EP0946775B1 - Metallpulvermischung auf eisenbasis und damit hergestelltes bauteil - Google Patents

Metallpulvermischung auf eisenbasis und damit hergestelltes bauteil Download PDF

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Publication number
EP0946775B1
EP0946775B1 EP97939050A EP97939050A EP0946775B1 EP 0946775 B1 EP0946775 B1 EP 0946775B1 EP 97939050 A EP97939050 A EP 97939050A EP 97939050 A EP97939050 A EP 97939050A EP 0946775 B1 EP0946775 B1 EP 0946775B1
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EP
European Patent Office
Prior art keywords
powder
weight
constituent
mixture
sintering
Prior art date
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Expired - Lifetime
Application number
EP97939050A
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English (en)
French (fr)
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EP0946775A1 (de
Inventor
Paritosh Maulik
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Federal Mogul Coventry Ltd
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Federal Mogul Sintered Products Ltd
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    • 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
    • F01L1/00—Valve-gear or valve arrangements, e.g. lift-valve gear
    • F01L1/12—Transmitting gear between valve drive and valve
    • F01L1/14—Tappets; Push rods
    • F01L1/16—Silencing impact; Reducing wear
    • 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
    • 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
    • C22C33/0214—Using a mixture of prealloyed powders or a master alloy comprising P or a phosphorus compound
    • 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
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making 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%
    • C22C33/0285—Making 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%

Definitions

  • This invention is concerned with iron-based powders which can be compacted and sintered to form components.
  • the invention is concerned with powders for forming components in a cost effective way, the components having high wear resistance and high resistance to Hertzian stress, ie the contact stress which acts when elastic contact is made between two bodies whose geometries are defined by circular arcs. Such stresses are experienced, eg, when components make rolling contact with one another.
  • An example of such a component is a roller follower in the valve train of an internal combustion engine in which the roller follower, instead of the more common sliding tappet, engages a cam lobe.
  • the invention is also concerned with components made from such powders.
  • WO 91/18123 describes an iron-based powder which contains 3 to 15% by weight of molybdenum and/or 3 to 20% by weight of tungsten. The powder also comprises 0.2 to 1% by weight of phosphorus and 0.5 to 1.5% by weight of carbon. This powder is stated to enable high density and hardness to be achieved. The phosphorus and carbon are added, as a mixture of Fe 3 P and graphite powder.
  • WO 95/32827 describes an iron-based powder which contains 0.6 to 2.0% of molybdenum, 0.2 to 0.8% of phosphorus, and 0.2 to 0.8% by weight of carbon.
  • EP 0 480 495 A describes a sintered component made from powder mixture of iron powder, manganese sulphide, graphite, and a pre-alloyed powder comprising 8 to 12% by weight chromium, 0.5 to 3% by weight molybdenum, 1.5% by weight maximum vanadium, 0.2% by weight maximum carbon, 2% by weight maximum impurities and the balance iron, the carbon level in the mixture being up to 1.5% by weight.
  • the invention provides a powder mixture suitable for use in a compaction and sintering process, characterised in that the mixture comprises a first constituent which is substantially carbon-free and is formed by one or more alloyed powders, the first constituent having a composition lying in the range expressed in % by weight: 8 to 12 chromium, 0.5 to 3 molybdenum, optionally up to a total of 10 of at least one metal selected from vanadium, cobalt and tungsten, a maximum of 2 of other materials including impurities, and the balance iron, the mixture also comprising a second constituent formed by sufficient carbon powder to bring the total carbon content of the mixture to 1.5 to 3.0% by weight, and a third constituent formed by sufficient ferrophosphorus powder to bring the total phosphorus content of the mixture to 0.1 to 0.5% by weight.
  • a powder according to the invention can be cold compacted in a single step to form a green body, eg at compaction pressures of less than 800 MPa, and can be sintered in a dissociated ammonia or other protective atmosphere in excess of 1130°C to a density of about 7.1 to 7.4 Mgm -3 .
  • the components so produced have a high hardness (above 60 HRA).
  • Rolling contact fatigue tests in which the components are subjected to Hertzian stress enable a calculation of the endurance limit to be made, the endurance limit being the safe stress level which the component can endure rolling contact for 200 million cycles.
  • Components according to the invention were found to be capable of enduring stresses in the vicinity of 2,000 MPa. Conventional materials made by a one step cold or warm compaction and sintering route have an endurance limit below 1800 MPa (or in most cases below 1500 MPa).
  • the term "substantially carbon-free" is intended to mean that the constituent contain less than 0.1% by weight of carbons.
  • said first constituent may be formed from a single alloy powder, having the composition stated, or may be formed by two or more alloy powders which in combination have the composition stated.
  • Such alloy powders are well-known and are produced by water atomisation. Where one or more of vanadium, cobalt and tungsten is included, this may form 5 to 10% by weight of the first constituent.
  • the chromium range (which is preferably 9 to 11% by weight) is selected to give strength without greatly reducing compressibility.
  • the molybdenum range is selected to be high enough to give sufficient strength but not so high as to cause brittleness (the molybdenum range is preferably 1.5 to 2.5% by weight).
  • the phosphorus range is selected to be high enough for sufficient densification but not so high as effect shape or size control or cause brittleness.
  • the carbon range is selected to be high enough for good hardness but not so high that control of the sintered structure is lost, resulting in brittleness, or loss of size or shape control during sintering.
  • the invention gives a low cost route for achieving the object of the invention. Where additional wear resistance is required, the option of including one or more of vanadium, cobalt and tungsten in the first constituent is selected.
  • a powder mixture according to the invention may also optionally have a solid lubricant and/or a machining aid added thereto.
  • a solid lubricant and/or a machining aid examples include mica, hexagonal boron nitride, manganese sulphide, molybdenum disulphide, calcium fluoride, and barium fluoride. It is, of course, necessary that such additions, either due to coarse particle size or excessive volume fraction, do not act as stress raisers locally.
  • the invention also provides a sintered component made by compacting a powder mixture according to the invention and sintering it.
  • a component may, for example, be a cam lobe, a tappet shim, or a roller.
  • said component has an endurance limit in excess of 1800 MPa.
  • the component can be hydrogen annealed, if desired.
  • the invention also provides a method of manufacturing a component comprising cold compacting a powder mixture according to the invention in a one step operation, and sintering.
  • the cold compacting may be at a pressure of less than 800 MPa.
  • the sintering may be one step carried out in a continuous sintering furnace.
  • the drawing is a graphical representation of the results of tests carried out on components made according to Examples 1 and 2 and on components made from comparative powder mixtures.
  • a powder mixture having three constituents was prepared.
  • the first constituent was a substantially carbon-free base alloy powder having a nominal composition of 10% by weight chromium, 2% by weight molybdenum, and a balance of iron except for inevitable impurities.
  • the second constituent was graphite powder and the third constituent ferrophosphorus powder, ie an alloy of iron and phosphorus, comprising 26% by weight of phosphorus.
  • the constituents were mixed in the proportions by weight 96.5:2:1.5 giving a powder mixture having the approximate composition by weight: 9.7% chromium, 1.9% molybdenum, 2% carbon, 0.4% phosphorus, balance iron and inevitable impurities.
  • a standard fugitive compaction lubricant was added to the powder mixture.
  • the powder was compacted at a pressure of 620 MPa and sintered in a conventional continuous sintering furnace at a temperature in excess of 1130°C in a dissociated NH 3 atmosphere to make components in the form of 23mm diameter cylinders 10mm thick.
  • the density of the green body was 6.3 Mgm -3 and that of the final component was 7.4 Mgm -3 .
  • the components had a hardness of 74 HRA. No subsequent heat treatments or surface treatments were applied.
  • the components were ground to a 20mm outside diameter and a surface roughness of 0.4 microns Ra.
  • Four of the components were subjected to a rolling contact fatigue test to establish their endurance.
  • the samples were tested by being loaded between two tungsten carbide rollers and lubricated with oil.
  • the stress applied varied between 2000 and 2200 MPa and the rotation was at 7000 rpm.
  • the test machine was operated in such a way that it ran for 10 8 cycles or until a critical level of pitting or surface damage in the component caused vibration beyond a certain threshold whereupon a trip switches off the machine.
  • the results obtained with the components made in Example 1 are represented by triangles, with the X-axis being a log scale of number of cycles to failure and the Y- axis being a linear scale of Hertzian stress in MPa. Specifically, one component was stressed at 2223 MPa and failed at 15.62 million cycles, the second was stressed at 2150 MPa and failed at 17.39 million cycles, the third was stressed at 2071 MPa and failed at 32.97 million cycles, and the fourth was stressed at 2015 MPa and failed at 28.64 million cycles. The plot obtained for stress against number of cycles enables the endurance limit to be calculated and this was found to be in the vicinity of 2000 MPa.
  • Example 2 was the same as example 1 except that the constituents were mixed in the proportions by weight 96:2.5:1.5 giving a powder mixture having the approximate composition by weight: 9.6% chromium, 1.9% molybdenum, 2.5% carbon, 0.4% phosphorus, balance iron and inevitable impurities.
  • the density of the green body was 6.4 Mgm -3 and that of the final component was 7.4 Mgm -3 .
  • the components had a hardness of 75 HRA. No subsequent heat treatments or surface treatments were applied.
  • the drawing shows the test results for the components made according to Example 2 as octagons. Specifically, one component was stressed at 2214 MPa and failed at 8.4 million cycles, the second was stressed at 2132 MPa and failed at 8.82 million cycles, the third was stressed at 2074 MPa and failed at 17.22 million cycles, and the fourth was stressed at 2013 MPa and reached 100 million cycles without failure (this point is plotted on the 100 million line). The plot obtained for stress against number of cycles enables the endurance limit to be calculated and this was found to be in the vicinity of 2000 MPa.
  • the drawing also shows the results of identical tests for components made according to four comparative examples.
  • comparative example 1 represented by stars in the drawing
  • components were made by warm compaction and sintering from a powder containing 1.8% by weight nickel, 0.5% by weight molybdenum, and 1.5% by weight copper as an alloy with iron, and 0.5% by weight carbon added as graphite.
  • the results were: stress 1361 MPa, failures at 7.14 and 7.06 million cycles (shown as one point on the drawing as the points are substantially at the same location); stress 1241 MPa, failure at 13.02 million cycles; and stress 1463 MPa, failure at 4.54 million cycles.
  • comparative example 2 represented by the squares in the drawing
  • components were made by warm compaction and sintering from a powder containing 1.5% by weight molybdenum as an alloy with iron, and 0.5% by weight carbon added as graphite. Specifically, the results were: stress 1430 MPa, failures at 5.54, 4.03, 3.78 and 3.53 million cycles (three of these points merge in the drawing).
  • comparative example 3 represented by the crosses in the drawing
  • components were made by warm compaction and sintering from a powder containing 1.8% by weight nickel, 0.5% by weight molybdenum, and 1.5% by weight copper as an alloy with iron, and 0.5% by weight carbon added as graphite.
  • the components were given an additional carburising surface treatment (thus, giving them an advantage relative to the components of Examples 1 and 2).
  • the results were: stress 1900 MPa, failure at 3.53 million cycles; stress 1772 MPa, failure at 73.16 million cycles; stress 1670 MPa, failure at 56.95 million cycles; and stress 1593 MPa, reached 100 million cycles without failure (this point is plotted on the 100 million cycle line).
  • comparative example 4 represented by the diamonds in the drawing
  • components were made by warm compaction and sintering from a powder containing 1.5% by weight molybdenum as an alloy with iron, and 0.5% by weight carbon added as graphite. After sintering, the components were given an additional carburising surface treatment (thus, giving them an advantage relative to the components of Examples 1 and 2). Specifically, the results were: stress 2075 MPa, failure at 26.21 million cycles; stress 2019 MPa, failure at 32.51 million cycles; stress 1862 MPa, failure at 92.48 million cycles; and stress 1674 MPa, reached 100 million cycles without failure (this point is plotted on the 100 million cycle line).

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

Claims (9)

  1. Pulvergemisch, das zur Verwendung in einem Verdichtungs- und Sinterverfahren geeignet ist, dadurch gekennzeichnet, dass das Gemisch einen ersten Bestandteil umfasst, der im wesentlichen kohlenstofffrei ist, indem er weniger als 0,1% C enthält, und aus einem oder mehreren Legierungspulvern aufgebaut ist, wobei der erste Bestandteil eine Zusammensetzung aufweist, die ausgedrückt in Gew.-% im Bereich von 8 bis 12 Chrom, 0,5 bis 3 Molybdän, gegebenenfalls insgesamt bis zu 10 von mindestens einem Metall, ausgewählt aus Vanadium, Cobalt und Wolfram, maximal 2 von anderen Materialien einschließlich Verunreinigungen und der Rest Eisen, liegt, wobei das Gemisch auch einen zweiten Bestandteil, der aus ausreichend Kohlenstoffpulver aufgebaut ist, um den Gesamtkohlenstoffgehalt des Gemischs auf 1,5 bis 3,0 Gew.-% zu bringen, und einen dritten Bestandteil umfasst, der aus ausreichend Eisenphosphorpulver aufgebaut ist, um den Gesamtphosphorgehalt des Gemischs auf 0,1 bis 0,5 Gew.-% zu bringen.
  2. Pulvergemisch nach Anspruch 1, dadurch gekennzeichnet, dass der erste Bestandteil aus einem einzigen Legierungspulver aufgebaut ist, welches die angegebene Zusammensetzung aufweist.
  3. Pulvergemisch nach Anspruch 1, dadurch gekennzeichnet, dass der erste Bestandteil aus zwei oder mehr Legierungspulvern aufgebaut ist, welche in Kombination die angegebene Zusammensetzung aufweisen.
  4. Pulvergemisch nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Bereich von Chrom im ersten Bestandteil 9 bis 11 Gew.-% geträgt.
  5. Pulvergemisch nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Bereich von Molybdän im ersten Bestandteil 1,5 bis 2,5 Gew.-% beträgt.
  6. Gesinterte Komponente, die durch Verdichten eines Pulvers nach einem der Ansprüche 1 bis 5 und dessen Sintern hergestellt ist.
  7. Verfahren zur Herstellung einer Komponente, umfassend kaltes Verdichten eines Pulvers nach einem der Ansprüche 1 bis 5 in einem Einschrittverfahren und Sintern.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das kalte Verdichten bei einem Druck von weniger als 800 MPa durchgeführt wird.
  9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass das Sintern in einem kontinuierlichen Sinterofen durchgeführt wird.
EP97939050A 1996-10-11 1997-09-08 Metallpulvermischung auf eisenbasis und damit hergestelltes bauteil Expired - Lifetime EP0946775B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9621232.9A GB9621232D0 (en) 1996-10-11 1996-10-11 Powder mixture and component made therefrom
GB9621232 1996-10-11
PCT/GB1997/002396 WO1998016666A1 (en) 1996-10-11 1997-09-08 Iron based metal powder mixture and component made therefrom

Publications (2)

Publication Number Publication Date
EP0946775A1 EP0946775A1 (de) 1999-10-06
EP0946775B1 true EP0946775B1 (de) 2000-11-22

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EP97939050A Expired - Lifetime EP0946775B1 (de) 1996-10-11 1997-09-08 Metallpulvermischung auf eisenbasis und damit hergestelltes bauteil

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EP (1) EP0946775B1 (de)
KR (1) KR20000048952A (de)
DE (1) DE69703589T2 (de)
ES (1) ES2152106T3 (de)
GB (2) GB9621232D0 (de)
WO (1) WO1998016666A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009018610B4 (de) * 2008-04-25 2013-08-01 Hitachi Powdered Metals Co., Ltd. Gesintertes Maschinenbauteil

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120172548A1 (en) 2007-05-02 2012-07-05 Lg Chem, Ltd. Polyolefin and preparation method thereof
JP5733861B2 (ja) * 2008-12-22 2015-06-10 ホガナス アクチボラグ （パブル） 機械加工性改善組成物
EP2659014B1 (de) * 2010-12-30 2017-04-05 Höganäs AB (publ) Pulver auf eisenbasis für pulverspritzgiessen
JP5939384B2 (ja) * 2012-03-26 2016-06-22 日立化成株式会社 焼結合金およびその製造方法
RU2597452C2 (ru) * 2014-09-11 2016-09-10 Павел Аркадьевич Киселёв Антифрикционные материалы на основе железа

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5462108A (en) * 1977-10-27 1979-05-18 Nippon Piston Ring Co Ltd Abrasion resistant sintered alloy
JPS58171551A (ja) * 1982-04-01 1983-10-08 Sumitomo Electric Ind Ltd 耐摩耗性焼結合金の製造方法
JPS6070163A (ja) * 1983-09-28 1985-04-20 Nippon Piston Ring Co Ltd 耐摩耗性焼結合金部材
JPS6164854A (ja) * 1984-09-04 1986-04-03 Nissan Motor Co Ltd 耐摩耗性焼結合金
SE468466B (sv) * 1990-05-14 1993-01-25 Hoeganaes Ab Jaernbaserat pulver och noetningsresistent varmhaallfast komponent framstaelld av detta samt saett att framstaella komponenten

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009018610B4 (de) * 2008-04-25 2013-08-01 Hitachi Powdered Metals Co., Ltd. Gesintertes Maschinenbauteil

Also Published As

Publication number Publication date
KR20000048952A (ko) 2000-07-25
GB2318126B (en) 2000-09-20
DE69703589T2 (de) 2001-06-21
EP0946775A1 (de) 1999-10-06
ES2152106T3 (es) 2001-01-16
DE69703589D1 (de) 2000-12-28
GB2318126A (en) 1998-04-15
GB9621232D0 (en) 1996-11-27
WO1998016666A1 (en) 1998-04-23
GB9718854D0 (en) 1997-11-12

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