CN114231777B - Bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy, preparation method and application - Google Patents

Bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy, preparation method and application Download PDF

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CN114231777B
CN114231777B CN202111522049.XA CN202111522049A CN114231777B CN 114231777 B CN114231777 B CN 114231777B CN 202111522049 A CN202111522049 A CN 202111522049A CN 114231777 B CN114231777 B CN 114231777B
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rare earth
magnesium alloy
bromine
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refining agent
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CN114231777A (en
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龚政轩
庞松
季松
候正全
肖旅
陈舸
董喜旺
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Shanghai Space Precision Machinery Research Institute
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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
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • 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
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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Abstract

The invention discloses a bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy, which comprises CaCl 2 、BaCl 2 、NaCl、CaF 2 、BaBr 2 Bromide and KCl; the refining agent increases the content of the specific gravity agent, improves the density of the flux, adds part of bromine salt as the fluxing agent, improves the spreadability, slagging capability and refining capability of the refining agent, can fully remove impurities in the magnesium melt in a short standing time after refining, does not generate flux inclusion or influence the grain refining effect, effectively shortens the refining process, and is particularly suitable for refining treatment of the rare earth content magnesium alloy with high melt viscosity and high density. The invention also discloses a preparation method and application of the bromine-containing refining agent.

Description

Bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy, preparation method and application
Technical Field
The invention belongs to the technical field of metal materials and metallurgy, and particularly relates to a bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy, a preparation method and application thereof.
Background
The magnesium and the magnesium alloy are used as the lightest metal structure materials, have the advantages of small density, high specific strength and rigidity, good damping performance and strong electromagnetic shielding capability, have huge lightweight potential, and have wide application prospect in the fields of aerospace, military industry, automobiles, 3C products and the like.
In recent years, with the development of aerospace and defense war industry, a non-main bearing structural part puts higher requirements on the room-temperature and high-temperature toughness of materials, and the performance of the traditional magnesium alloy is gradually difficult to meet the service requirements. In the research, the introduction of rare earth elements into magnesium can effectively improve the comprehensive service performance of magnesium alloy. The rare earth atoms are subjected to solid solution in a magnesium matrix during heat treatment to cause strong lattice distortion, reduce the difference of basal plane and non-basal plane slip resistance, and play a role in improving the mechanical property of the alloy and increasing the plasticity of the alloy. The rare earth magnesium alloy can also separate out a rare earth-rich phase in the subsequent aging process, and greatly improves the room high-temperature mechanical strength, heat resistance and creep resistance of the alloy. In recent years, rare earth magnesium alloys such as VW63Z are developed, the tensile strength of the developed large-scale complex casting body at room temperature reaches 330MPa, the elongation rate exceeds 3 percent, and the large-scale complex casting body is applied to batch engineering on various types of spacecraft products.
However, magnesium and rare earth are very active in chemical properties, and alloy melt is very easy to react with the atmosphere at high temperature to form impurities such as magnesium oxide, rare earth oxide, carbide and the like, and the impurities are often accompanied with shrinkage porosity and can form micro cracks in magnesium alloy, so that the mechanical property of the material is greatly reduced, and therefore, a refining agent is required to be added into the melt to remove various inclusions when the magnesium alloy is smelted. At present, JDMJ or RJ6 is mostly adopted to refine rare earth magnesium alloy. JDMJ has excellent refining effect in purifying ZM5, ZM6 and other magnesium alloys, but the flux contains 40-50% of MgCl 2 The rare earth chloride can react with rare earth elements such as Gd, Y and the like to generate rare earth chloride, chemical loss of rare earth atoms is generated, waste of the rare earth elements is caused, and material cost is increased. CaCl for RJ6 2 In place of MgCl 2 The rare earth elements cannot be burnt, the purification effect is good when magnesium alloy melts with low rare earth content such as ZM6 and EV31 are processed, but when alloys with higher rare earth content such as VW63Z are purified, the RJ6 spreadability is poor due to the fact that the total amount of rare earth atoms is large, the alloy density is high and the viscosity is high, the purification efficiency is general, the alloys are easy to float on the surface of the melts, the alloys are slow to settle, the alloys need to stand for a long time after refining is completed, or serious flux impurities can appear in castings. And long-time standing can cause Gd and Y with higher specific gravity in the rare earth magnesium alloy to settle, aggravate the nonuniformity of a melt and cause serious component segregation in a casting. In addition, the rare earth magnesium alloy is refined crystal grains, zr element is often added, zr is easy to settle in the long-time standing process, the crystal grain refining capability is reduced rapidly, and the performance and the elongation of the alloy are influenced. In view of the above situation, patent CN1537962A is used in refining agentRare earth chloride is added to inhibit the loss of rare earth atoms and effectively improve the melt refining effect and the rare earth yield. In patents CN1563445A and CN101260482A, cryolite is added into the refining agent to improve the slag forming capability of the flux, and rare earth compounds and zirconium compounds are added to inhibit the loss of rare earth and Zr, so that the melt has good wettability, impurities are fully adsorbed, and the melt refining effect is improved. However, when the flux is applied to magnesium alloys with high rare earth content and large smelting amount, the problems of slow sedimentation, difficult separation and long standing time still exist, and the addition of Zr compounds is easy to become inclusion of the flux, thereby influencing the purification efficiency of the refining agent.
In addition, as the size of the casting increases and the amount of smelting increases, in order to avoid the inclusion of flux in the casting, the standing time needs to be further prolonged to fully settle the inclusion, so that the problems of coarsening of crystal grains and segregation of specific gravity are further increased, and no good method for solving the contradiction exists at present. Therefore, it is very important to develop a bromine-containing refining agent for a rapid sedimentation rare earth magnesium alloy.
Disclosure of Invention
The invention aims to overcome the defects and provide a bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy 2 、BaCl 2 、NaCl、CaF 2 、BaBr 2 Bromide and KCl; the refining agent of the invention aims at the problems of slow sedimentation, poor separability and long standing time of the refining agent in the rare earth magnesium alloy, increases the content of the specific gravity agent, improves the density of the refining agent, adds partial bromine salt as a fluxing agent, improves the spreadability, slagging capability and refining capability of the refining agent, has good wetting, adsorption and capture capabilities on inclusions in the alloy in the refining process, has larger specific gravity difference with the magnesium alloy melt, can be quickly separated from the magnesium alloy melt, realizes the effective removal of inclusions in the magnesium alloy melt on the basis of not influencing the grain refining effect, can reduce the loss of rare earth atoms and Zr particles in the standing process, can realize the full removal of the inclusions in the magnesium alloy melt in shorter standing time after refining, does not generate flux inclusions, does not influence the grain refining effect, effectively and can realize the full removal of the inclusions in the magnesium alloy melt, and can improve the grain refining effectShortening the refining process, and is particularly suitable for refining magnesium alloy with high melt viscosity and high density and rare earth content. The invention also provides a preparation method and application of the bromine-containing refining agent.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
a bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy comprises the following components in percentage by mass:
Figure BDA0003407882310000031
the bromide is KBr, naBr or CaBr 2 One or a combination of more than one of them.
The preparation method of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy comprises the following steps:
s1, adding CaCl 2 、BaCl 2 、NaCl、CaF 2 、BaBr 2 Drying and dehydrating the bromide and the KCl at the temperature of between 200 and 230 ℃ respectively, and storing the obtained product in a dry closed container for later use;
s2, heating the crucible to 230-270 ℃;
s3, adding CaCl 2 Uniformly mixing NaCl and KCl to obtain mixed salt A; adding BaCl 2 、BaBr 2 Mixing with bromide to obtain mixed salt B;
s4, adding the mixed salt A into the crucible, heating to partially melt, adding the mixed salt B, and heating the crucible to 720-790 ℃ until the mixed salt is completely melted;
s5, stirring the completely melted mixed salt, pouring the mixed salt into a mold, and solidifying and cooling to obtain a block-shaped flux;
s6, crushing the massive flux and mixing with CaF 2 Mixing, grinding, sieving, and placing in a dry sealed container.
Further, in the preparation method of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy, the raw materials added in the steps S3 and S6 are in the following ratio:
Figure BDA0003407882310000041
the bromide is KBr, naBr or CaBr 2 One or a combination of more than one of them.
Further, in the preparation method of the bromine-containing refining agent for the rapidly-settling rare earth magnesium alloy, in the step S5, the completely-melted mixed salt is stirred for 1 to 20min and then poured into a mold.
The application of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy comprises the following steps:
(1) Brushing a coating on the crucible, then placing pure magnesium into the crucible, heating until the pure magnesium is completely melted, and spreading a covering agent on the surface of the melted pure magnesium in the heating process;
(2) After the pure magnesium is completely melted, heating to 700-850 ℃;
(3) Adding a rare earth intermediate alloy into the product obtained in the step (2), melting, uniformly stirring, and skimming;
(4) Adding the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy according to claim 1 into the product obtained in the step (3) for refining;
(5) And after refining, carrying out slag removal and standing on the obtained product to obtain the magnesium alloy melt.
Further, in the application of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy, the mass of the bromine-containing refining agent added in the step (4) accounts for 1-5% of the mass of the magnesium alloy melt obtained in the step (5).
Further, in the application of the bromine-containing refining agent for the rapid-settling rare earth magnesium alloy, the refining time in the step (4) is 5-30 min, and a refining spoon is continuously used for stirring or inert gas is continuously introduced during refining;
and (5) standing for 10-20 min.
Further, in the application of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy, the mass percentage of the rare earth elements in the rare earth intermediate alloy added in the step (2) to the mass of the magnesium alloy melt obtained in the step (5) is not less than 6%.
Further, in the application of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy, the rare earth elements in the rare earth intermediate alloy added in the step (2) include one or more of Gd, Y, nd, la, ce, sm, sc, er, dy, ho, yb and Eu.
Further, in the application of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy, the coating in the step (1) is a mixed solution of talcum powder, water glass and water; the covering agent in the step (2) is one or more of RJ-1, RJ-2 or JDMF; the mass of the added covering agent is not more than 5 percent of the total weight of the pure magnesium and the rare earth intermediate alloy.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy, mgCl is added 2 Based on a-KCl-NaCl mixed molten salt system, caCl with good adsorption effect on chloride and impurities in alloy is adopted 2 Substituted MgCl 2 As a main slagging component, the rare earth element is not lost;
(2) In the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy, the proportion of chlorine salt, fluorine salt and bromine salt is adjusted, and BaBr is added 2 KBr, naBr or CaBr 2 When bromide salt is used as a fluxing agent, as the radius of bromide ions is larger than that of chloride ions, the attraction capacity to cations under the same charge is reduced, so that the polarity among ionic compounds is weakened, the surface tension and viscosity among refining agent-melt and refining agent-inclusion interfaces are reduced, and the spreadability of the refining agent in the melt and the adsorption capacity to the inclusions are improved;
(3) In the bromine-containing refining agent for rapidly settling the rare earth magnesium alloy, the specific gravity agent BaCl is increased 2 The density of the refining agent is improved, the density of the added bromine salt is also higher than that of the chlorine salt and the fluorine salt, the density of the refining agent can be further improved, the specific gravity difference between the refining agent and the magnesium melt is increased, and the separability of the flux is improved;
(4) The refining agent prepared by the invention has proper melting point, viscosity, density and surface tension, good spreadability and strong slagging capacity, can effectively and comprehensively capture impurities in the melt, realizes quick separation of the metal melt, can fully remove the impurities in the magnesium melt in a short standing time, does not generate flux impurities, does not influence the grain refining effect, can be effectively applied to industrial production, and is particularly suitable for refining treatment of rare earth-containing magnesium alloy with high melt viscosity and density.
Drawings
FIG. 1 is a solidification structure of a certain part of a large VW63Z magnesium alloy casting obtained by resin sand casting in example 3 by using a refining agent of the invention;
FIG. 2 shows the solidification structure of a part of a large VW63Z magnesium alloy casting produced by resin sand casting according to comparative example 3 and treated with a conventional refining agent.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention provides a bromine-containing refining agent for rapidly settling rare earth magnesium alloy, which aims at the problems that the melt of the rare earth magnesium alloy, particularly the magnesium alloy with high rare earth content has large viscosity and density, the refining agent in the rare earth magnesium alloy settles slowly, the separability is poor, the standing time is long, the casting is easy to be mixed with flux, the crystal grains are easy to coarsen after refining and standing, and the like, and the bromine-containing refining agent for rapidly settling rare earth magnesium alloy comprises the following components in percentage by mass: caCl 2 ：18-35％；BaCl 2 ：10-22％；NaCl：0-10％；CaF 2 ：1-8％；BaBr 2 :0.5-12%; bromide: 0 to 25 percent; KCl: and (4) the balance. Wherein the bromide is KBr, naBr or CaBr 2 . The purity of the components can be analytical purity, chemical purity and other industrial purities and purities above. The refining agent can be used for removing impurity elements and nonmetallic inclusions in the process of smelting rare earth magnesium alloyThe refining treatment has the advantages of good refining effect and short refining process, can fully remove impurities in the magnesium melt in a short standing time, does not produce flux inclusion, does not influence the grain refining effect, and can be effectively applied to industrial production.
The preparation method of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy comprises the following steps:
s1, respectively drying and dehydrating the raw materials at 200-230 ℃, and storing the raw materials in a dry closed container for later use; in this step, the drying sealed container may be a drying dish or a sealed bag with a moisture-proof function, or may be sealed in a vacuum bag and evacuated.
S2, heating the crucible to 250 ℃, and adding CaCl uniformly mixed according to a designed proportion 2 NaCl and KCl, heating to partially melt, and adding BaCl uniformly mixed according to a designed proportion 2 、BaBr 2 And bromide, heating the crucible to 720-790 ℃, stirring for 1-20 min after the mixed salt is completely melted, pouring into a mold, and solidifying and cooling into blocks; in the step, the crucible material can be a graphite crucible, a corundum crucible or an iron crucible, and only the material which can bear corresponding high temperature and can not react with molten salt is required to be used as the material of the crucible; in the step, the stirring mode is mechanical stirring, the material of the stirring rod can be the same as or different from that of the crucible, and only the corresponding high temperature can be ensured and the stirring rod cannot react with the molten salt; in the step, the stirring temperature and time depend on the overflow condition of the flux flue gas at the crucible opening, and when the flue gas overflows violently, the crucible temperature is properly reduced and the stirring time is shortened so as to reduce the loss of volatile components in the flux preparation process.
S3, crushing the block-shaped flux obtained in the step S2, and mixing with CaF 2 Mixing, grinding in ball mill, sieving to remove grinding material, and packaging in dry sealed container.
The application method of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy comprises the following steps:
s1, brushing a coating on a crucible, putting pure magnesium into the crucible according to set alloy component ingredients, heating until the pure magnesium is completely melted, spraying a covering agent to prevent combustion, and continuously heating to 700-850 ℃ after the pure magnesium is completely melted; in this step, the covering agent includes, but is not limited to, any one or more of RJ-1, RJ-2, JDMF, etc. The amount of the covering agent should be not more than 5% of the total weight of the pure magnesium and the intermediate alloy.
S2, adding rare earth intermediate alloy according to the set alloy component ingredients, stirring uniformly, skimming, then refining for 5-30 min, scattering a refining agent which is preheated and accounts for 1-5% of the total weight of the alloy into the melt during refining, and continuously stirring with a refining spoon or introducing inert gas; in this step, the rare earth elements in the rare earth intermediate alloy include, but are not limited to, any one or more of Gd, Y, nd, la, ce, sm, sc, er, dy, ho, yb and Eu; preferably, the mass percentage of the rare earth elements in the rare earth intermediate alloy to the mass of the finally obtained magnesium alloy melt is more than or equal to 6wt.%.
After a great deal of research, the mass fraction of rare earth has important influence on the selection of the refining agent, and the inventor thinks that: the density and viscosity of the alloy melt gradually increase with the increase of the content of rare earth in the magnesium alloy. Production verification shows that when the mass fraction of the total rare earth in the magnesium alloy melt is more than or equal to 6wt.%, the problems of poor spreadability and slow sedimentation begin to exist by using the traditional refining agent, and the refining agent prepared by the invention can well solve the problem.
And S3, after the refining treatment is finished, fishing out slag and standing to obtain the magnesium alloy melt with good refining effect.
Example 1
A bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy comprises the following components by mass percent: KCl:33% of CaCl 2 ：30％；BaCl 2 ：10％；NaCl：5％；CaF 2 ：2％；BaBr 2 ：5％；KBr：10％；CaBr 2 ：5％。
The invention discloses a preparation method of a bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy, which comprises the following steps: drying and dehydrating the raw materials at 210 ℃ respectively, and storing the raw materials in a dry closed container for later use; the crucible is heated to 2 deg.CAdding CaCl which is weighed according to the designed mass fraction and is uniformly mixed after the temperature of 50 DEG C 2 NaCl and KCl, heating to partially melt, and adding BaCl uniformly mixed according to a designed proportion 2 、BaBr 2 And KBr, heating the crucible to 750 ℃, stirring for 5min after the flux is completely melted, pouring into a mold, and solidifying and cooling into blocks; crushing the obtained block flux and CaF 2 Mixing, grinding in ball mill, sieving, and packing in dry sealed container.
The preparation and application method of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy comprises the following steps: the components are mixed according to the components of Mg-5Gd-3Nd-0.4Zr alloy. Brushing a coating on the crucible, putting pure magnesium into the crucible, heating, spraying a covering agent to prevent combustion, heating to 760 ℃ after the pure magnesium is molten, adding an intermediate alloy, uniformly stirring, skimming, and then carrying out refining treatment for 5min, spraying a refining agent accounting for 1.5 percent of the total weight of the alloy after preheating into the melt during refining, and continuously stirring by using a refining spoon or introducing inert gas; and after the refining treatment is finished, fishing out slag and standing for 10min to obtain the magnesium alloy melt with good refining effect. The metal type sample is poured by gravity, the T6 tensile strength is 270MPa, the elongation is 2.1%, and no inclusion is detected in a fracture.
Example 2
A bromine-containing refining agent for rapidly settling rare earth magnesium alloy comprises the following components in percentage by mass: KCl:36% of CaCl 2 ：25％；BaCl 2 ：13％；NaCl：0.5％；CaF 2 ：1％；BaBr 2 ：8％；NaBr：4.5％；CaBr 2 ：12％。
The preparation method of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy comprises the following steps: drying and dehydrating the raw materials at 220 ℃ respectively, and storing the raw materials in a dry closed container for later use; heating the crucible to 250 ℃, and adding CaCl which is weighed according to the designed mass fraction and is uniformly mixed 2 NaCl and KCl, heating to partially melt, and adding BaCl uniformly mixed according to a designed proportion 2 、BaBr 2 Heating the crucible to 760 ℃, stirring for 10min after the flux is completely melted, pouring into a mold, and solidifying and cooling into blocks; breaking the block fluxCrushing with CaF 2 Mixing, grinding in ball mill, sieving, and drying in sealed container.
An application method of a bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy comprises the following steps: the alloy is prepared according to the components of Mg-10Gd-3Y-0.5 Zr. Brushing a coating on a crucible, placing pure magnesium into the crucible, heating, spraying a covering agent to prevent combustion, heating to 750 ℃ after the pure magnesium is molten, adding an intermediate alloy, uniformly stirring, skimming, and then carrying out refining treatment for 10min, spraying a refining agent which is preheated and accounts for 2% of the total weight of the alloy into the melt during refining, and continuously stirring by using a refining spoon or introducing inert gas; and after the refining treatment is finished, fishing the slag and standing for 15min to obtain the magnesium alloy melt with good refining effect. A large resin sand mold casting is poured in a differential pressure mode, the tensile strength of a body sampling T6 is 350MPa, the elongation is 2%, and no impurities are detected in fractures.
Example 3
A bromine-containing refining agent for rapidly settling rare earth magnesium alloy comprises the following components in percentage by mass: KCl:31% of CaCl 2 ：20％；BaCl 2 ：15％；NaCl：0.5％；CaF 2 ：1.5％；BaBr 2 ：5％；KBr：13％；NaBr：2％；CaBr 2 ：12％。
The invention discloses a preparation method of a bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy, which comprises the following steps: drying and dehydrating the raw materials at 230 ℃ respectively, and storing the raw materials in a dry closed container for later use; heating the crucible to 250 ℃, adding CaCl which is weighed according to the designed mass fraction and uniformly mixed 2 NaCl and KCl, heating to partially melt, and adding BaCl uniformly mixed according to a designed proportion 2 、BaBr 2 Heating the crucible to 760 ℃, stirring for 15min after the flux is completely melted, pouring into a mold, and solidifying and cooling to form blocks; crushing the obtained block flux and CaF 2 Mixing, grinding in a ball mill, sieving, and packaging in a dry sealed container to obtain the refining agent with room temperature density of 2.56g/cm 3 。
An application method of a bromine-containing refining agent for rapid sedimentation rare earth magnesium alloy comprises the following steps: the alloy is prepared according to the components of Mg-6Gd-3Y-0.4 Zr. Brushing a coating on the crucible, putting pure magnesium into the crucible, heating, spraying a covering agent to prevent combustion, heating to 770 ℃ after the pure magnesium is molten, adding an intermediate alloy, uniformly stirring, skimming, and then carrying out refining treatment for 15min, spraying a refining agent accounting for 2.5 percent of the total weight of the alloy after preheating into the melt during refining, and continuously stirring by using a refining spoon or introducing inert gas; and after the refining treatment is finished, fishing the slag and standing for 20min to obtain the magnesium alloy melt with good refining effect. A large resin sand mold casting is poured in a differential pressure mode, the tensile strength of a body sample T6 is 330MPa, the elongation is 4%, the alloy structure of the same part is shown in figure 1, the volume fraction of inclusions is 0.13%, and no inclusions are detected in fractures.
Comparative example 1
The comparative example is the comparative example of example 1, and is different from example 1 only in that JDMJ refining agent is adopted as the refining agent, mg-5Gd-3Nd-0.4Zr magnesium alloy gravity casting metal type samples obtained by the same smelting process as example 1 have the advantages that the tensile strength of a body T6 is 225MPa, the elongation is 0.9 percent, and slag inclusion is detected at a fracture.
Comparative example 2
The comparative example is the comparative example of the example 2, and is different from the example 2 only in that the JDMJ refining agent is adopted as the refining agent, the body of the same part of the Mg-10Gd-3Y-0.5Zr magnesium alloy large-scale casting of the resin sand mold is subjected to body sampling by adopting the same smelting process as the example 2, the T6 tensile strength is 320MPa, and the elongation is 1.8%.
Comparative example 3
This comparative example is a comparative example to example 3, and differs from example 3 only in that the refining agent used was RJ6 refining agent, and the room temperature density of the refining agent in this comparative example was 2.27g/cm 3 The metallographic structure of the same part of a Mg-6Gd-3Y-0.4Zr magnesium alloy certain differential pressure casting resin sand mould large casting obtained by the same melting process as that of the embodiment 3 is shown in a figure 2, the tensile strength of a body T6 is 285MPa, the elongation is 2.4 percent, and potassium fluozirconate and carbide inclusions are detected at a fracture.
As can be seen from the examples 1 to 3 and the comparative examples 1 to 3, the refining agent disclosed by the invention can effectively improve the tensile strength and the elongation of the magnesium alloy casting and has an excellent impurity removal effect.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are not particularly limited to the specific examples described herein.

Claims (7)

1. The application of the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy is characterized by comprising the following steps:
(1) Brushing a coating on the crucible, then placing pure magnesium into the crucible, heating until the pure magnesium is completely melted, and spreading a covering agent on the surface of the melted pure magnesium in the heating process;
(2) After the pure magnesium is completely melted, heating to 700-850 ℃;
(3) Adding a rare earth intermediate alloy into the product obtained in the step (2), melting, uniformly stirring, and skimming;
(4) Adding a bromine-containing refining agent for rapidly settling rare earth magnesium alloy into the product obtained in the step (3) for refining;
(5) After refining, the obtained product is subjected to slag removal and standing to obtain a magnesium alloy melt;
in the step (4), the bromine-containing refining agent for the rapid sedimentation rare earth magnesium alloy comprises the following components in percentage by mass:
CaCl 2 18~35%；
BaCl 2 10~22%；
NaCl 0.5~10%；
CaF 2 1~8%；
BaBr 2 0.5~12%；
KBr, naBr or CaBr 2 15 to 25 percent of more than one of the raw materials;
the balance of KCl;
the mass percentage of the rare earth elements in the rare earth intermediate alloy added in the step (2) in the mass of the magnesium alloy melt obtained in the step (5) is more than or equal to 6%.
2. The application of the bromine-containing refining agent for the fast settling rare earth magnesium alloy according to claim 1, wherein in the step (4), the preparation method of the bromine-containing refining agent for the fast settling rare earth magnesium alloy comprises the following steps:
s1, adding CaCl 2 、BaCl 2 、NaCl、CaF 2 、BaBr 2 KCl and KBr, naBr or CaBr 2 Respectively drying and dehydrating at 200-230 ℃, and storing in a dry closed container for later use;
s2, heating the crucible to 230-270 ℃;
s3 adding CaCl 2 Uniformly mixing NaCl and KCl to obtain mixed salt A; adding BaCl 2 、BaBr 2 And KBr, naBr or CaBr 2 Mixing more than one of the raw materials uniformly to obtain mixed salt B;
s4, adding the mixed salt A into the crucible, heating until the mixed salt A is partially melted, adding the mixed salt B into the crucible, and heating the crucible to 720-790 ℃ until the mixed salt is completely melted;
s5, stirring the completely melted mixed salt, pouring the mixed salt into a mold, and solidifying and cooling to obtain a block-shaped flux;
s6, crushing the massive flux and mixing with CaF 2 Mixing, grinding, sieving, and placing in a dry sealed container.
3. The application of the bromine-containing refining agent for the rapidly settling rare earth magnesium alloy as claimed in claim 2, wherein in the step S5, the completely melted mixed salt is poured into a mold after being stirred for 1 to 20min.
4. The application of the bromine-containing refining agent for the rapidly-settling rare earth magnesium alloy as claimed in claim 1, wherein the mass of the bromine-containing refining agent added in the step (4) accounts for 1-5% of the mass of the magnesium alloy melt obtained in the step (5).
5. The application of the bromine-containing refining agent for the rapidly settling rare earth magnesium alloy as claimed in claim 1, wherein the refining time in the step (4) is 5 to 30min, and a refining spoon is continuously used for stirring or inert gas is introduced during refining;
and (5) standing for 10 to 20min.
6. The application of the bromine-containing refining agent for the rapidly-settling rare earth magnesium alloy as claimed in claim 1, wherein the rare earth element in the rare earth intermediate alloy added in the step (2) comprises more than one of Gd, Y, nd, la, ce, sm, sc, er, dy, ho, yb or Eu.
7. The application of the bromine-containing refining agent for the rapidly-settling rare earth magnesium alloy according to claim 1, wherein the coating in the step (1) is a mixed solution of talcum powder, water glass and water; the covering agent in the step (2) is more than one of RJ-1, RJ-2 or JDMF; the mass of the added covering agent is not more than 5 percent of the total weight of the pure magnesium and the rare earth master alloy.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2451762C1 (en) * 2011-04-05 2012-05-27 Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) Flux metal for melting and refinement of yttrium containing magnesium alloys
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
CN110029258A (en) * 2019-04-26 2019-07-19 陕西鼎卓材料科技有限公司 A kind of high tough wrought magnesium alloy and preparation method thereof
CN113174505A (en) * 2021-04-08 2021-07-27 上海交通大学 Refining flux for magnesium-lithium alloy and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2451762C1 (en) * 2011-04-05 2012-05-27 Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) Flux metal for melting and refinement of yttrium containing magnesium alloys
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
CN110029258A (en) * 2019-04-26 2019-07-19 陕西鼎卓材料科技有限公司 A kind of high tough wrought magnesium alloy and preparation method thereof
CN113174505A (en) * 2021-04-08 2021-07-27 上海交通大学 Refining flux for magnesium-lithium alloy and preparation method thereof

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