素鋼、炭素工具鋼
、低合金鋼、加工硬化したステンレス鋼などの鋼類；銅
、アルミニウム、黄銅などの非鉄金属類；亜鉛、マグネ
シウムなどの蒸気圧の高い金属およびそれらの合金類な
ども、本発明方法の対象となり得る。There are almost no restrictions on the substrates that can be subjected to the method of the invention. In other words, in addition to heat-resistant materials that were targets for forming a titanium nitride coating layer made of TiN by conventional methods, materials that could not be conventionally formed for titanium nitride coating layers made of TiN, such as plastics. organic materials such as; steels such as carbon steel, carbon tool steel, low alloy steel, and work-hardened stainless steel that soften rapidly at temperatures above 200°C; nonferrous metals such as copper, aluminum, and brass; Metals with high vapor pressure and their alloys can also be subjected to the method of the present invention.
発明の効果 本発明によれば、下記の様な顕著な効果が達成される。Effect of the invention According to the present invention, the following remarkable effects are achieved.
従来存在しなかったＴｉ２Ｎを主体とする窒化チタン被
覆層を形成することかできる。A titanium nitride coating layer mainly composed of Ti2N, which has not existed in the past, can be formed.
処理温度に関して、被覆の対象となる基材に対する制限
が極めて少ない。Regarding the treatment temperature, there are very few restrictions on the substrate to be coated.
窒化チタン被覆層の基材に対する密着性が極めて高い。The adhesion of the titanium nitride coating layer to the base material is extremely high.
窒化チタン被覆層の硬度が高い。The hardness of the titanium nitride coating layer is high.
窒化チタン被覆層は、美観に優れている。The titanium nitride coating layer has excellent aesthetic appearance.
実施例
以下に実施例および比較例を示し、本発明の特徴とする
ところをより一層明確にする。EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention.
実施例Ｉ
ＨＣＤ方式によるイオンブレーティング装置を使用して
、本発明方法によるＴｉ２ Ｎを主体とする窒化チタン
被覆層の形成を行なった。以下に操作条件を示す。Example I A titanium nitride coating layer mainly composed of Ti2N was formed by the method of the present invention using an ion blating apparatus using an HCD method. The operating conditions are shown below.
＊温度−室温
＊時間＝１５分
＊ビーム電流＝１８０Ａ
＊バイアス電圧＝３０Ｖ
＊ガス流ｆｆ１＝ＡｒＬＯ十Ｎ ２５６．７＝６６．７
３ＣＣＭ＊ガス圧力＝ ３．４ ｘ １Ｏ−３Ｔｏｒｒ
＊ガス混合比（Ａ ｒ／Ｎ２） ＝３０／１７０＊治具
回転速度＝１１．７ｒｐｍ
なお、上記のガス圧力については、チタンの溶融・蒸発
を開始する前の定常状態における炉内圧力であり、溶融
・蒸発の開始後は、ｌＸｌ０−１〜Ｉ Ｘ １０−４Ｔ
ｏｒｒの範囲で緩やかに変動する。*Temperature - room temperature * Time = 15 minutes * Beam current = 180A * Bias voltage = 30V * Gas flow ff1 = ArLO ten N 256.7 = 66.7
3CCM*Gas pressure = 3.4 x 1O-3Torr
*Gas mixing ratio (A r/N2) = 30/170 * Jig rotation speed = 11.7 rpm The above gas pressure is the furnace pressure in the steady state before starting melting and evaporation of titanium. , after the start of melting and evaporation, lXl0-1~IX10-4T
It fluctuates slowly within the range of orr.
また、第１表に基材として使用した各材料に関して、処
理面基材硬度、処理後基材硬度および皮膜硬度をそれぞ
れ示す。Table 1 also shows the treated surface base material hardness, post-treatment base material hardness, and film hardness for each material used as the base material.
尚、下記の各表において、「不能」とあるのは、圧痕不
明瞭または視野が暗いために、測定不能であったことを
意味する。In each of the tables below, "unable" means that measurement was impossible because the indentation was unclear or the visual field was dark.
実施例２
第２表に示す基材を使用する以外は実施例１と同様にし
て、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆層
の形成を行なった。Example 2 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the substrate shown in Table 2 was used.
結果を第２表に示す。The results are shown in Table 2.
実施例３
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 3 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１５分
＊ビーム電流＝１８０Ａ
＊バイアス電圧＝９０ｖ
＊ガス流量＝ＡｒｌＯ十Ｎ ２５６．７＝６６．７８Ｃ
ＣＭ＊ガス圧力＝ ３．４ Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ ２ ） ＝ ３０／１７０
＊治具回転速度＝１１．７ｒｐｍ
第３表に結果を示す。*Temperature = Room temperature * Time = 15 minutes * Beam current = 180A * Bias voltage = 90V * Gas flow rate = ArlO 1N 256.7 = 66.78C
CM*Gas pressure = 3.4 X 1O-3Torr*Gas mixing ratio (A r / N 2 ) = 30/170
*Jig rotation speed = 11.7 rpm The results are shown in Table 3.
実施例４
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 4 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間−１５分
＊ビーム電流＝１８０Ａ
＊バイアス電圧−５ｖ
＊ガス流量＝Ａｒｌｏ十Ｎ ２５６．７＝６６．７８Ｃ
ＣＭ＊ガス圧力＝ ３．４ Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ ２ ） ＝ ３０／１７０
＊治具回転速度＝１１．７ｒｐｍ
第４表に結果を示す。*Temperature = room temperature *Time - 15 minutes *Beam current = 180A *Bias voltage -5V *Gas flow rate = Arlo 1N 256.7 = 66.78C
CM*Gas pressure = 3.4 X 1O-3Torr*Gas mixing ratio (A r / N 2 ) = 30/170
*Jig rotation speed = 11.7 rpm Table 4 shows the results.
実施例５
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２Ｎを主体とする窒化チタン被覆層
の形成を行なった。Example 5 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１５分
＊ビーム電流＝１８０Ａ
＊バイアス電圧＝５Ｖ
＊ガス流量−Ａｒ１５＋Ｎ ２５１．７ ＝ ６６．
７８ＣＣＭ＊ガス圧力＝ ３．４ Ｘ １Ｏ−３Ｔｏｒ
ｒ＊ガス混合比（Ａ ｒ ／ Ｎ２ ） ＝４５／１５
５＊治具回転速度＝１１．７ｒｐｍ
第５表に結果を示す。*Temperature = room temperature *Time = 15 minutes *Beam current = 180A *Bias voltage = 5V *Gas flow rate - Ar15 + N 251.7 = 66.
78CCM*Gas pressure = 3.4 x 1O-3Tor
r*Gas mixing ratio (A r / N2) = 45/15
5*Jig rotation speed=11.7 rpm Table 5 shows the results.
実施例６
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 6 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間−１５分
＊ビーム電流＝１８０Ａ
＊バイアス電圧＝３０Ｖ
＊ガス流Ｊｉｔ＝Ａｒ７．５ ＋Ｎ ２５９．２＝６６
．７ ＳＣＣＭ＊ガス圧力＝ ３．４ Ｘ １Ｏ−３Ｔ
ｏｒｒ＊ガス混合比（Ａ ｒ ／ Ｎ２ ） ＝２２．
５／１７７．５＊治具回転速度＝１１．７ｒｐｍ
第６表に結果を示す。*Temperature = Room temperature * Time - 15 minutes * Beam current = 180A * Bias voltage = 30V * Gas flow Jit = Ar7.5 +N 259.2 = 66
．． 7 SCCM*Gas pressure = 3.4 x 1O-3T
orr*gas mixture ratio (A r / N2) = 22.
5/177.5*Jig rotation speed=11.7 rpm The results are shown in Table 6.
実施例７
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２Ｎを主体とする窒化チタン被覆層
の形成を行なった。Example 7 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１５分
＊ビーム電流＝１６０Ａ
＊バイアス電圧−３０Ｖ
＊ガス流量−ＡｒｌＯ＋Ｎ ２５６．７＝６６．７８Ｃ
ＣＭ＊ガス圧力＝ ３．４ Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ２ ） ＝３０／１７０＊治
具回転速度＝１１．７ｒｐｍ
第７表に結果を示す。*Temperature = room temperature *Time = 15 minutes *Beam current = 160A *Bias voltage -30V *Gas flow rate - ArlO+N 256.7 = 66.78C
CM*Gas pressure=3.4×1O-3Torr*Gas mixing ratio (Ar/N2)=30/170*Jig rotation speed=11.7rpm The results are shown in Table 7.
実施例８
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２Ｎを主体とする窒化チタン被覆層
の形成を行なった。Example 8 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１５分
＊ビーム電流＝１２０Ａ
＊バイアス電圧＝３０Ｖ
＊ガス流量＝Ａｒｌｏ＋Ｎ ２５Ｂ、７＝６６．７８Ｃ
ＣＭ＊ガス圧力＝ ３．４ Ｘ １０’−３Ｔｏｒｒ＊
ガス混合比（Ａ ｒ ／ Ｎ ２ ） ＝ ３０／１７
０＊治具回転速度＝１１．７ｒｐｍ
第８表に結果を示す。*Temperature = Room temperature * Time = 15 minutes * Beam current = 120A * Bias voltage = 30V * Gas flow rate = Arlo + N 25B, 7 = 66.78C
CM*Gas pressure=3.4 X 10'-3Torr*
Gas mixture ratio (A r / N 2 ) = 30/17
0*Jig rotation speed=11.7 rpm Table 8 shows the results.
実施例９
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 9 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１５分
＊ビーム電流＝２００Ａ
＊バイアス電圧−３０Ｖ
＊ガス流量＝ＡｒｌＯ＋Ｎ ２５６．７＝６６．７８Ｃ
ＣＭ＊ガス圧力＝３．４ Ｘｌ０−３Ｔｏｒｒ＊ガス混
合比（Ａ ｒ ／ Ｎ ２ ） ＝ ３０／１７０＊治
具回転速度＝１１．７ｒｐｍ
第９表に結果を示す。*Temperature = Room temperature * Time = 15 minutes * Beam current = 200A * Bias voltage -30V * Gas flow rate = ArlO + N 256.7 = 66.78C
CM*Gas pressure=3.4 Xl0-3Torr*Gas mixing ratio (Ar/N2)=30/170*Jig rotation speed=11.7rpm The results are shown in Table 9.
実施例１０
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 10 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１５分
＊ビーム電流＝１８０Ａ
＊バイアス電圧＝３０Ｖ
＊ガス流量＝Ａｒ７．５＋ Ｎ２４２．５＝５０８ＣＣ
Ｍ＊ガス圧力＝ ２．３７ Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ ２ ） ＝ ３０／１７０
＊治具回転速度−１１．７ｒｐｍ
第１０表に結果を示す。*Temperature = Room temperature * Time = 15 minutes * Beam current = 180A * Bias voltage = 30V * Gas flow rate = Ar7.5 + N242.5 = 508CC
M*Gas pressure = 2.37 X 1O-3Torr*Gas mixing ratio (A r / N 2 ) = 30/170
*Jig rotation speed - 11.7 rpm The results are shown in Table 10.
実施例１１
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 11 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１５分
＊ビーム電流＝１８０Ａ
＊バイアス電圧＝３０Ｖ
＊ガス流量−Ａｒ５ ＋Ｎ ２６１．７＝６６．７８Ｃ
ＣＭ＊ガス圧力＝ ３．４ Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ ２ ） ＝ １５／１８５
＊治具回転速度＝１１．７ｒｐｍ
第１１表に結果を示す。*Temperature = Room temperature * Time = 15 minutes * Beam current = 180A * Bias voltage = 30V * Gas flow rate - Ar5 +N 261.7 = 66.78C
CM*Gas pressure = 3.4 x 1O-3Torr*Gas mixing ratio (A r / N 2 ) = 15/185
*Jig rotation speed = 11.7 rpm Table 11 shows the results.
実施例１２
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 12 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間−１５分
＊ビーム電流＝１２０Ａ
＊バイアス電圧＝３０ｖ
＊ガス流ｔ−Ａｒ１０十Ｎ ２５６．７＝６８．７８Ｃ
ＣＭ＊ガス圧力＝ ３．４ Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ ２ ） ＝ ３０／１７０
＊治具回転速度＝１１．７ｒｐｍ
第１２表に結果を示す。*Temperature = room temperature *Time - 15 minutes *Beam current = 120A *Bias voltage = 30V *Gas flow t-Ar10N 256.7 = 68.78C
CM*Gas pressure = 3.4 X 1O-3Torr*Gas mixing ratio (A r / N 2 ) = 30/170
*Jig rotation speed = 11.7 rpm Table 12 shows the results.
尚、第１２表以下の記載において、ＰＰＳ樹脂：Ｒ４と
あるのは、機械的特性に優れたポリフェニレンサルファ
イド樹脂を意味し、ＰＰＳ樹脂：Ｒ８とあるのは、電気
的特性に優れたポリフェニレンサルファイド樹脂を意味
する。どちらのＰＰＳ樹脂もガラス繊維入り材料であり
、第１２表において、Ｇ部及びＭ部とあるのは、それぞ
れガラス繊維部及び樹脂基地部を意味する。In addition, in the descriptions in Table 12 and below, PPS resin: R4 means polyphenylene sulfide resin with excellent mechanical properties, and PPS resin: R8 means polyphenylene sulfide resin with excellent electrical properties. means. Both PPS resins are glass fiber-containing materials, and in Table 12, part G and part M mean the glass fiber part and the resin base part, respectively.
実施例１３
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 13 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１０分
＊ビーム電流＝１２０Ａ
＊バイアス電圧＝３０ｖ
＊ガス流量−Ａｒ５ ＋Ｎ ２６１．７＝６６．７８Ｃ
ＣＭ＊ガス圧力＝ ３．４ Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ ２ ） ＝ １５／１８５
＊治具回転速度＝１１．７ｒｐｍ
第１３表に結果を示す。*Temperature = Room temperature * Time = 10 minutes * Beam current = 120A * Bias voltage = 30V * Gas flow rate - Ar5 +N 261.7 = 66.78C
CM*Gas pressure = 3.4 x 1O-3Torr*Gas mixing ratio (A r / N 2 ) = 15/185
*Jig rotation speed = 11.7 rpm Table 13 shows the results.
実施例１４
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２ Ｎを主体とする窒化チタン被覆
層の形成を行なった。Example 14 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝１０分
＊ビーム電流＝１２０Ａ
＊バイアス電圧−３０Ｖ
＊ガス流量＝Ａｒ７．５＋ Ｎ２４２．５＝５０ ＳＣ
ＣＭ＊ガス圧力＝２．７３Ｘ １Ｏ−３Ｔｏｒｒ＊ガス
混合比（Ａ ｒ ／ Ｎ ２ ） ＝ ３０／１７０＊
治具回転速度＝１１．７ｒｐｍ
第１４表に結果を示す。*Temperature = Room temperature * Time = 10 minutes * Beam current = 120A * Bias voltage -30V * Gas flow rate = Ar7.5 + N242.5 = 50 SC
CM*Gas pressure = 2.73X 1O-3Torr*Gas mixing ratio (Ar/N2) = 30/170*
Jig rotation speed = 11.7 rpm Table 14 shows the results.
実施例１５
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴ１２Ｎを主体とする窒化チタン被覆層
の形成を行なった。Example 15 A titanium nitride coating layer mainly composed of T12N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝９分２０秒
＊ビーム電流＝１２０Ａ
＊バイアス電圧＝３０ｖ
＊ガス流量−Ａｒ５ ＋Ｎ ２４２．５＝４７．５８Ｃ
ＣＭ＊ガス圧カー ２．２６Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ ２ ） ＝ ２１７１７９
＊治具回転速度−１１，７ｒｐｍ
第１５表に結果を示す。*Temperature = room temperature *Time = 9 minutes 20 seconds *Beam current = 120A *Bias voltage = 30v *Gas flow rate - Ar5 +N 242.5 = 47.58C
CM*Gas pressure car 2.26X 1O-3Torr*Gas mixing ratio (A r / N 2 ) = 217179
*Jig rotation speed - 11.7 rpm The results are shown in Table 15.
実施例１６
以下に示す操作条件を採用する以外は実施例１と同様に
して、基材上にＴｉ２Ｎを主体とする窒化チタン被覆層
の形成を行なった。Example 16 A titanium nitride coating layer mainly composed of Ti2N was formed on a substrate in the same manner as in Example 1 except that the operating conditions shown below were adopted.
＊温度＝室温
＊時間＝９分
＊ビーム電流＝１２０Ａ
＊バイアス電圧＝３０Ｖ
＊ガス流量＝Ａｒ５ ＋Ｎ ２２８．３＝３３．３８Ｃ
ＣＭ＊ガス圧力＝ １．７２Ｘ １Ｏ−３Ｔｏｒｒ＊ガ
ス混合比（Ａ ｒ ／ Ｎ２ ） ＝３０／１７０＊治
具回転速度＝１１．７ｒｐｍ
第１６表に結果を示す。*Temperature = room temperature *Time = 9 minutes *Beam current = 120A *Bias voltage = 30V *Gas flow rate = Ar5 +N 228.3 = 33.38C
CM*Gas pressure = 1.72X 1O-3Torr*Gas mixing ratio (A r / N2) = 30/170*Jig rotation speed = 11.7 rpm The results are shown in Table 16.
実験例１
実施例８と同様にして得られたＴｉ２ Ｎ皮膜を有する
アルミニウム、銅および黄銅試片を第１図に示すように
して１８０°曲げ加工し、矢印の方向からＡ−Ａ’力方
向表面状態を撮影した。Experimental Example 1 An aluminum, copper, and brass specimen having a Ti2N film obtained in the same manner as in Example 8 was bent by 180° as shown in Fig. 1, and the A-A' force direction was bent from the direction of the arrow. The surface condition was photographed.
第１７表に試片の寸法及び曲げ状況を示し、第２〜第４
図に各試片の表面状態の顕微鏡写真（４００倍）を示す
。Table 17 shows the dimensions and bending conditions of the specimens.
The figure shows a micrograph (400x magnification) of the surface condition of each specimen.
１８０°曲げ加工後にも、Ｔｉ２Ｎ皮膜に亀裂が認めら
れたものの、皮膜と試片との剥離は認められなかった。Although cracks were observed in the Ti2N film even after the 180° bending process, no peeling between the film and the specimen was observed.
試片
アルミニウム
銅
黄銅
第１７表
ｔ （ｍｍ） ｃ （ｍｍ）
１．０ １．４
１．０ １．４
１．４ ５．０
実験例２
ｗ（＋ｎｍ）
１０、０
１０、０
１０、０
実施例１と同様にして得られたＴｉ２ Ｎ皮膜を有する
カッター刃Ｉ（材質５Ｋ−２） 、カッター刃■（材質
５ＫＳ−７）およびミシン針（材質５ＷＲ８−９２Ａ）
の断面組織の顕微鏡写真（１０００倍）をそれぞれ第５
〜７図として示す。Sample aluminum copper brass Table 17 t (mm) c (mm) 1.0 1.4 1.0 1.4 1.4 5.0 Experimental example 2 w (+nm) 10, 0 10, 0 10, 0 Cutter blade I (material 5K-2), cutter blade ■ (material 5KS-7) and sewing machine needle (material 5WR8-92A) having a Ti2N film obtained in the same manner as in Example 1.
Micrographs (1000x) of the cross-sectional structure of
- Shown as Figure 7.
いずれの場合にも、試片とＴｉ２ Ｎ皮膜とが密着して
いることが明らかである。In either case, it is clear that the specimen and the Ti2N film are in close contact.
実験例３
実施例２と同様にして得られたＴｉ２Ｎ皮膜を有する銅
および黄銅ならびに実施例９と同様にして得られたＴｉ
２Ｎ皮膜を有するアルミニウムの断面組織の顕微鏡写真
（１０００倍）をそれぞれ第８〜１０図として示す。Experimental Example 3 Copper and brass with a Ti2N film obtained in the same manner as in Example 2 and Ti obtained in the same manner as in Example 9
Micrographs (1000x magnification) of the cross-sectional structure of aluminum having a 2N film are shown in FIGS. 8 to 10, respectively.
いずれの場合にも、試片とＴｉ２ Ｎ皮膜とが密着して
いることが明らかである。In either case, it is clear that the specimen and the Ti2N film are in close contact.
実験例４
実験例１で得られたカッター刃Ｉ（材質５Ｋ−２）の表
面に形成された皮膜のＸ線回折図を第１１図として示す
。Experimental Example 4 FIG. 11 shows an X-ray diffraction diagram of the film formed on the surface of the cutter blade I (material 5K-2) obtained in Experimental Example 1.
形成された皮膜が実質的にＴｉ２Ｎにより構成されてい
ることが明らかである。It is clear that the film formed consists essentially of Ti2N.
第１図は、Ｔｉ２Ｎ皮膜を有するアルミニウム、銅およ
び黄銅試片を１８０°曲げ加工した状態を示す図面であ
る。
第２〜４図は、第１図に示す方法により曲げ加工された
アルミニウム、銅および黄銅各試片の表面状態を示す図
面に代える顕微鏡写真（４００倍）である。
第５〜７図は、Ｔｉ２ Ｎ皮膜を有するカッター刃■、
カッター刃■およびミシン針の断面組織を示す図面に代
わる顕微鏡写真（１０００倍）である。
第８〜１０図は、Ｔｉ２ Ｎ皮膜を有する銅および黄銅
ならびにＴｉ２Ｎ皮膜を有するアルミニウムの断面組織
を示す図面に代わる顕微鏡写真（１０００倍）である。
第１１図は、実験例１で得られたカッター刃Ｉの表面に
形成された皮膜のＸ線回折図である。
（以 上）
第
図
第
に
ト・′１
偽
図
デ
図
慣 ８
図・
第
図
〒１０
図
手続辛甫正書（方式）
平成２年１０月１７日
特許庁長官 植 松 敏 殿
事件の表示
平成２年特許願第１７６８４３号
発明の名称
Ｔｉ２Ｎ被覆層を有する物体およびその製造方法
補正をする者
事件との関係 特許出願人
大 阪 府FIG. 1 is a drawing showing a state in which an aluminum, copper, and brass specimen having a Ti2N film was bent by 180°. 2 to 4 are micrographs (magnified at 400 times) in place of drawings showing the surface conditions of aluminum, copper, and brass specimens bent by the method shown in FIG. 1. Figures 5 to 7 show cutter blades with Ti2N coating;
This is a micrograph (1000x magnification) in place of a drawing showing the cross-sectional structure of the cutter blade (1) and the sewing machine needle. Figures 8 to 10 are micrographs (1000x magnification) in place of drawings showing cross-sectional structures of copper and brass with Ti2N coatings and aluminum with Ti2N coatings. FIG. 11 is an X-ray diffraction diagram of the film formed on the surface of the cutter blade I obtained in Experimental Example 1. (Above) Fig. 1. False Fig. 8 Fig. 10 Fig. 10 Procedural Procedures in the Shinho Book (Method) October 17, 1990 Indication of the case of Mr. Satoshi Uematsu, Commissioner of the Japan Patent Office 1990 Patent Application No. 176843 Name of the invention Relationship with the case of a person who amends an object having a Ti2N coating layer and its manufacturing method Patent applicant Osaka Prefecture
Claims (2)
る物体。(1) An object having a titanium nitride coating layer mainly composed of Ti_2N.
０＾−＾１〜１×１０＾−＾４Ｔｏｒｒの条件下且つＡ
ｒ／Ｎ＿２＝１／１５〜１／３（モル比）の混合ガス雰
囲気中で被覆層を形成すべき物体を物理的蒸着法に供し
、Ｔｉ＿２Ｎ層を形成させることを特徴とするＴｉ＿２
Ｎを主体とする窒化チタン被覆層を有する物体の製造方
法。(2) Temperature = room temperature to 600°C and gas pressure = 1 x 1
Under conditions of 0^-^1 to 1 x 10^-^4 Torr and A
Ti_2 characterized by subjecting an object on which a coating layer is to be formed to a physical vapor deposition method in a mixed gas atmosphere of r/N_2 = 1/15 to 1/3 (molar ratio) to form a Ti_2N layer.
A method for manufacturing an object having a titanium nitride coating layer mainly composed of N.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2176843A JPH0776415B2 (en) | 1990-07-03 | 1990-07-03 | Method for manufacturing object having Ti2N coating layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2176843A JPH0776415B2 (en) | 1990-07-03 | 1990-07-03 | Method for manufacturing object having Ti2N coating layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0466659A true JPH0466659A (en) | 1992-03-03 |
| JPH0776415B2 JPH0776415B2 (en) | 1995-08-16 |
Family
ID=16020802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2176843A Expired - Lifetime JPH0776415B2 (en) | 1990-07-03 | 1990-07-03 | Method for manufacturing object having Ti2N coating layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776415B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6119489A (en) * | 1998-08-31 | 2000-09-19 | Hna Holdings, Inc. | Knitting machine parts resistant to abrasion by yarn of cut-resistant fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01290784A (en) * | 1988-05-16 | 1989-11-22 | Kobe Steel Ltd | Wear-resistant composite member |
-
1990
- 1990-07-03 JP JP2176843A patent/JPH0776415B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01290784A (en) * | 1988-05-16 | 1989-11-22 | Kobe Steel Ltd | Wear-resistant composite member |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6119489A (en) * | 1998-08-31 | 2000-09-19 | Hna Holdings, Inc. | Knitting machine parts resistant to abrasion by yarn of cut-resistant fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0776415B2 (en) | 1995-08-16 |
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