US20200071803A1 - Sintered steel alloy for wear resistance at high temperatures and fabrication method of valve-seat using the same - Google Patents

Sintered steel alloy for wear resistance at high temperatures and fabrication method of valve-seat using the same Download PDF

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US20200071803A1
US20200071803A1 US16/270,091 US201916270091A US2020071803A1 US 20200071803 A1 US20200071803 A1 US 20200071803A1 US 201916270091 A US201916270091 A US 201916270091A US 2020071803 A1 US2020071803 A1 US 2020071803A1
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steel alloy
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Kyu Han Kim
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Yoosung Enterprise Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12Both compacting and sintering
    • B22F3/16Both compacting and sintering in successive or repeated steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24After-treatment of workpieces or articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24After-treatment of workpieces or articles
    • B22F3/26Impregnating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/008Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of engine cylinder parts or of piston parts other than piston rings
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0068Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0242Making ferrous alloys by powder metallurgy using the impregnating technique
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20Ferrous alloys, e.g. steel alloys containing chromium with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/30Ferrous alloys, e.g. steel alloys containing chromium with cobalt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/60Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01LCYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00Lift-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
    • F01L3/02Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24After-treatment of workpieces or articles
    • B22F2003/248Thermal after-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00Metallic composition of the powder or its coating
    • B22F2301/35Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

Definitions

  • the present invention relates to a sintered steel alloy for wear resistance at high temperatures, which is applied to a valve seat for an internal combustion engine, and more particularly, to a sintered steel alloy for wear resistance at high temperatures, in which a composition of the sintered steel alloy is changed to maximize its heat resistance as well as its wear resistance, and a method of manufacturing a valve seat using the same.
  • a valve seat for an internal combustion engine is a ring-shaped sintered body, which maintains the airtightness of intake/exhaust valves in an opening/closing process of the intake valve and the exhaust valve.
  • a valve seat 18 performs a sealing function by contacting head portions of the intake valve and the exhaust valve while the valve seat 18 is inserted into a cylinder head 24 .
  • the valve seat 18 contacts the intake/exhaust valves in a closing stroke of the exhaust valve, and performs a function of preventing leakage of exhaust gas in an opening stroke of the exhaust valve.
  • physical requirements such as wear resistance or heat resistance be sufficient to withstand continuous friction with the intake/exhaust valves and continuous chemical reactions with the exhaust gas.
  • the internal combustion engine employs a method of combusting a liquid fuel and a gas fuel as well, and a wider variety of forms of combustion products are formed by means of the liquid fuel and the gas fuel, so that there is a need to further reinforce physical conditions such as wear resistance and heat resistance to be able to withstand the combustion products from the liquid fuel and the gas fuel.
  • Patent Document 1 KR10-2004-0025003 A
  • Patent Document 2 KR10-2012-0125817 A
  • Patent Document 3 KR10-0461304 B1
  • the present invention is directed to providing a sintered steel alloy for wear resistance at high temperatures, in which a composition of the sintered steel alloy is changed to maximize its heat resistance as well as its wear resistance and extend a service life of a valve seat, and a method of manufacturing a valve seat using the same.
  • a sintered alloy including: 10.0 to 14.0 parts by weight of cobalt powder; 5.0 to 9.0 parts by weight of molybdenum powder ; 1.5 to 4.1 parts by weight of chromium powder; 0.7 to 1.3 parts by weight of carbon powder; 1.0 to 1.8 parts by weight of manganese powder; 0.4 to 1.2 parts by weight of silicon powder; 0.2 to 0.8 parts by weight of sulfur powder; and 0.1 to 0.7 parts by weight of vanadium powder, based on 100 parts by weight of iron powder.
  • a manufacturing method including: a mixing operation of evenly mixing the sintered alloy; a pressurizing operation of pressurizing a resulting mixture formed in the mixing operation at a set pressure; a sintering operation of sintering a resulting molded body formed in the pressurizing operation along with an infiltrate to infiltrate copper into the molded body; a low temperature treatment operation of treating a resulting sintered body formed in the sintering operation at a low temperature to change residual austenite into martensite; and a heat treatment operation of tempering a resulting low temperature treated body formed in the low temperature treatment operation to remove a residual stress therefrom.
  • the present invention has at least the following effects.
  • cobalt, molybdenum, or chromium and a component for increasing strength are added into the composition of the valve seat to form complex carbides, so that the precipitated particles and the amount of solid solubility of an iron matrix for the valve seat are increased and a service life of the valve seat is extended.
  • silicon or vanadium is added into the composition of the valve seat to disperse micro-spherical particles into the iron matrix, so that a loss of carbide particles is decreased in an abrasion process of the valve seat, an amount of abrasion is reduced, and a service life of the valve seat is extended.
  • the composition of the valve seat may be applied to any internal combustion engine using a gas fuel as well as a liquid fuel.
  • FIG. 1 is a diagram illustrating an installation state of a valve seat according to the related art
  • FIG. 2 is an optical microscope picture (500 ⁇ magnification) of Example 1 according to the present invention.
  • FIG. 3 is an optical microscope picture (500 ⁇ magnification) of Example 2 according to the present invention.
  • FIG. 4 is an optical microscope picture (500 ⁇ magnification) of Example 3 according to the present invention.
  • a sintered steel alloy according to the present invention represents a sintered alloy applied to an internal combustion engine, and particularly applied to a valve seat that maintains airtightness of intake/exhaust valves in an opening/closing process of the intake valve and the exhaust valve and also minimizes damage in a contact process with combustion products.
  • the composition of the sintered steel alloy according to the present invention includes a sintered alloy, in which iron powder is a main component, as well as an infiltrate, which is infiltrated into the sintered alloy, and the sintered alloy includes: 10.0 to 14.0 parts by weight of cobalt powder; 5.0 to 9.0 parts by weight of molybdenum powder; 1.5 to 4.1 parts by weight of chromium powder; 0.7 to 1.3 parts by weight of carbon powder; 1.0 to 1.8 parts by weight of manganese powder; 0.4 to 1.2 parts by weight of silicon powder; 0.2 to 0.8 parts by weight of sulfur powder; and 0.1 to 0.7 parts by weight of vanadium powder, based on 100 parts by weight of the iron powder.
  • the infiltrate is copper powder which amounts to 10.0 to 20.0 parts by weight based on 100 parts by weight of the iron powder.
  • the infiltrate is infiltrated into the sintered alloy so that, in the case of the composition of the sintered steel alloy, complex carbides such as a cobalt-based hard particle phase, a molybdenum-based hard particle phase or a chromium-based hard particle phase are evenly dispersed in a martensite matrix, particularly an intermetallic compound between the manganese and sulfur or the manganese and carbon serves as a lubricant, and particles are refined by means of the silicon or the vanadium.
  • complex carbides such as a cobalt-based hard particle phase, a molybdenum-based hard particle phase or a chromium-based hard particle phase are evenly dispersed in a martensite matrix, particularly an intermetallic compound between the manganese and sulfur or the manganese and carbon serves as a lubricant, and particles are refined by means of the silicon or the vanadium.
  • a reason for infiltrating the infiltrate into the sintered alloy to manufacture the valve seat is to further increase heat resistance at high temperatures, wear resistance at high temperatures and corrosion resistance at contact portions with the intake/exhaust valves.
  • the valve seat manufactured of the composition of the sintered steel alloy (hereinafter, collectively referred to as the composition) is a material of high strength, in which its final product has a hardness (HRA) of at least 71 to 81 and maintains a density (g/cm 3 ) of at least 7.4 to 8.1.
  • HRA hardness
  • g/cm 3 density
  • the cobalt (Co) reacts with iron, molybdenum or carbon to precipitate complex carbides, and thus it is evenly dispersed in the matrix and contributes to wear resistance, while a part of the cobalt is solid-solved in the matrix, so that heat resistance is increased. If a content of the cobalt is less than 10.0 parts by weight, the precipitated particles and the amount of solid solubility of the matrix are decreased, and thus wear resistance and heat resistance deteriorate. If a content of the cobalt is more than 14.0 parts by weight, a matrix metal becomes vulnerable due to an excess of precipitated particles, and thus machinability deteriorates.
  • the molybdenum (Mo) is solid-solved in the matrix or forms an intermetallic compound in a complex carbide state, and thus wear resistance and heat resistance are improved. If a content of the molybdenum is less than 5.0 parts by weight, the amount of solid solubility of the matrix and intermetallic compounds are decreased, and thus wear resistance and heat resistance deteriorate. If a content of the molybdenum is more than 9.0 parts by weight, the amount of solid solubility of the matrix metal is excessive, and thus causes the matrix metal to become vulnerable.
  • the chromium (Cr) is a component that reacts with the carbon within the matrix to form complex carbides and improve wear resistance, and is also solid-solved in the matrix to improve heat resistance.
  • a content thereof may be 1.5 parts by weight to 4.1 parts by weight.
  • a content of the chromium is less than 1.5 parts by weight, an amount of complex carbides is decreased, and thus wear resistance and heat resistance deteriorate. If a content of the chromium is more than 4.1 parts by weight, the amount of solid solubility of the matrix metal is excessive, and thus the product becomes vulnerable.
  • the carbon (C) is a component that is solid-solved or dispersed in the matrix to reinforce the matrix, and that also reacts with the cobalt, chromium or molybdenum to form complex carbides.
  • the carbon (C) performs a function of increasing the strength and hardness of the matrix and also increasing its wear resistance or heat resistance.
  • a content of the carbon is less than 0.7 parts by weight, ferrite is excessively formed in the matrix metal along with pearlite, and thus the matrix is softened and strength and wear resistance deteriorate. If a content of the carbon is more than 1.3 parts by weight, a carbon residue remaining after forming pearlite forms cementite, and thus the matrix steel becomes vulnerable.
  • the manganese (Mn) is a component that reacts with sulfur present in the iron matrix to form MnS and improves self-lubrication. If a content of the manganese is less than 1.0 part by weight, the MnS is formed, and thus a function of self-lubrication deteriorates. If a content of the manganese is more than 1.8 parts by weight, there is concern of segregation in addition to forming of the MnS.
  • the silicon (Si) is a component that is added for the purpose of adjusting and refining a crystal grain of the iron matrix and also improving wear resistance or heat resistance.
  • a content of the silicon may be 0.4 to 1.2 parts by weight.
  • the sulfur (S) is a component that is added into the iron matrix and dispersed in a grain boundary of the matrix in the form of MnS.
  • the MnS is not decomposed as a compound at high temperatures but maintains a stabilized state in a grain boundary of a sintered body after going through a sintering process and deteriorates a friction coefficient in a process of processing the final product, and thus machinability is increased.
  • a content of the sulfur may be 0.2 to 0.8 parts by weight.
  • the manganese and the sulfur may be mixed at a ratio of approximately 6:4 so that efficiency is increased according to forming of the MnS.
  • a content of the MnS (Mn+S) is less than 1.25 parts by weight, it plays an insignificant role in remaining in the matrix of the sintered body. If a content of the MnS (Mn+S) is more than 2.6 parts by weight, the strength of the matrix is weakened, thus causing damage to the valve seat.
  • the vanadium (V) is a component that is added for the purpose of adjusting and refining a crystal grain of the iron matrix and also improving heat resistance.
  • a content of the vanadium may be 0.1 to 0.7 parts by weight. If the vanadium exceeds the required value, the crystal grain is coarsened, thus causing destruction of the final product of the valve seat.
  • the present invention includes: a mixing operation of mixing the composition to manufacture a mixture; a pressurizing operation of pressurizing the mixture; a sintering operation of sintering a resulting body; a low temperature treatment operation of changing residual austenite into martensite; and a heat treatment operation of removing a residual stress therefrom.
  • the mixing operation is an operation of evenly mixing the steel alloy powder, a high speed tool steel powder, a superalloy powder, a manganese sulfide powder, a carbon power and the like in accordance with the required amount of each in a mixer.
  • the pressurizing operation is an operation of compressing a mixture formed in the mixing operation to mold at a density suitable for the valve seat, and is also an operation of pressurizing the mixture at a surface pressure of 6 to 10 tons/cm 2 to improve precision.
  • the sintering operation is an operation of sintering a molded body molded in the pressurizing operation in a temperature range of 1120 ⁇ 20 C. for 30 ⁇ 10 minutes to form a sintered body, and includes an operation of infiltrating 10.0 to 20.0 parts by weight of the copper powder into the sintered body.
  • a sintering temperature is less than 1100° C. in the sintering operation, powder particles are not smoothly dispersed and a matrix structure is weakened. If the sintering temperature is more than 1140° C., a crystal grain is coarsened and mechanical properties deteriorate.
  • sintering is performed in a state in which 10.0 to 20.0 parts by weight of the copper powder are inserted and copper particles are infiltrated into the pores of the matrix structure, so that the strength of the matrix is reinforced and a lubrication role is also increased.
  • the low temperature treatment operation is an operation of changing residual austenite into martensite by cooling the sintered body formed in the sintering operation in a temperature range of ⁇ 120 ⁇ 10° C. for 20 ⁇ 5 minutes, so that the aging of the composition is prevented from being changed, a mechanical property is improved, and structural stability is induced.
  • the heat treatment operation is an operation of tempering a low temperature treated body formed in the low temperature treatment operation to remove a residual stress therefrom, and is also an operation of heating in a temperature range of 600 ⁇ 20 ° C. for 120 ⁇ 10 minutes to give toughness to the matrix structure.
  • an operation of removing foreign materials like burrs from the final product and performing a mechanical processing process such as forging or polishing to obtain a completed product may be included, but description thereof will be omitted herein.
  • the completed product of the valve seat having gone through the operations above, has a hardness (HRA) of about 71 to 81 and a density (g/cm 3 ) of about 7.4 to 8.1, and it can be seen that it provides appropriate hardness and density to be used with liquid fuels and solid fuels.
  • HRA hardness
  • g/cm 3 density
  • Example 1 Example 2
  • Example 3 (parts by weight) (Sample 1) (Sample 2) (Sample 3)
  • Cobalt powder 12 14
  • Molybdenum powder 7 9
  • Chromium powder 3 4.1
  • Carbon powder 1.0
  • 1.3 0.7
  • Manganese powder 1.5 1.8
  • Silicon powder 1.0
  • 1.2 0.4
  • Sulfur powder 0.5 0.8 0.2 Vanadium powder 0.5 0.7 0.1 Copper powder 15 15 15 15 Iron powder 100
  • 100 100
  • a mixture was manufactured by mixing compositions having the composition ratios of Examples 1 to 3 of Table 1 in a mixer, and the mixture was pressurized at a surface pressure of 10 tons/cm 3 , and then sintered and infiltrated at 1120° C. for 30 minutes in a heat treatment furnace.
  • a low temperature treated body was manufactured by quenching a sintered body that was subjected to sintering and copper infiltration in the sintering operation in a temperature range of ⁇ 120° C. for 20 minutes, and then the low temperature treated body was heated in a temperature range of 600° C. for 120 minutes and tempered.
  • Samples 1 to 3 showed similar density and hardness values, and particularly, it can be seen that hard particles and elements for improving processability were evenly distributed within the martensite matrix structure.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Powder Metallurgy (AREA)

Abstract

Disclosed is a sintered steel alloy for wear resistance at high temperatures, which is applied to a valve seat of an internal combustion engine including an automobile. The sintered steel alloy includes: 10.0 to 14.0 parts by weight of cobalt powder; 5.0 to 9.0 parts by weight of molybdenum powder; 1.5 to 4.1 parts by weight of chromium powder; 0.7 to 1.3 parts by weight of carbon powder; 1.0 to 1.8 parts by weight of manganese powder; 0.4 to 1.2 parts by weight of silicon powder; 0.2 to 0.8 parts by weight of sulfur powder; and 0.1 to 0.7 parts by weight of vanadium powder, based on 100 parts by weight of iron powder, and thus a service life of the valve seat is extended.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application claims priority to and the benefit of Korean Patent Application No. 10-2018-0104490, filed on Sep. 3, 2018, the disclosure of which is incorporated herein by reference in its entirety.
  • BACKGROUND 1. Field of the Invention
  • The present invention relates to a sintered steel alloy for wear resistance at high temperatures, which is applied to a valve seat for an internal combustion engine, and more particularly, to a sintered steel alloy for wear resistance at high temperatures, in which a composition of the sintered steel alloy is changed to maximize its heat resistance as well as its wear resistance, and a method of manufacturing a valve seat using the same.
  • 2. Discussion of Related Art
  • In general, a valve seat for an internal combustion engine is a ring-shaped sintered body, which maintains the airtightness of intake/exhaust valves in an opening/closing process of the intake valve and the exhaust valve. As shown in FIG. 1, a valve seat 18 performs a sealing function by contacting head portions of the intake valve and the exhaust valve while the valve seat 18 is inserted into a cylinder head 24.
  • The valve seat 18 contacts the intake/exhaust valves in a closing stroke of the exhaust valve, and performs a function of preventing leakage of exhaust gas in an opening stroke of the exhaust valve. Thus, in sintering the valve seat 18, there is a demand that physical requirements such as wear resistance or heat resistance be sufficient to withstand continuous friction with the intake/exhaust valves and continuous chemical reactions with the exhaust gas.
  • Accordingly, there is much ongoing research on improving the wear resistance and heat resistance of the valve seat. As an example, it is widely known that there is a method of dispersing cobalt-based or chromium-based carbides into an iron matrix or a method of dispersing hard particles in a form of ferro-chromium (Fe—Cr)-based or ferro-molybdenum (Fe—Mo)-based intermetallic compounds.
  • As other examples that improve the wear resistance and heat resistance of the valve seat, it is known that there are an infiltration method using a power metallurgy method of adding various kinds of alloys that have excellent wear resistance and heat resistance into the iron matrix, an addition method of adding hard particles, a manufacturing method by means of controlling of a matrix alloy, a sinter forging method, and the like.
  • However, the internal combustion engine employs a method of combusting a liquid fuel and a gas fuel as well, and a wider variety of forms of combustion products are formed by means of the liquid fuel and the gas fuel, so that there is a need to further reinforce physical conditions such as wear resistance and heat resistance to be able to withstand the combustion products from the liquid fuel and the gas fuel.
  • PRIOR ART DOCUMENTS Patent Documents
  • Patent Document 1 KR10-2004-0025003 A
  • Patent Document 2 KR10-2012-0125817 A
  • Patent Document 3 KR10-0461304 B1
  • SUMMARY OF THE INVENTION
  • The present invention is directed to providing a sintered steel alloy for wear resistance at high temperatures, in which a composition of the sintered steel alloy is changed to maximize its heat resistance as well as its wear resistance and extend a service life of a valve seat, and a method of manufacturing a valve seat using the same.
  • According to one aspect of the present invention, there is provided a sintered alloy including: 10.0 to 14.0 parts by weight of cobalt powder; 5.0 to 9.0 parts by weight of molybdenum powder ; 1.5 to 4.1 parts by weight of chromium powder; 0.7 to 1.3 parts by weight of carbon powder; 1.0 to 1.8 parts by weight of manganese powder; 0.4 to 1.2 parts by weight of silicon powder; 0.2 to 0.8 parts by weight of sulfur powder; and 0.1 to 0.7 parts by weight of vanadium powder, based on 100 parts by weight of iron powder.
  • According to another aspect of the present invention, there is provided a manufacturing method including: a mixing operation of evenly mixing the sintered alloy; a pressurizing operation of pressurizing a resulting mixture formed in the mixing operation at a set pressure; a sintering operation of sintering a resulting molded body formed in the pressurizing operation along with an infiltrate to infiltrate copper into the molded body; a low temperature treatment operation of treating a resulting sintered body formed in the sintering operation at a low temperature to change residual austenite into martensite; and a heat treatment operation of tempering a resulting low temperature treated body formed in the low temperature treatment operation to remove a residual stress therefrom.
  • As described above, the present invention has at least the following effects.
  • Firstly, cobalt, molybdenum, or chromium and a component for increasing strength are added into the composition of the valve seat to form complex carbides, so that the precipitated particles and the amount of solid solubility of an iron matrix for the valve seat are increased and a service life of the valve seat is extended.
  • Secondly, silicon or vanadium is added into the composition of the valve seat to disperse micro-spherical particles into the iron matrix, so that a loss of carbide particles is decreased in an abrasion process of the valve seat, an amount of abrasion is reduced, and a service life of the valve seat is extended.
  • Thirdly, manganese, sulfur and the like are added into the composition of the valve seat to improve self-lubrication, so that the machinability of the valve seat is improved, abrasion is also minimized in a friction process with the intake/exhaust valves, and a service life of the valve seat is further extended.
  • Lastly, a sintering process is performed while copper powder is infiltrated into the composition of the valve seat, so that wear resistance and heat resistance are improved in comparison with an existing valve seat, and the composition of the valve seat may be applied to any internal combustion engine using a gas fuel as well as a liquid fuel.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The above and other objects, features and advantages of the present invention will become more apparent to those of ordinary skill in the art by describing in detail exemplary embodiments thereof with reference to the accompanying drawings, in which:
  • FIG. 1 is a diagram illustrating an installation state of a valve seat according to the related art;
  • FIG. 2 is an optical microscope picture (500× magnification) of Example 1 according to the present invention;
  • FIG. 3 is an optical microscope picture (500× magnification) of Example 2 according to the present invention; and
  • FIG. 4 is an optical microscope picture (500× magnification) of Example 3 according to the present invention.
  • DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
  • Hereinafter, a composition according to the present invention will be described.
  • As shown in FIGS. 2 to 4, a sintered steel alloy according to the present invention represents a sintered alloy applied to an internal combustion engine, and particularly applied to a valve seat that maintains airtightness of intake/exhaust valves in an opening/closing process of the intake valve and the exhaust valve and also minimizes damage in a contact process with combustion products.
  • Although only application of the sintered steel alloy for wear resistance at high temperatures to a valve seat is described here, it can also naturally be applied to a cylinder liner, a valve guide or the like within the same technical scope.
  • The composition of the sintered steel alloy according to the present invention includes a sintered alloy, in which iron powder is a main component, as well as an infiltrate, which is infiltrated into the sintered alloy, and the sintered alloy includes: 10.0 to 14.0 parts by weight of cobalt powder; 5.0 to 9.0 parts by weight of molybdenum powder; 1.5 to 4.1 parts by weight of chromium powder; 0.7 to 1.3 parts by weight of carbon powder; 1.0 to 1.8 parts by weight of manganese powder; 0.4 to 1.2 parts by weight of silicon powder; 0.2 to 0.8 parts by weight of sulfur powder; and 0.1 to 0.7 parts by weight of vanadium powder, based on 100 parts by weight of the iron powder. The infiltrate is copper powder which amounts to 10.0 to 20.0 parts by weight based on 100 parts by weight of the iron powder.
  • At this time, the infiltrate is infiltrated into the sintered alloy so that, in the case of the composition of the sintered steel alloy, complex carbides such as a cobalt-based hard particle phase, a molybdenum-based hard particle phase or a chromium-based hard particle phase are evenly dispersed in a martensite matrix, particularly an intermetallic compound between the manganese and sulfur or the manganese and carbon serves as a lubricant, and particles are refined by means of the silicon or the vanadium.
  • In other words, a reason for infiltrating the infiltrate into the sintered alloy to manufacture the valve seat is to further increase heat resistance at high temperatures, wear resistance at high temperatures and corrosion resistance at contact portions with the intake/exhaust valves.
  • The valve seat manufactured of the composition of the sintered steel alloy (hereinafter, collectively referred to as the composition) is a material of high strength, in which its final product has a hardness (HRA) of at least 71 to 81 and maintains a density (g/cm3) of at least 7.4 to 8.1.
  • In the meantime, the cobalt (Co) reacts with iron, molybdenum or carbon to precipitate complex carbides, and thus it is evenly dispersed in the matrix and contributes to wear resistance, while a part of the cobalt is solid-solved in the matrix, so that heat resistance is increased. If a content of the cobalt is less than 10.0 parts by weight, the precipitated particles and the amount of solid solubility of the matrix are decreased, and thus wear resistance and heat resistance deteriorate. If a content of the cobalt is more than 14.0 parts by weight, a matrix metal becomes vulnerable due to an excess of precipitated particles, and thus machinability deteriorates.
  • Also, the molybdenum (Mo) is solid-solved in the matrix or forms an intermetallic compound in a complex carbide state, and thus wear resistance and heat resistance are improved. If a content of the molybdenum is less than 5.0 parts by weight, the amount of solid solubility of the matrix and intermetallic compounds are decreased, and thus wear resistance and heat resistance deteriorate. If a content of the molybdenum is more than 9.0 parts by weight, the amount of solid solubility of the matrix metal is excessive, and thus causes the matrix metal to become vulnerable.
  • Further, the chromium (Cr) is a component that reacts with the carbon within the matrix to form complex carbides and improve wear resistance, and is also solid-solved in the matrix to improve heat resistance. A content thereof may be 1.5 parts by weight to 4.1 parts by weight.
  • If a content of the chromium is less than 1.5 parts by weight, an amount of complex carbides is decreased, and thus wear resistance and heat resistance deteriorate. If a content of the chromium is more than 4.1 parts by weight, the amount of solid solubility of the matrix metal is excessive, and thus the product becomes vulnerable.
  • Moreover, the carbon (C) is a component that is solid-solved or dispersed in the matrix to reinforce the matrix, and that also reacts with the cobalt, chromium or molybdenum to form complex carbides. The carbon (C) performs a function of increasing the strength and hardness of the matrix and also increasing its wear resistance or heat resistance.
  • If a content of the carbon is less than 0.7 parts by weight, ferrite is excessively formed in the matrix metal along with pearlite, and thus the matrix is softened and strength and wear resistance deteriorate. If a content of the carbon is more than 1.3 parts by weight, a carbon residue remaining after forming pearlite forms cementite, and thus the matrix steel becomes vulnerable.
  • Also, the manganese (Mn) is a component that reacts with sulfur present in the iron matrix to form MnS and improves self-lubrication. If a content of the manganese is less than 1.0 part by weight, the MnS is formed, and thus a function of self-lubrication deteriorates. If a content of the manganese is more than 1.8 parts by weight, there is concern of segregation in addition to forming of the MnS.
  • Further, the silicon (Si) is a component that is added for the purpose of adjusting and refining a crystal grain of the iron matrix and also improving wear resistance or heat resistance. A content of the silicon may be 0.4 to 1.2 parts by weight.
  • Moreover, the sulfur (S) is a component that is added into the iron matrix and dispersed in a grain boundary of the matrix in the form of MnS. The MnS is not decomposed as a compound at high temperatures but maintains a stabilized state in a grain boundary of a sintered body after going through a sintering process and deteriorates a friction coefficient in a process of processing the final product, and thus machinability is increased. In particular, a content of the sulfur may be 0.2 to 0.8 parts by weight.
  • The manganese and the sulfur may be mixed at a ratio of approximately 6:4 so that efficiency is increased according to forming of the MnS.
  • If a content of the MnS (Mn+S) is less than 1.25 parts by weight, it plays an insignificant role in remaining in the matrix of the sintered body. If a content of the MnS (Mn+S) is more than 2.6 parts by weight, the strength of the matrix is weakened, thus causing damage to the valve seat.
  • Also, the vanadium (V) is a component that is added for the purpose of adjusting and refining a crystal grain of the iron matrix and also improving heat resistance. A content of the vanadium may be 0.1 to 0.7 parts by weight. If the vanadium exceeds the required value, the crystal grain is coarsened, thus causing destruction of the final product of the valve seat. Hereinafter, a manufacturing method according to the present invention will be described.
  • First of all, the present invention includes: a mixing operation of mixing the composition to manufacture a mixture; a pressurizing operation of pressurizing the mixture; a sintering operation of sintering a resulting body; a low temperature treatment operation of changing residual austenite into martensite; and a heat treatment operation of removing a residual stress therefrom.
  • Also, the mixing operation is an operation of evenly mixing the steel alloy powder, a high speed tool steel powder, a superalloy powder, a manganese sulfide powder, a carbon power and the like in accordance with the required amount of each in a mixer.
  • Further, the pressurizing operation is an operation of compressing a mixture formed in the mixing operation to mold at a density suitable for the valve seat, and is also an operation of pressurizing the mixture at a surface pressure of 6 to 10 tons/cm2 to improve precision.
  • Moreover, the sintering operation is an operation of sintering a molded body molded in the pressurizing operation in a temperature range of 1120±20 C. for 30±10 minutes to form a sintered body, and includes an operation of infiltrating 10.0 to 20.0 parts by weight of the copper powder into the sintered body.
  • If a sintering temperature is less than 1100° C. in the sintering operation, powder particles are not smoothly dispersed and a matrix structure is weakened. If the sintering temperature is more than 1140° C., a crystal grain is coarsened and mechanical properties deteriorate.
  • In the sintering operation, sintering is performed in a state in which 10.0 to 20.0 parts by weight of the copper powder are inserted and copper particles are infiltrated into the pores of the matrix structure, so that the strength of the matrix is reinforced and a lubrication role is also increased.
  • Also, the low temperature treatment operation is an operation of changing residual austenite into martensite by cooling the sintered body formed in the sintering operation in a temperature range of −120±10° C. for 20±5 minutes, so that the aging of the composition is prevented from being changed, a mechanical property is improved, and structural stability is induced.
  • Further, the heat treatment operation is an operation of tempering a low temperature treated body formed in the low temperature treatment operation to remove a residual stress therefrom, and is also an operation of heating in a temperature range of 600±20 ° C. for 120±10 minutes to give toughness to the matrix structure.
  • Moreover, as a post-processing operation of the heat treatment operation, an operation of removing foreign materials like burrs from the final product and performing a mechanical processing process such as forging or polishing to obtain a completed product may be included, but description thereof will be omitted herein.
  • The completed product of the valve seat, having gone through the operations above, has a hardness (HRA) of about 71 to 81 and a density (g/cm3) of about 7.4 to 8.1, and it can be seen that it provides appropriate hardness and density to be used with liquid fuels and solid fuels.
  • Hereinafter, Examples of the present invention will be described.
  • TABLE 1
    Components Example 1 Example 2 Example 3
    (parts by weight) (Sample 1) (Sample 2) (Sample 3)
    Cobalt powder 12 14 10
    Molybdenum powder 7 9 5
    Chromium powder 3 4.1 1.5
    Carbon powder 1.0 1.3 0.7
    Manganese powder 1.5 1.8 1.0
    Silicon powder 1.0 1.2 0.4
    Sulfur powder 0.5 0.8 0.2
    Vanadium powder 0.5 0.7 0.1
    Copper powder 15 15 15
    Iron powder 100 100 100
  • First of all, a mixture was manufactured by mixing compositions having the composition ratios of Examples 1 to 3 of Table 1 in a mixer, and the mixture was pressurized at a surface pressure of 10 tons/cm3, and then sintered and infiltrated at 1120° C. for 30 minutes in a heat treatment furnace.
  • Then, a low temperature treated body was manufactured by quenching a sintered body that was subjected to sintering and copper infiltration in the sintering operation in a temperature range of −120° C. for 20 minutes, and then the low temperature treated body was heated in a temperature range of 600° C. for 120 minutes and tempered.
  • Then, a heat treated body that was subjected to the heat treatment operation was drawn out, Samples 1 to 3 were manufactured, and then an abrasion loss was measured using an abrasion tester (Rig Tester, nitrogen atmosphere; 0.2 mm Offset; SUH35+Tuff valve, speed: 3,500 rpm, temperature: 350° C., time: 2 hours). From the results, in the case of Examples 1 to 3 (Samples 1 to 3), it can be seen that an overall abrasion loss of the valve and valve seat amounts to 48 μm on average, which is appropriate for a material of the valve seat.
  • In other words, as shown in FIGS. 2 to 4, Samples 1 to 3 showed similar density and hardness values, and particularly, it can be seen that hard particles and elements for improving processability were evenly distributed within the martensite matrix structure.
  • In particular, it can be seen that the wear resistance and heat resistance of the valve seat were increased when the copper alloy was filled into the pores of the matrix structure.
  • As stated above, the present invention is not limited to the exemplary embodiments described above, and it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims, and such modifications fall within the scope of the present invention.

Claims (9)

What is claimed is:
1. A sintered steel alloy for wear resistance at high temperatures, comprising: 10.0 to 14.0 parts by weight of cobalt powder; 5.0 to 9.0 parts by weight of molybdenum powder; 1.5 to 4.1 parts by weight of chromium powder; 0.7 to 1.3 parts by weight of carbon powder; 1.0 to 1.8 parts by weight of manganese powder; 0.4 to 1.2 parts by weight of silicon powder; 0.2 to 0.8 parts by weight of sulfur powder; and 0.1 to 0.7 parts by weight of vanadium powder, based on 100 parts by weight of iron powder.
2. The sintered steel alloy of claim 1, wherein 10.0 to 20.0 parts by weight of copper powder based on 100 parts by weight of the iron powder is further added as an infiltrate into a composition of the sintered steel alloy.
3. A method of manufacturing a valve seat using a sintered steel alloy for wear resistance at high temperatures, the method comprising:
a mixing operation of evenly mixing the sintered steel alloy described in claim 1;
a pressurizing operation of pressurizing a resulting mixture formed in the mixing operation at a set pressure;
a sintering operation of sintering a resulting molded body formed in the pressurizing operation along with the infiltrate described in claim 2 to infiltrate copper into the molded body;
a low temperature treatment operation of treating a resulting sintered body formed in the sintering operation at low temperatures to change residual austenite into martensite; and
a heat treatment operation of tempering a resulting low temperature treated body formed in the low temperature treatment operation to remove a residual stress therefrom.
4. The method of claim 3, wherein the pressurizing operation includes pressurizing the composition of the valve seat at a surface pressure of 6 to 10 tons/cm3.
5. The method of claim 3, wherein a final product after the heat treatment operation has a hardness (HRA) of 71 to 81.
6. The method of claim 3, wherein a final product after the heat treatment operation has a density (g/cm3) of 7.4 to 8.1.
7. The method of claim 3, wherein the molded body is sintered and copper-infiltrated in a temperature range of 1120±20° C. for 30±10 minutes in the sintering operation.
8. The method of claim 3, wherein the low temperature treatment operation includes cooling a sintered body formed in the sintering operation in a temperature range of −120±10° C. for 20±5 minutes.
9. The method of claim 3, wherein the heat treatment operation includes heating a low temperature heated body formed in the low temperature treatment operation in a temperature range of 600±20° C. for 120±10 minutes.
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US11988294B2 (en) 2021-04-29 2024-05-21 L.E. Jones Company Sintered valve seat insert and method of manufacture thereof

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