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EP0719349B1 - Procede de production des articles frittes - Google Patents

Procede de production des articles frittes Download PDF

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Publication number
EP0719349B1
EP0719349B1 EP94926797A EP94926797A EP0719349B1 EP 0719349 B1 EP0719349 B1 EP 0719349B1 EP 94926797 A EP94926797 A EP 94926797A EP 94926797 A EP94926797 A EP 94926797A EP 0719349 B1 EP0719349 B1 EP 0719349B1
Authority
EP
European Patent Office
Prior art keywords
weight
content
sintering
sintered
molybdenum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94926797A
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German (de)
English (en)
Other versions
EP0719349A1 (fr
Inventor
Norbert Dautzenberg
Karl-Heinz Lindner
Klaus Vossen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
QMP Metal Powders GmbH
Original Assignee
Mannesmann AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE4331938A external-priority patent/DE4331938A1/de
Application filed by Mannesmann AG filed Critical Mannesmann AG
Publication of EP0719349A1 publication Critical patent/EP0719349A1/fr
Application granted granted Critical
Publication of EP0719349B1 publication Critical patent/EP0719349B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • C22C33/0264—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/08—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of toothed articles, e.g. gear wheels; of cam discs
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten 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
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
    • B22F2009/0828—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid with water
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S75/00—Specialized metallurgical processes, compositions for use therein, consolidated metal powder compositions, and loose metal particulate mixtures
    • Y10S75/95—Consolidated metal powder compositions of >95% theoretical density, e.g. wrought

Definitions

  • the invention relates to a method for producing sintered parts according to the preamble of claim 1.
  • the production of mechanical components from ferrous materials by means of sintering technology has the great advantage over production using metal-cutting shaping (e.g. turning, drilling, milling) that the actual shaping can be carried out in a single operation, practically without the generation of waste material, and therefore for series parts is possible faster and cheaper.
  • the parts are pressed, for example, on a hydraulic metal powder press in a molding tool using a pressing pressure of, for example, 7 t / cm 2 to give green bodies and then in an oven at about 1120-1150 ° C (normal sintering) or also at about 1250-1280 ° C ( High temperature sintering) to obtain sufficient static and dynamic strength.
  • sintered parts Due to the manufacturing process, sintered parts always have a lower density than that of the corresponding solid material (theoretical density) because they are penetrated by pores.
  • the actual density of the sintered parts is usually around 80-92% of the theoretical density, depending on the pressure applied and the shape of the part. This inevitably results in an impairment of the mechanical properties, which means that sintered parts have so far rarely been used with particularly high mechanical stress, especially since larger dimensions to compensate for this disadvantage cannot generally be accepted because of the associated increase in volume and weight.
  • the pores contained in the sintered part can act as internal notches, which can lead to a drastic reduction, in particular of the dynamic strength properties.
  • An iron-based powder is known from WO 91/19582, which is intended to ensure a comparatively high impact strength. It prescribes 0.3 - 0.7% by weight phosphorus and 0.3 - 3.5% by weight molybdenum as alloying elements. Any other alloying elements present are limited to a maximum of 2% by weight.
  • the 6 contents of molybdenum are preferably 0.5-2.5% by weight and of phosphorus 0.4-0.6% by weight (addition in particular in the form of Fe 3 P).
  • An upper limit of 0.07% by weight is recommended for carbon.
  • This iron-based powder is suitable for normal sintering temperatures (below 1450 ° C).
  • the test results shown in this document show that optimum proportions exist for both phosphorus and molydbdenum, in which the impact strength is particularly high.
  • the impact strength of a powder with 0.5% by weight phosphorus with a molybdenum content of 0-1.0% by weight rises steeply, reaches a maximum in the range 1-2% by weight and falls beyond 3.5% by weight. Molybdenum even down to below the initial values.
  • DE 29 43 601 C2 discloses a pre-alloyed steel powder Manufacture of high-strength sintered parts known, the 0.35 to 1.50% Mn, 0.2 up to 5.0% Cr, 0.1 to 7.0% Mo, 0.01 to 1.0 V, maximum 0.10% Si, maximum 0.01% Al, maximum 0.05% C, maximum 0.004% N, maximum 0.25% Oxygen, balance iron and other manufacturing-related impurities contains.
  • the low C content is required to be a good one
  • To enable the steel powder to be pressed by water atomization a corresponding melt and subsequent reduction annealing 1000 ° C is generated. Before pressing, it turns into green Steel powder in the usual way with lubricants (e.g.
  • the object of the invention is therefore a method of the generic type Specify with which Sintered parts can be produced with high density, with good Surface hardenability especially good dynamic Have strength properties and therefore without using the complex double sintering technology or a forging process for mechanically particularly strong components can be used, especially as gears for automotive transmissions and the like stressed components.
  • a steel powder produced for example, by gas atomization, gas-liquid atomization or preferably by water atomization of a steel melt containing molybdenum and subsequent reduction and soft annealing at 850-950 ° C., after mixing with conventional lubricants of powder metallurgy (e.g. Zinc stearate) can be processed into components which only have an extremely small pore volume, ie a density close to the theoretically highest possible density of the material (eg 95 to 98%). All that is required is a simple pressing using customary pressures in the range 6.0-8.0 t / cm 2 , preferably 6.5-7.5 t / cm 2 .
  • powder metallurgy e.g. Zinc stearate
  • Sintering temperatures can range from 1050 to 1350 ° C, with higher temperatures being preferred. This means around up to 1150 ° C when using belt furnaces and around 1250 - 1300 ° C with walking beam furnaces (high temperature sintering). High-temperature sintering can further increase the density that can be achieved compared to normal sintering.
  • the powder mixture according to the invention is characterized in that it is practically phosphorus-free, that is to say it contains phosphorus only as an impurity (P ⁇ 0.02% by weight).
  • the minimum required molybdenum content of the molten steel that is to be used for the powder production depends on the intended sintering temperature during the later production of the sintered parts. A content of 4.0% by weight is already sufficient in any case. In economic reasons, an upper limit of 5% by weight, preferably even only 4.5% by weight, should not be exceeded. At a sintering temperature of 1120 ° C 3.8% by weight of molybdenum and at 1280 ° C even 2.7 6% by weight are sufficient.
  • the molten steel must not only be practically phosphorus-free but must also have no significant carbon content (C ⁇ 0.01% by weight) so that the powder is sufficiently soft and easy to press remains.
  • the strength can be increased in individual cases, albeit this should even be avoided if possible, admixed with the 6-graphite powder which, however, has a maximum carbon content of 0.06% by weight may result in the powder mixture.
  • the powder can also contain the usual impurities contain a molten steel.
  • Carbon black molybdenum are other metallic Alloy additions are not required, but usually do not interfere, if they don't take on too large values. Overall, these should additional alloying elements a sum of 1.0% by weight, preferably not exceed 0.5% by weight.
  • To increase the strength of the Alloy can include the addition of chromium (preferably without further additional alloying elements) within the stated limits be appropriate.
  • a reducing atmosphere in particular in an atmosphere containing at least 10% by volume, preferably 20-40% by volume, of hydrogen.
  • forming gas ie a mixture of H 2 and N 2 .
  • Higher H 2 contents tend to improve the density that can be achieved during sintering, which, because of the setting of the powder mixture according to the invention, takes place exclusively in the alpha phase and therefore strongly promotes density sintering (without the formation of a liquid phase).
  • the cooling after sintering does not require any special measures.
  • the sintered parts have a purely ferritic structure made of FeMo mixed crystals.
  • the sintered parts can then be calibrated be subjected to deformation in the surface area (Leveling the roughness) and thus to a better one Surface quality and dimensional accuracy.
  • case hardening is carried out, which is particularly suitable for Gears and similarly stressed parts is recommended as they become one substantial increase in surface hardness and for the introduction of Residual compressive stresses.
  • gears it is advisable to use the Case hardening to subject the tooth area to soft scraping. After hardening the gears, the usual grinding of Drilling and plane surfaces are done.
  • the sintered parts produced in this way have a close to theoretical maximum density, being particularly remarkable is that the remaining pores are small, self-contained and round are and therefore have no significant notch effect. Hence arise excellent dynamic strength values as well as after a Case hardening at the same time also high surface hardness, which for the Wear resistance and e.g. the tooth flank capacity of are crucial.
  • Figures 1 and 2 show in different magnifications Cross section of sintered parts produced according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Forging (AREA)

Claims (14)

  1. Procédé de fabrication de produits frittés, à haute ténacité et à masse volumique importante par frittage à une température de frittage TS se trouvant dans la plage d'environ 1 050 à 1 350 °C d'ébauches de compact comprimées à froid, dans lequel les ébauches de compact sont fabriquées à partir d'un mélange de poudre prêt à être comprimé, composé de poudre d'acier, laquelle est produite, avec les impuretés habituelles, par atomisation, surtout par atomisation aqueuse, d'une masse fondue de molybdène-acier ne contenant ni carbone ni phosphore, dont la teneur en molybdène en fonction de la température de frittage Ts est d'au moins Mo (% en masse) = 16,1 Ts 100o - 0,7 Ts 100o - 88,7 suivie d'un recuit de réduction et d'adoucissement, et laquelle est ensuite mélangée aux lubrifiants habituels ainsi qu'éventuellement mélangée à de faibles quantités de poudre de graphite pour qu'une teneur en carbone s'établisse, et dans lequel la teneur en carbone du mélange de poudre est limitée à un maximum de 0,06 % en masse et le recuit de réduction a lieu dans la plage de température de 850 à 950 °C.
  2. Procédé selon la revendication 1,
       caractérisé en ce que,
       la teneur en autres éléments d'alliage métalliques dans la masse fondue d'acier est limitée à un total d'au maximum 1,0 % en masse, de préférence 0,5 % en masse.
  3. Procédé selon la revendication 2,
       caractérisé en ce que,
       du chrome, en particulier du chrome sans autres éléments d'alliage divers, est ajouté à la masse fondue.
  4. Procédé selon l'une des revendications 1 à 3,
       caractérisé en ce que,
       la teneur en molybdène est d'au moins 3,2 % en masse pour une température de frittage de 1 280 °C.
  5. Procédé selon l'une des revendications 1 à 3,
       caractérisé en ce que,
       la teneur en molybdène est d'au moins 4,3 % en masse pour une température de frittage de 1 120 °C.
  6. Procédé selon l'une des revendications 1 à 5,
       caractérisé en ce que,
       la teneur en molybdène est limitée à un maximum de 5,0 % en masse, de préférence à 4,5 % en masse.
  7. Procédé selon l'une des revendications 1 à 6,
       caractérisé en ce que,
       la teneur en carbone (poudre de graphite) est limitée à un maximum de 0,04 % en masse, notamment à 0,02 % en masse.
  8. Procédé selon l'une des revendications 1 à 7,
       caractérisé en ce que,
       les ébauches de compact sont comprimées par compression uniaxiale avec une pression de formage de 6,0 à 8,0 t/cm2, en ce que le frittage qui suit se fait sous une atmosphère contenant au moins 10 % en volume d'hydrogène, notamment une atmosphère de N2/H2, et en ce que les pièces frittées sont à structure ferritique.
  9. Procédé selon la revendication 8,
       caractérisé en ce que,
       la proportion en H2 est de 20 à 40 % en volume.
  10. Procédé selon la revendication 9,
       caractérisé en ce que,
       la pression de formage est de 6,5 à 7,5 t/cm2.
  11. Procédé selon l'une des revendications 1 à 10,
       caractérisé en ce que,
       la température de frittage est de 1 250 à 1 300°C.
  12. Procédé selon l'une des revendications 1 à 11,
       caractérisé en ce que,
       les pièces frittées sont ensuite soumises à un calibrage.
  13. Procédé selon l'une des revendications 1 à 12,
       caractérisé en ce que,
       les pièces frittées et, le cas échéant, calibrées, en particulier produites sous la forme de roues dentées, sont soumises à un procédé de cémentation.
  14. Procédé selon la revendication 13,
       caractérisé en ce que,
       les roues dentées frittées et calibrées sont rasées dans la zone d'engrenage avant la cémentation.
EP94926797A 1993-09-16 1994-09-09 Procede de production des articles frittes Expired - Lifetime EP0719349B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4331938A DE4331938A1 (de) 1993-09-16 1993-09-16 Molybdänhaltiges Eisenbasispulver
DE4331938 1993-09-16
DE9409832U 1994-06-09
DE9409832U DE9409832U1 (de) 1993-09-16 1994-06-09 Metallpulvermischung
PCT/DE1994/001087 WO1995008006A1 (fr) 1993-09-16 1994-09-09 Procede de preparation d'un melange de poudres et son utilisation

Publications (2)

Publication Number Publication Date
EP0719349A1 EP0719349A1 (fr) 1996-07-03
EP0719349B1 true EP0719349B1 (fr) 1998-04-29

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP94926797A Expired - Lifetime EP0719349B1 (fr) 1993-09-16 1994-09-09 Procede de production des articles frittes

Country Status (7)

Country Link
US (1) US5628046A (fr)
EP (1) EP0719349B1 (fr)
JP (1) JP3572078B2 (fr)
AT (1) ATE165628T1 (fr)
CA (1) CA2165087C (fr)
ES (1) ES2115257T3 (fr)
WO (1) WO1995008006A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10306353A (ja) 1997-04-30 1998-11-17 Nippon Piston Ring Co Ltd シンクロナイザリング
SE9702299D0 (sv) * 1997-06-17 1997-06-17 Hoeganaes Ab Stainless steel powder
US6042949A (en) * 1998-01-21 2000-03-28 Materials Innovation, Inc. High strength steel powder, method for the production thereof and method for producing parts therefrom
SE9803171D0 (sv) * 1998-09-18 1998-09-18 Hoeganaes Ab Warm compaction of steel powders
US6514307B2 (en) * 2000-08-31 2003-02-04 Kawasaki Steel Corporation Iron-based sintered powder metal body, manufacturing method thereof and manufacturing method of iron-based sintered component with high strength and high density
JP2004324712A (ja) * 2003-04-23 2004-11-18 Mitsubishi Materials Corp モータ式燃料ポンプの耐摩耗性軸受

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Also Published As

Publication number Publication date
ES2115257T3 (es) 1998-06-16
US5628046A (en) 1997-05-06
ATE165628T1 (de) 1998-05-15
CA2165087C (fr) 2004-07-06
CA2165087A1 (fr) 1995-03-23
JP3572078B2 (ja) 2004-09-29
WO1995008006A1 (fr) 1995-03-23
JPH09502766A (ja) 1997-03-18
EP0719349A1 (fr) 1996-07-03

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