CN1219088C - Mangnesium alloy zirconium compound silicon-removing flux and its production method - Google Patents
Mangnesium alloy zirconium compound silicon-removing flux and its production method Download PDFInfo
- Publication number
- CN1219088C CN1219088C CN 03141550 CN03141550A CN1219088C CN 1219088 C CN1219088 C CN 1219088C CN 03141550 CN03141550 CN 03141550 CN 03141550 A CN03141550 A CN 03141550A CN 1219088 C CN1219088 C CN 1219088C
- Authority
- CN
- China
- Prior art keywords
- magnesium
- magnesium alloy
- chloride
- flux
- fluoride
- 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 - Fee Related
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a magnesium alloy zirconium compound silicon removing fusing agent and a production method thereof. The mass percentage of components of the magnesium alloy zirconium compound silicon removing fusing agent comprises 30 to 45% of aqueous magnesium chloride, 15 to 25% of potassium chloride, 5 to 12% of barium chloride, 10 to 17% of calcium fluoride, 10 to 25% of magnesium fluoride, 3 to 8% of sodium fluoride, 2 to 8% of zirconium tetrachloride and/or potassium fluorozirconide. Firstly, a crucible is heated, the potassium chloride and the barium chloride are added, the calcium fluoride, the magnesium fluoride and the sodium fluoride are added after parts of the potassium chloride and the barium chloride are heated to be melted, the components are uniformly stirred and poured into blocks after being heated to 750 to 790 DEG C, and the components are loaded in a ball mill after being crushed, are added with the magnesium chloride, the tetrachloride and/or potassium fluorozirconide to be milled into powder and are prepared into the fusing agent. The magnesium alloy zirconium compound silicon removing fusing agent provided by the present invention has good deslagging performance, effectively reduces the silicon content in magnesium alloy and particularly has better eliminating effect on Mg2Si, so the mechanical performance and the corrosion resisting performance of the magnesium alloy are improved.
Description
The technical field is as follows:
the invention relates to a magnesium alloy desilicication flux and a production method thereof, in particular to a magnesium alloy zirconium compound desilicication flux and a production method thereof, belonging to the technical field of metal materials and metallurgy.
Background art:
the magnesium alloy has the advantages of small density, high specific strength and specific stiffness, good damping performance, good electromagnetic shielding performance and the like, and becomes an important light material in the automobile and electronic industry in recent years. China is a large magnesium resource country, but most of magnesium is exported in a low-price raw material form, and the main reason is that the content of non-metallic inclusions and harmful impurity elements in the magnesium alloy is high. As magnesium metal is increasingly used in industry, higher requirements are put on the purity of magnesium, and it is generally required to effectively remove silicon, iron, nickel, copper and other metal impurities in magnesium. At present, the magnesium alloy is mostly produced by adopting a silicothermic method in China, and the silicon content in the magnesium is higher. Silicon is a harmful inclusion in magnesium alloy, has low solid solubility in magnesium, and exists in the forms of simple substance, oxide and magnesium silicide. Research work shows that the impurity silicon in the magnesium alloy accounts for 10.58 percent of the content of the simple substance silicon in the magnesium alloy, and accounts for SiO2The form is 7.94%, and the rest is Mg2The form of Si exists. Due to insoluble phase Mg2Si has larger potential difference with the matrix, which can reduce the corrosion resistance of the alloy; and a brittle phase Mg2Si cannot be dissolved by heat treatment, thereby reducing the plasticity of the alloy. Therefore, the silicon removal of magnesium alloy is mainly to remove Mg2And (3) Si. At present, the only treatment method for crude magnesium with high silicon content is to mix and smelt with a proper amount of low silicon content to dilute silicon impurities, but the original secondary magnesium is reduced to tertiary magnesium, which is obviously not an ideal method. RJ2 flux is currently commonly used to refine magnesium alloys, the flux being such that, in addition to K, Na two metal impuritiesIt is difficult to remove other metal impurities (e.g., Si, Fe, Ni, etc.). The RJ2 flux refining process relies on adsorption to remove non-metallic impurities, and the reaction formula is as follows: in the formula: x-a non-metallic impurity, MeClx-a certain metal chloride. MgCl contained in the flux2Can remove certain oxidation impurities (such as MgO, CaO, Fe) represented by MgO2O3And Al2O3Etc.); when the flux contains 10% -15% of CaF2When SiO can be removed2And small amounts of aluminum, but for Mg2The removal of Si does not work. The flux has insufficient adsorption to inclusions in the magnesium melt, and the flux is easy to be mixed into alloy liquid to become flux inclusions, so that the performance of the alloy is seriously influenced. At present, the Chinese medicine is better for domestic useThe magnesium alloy flux is a JDMJ magnesium alloy refining agent developed by Shanghai university of transportation, has the double effects of flux protection and gas protection, can effectively prevent magnesium alloy liquid from being oxidized, improves the metallurgical quality of magnesium alloy, releases harmful gas far lower than the national emission standard, and is beneficial to environmental protection and the health of operators. Such as that described in the literature "development of novel pollution-free magnesium alloy flux" (Dian Chun spring, Dingwenjiang, etc., Special casting and non-ferrous alloys, 1997, (4): 48-50). Although the flux has excellent slag removal performance, it has no effect of removing silicon.
The reports on the formula of the silicon removal flux for magnesium alloy are very few at present, and the magnesium alloy silicon removal flux is introduced in the document Zhaichun spring, Zhai Xiao Du, Dingwenjiang and the like mechanical engineering materials 2001, 25 (1): 6-10, and comprises the following components: 20-35% MgCl2，16-29％KCl，12-23％CaF2，8-12％BaCl2，8-12％MgF2. The flux has certain SiO removal effect2But removing Mg2Si has poor capability. Although cobalt halide or titanium tetrachloride can chemically react with silicon to produce volatile gases or reduce the silicon content of magnesium by physical adsorption causing products to sink into the slag: in the formula: impurities in X-magnesium, Me-additive. But cobalt halidesThe price of the product is expensive and difficult to popularize and apply. And the addition of titanium tetrachloride and the introduction of argon gas into a closed container for refining have complex equipment, thereby greatly improving the cost of the alloy. Therefore, it is necessary to develop a new magnesium alloy silicon removal flux.
The invention content is as follows:
the invention aims to overcome the defects of poor silicon removal effect and difficult Mg removal of the existing magnesium alloy flux2The defect of Si, the composition of the existing flux is adjusted, and a flux capable of removing SiO is provided2And can effectively remove Mg2The magnesium alloy silicon-removing flux of Si has better slag-removing effect, convenient operation and low cost.
In order to realize the purpose, the invention provides a silicon-removing flux of a magnesium alloy zirconium compound and a production method thereof, wherein the flux adopts hydrous magnesium chloride (MgCl)2·6H2O), and sodium fluoride (NaF) and zirconium tetrachloride (ZrCl) are added4) And/or potassium fluorozirconates (K)2ZrF6). The range of the components (mass percent) is as follows: 30-45% aqueous magnesium chloride (MgCl)2·6H2O), 15-25% potassium chloride (KCl), 5-12% barium chloride (BaCl)2) 10-17% calcium fluoride (CaF)2) 10-25% of magnesium fluoride (MgF)2) 3-8% of sodium fluoride (NaF) and 2-8% of zirconium tetrachloride (ZrCl)4) And/or potassium fluorozirconates (K)2ZrF6)。
The production method of the magnesium alloy desilicication flux provided by the invention comprises the following steps: heating the crucible to a certain temperature, adding potassium chloride and barium chloride, heating to partially melt, adding calcium fluoride, magnesium fluoride and sodium fluoride, heating to 750-. Crushing, ball milling, adding magnesium chloride, zirconium tetrachloride and/or potassium fluorozirconate, ball milling to powder, and sieving with No. 20-40 sieve. The prepared flux is put into a closed container for standby.
When the magnesium alloy is used, when the temperature of the magnesium alloy is raised to 760 ℃ below zero in a resistance crucible furnace, 3 percent of silicon-removing flux is continuously scattered on the liquid surface, and meanwhile, a refining spoon is used for stirring up and down to enable the magnesium liquid to circularly flow so as to prolong the flow of the solvent liquid drops, and the magnesium alloy is usually kept for about 10 minutes until the liquid surface is a bright mirror surface.
The flux uses CaF2、MgF2Mixed fluoride salt composed of NaF, calcium fluoride in flux can be removed by SiO in refining process2Silicon in the form of a gas, undergoes a chemical action such that the silicon is volatilized off in the gas state, however, CaF2Can not remove Mg2And (3) Si. Mgf in flux2The following reactions take place during the refining process, to make SiO2Is further removed. In addition, MgF is added in the using process of the flux2Will also react with MgCl2The crystal water in the solution acts to separate out HF, the generated HF can effectively remove Mg2Si， ， 。
In addition, a zirconium compound with higher activity is added into the flux to remove silicon. During the refining process, the zirconium compound reacts with silicon, an impurity in magnesium, to form refractory intermetallic compounds with low solubility in magnesium, and then the refractory intermetallic compounds settle down. Zirconium ZrCl4And/or K2ZrF6Is added in the form of (1). Zirconium tetrachloride ZrCl4The following effects can occur with magnesium as follows, and K is2ZrF6The reaction with Mg is as follows, the density difference between the generated simple substance Zr and the molten magnesium is large, and the chemical activity of the zirconium is strong, so that the zirconium and the Si in the magnesium can generate a magnesium-insoluble compound to be precipitated into the slag. Zr can also react with H in magnesium melt2A solid compound is formed, thereby reducing the amount of hydrogen dissolved in the magnesium.
The magnesium alloy zirconium compound desilicication flux provided by the invention has the remarkable advantages that the flux overcomes the defects of poor desilicication effect and difficulty in removing Mg of the existing magnesium alloy flux2Si deficiency, effective reduction of silicon content in magnesium alloys, particularly for Mg2Si has a good removing effect, so that the mechanical property and the corrosion resistance of the magnesium alloy are improved. Meanwhile, the flux has excellent slag removal performance, convenient operation and low cost. The flux has larger density difference with the alloy liquid, proper viscosity and good chemical stability, and is not easy to be mixed into the alloy liquid to generate the inclusion of the flux. The flux has less harmful gas and meets the industrial sanitary standard and the exhaust emission requirement.
The specific implementation mode is as follows:
the technical solution of the present invention is further described below by specific examples.
Example 1:
the magnesium alloy zirconium compound silicon-removing flux comprises the following components in percentage by mass: 45% aqueous magnesium chloride (MgCl)2·6H2O), 15% potassium chloride (KCl), 8% barium chloride (BaCl)2) 10% calcium fluoride (CaF)2) 11% magnesium fluoride (MgF)2) Sodium fluoride (NaF) 4%, zirconium tetrachloride (ZrCl) 7%4)。
The production method of the magnesium alloy silicon-removing flux comprises the following steps: heating the crucible to about 300 ℃, adding potassium chloride and barium chloride, heating to partially melt, adding calcium fluoride, magnesium fluoride and sodium fluoride, heating to about 750 ℃, uniformly stirring, and casting into blocks. Crushing, ball milling, adding magnesium chloride and zirconium tetrachloride, ball milling to powder, and sieving with No. 20 sieve. The prepared flux is put into a closed container for standby.
When the magnesium alloy is used, when the temperature of the magnesium alloy is raised to 760 ℃ below zero in a smelting furnace, 3 percent of silicon-removing flux is continuously scattered on the liquid surface, and meanwhile, a refining spoon is used for stirring up and down to enable the magnesium liquid to circularly flow so as to prolong the flow of the solvent liquid drops and keep the temperature for about 10 minutes until the liquid surface is a bright mirror surface. The silicon content of the AZ91 magnesium alloy can be reduced from 0.069% to below 0.018%.
Example 2:
silicon melting of magnesium alloy zirconium compoundThe components (mass percent) of the agent are as follows: 30% aqueous magnesium chloride (MgCl)2·6H2O), 15% potassium chloride (KCl), 5% barium chloride (BaCl)2) 12% calcium fluoride (CaF)2) 25% magnesium fluoride (MgF)2) 5% of sodium fluoride (NaF) and 8% of potassium fluorozirconate (K)2ZrF6)。
The production method of the magnesium alloy silicon-removing flux comprises the following steps: heating the crucible to about 250 ℃, adding potassium chloride and barium chloride, heating to partially melt, adding calcium fluoride, magnesium fluoride and sodium fluoride, heating to about 760 ℃, uniformly stirring, and casting into blocks. Crushing, ball milling, adding magnesium chloride and potassium fluorozirconate, ball milling to powder, and sieving with No. 30 sieve. The prepared flux is put into a closed container for standby.
When the magnesium alloy is used, when the temperature of the magnesium alloy is raised to 760 ℃ below zero in a smelting furnace, 3 percent of silicon-removing flux is continuously scattered on the liquid surface, and meanwhile, a refining spoon is used for stirring up and down to enable the magnesium liquid to circularly flow so as to prolong the flow of the solvent liquid drops and keep the temperature for about 10 minutes until the liquid surface is a bright mirror surface. The silicon content of the AZ91 magnesium alloy can be reduced from 0.069% to below 0.014%.
Example 3:
the magnesium alloy zirconium compound silicon-removing flux comprises the following components in percentage by mass: 30% aqueous magnesium chloride (MgCl)2·6H2O), 23% potassium chloride (KCl), 10% barium chloride (BaCl)2) 16% calcium fluoride (CaF)2) 10% magnesium fluoride (MgF)2) 7% sodium fluoride (NaF), 2% zirconium tetrachloride (ZrCl)4) And 2% of potassium fluorozirconate (K)2ZrF6)。
The production method of the magnesium alloy silicon-removing flux comprises the following steps: heating the crucible to about 350 ℃, adding potassium chloride and barium chloride, heating to partially melt, adding calcium fluoride, magnesium fluoride and sodium fluoride, heating to about 790 ℃, uniformly stirring, and casting into blocks. Crushing, ball milling, adding magnesium chloride, zirconium tetrachloride and potassium fluorozirconate, ball milling to powder, and sieving with No. 40 sieve. The prepared flux is put into a closed container for standby.
When the magnesium alloy is used, when the temperature of the magnesium alloy is raised to 760 ℃ below zero in a smelting furnace, 3 percent of silicon-removing flux is continuously scattered on the liquid surface, and meanwhile, a refining spoon is used for stirring up and down to enable the magnesium liquid to circularly flow so as to prolong the flow of the solvent liquid drops and keep the temperature for about 10 minutes until the liquid surface is a bright mirror surface. The silicon content of the AZ91 magnesium alloy can be reduced from 0.069% to below 0.012%.
Claims (2)
1. The silicon-removing flux for the zirconium compound of the magnesium alloy is characterized by comprising the following components in percentage by mass: 30-45% of hydrous magnesium chloride, 15-25% of potassium chloride, 5-12% of barium chloride, 10-17% of calcium fluoride, 10-25% of magnesium fluoride, 3-8% of sodium fluoride and 2-8% of zirconium tetrachloride and/or potassium fluorozirconate.
2. A process for preparing the silicon-removing flux of Zr compound for magnesium alloy as claimedin claim 1 includes such steps as heating crucible, adding potassium chloride and barium chloride, heating to partially melt, adding calcium fluoride, magnesium fluoride and sodium fluoride, heating to 750-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141550 CN1219088C (en) | 2003-07-10 | 2003-07-10 | Mangnesium alloy zirconium compound silicon-removing flux and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141550 CN1219088C (en) | 2003-07-10 | 2003-07-10 | Mangnesium alloy zirconium compound silicon-removing flux and its production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1477218A CN1477218A (en) | 2004-02-25 |
| CN1219088C true CN1219088C (en) | 2005-09-14 |
Family
ID=34155350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03141550 Expired - Fee Related CN1219088C (en) | 2003-07-10 | 2003-07-10 | Mangnesium alloy zirconium compound silicon-removing flux and its production method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1219088C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798635B (en) * | 2010-04-21 | 2012-02-22 | 上海交通大学 | Zirconium compound cake smelted from magnesium alloy and preparation method thereof |
| CN102851524A (en) * | 2012-08-22 | 2013-01-02 | 淄博宏泰防腐有限公司 | Novel flux for ZK60 magnesium alloy, and preparation method and usage method thereof |
| CN104313360A (en) * | 2014-11-14 | 2015-01-28 | 重庆大学 | Method for purifying magnesium melt by adding zirconium |
| CN107400783A (en) * | 2017-01-18 | 2017-11-28 | 青海三工镁业有限公司 | A kind of high purity magnesium refining agent and high purity magnesium refinery practice |
-
2003
- 2003-07-10 CN CN 03141550 patent/CN1219088C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1477218A (en) | 2004-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111378848B (en) | Pre-melted slag for electroslag remelting for improving purity of GH4169 alloy return and preparation method thereof | |
| CN108441658B (en) | High-strength magnesium alloy capable of rapidly reacting with medium and preparation method thereof | |
| LU500368B1 (en) | Preparation method for copper or copper alloy material, and refining agent for refining | |
| CN109295330B (en) | Method for refining nitride inclusions in nickel-based wrought superalloy | |
| CN101220433A (en) | High-alumina magnesium alloy | |
| CN1195087C (en) | Magnesium alloy boride iron illiminating flux and its production method | |
| WO2023125262A1 (en) | Modified aluminum alloy and preparation method therefor | |
| CN100529129C (en) | Mg-Gd-Y-Zr magnesium alloy refining flux and producing method thereof | |
| CN108048676A (en) | The method that thermit reduction prepares aluminium lanthanum intermediate alloy | |
| WO2023241681A1 (en) | Aluminum alloy additive, and preparation method therefor and use thereof | |
| CN110819817B (en) | Basic slag system for aluminum-titanium-containing nickel-based high-temperature alloy and electroslag remelting method | |
| CN104928549B (en) | A kind of casting magnesium-rare earth alloy of high-strength high-elasticity modulus and preparation method thereof | |
| CN1219088C (en) | Mangnesium alloy zirconium compound silicon-removing flux and its production method | |
| CN102296188A (en) | Iron removing agent and iron removal preparation method of regenerated aluminum alloy | |
| CN1142301C (en) | Flux for removing iron from Mg alloy and its preparing process | |
| CN108751971B (en) | In-situ synthesized FeSix/diopside complex phase metal ceramic and preparation method thereof | |
| US5997606A (en) | Production of titanium slag | |
| CN1180104C (en) | Magnesium alloy rare earth compound flux and its production method | |
| CN1186470C (en) | Composite melting agent for reinfing crystal grains of aluminium magnesium alloy and preparation thereof | |
| CN109022830A (en) | A kind of microwave-ultrasonic combines the method for preparing high chromium product with salt Ore Leaching chromite | |
| CN1151294C (en) | Magnesium alloy desilicon flux and production method | |
| CN1563457A (en) | Covering flux of vitrous body of magnesium alloy and manufacturing method | |
| CN109487091B (en) | Electroslag remelting arc striking agent and preparation method thereof | |
| CN105970024A (en) | Abrasion-resistant composite material for automobile brake pads | |
| CN113106282A (en) | Low-iron low-silicon aluminum liquid and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: NATIONAL ENGINEERING RESEARCH CENTER OF LIGHT ALL Free format text: FORMER OWNER: SHANGHAI JIAOTONG UNIV. Effective date: 20081010 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20081010 Address after: No. nine, Jing Jing Road, Songjiang hi tech park, Shanghai, 1501 Patentee after: Shanghai Light Alloy Net Forming National Engineering Research Center Co., Ltd. Address before: No. 1954, Huashan Road, Shanghai Patentee before: Shanghai Jiao Tong University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050914 Termination date: 20190710 |