JPH04368A - Wear resistant coating film and production thereof - Google Patents
Wear resistant coating film and production thereofInfo
- Publication number
- JPH04368A JPH04368A JP9927590A JP9927590A JPH04368A JP H04368 A JPH04368 A JP H04368A JP 9927590 A JP9927590 A JP 9927590A JP 9927590 A JP9927590 A JP 9927590A JP H04368 A JPH04368 A JP H04368A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- coating
- nitrogen
- film
- chromium
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 47
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 27
- 238000007733 ion plating Methods 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 27
- 239000011651 chromium Substances 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 abstract description 8
- 238000010894 electron beam technology Methods 0.000 abstract description 3
- 238000004299 exfoliation Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000010953 base metal Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000013459 approach Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000009661 fatigue test Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000008016 vaporization Effects 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はピストンリングなどの摺動部品の摺動母材面に
形成された耐摩耗及び耐剥離性に優れた被膜及びその製
造法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a coating with excellent wear resistance and peeling resistance formed on the sliding base material surface of a sliding component such as a piston ring, and a method for manufacturing the same. It is.
（従来の技術）
内燃機関におけるピストンリングのような摺動部品の摺
動面は、耐摩耗性が要求されており、硬質クロムめっき
が優れた耐摩耗性を有することから、従来から摺動母材
面に硬質クロムめっきを施した部品が多用されている。(Prior art) The sliding surfaces of sliding parts such as piston rings in internal combustion engines are required to have wear resistance, and hard chrome plating has excellent wear resistance. Parts with hard chrome plating on the material surface are often used.
然し乍ら、近年内燃機関の高出力化、排気ガス対策など
のため、ピストンリングが受ける熱負荷が増大し、摺動
母材面に硬質クロムめっきを施した従来のピストンリン
グでは、耐摩耗性が不足するようになり、上記のような
苛酷な条件下でも使用できる優れた耐摩耗性のピストン
リングの開発が望まれている。However, in recent years, due to the increase in output of internal combustion engines and measures to reduce exhaust gas, the heat load that piston rings receive has increased, and conventional piston rings with hard chrome plating on the sliding base material lack wear resistance. Therefore, it is desired to develop a piston ring with excellent wear resistance that can be used even under the above-mentioned severe conditions.
このような要望に応えるため、摺動母材面に金属の窒化
物又は炭化物の被膜をイオンプレーティング法により被
膜させたピストンリングが、特開昭５７−５７８６８号
及び特開昭５７−６５８３７号公報に開示されている。In order to meet these demands, piston rings in which the sliding base material surface is coated with a metal nitride or carbide film by ion plating are disclosed in Japanese Patent Laid-Open No. 57-57868 and Japanese Patent Laid-Open No. 57-65837. Disclosed in the official gazette.
前者はピストンリング本体の摺動面に、ＰＶＤ法により
、ＴｉＮ 、、Ｔｉｃ 、 ＣｒＮ等の超硬質物質から
なる被膜を形成させたピストンリングであり、後者は少
くとも摺動外周面に窒化チタン被膜を形成し、酸膜の硬
さをＩ（Ｖ１３００以上、厚さを３〜２０μｍ、且つ摺
動外周面あらさを２μｍ以下としたピストンリングであ
る。The former is a piston ring in which a coating made of an ultra-hard material such as TiN, Tic, CrN, etc. is formed on the sliding surface of the piston ring body using the PVD method, and the latter is a piston ring that has a titanium nitride coating on at least the outer circumferential surface of the sliding surface. This piston ring has an acid film hardness of I (V1300 or more, a thickness of 3 to 20 μm, and a sliding outer peripheral surface roughness of 2 μm or less).
これら金属窒化物及び炭化物を摺動母材面に被覆させた
ピストンリングは、硬質クロムめっきを施したピストン
リングに較べ、優れた耐摩耗性を有するが、これら金属
窒化物及び炭化物の母材金属との密着性が良好でなく、
加えてその熱膨張係数が母材金属に較べて著しく小さい
ことから、機関の運転中に母材表面から剥離し易いとい
う問題を有している。一方母材に直接窒化処理を施すこ
とにより、窒化物層を形成させて耐摩耗性を改善する方
法もあるが、母材の化学組成に制約をうけるという問題
を有するうえ、耐摩耗性においてもＴｉＮ、 Ｔｉｃ
、、ＣｒＮなどに較べて不充分である。Piston rings whose sliding base metal surfaces are coated with these metal nitrides and carbides have superior wear resistance compared to piston rings coated with hard chromium plating. Poor adhesion with
In addition, since its coefficient of thermal expansion is significantly smaller than that of the base metal, it has the problem of being easily peeled off from the base metal surface during engine operation. On the other hand, there is a method of directly nitriding the base material to form a nitride layer and improve wear resistance, but this has the problem of being limited by the chemical composition of the base material, and also has poor wear resistance. TiN, Tic
, , is insufficient compared to CrN and the like.
（発明が解決しようとする課題）
摺動母材面に施された従来の被膜の有する前記のような
問題点を解消し、高出力、排気ガス対策などにより熱負
荷が増大した内燃機関の苛酷な条件下で使用されるピス
トンリングなどの摺動部品の摺動面として使用され、充
分な耐摩耗、耐剥離性を有するよう、摺動母材面に形成
される被膜及びその製造法を本発明は提供するものであ
る。(Problems to be Solved by the Invention) The above-mentioned problems of conventional coatings applied to the sliding base material surface can be solved, and the problem can be solved by solving the problems of internal combustion engines, which have increased heat loads due to high output and exhaust gas countermeasures. This paper describes the coating formed on the sliding base material surface and its manufacturing method so that it is used as the sliding surface of sliding parts such as piston rings used under various conditions, and has sufficient wear resistance and peeling resistance. The invention provides.
（処理を解決するための手段及び作用）上記の目的を達
成するため、本発明では、ピストンリングなどの摺動母
材面に形成された被膜であって、該被膜がクロム及び窒
素よりなり、該被膜の窒素濃度を、該母材面に対して垂
直方向に、母材面から連続的に被膜表面に増加させるこ
とにより、密着性、耐摩耗性、耐剥離性の改良された被
膜及びその製造法を提供する。(Means and effects for solving the process) In order to achieve the above object, the present invention provides a coating formed on the surface of a sliding base material such as a piston ring, the coating consisting of chromium and nitrogen, By increasing the nitrogen concentration of the coating continuously from the base material surface to the coating surface in a direction perpendicular to the base material surface, a coating with improved adhesion, abrasion resistance, and peeling resistance and its Provide manufacturing method.
本発明による被膜は、外周は硬質の窒化クロムとなり優
れた耐摩耗性を示すうえ、而かも内層にはクロムを含有
し、且つクロムが母材面に接する側で高濃度に存在する
ので、母材面との密着性が良好であり、使用中母材面か
ら剥離することがない。この被膜は、母材を２００〜６
００°Ｃの温度に加熱し、蒸着開始後、窒素分圧をＯか
ら３ｘｌＯ−’Ｔｏｒｒへ連続的に上昇させながら・イ
オンプレーティングを行うことによって得られる。母材
温度が２００ ”Ｃより低いと被膜の密着性が乏しく、
６００゛Ｃを越えると母材の変形、硬度低下などが生し
、得策でない。又窒素分圧が３ Ｘ Ｉ ０−３Ｔｏｒ
ｒを越えると、被膜の最外周表面に形成される窒化クロ
ム層がポーラスとなり、硬度が低くなって耐摩耗性が低
下する。従って窒素分圧を３ Ｘｌ０−３Ｔｏｒｒ −
。The coating according to the present invention has a hard chromium nitride on the outer periphery and exhibits excellent wear resistance, and furthermore, the inner layer contains chromium, and chromium is present in high concentration on the side in contact with the base metal surface. It has good adhesion to the material surface and does not peel off from the base material surface during use. This coating has a base material of 200 to 6
It is obtained by heating to a temperature of 00°C and performing ion plating while continuously increasing the nitrogen partial pressure from O to 3xlO-'Torr after starting vapor deposition. If the base material temperature is lower than 200"C, the adhesion of the coating will be poor,
If the temperature exceeds 600°C, the base material will be deformed and its hardness will decrease, which is not a good idea. Also, the nitrogen partial pressure is 3 X I 0-3 Tor
When r is exceeded, the chromium nitride layer formed on the outermost surface of the coating becomes porous, resulting in a decrease in hardness and wear resistance. Therefore, the nitrogen partial pressure is 3 Xl0-3Torr -
.
ｆ）ｆ
以上に上昇すること植好ましい。本゛発明によりえられ
る被膜は窒素分圧０、即ち、窒素ガスの導入前、クロム
を蒸発材としてイオンプレーティングを行うので、母材
表面にまず金属クロム膜が形成される。このクロム膜は
熱膨張係数が母材に近いため熱応力の影響を受けにくく
、母材に密着し、しかも柔軟性に冨んでいる。その後徐
々に窒素分圧を上げながら引続きイオンプレーティング
を行うので、蒸発したクロムの一部は窒化クロムに転換
されてブレーティングされる。このクロムと窒化クロム
の膜は硬度も高く、柔軟性にもとむため被膜の密着性は
良く、又、耐摩耗性にも優れる。f) It is preferable that the temperature rises above f. The film obtained according to the present invention has a nitrogen partial pressure of 0, that is, ion plating is performed using chromium as an evaporating agent before nitrogen gas is introduced, so that a metallic chromium film is first formed on the surface of the base material. This chromium film has a coefficient of thermal expansion close to that of the base material, so it is less affected by thermal stress, adheres closely to the base material, and is highly flexible. Thereafter, ion plating is performed while gradually increasing the nitrogen partial pressure, so that a part of the evaporated chromium is converted to chromium nitride and plated. This chromium and chromium nitride film has high hardness and flexibility, so the film has good adhesion and excellent wear resistance.
本発明による被膜はいかなる機関の摺動部品の摺動面に
も製造可能であるが、特に高負荷の内燃機関の摺動部品
、例えばピストンリング、スチールオイルリングのスペ
ーサ、及びレールなどの摺動部での使用が好ましいと云
える。The coating according to the present invention can be produced on the sliding surfaces of sliding parts of any engine, but is particularly suitable for sliding parts of high-load internal combustion engines, such as piston rings, spacers of steel oil rings, and sliding surfaces of rails. It can be said that it is preferable to use it in the section.
以下に実施例を示して本発明を説明する。The present invention will be explained below with reference to Examples.
使用したイオンプレーティング装置の概要を第一図に示
す、母材保持具２に保持された母材１をヒーター３で加
熱し、図示しない温度調節器で母材ｌを所定温度に加熱
、保持するようにしである。The outline of the ion plating apparatus used is shown in Figure 1. A base material 1 held in a base material holder 2 is heated with a heater 3, and a temperature controller (not shown) is used to heat and hold the base material 1 at a predetermined temperature. That's what I do.
母材１の下方には蒸発源とする金属５を収容する水冷鋼
るつぼ６が設置され、これらは容器９内に収容されてい
る。容器９の側壁には窒素ガスを容器９内に導入する導
入管１１と金属５を蒸発させる為の電子銃８が取りつけ
られている。電子銃８からでた電子を蒸発金属５に照射
するようにるつぼ６の周りには収束コイル７が設置され
ている。A water-cooled steel crucible 6 containing metal 5 as an evaporation source is installed below the base material 1, and these are housed in a container 9. An introduction pipe 11 for introducing nitrogen gas into the container 9 and an electron gun 8 for vaporizing the metal 5 are attached to the side wall of the container 9. A converging coil 7 is installed around the crucible 6 so as to irradiate the evaporated metal 5 with electrons emitted from the electron gun 8.
容器９内は図示しない真空ポンプによって減圧されるよ
うになっている。また、るつぼ６と保持具２との間には
シャッター１０が設けられている。The pressure inside the container 9 is reduced by a vacuum pump (not shown). Further, a shutter 10 is provided between the crucible 6 and the holder 2.
二のような装置を使用して５ＵＳ−４４０Ｃステンレス
鋼製の５０Ｘ５０Ｘ１０ｍｍの板材を使用し容器９内を
真空にしておいてから導入管１１からアルゴンガスを導
入して容器９内の圧力をＩ Ｘ １０−’ｔｏｒｒとし
、母材１を陰極として放電して、母材１の表面を清浄し
た。Using a device like 2 above, use a 50 x 50 x 10 mm plate made of 5US-440C stainless steel to evacuate the inside of the container 9, and then introduce argon gas from the introduction pipe 11 to reduce the pressure inside the container 9. The surface of the base material 1 was cleaned by discharging at 10-' torr and using the base material 1 as a cathode.
次に母材１を４００°Ｃに加熱しながら容器９内を５
Ｘ １０−’ｔｏｒｒまで減圧したのち、るつぼ６内に
収容された金属クロム５に電子銃８から電子ビームを照
射して金属クロム５を蒸発させた。ついでシャ、ター１
０をひらいて蒸着を開始し、蒸着開始３０秒後室素ガス
を導入管１１から吹き出させ、２０分かけて容器９内窒
素分圧を３×ｌＱ−’ｔｏｒｒまで連続的に上昇させ、
その分圧に２分間保持し、シャッター１０を閉した、母
材１が冷却してから表面に蒸着被膜が形成された母材１
を容器９から取り出した。電子ビームの電力は３５Ｖ５
００Ａ、収束コイル電流は２５０Ａ、窒素ガスの最終流
量は１０００ｃｃ／ｍｉｎであった。かくして形成され
た蒸着被膜について以下の試験を行った。Next, while heating the base material 1 to 400°C, the inside of the container 9 is
After the pressure was reduced to X 10-'torr, the metal chromium 5 housed in the crucible 6 was irradiated with an electron beam from the electron gun 8 to evaporate the metal chromium 5. Next, Sha, Tar 1
0 to start vapor deposition, 30 seconds after the start of vapor deposition, nitrogen gas was blown out from the introduction tube 11, and the nitrogen partial pressure in the container 9 was continuously increased to 3 x lQ-'torr over 20 minutes.
The partial pressure was maintained at that partial pressure for 2 minutes, and the shutter 10 was closed. After the base material 1 had cooled, a vapor deposition film was formed on the surface of the base material 1.
was taken out from container 9. The power of the electron beam is 35V5
00A, the converging coil current was 250A, and the final flow rate of nitrogen gas was 1000cc/min. The following tests were conducted on the vapor deposited film thus formed.
（１）Ｘ線マイクロアナライザーによる窒素濃度および
クロム濃度の変化の分析
被膜中のクロム及び窒素の平均濃度変化を調べるため表
面に垂直方向に試料を切断し、Ｘ線マイクロアナライザ
ーにより表面から内部に向かって線分析を行った。その
結果は第２図に示す通りである。(1) Analysis of changes in nitrogen and chromium concentrations using an X-ray microanalyzer In order to examine changes in the average concentrations of chromium and nitrogen in the coating, the sample was cut perpendicular to the surface, and an X-ray microanalyzer was used to analyze the change in nitrogen and chromium concentrations from the surface to the inside. Line analysis was performed. The results are shown in FIG.
同図から被膜中のクロム濃度はクロムのみが蒸着された
母材に接する最内層で高く、表面に近づくに従って低く
なっており、被膜中の窒素濃度は母材に接する最内層で
最も低く、表面に近づくに従って高くななっていること
が判る。The figure shows that the chromium concentration in the film is highest in the innermost layer in contact with the base material, where only chromium is vapor-deposited, and decreases as it approaches the surface.The nitrogen concentration in the film is lowest in the innermost layer in contact with the base material, and decreases as it approaches the surface. It can be seen that the value increases as the value approaches .
（２）Ｘ線回折による最表面組繊の分析Ｘ線回折により
蒸着被膜の最表面組繊の分析を行った。その結果及びＡ
ＳＴＭカードでＣｒＮで有ることが判る。(2) Analysis of the outermost surface fibers by X-ray diffraction The outermost surface fibers of the vapor-deposited film were analyzed by X-ray diffraction. The results and A
The STM card shows that it is CrN.
（３）衝撃試験
外部からの衝撃に対する剥離抵抗力を調べるため、ショ
ツトブラストを使用して１〜２ＩＩＴＩｎの鋼球を表面
の被膜に衝突させ、被膜の剥離に至る迄の時間を測定し
た。(3) Impact test In order to examine the peeling resistance against external impact, a steel ball of 1 to 2 IITIn was made to collide with the surface coating using shot blasting, and the time until the coating peeled off was measured.
この試験及び後述する熱疲労試験については、比較のた
めに窒素分圧３ Ｘ １０−”ｔｏｒｒの一定分圧で２
０分間保持し、その他は前記と同様の条件でＣｒＳのみ
を蒸着させた試料についても同様の試験を行った。For this test and the thermal fatigue test described below, for comparison, the nitrogen partial pressure was 2
A similar test was also conducted on a sample in which only CrS was deposited under the same conditions as above except that the sample was held for 0 minutes.
その結果、ＣｒＮのみから成る比較の被膜は、１０分で
部分的な剥離が観察され、１５分で全部剥離したのに対
し、本発明の被膜は密着性が良好で、外部からの衝撃に
対する耐剥離性が著しく価れていることが判る。As a result, for the comparative coating made only of CrN, partial peeling was observed in 10 minutes, and complete peeling was observed in 15 minutes, whereas the coating of the present invention had good adhesion and was resistant to external impact. It can be seen that the releasability is significantly improved.
（４）熱疲労試験
加熱、冷却の繰り返しによる熱疲労耐性を調べるため、
試料を室温から１分間かけて４５０°Ｃに加熱し、その
温度に１分間保持してから１分間かけて室温迄冷却し、
１分後再び１分間かけて４５０°Ｃに加熱する熱サイク
ルを繰り返し、被膜の亀裂発生状態の観察と被膜の剥離
に至る迄の繰り返し回数の測定を行った。その結果、Ｃ
ｒＮのみからなる比較の被膜は２５０回の繰り返し時に
、亀裂が発生し、５００回の繰り返しで一部が剥離した
のに対し、本発明の被膜は５００回の繰り返しでも亀裂
、剥離何れも認められず本発明の被膜は加熱、冷却の繰
り返しに伴う亀裂の発生や剥離に対する抵抗力が著しく
優れていることが判る。(4) Thermal fatigue test To examine thermal fatigue resistance due to repeated heating and cooling,
The sample was heated from room temperature to 450 °C over 1 minute, held at that temperature for 1 minute, and then cooled to room temperature over 1 minute.
After 1 minute, the thermal cycle of heating to 450° C. for 1 minute was repeated, and the state of cracking in the coating was observed and the number of repetitions until the coating peeled off was measured. As a result, C
Whereas the comparative film made only of rN cracked after 250 repetitions and partially peeled off after 500 repetitions, the film of the present invention showed no cracking or peeling even after 500 repetitions. First, it can be seen that the coating of the present invention has excellent resistance to cracking and peeling due to repeated heating and cooling.
（５）Ｘ線回折による組繊の分析
本発明に係わる被膜は前述のように内部から表面に連続
的に化学組成が変化しており被膜を構成する相の種類も
当然内部から表面にかけて変化していることが想像され
るがこれらをＸ線回折によって直接調べることができな
い。そこで被膜を構成する相を調べるために０．３〜３
×１０ ””ｔｏｒｒの範囲内の一定窒素分圧で形成さ
せた被膜についてＸ線回折による組繊の分析を行った。(5) Analysis of composite fibers by X-ray diffraction As mentioned above, the chemical composition of the coating according to the present invention changes continuously from the inside to the surface, and the types of phases that make up the coating naturally change from the inside to the surface. However, these cannot be directly investigated by X-ray diffraction. Therefore, in order to investigate the phase that constitutes the film,
The composite fibers were analyzed by X-ray diffraction on the coating formed at a constant nitrogen partial pressure within the range of ×10 ”” torr.
窒素分圧以外の条件は前記試験に於けると同様である。Conditions other than nitrogen partial pressure were the same as in the previous test.
分析結果は第１表の通りである。The analysis results are shown in Table 1.
同表から本発明に係わる被膜は窒素分圧は始めはゼロ、
次いで連続的に上昇させて形成させたのであるから、ク
ロムのみからなる蒸着層の上にクロムとクロム窒化物と
からなる蒸着層が形成されていて、さらにその上にはク
ロム窒化物のみからなる層が形成されていて、クロム濃
度は内側から表面へと連続的に低下し、窒素濃度は内側
から表面へと連続的に上昇していることが推察され、こ
れはＸ線マイクロアナライザーによる前記線分析結果と
良く一致している。From the same table, the nitrogen partial pressure of the coating according to the present invention is initially zero,
Then, since it was formed by continuously raising the chromium, a vapor deposition layer consisting of chromium and chromium nitride was formed on the vapor deposition layer consisting only of chromium, and on top of that a vapor deposition layer consisting only of chromium nitride. It is inferred that a layer has been formed, with the chromium concentration decreasing continuously from the inside to the surface, and the nitrogen concentration continuously increasing from the inside to the surface. It is in good agreement with the analytical results.
前記衝撃試験及び熱疲労試験で本発明に係わる被膜が優
れた成績を示したのは、本発明の被膜は母材に接する内
層がクロムに冨み、表面に近づくに従って硬質のクロム
窒化物の四が連続的に増大しているので、母材との密着
性が良好である上に、熱膨張係数が母材に接している内
層で母材のそれと大差なく、表面に近づくに従って連続
的に低下していることによるものとして考えられる。The reason why the coating according to the present invention showed excellent results in the impact test and thermal fatigue test is that the inner layer in contact with the base metal is rich in chromium, and as it gets closer to the surface, the hard chromium nitride 4 increases continuously, so it has good adhesion to the base material, and the coefficient of thermal expansion is not much different from that of the base material in the inner layer that is in contact with the base material, but it decreases continuously as it approaches the surface. This may be due to what you are doing.
（６）摩耗試験
耐摩耗性については、科研式摩耗試験機により前記Ｘ線
回折分析に供した試料をピンとし、相手ドラムにはＦＣ
−２５材を使用し、荷重２■、摩搾速度０．２５ｍ／ｓ
ｅｃ潤滑液としてｐｈ−２の硫酸水溶液を用い行った。(6) Wear test For wear resistance, the sample subjected to the X-ray diffraction analysis was used as a pin using a Kaken-type abrasion tester, and the mating drum was equipped with FC.
-25 material used, load 2■, grinding speed 0.25m/s
A sulfuric acid aqueous solution of pH-2 was used as the EC lubricant.
比較のために硬質クロムめっきを施したビン６二ついて
も同様の試験を行った６
試験結果は第３図に示す通りである。同図から本発明の
被膜は被膜中の表面からどの深さの位置でも硬質クロム
めっき層よりも優れた耐摩耗性を有していることが理解
されよう。For comparison, a similar test was conducted using 6 bottles with hard chrome plating.6 The test results are shown in Figure 3. It will be understood from the figure that the coating of the present invention has better wear resistance than the hard chromium plating layer at any depth from the surface of the coating.
第３図から窒素分圧１．０〜１．５ Ｘ １０−”ｔｏ
ｒｒで蒸着されたＣｒ、Ｎ及びＣｒ２Ｎ 十ＣｒＮの箇
所で最も耐摩耗性に優れていることがわかる。従って、
最終窒素分圧を１．０〜１．５ Ｘ １０−２ｔｏｒｒ
のところで固定し蒸着することにより、最も耐摩耗性に
すくれ且つ密着性に優れた被膜を得ることができる。From Figure 3, the nitrogen partial pressure is 1.0 to 1.5 x 10-”to
It can be seen that the wear resistance is the best at the locations where Cr, N, and Cr2N + CrN were deposited using rr. Therefore,
Final nitrogen partial pressure 1.0-1.5 x 10-2 torr
By fixing and vapor-depositing at a certain point, it is possible to obtain a coating with the highest wear resistance and excellent adhesion.
（発明の効果）
以上の結果から本発明に係わる被膜は従来から耐摩耗性
に優れるといわれている硬質クロＪ、めっきよりも更に
優れた耐摩耗性を有しており、その上、外部からの衝撃
や、熱疲労に対する抵抗力が従来技術の金属窒化物より
なる被膜にくらべ著しく改善されていることが判る。(Effects of the Invention) From the above results, the coating according to the present invention has even better wear resistance than hard black J or plating, which has been said to have excellent wear resistance. It can be seen that the resistance to impact and thermal fatigue is significantly improved compared to the prior art coating made of metal nitride.
また、その形成法はイオンプレーティング法で窒素分圧
を制御するだけで容易になされ工業上の利用価値は大き
い。In addition, its formation is easy by simply controlling the nitrogen partial pressure using an ion plating method, and has great industrial utility value.
第１図は本発明乙こ使用したイオンプレーティング装置
の概要図である
第２図は本発明によりえられた被膜の線分析結果を示す
図である。
第３図は各種窒素分圧でのイオンプレーティングにより
えられた被膜の摩耗試験結果を示す図である。
１・・・摺動母材、２・−母材保持具、３・・・ヒータ
ー５・・・蒸発源金属、６・・・水冷るつぼ、７・・・
収束コイル、ε・・・電子銃及び計導入口、９・・・真
空容器、１０・・・シャッター １１・・・窒素ガス導
入口。
代理人 弁理士 桑 原 英 明第２
図FIG. 1 is a schematic diagram of an ion plating apparatus used in the present invention. FIG. 2 is a diagram showing the results of line analysis of a film obtained according to the present invention. FIG. 3 is a diagram showing the results of an abrasion test of coatings obtained by ion plating at various nitrogen partial pressures. DESCRIPTION OF SYMBOLS 1... Sliding base material, 2... Base material holder, 3... Heater 5... Evaporation source metal, 6... Water-cooled crucible, 7...
Convergent coil, ε...Electron gun and meter inlet, 9...Vacuum container, 10...Shutter 11...Nitrogen gas inlet. Agent Patent Attorney Hideaki Kuwahara Figure 2
Claims (3)
素よりなる被膜であって、被膜の表面及び表面近接した
被膜組繊がＣｒＮであり、該被膜における窒素濃度が該
母材面の垂直方向に、該母材表面から該被膜表面に連続
的に増加していることを特徴とする耐摩耗性被膜。(1) A coating made of chromium and nitrogen formed on the sliding base material surface of a sliding component, in which the surface of the coating and the coating fibers near the surface are CrN, and the nitrogen concentration in the coating is A wear-resistant coating, characterized in that it increases continuously from the base material surface to the coating surface in a direction perpendicular to the plane.
耐摩耗性被膜。(2) The wear-resistant coating according to claim (1), wherein the sliding component is a piston ring.
る被膜をイオンプレーティング法で製造する方法におい
て、該イオンプレーティング操作の窒素分圧を連続的に
変化させて行うことを特徴とするクロム及び窒素よりな
る耐摩耗性被膜の製造法。(3) In the method of manufacturing a coating made of chromium and nitrogen on the sliding base material surface of sliding parts by ion plating, the ion plating operation is performed by continuously changing the nitrogen partial pressure. A manufacturing method for a wear-resistant coating consisting of chromium and nitrogen.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9927590A JPH04368A (en) | 1990-04-17 | 1990-04-17 | Wear resistant coating film and production thereof |
| GB9107539A GB2243162B (en) | 1990-04-17 | 1991-04-10 | A wear-resistant coating |
| DE19914112422 DE4112422A1 (en) | 1990-04-17 | 1991-04-16 | ABRASION RESISTANT COATING |
| FR9104692A FR2660939B1 (en) | 1990-04-17 | 1991-04-17 | WEAR RESISTANT COATING AND MANUFACTURING METHOD THEREOF. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9927590A JPH04368A (en) | 1990-04-17 | 1990-04-17 | Wear resistant coating film and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04368A true JPH04368A (en) | 1992-01-06 |
Family
ID=14243127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9927590A Pending JPH04368A (en) | 1990-04-17 | 1990-04-17 | Wear resistant coating film and production thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH04368A (en) |
| DE (1) | DE4112422A1 (en) |
| FR (1) | FR2660939B1 (en) |
| GB (1) | GB2243162B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0639994A (en) * | 1992-07-22 | 1994-02-15 | Mitsui Eng & Shipbuild Co Ltd | Manufacture of gravure printing roller |
| DE4419713A1 (en) * | 1993-06-07 | 1994-12-08 | Teikoku Piston Ring Co Ltd | Bearing element and process for its production |
| JPH0987830A (en) * | 1995-09-28 | 1997-03-31 | Nippon Piston Ring Co Ltd | Sliding member for compressor |
| US6631907B1 (en) | 1994-12-27 | 2003-10-14 | Nippon Piston Ring Co., Ltd. | Nitride-plated piston ring for internal combustion engines |
| JP2008505251A (en) * | 2004-07-03 | 2008-02-21 | フェデラル−モーグル ブルシャイト ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method and piston ring for producing a coating layer on a piston ring |
| JP2021063296A (en) * | 2011-10-21 | 2021-04-22 | イドロメカニーク・エ・フロットマン | Friction part operating in lubricated medium |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9005321D0 (en) * | 1990-03-09 | 1990-05-02 | Matthews Allan | Modulated structure composites produced by vapour disposition |
| GB2264718B (en) * | 1992-03-04 | 1995-04-26 | Univ Hull | Coatings produced by vapour deposition |
| CH684617B5 (en) * | 1992-03-26 | 1995-05-15 | Bloesch W Ag | Surface coating. |
| JP2771947B2 (en) * | 1994-04-21 | 1998-07-02 | 株式会社リケン | Sliding member |
| CN1068388C (en) * | 1994-07-30 | 2001-07-11 | 株式会社理研 | Sliding material and method for preparing thereof |
| CN1068412C (en) * | 1994-07-30 | 2001-07-11 | 株式会社理研 | Piston ring |
| EP0702097B1 (en) * | 1994-07-30 | 1999-11-10 | Kabushiki Kaisha Riken | Sliding members |
| US5672386A (en) * | 1994-10-27 | 1997-09-30 | Kabushiki Kaisha Riken | Process for forming a coating of chromium and nitrogen having good wear resistance properties |
| US5587227A (en) * | 1994-10-27 | 1996-12-24 | Kabushiki Kaisha Riken | Coating of chromium and nitrogen having good wear resistance properties |
| US5601293A (en) * | 1994-12-22 | 1997-02-11 | Teikoku Piston Ring Co., Ltd. | Sliding member with hard ternery film |
| US5605741A (en) * | 1995-06-02 | 1997-02-25 | Dana Corporation | Hybrid face coating for piston ring |
| JPH0931628A (en) * | 1995-07-25 | 1997-02-04 | Riken Corp | Sliding member and its production |
| DE19648160C2 (en) * | 1996-11-21 | 1998-09-10 | Ae Goetze Gmbh | Compression piston ring |
| WO1998041771A1 (en) * | 1997-03-19 | 1998-09-24 | Caterpillar Inc. | Track and/or hinge pin having improved abrasion, corrosion and galling resistance |
| DE10207078B4 (en) * | 2002-02-20 | 2004-02-12 | Federal-Mogul Burscheid Gmbh | Piston ring with a PVD coating |
| DE10256063A1 (en) | 2002-11-30 | 2004-06-17 | Mahle Gmbh | Process for coating piston rings for internal combustion engines |
| US20050207831A1 (en) * | 2004-03-17 | 2005-09-22 | Van Der Moere Donald R | Coated piston pin |
| DE102004028486A1 (en) * | 2004-06-11 | 2005-12-29 | Mahle Gmbh | sliding |
| DE102007025949A1 (en) | 2007-06-04 | 2008-12-11 | Federal-Mogul Burscheid Gmbh | Abrasion-resistant coating for carrier material such as piston ring useful in internal combustion engine, comprises wear-resistant layer on the carrier material, running-in layer on the wear-resistant layer, and adhesion-promoting layer |
| DE102011076453B4 (en) * | 2011-05-25 | 2013-08-01 | Federal-Mogul Burscheid Gmbh | Piston ring with composite coating |
| US9580817B2 (en) * | 2012-12-04 | 2017-02-28 | Vergason Technology, Inc. | Bilayer chromium nitride coated articles and related methods |
| US11156291B2 (en) | 2017-06-02 | 2021-10-26 | Mahle International Gmbh | Piston ring and method of manufacture |
| US11162586B2 (en) | 2017-06-02 | 2021-11-02 | Mahle International Gmbh | Piston ring and method of manufacture |
| US11047478B2 (en) | 2017-06-02 | 2021-06-29 | Mahle International Gmbh | Piston ring and method of manufacture |
| DE102020006953B4 (en) | 2020-09-21 | 2022-06-02 | Federal-Mogul Burscheid Gmbh | Piston ring with transition layer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62188856A (en) * | 1986-02-13 | 1987-08-18 | Riken Corp | Piston ring |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1352241A (en) * | 1971-04-13 | 1974-05-08 | Wilkinson Sword Ltd | Razor blades |
| DE2705225C2 (en) * | 1976-06-07 | 1983-03-24 | Nobuo Tokyo Nishida | Ornamental part for clocks etc. |
| AT381268B (en) * | 1982-05-05 | 1986-09-25 | Ver Edelstahlwerke Ag | TOOL AND METHOD FOR THE PRODUCTION THEREOF |
| JPS60221565A (en) * | 1984-04-19 | 1985-11-06 | Matsushita Electric Ind Co Ltd | Diamond parts and its production |
| JPS60234965A (en) * | 1984-05-04 | 1985-11-21 | Diesel Kiki Co Ltd | Manufacture of thin film |
| JPS6222314A (en) * | 1985-07-22 | 1987-01-30 | 株式会社ボッシュオートモーティブ システム | Manufacture of thin film |
| JPS62283258A (en) * | 1986-05-31 | 1987-12-09 | Riken Corp | Piston ring |
| GB9005321D0 (en) * | 1990-03-09 | 1990-05-02 | Matthews Allan | Modulated structure composites produced by vapour disposition |
-
1990
- 1990-04-17 JP JP9927590A patent/JPH04368A/en active Pending
-
1991
- 1991-04-10 GB GB9107539A patent/GB2243162B/en not_active Expired - Fee Related
- 1991-04-16 DE DE19914112422 patent/DE4112422A1/en active Granted
- 1991-04-17 FR FR9104692A patent/FR2660939B1/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62188856A (en) * | 1986-02-13 | 1987-08-18 | Riken Corp | Piston ring |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0639994A (en) * | 1992-07-22 | 1994-02-15 | Mitsui Eng & Shipbuild Co Ltd | Manufacture of gravure printing roller |
| DE4419713A1 (en) * | 1993-06-07 | 1994-12-08 | Teikoku Piston Ring Co Ltd | Bearing element and process for its production |
| US5582414A (en) * | 1993-06-07 | 1996-12-10 | Teikoku Piston Ring Co., Ltd. | Sliding member and method for manufacturing the same |
| DE4419713C2 (en) * | 1993-06-07 | 1997-01-09 | Teikoku Piston Ring Co Ltd | Sliding element and method for its production and use of the sliding element as a piston ring |
| US6631907B1 (en) | 1994-12-27 | 2003-10-14 | Nippon Piston Ring Co., Ltd. | Nitride-plated piston ring for internal combustion engines |
| JPH0987830A (en) * | 1995-09-28 | 1997-03-31 | Nippon Piston Ring Co Ltd | Sliding member for compressor |
| JP2008505251A (en) * | 2004-07-03 | 2008-02-21 | フェデラル−モーグル ブルシャイト ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method and piston ring for producing a coating layer on a piston ring |
| JP2021063296A (en) * | 2011-10-21 | 2021-04-22 | イドロメカニーク・エ・フロットマン | Friction part operating in lubricated medium |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9107539D0 (en) | 1991-05-29 |
| DE4112422C2 (en) | 1992-07-23 |
| DE4112422A1 (en) | 1991-10-24 |
| GB2243162B (en) | 1993-10-06 |
| FR2660939A1 (en) | 1991-10-18 |
| FR2660939B1 (en) | 1995-09-29 |
| GB2243162A (en) | 1991-10-23 |
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