WO1999031289A1 - Element a glissement pourvu d'un film de nitrure chromique - Google Patents
Element a glissement pourvu d'un film de nitrure chromique Download PDFInfo
- Publication number
- WO1999031289A1 WO1999031289A1 PCT/JP1998/005691 JP9805691W WO9931289A1 WO 1999031289 A1 WO1999031289 A1 WO 1999031289A1 JP 9805691 W JP9805691 W JP 9805691W WO 9931289 A1 WO9931289 A1 WO 9931289A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chromium nitride
- sliding member
- nitride film
- sliding
- film
- Prior art date
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- 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
-
- 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
- C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
- C23C12/02—Diffusion in one step
-
- 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
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
Definitions
- the present invention relates to a sliding member having a chromium nitride film formed thereon, and more specifically, a sliding member having significantly improved storage resistance due to a novel combination of the crystal structure and crystal orientation of chromium nitride. It is about. Back technology
- chromium nitride as a film for a sliding member is known, for example, from Japanese Patent Application Laid-Open No. 6-63692.
- This publication discloses that a chromium nitride layer is formed on the surfaces of a vane, a roller, and a shaft of a rotary compressor by ion plating or metallizing.
- Japanese Patent Application Laid-Open No. HEI 2-129360 discloses a steel material in which a CrN film having a (220) plane showing the maximum diffraction intensity is formed by an ion plating method.
- Japanese Patent Application Laid-Open Nos. 2-175758-8 and 2-175858-58 disclose that the (2200) plane shows the maximum diffraction intensity in the CrN single phase.
- a steel material in which a film comprising a precipitation phase of is formed by an ion plating method.
- ion plating was adjusted to control the precipitation of Cr and Cr 2 N, and the wear resistance was improved by using a single phase of Cr N.
- Japanese Patent Publication No. 7-189955 proposes that a chromium carbonitride film be formed on sliding parts of a rotary compressor by ion plating.
- the sliding characteristics of the C r N structure is chromium nitride film formed by the conventional ion plating is good, sliding properties in C r 2 N was poor.
- a research paper on the wear characteristics of chromium nitride formed by PVD (Physical vapor deposition) (Proc, Int.Compressor En. Conf., Purdue (1996) Similarly, TARY COMPRESSOR FOR HFC-134a) states that Cr 2 N has poorer sliding characteristics than Cr N.
- chromium nitride is identified as CrN by X-ray diffraction, and iron nitride is also formed in addition to chromium nitride.
- the present invention provides a sliding member having a chromium nitride film formed on a sliding surface of a base material, wherein the chromium nitride has a Cr 2 N structure, and the sliding surface has a Cr 2 N 2)
- FIG. 1 is an X-ray diffraction chart of the Cr 2 N powder.
- FIG. 2 is an X-ray diffraction chart of the (002) oriented Cr 2 N film according to Example 1.
- FIG. 3 is a diagram showing a unit cell of hexagonal C r z N.
- FIG. 4 is a metallographic micrograph (3000 ⁇ magnification) showing the layer structure of the (002) -oriented Cr 2 N film according to Example 1.
- FIG. 5 is a diagram illustrating a wear resistance test method.
- FIG. 6 is a graph showing the results of the wear resistance test.
- FIG. 7 is an X-ray diffraction chart of Cr 2 N by the PVD method without (002) orientation.
- FIG. 8 is a diagram for explaining the wear resistance method.
- FIG. 9 is a graph showing the results of the wear resistance test.
- FIG. 10 is a photograph similar to FIG. 4 of SKD61 having a carbon content of 0.4% in Example 3.
- FIG. 11 is a diagram showing the type of base material, the amount of carbon, the processing time and the adhesion in Example 3, and the thickness of the film in a bar graph. Detailed description of the invention
- Cr 2 N has a hexagonal structure.
- Fig. 1 shows an X-ray diffraction chart of Cr, N powder (ASTM powder data card 35-0803).
- FIG. 2 shows an X-ray diffraction chart (measurement conditions—Cu tube, tube voltage 30 kV, tube current 150 mA) of the Cr 2 N film according to one embodiment of the present invention.
- the beaks such as (111), (110), (112), (300) and (113) seen in Fig. 1 disappear in Fig. 2 and
- the (002) beak at about 40 ° is strong, and the (004) beak is slightly observed. Therefore, the film in Fig. 2 is strongly oriented to (002).
- the (002) plane orientation means that the beak strength of (002) parallel to the sliding surface is higher than that of another index, and more preferably, the following formula X. .
- the value of 2 is preferably 40 to 100%, more preferably 60 to 100%.
- I hkl is the X-ray diffraction intensity.
- the Cr z N film in the present invention is a film whose surface can identify a Cr 2 N structure by X-ray diffraction under the conditions described with reference to FIG. If this structure can be identified, a small amount of elements other than Cr, N, and C, such as Fe and 0, may be dissolved in Cr 2 N. It is preferable that metal chromium other than Cr z N does not exist.
- the thickness of the Cr 2 N film is preferably 1 to 30, more preferably 3 to 15 zm.
- the base material in the present invention iron, carbon steel, alloy steel, iron, and a sintered material thereof can be used. By nitriding the surface of these materials in advance, nitrogen of C ⁇ ⁇ 2N can be supplied from the base material side.
- the present inventors have succeeded in producing (002) -oriented Cr 2 N by setting the reaction temperature at 800 to 100 O'C in the flowing eyebrow furnace method disclosed in the above-mentioned Patent No. 2584217.
- the formation of Cr 2 N having the (002) orientation may be performed by a powder packing method or a PVD method instead of the fluidized eyebrow furnace method.
- the chromium nitride film may be substantially composed of Cr, ⁇ , and C. That is, when the amount of carbon Hosozai often are carbon in Amizai during nitriding chrome film formation is incorporated into the film, or carbon film without precipitation maintains the Cr 2 N structure, or below As described above, chromium carbon may precipitate between Cr 2 N and the net base material. The carbon in the Cr 2 N coating improves the sliding properties by increasing the hardness of the coating.
- the composition of the chromium nitride film is preferably composed of 5.5 to 17.5% by weight of N, 0.5 to 6.5% by weight of C, and the balance being Cr.
- the adhesion of the chromium nitride film can be enhanced by interposing chromium carbide between the chromium nitride film and the substrate in a layered or granular manner.
- the formation of chromium carbonate can be controlled by the processing conditions and the carbon content of the substrate.
- the sliding member of the present invention has a feature that the effect of the lubricating oil cannot be sufficiently expected, and the abrasion hardly occurs even under the mixed / boundary lubrication condition where the abrasion due to the false adhesion between the sliding materials is likely to occur. Therefore, the sliding member of the present invention can be used for transportation parts, air-conditioning parts, mechanical parts, etc., which require abrasion resistance under mixing and boundary conditions.
- the reason why such excellent sliding properties can be obtained is that Cr atoms and N atoms are alternately stacked in the (002) direction of the hexagonal Cr 2 N structure (see Fig. 3). Therefore, if hexagonal Cr 2 N is oriented on the (002) plane on the sliding surface, the sliding surface and the (002) plane will coincide.
- a fluidized bed furnace reaction was carried out using a nitrided base material of hot working die (SKD61) bin (diameter 6mm, surface roughness 0.8 ⁇ mRz) under the following conditions.
- the nitriding was performed by gas soft nitriding at 580 or 4 hours.
- Treatment agent Cr powder (particle size # 100 ⁇ : L50): alumina powder (particle size # 80)
- FIG. 2 shows an X-ray diffraction chart of Cr 2 N.
- This analysis chart is The X-rays were obtained by projecting X-rays at an incident angle of 20.15 degrees from the surface of the Cr 2 N layer obtained using the method. From this, it was identified that the surface was parallel to the (002) plane as shown in FIG.
- the hardness of the Cr 2 N film was Hv 1450-1650, and the roughness was 2. O ⁇ inRz.
- One barrel of SKD6 with Cr 2 N film formed is barrel-polished 1. After polishing to OAtmRz, the counterpart ring 2 (FC2 50 ⁇ iron: roughness 1. 0 zmRz) and 98 ON, and the abrasion test was performed by rotating the counterpart ring 2 half-immersed in the mixture 3 of the refrigerant and the refrigerating machine oil at 500 rpm. Under these evaluation conditions, it was estimated from the friction coefficient that mixed lubrication conditions were satisfied.
- Fig. 6 shows the test results.
- the sliding surface according to the present invention when the sliding surface according to the present invention was formed with the (002) orientation Cr 2 ⁇ , the amount of wear was small. This shows that the wear amount is less than half that of Cr: N (Fig. 7) by the PVD method, which shows almost no orientation.
- the sliding surface according to the present invention is formed of the (002) oriented Cr 2 N, the amount of wear is smaller than that of any of the other comparative examples, and in particular, PVD—CrN, which is conventionally said to have the best wear resistance, is used. It can be seen that the abrasion resistance is better than that.
- Example 2
- the hot die die and high speed tool heat treatment material bin with Cr 2 N, vanadium carbide and chromium carbide film formed in Example 1 were tested using the disk Z bin type test method shown in Fig. 8. The amount of wear was measured.
- reference numeral 6 denotes the above-mentioned bin
- reference numeral 7 denotes a mating disk (FC 250 ⁇ iron: roughness 1.0 zmRz).
- the test conditions were a load of 88 ON, a disk rotation speed of 1. OmZs, and a low-viscosity oil jet S.
- Figure 9 shows the results of trial K. This result shows the same tendency as in FIG. Example 3
- the flowing eyebrow furnace reaction was performed by changing the processing conditions in Example 1 as follows and increasing or decreasing the carbon content of the substrate. Except for the nitrogen content SUH35, SKD6 of Example 1 was used.
- Treatment agent Cr powder (particle size # 100 ⁇ : I50): alumina powder (particle size # 80)
- Figure 11 shows the results of the judgment based on the size of the crack generated around the indentation.
- the white portions indicate the thickness of the carbide bonded by C and Cr of the base material
- the black solid portions indicate the thickness of the chromium nitride film.
- chromium carbide The state of formation of chromium carbide varies greatly depending on the contents of carbon and nitrogen in the iron base material. If a certain amount of nitrogen is present and the amount of carbon is different, if the amount of carbon formed is small, chromium carbides will be present as granular or discontinuous eyebrows near the interface between the film and the base material, and if the amount of carbon is low, the amount of carbon will decrease. In many cases, chromium carbide exists as a continuous layer between the chromium nitride layer and the substrate.
- Fig. 10 shows the structure of chromium oxide film after nitriding SKD61 with a carbon content of 0.4% for 4 hours.
- This chromium nitride also had a Cr 2 N structure, and its (002) plane was parallel to the surface.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Physical Vapour Deposition (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52818999A JP4355033B2 (ja) | 1997-12-16 | 1998-12-16 | 窒化クロム皮膜を形成した摺動部材 |
DE69840380T DE69840380D1 (de) | 1997-12-16 | 1998-12-16 | Gleitteil mit darauf geformten chromnitridfilm |
EP98961369A EP0972851B1 (en) | 1997-12-16 | 1998-12-16 | Sliding member having chromium nitride film formed thereon |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9/363515 | 1997-12-16 | ||
JP36351597 | 1997-12-16 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1999031289A1 true WO1999031289A1 (fr) | 1999-06-24 |
WO1999031289A8 WO1999031289A8 (fr) | 1999-08-19 |
Family
ID=18479511
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/005691 WO1999031289A1 (fr) | 1997-12-16 | 1998-12-16 | Element a glissement pourvu d'un film de nitrure chromique |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0972851B1 (ja) |
JP (1) | JP4355033B2 (ja) |
KR (1) | KR100300110B1 (ja) |
DE (1) | DE69840380D1 (ja) |
WO (1) | WO1999031289A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6466813B1 (en) | 2000-07-22 | 2002-10-15 | Koninklijke Philips Electronics N.V. | Method and apparatus for MR-based volumetric frameless 3-D interactive localization, virtual simulation, and dosimetric radiation therapy planning |
JP2006077328A (ja) * | 2004-09-09 | 2006-03-23 | Ina-Schaeffler Kg | 耐摩耗性被覆及びその製造方法 |
WO2014142190A1 (ja) * | 2013-03-12 | 2014-09-18 | 日立ツール株式会社 | 硬質皮膜、硬質皮膜被覆部材、及びそれらの製造方法 |
CN108386444A (zh) * | 2018-03-06 | 2018-08-10 | 南昌工程学院 | 一种低速式自润滑高温滚动轴承及其制造方法 |
WO2023090275A1 (ja) * | 2021-11-16 | 2023-05-25 | 出光興産株式会社 | 固体潤滑材、摺動部材及び固体潤滑材の形成方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6802457B1 (en) | 1998-09-21 | 2004-10-12 | Caterpillar Inc | Coatings for use in fuel system components |
GB0410729D0 (en) * | 2004-05-14 | 2004-06-16 | Teer Coatings Ltd | Coating with hard wear and non-stick characteristics |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06287743A (ja) * | 1993-04-02 | 1994-10-11 | Nippon Steel Corp | 薄膜形成方法 |
JPH08296030A (ja) * | 1995-04-28 | 1996-11-12 | Nippon Piston Ring Co Ltd | 内燃機関用ピストンリング |
JP2584217B2 (ja) * | 1986-11-18 | 1997-02-26 | 株式会社豊田中央研究所 | 表面処理方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2643071B1 (fr) * | 1989-02-16 | 1993-05-07 | Unirec | Procede de depot en phase vapeur a basse temperature d'un revetement ceramique du type nitrure ou carbonitrure metallique |
EP0702097B1 (en) * | 1994-07-30 | 1999-11-10 | Kabushiki Kaisha Riken | Sliding members |
-
1998
- 1998-12-16 JP JP52818999A patent/JP4355033B2/ja not_active Expired - Fee Related
- 1998-12-16 DE DE69840380T patent/DE69840380D1/de not_active Expired - Lifetime
- 1998-12-16 WO PCT/JP1998/005691 patent/WO1999031289A1/ja active IP Right Grant
- 1998-12-16 EP EP98961369A patent/EP0972851B1/en not_active Expired - Lifetime
-
1999
- 1999-08-13 KR KR1019997007333A patent/KR100300110B1/ko not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2584217B2 (ja) * | 1986-11-18 | 1997-02-26 | 株式会社豊田中央研究所 | 表面処理方法 |
JPH06287743A (ja) * | 1993-04-02 | 1994-10-11 | Nippon Steel Corp | 薄膜形成方法 |
JPH08296030A (ja) * | 1995-04-28 | 1996-11-12 | Nippon Piston Ring Co Ltd | 内燃機関用ピストンリング |
Non-Patent Citations (1)
Title |
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See also references of EP0972851A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6466813B1 (en) | 2000-07-22 | 2002-10-15 | Koninklijke Philips Electronics N.V. | Method and apparatus for MR-based volumetric frameless 3-D interactive localization, virtual simulation, and dosimetric radiation therapy planning |
JP2006077328A (ja) * | 2004-09-09 | 2006-03-23 | Ina-Schaeffler Kg | 耐摩耗性被覆及びその製造方法 |
KR101282483B1 (ko) * | 2004-09-09 | 2013-07-04 | 섀플러 테크놀로지스 아게 운트 코. 카게 | 내마모성 코팅 및 그 제조 방법 |
WO2014142190A1 (ja) * | 2013-03-12 | 2014-09-18 | 日立ツール株式会社 | 硬質皮膜、硬質皮膜被覆部材、及びそれらの製造方法 |
JPWO2014142190A1 (ja) * | 2013-03-12 | 2017-02-16 | 三菱日立ツール株式会社 | 硬質皮膜、硬質皮膜被覆部材、及びそれらの製造方法 |
CN108386444A (zh) * | 2018-03-06 | 2018-08-10 | 南昌工程学院 | 一种低速式自润滑高温滚动轴承及其制造方法 |
WO2023090275A1 (ja) * | 2021-11-16 | 2023-05-25 | 出光興産株式会社 | 固体潤滑材、摺動部材及び固体潤滑材の形成方法 |
Also Published As
Publication number | Publication date |
---|---|
DE69840380D1 (de) | 2009-02-05 |
EP0972851A4 (en) | 2006-06-14 |
EP0972851B1 (en) | 2008-12-24 |
EP0972851A2 (en) | 2000-01-19 |
KR20000071064A (ko) | 2000-11-25 |
JP4355033B2 (ja) | 2009-10-28 |
KR100300110B1 (ko) | 2001-09-22 |
WO1999031289A8 (fr) | 1999-08-19 |
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