EP0439775B1 - Matériau en molybdène, en particulier pour la fabrication de lampes - Google Patents

Matériau en molybdène, en particulier pour la fabrication de lampes Download PDF

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Publication number
EP0439775B1
EP0439775B1 EP90124464A EP90124464A EP0439775B1 EP 0439775 B1 EP0439775 B1 EP 0439775B1 EP 90124464 A EP90124464 A EP 90124464A EP 90124464 A EP90124464 A EP 90124464A EP 0439775 B1 EP0439775 B1 EP 0439775B1
Authority
EP
European Patent Office
Prior art keywords
molybdenum
ppm
potassium
content
aluminum
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
EP90124464A
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German (de)
English (en)
Other versions
EP0439775A1 (fr
Inventor
Cosetta Dr. Setti
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.)
Osram GmbH
Original Assignee
Patent Treuhand Gesellschaft fuer Elektrische Gluehlampen mbH
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
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Publication of EP0439775A1 publication Critical patent/EP0439775A1/fr
Application granted granted 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
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum

Definitions

  • molybdenum material is to be understood as meaning materials which are used for various purposes, preferably in lamp construction.
  • the final product of molybdenum production which is initially available as a sintered rod, is then only further processed purely mechanically, so that nothing changes in the chemical composition.
  • the desired primary materials are created by rolling, hammering and drawing. More specifically, wires or pins are initially created in these processes. Tubes or tape material for the film production are then in turn produced from pins or wires as semi-finished products.
  • a suitable additional doping with aluminum has now succeeded in overcoming both difficulties.
  • Aluminum chemically binds the potassium and silicon to a high temperature resistant compound and thus holds the potassium, which is otherwise in an uncontrolled manner during the reduction process would evaporate partially (ie up to 50%!).
  • a desired, precisely defined amount of potassium can now be recorded in the molybdenum material. 0.8 to 2.0 times the potassium is particularly advantageous.
  • the potassium previously had to be over-doped, so that during the manufacturing process a partial amount which could not be determined evaporated, which in turn led to a dispersion of the material properties. This is now prevented by the addition of aluminum.
  • silicon silicon.
  • This positive property is achieved by adding 80-600 ppm by weight of aluminum; particularly good results are shown when using 100-300 ppm.
  • the potassium-stabilizing effect of aluminum is masked by its gettering properties, in particular for O 2 (cf. Mikrochimica Acta, 1987, I, pp. 437-444).
  • the thermal and mechanical behavior is also affected; in particular, this material is no longer suitable for lamp manufacture.
  • a first type of molybdenum uses a doping of approximately 160 ppm aluminum, 275 ppm potassium and 500 ppm silicon.
  • the gap is less than 1%, while the number of bends is 11.5. These values are measured on a wire with a diameter of 600 ⁇ m.
  • a second type of molybdenum uses a doping of approximately 150 ppm aluminum, 150 ppm potassium and 300 ppm silicon.
  • the gap is about 8%, while the number of bends is 6, again measured on a wire with a diameter of 600 ⁇ m.
  • Each of the two exemplary embodiments is suitable, on its own, for encompassing the wide range of applications which have hitherto been covered by various types of molybdenum.
  • the invention can also be targeted be used to optimize the crystal structure of the molybdenum material with regard to a very specific application, since the type of structure determines the properties of the material.
  • This table shows the improvement of the properties, in particular the reduction in the variation in the potassium content, in an impressive manner.
  • the process for the production of the molybdenum material runs in principle according to the Coolidge process:
  • the starting material for the production of the molybdenum products is MoO3 with a purity of 99.97% by weight.
  • the MoO3 is reduced to Mo at MoO2 at temperatures of approx. 500 - 600 ° C (1st step) or 1000 - 1100 ° C (2nd step).
  • These reductions in molybdenum oxide are carried out in a manner known per se with an H2 / N2 mixture and pure H2 gas.
  • a rotary kiln is advantageously used instead of a feed oven to be equipped with boats.
  • the molybdenum trioxide which is initially present as a powder, is added either before (as in the case of embodiment 2) or after (as in the case of embodiment 1) the first reduction as dopants as potassium and silicon in a manner known per se as an aqueous potassium silicate solution.
  • the aluminum is added as nitrate (Al (NO3) 3).
  • Al (NO3) 3 nitrate
  • AlCl3 another unstable aluminum compound
  • a compound of high stability for example Al2O3 is unsuitable since the aluminum would not be released despite the high temperatures during the reductions.
  • the molybdenum powder is pressed on hydraulic presses in steel matrices. Presintering may be advantageous at this point. Then the usual high sintering takes place in the direct current passage (5000 A) in a sintered bell at temperatures up to 2000 ° C. This process is used more with higher doping (embodiment 1). Alternatively, this process can now be carried out in a push-through furnace to increase capacity and save energy. which is mainly used for lower doping (embodiment 2). The sintered rod formed is then processed into molybdenum wire by rolling, hammering and drawing.
  • This wire can now be used as a power supply, holder pin or so-called electrode (for example for automotive halogen incandescent lamps) or as a core wire for the manufacture of tungsten filaments.
  • the strip material for the foils can be obtained from the molybdenum wire by further rolling, while the tubes are produced by rolling the wire and then longitudinally bending it into a "tube".
  • the doping of the molybdenum with potassium, silicon, aluminum (for example 275 ppm K) according to the invention has nothing to do with the coincidentally similar doping of the tungsten with the same substances (for example 75 ppm K). While according to the invention the doping in the case of molybdenum improves a whole range of properties, in the case of tungsten this doping is primarily responsible for the growth in the length of the grains, which is ultimately intended to prevent the tungsten wire from sagging. The powder metallurgical behavior of both elements is also not comparable (tungsten is sintered at 2800 ° C). The reactions of molybdenum when doping and reducing differ fundamentally from those of tungsten.
  • molybdenum does not form a stable ⁇ phase during the reduction, which means that the Potassium in the crystal lattice - as happens with tungsten - would allow.
  • the effect of doping with molybdenum can therefore be characterized as a surface effect with respect to the crystal structure.
  • the molybdenum wire according to the invention is used, for example, in a motor vehicle halogen incandescent lamp which has a cylindrical bulb made of tempered glass or quartz glass, in which the two luminous elements for low beam and high beam are held by means of three current leads. A dimming screen may also be provided. Such a lamp is described for example in DE-OS 28 29 677.
  • the power supply lines and possibly also the anti-glare shield are made from molybdenum wire with the addition of 150 ppm aluminum, 150 ppm potassium and 300 ppm silicon.
  • the molybdenum wire can be used for the holder pins and foils, in the case of a hard glass bulb it is used for the continuous power supply (electrodes).
  • Another area of application is a one-sided or two-sided squeezed high-voltage halogen incandescent lamp with a long axial lamp or a halogen lamp squeezed on one side with a U-shaped or V-shaped curved lamp.
  • the power supply remote from the base can be supported in the bulb, as described in DE-GM 88 12 010.
  • support brackets for the luminous element can be provided (for example EP-OS 150 503).
  • the U-shaped or V-shaped lamp body can be held at the end remote from the base by a frame (see, for example, EP-OS 173 995).
  • the above preferred exemplary embodiment is also used in these cases.
  • the filament wire is wound on a core wire made of molybdenum, which is ultimately released again by immersion in an acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Vessels And Coating Films For Discharge Lamps (AREA)
  • Glass Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)
  • Catalysts (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Claims (6)

  1. Matériau à base de molybdène pour la fabrication de lampes, le molybdène n'étant dopé que par du potassium, du silicium et de l'aluminium, caractérisé en ce que la teneur en aluminium est comprise entre 80 et 600 ppm en poids, le rapport pondéral Al/K étant d'environ 1:0,8 à 1:2,0, tandis que le rapport pondéral aluminium/silicium est d'environ 1:1,8 à 1:3,8.
  2. Matériau à base de molybdène suivant la revendication 1, caractérisé en ce que la teneur en aluminium est comprise entre 100 et 300 ppm.
  3. Matériau à base de molybdène suivant la revendication 2, caractérisé en ce que la teneur en aluminium est comprise entre 140 et 180 ppm.
  4. Matériau à base de molybdène suivant l'une des revendications précédentes, caractérisé en ce que la teneur en potassium est comprise entre 100 et 400 ppm et la teneur en silicium est comprise entre 200 et 700 ppm (toutes les deux en partie en poids).
  5. Matériau à base de molybdène suivant la revendication 4, caractérisé en ce que la teneur en potassium est comprise entre 250 et 300 ppm et la teneur en silicium est comprise entre 400 et 600 ppm.
  6. Matériau à base de molybdène suivant la revendication 4, caractérisé en ce que la teneur en potassium est comprise entre 130 et 170 ppm et la teneur en silicium est comprise entre 270 et 320 ppm.
EP90124464A 1990-02-01 1990-12-17 Matériau en molybdène, en particulier pour la fabrication de lampes Expired - Lifetime EP0439775B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4002974 1990-02-01
DE4002974A DE4002974A1 (de) 1990-02-01 1990-02-01 Molybdaenmaterial, insbesondere fuer die lampenherstellung

Publications (2)

Publication Number Publication Date
EP0439775A1 EP0439775A1 (fr) 1991-08-07
EP0439775B1 true EP0439775B1 (fr) 1994-10-26

Family

ID=6399219

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90124464A Expired - Lifetime EP0439775B1 (fr) 1990-02-01 1990-12-17 Matériau en molybdène, en particulier pour la fabrication de lampes

Country Status (7)

Country Link
EP (1) EP0439775B1 (fr)
JP (1) JP2766081B2 (fr)
KR (1) KR0178038B1 (fr)
AT (1) ATE113318T1 (fr)
DE (2) DE4002974A1 (fr)
ES (1) ES2060913T3 (fr)
HU (1) HU210281B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE9415217U1 (de) 1994-09-21 1996-01-25 Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH, 81543 München Hochdruckentladungslampe
DE19603301C2 (de) * 1996-01-30 2001-02-22 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Elektrische Lampe mit Molybdänfoliendurchführungen für ein Lampengefäß aus Quarzglas
DE19603300C2 (de) * 1996-01-30 2001-02-22 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Elektrische Lampe mit Molybdänfoliendurchführungen für ein Lampengefäß aus Quarzglas

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676083A (en) * 1969-01-21 1972-07-11 Sylvania Electric Prod Molybdenum base alloys
JPS57123625A (en) * 1981-01-23 1982-08-02 Toshiba Corp Bulb
DE3467774D1 (en) * 1983-02-10 1988-01-07 Toshiba Kk Molybdenum board and process of manufacturing the same
JPS60194043A (ja) * 1984-03-14 1985-10-02 Toshiba Corp 管球ウエルズ
JPS63114935A (ja) * 1986-10-31 1988-05-19 Tokyo Tungsten Co Ltd モリブデンるつぼ及びその製造方法
JPH0232340B2 (ja) * 1986-12-25 1990-07-19 Tokyo Tungsten Kk Moribudenzai
JPS63192840A (ja) * 1987-02-06 1988-08-10 Tokyo Tungsten Co Ltd ドツトプリンタ用モリブデン材料

Also Published As

Publication number Publication date
JPH04214836A (ja) 1992-08-05
KR0178038B1 (ko) 1999-02-18
HU908037D0 (en) 1991-06-28
KR910021490A (ko) 1991-12-20
DE4002974A1 (de) 1991-08-08
EP0439775A1 (fr) 1991-08-07
ES2060913T3 (es) 1994-12-01
JP2766081B2 (ja) 1998-06-18
HU210281B (en) 1995-03-28
HUT62946A (en) 1993-06-28
ATE113318T1 (de) 1994-11-15
DE59007562D1 (de) 1994-12-01

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