EP0244253A1 - Oberflächenbehandlung von Titangegenständen - Google Patents

Oberflächenbehandlung von Titangegenständen Download PDF

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Publication number
EP0244253A1
EP0244253A1 EP19870303900 EP87303900A EP0244253A1 EP 0244253 A1 EP0244253 A1 EP 0244253A1 EP 19870303900 EP19870303900 EP 19870303900 EP 87303900 A EP87303900 A EP 87303900A EP 0244253 A1 EP0244253 A1 EP 0244253A1
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EP
European Patent Office
Prior art keywords
titanium
valve
article
layer
titanium alloy
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.)
Granted
Application number
EP19870303900
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English (en)
French (fr)
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EP0244253B1 (de
Inventor
Kyo Takahashi
Yoshitoshi Hagiwara
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.)
Honda Motor Co Ltd
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Honda Motor Co Ltd
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Publication date
Application filed by Honda Motor Co Ltd filed Critical Honda Motor Co Ltd
Publication of EP0244253A1 publication Critical patent/EP0244253A1/de
Application granted granted Critical
Publication of EP0244253B1 publication Critical patent/EP0244253B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C23C8/06—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 using gases
    • C23C8/08—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 using gases only one element being applied
    • C23C8/10—Oxidising

Definitions

  • the present invention relates to the surface treatment of titanium articles, especially titanium metal or titanium alloy articles which may be adapted for use in engines for motorcycles or other vehicles.
  • Engine parts for motorcycles and other motor vehicles may usefully be manufactured from titanium or titanium alloys.
  • the advantages of using titanium metal are that titanium products exhibit the properties of lightness, great hardness, high heat resistance, etc.; therefore there has been a tendency for titanium- based parts to be used in high performance motor vehicles such as vehicles used for motor racing or motorcycle racing.
  • wear resistance and seizure resistance must be considered and furthermore removal of the oxide layer on the titanium metal is necessary in order to improve durability.
  • the process for producing such articles generally involves stamp forging the titanium metal, removing the hard titanium oxide outer layer on the metal surface and then subjecting the surface to molybdenum injection welding or to nitrogen treatment. Furthermore, heat treatment should be performed in an argon atmosphere or in vacuo. Valves, valve retainers and connecting rods are. examples of articles which may be manufactured in such a manner from titanium.
  • a titanium or titanium alloy article at least part of the surface of which comprises a surface treatment oxide covering produced by direct oxidation of the titanium or titanium alloy of the surface, the said surface treatment oxide covering comprising a hard titanium oxide outer. layer, a heat-modified titanium or titanium alloy inner layer one surface of which contacts the unchanged titanium metal or titanium alloy, and a chemically modified titanium or titanium alloy intermediate layer between the hard titanium oxide outer layer and the heat-modified titanium or titanium alloy inner layer.
  • the "hard titanium oxide layer” is defined as a titanium oxide layer which registers at least 500° on the Vicker Scale of Hardness.
  • a process for treating the surface of a titanium or titanium alloy article which comprises heat treating the titanium or titanium alloy article in an oxygen-containing atmosphere at a temperature below 800°C for a period of time, preferably from 1 minute to less than 10 hours, whereby a surface treatment oxide covering comprising a hard titanium oxide outer layer, a heat-modified titanium or titanium alloy inner layer one surface of which contacts the unchanged titanium metal or titanium alloy, and a chemically modified titanium or titanium alloy intermediate layer between the har- S titanium oxide outer layer and the heat-modified titanium or titanium alloy inner layer is formed on at least part of the surface of the said article.
  • the heat treatment is preferably carried out at a temperature in the range of from 500 to 800°C.
  • the hard titanium oxide outer layer forming the outer surface of the surface treatment oxide covering may form the outer surface of the article.
  • the surface treatment oxide layer itself may strengthen the construction of the articles; such a strengthening effect is not produced by the surface treatment disclosed in the prior art.
  • Further advantages are the lightness and compactness of the articles.
  • the hard titanium oxide outer layer can be used effectively, thus making the use of materials more efficient.
  • Titanium articles for use as engine components such as valves, valve retainers adapted for use in the valve actuating mechanism of an engine, connecting rods adapted to connect the piston and the crankshaft of an engine and so on are examples of articles which are usefully treated according to the present invention.
  • the hard titanium oxide layer on the outer surface can improve the sliding action of such articles in slidable contact with other engine parts and it can also improve the weight of the engine reciprocating mass.
  • the hard titanium oxide outer layer can have the same or greater hardness than the surfaces obtained by treatments according to the prior art and thus has good wear resistance and good seizure resistance. Accordingly there is no need for further surface treatment such as molybdenum injection welding and nitrogen treatment. Thus the process of the present invention can improve efficiency by removing the need for various kinds of pre-treatment and after treatment steps such as finishing and stress-relieving treatments.
  • an atmospheric oven i.e. an oven in which articles are heated in air
  • an atomospheric oven may be used to effect heat treatment in the temperature range 500-800°C.
  • Fig 1A shows a cross-section through the manufactured surface produced by applying a finishing process on the titanium metal surface after stamping it to the required form of article.
  • the outer surface is the base material 1 of the titanium metal itself.
  • the product is put into an oven such as an atmospheric oven with an oxygen-containing atmosphere and is heated at a temperature below 800°C for a period of several minutes to a few hours.
  • the "surface treatment oxide covering” comprises a hard titanium oxide outer layer 2, a chemically modified titanium or titanium alloy intermediate layer 3 and a heat modified titanium or titanium alloy inner layer 4.
  • the hard titanium oxide outer layer 2 is a layer of titanium oxide
  • the surface of the article is very hard, registering over 500° on the Vicker Scale of Hardness.
  • Such a surface is substantially as hard as a surface produced by the prior art methods.
  • the surface after heat treatment according to the invention does not require any additional finishing process after the heat treatment.
  • the treated surface is acceptable as the outer surface of the product.
  • Various types of chemical compounds are formed in the chemically modified titanium or titanium alloy intermediate layer 3 by the combination of titanium with oxygen, nitrogen and carbon dioxide in the atmospheric air within the oven.
  • the thickness of the surface treatment oxide covering can be reasonably controlled depending on the temperature and the time of the treatment. If the temperature is too high, however, stress would be generated in the product. Thus a temperature of below 800°C is desirably used. It is preferable to maintain the temperature above a minimum of 500°C. While it is possible to carry out the heat treatment at a lower temperature using a long time period, this may decrease efficiency. Consequently, it is preferable to use a heat treatment temperature of 500-800°C.
  • the treatment time can vary from several minutes to a few hours depending on the heat treatment temperature chosen.
  • a preferred treatment time is 3-5 hours.
  • Fig 2 is an outside view of a motorcycle engine which comprises components produced according to the present invention.
  • the engine E consists of a cylinder S and a cylinder head H, and a piston P is slidably mounted in the cylinder S.
  • the following is a description of the intake valve mechanism (the exhaust valve mechanism is identical with the intake valve mechanism).
  • the intake valve 5a is slidably mounted in the valve guide 6.
  • the valve retainer 7 is fixed at the end portion of the intake valve 5a and the valve spring 8 is disposed between the valve retainer 7 and the valve guide 6.
  • the end tip of the intake valve 5a is in contact wih the tappet screw 9A which is screwed on to the forward end portion; of the rocker arm 9, the rocker arm 9 being pivotally movable in both the upward and downward directions by means of a cam 10 formed on the cam shaft so that the intake valve 5a is lifted at the predetermined angle.
  • a connecting rod 11 made of titanium metal is connected to the piston P.
  • the connecting rod 11 is connected to the piston pin 13 at the small end thereof and connected to the crankshaft 15 at the big end thereof.
  • the intake valve 5a, the valve retainer 7 and the connecting rod 11 as mentioned hereinabove have surface treatment oxide coverings made by the process of the invention.
  • Fig 3 illustrates on an enlarged scale the intake valve 5a which is made of the titanium metal.
  • the intake valve 5a has a valve stem 16 and a valve poppet means 17, and is completely contacted by the valve seat 19 provided in the intake port.
  • the intake valve 5a is manufactured by the above mentioned heat treatment process according to the invention and its whole surface comprises a hard titanium oxide outer layer 2, a chemically modified titanium or titanium alloy intermediate layer 3 and a heat-modified titanium or titanium alloy inner layer 4.
  • the hardness of the intake valve surface is either equal to or better than that of a valve produced by the prior art process, that is, the surface registers at least 500° on the Vickers Scale of Hardness. Therefore, further surface treatment of the valve stem 16 which can be used in sliding contact with the valve retainer 6 is not required.
  • the wear resistance of the valve poppet means should be improved without the need for surface treatment using an expensive beryllium-copper alloy on the seating portion of the valve seat.
  • the inside diameter T of an intake valve 5a having a surface treatment oxide covering is substantially the same as that of an intake valve according to the prior art having an injection layer. Consequently it is possible to narrow the outer diameter T 1 of the intake valve 5a to an extent equal to that given by the prior art injection layer.
  • the inside diameter To is just identical with that of a prior art valve comprising base metal in order to produce a valve of similar strength.
  • the presence of the hard titanium oxide outer layer 2 in the surface generally has a negligible effect on the durability for a given product strength.
  • Fig 4 shows the valve stem 16 of the intake valve 5a on an enlarged scale.
  • the cotter 20 is mounted into the cotter groove 21 which is formed at the end portion of the valve stem 16 which should be the stress centre of the valve stem 16.
  • the connecting portion 23 between the reinforcing layer 22 and the valve stem 16 is surrounded by the cotter 20.
  • the upper end of the reinforcing layer 22 projects from the upper surface of the cotter 20 in the direction of the rocker arm 9.
  • the reinforcing layer 22 is conveniently made of material of sufficient strength to be resistant to the impact stress and wear caused by the rocker arm 9.
  • a suitable reinforcing layer material is an iron alloy such as JIS SCM440 (chrome-molvbdenum steel) which may be attached to the valve stem 16 by friction welding.
  • the end portion of the valve stem 16 may be hardened to > 50° on the Rockwell Scale of Hardness by heat treatment, this being equal to the hardness of a common iron valve.
  • the heat-modified titanium or titanium alloy inner layer 24 is formed in the titanium valve stem 16 adjacent the connecting portion 23 where it is surrounded by the valve cotter 20 and does not extend to the cotter groove 21.
  • the cotter groove 21 at the stress centre can be protected from various weaknesses generated by the connecting portion 23 and the heat-modified titanium or titanium alloy inner layer 24. It is desirable to position both the connecting portion 23 and the heat-modified titanium or titanium alloy inner layer 24 within the zone surrounded by the cotter 20 above the cotter groove 21 in order to maintain reasonable strenqth.
  • the tip end 9b of the tappet adjust screw 9a provided in the forward portion of the rocker arm 9 is adapted to contact the reinforcing layer 22.
  • the forward end portion of the rocker arm 9 is swung in the direction indicated by arrow B and then the valve stem 16 is moved in the up and down directions as indicated by arrow C.
  • the tip end portion 9b of the tappet adjust screw will subject the reinforcing layer 22 to an impact force in a direction tangential to the valve stem 16 (indicated by arrow D) which tends to break the connecting portion 23.
  • connecting portion 23 is surrounded by the cotter 20, the impact force imparted by the rocker arm 9 is absorbed by the cotter 20. The impact force acting on the connectinq portion 23 will be lowered and so the connecting portion 23 may be strong enough to resist the tendency to break.
  • Such a connecting portion 23 is stronger than those described in the prior art which are not surrounded by the cotter with a consequent improvement in endurance characteristics.
  • the same construction can also be adapted to the exhaust valve 5b. Materials for the reinforcing layer 22 can be selected as desired dependent upon the usage and so on.
  • An exhaust valve 5b manufactured in accordance with the process of the present invention will be described with reference to Figs 6 and 7. Since the exhaust valve 5b and especially the poppet means of said exhaust valve 5b always operate at high tempaerature, the titanium metal surface will be easily oxidized. Since the exhaust valve is usually subjected to high stress, it is desirable to prevent such oxidation. Therefore on the exhaust valve 5b there is provided an oxide prevention layer 26 on the surface of the joint at the connection between the poppet means 17 and the valve stem 16.
  • the exhaust valve 5b is made of a titanium' alloy composed of Ti-6Al-4V. Another alloy such as for example Ti-6Al-2Sn-4Zr-2Mo can also conveniently be used.
  • the oxide prevention layer 26 may be made by a prior art method in which an aluminium compound is injected into the surface of the titanium metal valve. The injection initially produces an aluminium layer on the oxidized joint portion 25 and then a chemical combined layer is formed by a diffusion reaction between the aluminium layer and the surface of the titanium layer 27. Finally the oxide prevention layer 26 covers the strong joint portion 25 such that said joint portion 25 is not contacted directly by the exhaust gas. By ensuring that the oxide prevention layer 26 will cover the titanium layer 27 on the joint portion 25, the surface of the titanium layer 27 can be protected from oxidation. Tin can conveniently be used as the metal for the oxide prevention layer 26.
  • the method for manufacturing the oxide prevention layer 26 is not limited to injection welding.
  • the oxide prevention layer be made strong integrally with the titanium metal by means of the diffusion joint.
  • the oxide prevention layer 26 may be prepared using a prior art process. If the oxide prevention layer is to be added after the surface treatment oxide covering is already present, the process for preparing the oxide prevention layer should be directed to the concerned area.
  • the joint portion 25 on which the oxide prevention layer 26 is formed should be curved to the least extent possible at the connecting point between the poppet means 17 and the valve stem 16 where the stress concentration will be a maximum.
  • Fig 7 shows the oxide resistance characteristics of an oxide prevention layer 26.
  • This graph shows the variation of hardness caused by oxidation at various distances from the surface of each joint portion for a titanium metal valve comprising a Ti-6Al-4V alloy without the oxide prevention layer. Where the titanium metal is oxidized, the oxide layer increases the surface hardness. The dotted line represents conventional behaviour. Thus, it can be seen that the hardness rapidly increases at the titanium surface.
  • the hardness characteristic of a preferred embodiment of the present invention is shown as a continuous line in Fig 7. This shows the maintenance of the same hardness on going from the surface to the inside portion thereof; that is to say, it is hardly oxidized.
  • Formation of the oxide prevention layer 26 on the joint portion should not adversely affect the titanium layer 27 on the joint portion 25. Therefore, it is possible to avoid any adverse effects caused by the oxide layer such as variation of strength along an exhaust valve that is used under such conditions of high temperature and an oxygen-containing atmosphere.
  • the oxide prevention layer can also be adapted to the intake valve 5a.
  • Fig 8 shows the valve retainer 7 on an enlarged scale.
  • the valve retainer 7 is manufactured having a step portion which can be used to support the end portion of the valve spring.
  • a surface treatment oxide covering comprising a hard titanium oxide outer layer 2, a chemically modified titanium or titanium alloy intermediate layer 3 and a heat-modified titanium or titanium alloy inner layer 4 is formed on the whole surface thereof by means of heat treatment according to the present invention.
  • the valve retainer undergoes nitrogen treatment on the whole surface thereof under high temperature conditions, for example 800-1000°C, resulting in the formation of a comparatively rough surface (the nitrogen treatment layer).
  • the rough surface wears the end of the valve spring, forming a sharp edge which reciprocally wears the area of the valve retainer in contact therewith.
  • valve spring end In order to avoid such reciprocal wear of surfaces as much as possible, the valve spring end should be moulded so that it is difficult to form a hard edge. Since nitrogen treatment requires high temperatures, over 800°C, stress produced by heat deformation must be relieved by a skilful and complicated process in order to maintain the shape of the article after heat treatment.
  • the surface of a valve retainer comprising a surface treatment oxide covering according to the present invention is very smooth compared with the surface of a valve retainer which has undergone nitrogen treatment and it also has high surface hardness, thus giving good wear resistance.
  • An article prepared by the process of the present invention experiences little reciprocal surface wear between the valve retainer and the end of the valve spring 8. Thus even if a rough edge is produced by the method of manufacture nevertheless it may be durable enough and there is no need for additional special treatment. Since the heat treatment process requires a comparatively low temperature (below 800°C) any heat deformities may be small enough that there will be no need to remove them.
  • Fig 9 shows the connecting rod 11 in detail.
  • the connecting rod 11 has a hard titanium oxide outer layer 2, a chemically modified titanium or titanium alloy intermediate layer 3 and a heat-modified titanium or titanium alloy inner layer 4 produced by the process of the invention.
  • the surface treatment layer is provided on the point where the small end portion 12 thereof contacts the piston 13.
  • a bush made of copper is inserted in order to maintain wear resistance and protect against the reciprocating rod.
  • the reciprocating rod which is inserted into the crankshaft, carries a surface treatment layer formed by the molybdenum injection welding in order to maintain the wear resistance.
  • the connecting rod 11 comprises a surface treatment oxide covering on the portion of the small end thereof which contacts the piston pin 13, there should be no need for the copper bush. i.e. there is no need for the insertion process for the copper bush and the prior art treatment process therefor. Since the big end of the connecting rod at the point at which it contacts the crankshaft 15, is also covered by a surface treatment oxide covering, no treatment such as molybdenum injection welding is needed.
  • the surface treatment oxide covering on the whole surface, such as the present embodiment, or only on part of the surface by masking the remainder of the surface from oxyqen.
  • a partial oxide surface treatment covering may be formed on other articles as required.
  • this layer as required in the prior art since it is fully utilised.
  • it can save material, and can improve the compactness and the lightness of the product.
  • articles in a reciprocating mechanism such as a valve actuating system, it is remedial to improve the sliding- interaction to improve the performance.
  • the use of an atmospheric oven in the production of articles makes it possible to produce such heat treated articles cheaply.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
EP19870303900 1986-04-30 1987-04-30 Oberflächenbehandlung von Titangegenständen Expired - Lifetime EP0244253B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP100530/86 1986-04-30
JP10053086A JPS62256956A (ja) 1986-04-30 1986-04-30 チタン系製品の表面処理方法

Publications (2)

Publication Number Publication Date
EP0244253A1 true EP0244253A1 (de) 1987-11-04
EP0244253B1 EP0244253B1 (de) 1991-01-23

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EP19870303900 Expired - Lifetime EP0244253B1 (de) 1986-04-30 1987-04-30 Oberflächenbehandlung von Titangegenständen

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EP (1) EP0244253B1 (de)
JP (1) JPS62256956A (de)
DE (1) DE3767550D1 (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2211211B (en) * 1987-10-17 1991-08-21 Rolls Royce Plc Method of providing titanium and alloys thereof with a protective coating
EP0533128A1 (de) * 1991-09-17 1993-03-24 Hitachi Metals, Ltd. Kolbenring aus Titan-Legierung und Verfahren zur Herstellung
EP0605444A1 (de) * 1991-09-20 1994-07-13 Kemp Dev Corp Verfahren und vorrichtung zur oberflächenhärtung eines werkstückes aus refraktärem metall.
EP0719874A1 (de) * 1994-12-26 1996-07-03 Shincron Co., Ltd. Verfahren und Vorrichtung zur Herstellung dünner Schichten von metallischen Verbindungen
WO1998002595A1 (en) * 1996-07-17 1998-01-22 The University Of Birmingham Surface oxidation of a titanium or titanium alloy article
WO1999004055A1 (en) * 1997-07-19 1999-01-28 The University Of Birmingham Method of case hardening
EP0905271A1 (de) * 1996-03-26 1999-03-31 Citizen Watch Co. Ltd. Titan der titanlegierung und oberflächenbehandlungsverfahren dafür
EP1174593A3 (de) * 2000-07-18 2003-04-02 Fuji Oozx Inc. Hubventil aus Titanlegierung und Verfahren zu dessen Herstellen
GB2458518A (en) * 2008-03-20 2009-09-23 Minebea Co Ltd An aerospace bearing
EP2246582A3 (de) * 2009-04-30 2013-02-20 Yamaha Hatsudoki Kabushiki Kaisha Gleitkomponente für Verbrennungsmotoren, Verbrennungsmotor, Transporter und Verfahren zur Herstellung der Gleitkomponente für Verbrennungsmotoren

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2826561B2 (ja) * 1988-12-28 1998-11-18 三菱自動車工業株式会社 チタンまたはチタン合金の表面処理方法
US7767267B2 (en) * 2003-06-04 2010-08-03 Wide Open Coatings, Inc. Method of producing a coated valve retainer
EP2674506B1 (de) 2011-02-10 2017-04-12 Nippon Steel & Sumitomo Metal Corporation Abriebfestes Bauteil aus einer Titanlegierung mit hervorragender Ermüdungsfestigkeit
WO2016084980A1 (ja) 2014-11-28 2016-06-02 新日鐵住金株式会社 チタン合金部材およびチタン合金部材の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0146284A1 (de) * 1983-11-29 1985-06-26 Sony Corporation Verfahren zur Herstellung von dielektrischen Metalltitanaten
DD226018A1 (de) * 1984-05-07 1985-08-14 Ardenne Manfred Verfahren zum aufbringen von tio tief 2 -schichten durch reaktives hochratezerstaeuben

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5614743B2 (de) * 1972-09-13 1981-04-06
JPS5910429B2 (ja) * 1977-03-30 1984-03-08 シチズン時計株式会社 チタンおよびチタン合金の表面硬化法
JPS62180051A (ja) * 1986-02-03 1987-08-07 Hitachi Ltd チタン合金製タ−ビン翼のエロ−ジヨン防止法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0146284A1 (de) * 1983-11-29 1985-06-26 Sony Corporation Verfahren zur Herstellung von dielektrischen Metalltitanaten
DD226018A1 (de) * 1984-05-07 1985-08-14 Ardenne Manfred Verfahren zum aufbringen von tio tief 2 -schichten durch reaktives hochratezerstaeuben

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, unexamined applications, C field, vol. 9, no. 271, October 29, 1985 THE PATENT OFFICE JAPANESE GOVERNMENT page 136 C 311; JP-A 60 121 276 (SONY K.K.) *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2211211B (en) * 1987-10-17 1991-08-21 Rolls Royce Plc Method of providing titanium and alloys thereof with a protective coating
EP0533128A1 (de) * 1991-09-17 1993-03-24 Hitachi Metals, Ltd. Kolbenring aus Titan-Legierung und Verfahren zur Herstellung
EP0605444A1 (de) * 1991-09-20 1994-07-13 Kemp Dev Corp Verfahren und vorrichtung zur oberflächenhärtung eines werkstückes aus refraktärem metall.
EP0605444A4 (de) * 1991-09-20 1994-11-17 Kemp Dev Corp Verfahren und vorrichtung zur oberflächenhärtung eines werkstückes aus refraktärem metall.
EP0719874A1 (de) * 1994-12-26 1996-07-03 Shincron Co., Ltd. Verfahren und Vorrichtung zur Herstellung dünner Schichten von metallischen Verbindungen
EP0905271A1 (de) * 1996-03-26 1999-03-31 Citizen Watch Co. Ltd. Titan der titanlegierung und oberflächenbehandlungsverfahren dafür
EP0905271A4 (de) * 1996-03-26 2001-06-06 Citizen Watch Co Ltd Titan der titanlegierung und oberflächenbehandlungsverfahren dafür
US6210807B1 (en) 1996-07-17 2001-04-03 The University Of Birmingham Surface oxidation of a titanium or titanium alloy article
WO1998002595A1 (en) * 1996-07-17 1998-01-22 The University Of Birmingham Surface oxidation of a titanium or titanium alloy article
WO1999004055A1 (en) * 1997-07-19 1999-01-28 The University Of Birmingham Method of case hardening
US6833197B1 (en) 1997-07-19 2004-12-21 The University Of Birmingham Method of case hardening
EP1174593A3 (de) * 2000-07-18 2003-04-02 Fuji Oozx Inc. Hubventil aus Titanlegierung und Verfahren zu dessen Herstellen
KR100786359B1 (ko) * 2000-07-18 2007-12-14 후지 오오젝스 가부시키가이샤 티타늄 합금 포펫 밸브 제조 방법
GB2458518A (en) * 2008-03-20 2009-09-23 Minebea Co Ltd An aerospace bearing
GB2458518B (en) * 2008-03-20 2010-06-30 Minebea Co Ltd An aerospace bearing component
EP2246582A3 (de) * 2009-04-30 2013-02-20 Yamaha Hatsudoki Kabushiki Kaisha Gleitkomponente für Verbrennungsmotoren, Verbrennungsmotor, Transporter und Verfahren zur Herstellung der Gleitkomponente für Verbrennungsmotoren
US8479704B2 (en) 2009-04-30 2013-07-09 Yamaha Hatsudoki Kabushiki Kaisha Sliding component for internal combustion engine, internal combustion engine, transporter, and method for producing the sliding component for internal combustion engine

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Publication number Publication date
EP0244253B1 (de) 1991-01-23
DE3767550D1 (de) 1991-02-28
JPS62256956A (ja) 1987-11-09

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