CN101501177A - Molten salts for the refining of MG alloys - Google Patents
Molten salts for the refining of MG alloys Download PDFInfo
- Publication number
- CN101501177A CN101501177A CNA2007800250005A CN200780025000A CN101501177A CN 101501177 A CN101501177 A CN 101501177A CN A2007800250005 A CNA2007800250005 A CN A2007800250005A CN 200780025000 A CN200780025000 A CN 200780025000A CN 101501177 A CN101501177 A CN 101501177A
- Authority
- CN
- China
- Prior art keywords
- fused salt
- magnesium
- magnesium alloy
- licl
- molten salt
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- 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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (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)
Abstract
The present invention relates to a molten salt for refining magnesium alloys, especially Sr- containing magnesium alloys, and more specifically, relates to a molten salt for refining magnesium alloys to effectively remove impurities and to minimize the loss of Sr from Sr- containing magnesium molten alloy melt. This molten salt is a LiCl-KCl binary molten salt, a LiCl-KCl-NaCl ternary molten salt, or a binary or ternary molten salt containing 20% or less of MgCl2 or CaCl2 based on the total weight thereof. The molten salt may include 10 wt% or less of impurities in the working procedure.
Description
Technical field
The present invention relates to a kind of fused salt that is used for the refined magnesium alloy, relate in particular to and be used for the fused salt that refining contains the magnesium alloy of Sr, more particularly, the present invention relates to a kind of fused salt that is used for the refined magnesium alloy, thereby remove impurity effectively and will contain the minimization of loss of the Sr in the melts (Sr-containing magnesiummolten alloy melt) of the magnesium molten alloy of Sr.
Background technology
Even contain the magnesium alloy of Sr because it is in light weight, intensity is high and at high temperature also have high creep property when casting contains the magnesium alloy of Sr in formation contains the process of intermetallic compound of Sr, receive publicity as material of future generation so contain the magnesium alloy of Sr.
Based on these character, the Mg-Al-Sr alloy is as the application phenomenal growth of the parts of motor vehicle or aircraft (particularly as the high temperature magnesium-alloy material) recently.By in stove, this parts being made in Mg-Al-Sr magnesium alloy ingot fusing and the die casting mainly carried out subsequently.Therefore, have high-quality the finished product, must prepare and have high-quality Mg-Al-Sr magnesium alloy ingot in order to produce.
Prepare magnesium alloy ingot in this manner, that is, in stove, melt, and add the high purity alloys metal that comprises Al or Zn at about 700 ℃ of following pure Mg ingot castings with at least 99%, thereby regulate the final alloy compositions of magnesium alloy ingot, with the form of magnesium alloy ingot it is solidified then.Yet, because the avidity height of magnesium and oxygen, thus in stove molten magnesium and add to produce inevitably in the process of alloyed metal and comprise MgO, Mg
3N
2, MgAl
2O
4, intermetallic compound etc. various impurity and inclusion.In addition, because these inclusiones have and the similar proportion of fused magnesium, so their separation are needed long time by floating or precipitation.Therefore, in order to increase the purpose of magnesium alloy productive rate, need to shorten and remove the required time of inclusion.For this reason, utilize Ar to bubble floating and separates these inclusiones by gas, and the surface of adding the fused salt of chloride-based to fused magnesium, thereby absorption and removal inclusion.In addition, proportion is responsible for absorbing and removing various impurity than when high some fused salts of the proportion of magnesium are in being deposited in fused magnesium.
The example that is used to prepare the fused salt of magnesium alloy is CaCl
2-MgCl
2Although and slightly different, great majority all adopt CaCl to the component of fused salt according to manufacturers
2And MgCl
2
In order to prepare the Mg-Al-Sr magnesium alloy ingot, have high-quality Sr metal and be added in the fused magnesium, thereby melt Sr equably.Fusing point is to need long-time fusing near 777 ℃ the fused magnesium of Sr 700 ℃.Therefore, after having added Sr, in stove, provide water screw or screw rod, thereby fused magnesium is applied rotary power, thereby shorten the time period that Sr melts.
Summary of the invention
Technical problem
Yet, in process of production, be deposited in the fused magnesium or the lip-deep various impurity that swim in fused magnesium invade in the melts of magnesium molten alloy, and after the Sr fusion, need to remove for a long time these impurity undesirably.Under the situation of using the fused salt be generally used for removing this impurity now, Sr is melted and combines with fused salt, thereby the concentration of Sr is greatly diminished in the magnesium.
Therefore, in order to improve the productive rate of the magnesium alloy ingot that contains Sr, should develop refining fused salt with novel composition.
The present invention keeps it in mind the above-mentioned problems in the prior art, and a kind of fused salt that is used for the refined magnesium alloy is provided, and this fused salt can be removed impurity effectively, makes the minimization of loss of Sr simultaneously when preparation contains the magnesium alloy of Sr.
Technical scheme
According to the present invention, the fused salt that is used for the refined magnesium alloy can contain 20% or still less MgCl for LiCl-KCl binary fused salt, LiCl-KCl-NaCl ternary fused salt or based on the gross weight of fused salt
2Or CaCl
2Binary or ternary fused salt.
In process of production, described fused salt can comprise 10wt% or impurity still less, for example, the muriate of Fe, Al, Rb, La, Ce, Nd, Ba, Br, Sr, Cs, Mn, Co, Ni, Zn and Cr, fluorochemical, nitride and oxide compound or intermetallic compound.
The component that is used for the fused salt of refined magnesium alloy according to the present invention obtains based on following principle.
Owing to use MgCl
2Replacement is as fused salt, so fusing and and the MgCl of the Sr in the melts of needs consideration magnesium molten alloy
2Combination, therefore shown in following reaction 1 Sr in fused salt with SrCl
2Form fusing.
Reaction 1
MgCl
2(fused salt)+Sr (Mg alloy) → Mg (Mg alloy)+SrCl
2(fused salt)
The reason that above reaction takes place is SrCl
2On thermodynamics, compare MgCl
2More stable.Its thermodynamic stability is compared, and fused salt is according to MgCl
2＜CaCl
2＜NaCl＜SrCl
2The order of＜KCl＜LiCl can be more stable towards LiCl.Therefore, has minimum MgCl when having prepared
2Or CaCl
2Fused salt when being used for the fused salt of refined magnesium alloy, the minimization of loss of expectation Sr.
In addition, remove various impurity effectively in order to utilize fused salt from the melts of magnesium molten alloy, fused salt should exist with solution state under the temperature that is used for the refining melts.Like this, fused salt should have low viscosity (that is, high flowability), thereby the speed of reaction of fused salt increases in the melts of magnesium molten alloy, and removes impurity at short notice.Have low viscous fused salt and have low fusing point usually.
Beneficial effect
According to the as above fused salt that is used for the refined magnesium alloy of structure, contain in the process of magnesium alloy of Sr in preparation, can remove impurity effectively, also can be with the minimization of loss of Sr.
Embodiment
Based on the fact of in technical scheme, describing, simultaneously the salt composition of the minimization of loss of the Sr in the fused magnesium is estimated removing impurity effectively, and tested.According to purpose of the present invention, the result of some components in a plurality of test-results has been shown below in the table 1.Unless following concrete in addition definition, otherwise % represents wt%.
As test conditions, magnesium alloy is made up of 96%Mg-3%Al-1%Sr, and the weight ratio of magnesium alloy and fused salt is set to 10:1, and technological temperature is set to 700 ℃.In addition, after reacting, studied the component of magnesium alloy and the component of fused salt, thereby determined the extent of damage of Sr with fused salt.
Table 1
Can be clear that from table 1, comprise MgCl
2And CaCl
2In the comparative examples 1 and comparative examples 2 of fused salt as main ingredient, observe in the 96%Mg-3%Al-1%Sr magnesium alloy of initial use and lost most Sr, therefore remained 1ppm or amount still less.
Yet in the example 1 of the binary fused salt that utilizes 45%LiCl-55%KCl, magnesium alloy is confirmed as 96%Mg-3%Al-0.99%Sr-0.01K after the reaction, and therefrom Sr has only lost about 0.01% amount as can be seen.Like this, the suitable ingredients of fused salt is 35～55%LiCl-45～65%KCl.
In the example 2 of the ternary fused salt that utilizes 41%LiCl-50%KCl-9%NaCl, magnesium alloy is confirmed as Mg-3Al-0.79Sr-0.11Na after the reaction, and therefrom Sr has lost about 0.21% amount as can be seen.Like this, the component of fused salt is shown as LiCl that umber ratio by weight is 0.6～1.5:1 and KCl and comprises 15% or be suitable during still less NaCl based on the gross weight of fused salt.
Contain 5% CaCl in utilization
2The example 3 of 42.5%LiCl-52.5%KCl in, magnesium alloy is confirmed as Mg-3Al-0.63Sr-0.17Ca after the reaction, therefrom Sr has lost about 0.37% amount as can be seen.In addition, contain 5% MgCl in utilization
2The example 4 of fused salt of 42.5%LiCl-52.5%KCl in, magnesium alloy is confirmed as Mg-3Al-0.54Sr after the reaction, therefrom Sr has lost about 0.46% amount as can be seen.Like this, as can be seen, fused salt is consisted of contains LiCl that portion rate by weight is 0.4～1.7:1 and KCl and based on 20% or still less CaCl of fused salt gross weight
2Or MgCl
2And during based on 15% or still less NaCl of fused salt gross weight, the loss of Sr is remained on 50% the level that is not more than effectively in the melts of magnesium molten alloy.
Claims (3)
1, a kind of fused salt that is used for the refined magnesium alloy is used for removing the impurity of the melts of magnesium molten alloy, and described fused salt comprises:
The LiCl of 35～55wt% and the KCl of 45～65wt%.
2, a kind of fused salt that is used for the refined magnesium alloy is used for removing the impurity of the melts of magnesium molten alloy, and described fused salt comprises:
The umber ratio is the LiCl of 0.6～1.5:1 and KCl and based on 15% or still less NaCl of fused salt gross weight by weight.
3, a kind of fused salt that is used for the refined magnesium alloy is used for removing the impurity of the melts of magnesium molten alloy, and described fused salt comprises:
By weight the umber ratio be the LiCl of 0.4～1.7:1 and KCl, based on 20% or still less CaCl of fused salt gross weight
2Or MgCl
2And 15% or NaCl still less.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060061048A KR100760581B1 (en) | 2006-06-30 | 2006-06-30 | Molten salts for the refining of mg alloys |
| KR10-2006-0061048 | 2006-06-30 | ||
| KR1020060061048 | 2006-06-30 | ||
| PCT/KR2007/003201 WO2008002111A1 (en) | 2006-06-30 | 2007-07-02 | Molten salts for the refining of mg alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101501177A true CN101501177A (en) | 2009-08-05 |
| CN101501177B CN101501177B (en) | 2012-09-19 |
Family
ID=38738413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800250005A Expired - Fee Related CN101501177B (en) | 2006-06-30 | 2007-07-02 | Molten salts for the refining of MG alloys |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100760581B1 (en) |
| CN (1) | CN101501177B (en) |
| RU (1) | RU2417266C2 (en) |
| WO (1) | WO2008002111A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914699A (en) * | 2010-07-26 | 2010-12-15 | 中国科学院长春应用化学研究所 | Fused salt electrosynthesis method of hydrogen storage alloy containing magnesium, lithium, sodium and potassium |
| CN103710548A (en) * | 2013-12-24 | 2014-04-09 | 上海交通大学 | Aluminum/aluminum alloy efficient silica removal flux as well as preparation method and use thereof |
| CN105624431A (en) * | 2014-10-31 | 2016-06-01 | 云南新立有色金属有限公司 | Method for cleaning ladle inner container |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468976B (en) * | 2013-10-12 | 2014-10-08 | 青海三工镁业有限公司 | No-pollution green environment-friendly fluxing agent for magnesium and magnesium alloy and preparation method thereof |
| CN103805791B (en) * | 2014-03-03 | 2016-01-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Crude magnesium is except aluminium method of refining and crude magnesium are except aluminium refining flux |
| CN105463228B (en) * | 2015-12-04 | 2018-03-30 | 福建省闽华电源股份有限公司 | A kind of metal melting protective agent based on chloride and preparation method thereof |
| US20210010104A1 (en) * | 2017-09-07 | 2021-01-14 | Industry-University Cooperation Foundation Hanyang University Erica Campus | Molten salt composition for smelting magnesium using solid oxide membrane (som) process |
| KR102235356B1 (en) * | 2019-06-26 | 2021-04-01 | 부경대학교 산학협력단 | Method of metal carbide coating of diamond particles and diamond particles coated with metal carbide manufactured by same method |
| KR102444651B1 (en) * | 2020-11-04 | 2022-09-20 | 한국재료연구원 | Flux for refining molten magnesium and method of refining molten magnesium using the same |
| CN114657407B (en) * | 2022-03-29 | 2022-11-18 | 河北钢研德凯科技有限公司 | Protective solvent for DKM7 alloy smelting and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4384887A (en) | 1979-11-14 | 1983-05-24 | The Dow Chemical Co. | Process of making salt-coated magnesium granules |
| US4559084A (en) | 1981-05-26 | 1985-12-17 | The Dow Chemical Company | Salt-coated magnesium granules |
| JPH03138389A (en) * | 1989-10-23 | 1991-06-12 | Kawasaki Steel Corp | Zn-mg alloy plated steel sheet having excellent plating adhesion and corrosion resistance and its production |
| KR20000006623A (en) * | 1999-07-06 | 2000-02-07 | 이인호 | A method for manufacturing a disintegrative core for a high pressure casting, a core and a method for extracting the core |
| CN1108389C (en) * | 2000-06-27 | 2003-05-14 | 北京科技大学 | Process for in-situ alloying and reaction particles reiforced metal-base composition |
-
2006
- 2006-06-30 KR KR1020060061048A patent/KR100760581B1/en active IP Right Grant
-
2007
- 2007-07-02 CN CN2007800250005A patent/CN101501177B/en not_active Expired - Fee Related
- 2007-07-02 RU RU2009100952/02A patent/RU2417266C2/en not_active IP Right Cessation
- 2007-07-02 WO PCT/KR2007/003201 patent/WO2008002111A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914699A (en) * | 2010-07-26 | 2010-12-15 | 中国科学院长春应用化学研究所 | Fused salt electrosynthesis method of hydrogen storage alloy containing magnesium, lithium, sodium and potassium |
| CN103710548A (en) * | 2013-12-24 | 2014-04-09 | 上海交通大学 | Aluminum/aluminum alloy efficient silica removal flux as well as preparation method and use thereof |
| CN105624431A (en) * | 2014-10-31 | 2016-06-01 | 云南新立有色金属有限公司 | Method for cleaning ladle inner container |
| CN105624431B (en) * | 2014-10-31 | 2018-06-19 | 云南冶金新立钛业有限公司 | Method for cleaning ladle inner container |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101501177B (en) | 2012-09-19 |
| KR100760581B1 (en) | 2007-09-20 |
| RU2417266C2 (en) | 2011-04-27 |
| RU2009100952A (en) | 2010-08-10 |
| WO2008002111A1 (en) | 2008-01-03 |
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Granted publication date: 20120919 Termination date: 20160702 |