US3918923A - Wear resistant sintered alloy - Google Patents

Wear resistant sintered alloy Download PDF

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Publication number
US3918923A
US3918923A US382307A US38230773A US3918923A US 3918923 A US3918923 A US 3918923A US 382307 A US382307 A US 382307A US 38230773 A US38230773 A US 38230773A US 3918923 A US3918923 A US 3918923A
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Prior art keywords
sulfide
alloy
metal
iron
sintered
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US382307A
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English (en)
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Hiroshi Inoue
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Riken Piston Ring Industrial Co Ltd
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Riken Piston Ring Industrial Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0221—Using a mixture of prealloyed powders or a master alloy comprising S or a sulfur compound
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01C—ROTARY-PISTON OR OSCILLATING-PISTON MACHINES OR ENGINES
    • F01C19/00—Sealing arrangements in rotary-piston machines or engines
    • F01C19/005—Structure and composition of sealing elements such as sealing strips, sealing rings and the like; Coating of these elements

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  • ABSTRACT An iron base sintered alloy having high wear resistance produced in a feasible and effective way. provided by compounding molybdenum disulfide or the like metal sulfide having its melting point higher than the sintering temperature of the alloy.
  • Sulphur in the sulfide forms iron sulfide which improves wear resisting property of the alloy. while. metallic component of the sulfide diffuses throughout the base metal and serves to enhance the strength of matrix.
  • FIGJA FIGJB FIG.2A FIG.2B
  • FIG.2C FIG.2D
  • the present invention relates to wear resistant sintered alloy suitable for high speed sliding members or the like.
  • cast iron of pearlitic structure has been used widely as a material of such sliding members. It is considered that the self-lubricating and oil retaining properties of graphite itself contained in the cast iron, together with pearlitic structure of the matrix, make the material wear resistant. Therefore, wear resistance of such cast iron will be increased by increasing graphite content, but there is a limit for the carbon content of cast iron, and it is difficult to make the content of free graphite more than 3%.
  • sintered alloy obtained by the powder metallurgical process is porous and has good oil retaining or holding property. Therefore, excellent wear resistant material would be obtained according to the powder metallurgical process by adding some of the elements which increase wear resisting property of the material.
  • an object of the present invention is to provide a sintered alloy having high wear resistance produced in a more feasible and effective process.
  • Another object of the present invention is to provide a sintered alloy suitable for apex seals of rotary piston engine.
  • a sintered alloy made by a process comprising the steps of preparing powder mixture by weight of 1.0-1.8% carbon, (LS-2.0% chromium, 0.5-l.0% nickel, 2.0-8.0% metal sulfide or sulfides and rest of iron, forming said powder mixture by compressing, and sintering said formed powder mixture, wherein said metal sulfide or sulfides having melting point higher than sintering temperature of said formed powder mixture.
  • Metallic component of the sulfide diffuses into the base metal and serves to enhance the strength of matrix.
  • the alloy is particularly suitable for the apex seal of rotary piston engine, and capable of forming to its shape precisely by machining.
  • FIGS. HA) and KB) are micrographs (X 400 X 1.5) showing the structures of one example of the sintered alloys according to the present invention, in which FIG. 1(A) is as polished and FIG. 1(B) is as polished and etched by 2% HNO; alcoholic solution.
  • FIGS. 2(A)( D) are photographs taken by the electron microprobe analysis, in which,
  • FIG. 2(A) shows absorbed electron image
  • FIG. 2(B) shows L -characteristic X-ray image of molybdenum
  • FIGS. 2(C) and (D) show K, -characteristic X-ray images of sulphur and iron, respectively.
  • FIG. 3 is a graph illustrating the variation of tensile strength of the alloy according to the present invention in relationship with different molybdenum disulfide contents.
  • FIG. 4 is a graph illustrating the amount of wear of apex seal made of the alloy according to the present invention in comparison with those made of molybdenum-copper-cast iron, graphite and sulphurized sintered alloy respectively, after the actual engine test.
  • chromium under 100 mesh ferrochromium containing 60% chromium by weight
  • molybdenum disulfide M08 powder of 10 microns in average size.
  • the mixture was compressed under 4 ton/cm pressure to form X 10 X 6 mm size specimens with density of 6.6 gram/cm.
  • the formed specimens were then sintered at 1,120C for 30 minutes in a prepared atmosphere of RX gas of 24% CO, 31% H and 45% N in average composition and 0C dew point.
  • the RX gas here means reducing gas mixture obtained by modifying hydrocarbon gases.
  • specimens were cooled to 500C over 40 minutes, and then cooled in furnace to room temperature.
  • Density of the sintered specimens was 6.0 gram/cm.
  • FIG. 1 Microstructures of the specimen are shown in FIG. 1.
  • FIG. 1(A) is a micrograph of specimen as polished
  • FIG. 1(B) is a micrograph of the same specimen etched by 2% I-INO; alcoholic solution, wherein black portions indicate pores, grey portions indicate sulfides, white portions located at the grain boundaries indicate free cementites and matrix is pearlite.
  • FIGS. 2 show photographs taken by the electron microprobe analysis, wherein FIG. 2(A) indicates absorbed electron image showing the region including sulfide, FIG. 2(B) indicates L a characteristic X-ray image of molybdenum, FIG. 2(C) indicates K a characteristic X-ray image of sulphur and FIG. 2(D) indicates K or characteristic X-ray image of iron.
  • the sulfide formed is iron sulfide and molybdenum does not remain in the sulfide, but diffuses uniformly into the matrix.
  • FIG. 3 is a graph indicating tensile strength of the sintered alloy made by the process mentioned above, but changing the amount of molybdenum disulfide additron.
  • the tensile strength decreases with an increase of amount of molybdenum disulfide, but it will retains about 13 kg/mm at 8% molybdenum disulfide addition, which strength would be enough for the practical use.
  • Samples obtained by the above mentioned process were machined to the shape of apex seal for rotary piston engine and mounted on a rotary piston and assembled in the center housing having a chromium plated trochoidal inner surface, and subjected to 300 hours actual engine test.
  • No. 1 in FIG. 4 shows the wear amount of the tested apex seals.
  • No. 2 and No. 3 show the wear amount of seals each made of molybdenum-copper-cast iron and graphite respectively, both were tested for 100 hours.
  • No. 4 shows the wear amount of apex seals made by the similar process as No. 1, except that in this case molybdenum was added in the form of ferromolybdenum containing 60% molybdenum and the sintered alloy was thereafter gas sulphurized. Running test in this case was performed for 300 hours.
  • Test results show that the apex seals according to the present invention is extremely excellent in wear resistance as compared with those of the other three materials. Wear of the cylinder wall after the test was practically negligible small except the case of No. 2 in which wavelike wears of about 8 micron depth were observed on the wall surface.
  • carbon is a basic element which imparts wear resistance and mechanical strength to the alloy. It makes the matrix pearlitic, further precipitates free cementite to make the alloy endurable against hard sliding mating 3118. p Carbon content of less than 1% will not be sufficient for such purposes, but the content of more than 1.8% would rather deteriorate the mechanical properties because of the precipitation of excessive cementite.
  • Chromium increases mechanical strength and wear resistance of the alloy, but it is not preferable to contain chromium more than 2%, because the alloy becomes too hard due to increase of chromium carbide content.
  • Nickel improves the alloy structure and increases mechanical strength and wear resistance. However, it requires considerably high temperature to difiuse nickel into the matrix uniformly. Therefore, it is preferable to limit nickel content to less than 1% for the present sintering temperature.
  • the metal sulfide which is considered as a carrier of the sulphur into the alloy
  • sulfide or sulfides of such metals as aluminium, chromium, cobalt, tungsten, copper, lead and molybdenum may be recommended for the use in consideration of its melting point, affinity of each metal to sulphur comparing to that of iron, and the effect of each metal on the mechanical properties of the alloy.
  • lf melting point of a metal sulfide is lower than the sintering temperature, sulphur may come out of the alloy and cause not only decrease of sulphur content but contamination of the sintering atmospheric gases, so that it is necessary that the melting point of metal sulfide is higher than the sintering temperature of usual iron base sintered alloy which is approximately 1050 ll50C.
  • the quantity of metal sulfide prefferably to be added to less than 8% from the reason mainly of the adverse effect on mechanical strength of the alloy as shown in FIG. 3, but in case of less than 0.5%, it has little effect on wear resisting property, and it is recommended to add more than 2% to retain remarkable effect even when mechanical parts are used under severe conditions.
  • the alloy of the present invention is porous and has good oil retaining property. Moreover, a higher proportion of iron sulfide of high wear resisting property is easily formed within the base metal which itself is wear resistant, without any problems of such as harmful gas generation. Further, metallic component of the metal sulfide diffuses into the base metal and serves to enhance the strength of matrix.
  • the alloy of high wear resistance and good oil retaining property and still retaining enough mechanical strength may be obtained in a feasible and effective way.
  • the alloy is not only suitable in use for the ordinary sliding mechanical parts, but is also particularly usable for the members used under severe conditions, like the apex seal of rotary piston engine, in which the breaking of lubricating oil film may occur due to very high speed sliding at high ambient temperature.
  • many of the metal sulfides used in the present invention have excellent selflubricating property, so that the products of high compressed density may be obtained with such sulfides even under less compressive load and with less additional lubricant at the step of forming, and this may also enable the use of existing equipments.
  • the sulfide may also improve the machinability of sintered alloy which heretofore has been considered as inferior.
  • a method of preparing a wear-resistant iron-base alloy comprising the steps of:
  • step of sintering comprises heating said form at l,lC for 30 minutes in a reducing gas atmosphere.
  • a wear resistant simered alloy prepared f a said one or more metal sulfides comprises molybdenum mixture of powders comprising: 1 disulfide- 1.0-1.s% carbon, 0.s-2.0% chromium, (LS-1.0%)

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
US382307A 1972-08-16 1973-07-25 Wear resistant sintered alloy Expired - Lifetime US3918923A (en)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4204031A (en) * 1976-12-06 1980-05-20 Riken Corporation Iron-base sintered alloy for valve seat and its manufacture
US4233073A (en) * 1977-05-02 1980-11-11 Riken Piston Ring Industrial Co., Ltd. Iron-base sintered alloy for valve seat and method of making the same
US4261741A (en) * 1977-11-07 1981-04-14 Centre Stephanois De Recherches Mecaniques Hydromecanique Et Frottement Antifriction alloy
US4491477A (en) * 1981-08-27 1985-01-01 Toyota Jidosha Kabushiki Kaisha Anti-wear sintered alloy and manufacturing process thereof
DE3413593C1 (de) * 1984-04-11 1985-11-07 Bleistahl GmbH, 5802 Wetter Verfahren zur Herstellung von Ventilsitzringen
EP0438025A2 (en) * 1990-01-16 1991-07-24 Carrier Corporation Method and apparatus for reducing scroll compressor tip leakage
US5133652A (en) * 1989-11-17 1992-07-28 Matsushita Electric Industrial Co., Ltd. Rotary compressor having an aluminum body cast around a sintered liner
US5403371A (en) * 1990-05-14 1995-04-04 Hoganas Ab Iron-based powder, component made thereof, and method of making the component
US5869195A (en) * 1997-01-03 1999-02-09 Exxon Research And Engineering Company Corrosion resistant carbon steel
WO2000000656A1 (es) * 1998-06-30 2000-01-06 Aplicaciones De Metales Sinterizados, Sa Material compuesto de alta resistencia al desgaste y piezas obtenidas con el mismo
US6402488B2 (en) * 2000-01-31 2002-06-11 Sumitomo Electric Industries, Ltd. Oil pump
EP1347067A1 (en) * 2002-03-12 2003-09-24 Kabushiki Kaisha Riken Iron-based sintered alloy for use as valve seat and its production method
US20070065330A1 (en) * 2005-09-22 2007-03-22 C2C Technologies, Inc. Dynamic seal
US20070259199A1 (en) * 2003-05-14 2007-11-08 Volker Arnhold Oil pump
US20080213117A1 (en) * 2005-02-22 2008-09-04 Mitsubishi Materials Pmg Corporation Pump Rotor
US20130084203A1 (en) * 2011-09-30 2013-04-04 Hitachi Powdered Metals Co., Ltd. Iron-based sintered sliding member and production method therefor
EP2781283A1 (en) * 2013-03-19 2014-09-24 Hitachi Chemical Company, Ltd. Iron base sintered sliding member and method for producing same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2557862A (en) * 1947-11-19 1951-06-19 Armco Steel Corp Internal-combustion engine valve
US3177564A (en) * 1962-03-28 1965-04-13 Gert Deventer Fabricating self-lubricating articles
US3350178A (en) * 1963-05-14 1967-10-31 Wall Colmonoy Corp Sealing device
US3692515A (en) * 1968-07-30 1972-09-19 Latrobe Steel Co Ferrous alloys and abrasion resistant articles thereof
US3705020A (en) * 1971-02-02 1972-12-05 Lasalle Steel Co Metals having improved machinability and method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2557862A (en) * 1947-11-19 1951-06-19 Armco Steel Corp Internal-combustion engine valve
US3177564A (en) * 1962-03-28 1965-04-13 Gert Deventer Fabricating self-lubricating articles
US3350178A (en) * 1963-05-14 1967-10-31 Wall Colmonoy Corp Sealing device
US3692515A (en) * 1968-07-30 1972-09-19 Latrobe Steel Co Ferrous alloys and abrasion resistant articles thereof
US3705020A (en) * 1971-02-02 1972-12-05 Lasalle Steel Co Metals having improved machinability and method

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4204031A (en) * 1976-12-06 1980-05-20 Riken Corporation Iron-base sintered alloy for valve seat and its manufacture
US4233073A (en) * 1977-05-02 1980-11-11 Riken Piston Ring Industrial Co., Ltd. Iron-base sintered alloy for valve seat and method of making the same
US4261741A (en) * 1977-11-07 1981-04-14 Centre Stephanois De Recherches Mecaniques Hydromecanique Et Frottement Antifriction alloy
US4491477A (en) * 1981-08-27 1985-01-01 Toyota Jidosha Kabushiki Kaisha Anti-wear sintered alloy and manufacturing process thereof
DE3413593C1 (de) * 1984-04-11 1985-11-07 Bleistahl GmbH, 5802 Wetter Verfahren zur Herstellung von Ventilsitzringen
US4599110A (en) * 1984-04-11 1986-07-08 Bleistahl G.M.B.H. Process for the production of valve seat rings
US5133652A (en) * 1989-11-17 1992-07-28 Matsushita Electric Industrial Co., Ltd. Rotary compressor having an aluminum body cast around a sintered liner
EP0438025A2 (en) * 1990-01-16 1991-07-24 Carrier Corporation Method and apparatus for reducing scroll compressor tip leakage
EP0438025A3 (en) * 1990-01-16 1993-04-07 Carrier Corporation Method and apparatus for reducing scroll compressor tip leakage
US5403371A (en) * 1990-05-14 1995-04-04 Hoganas Ab Iron-based powder, component made thereof, and method of making the component
US5869195A (en) * 1997-01-03 1999-02-09 Exxon Research And Engineering Company Corrosion resistant carbon steel
WO2000000656A1 (es) * 1998-06-30 2000-01-06 Aplicaciones De Metales Sinterizados, Sa Material compuesto de alta resistencia al desgaste y piezas obtenidas con el mismo
US6402488B2 (en) * 2000-01-31 2002-06-11 Sumitomo Electric Industries, Ltd. Oil pump
EP1347067A1 (en) * 2002-03-12 2003-09-24 Kabushiki Kaisha Riken Iron-based sintered alloy for use as valve seat and its production method
US20030230164A1 (en) * 2002-03-12 2003-12-18 Hiroji Henmi Iron-based sintered alloy for use as valve seat and its production method
US6802883B2 (en) 2002-03-12 2004-10-12 Kabushiki Kaisha Riken Iron-based sintered alloy for use as valve seat and its production method
US20070259199A1 (en) * 2003-05-14 2007-11-08 Volker Arnhold Oil pump
US20080213117A1 (en) * 2005-02-22 2008-09-04 Mitsubishi Materials Pmg Corporation Pump Rotor
US7632083B2 (en) * 2005-02-22 2009-12-15 Mitsubishi Materials Pmg Corp. Anti-galling pump rotor for an internal gear pump
US20070065330A1 (en) * 2005-09-22 2007-03-22 C2C Technologies, Inc. Dynamic seal
US20130084203A1 (en) * 2011-09-30 2013-04-04 Hitachi Powdered Metals Co., Ltd. Iron-based sintered sliding member and production method therefor
US9637811B2 (en) * 2011-09-30 2017-05-02 Hitachi Powdered Metals Co., Ltd. Iron-based sintered sliding member and production method therefor
EP2781283A1 (en) * 2013-03-19 2014-09-24 Hitachi Chemical Company, Ltd. Iron base sintered sliding member and method for producing same
US9744591B2 (en) 2013-03-19 2017-08-29 Hitachi Chemical Company, Ltd. Iron base sintered sliding member and method for producing same

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