EP0679736A1 - Verbesserung der Oberflächeneigenschaften eines Maschinenventils aus einer Titanlegierung - Google Patents

Verbesserung der Oberflächeneigenschaften eines Maschinenventils aus einer Titanlegierung Download PDF

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Publication number
EP0679736A1
EP0679736A1 EP94201220A EP94201220A EP0679736A1 EP 0679736 A1 EP0679736 A1 EP 0679736A1 EP 94201220 A EP94201220 A EP 94201220A EP 94201220 A EP94201220 A EP 94201220A EP 0679736 A1 EP0679736 A1 EP 0679736A1
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Prior art keywords
nickel
valve
coat layer
layer
particles
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EP94201220A
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English (en)
French (fr)
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EP0679736B1 (de
Inventor
Kazuyoshi Kurosawa
Yoshio Matsumura
Takeji Kenmoku
Shinichi Umino
Eiji Hirai
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Fuji Oozx Inc
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Fuji Oozx Inc
Fuji Valve Co Ltd
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Priority to DE1994608829 priority Critical patent/DE69408829T2/de
Priority to EP19940201220 priority patent/EP0679736B1/de
Publication of EP0679736A1 publication Critical patent/EP0679736A1/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • F01L3/04—Coated valve members or valve-seats

Definitions

  • the present invention relates to a method of improving surface properties of a titanium alloy valve.
  • a valve shaft In a moving valve mechanism, a valve shaft is very quickly and for very long period, reciprocated in a valve guide, go as to open and close acutely periodically the valve to comply the timing of the valve with the revolution rate of the engine. Therefore the side surface of the valve shaft slides always on the surface of a valve guide, at very high speed, and abrasion load is repeatedly applied on the contact surface of the valve shaft so as to abrade both the surfaces of the valve shaft and the valve guide. Therefore, when the valve is made from titanium or titanium alloy, it can have relatively high thermal resistance and wear resistance.
  • titanium alloy used in this specification includes titanium metal and titanium based alloy. Titanium metal and its alloy have higher relative strength, and significant durability, and its alloy evidences light and strong material.
  • a titanium based alloy containing 6 weight % of Al, and 4 weight % of V is a light weight and high strength material having higher thermal resistance to the temperature of operated engine, and higher tension strength at the high temperature of practical engine, and relative density heing 60 % of that of steel. Therefore, the titanium alloy has been expected in use for automobile components, e.g. engine valve material.
  • a titanium alloy While a titanium alloy has higher resistance, higher relative strength and higher thermal resistance, it has relatively lower thermal conductivity and not enough abrasion resistance. Therefore, when a titanic alloy is used for a reciprocating shaft of an engine valve and the like, the requirement for the engine valve Such as abrasion resistance and fatigue strength should be improved. On the other hand, an engine valve is abraded and fatigued because of repetition of sliding wears, and repetition of bending stress loading, and most of such loadings are applied on the surface of the valve. Therefore, most of factors to control the life of the engine valve, and to improve the performances of the valve are due to the condition of the surface. There have been a variety of proposals to modify or treat the surface of the titanium alloy valve, by forming specific coat layer on the surface of the titanium alloy in use for an engine valve.
  • a variety of plating techniques have been used as a technique for improving the surface properties of metal member.
  • a titanium alloy valve is plated so as to improve the abrasion resistance
  • the performances of the produced valve are dependent on a pretreatment, and post treatment of the surface thereof, the composition of the plating bath, and the operation conditions for plating. Therefore, it is very difficult to produce the valve to satisfy the requirements for automobile engine, and then it is very difficult to select appropriate plating conditions.
  • U. S. Patent No. 4,122,817 discloses an engine valve having a contact surface of formed of a alloy which exhibits wear-resistant properties, PbO corrosion resistance and oxidation resistance, and the alloy containing carbon 1.4 to 2.0 wt.%, molybdenum 4.0 to 6.0 wt.%, silicon 0.1 to 1.0 wt.%, nickel 8 to 13 wt.%, chromium 20 to 26 wt.%, manganese 0 to 3.0 wt.% with balance being iron.
  • Japanese (Unexamined) Patent Laid-open application No. 2-92494/1990 proposed an iron-based alloy powder in use for a material to be coated on a face of an engine valve, which comprises C; 1.0 to 2.5 wt. %, Si; 0.1 to 1.0 wt. %, Mn; 3 to 12 wt. %, Ni; 15 to 25 wt. %, Cr; 20 to 30 wt. %, Mo; 5 to 15 wt. %, B; 0.005 to 0.05 wt. %, Al; 0.01 to 0.1 wt. % and O; 0.01 to 0.05 wt. % with balance being Fe and impurities.
  • Japanese (Unexamined) Patent Laid-open application No. 5-49802/1993 proposed an engine valve having an alloy layer comprising Cr 10 to 60 wt.%, C 1 to 8 wt.%, total content of Mo, Ni, W, B, Si and Co; 5 to 20 wt.% with balance being iron, on a facing surface thereof, which is based on an austenite steel.
  • FIG. 1 is a flow sheet in accordance with a method of the present invention.
  • FIG. 2 shows schematically a side view of a titanium alloy valve to which a method of the present invention is applied.
  • the inventors have developed a method of improving the abrasion resistance of the surface of the valve by plating Ni-P on the surface of the titanium alloy valve. Further, the inventors have reviewed a variety of the conditions so as to select appropriate conditions for plating. An undercoat layer of nickel is formed by plating on the surface of the valve before plating Ni-P layer, and then, the coat layer adhered on the nickel undercoat layer is heated at a specific temperature and for a specific period, so as to disperse ceramic particles uniformly and homogeneously in the Ni-P metal matrix of the coat layer. Then, the inventors have found that some improvement of abrasion resistance of the valve can be attained under appropriate conditions for plating and heating procedures.
  • the improvement of the surface performance of an internal combustion engine valve made from titanium alloy can be attained by forming as a surface undercoat a nickel layer directly on a surface of the engine valve by plating, and then heating the resulting nickel undercoat at a specific condition, and further, forming as a top coat a three component coat layer comprising nickel, phosphorus and ceramic particles by plating.
  • the inventors have reviewed the relationship between hardness and strength (rotation bending fatigue strength) of the top coat formed on the surface of the titanium alloy valve and further the relationship of the abrasion resistance with the hardness of the top coat.
  • the ceramic particulate material to be uniformly dispersed within the three component coat in accordance with the present invention comprises material selected from the group consisting of silicon carbide (SiC), boron nitride (BN), silicon nitride (Si3N4), and the combination thereof.
  • SiC silicon carbide
  • BN boron nitride
  • Si3N4 silicon nitride
  • Such particulate material can be finely and uniformly dispersed in the coat layer to produce necessary hardness thereof.
  • Such ceramic material silicon carbide (SiC), boron nitride (BN), silicon nitride (Si3N4), as used in accordance with the present invention have an expanded utility in the application to a machine component, and an automobile component.
  • SiC and Si3N4 have been developed to be utilized in thin layer, coating and amorphous material in its application.
  • SiC silicon carbide
  • Si3N4 silicon nitride
  • Table 1 SiC Si3N4 Apparant density 2.3 - 3.34 2 - 2.3 Bending strength (kg/mm2) 6 - 95 5 - 500 Fracture toughness(MN/m3l2) 2.4 - 5.6 1 - 9 Thermal shock resistance ⁇ T(°C) 200 - 700 400 - 900 Hardness(Vickers:kg/mm2) 1,800 - 3,700 1,100 - 1,900
  • Table 1 indicates that the Si3N4 is good at bending strength, fracture strength and abrasion resistance in comparison with SiC.
  • the function of the particulate material is based on its higher strength; physical properties. Therefore, such ceramic particulate material as SiC and Si3N4 can be used merely or in combination.
  • component used for indicating "unit” constituting the coat layer to be formed on the surface of an engine valve means each component of nickel, phosphorus and particles of ceramic material; three components. Therefore, the fine particles of the ceramic material may be "SiC", "BN”, “Si3N4" and the combination thereof.
  • composition of the three component coat layer to be formed as an outer coat on the surface of the titanium alloy valve in accordance with the present invention may include Ni-P-SiC, Ni-P-BN, Ni-P-Si3N4, Ni-P-(SiC+BN), Ni-P-(SiC+Si3N4), Ni-P-(SiC+Si3N4) and Ni-P-(SiC+BN+Si3N4).
  • the factors to control the performance or feature of the three component coat to be formed as an outer coat on the surface of the titanium alloy valve may be the content of ceramic particulate material, size and size distribution of the ceramic particles, shape of the particles, and interfacial stability between the particles and metal matrix. Therefore, such factors should be selected in view of desired abrasion resistance of the three component coat layer comprising Ni-P-dispersed ceramic fine particles to be finally formed on the surface of the valve in accordance with the present invention.
  • the size of the ceramic particles to be dispersed in the coat layer is preferably below ten and several micrometer, and more preferably 1 to 5 micrometer. When the size is below one micrometer, and then the particles are very finely divided, the abrasion resistance improvement can not be expected so much.
  • One of SiC, BN and Si3N4 can be used, but the combination of the two or more selected from SiC, BN and Si3N4. Further, the size of the particles can be the same, or the different sizes of the particles can be used and further, the size distribution to get closest packing can be used.
  • the content of the particular material based on the weight of the coat layer is preferably 2 to 10 %, and more preferably 2 to 7 %.
  • the thickness of the three component coat layer comprising Ni-P-fine particles of ceramic material to be formed on the titanium alloy valve is preferably 10 to 30 micrometer. This thickness should be selected optionally in view of desired hardness of the coat layer, the coat of the preparation of the coat layer, and the productivity thereof.
  • FIG. 1 shows a flow sheet of the process of improving a surface performance of the valve in accordance with a method of the present invention.
  • the steps T1 to T13 represent each step for plating process, and the steps of T1 to T6 are for a preliminary procedures before Ni plating for production of an undercoat layer, and the steps of T8 to T10 are for the post treatments after Ni plating, and then, the steps of T12 to T13 are for the post treatments of plating to form as a top coat a three component layer of Ni-P-dispersed ceramic particles.
  • the preliminary treatment for plating is an essential step necessary for the plating, anal then the 80 % of the number badness is due to bad preliminary treatment. Therefore, the preliminary treatment should be carefully enough carried out.
  • the engine valve as available from the factory is as immersed in an oil, and a lot of oil or grease remains on the surface of the engine valve.
  • the step T1 of cleaning the valve should remove completely oil and grease from the valve, by a conventional process such as steam defatting process, or treatment with alkali solution.
  • An alkali defatting solution to he used in the step T1 may comprise the composition as shown in Table 2, to remove oil and grease remaining on the surface of the sample.
  • Table 2 Alkali material g/l sodium triphosphate (Na3PO4) 20 sodium orthosilicate (Na4SiO4) 20 non-ionic surfactant 0.5 to 2 Temperature of solution 60 to 70 °C
  • the sample After defatting by immersion at the step of T1, the sample may be further defatted by electrolysis, so as to remove completely powder ad oil remaining in finely irregulated surface which have not removed even by immersion defatting step, and so as to remove completely stains remaining on the surface.
  • the sample is chemically treated at the step of T2 by dipping in a chemical bath comprising the solution as shown in the following table, at room temperature until the bath generates red bubbles.
  • This chemically etching step is to remove a thin and tough oxide coat formed on the surface of the sample, so as to activate the surface.
  • the preferable solution composition ad condition for the chemical etching are as follows.
  • composition of chemical etching solution and condition thereof Composition of chemical etching solution and condition thereof :
  • the sample is washed with water at the step of T3, and then is dipped in an etching bath comprising the composition as shown in Table 4, at the step of T5 so as to remove a worked strained surface layer from the sample so as to expose a fresh and strainless crystal surface of the titanium alloy.
  • the composition of the etching solution and the condition to be used in the step of T3 are as follows.
  • composition of etching bath and the condition thereof Composition of etching bath and the condition thereof ;
  • the sample After etching step of T5, the sample is washed with water, and further, plated with nickel at the step of T7.
  • the object of Ni-plating at the step of T7 is to form an undercoat for improving adhesion strength with a top coat.
  • Ni ion source nickel sulfate, nickel chloride or nickel sulfamate can be used.
  • the costs thereof are in the order of nickel sulfate, nickel chloride and nickel sulfamate, and the solubility thereof are in the same order too.
  • NiCl2 ⁇ 6H2O is preferable for an anode dissolving agent.
  • the nickel plating can be operated at pH range of 3.0 to 6.2.
  • a buffer solution is necessary for maintaining pH at this range.
  • Boric acid (H3BO3) solution is preferable for this method, but the other agent such as nickel formate and nickel acetate can be used for pH buffering.
  • the current density is increased and the electroconductivity is increased so as to improve uniformity of electrodeposition, but the current efficiency is decreased.
  • the temperature of the bath is the higher, the higher the current density can be, and the lower the voltage can be, so as to reduce the hardness of the deposit thereby increasing the flexibility of the coat layer.
  • the resulting sample is nickel plated at the step of T7, by using a nickel plating bath containing nickel sulfamate, and having the composition as shown in Table 5, under the condition as shown in the lower portion of Table 5.
  • Table 5 Components Watt's bath Sulfamic bath nickel sulfate (NiSO4 ⁇ 6H2O) 220 -380 g/l nickel chloride (NiCl2 ⁇ 6H2O) 30 - 60 g/l 0 - 30 g/l nickel sulfamate (Ni(NH2SO3)2) 300 - 800 g/l boric acid (H3BO3) 30 - 40 g/l 30 g/l additives appropriate appropriate pH 3.0 - 4.8 3.5 - 4.5 bath temperature 40 - 65 °C 25 - 70 °C cathode current density (A/dm2) 2 - 10 2 - 15 agitation bubling doing
  • the thickness of nickel plated layer as in the step T7 is at least 1 micrometer, and preferably ranges 10 micrometer to 30 micrometer.
  • the thermal treatment is one of important keys of the present invention, and is to form a metal binding between the titanium alloy and Ni-plated undercoat, so as to improve adhesion strength of the both layers.
  • the thermal treatment is carried out at the temperature of 400 °C to 550 °C in an inert gas or in vacuum, for one to four hours.
  • the most preferable condition of the thermal treatment is in vacuum, at the temperature of 450 °C to 500 °C, and for one hour.
  • Dispersion coat plating
  • the dispersion plating is carried out at the step of T11. This is one of the important keys of the present invention.
  • the purpose of the dispersion plating is to form as a top coat a three component layer of Ni-P matrix containing uniformly dispersed fine ceramic particles, in order to improve abrasion resistance and thermal resistance of the top coat layer.
  • the features or the dispersion plating at the step of T11 resides in that while the phosphorus source and the ceramic fine particles being difficult to be dissolved are uniformly dispersed, metal matrix of Ni-P is deposited together with the deposition of fine ceramic particles, so that the three component layer of the metal matrix containing uniformly dispersed ceramic particles is deposited or formed.
  • Ni-P metal matrix and fine particles can enable to get synergistic effect which can not be obtained merely by one component coat layer.
  • Such synergistic function is one of the features of the dispersion plating in accordance with the present invention.
  • the plating bath and ceramic particles to be used in the step of T11 will be explained.
  • One example of the plating bath to be used in the step of T11 may be a Watt's bath and sulfamic bath containing as a phosphorus source 1 to 10 g/l of sodium hypophosphite.
  • the deposit of Ni-P formed by plating from the plating bath containing a phosphorus source is used as a matrix for dispersing ceramic fine particles.
  • the dispersion plating in the step of T11 is carried out in a plating suspension bath containing uniformly dispersed fine ceramic particles. Therefore, the bath should be agitated continuously so as to avoid precipitation. At the same time, uniform deposition should be carried out.
  • the size of the dispersed particles is preferably below ten and several micrometer, and more preferably 1 to 5 micrometer. When the size of the particles is below one micrometer, it is too small to get abrasion resistance. The improvement of the abrasion resistance can not be expected so much.
  • the thickness of the dispersion plated coat layer formed in the step of T11 can he adjusted to the range of 300 to 500 micrometer by selecting the plating bath composition and the plating conditions. However, in view of the requirements such as the necessary improvement of abrasion resistance and the reduction of the cost of the coat layer production, the thickness of the coat layer should be quite 10 to 30 micrometer.
  • the thermal treatment in the step of T13 is carried out after washing with water.
  • the dispersion plating produces a three component layer having a metal matrix of Ni-P, and dispersion phase of SiC, Si3N4 or BN or the combination thereof. Then the three component layer is treated thermally so as to harden, thereby improving an abrasion resistance thereof.
  • Thermal treatment is carried out at the temperature of 350 °C to 530 °C preferably 400 to 550 °C, for the period of one to four hours.
  • the most preferable condition is that the temperature is 450 to 500 °C, and the period is about one hour.
  • the fatigue limit of the coat layer containing dispersed particles can be 350 MPa at maximum. The reduction of the strength can be avoided in such coat layer. Therefore, it is understood that the hardness and the fatigue limit of the three component coat layer containing Ni-P-fine ceramic particles are dependent highly on the temperature at which the coat layer is treated.
  • the inventive method can enable to produce a titanium alloy engine valve with improved surface performance, having a three component coat layer of nickel, phosphorus and dispersed ceramic particles of boron nitride, silicone nitride or silicone carbide or the combination thereof, which is formed directly on the undercoat of nickel which is directly on the surface of the titanium alloy valve.
  • the present invention is further illustrated by the following examples to show the method of improvement of a valve shaft in accordance with the present invention, but should not he interpreted for the limitation of the invention.
  • the engine valve 1 made from titanium alloy of Ti-6Al-4V has a shape a shown in FIG. 2, having a expanded end 1b at one end of the valve shaft 1a and a groove 1c on the whole circumference of the shaft near to the other end of the shaft.
  • the sample was made from titanium alloy of Ti-6A1-4V, having such shaft shape.
  • the sample was dipped at the temperature at 70 °C for four minutes in an alkali defatting bath comprising the composition as shown in Table 6, so as to remove oil and grease attached on the surface of the sample.
  • Table 6 Alkali material g/l sodium triphosphate (Na3PO4) 20 sodium orthosilicate (Na4SiO4) 20 non-ionic surfactant 1
  • the resulting sample was nickel plated by using a nickel plating bath containing sulfamic nickel and having the composition as shown in Table 9, under the condition as shown in the lower portion of Table 9.
  • Table 9 Components Amount NiCl2 ⁇ 6H2O 20g/l Ni(NH2SO3)2 800g/l H3BO3 30g/l pH 4.0 bath temperature 40 °C cathode current density (A/dm2) 15
  • the formed nickel undercoat layer was measured at its thickness by electrolysis coating thickness meter, and the measured thick was 10 micrometer.
  • the sample was washed with water after nickel plating, and then, heated at the temperature of 550 °C vacuum, for three hours, so as to strengthen the metal binding between the sample and nickel undercoat layer.
  • the hardness of the resulting nickel undercoat layer was measured by a micro Vicker's hardness meter. The measured hardness is Hv 158.
  • Table 10 Components Amount NiCl2 ⁇ 6H2O 20g/l Ni(NH2SO3)2 800g/l H3BO3 30g/l sodium hypophospite 10g/l SiC* 250g/l pH 4.0 bath temperature 40 °C cathode current density (A/dm2) 15 * is available from and manufactured by Onoda Cement company limited; the size thereof is 3 micrometer.
  • the sample After washed with water, the sample was heated at 350 °C for one hour, so as to strengthen the metal binding between the undercoat nickel layer and the Ni-P-SiC three component coat layer.
  • the thickness of the formed Ni-P-SiC coating layer was measured by using fluoresence X ray thickness measurement method, and the measured thickness is 30 micrometer.
  • the hardness of the three component coating layer was measured by a micro Vicker's hardness meter, the resulting hardness is 644 Hv.
  • the particles of SiC was replaced by Si3N4 particles available from Toshiba Ceramic company limited, having 3 micrometer in size, but the example 1 was repeated except of this replacement, so as to form a Ni-P-Si3N4 three component coat layer.
  • the thickness of the coat layer was 30 micrometer, and the hardness thereof was 670 Hv.
  • the abrasion amounts after the durability test period at an engine valve shaft and an valve guide made from iron-based sintered alloy comprising 4-5 wt% of Cu, 1.5-2.5 wt% of C, 0.4-0.5 wt% of Sn, 0.1-0.5 wt% of P and remaining Fe, through which the shaft is reciprocated were measured.
  • Table 11 Abrasion amount(micrometer) Example 1 (micrometer) Example 2 (micrometer) shaft surface 1.2 0.9 valve guide surface 2.1 1.5
  • the improvement of the surface properties of an engine valve in accordance with the present invention can effect significantly abrasion resistance of the valve to satisfy the important requirement of the valve, such as the cost in manufacture, and productivity in automobile component manufacture. Further, because undercoat layer of nickel is formed directly on the surface of a valve, and then three component coat layer of nickel, phosphorus and ceramic particles of materials selected from the group consisting of silicone carbide, silicone nitride and boron nitride and the combination thereof is formed and further, thermal treatment of both layers can enable to improve the adherence between both layers, and resistance of the coat layer.
  • composition and properties of the coat layer can be easily and readily modified only by changing the composition of plating bath, and the plating conditions.
  • the conventional apparatuses being in the prior art; i.e. a conventional plating apparatus and heating apparatus can be used in a new method of improving the properties of the surface of the engine valve. Therefore, new facilities are not needed, and then the cost of manufacture can be reduced.
  • the valve shaft produced by a method of the present invention evidences an improved abrasion resistance at the reciprocation shaft of the valve, and the shaft have a harden surface due to the Ni-P-fine ceramics coating layer which have a Vicker's hardness of 250 to 600 in Hv.
  • the valve shaft produced by a method of the present invention can improve both of the abrasion resistance and fatigue resistance.

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EP19940201220 1994-04-28 1994-04-28 Verbesserung der Oberflächeneigenschaften eines Maschinenventils aus einer Titanlegierung Expired - Lifetime EP0679736B1 (de)

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Application Number Priority Date Filing Date Title
DE1994608829 DE69408829T2 (de) 1994-04-28 1994-04-28 Verbesserung der Oberflächeneigenschaften eines Maschinenventils aus einer Titanlegierung
EP19940201220 EP0679736B1 (de) 1994-04-28 1994-04-28 Verbesserung der Oberflächeneigenschaften eines Maschinenventils aus einer Titanlegierung

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EP19940201220 EP0679736B1 (de) 1994-04-28 1994-04-28 Verbesserung der Oberflächeneigenschaften eines Maschinenventils aus einer Titanlegierung

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EP0679736A1 true EP0679736A1 (de) 1995-11-02
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0681039B1 (de) * 1992-11-04 1997-09-10 Fuji Oozx Inc. Ventilschaftstruktur aus einer Titanlegierung für Motor
WO2009056239A1 (de) * 2007-11-02 2009-05-07 Märkisches Werk GmbH Ein- oder auslassventil für einen verbrennungsmotor sowie verfahren zu dessen herstellung
EP3061852A3 (de) * 2014-12-12 2016-11-23 Mahle International GmbH Gaswechselventil
WO2016198205A1 (de) * 2015-06-09 2016-12-15 Mahle International Gmbh Verfahren zum beschichten eines ventils einer brennkraftmaschine
DE102018218205A1 (de) * 2018-10-24 2020-04-30 Mahle International Gmbh Gaswechselventil

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55132787A (en) * 1979-03-28 1980-10-15 Tsuerure Ruutobitsuhi Rope unfolding apparatus
EP0441636A1 (de) * 1990-02-09 1991-08-14 Nihon Parkerizing Co., Ltd. Verfahren zur Oberflächebehandlung von Titanium enthaltenden Metallgegenständen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55132787A (en) * 1979-03-28 1980-10-15 Tsuerure Ruutobitsuhi Rope unfolding apparatus
EP0441636A1 (de) * 1990-02-09 1991-08-14 Nihon Parkerizing Co., Ltd. Verfahren zur Oberflächebehandlung von Titanium enthaltenden Metallgegenständen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9326, Derwent World Patents Index; AN 93-209069 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0681039B1 (de) * 1992-11-04 1997-09-10 Fuji Oozx Inc. Ventilschaftstruktur aus einer Titanlegierung für Motor
WO2009056239A1 (de) * 2007-11-02 2009-05-07 Märkisches Werk GmbH Ein- oder auslassventil für einen verbrennungsmotor sowie verfahren zu dessen herstellung
EP3061852A3 (de) * 2014-12-12 2016-11-23 Mahle International GmbH Gaswechselventil
WO2016198205A1 (de) * 2015-06-09 2016-12-15 Mahle International Gmbh Verfahren zum beschichten eines ventils einer brennkraftmaschine
DE102018218205A1 (de) * 2018-10-24 2020-04-30 Mahle International Gmbh Gaswechselventil

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DE69408829T2 (de) 1998-10-22
DE69408829D1 (de) 1998-04-09

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