CN116121610A - Magnesium-zirconium intermediate alloy and preparation method thereof - Google Patents

Magnesium-zirconium intermediate alloy and preparation method thereof Download PDF

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CN116121610A
CN116121610A CN202211725589.2A CN202211725589A CN116121610A CN 116121610 A CN116121610 A CN 116121610A CN 202211725589 A CN202211725589 A CN 202211725589A CN 116121610 A CN116121610 A CN 116121610A
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stirring
zirconium
magnesium
melt
intermediate alloy
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熊爱虎
姚茂海
罗天纵
吕晶
李�杰
代旺
许喆
王靖喜
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Hunan Rare Earth Metal Materials Research Institute Co ltd
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Hunan Rare Earth Metal Materials Research Institute Co ltd
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    • 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
    • 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
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Abstract

The application relates to a magnesium-zirconium intermediate alloy and a preparation method thereof, comprising the following steps: smelting metal magnesium under a high-frequency induction condition to obtain a first melt; adding zirconium metal into the first melt, and alternately stirring under the low-frequency induction condition to obtain a second melt; the alternate stirring comprises first stirring, second stirring and third stirring; the first stirring direction is that the upper layer melt flows upwards from the center, flows downwards from the side wall, and the lower layer melt flows upwards from the side wall and flows downwards from the center; the second stirring direction is that the melt flows upwards from the side wall and downwards from the center; the third stirring direction is that the melt flows upwards from the center and downwards from the side wall; and under the action of third stirring, carrying out fixed-point casting on the second melt to obtain the magnesium-zirconium intermediate alloy. The preparation method of the magnesium-zirconium intermediate alloy ensures that zirconium in the magnesium-zirconium intermediate alloy obtained by casting has fine granularity, dispersed zirconium particles, higher zirconium content, smaller component segregation and fewer inclusions.

Description

Magnesium-zirconium intermediate alloy and preparation method thereof
Technical Field
The application relates to the field of alloys, in particular to a magnesium-zirconium intermediate alloy and a preparation method thereof.
Background
Compared with the physical field refining method, dynamic grain recrystallization and other methods, the grain size of the magnesium alloy can be reduced from 100 mu m and above to less than 50 mu m under the action of 0.5 weight percent of zirconium particles, and the grain boundary precipitation is not damaged, so that the service performance of the magnesium material device is effectively improved.
Since the solubility of zirconium in magnesium is very low, when the zirconium content exceeds 0.6wt%, the magnesium and zirconium mechanically mix with each other to cause segregation problems. The traditional preparation method of the magnesium-zirconium intermediate alloy adopts magnesium to reduce potassium zirconate fluoride, but the method has higher reduction temperature (900-1000 ℃) and higher energy consumption; the volatilization of molten salt is serious, and the environmental protection problem is outstanding; zirconium particles are coarse and easy to agglomerate and settle, so that the composition segregation is serious, and slag inclusion is easy to generate.
Therefore, it is important to provide a magnesium-zirconium master alloy with less component segregation.
Disclosure of Invention
Based on the above, the application provides a magnesium-zirconium intermediate alloy with small zirconium granularity, dispersed zirconium particles and less component segregation and a preparation method thereof.
The technical scheme for solving the technical problems is as follows.
The preparation method of the magnesium-zirconium intermediate alloy comprises the following steps:
smelting metal magnesium under a high-frequency induction condition to obtain a first melt;
adding zirconium metal into the first melt, and alternately stirring under the low-frequency induction condition to obtain a second melt; the alternating stirring comprises first stirring, second stirring and third stirring; the first stirring direction is that the upper layer melt flows upwards from the center, flows downwards from the side wall, and the lower layer melt flows upwards from the side wall and flows downwards from the center; the second stirring direction is that the melt flows upwards from the side wall and downwards from the center; the third stirring direction is that the melt flows upwards from the center and downwards from the side wall;
and under the action of the third stirring, carrying out fixed-point casting on the second melt to obtain the magnesium-zirconium intermediate alloy.
In some embodiments, the method for preparing the magnesium-zirconium intermediate alloy comprises alternately stirring the magnesium-zirconium intermediate alloy to sequentially perform the third stirring and the second stirring, and then recirculating the magnesium-zirconium intermediate alloy to perform the first stirring, the second stirring and the third stirring.
In some embodiments, the method for preparing the magnesium-zirconium master alloy comprises the steps of first stirring the magnesium-zirconium master alloy, then stirring the magnesium-zirconium master alloy, and recycling the magnesium-zirconium master alloy to perform the first stirring, the second stirring and the third stirring.
In some embodiments, the method for preparing the magnesium-zirconium master alloy comprises the steps of first stirring the magnesium-zirconium master alloy, then stirring the magnesium-zirconium master alloy, and recycling the magnesium-zirconium master alloy to perform the first stirring, the second stirring and the third stirring.
In some embodiments, the method of preparing the magnesium-zirconium master alloy comprises alternately stirring the first stirring, the second stirring and the third stirring in a cycle.
In some embodiments, the magnesium-zirconium master alloy is prepared by the method, wherein the total time of the alternating stirring is 0.5-3 h.
In some embodiments, the frequency of the high frequency induction is 1000HZ to 4000HZ and the frequency of the low frequency induction is 20HZ to 200HZ.
In some of these embodiments, the smelting is performed at a first temperature and the alternating stirring is performed at a second temperature, the first temperature and the second temperature being each independently 700 ℃ to 800 ℃.
In some of these embodiments, the method of preparing the magnesium zirconium master alloy, the site-specific casting is performed at a third temperature ranging from 720 ℃ to 780 ℃.
In some of these embodiments, in the method for preparing a magnesium-zirconium master alloy, the step of preparing the magnesium-zirconium master alloy is performed in a three-phase induction atmosphere furnace using SF 6 And CO 2 The smelting power of the three-phase induction atmosphere furnace is 20 kW-300 kW.
In some embodiments, the method for preparing a magnesium-zirconium master alloy further comprises a step of depassivating the surface of the zirconium metal before the step of adding the zirconium metal to the first melt.
In some embodiments, the metal zirconium comprises 0.1wt% to 40wt% of the magnesium zirconium master alloy.
The application also provides a magnesium-zirconium intermediate alloy, which is prepared by the preparation method of the magnesium-zirconium intermediate alloy.
Compared with the prior art, the preparation method of the magnesium-zirconium intermediate alloy has the following beneficial effects:
according to the preparation method of the magnesium-zirconium intermediate alloy, after metal magnesium is smelted under the high-frequency induction condition, metal zirconium is added to alternately stir in different directions under the low-frequency induction condition, the stirring strength and the melt flow direction are controllable by the low-frequency induction mode with adjustable phase difference, and fixed-point casting is further carried out under the action of the specific stirring mode, so that zirconium in the obtained magnesium-zirconium intermediate alloy has fine granularity, dispersed and distributed zirconium particles, higher zirconium content, smaller component segregation and fewer inclusions.
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In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a first stirring mode;
FIG. 2 is a schematic diagram of a second stirring mode;
FIG. 3 is a schematic diagram of a third stirring mode;
FIG. 4 is a photograph of the magnesium-zirconium alloy ingot prepared in example 1;
FIG. 5 is a photograph of a cross-section of a magnesium-zirconium alloy ingot prepared in example 1;
FIG. 6 is a 100-fold microstructure of the magnesium-zirconium alloy ingot prepared in example 1;
FIG. 7 is a 500-fold microstructure of the magnesium-zirconium alloy ingot prepared in example 1;
FIG. 8 is an overall photograph of a magnesium-zirconium alloy ingot prepared in comparative example 1;
FIG. 9 is a photograph of a cross-section of a magnesium-zirconium alloy ingot prepared in comparative example 1;
FIG. 10 is a 100-fold microstructure of the magnesium-zirconium alloy ingot prepared in comparative example 1;
FIG. 11 is a 500-fold microstructure of the magnesium-zirconium alloy ingot prepared in comparative example 1;
FIG. 12 is an overall photograph of a magnesium-zirconium alloy ingot prepared in comparative example 2;
FIG. 13 is a photograph of a cross-section of a magnesium-zirconium alloy ingot produced in comparative example 2;
FIG. 14 is a 100-fold microstructure of the magnesium-zirconium alloy ingot prepared in comparative example 2;
FIG. 15 is a 500-fold microstructure of the magnesium-zirconium alloy ingot prepared in comparative example 2;
FIG. 16 is a statistical chart of the sizes of zirconium particles in the magnesium-zirconium alloy cast ingot prepared in example 1;
FIG. 17 is a statistical chart of the sizes of zirconium particles in the magnesium-zirconium alloy cast ingot prepared in comparative example 1.
Detailed Description
The technical scheme of the present application is described in further detail below in conjunction with specific embodiments. This application may be embodied in many different forms and is not limited to the embodiments described herein. It should be understood that these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the description of the present application, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or an implicit indication of the number of technical features being indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the weight described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
An embodiment of the present application provides a method for preparing a magnesium-zirconium intermediate alloy, which includes steps S10 to S30:
step S10: and smelting the magnesium metal under the high-frequency induction condition to obtain a first melt.
In some examples, in step S10, the frequency of the high frequency induction is 1000HZ to 4000HZ.
It is understood that the frequencies of the high frequency induction include, but are not limited to, 1000HZ, 1100HZ, 1200HZ, 1500HZ, 1800HZ, 2000HZ, 2200HZ, 2500HZ, 2800HZ, 3000HZ, 3200HZ, 3500HZ, 3800HZ, 4000HZ.
In some of these examples, in step S10, smelting is performed at a first temperature, the first temperature being 700 ℃ to 800 ℃.
It is understood that the first temperature includes, but is not limited to 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 780 ℃,800 ℃.
In some examples, in step S10, the temperature of the first melt is 680 ℃ to 780 ℃.
It is understood that the temperature of the first melt includes, but is not limited to 680 ℃, 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 780 ℃.
In some examples, in step S10, the purity of magnesium is greater than or equal to 99.95%.
Step S20: adding zirconium metal into the first melt, and alternately stirring under the low-frequency induction condition to obtain a second melt; the alternate stirring comprises first stirring, second stirring and third stirring; the first stirring direction is that the upper layer melt flows upwards from the center, flows downwards from the side wall, and the lower layer melt flows upwards from the side wall and flows downwards from the center; the second stirring direction is that the melt flows upwards from the side wall and downwards from the center; the third stirring direction is the flow of melt from the center upwards and from the side walls downwards.
It will be appreciated that with reference to fig. 1, in the first stirring, the melt in the molten pool is divided into an upper layer melt and a lower layer melt, the upper layer melt and the lower layer melt have different flow directions, the upper layer melt flows upward from the center, flows downward from the side wall, the lower layer melt flows upward from the side wall, flows downward from the center, and is conventional induction stirring; referring to fig. 2, in the second stirring, the melt is a whole, and flows upward from the side wall, flows downward from the center, and is reversely stirred; referring to fig. 3, in the third stirring, the melt is a whole, and flows upward from the center, downward from the side wall, and is positively stirred. It will further be appreciated that the direction of agitation of the first, second and third agitations is controlled by the induction circuit of the induction furnace itself.
In some examples, in step S20, alternating the agitation includes recirculating the first agitation, the second agitation, and the third agitation after sequentially performing the third agitation and the second agitation.
Further, after the third stirring is sequentially performed for 5min to 90min and the second stirring is performed for 5min to 30min, the first stirring, the second stirring and the third stirring are performed in a recycling manner.
In some examples, in step S20, alternating stirring includes first performing the second stirring, then recirculating the first stirring, the second stirring, and the third stirring.
Further, after the second stirring is performed for 5 to 90 minutes, the first stirring, the second stirring and the third stirring are performed in a recycling manner.
In some examples, in step S20, alternating stirring includes first performing third stirring, then recirculating the first stirring, the second stirring, and the third stirring.
Further, after the third stirring is performed for 5 to 90 minutes, the first stirring, the second stirring and the third stirring are performed in a recycling manner.
In some examples, in step S20, alternating the agitation includes cycling through the first agitation, the second agitation, and the third agitation.
It is to be understood that the first stirring, the second stirring, and the third stirring are performed cyclically, which means that one cycle is performed at this time after the first stirring, the second stirring, and the third stirring are sequentially performed, and then the first stirring, the second stirring, and the third stirring are sequentially performed, which is performed at this time as the second cycle.
In some examples, in step S20, the total time of the alternate stirring is 0.5h to 3h.
It is understood that the total time of alternating agitation includes, but is not limited to, 0.5h, 0.8h, 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h.
In some examples, in step S20, when the first stirring, the second stirring, and the third stirring are performed in a circulating manner, each stirring mode is independently maintained for 2 to 15 minutes.
It can be understood that after the first stirring for 2min, the second stirring is performed for 5min, and the third stirring is performed for 10min; the first stirring is resumed.
In some examples, in step S20, the number of cycles is 1 to 6.
In some examples, in step S20, the frequency of the low frequency induction is 20HZ to 200HZ.
It is understood that the frequencies of the low frequency induction include, but are not limited to, 20HZ, 50HZ, 70HZ, 80HZ, 100HZ, 120HZ, 140HZ, 150HZ, 160HZ, 180HZ, 200HZ.
In some examples, in step S20, the alternating agitation is performed at a second temperature, the second temperature being 700 ℃ to 800 ℃.
It is understood that the second temperature includes, but is not limited to 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 780 ℃,800 ℃.
In some of these examples, in step S20, metallic zirconium is immersed in the first melt by a charging device.
In some examples, in step S20, before the step of adding the metallic zirconium to the first melt, a step of depassivating the surface of the metallic zirconium is further included.
The zirconium dissolving capacity of the molten magnesium is effectively enhanced by removing the metal zirconium of the surface passivation layer.
In some examples, in step S20, the purity of the zirconium metal is greater than or equal to 99.4%.
In some examples, in step S20, the metallic zirconium is selected from at least one of zirconium sponge and zirconium dust.
Further, the granularity of the zirconium sponge is 0.5 mm-15 mm, and the thickness of the zirconium scraps is less than or equal to 1.2mm.
In some examples, in step S20, the metallic zirconium comprises 0.1wt% to 40wt% of the magnesium zirconium master alloy.
It is understood that the metal zirconium accounts for 0.1 to 40 weight percent of the magnesium-zirconium intermediate alloy, and refers to the mass ratio of the zirconium element to the whole magnesium-zirconium intermediate alloy; it is further understood that the mass ratio of the metal zirconium to the magnesium zirconium master alloy includes, but is not limited to, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt%, 40wt%
Step S30: and under the action of third stirring, carrying out fixed-point casting on the second melt to obtain the magnesium-zirconium intermediate alloy.
It will be appreciated that the fixed point casting directly casts the second melt in the smelting furnace into the mould without transferring the second melt and then casting into the mould; and by adopting a fixed-point casting mode, the sedimentation of zirconium particles in the melt transferring process is effectively avoided.
In some examples, in step S30, the site-directed casting is performed at a third temperature ranging from 720 ℃ to 780 ℃.
It is understood that the third temperature includes, but is not limited to 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 780 ℃.
In some of these examples, in step S30, the casting is performed under low frequency induction conditions.
And further, casting is carried out from a lateral discharge hole of the induction furnace, the furnace body is driven to topple by using a hydraulic cylinder, and the position of the pouring hole is maintained to be basically unchanged.
In some examples, in step S30, the gate-to-mold height differential is maintained between 30mm and 80mm.
In some examples, in step S30, the casting mold may be a waffle ingot, a plate, or a square.
In some of these examples, the step of preparing the magnesium zirconium master alloy is performed in a three-phase induction atmosphere furnace using SF 6 And CO 2 The smelting power of the three-phase induction atmosphere furnace is 20kW to 300kW.
It is understood that smelting power includes, but is not limited to, 20kW, 50kW, 80kW,100 kW, 150kW, 180kW, 200kW, 220kW, 250kW, 300kW.
According to the preparation method of the magnesium-zirconium intermediate alloy, after metal magnesium is smelted under the high-frequency induction condition, metal zirconium is added and alternating stirring in different directions is carried out under the low-frequency induction condition, the stirring strength and the melt flow direction are controllable by the low-frequency induction mode with adjustable phase difference, so that zirconium in the magnesium-zirconium intermediate alloy obtained by casting is fine in granularity, zirconium particles are dispersed and distributed, the zirconium content is higher, the component segregation is smaller, and the inclusion is less. And the preparation process is simple, and compared with the traditional magnesium reduction method, the preparation process has less pollution to the environment.
An embodiment of the application provides a magnesium-zirconium intermediate alloy, which is prepared by the preparation method of the magnesium-zirconium intermediate alloy.
An embodiment of the application provides an application of the magnesium-zirconium intermediate alloy in preparing magnesium-zirconium alloy products. Another embodiment of the present application provides a magnesium-zirconium alloy product, which comprises the magnesium-zirconium intermediate alloy.
In some embodiments, the material of the magnesium-zirconium alloy product may be the magnesium-zirconium intermediate alloy, that is, the magnesium-zirconium intermediate alloy is directly used for preparing the magnesium-zirconium alloy product. In other embodiments, the magnesium-zirconium alloy product may comprise other materials in addition to the magnesium-zirconium intermediate alloy described above.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The magnesium-zirconium master alloy and the preparation method thereof according to the present application are exemplified below, and it is understood that the magnesium-zirconium master alloy and the preparation method thereof according to the present application are not limited to the following examples.
The agitation A in each of the following examples and comparative examples is a first agitation, the upper layer melt flows upward from the center, downward from the side wall, and the lower layer melt flows upward from the side wall, downward from the center; b stirring is second stirring, and the melt flows upwards from the side wall and downwards from the center; stirring C is a third stirring, and the melt flows upward from the center and downward from the side wall.
Example 1
Proportioning 50kg of single furnace time, and 1:0.22 of mass ratio of magnesium to zirconium sponge, placing magnesium metal into a sealed three-phase induction atmosphere furnace, and adding 99% CO 2 And 1% SF 6 In the mixed atmosphere, heating in a high-frequency induction mode (90-100 kW, 1400-1500 HZ) until the mixture is completely melted, adding zirconium, and adding magnesium at 740-750 ℃. The induction furnace is regulated to low-frequency operation, and is stirred for 40min in a three-stage stirring mode, wherein the first stage is stirred in a C stirring mode (65-80 kW, 80-120 HZ) at the smelting temperature of 740-750 ℃; then the second section is stirred for 5min under the condition that the smelting temperature is maintained at 730 ℃ to 750 ℃ in a B stirring mode (40 to 65kW,40 to 80 HZ); the third section is to stir cooperatively and feed in sequenceStirring in the line A (40-50 kW, 70-100 HZ), stirring in the line B (40-65 kW, 40-80 HZ) and stirring in the line C (65-80 kW, 80-120 HZ), and running for 3min in sequence for 3 times. And (3) carrying out fixed-point casting from a side pouring opening of the induction furnace, wherein the induction furnace keeps low-frequency C stirring (70-80 kW, 100-120 HZ) in the casting process, the casting temperature is 730-740 ℃, a cast iron mould is adopted to obtain a magnesium-zirconium alloy cast ingot, the whole photo is shown in fig. 4, the cross-sectional photo is shown in fig. 5, the 100-fold micro-structure is shown in fig. 6, and the 500-fold micro-structure is shown in fig. 7.
Example 2
Substantially the same as in example 1, except that the three-stage stirring mode in example 1 was replaced with a two-stage stirring mode after the induction furnace was adjusted to the low frequency operation step, specifically: the induction furnace is regulated to low-frequency operation, and is divided into two stirring modes, wherein the first stirring mode is a B stirring mode (40-65 kW, 40-80 HZ), and the smelting temperature is maintained at 740-750 ℃ for 45min; the second stage was followed by co-stirring, and co-stirring was performed in sequence with stirring A (40-50 kW, 70-100 HZ), stirring B (40-65 kW, 40-80 HZ) and stirring C (65-80 kW, 80-120 HZ), and each stage was run for 3min in sequence, with the overall stirring time being the same as in example 1.
Example 3
Substantially the same as in example 1, except that the three-stage stirring mode in example 1 was replaced with a two-stage stirring mode after the induction furnace was adjusted to the low frequency operation step, specifically: the induction furnace is regulated to low-frequency operation, and is divided into two sections of stirring modes, wherein the first section is stirred for 45min in a C stirring mode (65-80 kW, 80-120 HZ) under the condition that the smelting temperature is maintained at 740-750 ℃; the second stage was followed by co-stirring, and co-stirring was performed in sequence with stirring A (40-50 kW, 70-100 HZ), stirring B (40-65 kW, 40-80 HZ) and stirring C (65-80 kW, 80-120 HZ), and each stage was run for 3min in sequence, with the overall stirring time being the same as in example 1.
Example 4
Substantially the same as in example 1, except that the three-stage stirring mode in example 1 was replaced with a cooperative stirring mode after the induction furnace was adjusted to the low frequency operation step, specifically: after the induction furnace is adjusted to low-frequency operation, stirring A (40-50 kW, 70-100 HZ), stirring B (40-65 kW, 40-80 HZ) and stirring C (65-80 kW, 80-120 HZ) are sequentially carried out, each stage is sequentially operated for 10min, and the whole stirring time is the same as that of the embodiment 1.
Comparative example 1
Comparative example 1 is a Mg-30Zr intermediate alloy commercially available from light alloy company, light alloy, gan state, prepared by a magnesium thermal reduction method, the ingot is a waffle ingot, the overall photograph is shown in fig. 8, the sectional photograph is shown in fig. 9, the 100-fold microstructure is shown in fig. 10, and the 500-fold microstructure is shown in fig. 11.
Comparative example 2
And (3) preparing materials according to the mass ratio of 50kg of single furnace time to magnesium and zirconium sponge of 1:0.22, placing the magnesium metal into a traditional medium frequency induction atmosphere furnace for smelting, all under medium frequency induction conditions (30-40 kW, 800-1000 HZ), adding zirconium after the magnesium metal is completely melted, and continuing stirring A under the medium frequency induction conditions, wherein the whole stirring time is the same as that of the embodiment 1. And (3) carrying out fixed-point casting from a side pouring port of the induction furnace, wherein the induction furnace maintains stirring operation of the intermediate frequency A in the casting process, the casting temperature is between 730 and 740 ℃, and a cast iron mould is adopted to obtain the magnesium-zirconium alloy cast ingot. The whole photograph of the cast ingot is shown in fig. 12, the sectional photograph is shown in fig. 13, the 100-fold microstructure is shown in fig. 14, and the 500-fold microstructure is shown in fig. 15.
As can be seen from FIGS. 4 to 15, the magnesium-zirconium intermediate alloy obtained by the preparation method in the examples has bright and smooth ingot appearance and less fracture inclusions, and zirconium particles in the microstructure are uniformly distributed along the magnesium matrix, compared with the comparative examples.
Comparative example 3
The procedure was substantially as in example 1, except that the induction furnace was set to low-frequency operation and then only A-stirring (40 to 50kW,70 to 100 HZ) was carried out, and the overall stirring time was the same as in example 1.
Comparative example 4
Substantially the same as in example 1, except that comparative example 4 was conducted in a conventional casting manner, i.e., the melt was poured into a transfer ladle and then into a mold.
Comparative example 5
Substantially the same as in example 1, except that in the fixed-point casting step from the side pouring port of the induction furnace in comparative example 5, the induction furnace was operated with low-frequency A stirring (40 to 50kW,70 to 100 HZ) at a casting temperature of 730℃to 740 ℃.
Comparative example 6
Substantially the same as in example 1, except that in the fixed point casting step from the side pouring port of the induction furnace in comparative example 6, the induction furnace was operated with low frequency B stirring (40 to 65kw,40 to 80 HZ) at a casting temperature of between 730 ℃ and 740 ℃.
Zirconium contents of different magnesium-zirconium alloy ingots in the same heat obtained in each example and comparative example were detected, and the results are shown in table 1.
TABLE 1 zirconium content of magnesium zirconium alloy ingots of different heats
Test (wt%) 1# ingot casting Ingot 2# 3# ingot casting Ingot 4# 5# ingot casting
Example 1 19.91 19.85 20.13 20.44 20.37
Example 2 18.61 18.56 19.25 20.54 21.90
Example 3 19.23 19.29 19.78 20.18 20.54
Example 4 18.57 18.20 18.61 19.22 19.39
Comparative example 2 13.47 14.79 16.22 17.57 23.60
Comparative example 3 15.56 16.23 17.43 22.22 22.84
Comparative example 4 17.45 18.16 20.52 21.06 22.84
Comparative example 5 16.83 17.38 18.20 19.31 21.78
Comparative example 6 15.02 15.28 17.43 17.85 22.68
As can be seen from table 1, in the magnesium-zirconium alloy ingots prepared in examples, the zirconium element yield was higher than that in comparative examples, and in particular, the zirconium content in example 1 was close to the designed 20wt% zirconium content; and the zirconium content difference between different magnesium-zirconium alloy cast ingots in the same furnace time is smaller.
Zirconium contents at different portions of the same magnesium-zirconium alloy ingot obtained in each of examples and comparative examples 1 and 4 were measured, and the results are shown in table 2.
TABLE 2 zirconium content of different parts of the same magnesium zirconium alloy ingot
Figure BDA0004029683380000131
Figure BDA0004029683380000141
As can be seen from table 2, the same magnesium-zirconium alloy ingots prepared in examples were less segregated in specific gravity at different positions of upper, middle and lower than those of comparative examples 1 and 4.
The sizes of zirconium particles in magnesium-zirconium alloy ingots of example 1 and comparative example 1 were counted, and the size statistics of example 1 and comparative example 1 are shown in fig. 16 to 17, respectively.
As is clear from fig. 16 to 17, the size of the zirconium particles in the magnesium-zirconium alloy ingot prepared in example 1 was smaller than that in comparative example 1, indicating that the zirconium particles were small in size.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. It should be understood that those skilled in the art, based on the technical solutions provided in the present application, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the claims attached in the present application. The scope of the patent application is therefore intended to be limited by the content of the appended claims, the description and drawings being presented to the extent that the claims are defined.

Claims (10)

1. The preparation method of the magnesium-zirconium intermediate alloy is characterized by comprising the following steps of:
smelting metal magnesium under a high-frequency induction condition to obtain a first melt;
adding zirconium metal into the first melt, and alternately stirring under the low-frequency induction condition to obtain a second melt; the alternating stirring comprises first stirring, second stirring and third stirring; the first stirring direction is that the upper layer melt flows upwards from the center, flows downwards from the side wall, and the lower layer melt flows upwards from the side wall and flows downwards from the center; the second stirring direction is that the melt flows upwards from the side wall and downwards from the center; the third stirring direction is that the melt flows upwards from the center and downwards from the side wall;
and under the action of the third stirring, carrying out fixed-point casting on the second melt to obtain the magnesium-zirconium intermediate alloy.
2. The method for producing a magnesium-zirconium intermediate alloy according to claim 1, wherein the alternate stirring is one selected from the following modes (1) to (4):
(1) After the third stirring and the second stirring are sequentially carried out, the first stirring, the second stirring and the third stirring are carried out in a recycling way;
(2) Firstly, carrying out second stirring, and then, carrying out first stirring, second stirring and third stirring in a recycling way;
(3) Firstly, carrying out third stirring, and then, carrying out first stirring, second stirring and third stirring in a recycling way;
(4) The first stirring, the second stirring and the third stirring are circularly carried out.
3. The method for producing a magnesium-zirconium intermediate alloy according to claim 2, wherein the total time of the alternate stirring is 0.5 to 3 hours.
4. The method for producing a magnesium-zirconium intermediate alloy according to claim 1, wherein the frequency of the high frequency induction is 1000HZ to 4000HZ, and the frequency of the low frequency induction is 20HZ to 200HZ.
5. The method of preparing a magnesium zirconium master alloy according to claim 1, wherein the smelting is performed at a first temperature and the alternating stirring is performed at a second temperature, the first temperature and the second temperature being each independently 700 ℃ to 800 ℃.
6. The method of preparing a magnesium zirconium master alloy according to claim 1, wherein the site-specific casting is performed at a third temperature ranging from 720 ℃ to 780 ℃.
7. The method for producing a magnesium-zirconium intermediate alloy according to any one of claims 1 to 6, wherein the step of producing the magnesium-zirconium intermediate alloy is performed in a three-phase induction atmosphere furnace using SF 6 And CO 2 The smelting power of the three-phase induction atmosphere furnace is 20 kW-300 kW.
8. The method of preparing a magnesium-zirconium master alloy according to any one of claims 1 to 6, further comprising the step of depassivating the surface of the metallic zirconium before the step of adding the metallic zirconium to the first melt.
9. The method for producing a magnesium-zirconium master alloy according to any one of claims 1 to 6, wherein the metallic zirconium is 0.1 to 40wt% of the magnesium-zirconium master alloy.
10. A magnesium zirconium intermediate alloy, characterized in that it is prepared by the method for preparing a magnesium zirconium intermediate alloy according to any one of claims 1 to 9.
CN202211725589.2A 2022-12-30 2022-12-30 Magnesium-zirconium intermediate alloy and preparation method thereof Pending CN116121610A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116732370A (en) * 2023-06-09 2023-09-12 湖南稀土金属材料研究院有限责任公司 Magnesium-based composite material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116732370A (en) * 2023-06-09 2023-09-12 湖南稀土金属材料研究院有限责任公司 Magnesium-based composite material and preparation method and application thereof

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