EP1466038B1 - Herstellung von magnesium-zirconium-legierungen - Google Patents

Herstellung von magnesium-zirconium-legierungen Download PDF

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Publication number
EP1466038B1
EP1466038B1 EP03700086A EP03700086A EP1466038B1 EP 1466038 B1 EP1466038 B1 EP 1466038B1 EP 03700086 A EP03700086 A EP 03700086A EP 03700086 A EP03700086 A EP 03700086A EP 1466038 B1 EP1466038 B1 EP 1466038B1
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European Patent Office
Prior art keywords
zirconium
magnesium
sponge
particles
master alloy
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EP03700086A
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English (en)
French (fr)
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EP1466038B9 (de
EP1466038A1 (de
EP1466038A4 (de
Inventor
Ma Qian
David Stjohn
Malcolm Timothy Frost
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Cast Centre Pty Ltd
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Cast Centre Pty Ltd
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Priority claimed from AUPS0042A external-priority patent/AUPS004202A0/en
Priority claimed from AUPS0043A external-priority patent/AUPS004302A0/en
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    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium

Definitions

  • the present invention relates to the addition of zirconium to pure magnesium or magnesium alloys and to a method of preparation of magnesium-zirconium (Mg-Zr) alloys, including Mg-Zr master alloys.
  • Mg-Zr magnesium-zirconium
  • Zirconium is a potent grain refiner for magnesium alloys which contain negligible amounts of elements with which zirconium forms stable compounds such as Al, Si, Fe, Ni, Co, Sn and Sb. Zirconium additions of about 1% by weight to such magnesium alloys can readily cause the grain size to decrease by 80% or more under normal cooling rates.
  • the exceptional grain refining ability makes zirconium an important alloying element for magnesium alloys that are not based on alloying with Al and Si.
  • zirconium containing Mg-RE-Zn alloys such as EZ33 (Mg-3.3RE-2.7Zn-0.6Zr) and ZE41 (Mg-1.2RE-4.2Zn-0.7Zr) offer a specific combination of elevated temperature and room temperature properties which are not readily achievable with the Mg-Al-Zn alloys.
  • zirconium-rich cores that exist in most of the magnesium grains. These zirconium-rich cores are believed to be the products of peritectic solidification. In order to achieve excellent grain refinement in commercial production, it is desirable to dissolve the full zirconium content (ie, about 0.6%) in a magnesium melt.
  • Zr-rich Mg-Zr master alloys are generally made by chemical reduction by magnesium of salt mixtures based on zirconium fluorides or zirconium chlorides.
  • MEL Magnesium Elektron Ltd
  • Zirmax trade mark
  • a similar type of Mg-Zr master alloy was developed in the United States at about the same time based on a chloride salt reduction process.
  • Zirmax type master alloys remain the primary zirconium alloying material used for the commercial production of zirconium-containing magnesium alloys.
  • Zirmax contains approximately 33% zirconium and 67% magnesium and most of the zirconium is present as various sizes of zirconium particles (mostly in the range of submicron to 10 ⁇ m) in a magnesium matrix.
  • Iodide zirconium sheet rolled to about 127 - 254 ⁇ m (0.005-0.010 in.) and cut into 6.35mm (1 ⁇ 4-in.) squares was added in a manner similar to that used for the fused lump zirconium. It was stirred for several minutes in the ladle. It was found that after 65 minutes of holding at temperature, the resultant soluble zirconium content merely reached 0.1% with 1% zirconium addition.
  • the use of zirconium powder was evaluated by adding it in various ways because zirconium powder is pyrophoric and some means of protecting the powder from oxidation had to be applied.
  • zirconium powder was pelleted with various binders, zirconium powder was enclosed in tight magnesium capsules, zirconium powder was compacted with magnesium powder, and zirconium powder was used in the form of sintered zirconium powder briquettes.
  • the solubility of zirconium in magnesium is influenced by the presence of a third element. It was reported that with the presence of Zn at a level around 3-4%, the solubility of Zr in magnesium could be increased from 0.6% to slightly over 0.7% and 5% zinc increases the solubility of Zr in magnesium to about 0.8%.
  • the sponge was essentially ground with the average size being reduced to about 12.7 ⁇ m or 0.0005 in.
  • the results showed that zirconium sponge produced a soluble zirconium content of about 0.62-0.66% in Mg-5Zn alloys with 3% zirconium addition after 3-4 minutes stirring. With 1% zirconium sponge addition, soluble zirconium contents in the range of 0.32 to 0.52% were achieved.
  • the authors found that the alloying efficiency decreased when the sponge fragments were decreased in size because when the particles became finer powder, the material burned up before it could be submerged beneath the melt. Therefore, some means of protecting the powder from oxidation had to be applied.
  • zirconium particles therefore have a strong tendency to settle in a magnesium melt unless stirred vigorously. The larger the particle, the faster it settles to the bottom of the melt. For example, a 15-micron zirconium particle has been found to fall at approximately 40 mm/min to the bottom of a magnesium melt at 780 °C and is therefore difficult to maintain such particles suspended in a melt at this temperature. By contrast, when the particle size is smaller than 3 microns, it can be readily suspended in as magnesium melt at the same temperature.
  • Passivity as "Lack of response of metal or mineral surface to chemical attack such as would take place with a clean, newly exposed surface. Due to various causes, including insoluble film produced by ageing, oxidation, or contamination; run-down of surface energy at discontinuity lattices; adsorbed layers."
  • the terms "depassivate”, “depassivated” and “depassivating” are to be understood to have meanings derived from the foregoing definition of "passivity”.
  • the present invention provides a method for treating zirconium metal, the method comprising chemically depassivating the zirconium metal.
  • the zirconium metal is zirconium sponge with the method forming treated zirconium sponge.
  • the zirconium sponge may be chemically depassivated by treatment with a source of fluoride ions.
  • the source of fluoride ions may be hydrofluoric acid.
  • the source of fluoride ions may be a mixture of hydrofluoric acid and nitric acid.
  • the hydrofluoric acid preferably has a concentration between 0.1% and 50%, more preferably between 0.1% and 5%, and most preferably between 0.1% and 2.5%, with the acid concentrations calculated as shown later in this specification. These acid concentration ranges correspond respectively to about 0.05 - 25 molar, 0.05 - 2.5 molar and 0.05 - 1.25 molar. Efficacy at concentrations less than 0.1% HF, for example 0.07% (about 0.035 molar), has been demonstrated.
  • the zirconium sponge may be treated with a solution containing fluoride ions to form treated zirconium sponge.
  • the zirconium sponge is preferably a porous agglomerate of zirconium grains.
  • the sponge is formed by the Kroll process.
  • the sponge comprises zirconium with only incidental impurities.
  • Hafnium is a common impurity in zirconium.
  • Fe, Ni, Al, Si, C, Co, Sn and Sb are undesirable as they are alloying inhibiting and their total concentration is preferably less than 1% and, more preferably less than 0.5%.
  • the zirconium sponge is in the physical form of small particles and each particle has a porous structure.
  • these zirconium sponge particles have the following properties:
  • treatment of zirconium sponge in accordance with the present invention has been found to improve the ability of molten magnesium/magnesium alloy to dissolve zirconium and to form a melt containing substantially evenly distributed particles of zirconium.
  • the present invention as given in the claims provides zirconium sponge comprising an agglomerate of zirconium particles and having a surface layer containing fluorine containing compounds at least partially coating at least some of the particles.
  • the fluorine containing compounds are preferably zirconium fluoride compounds and may be compounds of the formula ZrxFy.nH 2 O.
  • the present invention provides a method of manufacturing a magnesium-zirconium master alloy, the method comprising the steps of:
  • the sponge is mixed with the molten magnesium/magnesium alloy by stirring.
  • the present invention provides a magnesium-zirconium master alloy manufactured by a method according to the present invention.
  • the master alloy contains 10%-50%, more preferably 20%-40%, zirconium in magnesium/magnesium alloy.
  • at least 90% of the zirconium particles in the master alloy are sized less than 5 ⁇ m, more preferably less then 3 ⁇ m.
  • the average particle size is less than 5 ⁇ m.
  • the present invention provides a process for preparing a magnesium-zirconium master alloy containing dissolved zirconium and zirconium particles in the substantial absence of halide inclusions wherein 90% of the zirconium particles are sized less then 5 ⁇ m, preferably less than 3 ⁇ m.
  • the master alloy is cast as ingots, which term is to be understood to include briquettes, pellets and the like.
  • the present invention provides a method of adding zirconium as an alloying element to molten magnesium/magnesium alloy, the method comprising mixing a magnesium-zirconium master alloy according to the present invention with the molten magnesium/magnesium alloy.
  • the amount of zirconium added to the molten magnesium/magnesium alloy is greater than that required to saturate the magnesium/magnesium alloy with zirconium at the temperature of the melt.
  • the present invention provides a magnesium alloy containing zirconium prepared by a method according to the present invention.
  • Figures 1(a)-(c) are micrographs illustrating the grain refining ability of as-received and untreated zirconium sponge when added to pure magnesium at 730 °C. All three micrographs are of the same magnification.
  • Figure 1(a) is pure magnesium
  • Figure 1(b) is after addition of 1wt% untreated zirconium sponge followed by 30 minutes of manual stirring
  • Figure 1(c) is after addition of a further 1wt% untreated zirconium sponge followed by a further 30 minutes of manual stirring.
  • Figures 2(a)-(c) are micrographs illustrating the grain refining ability of as-received and untreated zirconium sponge when added to pure magnesium at 780 °C. All threemicrographs are of the same magnification as in Figures 1(a)-(c) .
  • Figure 2(a) is pure magnesium
  • Figure 2(b) is after addition of 1wt°s untreated zirconium sponge followed by two minutes of manual stirring and then 30 minutes holding at 780°C
  • Figure 2(c) is after a further holding of 210 minutes at 780°C.
  • Figures 3(a)-(c) are micrographs illustrating the grain refining ability of treated zirconium sponge of the present invention when added to pure magnesium at 680 °C. All three micrographs are of the same magnification as in the previous figures.
  • Figure 3(a) is pure magnesium
  • Figure 3(b) is after addition of 1 wt% treated zirconium sponge followed by 20 minutes of manual stirring
  • Figure 3(c) is after a further 10 minutes of manual stirring.
  • Figures 4(a)-(c) are micrographs illustrating the grain refining ability of treated zirconium sponge of the present invention when added to pure magnesium at 730 °C. All three micrographs are of the same magnification as in the previous figures.
  • Figure 4(a) is pure magnesium
  • Figure 4(b) is after addition of 1 wt% treated zirconium sponge followed by 30 minutes manual stirring
  • Figure 4(c) is after 30 minutes of holding and then a further two minutes of manual stirring.
  • Figures 5(a)-(c) are micrographs illustrating the grain refining ability of treated zirconium sponge of the present invention when added to pure magnesium at 800 °C. All micrographs are of the same magnification as in the previous figures.
  • Figure 5(a) is pure magnesium
  • Figure 5(b) is after addition of 1 wt% treated zirconium sponge followed by 30 minutes of manual stirring
  • Figure 5(c) is after 30 minutes of holding and then a further two minutes of manual stirring.
  • Figure 6 is a photograph showing the physical form of untreated (as received) zirconium sponge particles as used in one embodiment of the present invention.
  • Figure 7 is a micrograph showing a view of a typical microstructure of the zirconium sponge particles shown in Figure 6 after treatment in accordance with the present invention.
  • Figure 8 is a micrograph showing a view of an alternative microstructure for the zirconium sponge particles shown in Figure 6 after treatment in accordance with the present invention.
  • Figure 9 is a schematic diagram illustrating a method of adding treated zirconium sponge to molten magnesium.
  • Figures 10 and 11 show typical views of the microstructure of an ingot of master alloy produced according to the present invention.
  • Figures 12 and 13 show typical views of commercially available Zirmax master alloy.
  • Figures 14 and 15 show typical views of the microstructure of an ingot of master alloy produced according to the present invention.
  • Figure 16 is a micrograph showing reaction products left on zirconium sponge particles after treatment in accordance with the present invention.
  • the sponge was added, without treatment in accordance with the present invention, to two samples of molten magnesium at 730 and 780 °C respectively.
  • Cone samples ( ⁇ 30 ⁇ 20 ⁇ 25 mm) were collected at different times and examination showed little evidence of grain refinement (see Fig. 1 and Fig. 2 ) even when the melt was held at 780°C for 2 to 6 hours.
  • Wet chemical analyses of the soluble zirconium contents in the samples using 15% HCl acid showed negligible zirconium contents ( ⁇ 0.05%).
  • Zirconium sponge identical to that used in the Comparative Trial above was first immersed in an acid solution which was prepared in the following manner: 45ml of concentrated nitric acid (68.5%-69.5%) and 45ml of concentrated hydrofluoric acid (50%) were combined and diluted in water to a total of 1000ml. This gave an acid solution of approximately 3% HNO 3 and 2% HF, which equates to approximately 1.1 molar HF and 0.5 molar HNO 3 .
  • the zirconium sponge was left in this acid solution for 5 minutes. Bubbling was observed which indicated that the acid had probably at least partially removed the ZrO 2 layer and was dissolving some of the zirconium metal underneath. After removal from the acid solution the zirconium sponge was rinsed in ethanol and dried under heating lamps at approximately 50°C for 60 minutes. Water was also found to be a suitable rinsing agent.
  • the treated zirconium sponge used in preparing the alloys depicted in Figures 3-5 was prepared by immersing zirconium sponge identical to that used in the Comparative Trial in a HF solution for 5 minutes followed by rinsing in water and drying.
  • the HF solution was prepared by diluting 45ml of concentrated HF(50%) in water to a total of 1,000mls to give approximately 2.25% HF which equates to approximately 1 molar HF.
  • Treated zirconium sponge was prepared by immersing zirconium sponge identical to that used in the Comparative Trial in a 2% HF solution for 4 minutes followed by rinsing in water and drying. The reaction products of the treatment are evident as the white phases on the sponge particles in Figure 16 .
  • XPS analyses of treated and untreated sponge particles gave the results set out in Table 1 below.
  • the treated particles were immersed in 0.5% HF solution for 4 minutes, rinsed with water and dried. For each analysis given, information was collected from a depth of 5 nanometers or 10 atomic layers on the surfaces of six different large particles.
  • Table 1 XPS analyses of treated and untreated sponge particles Sponge Particles Surface composition in atom percentage C O Zr Fe Si F Cl Mg Hf Untreated 30.5 49.2 16.2 1.1 3.0 0 0 0 0 Treated particles 10.3 43.3 14.9 1.3 2.3 27.8 0 0 0 (black) Treated particles 26.0 41.1 15.6 1.1 1.7 27.4 0 0 0 (grey)
  • O is present in the form of ZrO 2 in all three cases studied and the detected F in the treated particles is present in the form of Zr x F y .nH 2 O, such as ZrF 4 .
  • the approach avoided the treated sponge being trapped in the dross and avoided the treated sponge not being wetted by the melt.
  • the sponge could be added to the melt in various other ways, such as by adding a compact of sponge particles, providing that it is successfully introduced below the surface.
  • the zirconium sponge particles can be directly added to the melt under certain circumstances.
  • cover gas such as 1% SF 6 (balance: 49.5% CO 2 and 49.5% dry air)
  • the concentration of oxygen above the surface of the magnesium melt is therefore very low
  • the sponge particles can be successfully added directly providing it is done quickly.
  • the zirconium sponge particles can be added at a height of 800 mm away from the melt surface through a steel funnel, where the bottom of the funnel is placed just above the melt surface. This allows the sponge particles to quickly get into the melt without being oxidised. This has been proved to be a very convenient way of adding small ( ⁇ 5mm) zirconium sponge particles to magnesium melts.
  • the melt was left for a couple of minutes to reheat to the correct temperature and was then stirred for 30 minutes. Three temperatures were used: 680°C, 730°C and 800°C. Cone samples were collected at different times after the addition of the treated zirconium sponge.
  • Figures 3 to 5 show a typical view of the grain structures achieved from the three tests, respectively.
  • the soluble zirconium content reached 0.56% at both 730°C and 800°C after 30 min. stirring. This is very close to the solubility limit of zirconium, ie, 0.6 wt%, in molten pure magnesium.
  • the soluble zirconium contents achievable by addition of the same amount of zirconium from Zirmax master alloy have been reported as generally less than 0.5% and are typically around 0.4% at 720°C - see Y. Tamura, N. Kono, T. Motegi and E. Sato, "Grain refining mechanism and casting structure of Mg-Zr alloys", Journal of Japan Institute of Light Metals, 1998, Vol. 48, No. 4, pp. 185-189 .
  • the use of pretreated zirconium sponge showed a better recovery compared with the use of the Zirmax master alloy.
  • a solution of 0.4% HF was prepared by adding 40ml of 10% HF to 960ml of water.
  • Zirconium sponge identical to that used in the Comparative Trial was immersed in the 0.4% HF at room temperature for 5 minutes and then rinsed in water and dried. The dry treated zirconium sponge were stored in a plastic bag.
  • FIGs 7 and 8 show typical views of the microstructure of the treated zirconium sponge. Owing to the gradual dissolution of the porous structure, each zirconium sponge particle will eventually be disintegrated into many fine zirconium particles sized about 2-3 ⁇ m. Production of a suspension of fine zirconium particles in the melt is enhanced by maintaining gentle stirring throughout.
  • the magnesium-zirconium melt produced as described above can be cast into different moulds, preferably into chill moulds.
  • the height of each ingot is not much greater than 500 mm unless the mould employed has an excellent chilling effect.
  • a low casting temperature such as 680 °C or lower is preferred. Cover gas should be used during casting.
  • FIGs 10 and 11 show typical views of the microstructure of the ingot produced according to the above description with 25% zirconium addition.
  • the white phases are zirconium particles.
  • Figures 12 and 13 show typical views of MEL's Zirmax master alloy. As can be seen, the zirconium particles present in the master alloy of the present invention are in general smaller than those present in Zirmax. Small zirconium particles are always highly preferred as discussed earlier.
  • a magnesium-zirconium master alloy containing approximately 50wt% zirconium was prepared by adding 440g of treated zirconium sponge particles to 440g of molten magnesium at 700°C with slow manual stirring for 90 minutes.
  • Figures 14 and 15 are typical views of the microstructure of an ingot cast on completion of the stirring in which the grey particles are zirconium and the white phases are magnesium.
  • Magnesium-zirconium master alloy containing approximately 25wt% zirconium (prepared in accordance with the present invention) was added to a crucible containing 30kg of molten magnesium at 730°C.
  • the master alloy was preheated to approximately 175°C prior to addition to the crucible and sufficient master alloy was added to give a zirconium addition of approximately 1wt%.
  • the melt was stirred with a mechanical stirrer at 150rpm for 5 minutes. Thereafter, the melt was allowed to settle for 15 minutes and a 30mm thick plate sample (160mm x 140mm) was then sand cast at 730°C. A plate sample of the pure magnesium was also sand cast at 730°C prior to addition of the master alloy.
  • the pure magnesium plate sample had an average grain size of approximately 10,000 ⁇ m. After alloying with the master alloy the resultant plate sample had an average grain size of 98 ⁇ m, a soluble zirconium content of 0.49% and a total zirconium content of 0.58%.

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Claims (8)

  1. Verfahren zur Herstellung einer Magnesium-Zirkonium-Vorlegierung, umfassend folgende Schritte:
    (a) Mischen von (i) Zirkoniumschwamm umfassend ein Agglomerat von Zirkoniumpartikeln und mit einer Oberflächenschicht enthaltend fluorhaltige Verbindungen, die zumindest einige der Partikel zumindest teilweise bedeckt, mit (ii) geschmolzenem Magnesium/geschmolzener Magnesiumlegierung, um eine Magnesium-Zirkonium-Schmelze zu bilden, die gelöstes Zirkonium und Zirkoniumpartikel enthält; und
    (b) Gießen der Magnesium-Zirkonium-Schmelze, so dass sie sich als Magnesium-Zirkonium-Vorlegierung verfestigt.
  2. Verfahren nach Anspruch 1, wobei 90% der Zirkoniumpartikel in der Magnesium-Zirkonium-Vorlegierung eine Größe von weniger als 5µm aufweisen.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Magnesium-Zirkonium-Vorlegierung 10-50 Gew.-% Zirkonium enthält.
  4. Verfahren nach Anspruch 1 oder 2, wobei die Magnesium-Zirkonium-Vorlegierung 20-40 Gew.-% Zirkonium enthält.
  5. Verfahren nach einem der vorstehenden Ansprüche, wobei 90% der Zirkoniumpartikel in der Magnesium-Zirkonium-Vorlegierung eine Größe von weniger als 3µm aufweisen.
  6. Verfahren nach einem der vorstehenden Ansprüche, wobei die fluorhaltigen Verbindungen Zirkoniumfluoridverbindungen sind.
  7. Verfahren nach Anspruch 6, wobei die Zirkoniumfluoridverbindungen die Formel ZrxFy.nH2O aufweisen und x, y und n ganze Zahlen sind.
  8. Verfahren zum Hinzufügen von Zirkonium als Legierungselement zu geschmolzenem Magnesium/geschmolzener Magnesiumlegierung, wobei das Verfahren das Mischen einer Magnesium-Zirkonium-Vorlegierung umfasst, die durch das Verfahren nach einem der vorstehenden Ansprüche mit dem geschmolzenen Magnesium/der geschmolzenen Magnesiumlegierung hergestellt wird.
EP03700086A 2002-01-18 2003-01-20 Herstellung von magnesium-zirconium-legierungen Expired - Lifetime EP1466038B9 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
AUPS004302 2002-01-18
AUPS0042A AUPS004202A0 (en) 2002-01-18 2002-01-18 Magnesium-zirconium master alloys and their manufacture
AUPS004202 2002-01-18
AUPS0043A AUPS004302A0 (en) 2002-01-18 2002-01-18 Metal alloying process
PCT/AU2003/000053 WO2003062492A1 (en) 2002-01-18 2003-01-20 Magnesium-zirconium alloying

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EP1466038A1 EP1466038A1 (de) 2004-10-13
EP1466038A4 EP1466038A4 (de) 2006-07-19
EP1466038B1 true EP1466038B1 (de) 2009-12-02
EP1466038B9 EP1466038B9 (de) 2010-07-14

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US (1) US20050161121A1 (de)
EP (1) EP1466038B9 (de)
CN (1) CN100393912C (de)
AT (1) ATE450634T1 (de)
AU (1) AU2003201396B2 (de)
DE (1) DE60330309D1 (de)
TW (1) TW200302285A (de)
WO (1) WO2003062492A1 (de)

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US20080216924A1 (en) * 2007-03-08 2008-09-11 Treibacher Industrie Ag Method for producing grain refined magnesium and magnesium-alloys
CN101358359B (zh) * 2008-08-27 2010-07-21 哈尔滨工程大学 一种电解MgCl2和K2ZrF6、ZrO2直接制备Mg-Zr合金的方法
CN101845564B (zh) * 2010-04-28 2011-06-29 娄底市兴鑫合金有限公司 一种生产镁锆中间合金的二次熔炼法
CN109182855B (zh) * 2018-08-22 2019-11-08 厦门火炬特种金属材料有限公司 一种可变形低膨胀镁合金
CN111272797B (zh) * 2020-03-09 2021-06-25 中南大学 一种利用锆石判断花岗岩体成矿性的矿产勘查方法
CN113063873B (zh) * 2021-03-29 2023-05-12 中国船舶重工集团公司第七二五研究所 一种用于海绵锆中氯含量的测定方法

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CN100393912C (zh) 2008-06-11
EP1466038B9 (de) 2010-07-14
TW200302285A (en) 2003-08-01
EP1466038A1 (de) 2004-10-13
AU2003201396B2 (en) 2007-08-23
CN1639389A (zh) 2005-07-13
US20050161121A1 (en) 2005-07-28
DE60330309D1 (de) 2010-01-14
EP1466038A4 (de) 2006-07-19
WO2003062492A1 (en) 2003-07-31
ATE450634T1 (de) 2009-12-15

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