US20070214910A1 - Salt Composition to be Used With Molten Magnesium - Google Patents

Salt Composition to be Used With Molten Magnesium Download PDF

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Publication number
US20070214910A1
US20070214910A1 US11/628,336 US62833605A US2007214910A1 US 20070214910 A1 US20070214910 A1 US 20070214910A1 US 62833605 A US62833605 A US 62833605A US 2007214910 A1 US2007214910 A1 US 2007214910A1
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Prior art keywords
salt composition
salt
srcl2
kcl
composition according
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Abandoned
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US11/628,336
Inventor
Per Bakke
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Magontec GmbH
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Individual
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Assigned to NORSK HYDRO TECHNOLOGY B.V. reassignment NORSK HYDRO TECHNOLOGY B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAKKE, PER
Publication of US20070214910A1 publication Critical patent/US20070214910A1/en
Assigned to MAGONTEC GMBH reassignment MAGONTEC GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NORSK HYDRO TECHNOLOGY B.V.
Abandoned 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
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • C22B9/106—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents the refining being obtained by intimately mixing the molten metal with a molten salt or slag
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/06—Obtaining aluminium refining
    • C22B21/062—Obtaining aluminium refining using salt or fluxing agents
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a salt composition for protecting, refining and/or recycling molten magnesium or magnesium alloys, which at the same time can be used as a fire extinguisher.
  • New die cast magnesium alloys containing Sr (AJ alloys) and/or Ca (AX alloys) are interesting for high temperature automotive applications for example within the powertrain segment.
  • Sr containing alloys traditional salt of the MgCl2-CaCl2-NaCl system that e.g. is used for melt protection and fire extinguishing cannot be used. This is due to the thermodynamic stability of SrCl2. If an Sr containing alloy is in contact with a salt of this type, Sr in the alloy will react with MgCl2 in the salt phase forming SrCl2, with significant depletion of Sr in the alloy as a result. If all MgCl2 is reacted before the alloy is free of Sr, NaCl2 will be the next to react, causing Na contamination in the alloy. Alloys with Ca behave exactly similar.
  • the present invention relates to a salt composition which is equally or more thermodynamic stable than the known salt compositions and which can be used in combination with the above mentioned alloys, and as a fire extinguisher.
  • this can be achieved by using a salt composition which consist of halogenides of strontium, potassium, cesium or mixtures thereof.
  • the salt composition is a chloride and/or fluoride.
  • the different ions of the salt composition a present in the following amounts: 33-47 wt-% Sr 2 + 14-38 wt-% K+ 26-39 wt-% Cl ⁇ 0.5-1.3 wt-% F ⁇
  • the salt composition consists of: 48-75 wt-% SrCl2 20-45 wt-% KCl 2-6 wt-% KF, and 0-30 wt-% CsCl
  • the binary KCl-SrCl2 salt has several eutectics, the one with lowest melting point, 584° C., at 42.5 at % SrCl2, which corresponds to 66 wt % SrCl2.
  • compositions close to the eutectic with lowest melting point is beneficial, as it will e.g. protect molten alloy from oxidation at temperatures from the melting point of the salt and upwards.
  • SrCl2-KGI salts with a composition close to the 66 wt % SrCl2 eutectic were prepared, solidified and crushed.
  • Ingots of AJ62 (Mg—6 wt % Al—2.5 wt % Sr) were melted in two identical steel crucibles simultaneously, and the SrCl2-KGI salt was added for protection.
  • the AJ62 alloy started to melt before the salt starts melting, some oxidation was observed before the salt started to melt. However, once the salt melted (at 584° G) it completely covered the alloy and stopped the oxidation. It was observed that due to its much higher density some drainage of salt along the crucible walls occurred.
  • bursting of salt pools at the metal-salt interface could also take place.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Salt composition for protecting, refining and/or recycling molten magnesium or magnesium alloys, where in that the salt composition consists of halogen ides of strontium, potassium, cesium or mixtures thereof.

Description

  • The invention relates to a salt composition for protecting, refining and/or recycling molten magnesium or magnesium alloys, which at the same time can be used as a fire extinguisher.
  • New die cast magnesium alloys containing Sr (AJ alloys) and/or Ca (AX alloys) are interesting for high temperature automotive applications for example within the powertrain segment. When working with Sr containing alloys traditional salt of the MgCl2-CaCl2-NaCl system that e.g. is used for melt protection and fire extinguishing cannot be used. This is due to the thermodynamic stability of SrCl2. If an Sr containing alloy is in contact with a salt of this type, Sr in the alloy will react with MgCl2 in the salt phase forming SrCl2, with significant depletion of Sr in the alloy as a result. If all MgCl2 is reacted before the alloy is free of Sr, NaCl2 will be the next to react, causing Na contamination in the alloy. Alloys with Ca behave exactly similar.
  • Consequently, the present invention relates to a salt composition which is equally or more thermodynamic stable than the known salt compositions and which can be used in combination with the above mentioned alloys, and as a fire extinguisher.
  • According to the invention this can be achieved by using a salt composition which consist of halogenides of strontium, potassium, cesium or mixtures thereof.
  • It has been found that these types of salts have advanced properties in the protection, refining and/or recycling of molten magnesium”), or magnesium alloys.
  • Preferably the salt composition is a chloride and/or fluoride. In a preferred embodiment of the invention the different ions of the salt composition a present in the following amounts:
    33-47 wt-% Sr2+
    14-38 wt-% K+
    26-39 wt-% Cl−
    0.5-1.3 wt-% F−
  • More preferably the salt composition consists of:
    48-75 wt-% SrCl2
    20-45 wt-% KCl
     2-6 wt-% KF, and
     0-30 wt-% CsCl
  • The binary KCl-SrCl2 salt has several eutectics, the one with lowest melting point, 584° C., at 42.5 at % SrCl2, which corresponds to 66 wt % SrCl2. For applications with magnesium alloys compositions close to the eutectic with lowest melting point is beneficial, as it will e.g. protect molten alloy from oxidation at temperatures from the melting point of the salt and upwards.
  • Addition of BaCl2 and/or CsCl can further reduce the melting temperature of the salt. However, BaCl2 can immediately be excluded due to toxicity. CsCl can be added, but in practice its cost will be prohibitive
    • EXPERIMENTS
  • SrCl2-KGI salts with a composition close to the 66 wt % SrCl2 eutectic were prepared, solidified and crushed. Ingots of AJ62 (Mg—6 wt % Al—2.5 wt % Sr) were melted in two identical steel crucibles simultaneously, and the SrCl2-KGI salt was added for protection. As the AJ62 alloy started to melt before the salt starts melting, some oxidation was observed before the salt started to melt. However, once the salt melted (at 584° G) it completely covered the alloy and stopped the oxidation. It was observed that due to its much higher density some drainage of salt along the crucible walls occurred. Depending on the amount of salt in the cover layer bursting of salt pools at the metal-salt interface could also take place.
  • To obtain optimum protection, continuous replacement of the salt being drained towards the bottom of the crucible is recommended.
  • To simulate the situations in recycling furnaces the crucibles were filled ⅓ of salt. the remainder being alloy AJ62. Both systems were kept at 6900 C. In one of the furnaces (crucible B) 1 wt % KF was added to modify the SrCl2-KCl salt. In the reference system (crucible A) SrCl2-KCl salt was used without any additions. Both crucibles were stirred violently to ensure intimate salt-metal contact as is the situation in recycling, both with the Hydro Magnesium recycling furnace where superheated molten salt is sprayed over the alloy in order to melt the alloy and to strip off the oxides covering the alloy parts (or ingots) (ref. U.S. Pat. No. 5,167,700), and in the traditional batchwise recycling where typically 5-15% salt is intimately mixed with the molten alloy to remove the oxides in the alloy. It is an absolute necessity for a recycling process that after the violent mechanical stirring salt and metal quickly separate into two distinct phases, and not in a condition where metal droplets stay in a kind of permanent suspension (emulsion) in the salt phase. The latter condition is often called “fish metal” or “magnesium caviar” and is completely prohibitive for a recycling process, especially in the salt furnace where the salt/metal ratio sometimes is >1, and thus no metal can be recovered. In these tests it turned out that the violent stirring caused a permanent fish metal in both furnaces, perhaps slightly less pronounced in crucible B. Next, the KF content of the salt in crucible B was increased to 2 wt % by adding pure KF in the right amounts followed by violent stirring.
  • Once the stirring was terminated in system 8, the salt and metal separated into two distinct phases, with no signs of fish metal. Repeated stirring followed by a quiescent period (“settling”) in crucible A resulted in even more pronounced fish metal than before the stirring. The KF content in the salt in crucible 8 was increased to 3 and 6 wt % in two steps. Excellent salt metal separation was observed in both cases right after termination of the stirring. The reference system (crucible A) was stirred in the same way, with no change of the salt metal separation properties. Towards the end of the experiment, 2 wt % of KF was added to system A under violent stirring, and this had an immediate positive effect on the fish metal. Even before the stirring was terminated, salt and metal separated into two distinct phases with no signs of fish metal. From these tests it is obvious that KF additions in the range of 2-6 wt % to the SrCl2-KCl salt has an extremely positive effect on salt-metal separation properties, making this salt an exceptionally good candidate for recycling of alloys containing Sr, Ca and/or rare earth elements (Ce, La, Nd, Pr) as there will be no loss of these elements to the flux.
  • In another experiment the electrical conductivity of the eutectic SrCl2-KCl flux and reference salt of the MgCl2-CaCl2-NaCl2 type was measured. The reference salt was taken from the salt furnace (described in U.S. Pat. No. 4,385,931) during an arbitrary day of regular production. The results of the conductivity measurements are shown in FIG. 1, showing the electrical conductivity of eutectic
  • SrCl2-KCl-salt and a reference salt, in which the y-axis is the electrical conductivity and the x-axis is the temperature in DC.
  • Although the results show some scatter, it is clear that in the temperature range of interest the electrical conductivity of the SrCl2-KCl salt is 2.5 to 3 times higher than the reference salt. This implies that the MgCl2-CaCl2-NaCl2 salt in the salt furnaces and the recycling furnaces can be successfully replaced by the SrCl2-KCl salt if the electrical supply system of the salt furnace is adjusted to take the difference in electrical conductivity into account. This enables processing of for example Sr-containing Mg alloys in this type of equipment.

Claims (15)

1. Salt composition for protecting, refining and/or recycling molten magnesium or magnesium alloys, characterised in that the salt composition consists of halogen ides of strontium, potassium, cesium or mixtures thereof.
2. Salt composition according to claim 1, characterised in that the salt composition is a chloride and/or fluoride.
3. Salt composition according to claim 2, characterized in that the salt composition consists of:
 33-47 wt-% Sr2+  14-31 wt-% K+  21-39 wt-% Cl− 0.5-1.3 wt-% F−
4. Salt composition according to claim 1, characterised in that the salt composition consists of:
48-75 wt-% SrCb 20-45 wt-% KCl  2-6 wt-% KF, and  0-30 wt-% CsCl.
5. Salt composition according to claim 4, characterised in that the salt composition consists of:
55-75 wt-% SrCl2 25-45 wt-% KCl, and  2-6 wt-% KF
6. Salt composition according to claim 5, characterised in that the salt composition consists of:
60-70 wt-% SrCl2 30-40 wt-% KCl and  2-6 wt-% KF
7. Salt composition according to claim 6, characterised in that the salt composition consists of:
65-67 wt-% SrGl2, 33-35 wt-% KGl and  2-6 wt-% KF
8. Salt composition according to claim 2, characterised in that the salt composition consists of:
48-75 wt-% SrCb 20-45 wt-% KCl  2-6 wt-% KF, and  0-30 wt-% CsCl.
9. Salt composition according to claim 3, characterised in that the salt composition consists of:
48-75 wt-% SrCb 20-45 wt-% KCl  2-6 wt-% KF, and  0-30 wt-% CsCl.
10. Salt composition according to claim 8, characterised in that the salt composition consists of:
55-75 wt-% SrCl2 25-45 wt-% KCl, and  2-6 wt-% KF
11. Salt composition according to claim 9, characterised in that the salt composition consists of:
55-75 wt-% SrCl2 25-45 wt-% KCl, and  2-6 wt-% KF
12. Salt composition according to claim 10, characterised in that the salt composition consists of:
60-70 wt-% SrCl2 30-40 wt-% KCl and  2-6 wt-% KF
13. Salt composition according to claim 11, characterised in that the salt composition consists of:
60-70 wt-% SrCl2 30-40 wt-% KCl and  2-6 wt-% KF
14. Salt composition according to claim 12, characterised in that the salt composition consists of:
65-67 wt-% SrGl2, 33-35 wt-% KGl and  2-6 wt-% KF
15. Salt composition according to claim 13, characterised in that the salt composition consists of:
65-67 wt-% SrGl2, 33-35 wt-% KGl and  2-6 wt-% KF
US11/628,336 2004-06-04 2005-01-21 Salt Composition to be Used With Molten Magnesium Abandoned US20070214910A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04013240 2004-06-04
EP04013240.9 2004-06-04
PCT/EP2005/000586 WO2005118891A2 (en) 2004-06-04 2005-01-21 Salt composition to be used with molten magnesium

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Publication Number Publication Date
US20070214910A1 true US20070214910A1 (en) 2007-09-20

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US11/628,336 Abandoned US20070214910A1 (en) 2004-06-04 2005-01-21 Salt Composition to be Used With Molten Magnesium

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US (1) US20070214910A1 (en)
EP (1) EP1786938B1 (en)
CN (1) CN101035915A (en)
AT (1) ATE407228T1 (en)
CA (1) CA2565563A1 (en)
DE (1) DE602005009551D1 (en)
EA (1) EA200602224A1 (en)
NO (1) NO20065569L (en)
PL (1) PL1786938T3 (en)
WO (1) WO2005118891A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012107865A1 (en) * 2012-08-27 2014-05-15 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Method for casting conservations from magnesium alloy involves melting half-wrought material containing magnesium alloy and magnesium fire-protection additive, filling melt to sand casting form, solidifying and removing conservation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB652235A (en) * 1946-08-29 1951-04-18 Magnesium Elektron Ltd Improvements in or relating to fluxes for the treatment of light alloys

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012107865A1 (en) * 2012-08-27 2014-05-15 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Method for casting conservations from magnesium alloy involves melting half-wrought material containing magnesium alloy and magnesium fire-protection additive, filling melt to sand casting form, solidifying and removing conservation

Also Published As

Publication number Publication date
CN101035915A (en) 2007-09-12
WO2005118891A3 (en) 2007-05-31
WO2005118891A8 (en) 2007-07-19
WO2005118891A2 (en) 2005-12-15
CA2565563A1 (en) 2005-12-15
DE602005009551D1 (en) 2008-10-16
PL1786938T3 (en) 2009-01-30
EP1786938A2 (en) 2007-05-23
EP1786938B1 (en) 2008-09-03
NO20065569L (en) 2006-12-04
ATE407228T1 (en) 2008-09-15
EA200602224A1 (en) 2007-04-27

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AS Assignment

Owner name: NORSK HYDRO TECHNOLOGY B.V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAKKE, PER;REEL/FRAME:018884/0837

Effective date: 20070105

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Owner name: MAGONTEC GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NORSK HYDRO TECHNOLOGY B.V.;REEL/FRAME:021133/0350

Effective date: 20080414

STCB Information on status: application discontinuation

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