US20120248711A1 - Piston ring - Google Patents

Piston ring Download PDF

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Publication number
US20120248711A1
US20120248711A1 US13/429,934 US201213429934A US2012248711A1 US 20120248711 A1 US20120248711 A1 US 20120248711A1 US 201213429934 A US201213429934 A US 201213429934A US 2012248711 A1 US2012248711 A1 US 2012248711A1
Authority
US
United States
Prior art keywords
coating
layer
piston ring
layers
thickness
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.)
Abandoned
Application number
US13/429,934
Other languages
English (en)
Inventor
Takatsugu Iwashita
Tomoyuki Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TPR Co Ltd
Original Assignee
TPR Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TPR Co Ltd filed Critical TPR Co Ltd
Assigned to TPR CO., LTD. reassignment TPR CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IWASHITA, TAKATSUGU, SATO, TOMOYUKI
Publication of US20120248711A1 publication Critical patent/US20120248711A1/en
Priority to US14/610,006 priority Critical patent/US9175771B2/en
Abandoned legal-status Critical Current

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02FCYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F5/00Piston rings, e.g. associated with piston crown
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16JPISTONS; CYLINDERS; SEALINGS
    • F16J9/00Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/26Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605Carbon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/16Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/44Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness

Definitions

  • the present invention relates to a piston ring for an internal combustion engine.
  • a carbon-based coating is known as a coating which has a low coefficient of friction, but the coating stress is high and self fracture occurs, so increasing the thickness is difficult.
  • Japanese Patent Publication (A) No. 2006-008853 proposes a carbon-based coating with a low coefficient of friction which is made a multilayer structure with a surface-most layer comprised of a soft layer and with soft layers and hard layers alternately laminated and which enables a smooth surface to be easily obtained.
  • Japanese Patent Publication (A) No. 2006-008853 does not define the hardness difference between the hard layer and the soft layer.
  • the soft layer is meant as a fitting layer
  • the hard layer is meant as a wear resistance layer, so the hardnesses are, in Example 1, soft layer: 18 GPa and hard layer: 42 GPa and, in Example 2, soft layer: 20 GPa and hard layer: 41 GPa.
  • the hardness difference between the soft layer and hard layer was large.
  • An object of the present invention is to provide a piston ring which is provided with a carbon-based coating which has a low friction property and excellent wear resistance.
  • the present invention provides a piston ring which has a carbon-based coating formed over its sliding surface, in which piston ring, the coating is a multilayer coating comprised of two types of layers having different hardnesses laminated in at least two layers each, a hardness difference between the two types of layers is 500 to 1700 HV, a high hardness layer has the same or greater thickness than a low hardness layer, and the coating as a whole has a thickness of 5.0 ⁇ m or more.
  • the high hardness layer has a thickness of 5 to 90 nm.
  • the surface on which the coating is formed has a base material roughness of 1.0 ⁇ mRz or less.
  • a surface-most layer of the coating is a high hardness layer.
  • a low hardness layer of the coating contains carbon alone or carbon and also Cr or Ti.
  • the carbon-based coating a multilayer coating of two types of layers which have a hardness difference of 500 to 1700 HV, increasing the thickness becomes possible and both a low friction property and excellent wear resistance are given. If the hardness difference is less than 500 HV, coating cracks cause the sliding surface to become rough, the coefficient of friction to become larger, and the wear of the opposing material to become greater as well. If the hardness difference becomes larger than 1700 HV, sliding causes the low hardness layer to become worn, stress concentrates at the surface relief parts of the high hardness layer (see FIG. 1B ), the coating chips, the coefficient of friction becomes larger, and wear at the opposing material also becomes greater. If the overall thickness of the coating is less than 5.0 ⁇ m, the wear resistance becomes insufficient.
  • FIGS. 1A to 1C show an embodiment of the present invention, wherein
  • FIG. 1A is a longitudinal cross-sectional view which shows one part of a piston ring
  • FIG. 1B is an enlarged cross-sectional view of a coating part
  • FIG. 1C is a view which shows one part of a coating surface after sliding
  • FIG. 2 is a schematic view of a reciprocating wear tester.
  • a piston ring 1 has a carbon-based coating 2 formed on its outer circumference.
  • the carbon-based coating 2 is a DLC (diamond-like carbon) coating comprised of a multilayer coating of two types of layers A and B with different hardnesses laminated in at least two layers each.
  • the two types of layers A and B are laminated in six layers each.
  • the surface-most layer is a layer A with a high hardness.
  • the hardness difference between the two types of layers A and B is 500 to 1700 HV.
  • the layer A with the high hardness (hereinafter referred to as the “high hardness layer A”) has a thickness of 5 to 90 nm, while the layer B with a low hardness (hereinafter referred to as the “low hardness layer B”) has the same or greater thickness.
  • the overall thickness of the carbon-based coating 2 is 5.0 ⁇ m or more.
  • the base material roughness of the outer circumference is 1.0 ⁇ mRz or less.
  • the low hardness layer B may contain Cr or Ti. If Cr or Ti is contained, the adhesion with the high hardness layer A is improved more.
  • the thickness of the high hardness layer A is smaller than 5 nm, the required widths of the high hardness layer A and the low hardness layer B which are exposed at the outer circumference after sliding (see FIG. 1C ) cannot be sufficiently secured, the oil retention property falls, and the low friction effect becomes insufficient. If the thickness becomes larger than 90 nm, the widths of the high hardness layer A and the low hardness layer B which are exposed at the outer circumference after sliding become too great, coating cracks occur, the coefficient of friction becomes greater, and the wear of the opposing material also becomes greater. If the base material roughness of the outer circumference is larger than 1.0 ⁇ mRz, sliding causes the low hardness layer B to wear, stress to concentrate at surface relief parts of the high hardness layer A (see FIG. 1B ), the coating to chip, the coefficient of friction to become greater, and the wear of the opposing material to also become greater. If the surface-most layer is a high hardness layer A, the surface of the opposing material can be quickly smoothened.
  • the above carbon-based coating 2 is formed using the PVD method by alternate sputtering (forming low hardness layer B) and ion plating (forming high hardness layer A).
  • the thicknesses of the layers are adjusted by changing the formation times, while the hardnesses are adjusted by changing the bias voltage.
  • FIG. 2 shows an outline of a reciprocating wear tester which is used for the test.
  • a pin-shaped top test piece 10 is held by a holding block 11 .
  • a hydraulic cylinder 12 is used to apply a downward load whereby a bottom test piece 13 is pressed against.
  • a flat disk shaped bottom test piece 13 is held by a movable block 14 and is made to move back and forth by a crank mechanism 15 .
  • Reference numeral 16 indicates a load cell.
  • Top test piece pin-shaped test piece for piston ring given DLC coating

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
US13/429,934 2011-03-28 2012-03-26 Piston ring Abandoned US20120248711A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/610,006 US9175771B2 (en) 2011-03-28 2015-01-30 Piston ring

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-069676 2011-03-28
JP2011069676A JP2012202522A (ja) 2011-03-28 2011-03-28 ピストンリング

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/610,006 Continuation US9175771B2 (en) 2011-03-28 2015-01-30 Piston ring

Publications (1)

Publication Number Publication Date
US20120248711A1 true US20120248711A1 (en) 2012-10-04

Family

ID=45811322

Family Applications (2)

Application Number Title Priority Date Filing Date
US13/429,934 Abandoned US20120248711A1 (en) 2011-03-28 2012-03-26 Piston ring
US14/610,006 Active US9175771B2 (en) 2011-03-28 2015-01-30 Piston ring

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/610,006 Active US9175771B2 (en) 2011-03-28 2015-01-30 Piston ring

Country Status (7)

Country Link
US (2) US20120248711A1 (zh)
EP (1) EP2505685B1 (zh)
JP (1) JP2012202522A (zh)
KR (1) KR20120110041A (zh)
CN (1) CN102705102B (zh)
BR (1) BR102012006917B1 (zh)
IN (1) IN2012DE00922A (zh)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130043659A1 (en) * 2010-01-29 2013-02-21 Nippon Piston Ring Co., Ltd. Piston ring
US20150362071A1 (en) * 2013-01-21 2015-12-17 Federal-Mogul Burscheid Gmbh Sliding element, in particular a piston ring, having a coating
US20160003356A1 (en) * 2013-02-28 2016-01-07 Nippon Piston Ring Co., Ltd. Hard carbon coating film
US9551419B2 (en) * 2015-04-22 2017-01-24 Federal-Mogul Corporation Coated sliding element
US20180231125A1 (en) * 2015-08-10 2018-08-16 Nippon Itf, Inc. Piston ring and engine
US10059899B2 (en) * 2012-10-23 2018-08-28 Mahle International Gmbh Component having a coating and method for the production thereof
US20180245200A1 (en) * 2015-09-09 2018-08-30 Kabushiki Kaisha Riken Sliding member and piston ring
US10072756B2 (en) 2014-01-15 2018-09-11 Federal-Mogul Burscheid Gmbh Sliding element, in particular piston ring
US10087513B2 (en) 2014-01-31 2018-10-02 Nippon Piston Ring Co., Ltd Piston ring and manufacturing method therefor
US10329509B2 (en) 2015-01-29 2019-06-25 Jtekt Corporation Amorphous hydrocarbon based film, and sliding member and sliding system with said film
US10487730B2 (en) * 2015-12-21 2019-11-26 Mahle Metal Leve S/A Sliding element
US10578214B2 (en) 2015-07-31 2020-03-03 Nippon Piston Ring Co., Ltd Piston ring and manufacturing method therefor
US10619739B2 (en) 2015-07-31 2020-04-14 Nippon Piston Ring Co., Ltd Piston ring
CN112534084A (zh) * 2018-10-16 2021-03-19 舍弗勒技术股份两合公司 特别是用于配气机构系统的部件以及生产这种部件的方法
US11143302B2 (en) * 2016-06-30 2021-10-12 Mahle Metal Leve S/A Sliding element for internal combustion engines
US20220033975A1 (en) * 2018-11-08 2022-02-03 Nanofilm Technologies International Limited Ta-c based coatings with improved hardness
US11242929B2 (en) * 2018-06-29 2022-02-08 Tpr Co., Ltd. Piston ring
US11261519B2 (en) * 2015-12-18 2022-03-01 Nippon Itf, Inc. Coating film, manufacturing method therefor, and PVD apparatus

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10458548B2 (en) 2015-08-10 2019-10-29 Nippon Itf, Inc. Piston ring and method for manufacturing same
JP6413060B1 (ja) * 2017-05-11 2018-10-31 日本アイ・ティ・エフ株式会社 硬質炭素膜とその製造方法および摺動部材
CN109355619A (zh) * 2018-09-25 2019-02-19 安庆帝伯格茨活塞环有限公司 一种具有软硬相间类金刚石涂层的活塞环及制备方法

Citations (1)

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US20100295251A1 (en) * 2006-11-14 2010-11-25 Takuma Sekiya Chromium nitride ion-plating coating and its production method, as well as piston ring used for internal combustion engine

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JP2000170594A (ja) 1998-12-08 2000-06-20 Teikoku Piston Ring Co Ltd シリンダライナとピストンリングとの組合せ
JP3995900B2 (ja) 2001-04-25 2007-10-24 株式会社神戸製鋼所 ダイヤモンドライクカーボン多層膜
JP2006008853A (ja) 2004-06-25 2006-01-12 Nissan Motor Co Ltd 硬質炭素皮膜摺動部材及びその製造方法
PT1915472T (pt) 2005-08-18 2018-12-06 Oerlikon Surface Solutions Ag Pfaeffikon Substrato revestido com uma estrutura em camadas compreendendo uma camada de carbono tetraédrico e uma camada exterior mais macia
JP2007070667A (ja) 2005-09-05 2007-03-22 Kobe Steel Ltd ダイヤモンドライクカーボン硬質多層膜成形体およびその製造方法
JP4839120B2 (ja) 2006-04-03 2011-12-21 株式会社リケン 積層皮膜を有するピストンリング
JP2008286354A (ja) * 2007-05-21 2008-11-27 Nippon Piston Ring Co Ltd 摺動部材
JP5828575B2 (ja) * 2008-03-04 2015-12-09 日産自動車株式会社 ピストンリング
CN102046844A (zh) * 2008-06-09 2011-05-04 纳峰科技私人有限公司 用于使涂层快速沉积于基体上的方法
DE102009028504C5 (de) * 2009-08-13 2014-10-30 Federal-Mogul Burscheid Gmbh Kolbenring mit einer Beschichtung
DE102009046281B3 (de) 2009-11-02 2010-11-25 Federal-Mogul Burscheid Gmbh Gleitelement, insbesondere Kolbenring, und Kombination eines Gleitelements mit einem Laufpartner

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100295251A1 (en) * 2006-11-14 2010-11-25 Takuma Sekiya Chromium nitride ion-plating coating and its production method, as well as piston ring used for internal combustion engine

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9464717B2 (en) * 2010-01-29 2016-10-11 Nippon Piston Ring Co., Ltd. Piston ring
US20130043659A1 (en) * 2010-01-29 2013-02-21 Nippon Piston Ring Co., Ltd. Piston ring
US10059899B2 (en) * 2012-10-23 2018-08-28 Mahle International Gmbh Component having a coating and method for the production thereof
US20150362071A1 (en) * 2013-01-21 2015-12-17 Federal-Mogul Burscheid Gmbh Sliding element, in particular a piston ring, having a coating
US9488275B2 (en) * 2013-01-21 2016-11-08 Federal-Mogul Burscheid Gmbh Sliding element, in particular a piston ring, having a coating
US20160003356A1 (en) * 2013-02-28 2016-01-07 Nippon Piston Ring Co., Ltd. Hard carbon coating film
US9863534B2 (en) * 2013-02-28 2018-01-09 Nippon Piston Ring Co., Ltd. Hard carbon coating film
US10072756B2 (en) 2014-01-15 2018-09-11 Federal-Mogul Burscheid Gmbh Sliding element, in particular piston ring
US10087513B2 (en) 2014-01-31 2018-10-02 Nippon Piston Ring Co., Ltd Piston ring and manufacturing method therefor
US10450527B2 (en) * 2015-01-29 2019-10-22 Jtekt Corporation Low-friction coating production method and sliding method
US10329509B2 (en) 2015-01-29 2019-06-25 Jtekt Corporation Amorphous hydrocarbon based film, and sliding member and sliding system with said film
US9816613B2 (en) * 2015-04-22 2017-11-14 Federal-Mogul Llc Coated sliding element
US20170130841A1 (en) * 2015-04-22 2017-05-11 Federal-Mogul Corporation Coated sliding element
US9551419B2 (en) * 2015-04-22 2017-01-24 Federal-Mogul Corporation Coated sliding element
US10578214B2 (en) 2015-07-31 2020-03-03 Nippon Piston Ring Co., Ltd Piston ring and manufacturing method therefor
US10619739B2 (en) 2015-07-31 2020-04-14 Nippon Piston Ring Co., Ltd Piston ring
US20180231125A1 (en) * 2015-08-10 2018-08-16 Nippon Itf, Inc. Piston ring and engine
US10634249B2 (en) * 2015-08-10 2020-04-28 Nippon Itf, Inc. Piston ring and engine
US20180245200A1 (en) * 2015-09-09 2018-08-30 Kabushiki Kaisha Riken Sliding member and piston ring
US10655208B2 (en) * 2015-09-09 2020-05-19 Kabushiki Kaisha Riken Sliding member and piston ring
US11261519B2 (en) * 2015-12-18 2022-03-01 Nippon Itf, Inc. Coating film, manufacturing method therefor, and PVD apparatus
US10487730B2 (en) * 2015-12-21 2019-11-26 Mahle Metal Leve S/A Sliding element
US11143302B2 (en) * 2016-06-30 2021-10-12 Mahle Metal Leve S/A Sliding element for internal combustion engines
US11242929B2 (en) * 2018-06-29 2022-02-08 Tpr Co., Ltd. Piston ring
CN112534084A (zh) * 2018-10-16 2021-03-19 舍弗勒技术股份两合公司 特别是用于配气机构系统的部件以及生产这种部件的方法
US11739426B2 (en) * 2018-10-16 2023-08-29 Schaeffler Technologies AG & Co. KG Component, in particular for a valve train system, and method for producing a component of this type
US20220033975A1 (en) * 2018-11-08 2022-02-03 Nanofilm Technologies International Limited Ta-c based coatings with improved hardness
US11643733B2 (en) * 2018-11-08 2023-05-09 Nanofilm Technologies International Limited ta-C based coatings with improved hardness

Also Published As

Publication number Publication date
BR102012006917A2 (pt) 2013-06-04
BR102012006917B1 (pt) 2021-04-20
CN102705102A (zh) 2012-10-03
EP2505685B1 (en) 2015-05-06
KR20120110041A (ko) 2012-10-09
IN2012DE00922A (zh) 2015-09-04
EP2505685A1 (en) 2012-10-03
US20150137457A1 (en) 2015-05-21
JP2012202522A (ja) 2012-10-22
CN102705102B (zh) 2016-03-23
US9175771B2 (en) 2015-11-03

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Owner name: TPR CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:IWASHITA, TAKATSUGU;SATO, TOMOYUKI;REEL/FRAME:027933/0983

Effective date: 20120312

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION