CN106623904A - Heat-resistant ferrous-based powder metallurgy self-lubricating CNG engine valve seat ring and manufacturing method thereof - Google Patents

Heat-resistant ferrous-based powder metallurgy self-lubricating CNG engine valve seat ring and manufacturing method thereof Download PDF

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Publication number
CN106623904A
CN106623904A CN201611007164.2A CN201611007164A CN106623904A CN 106623904 A CN106623904 A CN 106623904A CN 201611007164 A CN201611007164 A CN 201611007164A CN 106623904 A CN106623904 A CN 106623904A
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China
Prior art keywords
parts
heat
engine valve
based powder
cng engine
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CN201611007164.2A
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Chinese (zh)
Inventor
周以林
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Ma'anshan Hengxin Pressure Reducer Manufacturing Co Ltd
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Ma'anshan Hengxin Pressure Reducer Manufacturing Co Ltd
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Priority to CN201611007164.2A priority Critical patent/CN106623904A/en
Publication of CN106623904A publication Critical patent/CN106623904A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/08—Iron group metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a heat-resistant ferrous-based powder metallurgy self-lubricating CNG engine valve seat ring. The heat-resistant ferrous-based powder metallurgy self-lubricating CNG engine valve seat ring is manufactured by the following raw materials of, by weight, 6.3-6.7 parts of chromium, 4.3-4.7 parts of cobalt, 1.4-1.7 parts of nickel, 1.3-1.6 parts of silicon, 2.2-2.4 parts of praseodymium, 3.1-3.3 parts of tin, 14-16 parts of copper, 1.3-1.7 parts of nano-molybdenum disulfide, 0.5-0.8 part of aluminum hydroxide, 0.4-0.6 part of amino trimethylene phosphonic acid, 0.2-0.3 part of boron nitride, 0.1-0.3 part of ferric citrate, 1-3 parts of carbon fibers, 2-3 parts of quartz powder and 62-66 parts of iron. According to the heat-resistant ferrous-based powder metallurgy self-lubricating CNG engine valve seat ring, a layer of copper film is laid on the surface of modified nano-molybdenum disulfide and serves as a solid lubricant to be added into a base material, meanwhile, the boron nitride, the silicon, the praseodymium, the tin and other components are added, metallic grit phase transition is changed through sintering, infiltration and heat treatment processes, and the manufactured product is resistant to the high temperature of 800 DEG C or above.

Description

A kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers and its system Make method
Technical field
The present invention relates to automobile engine accessory technical field, more particularly to a kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers and preparation method thereof.
Background technology
Compressed natural gas (CNG), liquefied petroleum gas (LPG) and methyl alcohol etc. are environmental protections as the substitute fuel of internal combustion engine With the effective way of reasonable energy utilization.China's natural gas aboundresources, as engine washing fuel, its market prospects is huge. However, using novel energy, auto parts are particularly the applying working condition of engine valve retainer and can change, to its material Propose new requirement.The Valve seat circle of CNG engines is to control the important process portion that combustion gas suction is discharged with waste gas Part, undergoes at high temperature the erosion of air-flow and the high-frequency impact friction of valve, and condition of work is very severe.Once valve retainer By impact wear, cause valve air-tightness to reduce, engine efficiency, and a large amount of rows of harmful components gas will be greatly lowered Put.This requires that CNG engine valve retainers have a higher heat resistance, higher wearability and corrosion resistance.
Conventional valve retainer material includes casting alloy, forged steel product and the big class of powder metallurgy 3.Wherein powder metallurgy gas Seat ring is because having the advantages that less, suitable large batch of production big without cutting, stock utilization height, design freedom.General Properties of Powder Metallurgy Iron-based Material haves the shortcomings that low-density and sponginess, wear out failure easily occurs in use, at present, most often There are two kinds of solutions：One is that addition alloying element forms hard phase, improves the intensity and hardness of material, has been obtained Wearability：Two is the density and performance that material is improved by infiltration process.Document《Preparation technology is to iron-base steam valve base made by powder metallurgy The impact of circle compactness and performance》High-performance Fe-based powder metallurgy valve retainer is prepared for using sintering, infiltration, heat treatment.Grind Study carefully impact of the different process to the hole change of valve retainer, compactness, microscopic structure and mechanical property, determine that valve retainer is caused The optimum process condition of close property.As a result show, using infiltration or raising sintering temperature, the shape that can make hole tends to nodularization, greatly The big quantity and size for reducing hole, hence it is evident that improve the compactness of valve retainer.
Because valve retainer oil-free lubrication in the course of the work, weatherability are poor, service life is short, wear-resisting long-lasting difference, and Studied by way of adding hard particles, self-lubricating additive etc. and being combined using infiltration new technology at present seldom.Document In it is more single only with infiltration new technology, mode, obtained valve retainer idiosome poor toughness, cutting are poor, temperature-change resistance Low, service life is short etc..
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers and preparation method thereof.
The present invention is achieved by the following technical solutions：
A kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers, are prepared by the raw materials in：Chromium 6.3-6.7, cobalt 4.3-4.7, nickel 1.4-1.7, silicon 1.3-1.6, praseodymium 2.2-2.4, tin 3.1-3.3, copper 14-16, nanometer curing Molybdenum 1.3-1.7, aluminium hydroxide 0.5-0.8, ATMP 0.4-0.6, boron nitride 0.2-0.3, ironic citrate 0.1- 0.3rd, carbon fiber 1-3, silica flour 2-3, iron 62-66.
The preparation method of described a kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers, including with Lower step：
（1）Nano molybdenum disulfide is added in the ironic citrate aqueous solution that mass concentration is 5-15%, ultrasonic disperse is uniform, plus Enter ATMP and be heated to 50-70 DEG C, be sufficiently stirred for 12-24 hours, filtration drying；
（2）Copper powder is put into and be brought rapidly up in crucible electrical resistance furnace to being completely melt, add step（1）The stirring of material ultrasonic wave is mixed Even, insulation stands 20-25 minutes, molten metal Jing powder by gas-atomization equipment is obtained into copper clad of the particle diameter below 100 μm and is modified Nano molybdenum disulfide；
（3）By silica flour in 815-905 DEG C of high-temperature calcination 20-30 minute, it is immediately placed in water and is cooled to room temperature ultrasonic disperse 10- 15 minutes, it is spray-dried, in putting into appropriate absolute ethyl alcohol, adds boron nitride, carbon fiber, step（2）40-50 point of material grinding Clock, dries to absolute ethyl alcohol is completely removed, and obtains mixed powder；
（4）By ball milling mixing in iron powder and chromium, cobalt, nickel, silicon, praseodymium, the mixed powder machine of glass putty input, step is added（3）Mixed powder, hydrogen To 50-60 DEG C, stirring 30-40 minutes are vacuum dried heating alumina, are added in mould and are pressed into required form, are given birth to Base；
（5）The copper sheet of above-mentioned green compact and same shape is put in push rod furnace, in 1000-1200 DEG C under the protective atmosphere of hydrogen Sintering and infiltration 1-2 hours, with the water jacket type of cooling room temperature is cooled to；
（6）Valve retainer after the completion of sintering and infiltration is placed in batch-type furnace, 600-700 DEG C is heated to, 20-40 minutes are incubated, Oil quenching is heated to 245-255 DEG C to room temperature, is incubated 50-70 minutes, cooling discharging.
It is an advantage of the invention that：Modified nano molybdenum disulfide surface is covered one layer of copper film and is moistened as solid by the present invention Lubrication prescription is added in matrix material, and density contrast is little, physical and mechanical properties are close, improves its wellability and interface with matrix Bond strength is high, and density is significantly improved, and reduces segregation, while the intensity and frictional behaviour of material is improve, and clad can To play a part of evaporation or the oxidation of protecting kollag to cause from high temperature；Simultaneously the present invention also add boron nitride, silicon, The compositions such as praseodymium, tin, using sintering, infiltration, Technology for Heating Processing metallic phase transformation is changed, and is largely filled with valve retainer Hole, reduces the porosity of valve retainer material, the compactness of valve retainer is improve, so as to improve the tough of valve retainer Property, wearability, thermohardening and compactness, product high temperature resistant of the present invention reaches more than 800 DEG C.
Specific embodiment
A kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers, are prepared by the raw materials in： Chromium 6.3, cobalt 4.3, nickel 1.4, silicon 1.3, praseodymium 2.2, tin 3.1, copper 14, nano molybdenum disulfide 1.3, aluminium hydroxide 0.5, amino trimethylene Methylphosphonic acid 0.4, boron nitride 0.2, ironic citrate 0.1, carbon fiber 1, silica flour 2, iron 62.
The preparation method of described a kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers, including with Lower step：
（1）Nano molybdenum disulfide is added in the ironic citrate aqueous solution that mass concentration is 5-15%, ultrasonic disperse is uniform, plus Enter ATMP and be heated to 50-70 DEG C, be sufficiently stirred for 12-24 hours, filtration drying；
（2）Copper powder is put into and be brought rapidly up in crucible electrical resistance furnace to being completely melt, add step（1）The stirring of material ultrasonic wave is mixed Even, insulation stands 20-25 minutes, molten metal Jing powder by gas-atomization equipment is obtained into copper clad of the particle diameter below 100 μm and is modified Nano molybdenum disulfide；
（3）By silica flour in 815-905 DEG C of high-temperature calcination 20-30 minute, it is immediately placed in water and is cooled to room temperature ultrasonic disperse 10- 15 minutes, it is spray-dried, in putting into appropriate absolute ethyl alcohol, adds boron nitride, carbon fiber, step（2）40-50 point of material grinding Clock, dries to absolute ethyl alcohol is completely removed, and obtains mixed powder；
（4）By ball milling mixing in iron powder and chromium, cobalt, nickel, silicon, praseodymium, the mixed powder machine of glass putty input, step is added（3）Mixed powder, hydrogen To 50-60 DEG C, stirring 30-40 minutes are vacuum dried heating alumina, are added in mould and are pressed into required form, are given birth to Base；
（5）The copper sheet of above-mentioned green compact and same shape is put in push rod furnace, in 1000-1200 DEG C under the protective atmosphere of hydrogen Sintering and infiltration 1-2 hours, with the water jacket type of cooling room temperature is cooled to；
（6）Valve retainer after the completion of sintering and infiltration is placed in batch-type furnace, 600-700 DEG C is heated to, 20-40 minutes are incubated, Oil quenching is heated to 245-255 DEG C to room temperature, is incubated 50-70 minutes, cooling discharging.
There is following technical characteristic using CNG engine valve retainers obtained in the present invention：
（1）Density/(g cm-3)：7.82；
（2）Open porosity/%：0.03；
（3）Hardness/HRC：49；
（4）Maximum load Fmax/kN：2.372；
（5）Coefficient of friction：0.082.

Claims (2)

1. a kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers, it is characterised in that by following weight portion Raw material is made：Chromium 6.3-6.7, cobalt 4.3-4.7, nickel 1.4-1.7, silicon 1.3-1.6, praseodymium 2.2-2.4, tin 3.1-3.3, copper 14-16, Nano molybdenum disulfide 1.3-1.7, aluminium hydroxide 0.5-0.8, ATMP 0.4-0.6, boron nitride 0.2-0.3, lemon Lemon acid iron 0.1-0.3, carbon fiber 1-3, silica flour 2-3, iron 62-66.
2. the making of a kind of heat-resisting ferrous based powder metallurgical self-lubricating CNG engine valve retainers according to claim 1 Method, it is characterised in that comprise the following steps：
（1）Nano molybdenum disulfide is added in the ironic citrate aqueous solution that mass concentration is 5-15%, ultrasonic disperse is uniform, plus Enter ATMP and be heated to 50-70 DEG C, be sufficiently stirred for 12-24 hours, filtration drying；
（2）Copper powder is put into and be brought rapidly up in crucible electrical resistance furnace to being completely melt, add step（1）The stirring of material ultrasonic wave is mixed Even, insulation stands 20-25 minutes, molten metal Jing powder by gas-atomization equipment is obtained into copper clad of the particle diameter below 100 μm and is modified Nano molybdenum disulfide；
（3）By silica flour in 815-905 DEG C of high-temperature calcination 20-30 minute, it is immediately placed in water and is cooled to room temperature ultrasonic disperse 10- 15 minutes, it is spray-dried, in putting into appropriate absolute ethyl alcohol, adds boron nitride, carbon fiber, step（2）40-50 point of material grinding Clock, dries to absolute ethyl alcohol is completely removed, and obtains mixed powder；
（4）By ball milling mixing in iron powder and chromium, cobalt, nickel, silicon, praseodymium, the mixed powder machine of glass putty input, step is added（3）Mixed powder, hydrogen To 50-60 DEG C, stirring 30-40 minutes are vacuum dried heating alumina, are added in mould and are pressed into required form, are given birth to Base；
（5）The copper sheet of above-mentioned green compact and same shape is put in push rod furnace, in 1000-1200 DEG C under the protective atmosphere of hydrogen Sintering and infiltration 1-2 hours, with the water jacket type of cooling room temperature is cooled to；
（6）Valve retainer after the completion of sintering and infiltration is placed in batch-type furnace, 600-700 DEG C is heated to, 20-40 minutes are incubated, Oil quenching is heated to 245-255 DEG C to room temperature, is incubated 50-70 minutes, cooling discharging.
CN201611007164.2A 2016-11-16 2016-11-16 Heat-resistant ferrous-based powder metallurgy self-lubricating CNG engine valve seat ring and manufacturing method thereof Pending CN106623904A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101634238A (en) * 2009-08-31 2010-01-27 桐城市汽车部件有限公司 Temperature-pressure-die wall lubrication valve seat containing rare earth powder metallurgy and manufacturing method thereof
CN103537695A (en) * 2013-10-11 2014-01-29 芜湖市鸿坤汽车零部件有限公司 Powder metallurgy valve seat ring and manufacturing method thereof
CN103551578A (en) * 2013-10-11 2014-02-05 芜湖市鸿坤汽车零部件有限公司 Power metallurgy iron-based engine valve seat and production method thereof
CN103567433A (en) * 2013-10-10 2014-02-12 铜陵国方水暖科技有限责任公司 Powder metallurgy valve seat and preparation method thereof
CN103589967A (en) * 2013-10-23 2014-02-19 桐城市汽车部件有限公司 Rare earth-containing powder metallurgy natural gas engine valve seat ring
CN104399966A (en) * 2014-10-27 2015-03-11 奚杰 Powder metallurgy valve seat containing nano Fe
CN106077609A (en) * 2016-06-15 2016-11-09 张荣斌 High tenacity iron-base steam valve base made by powder metallurgy

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101634238A (en) * 2009-08-31 2010-01-27 桐城市汽车部件有限公司 Temperature-pressure-die wall lubrication valve seat containing rare earth powder metallurgy and manufacturing method thereof
CN103567433A (en) * 2013-10-10 2014-02-12 铜陵国方水暖科技有限责任公司 Powder metallurgy valve seat and preparation method thereof
CN103537695A (en) * 2013-10-11 2014-01-29 芜湖市鸿坤汽车零部件有限公司 Powder metallurgy valve seat ring and manufacturing method thereof
CN103551578A (en) * 2013-10-11 2014-02-05 芜湖市鸿坤汽车零部件有限公司 Power metallurgy iron-based engine valve seat and production method thereof
CN103589967A (en) * 2013-10-23 2014-02-19 桐城市汽车部件有限公司 Rare earth-containing powder metallurgy natural gas engine valve seat ring
CN104399966A (en) * 2014-10-27 2015-03-11 奚杰 Powder metallurgy valve seat containing nano Fe
CN106077609A (en) * 2016-06-15 2016-11-09 张荣斌 High tenacity iron-base steam valve base made by powder metallurgy

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Application publication date: 20170510