CN1537962A - Fluxing agent for refining magnesium alloy containing rare-earth - Google Patents
Fluxing agent for refining magnesium alloy containing rare-earth Download PDFInfo
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- CN1537962A CN1537962A CNA031182917A CN03118291A CN1537962A CN 1537962 A CN1537962 A CN 1537962A CN A031182917 A CNA031182917 A CN A031182917A CN 03118291 A CN03118291 A CN 03118291A CN 1537962 A CN1537962 A CN 1537962A
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Abstract
A flux used for refining RE-contained Mg alloy is prepared from high-purity NaCl, KCl, CaF2, BaCl2 and mixed RE chloride through smelting in graphite or stainless steel crucible in electric furnace, stirring, cooling, pouring in condensing mould, cooling, demoulding, and crushing. Its advantages are high smelting point, long stay time on the surface of molten metal, no chemical reaction on RE, and high refining effect.
Description
Use when [technical field] the present invention relates to a kind of magnesium alloy smelting that contains rare earth element, casting fire-retardant, anti-oxidant and have the flux of refining effect belongs to metallic substance and metallurgical class field.
[background technology 1 MAGNESIUM METAL chemical property is active; magnesium and magnesium alloy are in the melting and casting process; chemical reaction very easily takes place with airborne oxygen, nitrogen, aqueous vapor etc. in fused magnesium liquid; if bath surface is not protected; can very fast oxidizing fire near 700 ℃ of temperature the time, cause magnesium liquid scaling loss, the magnesium alloy oxide inclusion is serious even magnesium melt combustion explosion.Therefore, when magnesium alloy smelting, must carry out fire-retardant and refining, guarantee to obtain qualified magnesium alloy ingot its melt.In the magnesium alloy smelting process, contain the MgCl of heterogeneity the protection flux commonly used (as the RJ2 flux that generally adopts)
2, alkali such as KCl and alkaline-earth metal halogen, MgCl wherein
2Be the main component of flux, content is more than 40%～50%.When melting contains the magnesium alloy of rare earth composition, main component MgCl in rare earth element meeting in the alloy and the flux
2Chemical reaction takes place and cause the heavy losses of rare earth, the loss of rare earth composition sometimes can reach 15～30% even more serious.Especially when higher Mg-RE (rare earth) alloy of preparation content of rare earth; because the fusing point of rare earth is generally than higher; the temperature of alloy melting generally can be brought up to more than 850 ℃; when adopting common flux protection; the flux volatilization is serious; can't play well anti-oxidant fire-retardant and refining effect, and melting rare earth and MgCl have been aggravated under the high temperature
2Reaction and cause the scaling loss of rare earth further to increase, can't guarantee the recovery rate of rare earth and the quality of final magnesium alloy ingot.
Chinese patent 00125301.8 discloses the foaming flux that a kind of Mg-Al-Zn of being primarily aimed at alloy uses, and this flux comprises MgCl
2, NaCl, KCl, CaF
2, CaCl
2And the carbonate whipping agent etc., MgCl in the flux
2Content is 45%～75%, and the inert gas blown by whipping agent produces keeps the covering protection effect to magnesium liquid.But in this flux also mainly with MgCl
2Be main component, also exist rare earth and its reaction to cause the problem of loss.
Fire-retardant when [summary of the invention] cast smelting rare-earth-contained magnesium alloy at general flux, refining effect is undesirable, MgCl in the flux especially
2Can produce the problem that chemical reaction causes the rare earth loss with rare earth etc. main component, the invention provides a kind of flux that is exclusively used in preparation rare-earth-contained magnesium alloy (Mg-RE alloy).
It is technical pure or chemical pure NaCl, KCl, CaF that the present invention selects purity for use
2, BaCl
2And mixed rare earth chlorides is a raw material, under 100～120 ℃, in loft drier, remove planar water, even by the certain quality percentage mix, in resistance furnace, adopt graphite or Stainless Steel Crucible fusing, 700～800 ℃ of temperature of fusion, fully stir the fusing back fully, comes out of the stove after melt liquid is cooled to 600 ℃ and pour the condensation mould into, is cooled to the room temperature fragmentation and promptly obtains flux.
Each composition quality percentage ratio is in the flux: NaCl:10～20%; KCl:50～80%; CaF
2: 1～10%; BaCl
2: 1～10%; Rare earth chloride 2～10%, wherein rare earth chloride can be the mixed chloride of Cerium II Chloride, Lanthanum trichloride, rich lanthanum or rich neodymium.
The present invention has the fusing point higher than general flux; adopting differential thermal analysis to detect the flux fusing point is 540 ℃; fusing point than common flux is high more than 100 ℃; help prolonging after the flux melts in the magnesium liquid surface residence time; thereby play better fire-resisting protection effect, and do not have obvious chemical reaction with rare earth element in the magnesium alloy, the recovery rate that makes rare earth element is brought up to more than 90% from original 50%～75%; and good refining effect is arranged, can prepare high-quality qualified magnesium alloy ingot.
[description of drawings] Fig. 1: DTA measures flux fusing point of the present invention;
Fig. 2: flux is in the effect situation of bath surface, and wherein: Fig. 2-a: bath surface does not have flux protection, Fig. 2-b: the protective layer that uses flux protection alloy surface of the present invention to form, Fig. 2-c: use flux protection alloy surface reaction of the present invention to finish metal bath surface;
Fig. 3: utilize the Mg-RE alloy microscopic structure of flux preparation of the present invention, wherein: Fig. 3-a:Mg-17.47%Ce alloy microscopic structure.Fig. 3-b:Mg-31.48%Nd alloy microscopic structure.Fig. 3-c:Mg-2.83%Ce-Zn-Zr alloy microscopic structure, Fig. 3-d:Mg-2.86%Nd-Zn-Zr alloy microscopic structure;
Fig. 4: several Mg-RE alloy cast ingots that adopt flux preparation of the present invention.
[embodiment]
Embodiment 1
Flux component (mass percent) is: NaCl:10%; KCl:75%; CaF
2: 5%; BaCl
2: 2%; Cerium-rich mischmetal muriate: 8% (main component is a Cerium II Chloride).
Starting material are removed planar water under 110 ℃, mix in loft drier, in resistance furnace, adopt the plumbago crucible fusing, 700～800 ℃ of temperature of fusion, the constant resistance furnace temperature after arriving adds mixed raw materials, add-on is 1.0 kilograms of NaCl, 7.5 kilograms of KCl, 0.5 kilogram of CaF
2, 0.2 kilogram of BaCl
2With 0.8 kilogram of cerium-rich mischmetal muriate:, divide successively several times according to the crucible size to add, stir after the basic fusing, fully stirred 5～10 minutes the fusing back fully, after wholeization are clear, come out of the stove after melt liquid is cooled to 600 ℃ and pour the condensation mould into, be cooled to the room temperature fragmentation and promptly obtain flux.
Food ingredient be the magnesium alloy of 18% Rare-Earth Ce under 850 ℃ of smelting temperatures, this flux has good flame retardant effect, flux covers and reaches more than the 60min action time, satisfies the magnesium alloy smelting requirement.Flux has good refining effect, and melt degasification, slagging-off, impurity-eliminating effect are obvious, the ingot quality height.Sprinkle the flux particle through fragmentation on fusing magnesium liquid surface, flux melted rapidly and spread into the crucible surface area automatically about 10 second is 113cm
2The magnesium bath surface, form successive flux protection layer rapidly.When bath surface did not have flux protection, the rapid oxidation of melt generated the tawny oxide film, and oxide film is easy to break and makes melt oxidation degree aggravation (Fig. 2 (a)), continues oxidation, and magnesium liquid can very fast burning.After being sprinkled into flux on the melt, flux melts expansion rapidly to be protected alloy surface, the dark fine and close protective layer (Fig. 2 (b)) that flux forms.Under rational smelting temperature, the protective layer of liquid level very stops the alloy burning effectively, and can stir, operation such as degasification.Push the top layer after leaving standstill aside, can be observed metal bath surface as bright as a sixpence (Fig. 2 (c)).
Adopt the Mg-18%Ce rare earth alloy of this flux preparation, smelting temperature can reach 800～850 ℃, and the rare earth element ce in flux and the magnesium alloy do not have obvious chemical reaction, and the recovery rate of rare earth element ce is 97.1%.
Embodiment 2
Flux component (mass percent) is: NaCl:15%; KCl:70%; CaF
2: 5%; BaCl
2: 2%; Rich neodymium mixed rare-earth muriate: 8% (main component is a Neodymium trichloride).
Starting material are removed planar water under 110 ℃, mix in loft drier, in resistance furnace, adopt the plumbago crucible fusing, 700～800 ℃ of temperature of fusion, the constant resistance furnace temperature after arriving adds mixed raw materials, add-on is 1.5 kilograms of NaCl, 7.0 kilograms of KCl, 0.5 kilogram of CaF
2, 0.2 kilogram of BaCl
2With 0.8 kilogram of rich neodymium mixed rare-earth muriate, divide adding several times successively according to the crucible size, stir after the basic fusing, fully stirred 5～10 minutes the fusing back fully, after wholeization are clear, come out of the stove after melt liquid is cooled to 600 ℃ and pour the condensation mould into, be cooled to the room temperature fragmentation and promptly obtain flux.
Food ingredient be the magnesium alloy of 33% rare earth Nd under 900 ℃ of smelting temperatures, this flux has good flame retardant effect, flux covers and reaches more than the 60min action time, satisfies the magnesium alloy smelting requirement.Flux has good refining effect, and melt degasification, slagging-off, impurity-eliminating effect are obvious, the ingot quality height.
Adopt the Mg-33%Nd rare earth alloy of this flux preparation, smelting temperature can reach 850～900 ℃, and the rare earth element nd in flux and the magnesium alloy do not have obvious chemical reaction, and the rare earth element recovery rate is 95.4%.
Embodiment 3
Flux component (mass percent) is: NaCl:20%; KCl:65%; CaF
2: 2%; BaCl
2: 8%; Lanthanum rich mischmetal muriate: 5% (main component is a Lanthanum trichloride).
Starting material are removed planar water under 110 ℃, mix in loft drier, in resistance furnace, adopt the plumbago crucible fusing, 700～800 ℃ of temperature of fusion, the constant resistance furnace temperature after arriving adds mixed raw materials, add-on is 2 kilograms of NaCl, 6.5 kilograms of KCl, 0.2 kilogram of CaF
2, 0.8 kilogram of BaCl
2With 0.5 kilogram of lanthanum rich mischmetal muriate, divide adding several times successively according to the crucible size, stir after the basic fusing, fully stirred 5～10 minutes the fusing back fully, after wholeization are clear, come out of the stove after melt liquid is cooled to 600 ℃ and pour the condensation mould into, be cooled to the room temperature fragmentation and promptly obtain flux.
Food ingredient be the magnesium alloy of 30% Rare Earth Y under 900 ℃ of smelting temperatures, this flux has good flame retardant effect, flux covers and reaches more than the 60min action time, satisfies the magnesium alloy smelting requirement.Flux has good refining effect, and melt degasification, slagging-off, impurity-eliminating effect are obvious, the ingot quality height.
Adopt the Mg-30%Y rare earth alloy of this flux preparation, smelting temperature can reach 850～920 ℃, and the rare earth element y in flux and the magnesium alloy do not have obvious chemical reaction, and the rare earth element recovery rate is 89.8%.
Embodiment 4
Flux component (mass percent) is: NaCl:20%; KCl:60%; CaF
2: 2%; BaCl
2: 8%; Cerium-rich mischmetal muriate: 10% (main component is a Cerium II Chloride).
Starting material are removed planar water under 110 ℃, mix in loft drier, in resistance furnace, adopt the plumbago crucible fusing, 700～800 ℃ of temperature of fusion, the constant resistance furnace temperature after arriving adds mixed raw materials, add-on is 2.0 kilograms of NaCl, 6.0 kilograms of KCl, 0.2 kilogram of CaF
2, 0.8 kilogram of BaCl
2With 1.0 kilograms of cerium-rich mischmetal muriates, divide adding several times successively according to the crucible size, stir after the basic fusing, fully stirred 5～10 minutes the fusing back fully, after wholeization are clear, come out of the stove after melt liquid is cooled to 600 ℃ and pour the condensation mould into, be cooled to the room temperature fragmentation and promptly obtain flux.
Food ingredient be the Mg-Ce-Zn-Zr magnesium alloy of 3% Rare-Earth Ce under 720～760 ℃ of smelting temperatures, this flux has good flame retardant effect, flux covers and reaches more than the 60min action time, satisfies the magnesium alloy smelting requirement.Flux has good refining effect, and melt degasification, slagging-off, impurity-eliminating effect are obvious, the ingot quality height.
Adopt the Mg-3%Ce-Zn-Zr rare earth alloy of this flux preparation, smelting temperature can reach 720～760 ℃, and the rare earth element ce in flux and the magnesium alloy do not have obvious chemical reaction, and the rare earth element recovery rate is 94.3%.
Flux component (mass percent) is: NaCl:20%; KCl:65%; CaF
2: 2%; BaCl
2: 8%; Rich neodymium mixed rare-earth muriate: 5% (main component is a Neodymium trichloride).
Starting material are removed planar water under 110 ℃, mix in loft drier, in resistance furnace, adopt the plumbago crucible fusing, 700～780 ℃ of temperature of fusion, the constant resistance furnace temperature after arriving adds mixed raw materials, add-on is 2.0 kilograms of NaCl, 6.5 kilograms of KCl, 0.2 kilogram of CaF
2, 0.8 kilogram of BaCl
2With 0.5 kilogram of rich neodymium mixed rare-earth muriate, divide adding several times successively according to the crucible size, stir after the basic fusing, fully stirred 5～10 minutes the fusing back fully, after wholeization are clear, come out of the stove after melt liquid is cooled to 600 ℃ and pour the condensation mould into, be cooled to the room temperature fragmentation and promptly obtain flux.
Food ingredient be the Mg-Nd-Zn-Zr magnesium alloy of 3% rare earth Nd under 900 ℃ of smelting temperatures, this flux has good flame retardant effect, flux covers and reaches more than the 60min action time, satisfies the magnesium alloy smelting requirement.Flux has good refining effect, and melt degasification, slagging-off, impurity-eliminating effect are obvious, the ingot quality height.
Adopt the Mg-3%Nd-Zn-Zr rare earth alloy of this flux preparation, smelting temperature can reach 720～780 ℃, and the rare earth element nd in flux and the magnesium alloy do not have obvious chemical reaction, and the rare earth element recovery rate is 95.3%.
Claims (2)
1. magnesium-rare earth refining flux is characterized in that: it is technical pure or chemical pure NaCl, KCl, CaF that the present invention selects purity for use
2, BaCl
2Reaching mixed rare earth chlorides is raw material, and each composition quality percentage ratio is in the flux: NaCl:10～20%; KCl:50～80%; CaF
2: 1～10%; BaCl
2: 1～10%; Rare earth chloride 2～10%.
2. flux according to claim 1 is characterized in that: rare earth chloride can be the mixed chloride of Cerium II Chloride, Lanthanum trichloride, rich lanthanum or rich neodymium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118291 CN1216170C (en) | 2003-04-18 | 2003-04-18 | Fluxing agent for refining magnesium alloy containing rare-earth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118291 CN1216170C (en) | 2003-04-18 | 2003-04-18 | Fluxing agent for refining magnesium alloy containing rare-earth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1537962A true CN1537962A (en) | 2004-10-20 |
| CN1216170C CN1216170C (en) | 2005-08-24 |
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|---|---|---|---|
| CN 03118291 Expired - Fee Related CN1216170C (en) | 2003-04-18 | 2003-04-18 | Fluxing agent for refining magnesium alloy containing rare-earth |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398680C (en) * | 2006-08-14 | 2008-07-02 | 中国铝业股份有限公司 | Flux for heat resistant magnesium alloy |
| CN101831569A (en) * | 2010-06-01 | 2010-09-15 | 吉林大学 | Method for producing rare earth magnesium alloy by adopting rare earth oxide |
| CN102851523A (en) * | 2012-08-22 | 2013-01-02 | 淄博宏泰防腐有限公司 | Refining flux for smelting of WE43 magnesium alloy, and preparation and usage method thereof |
| CN103382525A (en) * | 2013-06-21 | 2013-11-06 | 燕山大学 | Magnesium alloy smelting protective fluxing agent and preparation method thereof |
| CN109055779A (en) * | 2018-09-19 | 2018-12-21 | 成都先进金属材料产业技术研究院有限公司 | The method of refining of magnesium refining agent and preparation method thereof and high purity magnesium |
| CN113106275A (en) * | 2021-04-09 | 2021-07-13 | 河北大有镁业有限责任公司 | Continuous production method of high-quality multi-element rare earth magnesium alloy with controllable end point component |
| CN113278839A (en) * | 2021-04-30 | 2021-08-20 | 上海交通大学 | Magnesium rare earth alloy melt purification and refinement composite treatment flux and application thereof |
| CN115354183A (en) * | 2022-08-26 | 2022-11-18 | 南昌大学 | Gadolinium-magnesium intermediate alloy purifying flux |
-
2003
- 2003-04-18 CN CN 03118291 patent/CN1216170C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398680C (en) * | 2006-08-14 | 2008-07-02 | 中国铝业股份有限公司 | Flux for heat resistant magnesium alloy |
| CN101831569A (en) * | 2010-06-01 | 2010-09-15 | 吉林大学 | Method for producing rare earth magnesium alloy by adopting rare earth oxide |
| CN102851523A (en) * | 2012-08-22 | 2013-01-02 | 淄博宏泰防腐有限公司 | Refining flux for smelting of WE43 magnesium alloy, and preparation and usage method thereof |
| CN103382525A (en) * | 2013-06-21 | 2013-11-06 | 燕山大学 | Magnesium alloy smelting protective fluxing agent and preparation method thereof |
| CN109055779A (en) * | 2018-09-19 | 2018-12-21 | 成都先进金属材料产业技术研究院有限公司 | The method of refining of magnesium refining agent and preparation method thereof and high purity magnesium |
| CN113106275A (en) * | 2021-04-09 | 2021-07-13 | 河北大有镁业有限责任公司 | Continuous production method of high-quality multi-element rare earth magnesium alloy with controllable end point component |
| CN113278839A (en) * | 2021-04-30 | 2021-08-20 | 上海交通大学 | Magnesium rare earth alloy melt purification and refinement composite treatment flux and application thereof |
| CN113278839B (en) * | 2021-04-30 | 2022-02-25 | 上海交通大学 | Magnesium rare earth alloy melt purification and refinement composite treatment flux and application thereof |
| CN115354183A (en) * | 2022-08-26 | 2022-11-18 | 南昌大学 | Gadolinium-magnesium intermediate alloy purifying flux |
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| Publication number | Publication date |
|---|---|
| CN1216170C (en) | 2005-08-24 |
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