JP6339812B2 - piston ring - Google Patents
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- JP6339812B2 JP6339812B2 JP2014014161A JP2014014161A JP6339812B2 JP 6339812 B2 JP6339812 B2 JP 6339812B2 JP 2014014161 A JP2014014161 A JP 2014014161A JP 2014014161 A JP2014014161 A JP 2014014161A JP 6339812 B2 JP6339812 B2 JP 6339812B2
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- piston ring
- amorphous carbon
- carbon film
- hmt115
- maximum peak
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 40
- 241000428199 Mustelinae Species 0.000 claims description 20
- 230000003746 surface roughness Effects 0.000 claims description 20
- 229910000838 Al alloy Inorganic materials 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002093 peripheral Effects 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229910001018 Cast iron Inorganic materials 0.000 description 3
- 210000002381 Plasma Anatomy 0.000 description 3
- 241000282898 Sus scrofa Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BLJRIMJGRPQVNF-JTQLQIEISA-N Timolol Chemical compound CC(C)(C)NC[C@H](O)COC1=NSN=C1N1CCOCC1 BLJRIMJGRPQVNF-JTQLQIEISA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000023298 conjugation with cellular fusion Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001678 elastic recoil detection analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007541 indentation hardness test Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 230000021037 unidirectional conjugation Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
- F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J10/00—Engine or like cylinders; Features of hollow, e.g. cylindrical, bodies in general
- F16J10/02—Cylinders designed to receive moving pistons or plungers
- F16J10/04—Running faces; Liners
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F5/00—Piston rings, e.g. associated with piston crown
Description
本発明は、非晶質炭素皮膜を形成したピストンリング（以下「リング」ともいう。）に関し、特に耐摩耗性及び耐スカッフ性に優れたピストンリングに関する。 The present invention relates to a piston ring (hereinafter also referred to as “ring”) having an amorphous carbon film formed thereon, and more particularly to a piston ring having excellent wear resistance and scuff resistance.
自動車エンジンでは、ピストンリングとシリンダ又はシリンダライナの摺動によって生じる摩擦損失の占める割合はエンジン全体損失の2〜3割程度と言われており、それ故この摩擦損失の低減は重要で、燃費を向上し、CO2排出削減への貢献は大きいと考えられている。ピストンリング摩擦損失に関係する因子としては、リング張力、リング形状、摩擦係数などがあるが、特にリング形状の維持は、摩擦損失の低減に寄与するだけでなく、シール性を維持し、燃焼エネルギーをロス無くクランクシャフトに伝達して高い機械効率を維持することにも貢献する。その点、優れた耐摩耗性により摩擦損失の少ないリング形状を維持することを可能にし、且つ摩擦係数の小さい非晶質炭素皮膜をピストンリングに形成することが注目される。 In automobile engines, it is said that the ratio of friction loss caused by the sliding of the piston ring and cylinder or cylinder liner is about 20 to 30% of the total engine loss. Therefore, it is important to reduce this friction loss. It is considered that the contribution to improvement and reduction of CO 2 emissions is great. Factors related to piston ring friction loss include ring tension, ring shape, friction coefficient, etc.In particular, maintaining the ring shape not only contributes to the reduction of friction loss, but also maintains sealability and combustion energy. Is also transmitted to the crankshaft without loss, contributing to maintaining high mechanical efficiency. In this regard, it is noted that an excellent carbon wear-resistant ring shape with little friction loss can be maintained and an amorphous carbon film having a small friction coefficient is formed on the piston ring.
一方、リングの摺動相手であるシリンダライナも、燃費の向上や、車両運動性能の向上を目的として、鋳鉄からアルミ合金へ軽量化の材料置換が進められている。アルミ合金としては、耐摩耗性に優れたアルミ合金、例えば、比較的硬い初晶Siの晶出した過共晶Al-Si合金が使用されるようになってきた。 On the other hand, the cylinder liner that is a sliding partner of the ring is also being replaced with a lighter material from cast iron to an aluminum alloy for the purpose of improving fuel efficiency and vehicle performance. As the aluminum alloy, an aluminum alloy excellent in wear resistance, for example, a hypereutectic Al—Si alloy crystallized with relatively hard primary Si has been used.
特許文献１は、鋳鉄シリンダライナを摺動相手材として、初期なじみ性に優れ、摩擦損失低減効果の大きな摺動部材を提供することを目的に、真空アーク放電法により成膜された非晶質炭素皮膜の表面に形成されるマクロパーティクルと呼ばれる微少突起に注目し、このマクロパーティクルの後処理による調整が、表面粗さパラメータである十点平均粗さ（Rz）と初期摩耗粗さ（Rpk）により管理できることを教示している。具体的には、Rzが0.7μm以下であり、且つRpkが0.07〜0.14μmであることを要件としている。 Patent Document 1 discloses an amorphous film formed by a vacuum arc discharge method for the purpose of providing a sliding member having a cast iron cylinder liner as a sliding counterpart material, excellent in initial conformability and having a large effect of reducing friction loss. Focusing on the micro-projections called macro particles formed on the surface of the carbon film, the adjustment by post-processing of the macro particles is the 10-point average roughness (Rz) and initial wear roughness (Rpk) which are the surface roughness parameters. It can be managed by Specifically, it is required that Rz is 0.7 μm or less and Rpk is 0.07 to 0.14 μm.
しかし、鋳鉄シリンダライナに代えてアルミ合金製シリンダライナを使用した場合、十点平均粗さと初期摩耗粗さを上記の所定の範囲に管理しても、非晶質炭素皮膜は、摺動によりスカッフを起こして傷が入ったり、ひどい場合には摩滅してしまうようなことが生じたりする可能性があった。 However, when an aluminum alloy cylinder liner is used in place of the cast iron cylinder liner, the amorphous carbon film can be scuffed by sliding even if the ten-point average roughness and the initial wear roughness are controlled within the above specified ranges. There was a possibility that it would cause scratches, and in the worst case it would wear out.
本発明は、自動車の低燃費化のため、アルミ合金製のシリンダ又はシリンダライナに対し、耐摩耗性及び耐スカッフ性に優れた非晶質炭素皮膜を形成したピストンリングを提供することを課題とする。 An object of the present invention is to provide a piston ring formed with an amorphous carbon film excellent in wear resistance and scuff resistance on an aluminum alloy cylinder or cylinder liner for reducing fuel consumption of an automobile. To do.
本発明者は、アルミ合金を相手材とした非晶質炭素皮膜の摩擦摩耗特性と非晶質炭素皮膜の表面粗さパラメータとの関係について、鋭意研究した結果、耐スカッフ性が、平均的な表面粗さよりも最大山高さを持つ突起に強く依存するという知見、また二次元の表面粗さパラメータよりもむしろ三次元の最大山高さに強く依存するという知見を得て、本発明の非晶質炭素皮膜形成ピストンリングに想到した。 As a result of earnest research on the relationship between the frictional wear characteristics of an amorphous carbon film with an aluminum alloy as a counterpart and the surface roughness parameter of the amorphous carbon film, the present inventor has found that the scuff resistance is average. With the knowledge that it depends strongly on the protrusion with the maximum peak height rather than the surface roughness, and that it strongly depends on the three-dimensional maximum peak height rather than the two-dimensional surface roughness parameter, We came up with a carbon film-forming piston ring.
すなわち、本発明のピストンリングは、摺動面に非晶質炭素皮膜を形成したピストンリングであって、前記非晶質炭素皮膜の表面におけるマルテンス硬さHMT115が5.0 GPa以上であり、前記マルテンス硬さHMT115と前記非晶質炭素皮膜表面の三次元表面粗さの最大山高さSpとの積が5.0 kPa・m以下で確実にスカッフを回避できることを特徴とする。前記マルテンス硬さHMT115は11.0 GPa未満であることが好ましく、前記最大山高さSpは0.5μm以下であることが好ましい。 That is, the piston ring of the present invention is a piston ring in which an amorphous carbon film is formed on a sliding surface, and the Martens hardness HMT115 on the surface of the amorphous carbon film is 5.0 GPa or more. The product of the thickness HMT115 and the maximum peak height Sp of the three-dimensional surface roughness of the amorphous carbon film surface is 5.0 kPa · m or less, so that scuffing can be avoided reliably . The Martens hardness HMT115 is preferably less than 11.0 GPa, and the maximum peak height Sp is preferably 0.5 μm or less.
また、前記非晶質炭素皮膜は、15.0〜40.0原子％の水素を含有していることが好ましく、膜厚が4.0〜10.0μmであることが好ましい。 The amorphous carbon film preferably contains 15.0 to 40.0 atomic% hydrogen, and preferably has a film thickness of 4.0 to 10.0 μm.
また、本発明のピストンリングは、アルミニウム合金製シリンダライナを摺動相手材として使用されることが好ましい。 Moreover, it is preferable that the piston ring of this invention uses an aluminum alloy cylinder liner as a sliding other material.
本発明のピストンリングは、ピストンリングに形成した非晶質炭素皮膜のマルテンス硬さHMT115が5.0 GPa以上で、少なくとも過共晶Al-Si合金のSi粒子と同レベル以上であり、共晶Al-Si合金製シリンダから脱落したSi粒子がアブレイジブとして摺動面に存在しても、非晶質炭素皮膜の摩耗を抑制することができる。また、前記マルテンス硬さHMT115と前記非晶質炭素皮膜表面の三次元表面粗さの最大山高さSpとの積を5.0 kPa・m以下としているので、非晶質炭素皮膜のHMT115が比較的大きい場合には、Spを小さくすることにより最大山高さを持つ突起によるスカッフを回避することができる。特に、最大山高さについて三次元表面粗さを採用したことは、評価の信頼性を著しく高め、確実なスカッフの回避に繋がり、結果的に、アルミ合金製シリンダライナに対し、優れた耐摩耗性及び耐スカッフ性を示し、自動車の低燃費化に貢献することができる。 The piston ring of the present invention has a Martens hardness HMT115 of the amorphous carbon film formed on the piston ring of 5.0 GPa or more and at least the same level as that of the Si particles of the hypereutectic Al-Si alloy. Even if Si particles dropped from the Si alloy cylinder are present on the sliding surface as abrading, the wear of the amorphous carbon film can be suppressed. Further, since the product of the Martens hardness HMT115 and the maximum peak height Sp of the three-dimensional surface roughness of the amorphous carbon film surface is 5.0 kPa · m or less, the HMT115 of the amorphous carbon film is relatively large. In some cases, by reducing Sp, it is possible to avoid scuffing due to the protrusion having the maximum peak height. In particular, the use of three-dimensional surface roughness for the maximum peak height significantly increases the reliability of the evaluation and leads to reliable scuffing. As a result, it has excellent wear resistance against aluminum alloy cylinder liners. In addition, it exhibits scuff resistance and can contribute to lower fuel consumption of automobiles.
本発明のピストンリングの摺動面に形成する非晶質炭素皮膜において、マルテンス硬さHMT115はナノインデンテーション法によって測定される。ナノインデンテーション法は、Berkovich圧子で荷重を測定面に連続して負荷・除荷し、所定の荷重下での表面からの押し込み深さを計測して硬さを求める方法である。このマルテンス硬さHMT115が低すぎると、過共晶Al-Si合金の初晶Siによって非晶質炭素皮膜が摩耗してしまうので、少なくとも5.0 GPa以上とする。さらに、マルテンス硬さHMT115が高すぎると、靱性が低くなって破壊しやすく、破壊によってスカッフを起こすおそれがあり、また非晶質炭素皮膜表面の三次元表面粗さの最大山高さSpが高すぎても高い局部応力が発生してスカッフを起こしやすくなるため、マルテンス硬さと最大山高さの積、すなわち、HMT115×Spが5.0 kPa・m以下となるように調整する必要がある。マルテンス硬さHMT115は5.0 GPa以上11.0 GPa未満であることが好ましく、6.0 GPa以上10.0 GPa未満であることがより好ましい。また三次元表面粗さの最大山高さSpは0.5μm以下であることが好ましく、0.4μm以下であることがより好ましい。 In the amorphous carbon film formed on the sliding surface of the piston ring of the present invention, the Martens hardness HMT115 is measured by a nanoindentation method. The nanoindentation method is a method in which a load is continuously loaded and unloaded with a Berkovich indenter and the indentation depth from the surface under a predetermined load is measured to obtain the hardness. If this Martens hardness HMT115 is too low, the amorphous carbon film will be worn by the primary crystal Si of the hypereutectic Al—Si alloy, so at least 5.0 GPa. Furthermore, if the Martens hardness HMT115 is too high, the toughness tends to be low and breakage may occur, and scuffing may occur due to the fracture, and the maximum peak height Sp of the three-dimensional surface roughness of the amorphous carbon film surface is too high. However, since high local stress is generated and scuffing is likely to occur, it is necessary to adjust the product of Martens hardness and maximum peak height, that is, HMT115 × Sp to be 5.0 kPa · m or less. The Martens hardness HMT115 is preferably 5.0 GPa or more and less than 11.0 GPa, and more preferably 6.0 GPa or more and less than 10.0 GPa. Further, the maximum peak height Sp of the three-dimensional surface roughness is preferably 0.5 μm or less, and more preferably 0.4 μm or less.
図１は、本発明の非晶質炭素皮膜表面をレーザー顕微鏡で観察した写真であるが、所定の面積内の最大山（1）は確実に観測することができ、三次元表面粗さの測定により、十点平均粗さのような線分析による表面粗さに比べ、遥かに精度が向上していることが理解できる。 FIG. 1 is a photograph of the surface of the amorphous carbon film of the present invention observed with a laser microscope. The maximum peak (1) within a predetermined area can be reliably observed, and the three-dimensional surface roughness is measured. Thus, it can be understood that the accuracy is far improved compared to the surface roughness by line analysis such as the ten-point average roughness.
前記非晶質炭素皮膜は、本発明の範囲のマルテンス硬度HMT115を有するためには、水素を含有していることが好ましい。非晶質炭素皮膜に水素が取り込まれると、炭素の結合手の切断を引き起こし、結合を終端させて残留応力の緩和が起こり、硬さと弾性率を下げることが可能となる。前記非晶質炭素皮膜は、不可避的不純物を除き、炭素と水素のみによって構成され、その場合、水素含有量は15〜40原子％であることが好ましく、20〜35原子％であることがより好ましい。 The amorphous carbon film preferably contains hydrogen in order to have a Martens hardness HMT115 within the range of the present invention. When hydrogen is taken into the amorphous carbon film, the bond of carbon is broken, the bond is terminated, the residual stress is relaxed, and the hardness and elastic modulus can be lowered. The amorphous carbon film is composed only of carbon and hydrogen except for inevitable impurities. In this case, the hydrogen content is preferably 15 to 40 atomic%, more preferably 20 to 35 atomic%. preferable.
また、前記非晶質炭素皮膜は、4.0〜10.0μmの膜厚を有することが好ましい。 The amorphous carbon film preferably has a thickness of 4.0 to 10.0 μm.
また、前記非晶質炭素皮膜は、密着性向上のため、ピストンリング母材との間に金属中間層を介して形成されることが好ましい。金属中間層は、炭化物生成自由エネルギーが低く、炭素と反応して炭化物を生成しやすい金属のSi、Ti、Cr、Mn、Zr、Nb、Wの群から選択された1又は2以上の元素からなる金属層とすることが好ましい。Crの金属層が特に好ましい。 The amorphous carbon film is preferably formed through a metal intermediate layer between the piston ring base material and the piston ring base material in order to improve adhesion. The metal intermediate layer is composed of one or more elements selected from the group consisting of Si, Ti, Cr, Mn, Zr, Nb, and W, which are low in carbide formation free energy and easily react with carbon to form carbide. It is preferable to use a metal layer. A Cr metal layer is particularly preferred.
また、本発明のピストンリングは、アルミニウム合金製のシリンダライナを摺動相手材として使用されることが好ましい。アルミニウム合金製のシリンダライナは、初晶Siが微細に分散した過共晶Al-Si合金製であることが好ましく、ダイキャストを含む鋳造により製造する場合はSi含有量が18〜22％であるのが好ましく、急冷凝固粉末を焼結固化後、熱間押出法により製造されたものではSi含有量は20〜30％が好ましい。一般に、熱間押出法によるAl合金は、パイプ材に製造され、所定の加工を施して、別の鋳造性の良いAl合金で製造されたシリンダブロックに鋳包まれる。 Moreover, it is preferable that the piston ring of this invention uses the cylinder liner made from an aluminum alloy as a sliding other material. The cylinder liner made of aluminum alloy is preferably made of a hypereutectic Al-Si alloy in which primary Si is finely dispersed, and when produced by casting including die casting, the Si content is 18 to 22%. In the case where the rapidly solidified powder is sintered and solidified and then manufactured by hot extrusion, the Si content is preferably 20 to 30%. In general, an Al alloy by a hot extrusion method is manufactured into a pipe material, subjected to predetermined processing, and encapsulated in a cylinder block manufactured from another Al alloy having good castability.
本発明のピストンリングに形成される非晶質炭素皮膜は、電源から基材に負のバイアス電圧を印加してプラズマ放電させ、炭化水素系ガスを分解、基材に析出させる所謂プラズマCVD法により形成される。好ましい膜厚（4.0〜10.0μm）や、金属中間層の形成を考慮すると、PIGプラズマCVD装置にスパッタターゲットも併設された装置を使用することが好ましい。もちろん、炭化水素系ガスとともにグラファイトターゲットをスパッタリングして、PVD法により、硬質炭素層を形成することも可能である。 The amorphous carbon film formed on the piston ring of the present invention is a so-called plasma CVD method in which a negative bias voltage is applied to a base material from a power source to cause plasma discharge, hydrocarbon gas is decomposed, and deposited on the base material. It is formed. In consideration of a preferable film thickness (4.0 to 10.0 μm) and formation of a metal intermediate layer, it is preferable to use an apparatus in which a sputtering target is also provided in addition to a PIG plasma CVD apparatus. Of course, it is also possible to form a hard carbon layer by PVD method by sputtering a graphite target together with a hydrocarbon gas.
実施例１
脱脂洗浄した矩形断面で外周面をバレルフェイス形状としたピストンリング母材（クロムめっき処理したSUS420J2 相当、呼称径（d）90 mm、厚さ（h1）1.2 mm、幅（a1）3.2 mm）を成膜治具に10本重ねてセットし、PIGプラズマガンとCr及びWCターゲットを備えたCVD装置の真空チャンバー内の回転テーブルに設置した。また、組成分析用試料として、外径25 mm、厚さ5 mmの焼入処理し、鏡面研磨したSKH51材を、ピストンリングの外周面と同様の動きをする治具にセットして設置した。装置内を所定の真空度まで排気した後、Arガスを導入し、PIGプラズマによるボンバードメントにより、母材表面のクリーニング処理を行った後、Crのスパッタリングにより、所定の時間、ピストンリング外周面にCr層を形成した。続いて、WCのスパッタリングを同時に処理し、WC/Crの傾斜層を形成した。そして、Crのスパッタリングを停止させ、WCのスパッタリングを実施しながら、Arガスに加えてC2H2ガスを導入して、WC/W-a-C:Hの傾斜層を形成した。最後にWCのスパッタリングを停止し、所定の時間、プラズマCVD法による非晶質炭素皮膜を形成した。ここで、成膜治具には、負のバイアス電圧を印加した。成膜後のピストンリングについて、その外周面にフィルムラップ処理を施し、表面粗さを調整した。
Example 1
Piston ring base material (corresponding to chrome-plated SUS420J2, nominal diameter (d) 90 mm, thickness (h1) 1.2 mm, width (a1) 3.2 mm) with a degreased and washed rectangular cross section and barrel face shape on the outer peripheral surface Ten pieces were set on a film forming jig and placed on a rotary table in a vacuum chamber of a CVD apparatus equipped with a PIG plasma gun and Cr and WC targets. As a sample for composition analysis, a SKH51 material that had been quenched and mirror-polished with an outer diameter of 25 mm and a thickness of 5 mm was set and installed on a jig that moved in the same manner as the outer peripheral surface of the piston ring. After evacuating the inside of the device to a predetermined degree of vacuum, Ar gas is introduced, the base material surface is cleaned by bombardment with PIG plasma, and then the outer surface of the piston ring is applied for a predetermined time by Cr sputtering. A Cr layer was formed. Subsequently, WC sputtering was simultaneously performed to form a WC / Cr gradient layer. Then, the sputtering of Cr was stopped, and while performing the sputtering of WC, a C 2 H 2 gas was introduced in addition to the Ar gas to form a WC / WaC: H gradient layer. Finally, the sputtering of WC was stopped, and an amorphous carbon film was formed by a plasma CVD method for a predetermined time. Here, a negative bias voltage was applied to the film forming jig. About the piston ring after film-forming, the film lapping process was performed to the outer peripheral surface, and surface roughness was adjusted.
次に、実施例１の非晶質炭素皮膜被覆ピストンリング及び組成分析用試料を次の各種測定に供した。 Next, the amorphous carbon film-coated piston ring and the composition analysis sample of Example 1 were subjected to the following various measurements.
[1] 膜厚測定
膜厚測定は、球面研磨法による所謂CALOTESTにより、積層被膜の基材面から各層の厚さを測定した。実施例１のピストンリングの中間層の厚さは0.8μm、非晶質炭素皮膜の厚さは5.6μmであった。
[1] Film thickness measurement For film thickness measurement, the thickness of each layer was measured from the base material surface of the laminated coating by so-called CALOTEST using a spherical polishing method. The thickness of the intermediate layer of the piston ring of Example 1 was 0.8 μm, and the thickness of the amorphous carbon film was 5.6 μm.
[2] マルテンス硬さHMT115の測定
マルテンス硬さHMT115は、ISO 14577-1（計装化押込み硬さ試験）に準拠し、超微小硬度計（島津製作所、DUH-211）を用いて、Berkovich圧子、試験モード：負荷-除荷試験、試験力：19.6 mN、負荷除荷速度：0.4877 mN/sec、負荷→除荷保持時間：5秒、Cf-Ap補正あり、の条件で行った。測定個所は、被膜表面近傍を平均粒径0.25μmのダイヤモンドペーストを塗布した直径30 mmの鋼球を用いて球面研磨し、研磨部分について行った。マルテンス硬さHMT115は、荷重-押込み深さ曲線から計算される。測定結果としては、10点測定し、平均値を採用した。実施例１のマルテンス硬さHMT115は8.1 GPaであった。
[2] Measurement of Martens hardness HMT115 Martens hardness HMT115 conforms to ISO 14577-1 (instrumentation indentation hardness test) and uses a very small hardness tester (Shimadzu Corporation, DUH-211), Berkovich Indenter, test mode: load-unloading test, test force: 19.6 mN, load unloading speed: 0.4877 mN / sec, load → unloading holding time: 5 seconds, with Cf-Ap correction. Measurement was performed on the polished portion by subjecting the vicinity of the coating surface to spherical polishing using a 30 mm diameter steel ball coated with a diamond paste having an average particle size of 0.25 μm. The Martens hardness HMT115 is calculated from a load-indentation depth curve. As a measurement result, 10 points were measured and an average value was adopted. The Martens hardness HMT115 of Example 1 was 8.1 GPa.
[3] 三次元表面粗さの最大山高さSpの測定
三次元表面粗さの最大山高さSpは、レーザー顕微鏡（オリンパス株式会社製OLS4000）により、カットオフ値λ=0.08 mm、測定範囲64μm×64μmとして測定した。測定結果としては、5点測定し、平均値を採用した。実施例１の最大山高さSpは0.31μmであった。上記マルテンス硬さHMT115と最大山高さSpとの積は2.53 kPa・mであった。
[3] Measurement of the maximum peak height Sp of the three-dimensional surface roughness The maximum peak height Sp of the three-dimensional surface roughness was measured with a laser microscope (OLS4000 manufactured by Olympus Corporation) with a cutoff value λ = 0.08 mm and a measurement range of 64 μm × Measurement was performed at 64 μm. As a measurement result, five points were measured and an average value was adopted. The maximum peak height Sp of Example 1 was 0.31 μm. The product of the Martens hardness HMT115 and the maximum peak height Sp was 2.53 kPa · m.
[4] 非晶質炭素皮膜の水素含有量分析
非晶質炭素皮膜中の水素含有量は、組成分析用試料を用いて、ラザフォード後方散乱分光法（RBS）／水素前方散乱分光法（HFS）により求めた。実施例１の水素含有量は31原子％であった。
[4] Hydrogen content analysis of amorphous carbon coatings The hydrogen content in amorphous carbon coatings was determined using Rusford backscattering spectroscopy (RBS) / hydrogen forward scattering spectroscopy (HFS) using a sample for composition analysis. Determined by The hydrogen content in Example 1 was 31 atomic%.
[5] 往復摺動試験
往復摺動試験は、Optimol社製のSRVIII型試験機を用い、シリンダライナに相当するアルミ合金製円板上をピストンリングが軸方向に往復摺動する試験により行った。ここで、アルミ合金製円板は、Al-80質量％、Si-20質量％の合金円板を研磨加工により表面粗さ（Rzjis-82）0.45〜0.65μmに調製したものを使用し、ピストンリングは、長さ約15 mmに切断したピストンリング片を使用した。試験条件は、垂直荷重300 N、往復幅2 mm、往復周波数60 Hz、円板温度100℃、潤滑下（市販エンジン油（0W-20SM）を1 cm3滴下）にて、試験時間90分とした。試験結果としては、試験後の摺動痕の光学顕微鏡観察と摩擦係数を記録したチャートの確認から、傷がなく、スカッフ（摩擦係数の急上昇）も確認されないものを○、傷及び／又はスカッフが確認されたものを×として評価した。加えて、非晶質炭素皮膜が摩滅して、ピストンリングの母材が摺動方向に1 mm以上露出した場合を摩滅とした。実施例１の往復摺動試験の結果は、傷もスカッフも確認されずに良好であった。
[5] Reciprocating sliding test The reciprocating sliding test was conducted by using a SRVIII type tester manufactured by Optimol, and a test in which the piston ring reciprocally slides in an axial direction on an aluminum alloy disk corresponding to a cylinder liner. . Here, the aluminum alloy disc is prepared by polishing an alloy disc of Al-80 mass% and Si-20 mass% to a surface roughness (Rzjis-82) of 0.45 to 0.65 μm by polishing. The ring used was a piston ring piece cut to a length of about 15 mm. The test conditions were a vertical load of 300 N, a reciprocating width of 2 mm, a reciprocating frequency of 60 Hz, a disc temperature of 100 ° C., and under lubrication (commercial engine oil (0W-20SM) dropped 1 cm 3 ), with a test time of 90 minutes. did. As a result of the test, ○, scratches and / or scuffs indicate that there is no scratch and no scuff (rapid increase in friction coefficient) is confirmed from the observation of the optical trace of the sliding trace after the test and the confirmation of the chart recording the friction coefficient. What was confirmed was evaluated as x. In addition, the case where the amorphous carbon film was worn away and the base material of the piston ring was exposed 1 mm or more in the sliding direction was defined as abrasion. The result of the reciprocating sliding test of Example 1 was good without any scratches or scuffing.
比較例１
実施例１の成膜後のピストンリングについて、その外周面のフィルムラップ処理時間を短くしたものを比較例１として、三次元表面粗さの最大山高さSpの測定と往復摺動試験を行った。最大山高さSpは0.79μm、HMT115×Sp＝6.40 kPa・m、往復摺動試験の結果は、相手材に傷が確認され、またスカッフも確認された。
Comparative Example 1
The piston ring after film formation of Example 1 was subjected to measurement of the maximum peak height Sp of the three-dimensional surface roughness and a reciprocating sliding test as Comparative Example 1 in which the film wrap processing time on the outer peripheral surface was shortened. . The maximum peak height Sp was 0.79 μm, HMT115 × Sp = 6.40 kPa · m, and the results of the reciprocating sliding test confirmed that the mating material was scratched and scuffed.
実施例２〜５及び比較例２〜４
プラズマCVDにおけるH2ガスとC2H2ガスの比率又はC2H2ガスの導入量を変えて非晶質炭素皮膜中の水素含有量を変更し、フィルムラップ処理におけるフィルムの粗さ、処理時間を変えて表面粗さを変更した以外は、実施例１と同様にして（但し、実施例２と比較例２、実施例３と比較例３、実施例４と実施例５は非晶質炭素皮膜の形成を一緒に行い、フィルムラップ処理のフィルム粗さおよび処理時間を変えただけであるので、水素含有量は同じである。）、ピストンリング及び組成分析用試料にCr等の中間層と非晶質炭素皮膜を形成した。
Examples 2 to 5 and Comparative Examples 2 to 4
By changing the ratio of H 2 gas to C 2 H 2 gas in plasma CVD or the amount of C 2 H 2 gas introduced to change the hydrogen content in the amorphous carbon film, the film roughness and processing in the film lapping process Except that the surface roughness was changed by changing the time, it was the same as Example 1 (however, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, Example 4 and Example 5 were amorphous) Since the carbon film is formed together and the film roughness and processing time of the film wrap process are only changed, the hydrogen content is the same.), The intermediate layer such as Cr in the piston ring and the sample for composition analysis And an amorphous carbon film was formed.
実施例２〜５及び比較例２〜４の測定結果について、実施例１及び比較例１の結果も併せて、表１に示す。 About the measurement result of Examples 2-5 and Comparative Examples 2-4, the result of Example 1 and Comparative Example 1 is also shown in Table 1.
表１から明らかなように、非晶質炭素皮膜のマルテンス硬さHMT115が5.0 GPa以上で、且つHMT115と三次元表面粗さの最大山高さSpとの積が5.0 kPa・m以下であれば、往復摺動試験において、傷の発生もスカッフの発生も確認されなかった。なお、マルテンス硬さHMT115が5.0 GPa未満の比較例４では非晶質炭素皮膜が摩滅していた。 As is apparent from Table 1, if the Martens hardness HMT115 of the amorphous carbon film is 5.0 GPa or more and the product of HMT115 and the maximum peak height Sp of the three-dimensional surface roughness is 5.0 kPa · m or less, In the reciprocating sliding test, neither generation of scratches nor scuffing was confirmed. In Comparative Example 4 where the Martens hardness HMT115 was less than 5.0 GPa, the amorphous carbon film was worn away.
1 最大山 1 maximum mountain
Claims (6)
6. The piston ring according to claim 1, wherein an aluminum alloy cylinder or cylinder liner is used as a sliding counterpart.
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