EP0721997A1 - Method of treating the surface of TI or TI alloy valve element - Google Patents

Method of treating the surface of TI or TI alloy valve element Download PDF

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Publication number
EP0721997A1
EP0721997A1 EP95300133A EP95300133A EP0721997A1 EP 0721997 A1 EP0721997 A1 EP 0721997A1 EP 95300133 A EP95300133 A EP 95300133A EP 95300133 A EP95300133 A EP 95300133A EP 0721997 A1 EP0721997 A1 EP 0721997A1
Authority
EP
European Patent Office
Prior art keywords
valve element
valve
covering layer
layer
nitriding
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.)
Withdrawn
Application number
EP95300133A
Other languages
German (de)
French (fr)
Inventor
Akiyoshi Mori
Takeji C/O Fuji Oozx Inc. Kenmoku
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.)
Fuji Oozx Inc
Original Assignee
Fuji Oozx Inc
Fuji Valve 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
Priority to JP5268633A priority Critical patent/JPH07119420A/en
Application filed by Fuji Oozx Inc, Fuji Valve Co Ltd filed Critical Fuji Oozx Inc
Priority to EP95300133A priority patent/EP0721997A1/en
Priority to CN95100732.7A priority patent/CN1127801A/en
Publication of EP0721997A1 publication Critical patent/EP0721997A1/en
Withdrawn legal-status Critical Current

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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
    • C23C28/00—Coating 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated

Definitions

  • the present invention relates to a method of treating the surface of a valve element in an engine valve moulded from Ti or Ti alloy, and especially a method of treating the outer circumferential surface of a stem of the valve element to improve wear resistance thereof.
  • the largest obstacle is increase in inertia mass owing to weight of a valve operating mechanism.
  • the valve element is moulded from Ti or Ti alloy having low specific gravity and high heat resistance, thereby lightening the valve element.
  • Ti or Ti alloy has Rockwell hardness (HRC) of about 30 to 40, thereby decreasing wear resistance of a stem which is always guided to a valve guide and slidably reciprocates at high speed, so that it is liable to cause baking or galling.
  • HRC Rockwell hardness
  • Japanese Utility Model Laid-Open Pub. No.4-103211 describes an engine valve in which salt bath soft nitriding is applied to the outer circumferential surface of a stem to increase wear resistance thereof.
  • a nitrided layer hardened layer
  • a method of treating the surface of Ti or Ti alloy valve element in an engine valve comprising a head and a stem, the method comprising the steps of forming an Fe covering layer on the outer circumferential surface of the stem which slidably contacts a valve guide; and applying nitriding to said covering layer to form a nitrided layer.
  • nitriding is applied to the covering layer, so that nitrogen deeply diffuses compared with a conventional engine valve in which nitriding is applied directly onto Ti.
  • relatively thick nitrided layer is formed. Accordingly, wear resistance is remarkably increased at the valve stem which slidably contacts a valve guide, thereby providing a durable engine valve.
  • Fig. 1 illustrates an engine valve according to the present invention, in which a valve element 3 which comprises a head 1 and a stem 2 is integrally moulded from Ti or Ti alloy (Ti-Al-V). On the whole surface of the valve element 3 except the head, there is formed a covering layer 4 from thermal spraying material of a heat-resisting steel or alloy steel such as Fe, Ni or Co as base.
  • the covering layer 4 may be made of the thermal spraying material like powder, rod or wire with thermal spraying means such as plasma and gas flame to provide thickness of 50 to 200 ⁇ m.
  • the outer circumferential surface of the valve element 3 Prior to formation of the covering layer 4, the outer circumferential surface of the valve element 3 may be a rough surface 5 by blasting treatment as shown in Fig. 2, thereby increasing bond strength of the spraying material to the surface of the element to increase peel resistance of the covering layer 4.
  • a nitrided layer 6 On the surface of the covering layer 4, there is formed a nitrided layer 6 with thickness of 10 to 30 ⁇ m.
  • the nitrided layer 6 is easily formed by general salt bath soft nitriding (Tufftriding).
  • a treating bath which contains KCN, KOCN and Na 4 [Fe(CN) 6 ] as main ingredient is heated to about 600°C, and the valve element 3 is immersed in the bath for 1 to 2 hours.
  • a compound (nitrided) layer which contains very hard carbide and nitride.
  • the compound layer provides excellent wear-, galling- and baking-resistance, thereby increasing wear resistance not only of a portion of the stem which slidably contacts a valve guide 7, but also of a stem face 8 which contacts a locker arm and a tappet (not shown), a valve face 9 which contacts a valve seat (not shown) and a cotter groove 10.
  • the covering layer 4 made of steel is formed on the surface of the Ti valve element, soft nitriding is applied on the surface of the covering layer 4 to form the nitrided layer 6, so that diffusion of nitrogen becomes deeper than a conventional direct nitriding on the surface of Ti valve element, thereby forming a thick nitrided layer 6 for usual treating time.
  • padding may be applied instead of thermal spraying, and material for thermal spraying may comprise cheaper carbon- or stainless-steel instead of the foregoing heat-resisting steel.
  • Nitriding may be gas-, liquid-, ion- or gas-carburizing nitriding instead of the salt bath soft nitriding.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

A covering layer made of heat-resistant steel is formed on the outer circumferential surface of a stem of a Ti or Ti alloy valve element in an engine valve. Then, nitriding is applied to the covering layer to achieve deeper diffusion of nitrogen into the layer, thereby forming a relatively thick nitrided layer.

Description

    BACKGROUND OF THE INVENTION
  • The present invention relates to a method of treating the surface of a valve element in an engine valve moulded from Ti or Ti alloy, and especially a method of treating the outer circumferential surface of a stem of the valve element to improve wear resistance thereof.
  • To increase allowable rotation speed of an engine, the largest obstacle is increase in inertia mass owing to weight of a valve operating mechanism. When the total weight of parts of the valve operating mechanism becomes larger, the higher rotation speed becomes, the lower followability of a cam to a valve element becomes, so that whirling motion occurs in the valve element, thereby involving decrease in output power. Thus, instead of a conventional heat-resistant steel, the valve element is moulded from Ti or Ti alloy having low specific gravity and high heat resistance, thereby lightening the valve element. However, in an engine valve in which the valve element is moulded from Ti or Ti alloy, Ti or Ti alloy has Rockwell hardness (HRC) of about 30 to 40, thereby decreasing wear resistance of a stem which is always guided to a valve guide and slidably reciprocates at high speed, so that it is liable to cause baking or galling.
  • To solve the disadvantage, Japanese Utility Model Laid-Open Pub. No.4-103211 describes an engine valve in which salt bath soft nitriding is applied to the outer circumferential surface of a stem to increase wear resistance thereof. But, in the engine valve, when soft nitriding is applied directly to the surface of Ti valve element for normal treating time such as 1.5 to 2 hours, a nitrided layer (hardened layer) is relatively thin, which does not satisfy suitable wear resistance and fatigue strength. Therefore, it required very long time to form a preferable nitrided layer, thereby decreasing productivity remarkably.
    • SUMMARY OF THE INVENTION
  • To solve the disadvantage, it is an object of the present invention to provide a method of treating the surface of Ti or Ti alloy valve element in an engine valve to improve wear resistance and durability of the valve.
  • According to the present invention, there is provided a method of treating the surface of Ti or Ti alloy valve element in an engine valve, the valve element comprising a head and a stem, the method comprising the steps of forming an Fe covering layer on the outer circumferential surface of the stem which slidably contacts a valve guide; and applying nitriding to said covering layer to form a nitrided layer.
  • After Fe covering layer is formed on the outer circumferential surface of the stem, nitriding is applied to the covering layer, so that nitrogen deeply diffuses compared with a conventional engine valve in which nitriding is applied directly onto Ti. Thus, relatively thick nitrided layer is formed. Accordingly, wear resistance is remarkably increased at the valve stem which slidably contacts a valve guide, thereby providing a durable engine valve.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The feature and advantage of the present invention will be described with respect to the following embodiment based on drawings wherein:
    • Fig. 1 is a central longitudinal sectional front view of an embodiment of an engine valve according to the present invention; and
    • Fig. 2 is an enlarged view of portion "A" in Fig. 1.
    DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
  • Fig. 1 illustrates an engine valve according to the present invention, in which a valve element 3 which comprises a head 1 and a stem 2 is integrally moulded from Ti or Ti alloy (Ti-Al-V). On the whole surface of the valve element 3 except the head, there is formed a covering layer 4 from thermal spraying material of a heat-resisting steel or alloy steel such as Fe, Ni or Co as base. The covering layer 4 may be made of the thermal spraying material like powder, rod or wire with thermal spraying means such as plasma and gas flame to provide thickness of 50 to 200µm.
  • Prior to formation of the covering layer 4, the outer circumferential surface of the valve element 3 may be a rough surface 5 by blasting treatment as shown in Fig. 2, thereby increasing bond strength of the spraying material to the surface of the element to increase peel resistance of the covering layer 4.
  • On the surface of the covering layer 4, there is formed a nitrided layer 6 with thickness of 10 to 30µm. The nitrided layer 6 is easily formed by general salt bath soft nitriding (Tufftriding). For example, a treating bath which contains KCN, KOCN and Na4 [Fe(CN)6] as main ingredient is heated to about 600°C, and the valve element 3 is immersed in the bath for 1 to 2 hours. Owing to diffusion in the surface layer of the steel covering layer 4 with cementation and nitriding, there is formed a compound (nitrided) layer which contains very hard carbide and nitride. The compound layer provides excellent wear-, galling- and baking-resistance, thereby increasing wear resistance not only of a portion of the stem which slidably contacts a valve guide 7, but also of a stem face 8 which contacts a locker arm and a tappet (not shown), a valve face 9 which contacts a valve seat (not shown) and a cotter groove 10.
  • As mentioned above, in the foregoing embodiment, after the covering layer 4 made of steel is formed on the surface of the Ti valve element, soft nitriding is applied on the surface of the covering layer 4 to form the nitrided layer 6, so that diffusion of nitrogen becomes deeper than a conventional direct nitriding on the surface of Ti valve element, thereby forming a thick nitrided layer 6 for usual treating time.
  • To form the covering layer 4, padding may be applied instead of thermal spraying, and material for thermal spraying may comprise cheaper carbon- or stainless-steel instead of the foregoing heat-resisting steel. Nitriding may be gas-, liquid-, ion- or gas-carburizing nitriding instead of the salt bath soft nitriding.
  • The foregoing merely relates to an embodiment of the present invention. Any changes and modifications may be made by person skilled in the art without departing from the scope of claims wherein:

Claims (3)

  1. A method of treating a surface of Ti or Ti alloy valve element in an engine valve, the valve element comprising a head and a stem, the method comprising the steps of:
    forming an Fe covering layer on an outer circumferential surface of the stem which slidably contacts a valve guide; and
    applying nitriding to said covering layer to form a nitrided layer.
  2. A method as defined in claim 1 wherein the step of forming the covering layer comprises thermal spraying.
  3. A method as defined in claim 1 wherein the step of nitriding comprises salt bath soft nitriding.
EP95300133A 1993-10-27 1995-01-11 Method of treating the surface of TI or TI alloy valve element Withdrawn EP0721997A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP5268633A JPH07119420A (en) 1993-10-27 1993-10-27 Method for treating surface of titanium or titanium alloy made engine valve
EP95300133A EP0721997A1 (en) 1993-10-27 1995-01-11 Method of treating the surface of TI or TI alloy valve element
CN95100732.7A CN1127801A (en) 1993-10-27 1995-01-24 Method of treating the surface of Ti and Ti alloy valve element

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP5268633A JPH07119420A (en) 1993-10-27 1993-10-27 Method for treating surface of titanium or titanium alloy made engine valve
EP95300133A EP0721997A1 (en) 1993-10-27 1995-01-11 Method of treating the surface of TI or TI alloy valve element
CN95100732.7A CN1127801A (en) 1993-10-27 1995-01-24 Method of treating the surface of Ti and Ti alloy valve element

Publications (1)

Publication Number Publication Date
EP0721997A1 true EP0721997A1 (en) 1996-07-17

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ID=37102017

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95300133A Withdrawn EP0721997A1 (en) 1993-10-27 1995-01-11 Method of treating the surface of TI or TI alloy valve element

Country Status (3)

Country Link
EP (1) EP0721997A1 (en)
JP (1) JPH07119420A (en)
CN (1) CN1127801A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1097778A2 (en) * 1999-10-20 2001-05-09 Duroc Ab Method for manufacturing objects of metallic material and objects manufactured with this method
WO2003074752A1 (en) * 2002-02-28 2003-09-12 Swagelok Company Case hardening of titanium
WO2016057481A1 (en) * 2014-10-06 2016-04-14 Caterpillar Inc. Nitrided engine valve with hvof coating

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1898046B (en) * 2003-12-22 2010-12-08 本田技研工业株式会社 Method of forming member

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111434A (en) * 1960-08-01 1963-11-19 Kobe Steel Ltd Surface hardening of metal body consisting of or containing titanium or zirconium
FR1453876A (en) * 1965-05-13 1966-07-22 Ct Tech De L Ind Horlogere Process for the treatment of parts with metal coatings of great hardness and with high protection against corrosion and parts with metal coatings obtained by this process
FR2148543A1 (en) * 1971-08-09 1973-03-23 Nissan Motor
JPS6082654A (en) * 1983-10-12 1985-05-10 Toyota Motor Corp Sliding member
EP0248431A2 (en) * 1986-06-04 1987-12-09 Politechnika Krakowska im. Tadeusza Kosciuszki Method of producing outer coating layers on heat and corrosion resistant austenitic steels
EP0266149A2 (en) * 1986-10-27 1988-05-04 Hitachi, Ltd. High wear-resistant member, method of producing the same, and valve gear using the same for use in internal combustion engine
JPH02129467A (en) * 1988-11-08 1990-05-17 Toyota Motor Corp Piston ring and manufacture thereof
EP0456847A1 (en) * 1987-06-26 1991-11-21 Bernex Gmbh Method of producing a wear- and corrosion-resistant protective coating layer, composed of an austenitic steel alloy and so produced protective layer
JPH0560241A (en) * 1991-09-02 1993-03-09 Teikoku Piston Ring Co Ltd Piston ring and manufacture thereof
JPH06173079A (en) * 1992-12-08 1994-06-21 Kobe Steel Ltd Ti or ti alloy material excellent in wear resistance and its production

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3111434A (en) * 1960-08-01 1963-11-19 Kobe Steel Ltd Surface hardening of metal body consisting of or containing titanium or zirconium
FR1453876A (en) * 1965-05-13 1966-07-22 Ct Tech De L Ind Horlogere Process for the treatment of parts with metal coatings of great hardness and with high protection against corrosion and parts with metal coatings obtained by this process
FR2148543A1 (en) * 1971-08-09 1973-03-23 Nissan Motor
JPS6082654A (en) * 1983-10-12 1985-05-10 Toyota Motor Corp Sliding member
EP0248431A2 (en) * 1986-06-04 1987-12-09 Politechnika Krakowska im. Tadeusza Kosciuszki Method of producing outer coating layers on heat and corrosion resistant austenitic steels
EP0266149A2 (en) * 1986-10-27 1988-05-04 Hitachi, Ltd. High wear-resistant member, method of producing the same, and valve gear using the same for use in internal combustion engine
EP0456847A1 (en) * 1987-06-26 1991-11-21 Bernex Gmbh Method of producing a wear- and corrosion-resistant protective coating layer, composed of an austenitic steel alloy and so produced protective layer
JPH02129467A (en) * 1988-11-08 1990-05-17 Toyota Motor Corp Piston ring and manufacture thereof
JPH0560241A (en) * 1991-09-02 1993-03-09 Teikoku Piston Ring Co Ltd Piston ring and manufacture thereof
JPH06173079A (en) * 1992-12-08 1994-06-21 Kobe Steel Ltd Ti or ti alloy material excellent in wear resistance and its production

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 14, no. 364 (M - 1007) 7 August 1990 (1990-08-07) *
PATENT ABSTRACTS OF JAPAN vol. 17, no. 374 (M - 1445) 14 July 1993 (1993-07-14) *
PATENT ABSTRACTS OF JAPAN vol. 18, no. 517 (C - 1254) 29 September 1994 (1994-09-29) *
PATENT ABSTRACTS OF JAPAN vol. 9, no. 222 (C - 302) 9 September 1985 (1985-09-09) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1097778A2 (en) * 1999-10-20 2001-05-09 Duroc Ab Method for manufacturing objects of metallic material and objects manufactured with this method
EP1097778A3 (en) * 1999-10-20 2002-08-21 Duroc Ab Method for manufacturing objects of metallic material and objects manufactured with this method
WO2003074752A1 (en) * 2002-02-28 2003-09-12 Swagelok Company Case hardening of titanium
WO2016057481A1 (en) * 2014-10-06 2016-04-14 Caterpillar Inc. Nitrided engine valve with hvof coating

Also Published As

Publication number Publication date
CN1127801A (en) 1996-07-31
JPH07119420A (en) 1995-05-09

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