WO2009083045A2 - Alliage de molybdène-silicium contenant un oxyde métallique stable - Google Patents

Alliage de molybdène-silicium contenant un oxyde métallique stable Download PDF

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Publication number
WO2009083045A2
WO2009083045A2 PCT/EP2008/007489 EP2008007489W WO2009083045A2 WO 2009083045 A2 WO2009083045 A2 WO 2009083045A2 EP 2008007489 W EP2008007489 W EP 2008007489W WO 2009083045 A2 WO2009083045 A2 WO 2009083045A2
Authority
WO
WIPO (PCT)
Prior art keywords
metal oxide
alloy
alloy according
molybdenum
silicon
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.)
Ceased
Application number
PCT/EP2008/007489
Other languages
German (de)
English (en)
Other versions
WO2009083045A3 (fr
Inventor
Pascal JÈHANNO
Mike BÖNING
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.)
Metallwerk Plansee GmbH
Original Assignee
Metallwerk Plansee GmbH
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
Application filed by Metallwerk Plansee GmbH filed Critical Metallwerk Plansee GmbH
Publication of WO2009083045A2 publication Critical patent/WO2009083045A2/fr
Publication of WO2009083045A3 publication Critical patent/WO2009083045A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases

Definitions

  • the invention relates to a Mo-Si alloy in which the silicon is completely dissolved. Furthermore, the invention relates to a method for producing the Mo-Si alloy and a sintered metal part consisting of it. The invention further relates to a slinger and the use thereof for the production of magnetic powders from the melt.
  • molybdenum and molybdenum alloys are widely used industrially because of their good mechanical strength properties at high temperatures.
  • the present invention is based on the general inventive idea that these objects by a molybdenum-silicon alloy in which the silicon is completely dissolved and having at least one at 1500 0 C stable metal oxide is dissolved.
  • the present invention therefore provides a molybdenum-silicon alloy in which the silicon is completely dissolved and contains at least one metal oxide in an amount of 0.01 wt .-% to 1 wt .-%, wherein the at least one metal oxide at 1500 0 C. has a free enthalpy G of less than -500 KJ / mol.
  • the at least one metal oxide is preferably selected such that it has a Gibbs free energy G of less than -700 kJ / mol at 1500 0 C.
  • the at least one metal oxide is very particularly preferably chosen so that it has a free energy G of less than -750 kJ / mol at 1500 0 C.
  • the present invention provides a process for producing the Mo-Si alloy, wherein Mo powder, Si powder and metal oxide powder are mixed and ground, then pressed at pressures of 100 to 500 MPa and then under reducing conditions Sintered 1000 to 1900 0 C and hot-compacted at temperatures of 1000 to 1700 0 C and pressures of 50 to 300 Mpa.
  • the invention further provides a sintered metal part of the Mo-Si alloy of the invention.
  • a sintered metal part may be in the form of a slinger and is excellent for the production of magnetic powders from the melt.
  • the microstructure of sintered metal parts is of the alloy according to the invention with a particle size greater than 7.0 according to ASTM E112-96, whereby in many cases on a transformation, for example, by forging, can be dispensed with.
  • the mixture of silicon and at least one with respect to the free enthalpy at 1500 0 C stable metal oxide is suitable for increasing the recrystallization temperature.
  • Sintered metal parts according to the invention also have longer service life in the production of permanent magnet powder in comparison with known Mo sintered metal parts.
  • the molybdenum-silicon alloy of the present invention is characterized in that silicon is completely dissolved in Mo.
  • the term is completely solved to understand that no intermetallic phases related to an XRD analysis occur.
  • the presence of intermetallic phases such as Mo 3 Si is not according to the invention.
  • the molybdenum-silicon alloy consists so far of a pure molybdenum-silicon mixed crystal phase.
  • the at least one metal oxide is used according to the invention in an amount of at least 0.01% by weight and not more than 1% by weight.
  • at least 0.02 wt .-% and particularly preferably at least 0.03 wt .-% metal oxide is used. Wt .-%.
  • the upper limit used is preferably 0.5% by weight and more preferably 0.3% by weight of metal oxide.
  • At least one metal oxide are metal oxides and mixtures thereof, which are stable at 1500 0 C based on the free enthalpy G, that is, have a free enthalpy of less than -500 KJ / mol.
  • metal oxides selected from magnesium oxide, calcium oxide, ZrO 2 , HfO 2 , TiO 2 , Al 2 O 3 , Y 2 O 3 , SrO, lanthanide oxides, and mixtures thereof can be selected.
  • magnesium oxide is used.
  • the silicon content of the molybdenum-silicon alloy based on the entire alloy containing the metal oxide or the metal oxides is preferably 0.01 to 1 wt .-%. More preferably, the silicon content based on the total alloy is between 0.02 and 0.4 Wt .-%. Particularly preferred is a silicon content based on the total alloy between 0.03 and 0.2 wt .-%.
  • the molybdenum-silicon alloy having the at least one metal oxide in an amount of 0.01% by weight to 1% by weight is prepared by mixing molybdenum powder, silicon powder and the at least one metal oxide powder. Subsequently, the powder mixture is ground and then pressed at pressures of 100 to 500 MPa. Preference is given to pressing cold isostatically.
  • the cold isostatic pressing is preferably carried out at a pressure of 180 to 220 MPa. Due to the friction effects occurring during cold isostatic pressing, the temperature increases in this case. The temperature is optionally adjusted by external cooling so that it takes place in a range of 20 to 60 0 C, preferably 20 to 40 0 C and particularly preferably 30 to 40 ° C.
  • the sintering of the molybdenum-silicon alloy takes place under reducing conditions.
  • Sintering preferably proceeds stepwise by heating to two intermediate temperatures. Typically, it is first heated from room temperature to a temperature in the range of 1000 to 1200 ° C. and this temperature maintained for a period of one to three hours. Subsequently, the temperature is further increased to a temperature of 1300 to 1500 0 C and annealed again for a period of half to two hours. Finally, the temperature is increased to 1800 to 1900 0 C and then maintained for 4 to 6 hours.
  • hot-compacted After cooling, hot-compacted. This is preferably carried out at 1000 to 1700 0 C and at pressures of 50 to 300 MPa. Particular preference is given to hot-isostatic pressing.
  • the hot isostatic pressing is usually carried out by raising the temperature to a temperature of 1300 to 1700 0 C.
  • the pressure is preferably 180 to 220 MPa.
  • the preferred temperature and pressure are advantageously maintained for a period of 4 to 6 hours.
  • the product obtained is a sintered metal part and can be supplied to a machining without processing difficulties, ie it formed during machining no cracks and formations. Alternatively, it is not possible to compress too hot-isostatically after sintering, but to reshape the alloy. After forming, machining is possible again. Due to the special properties of the alloy according to the invention, however, it is possible to completely or at least partially dispense with the forming step, because even the un-formed material has a fine microstructure.
  • the sintered metal parts according to the invention of the molybdenum-silicon alloy of the present invention are characterized by a particle size of at least 7.0 according to ASTM E112-96, preferably at least 7.5 and particularly preferably at least 8.0. This grain size is surprisingly provided by the sintered metal part according to the invention without forming.
  • the sintered metal part is a slinger.
  • a slinger is a cooling device for producing amorphous and / or microcrystalline powder. Slings are widely used in the art, i.a. for the production of permanent magnets. They are part of a Verdüsungsapparatur.
  • the slinger takes the geometric shape of a cylinder. If the slinger is used for the production of amorphous and / or microcrystalline powder, this is preferably cooled on the lateral surface.
  • the present invention reduces the grain size of the sintered metal parts that can be produced.
  • This effect is particularly significant in a mixture of 0.03 to 0.5 wt .-% of at least one metal oxide together with 0.02 to 0.04 wt .-% of silicon, each based on the total molybdenum-silicon alloy.
  • Very particularly good properties are obtained with a content of at least one metal oxide of 0.03 to 0.3 wt .-% and 0.03 to 0.2 wt .-% of silicon in each case based on the total molybdenum-silicon alloy.
  • the present invention relates to the use of a sintered metal part and in particular a slinger for the production of magnetic powders from the melt.
  • Magnetic powders from the melt are usually obtained by application to rotating disks, preferably so-called Slings, made.
  • a melt with a temperature of> 1400 0 C occurs on the rotating sintered metal part.
  • the sintered metal parts according to the invention in particular in the form of sling rings, are particularly suitable for producing magnetic powders comprising at least one rare earth element.
  • the service life of the sling rings is significantly increased compared to conventional sling rings.
  • the molybdenum-silicon alloys of the present invention in the form of sling rings can find excellent use therewith, magnetic powders of the type Sm-Co, Nd-Fe-B or Sm-TM and where TM is a mixture of Co, Fe, Cu, Zr and Hf represents.
  • ICPOES Inductive Coupled Plasma Optical Emission Spectroscopy
  • Type Metal oxide Metal oxide (mol% / mol%)
  • the determination of the oxygen content is known to the person skilled in the art and must take into account the relative proportions of the metal used.
  • the density was determined by Archimedian according to DIN ISO 3369. The samples to be examined were weighed once in air and then in water. After determining the two masses, the density was determined. A consideration of the residual oxygen content is necessary.
  • the ZwickRoell Zmart Pro and Zwick Maytech systems were used at 816 ° C and 1093 ° C respectively at 260 ° C and 538 ° C.
  • the sample shape used was an RHC sample according to FIG. 2 with the dimensions according to the following table
  • the test speed was 2.0 mm / min. With respect to the RRS-tensile specimens (5 x 25 mm), this corresponds at room temperature for a strain rate 1.33 x 10 -3 sec 1, and for the RHC-tensile specimens (3 x 15 mm) with HT a strain rate of 2.20 x 10 "3 sec-1 ,
  • Table 3 shows Rp 02 and R m data at different temperatures; Room temperature, 260 0 C, 538 0 C, 816 ° C and 1093 0 C (upper value at room temperature, second value from above at 260 ° C, third value from above at 538 0 C, fourth value from above at 816 0 C and fifth value from above at 1093 0 C).
  • the finished tensile specimens were tested for cracks by means of the dye penetration test before the tests. All samples were crack-free.
  • the behavior of the material without metal oxide from the brittle in the ductile range was determined in the comparative experiment for pure Mo, Mo with 0.1 wt .-% Si and Mo with 0.5 wt .-% Si.
  • the microstructure of the alloys according to the invention was examined microscopically.
  • the grain size was determined according to the line-cut method DIN ISO 643. The results are summarized in the table below.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

L'invention concerne un alliage Mo-Si dans lequel le silicium est complètement dissous, caractérisé en ce qu'il renferme au moins un oxyde métallique en une quantité de 0.01% en poids à 1% en poids, et en ce que l'oxyde métallique présente à 1500°C, une enthalpie libre G inférieure à - 500 KJ/mol. L'invention concerne en outre un procédé de production des alliages Mo-Si correspondants, ainsi que des pièces métalliques frittées en tant que bagues de lubrification centrifuge.
PCT/EP2008/007489 2007-12-21 2008-09-11 Alliage de molybdène-silicium contenant un oxyde métallique stable Ceased WO2009083045A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007061964A DE102007061964A1 (de) 2007-12-21 2007-12-21 Molybdän-Siliziumlegierung mit stabilem Metalloxid
DE102007061964.4 2007-12-21

Publications (2)

Publication Number Publication Date
WO2009083045A2 true WO2009083045A2 (fr) 2009-07-09
WO2009083045A3 WO2009083045A3 (fr) 2009-12-03

Family

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Family Applications (1)

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PCT/EP2008/007489 Ceased WO2009083045A2 (fr) 2007-12-21 2008-09-11 Alliage de molybdène-silicium contenant un oxyde métallique stable

Country Status (2)

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DE (1) DE102007061964A1 (fr)
WO (1) WO2009083045A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT16355U1 (de) * 2017-06-30 2019-07-15 Plansee Se Schleuderring
WO2025252909A1 (fr) * 2024-06-06 2025-12-11 Otto-Von-Guericke-Universität Magdeburg Alliage de molybdène destiné à être utilisé dans la plage de température de 500 °c à au moins 900° c

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514234A (en) * 1983-02-10 1985-04-30 Tokyo Shibaura Denki Kabushiki Kaisha Molybdenum board and process of manufacturing the same
US5842511A (en) 1996-08-19 1998-12-01 Alliedsignal Inc. Casting wheel having equiaxed fine grain quench surface
AT2017U1 (de) * 1997-05-09 1998-03-25 Plansee Ag Verwendung einer molybdän-/wolfram-legierung in bauteilen für glasschmelzen
AT7187U1 (de) * 2004-02-25 2004-11-25 Plansee Ag Verfahren zur herstellung einer molybdän-legierung

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT16355U1 (de) * 2017-06-30 2019-07-15 Plansee Se Schleuderring
US11065685B2 (en) 2017-06-30 2021-07-20 Plansee Se Slinger ring
WO2025252909A1 (fr) * 2024-06-06 2025-12-11 Otto-Von-Guericke-Universität Magdeburg Alliage de molybdène destiné à être utilisé dans la plage de température de 500 °c à au moins 900° c

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Publication number Publication date
DE102007061964A1 (de) 2009-07-09
WO2009083045A3 (fr) 2009-12-03

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