WO2023125263A1 - Alliage composite de terres rares pour modification d'alliage d'aluminium et son procédé de préparation - Google Patents

Alliage composite de terres rares pour modification d'alliage d'aluminium et son procédé de préparation Download PDF

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WO2023125263A1
WO2023125263A1 PCT/CN2022/141281 CN2022141281W WO2023125263A1 WO 2023125263 A1 WO2023125263 A1 WO 2023125263A1 CN 2022141281 W CN2022141281 W CN 2022141281W WO 2023125263 A1 WO2023125263 A1 WO 2023125263A1
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rare earth
melt
aluminum
alloy
refining
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PCT/CN2022/141281
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Chinese (zh)
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彭珞洲
答建成
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上海耀鸿科技股份有限公司
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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
    • C22C1/02—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
    • 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
    • C22C21/00—Alloys based on aluminium

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  • the invention relates to the technical field of alloy materials and preparation, in particular to a composite rare earth alloy for aluminum alloy modification and a preparation method thereof.
  • Aluminum alloy has excellent comprehensive properties such as light weight, wear resistance, low thermal expansion coefficient, good casting performance and the best matching relationship between product mechanical properties (optimum strength and plasticity), mainly composed of ⁇ -Al dendrites, eutectic silicon And Mg2Si equilibrium phase composition.
  • product mechanical properties mainly composed of ⁇ -Al dendrites, eutectic silicon And Mg2Si equilibrium phase composition.
  • coarse ⁇ -Al dendrites and flaky and bulk eutectic silicon seriously deteriorate its mechanical properties, especially the plasticity and tensile strength, which limits its application in actual industrial production.
  • the present invention provides a composite rare earth alloy for aluminum alloy modification that can further improve the mechanical properties of cast aluminum alloy, and improve the effect of modification and refinement, and a preparation method thereof.
  • Step S1 providing aluminum melt
  • Step S2 providing a modifier, a refiner, and a rare earth aluminum alloy, wherein the rare earth metal in the rare earth aluminum alloy is one or more selected from lanthanum, cerium, and yttrium;
  • step S3 under an inert gas atmosphere, the modification agent, the refiner, and the rare earth aluminum alloy are added to the aluminum melt and smelted to obtain the composite rare earth alloy for modifying the aluminum alloy.
  • the step S1 includes:
  • Step S11 providing aluminum ingots
  • Step S12 removing the oxide skin layer on the surface of the aluminum ingot
  • Step S13 cleaning and drying the aluminum ingot from which the scale layer has been removed
  • Step S14 melting the dried aluminum ingot to obtain an initial melt
  • Step S15 refining the initial melt to obtain the aluminum melt.
  • the preparation of the rare earth aluminum alloy includes the following steps:
  • the rare earth aluminum alloy is obtained by standing for a predetermined time and pouring.
  • the modifier is an aluminum-strontium master alloy
  • the refiner is an aluminum-titanium master alloy or an aluminum-titanium-boron master alloy.
  • the aluminum melt accounts for 86-88wt%
  • the aluminum-strontium master alloy accounts for 5.5-6.5wt%
  • the aluminum-titanium or aluminum-titanium The boron master alloy accounts for 0.1-0.2 wt%
  • the rare earth aluminum alloy (such as Al-10La, Al-20La, Al-10Ce, Al-20Ce, Al-10Y or Al-20Y) accounts for 6.5-7.5 wt%.
  • modification agent and/or the refining agent and/or the rare earth aluminum alloy are respectively subjected to descaling, ultrasonic cleaning, and refining treatment in sequence.
  • the modification agent and the refiner are added at intervals, and the rare earth aluminum alloy is added before the modification agent and the refiner, or together with the first addition , or added between the modification agent and the refiner.
  • the step S3 includes:
  • Step S301 adding the rare earth aluminum alloy into the aluminum melt and melting to obtain a first homogeneously mixed melt
  • Step S302 adding the modifying agent into the first homogeneously mixed melt and continuing smelting to obtain a second homogeneously mixed melt;
  • Step S303 adding the refining agent into the second homogeneously mixed melt and continuing to smelt to obtain the complex rare earth alloy.
  • step S301 includes:
  • the step S3 includes:
  • Step S311 adding the rare earth aluminum alloy and the modifier to the aluminum melt at the same time and continuing to melt to obtain a third homogeneously mixed melt;
  • Step S312 adding the refining agent into the third homogeneously mixed melt and continuing to smelt to obtain the complex rare earth alloy.
  • the refining agent is added after refining.
  • the step S3 includes:
  • Step S321 adding the modifier to the aluminum melt and continuing to melt to obtain the fourth homogeneously mixed melt
  • Step S322 adding the rare earth aluminum alloy into the fourth homogeneously mixed melt and continuing to smelt to obtain a fifth homogeneously mixed melt;
  • Step S323 adding the refining agent into the fifth homogeneously mixed melt and continuing to smelt to obtain the complex rare earth alloy.
  • the refining includes:
  • the added amount of the refining agent accounts for 0.1-0.3% of the added melt mass
  • the added amount of the slag remover accounts for 0.1-0.3% of the added melt mass
  • the components of the refining agent contain by mass:
  • the components of the slag remover contain by mass:
  • test the density of the melt when the density of the melt is less than 2.65g/ cm3 , then carry out the refining treatment; when the density of the melt is greater than or equal to 2.65g/ cm3 , that is, the refining process is not performed or the refining process is terminated.
  • the composite rare earth alloy for aluminum alloy modification according to the embodiment of the second aspect of the present invention contains strontium, titanium or titanium boron, and a rare earth metal, wherein, in the composite rare earth alloy, the rare earth metal: strontium: titanium or titanium
  • the mass ratio of the total amount of boron is 1:(0.1-1.2):(0.1-1.2)
  • the rare earth metal is one or more selected from lanthanum, cerium and yttrium.
  • the mutual poisoning effect between the modifier and the refiner is greatly overcome by introducing the rare earth metal, and the addition of the modifier and the refiner can be improved. quantity, while improving the effect of metamorphism and refinement;
  • the present invention rationally adjusts the process so that the modifier and the refiner are added at intervals, and the rare earth metal is added before the latter, which can further effectively avoid the mutual poisoning between the modifier and the refiner, which is beneficial to further Improve the effect of metamorphism and refinement;
  • Fig. 1 is the metallographic structure image of aluminum alloy before modification
  • Fig. 2 is an image of the metallographic structure of the aluminum alloy modified by using the composite rare earth alloy prepared in Example 1 of the present invention.
  • Step S1 providing aluminum melt.
  • first the aluminum melt is prepared.
  • Purification treatment may include the following steps, for example:
  • Step S11 providing aluminum ingots
  • Step S12 removing the oxide skin layer on the surface of the aluminum ingot
  • Step S13 cleaning and drying the aluminum ingot from which the scale layer has been removed
  • Step S14 melting the dried aluminum ingot to obtain an initial melt
  • Step S15 refining the initial melt to obtain the aluminum melt.
  • the oxide scale layer on its surface is first removed, then cleaned to remove surface scum, dried and then smelted, and the melt is refined.
  • the specific refining process will be described in detail later.
  • undesired impurities such as Fe, oxides, etc. can be removed. It is beneficial to further improve the modification and refinement of the composite rare earth alloy.
  • Fe and its oxides can be removed by adding manganese or aluminum-manganese alloy to form surface scum, for example.
  • Step S2 providing a modifier, a refiner, and a rare earth aluminum alloy, wherein the rare earth metal in the rare earth aluminum alloy is one or more selected from lanthanum, cerium, and yttrium.
  • the modifier may be, for example, an aluminum-strontium master alloy
  • the refiner may be, for example, an aluminum-titanium master alloy or an aluminum-titanium-boron master alloy. That is, conventional modifiers and refiners can be used.
  • the modifier and/or the refiner commercially available materials can be used, such as commercially available aluminum-strontium master alloys, aluminum-titanium master alloys, aluminum-titanium-boron master alloys, etc.; It is prepared by taking the corresponding metal strontium, titanium, titanium & boron, and melting them in aluminum melt to form a uniform alloy.
  • the dosage of the modifier and the refiner can be designed in combination with the amount of rare earth to be introduced and the specific composition of the aluminum alloy to be modified.
  • the design is carried out according to the mass ratio of rare earth metal: strontium: titanium or the total amount of titanium boron is 1: (0.1-1.2): (0.1-1.2).
  • the rare earth metal in the rare earth aluminum alloy considering the strontium in the modifier and the titanium and boron in the refiner, it is possible to select a group IIIB element with an intermediate electronic structure.
  • a group IIIB element with an intermediate electronic structure.
  • resources, etc. preferably, one or more of yttrium, lanthanum in lanthanide metals, and cerium are used.
  • the rare earth aluminum alloy therein for example, it can be prepared by the following method:
  • the rare earth aluminum alloy is obtained by standing for a predetermined time and pouring.
  • the alloy containing the rare earth metal for example, one or more of commercially available Al-10Ce, Al-20Ce, Al-20La, Al-10La, Al-20Y, and Al-10Y can be used.
  • aluminum-strontium master alloys aluminum-titanium master alloys or aluminum-titanium-boron master alloys, and rare-earth aluminum alloys
  • descaling, ultrasonic cleaning, and refining can be performed sequentially, respectively.
  • unwanted impurities and oxides can be further removed, which is beneficial to improving the refinement and modification of the composite rare earth alloy as a product.
  • step S3 under an inert gas atmosphere, the modification agent, the refiner, and the rare earth aluminum alloy are added to the aluminum melt and smelted to obtain the composite rare earth alloy for modifying the aluminum alloy.
  • the modifier, refiner, and rare earth aluminum alloy are prepared, the modifier, refiner, and rare earth aluminum alloy are added to the aluminum melt for further smelting under an inert gas atmosphere , to obtain a composite rare earth aluminum alloy.
  • the mutual poisoning effect between the modifier and the refiner is greatly overcome by introducing the rare earth metal, and the addition of the modifier and the refiner can be improved. volume, while improving the effect of metamorphism and refinement.
  • the inventors of the present invention have found through repeated research that by adjusting the order of adding the modifier, the refiner, and the rare earth aluminum alloy, the mutual poisoning between the modifier and the refiner can be further effectively avoided, which is beneficial to further Improves the effect of metamorphism and refinement.
  • the modifying agent and the refining agent are added at intervals, and the rare earth aluminum alloy is added before the modifying agent and the refining agent, or the one added first Add together, or add between the addition of the modifier and the refiner.
  • the poisoning effect of strontium and boron/titanium can be effectively overcome, which is beneficial to further improving the effect of modification and refinement.
  • step S3 can adopt the following three specific implementation modes:
  • the step S3 includes:
  • Step S301 adding the rare earth aluminum alloy into the aluminum melt and melting to obtain a first homogeneously mixed melt
  • Step S302 adding the modifying agent into the first homogeneously mixed melt and continuing smelting to obtain a second homogeneously mixed melt;
  • Step S303 adding the refining agent into the second homogeneously mixed melt and continuing to smelt to obtain the complex rare earth alloy.
  • the rare earth aluminum alloy is added first, and thereafter, the modifier and the refiner are sequentially added.
  • step S301 includes:
  • the step S3 includes:
  • Step S311 adding the rare earth aluminum alloy and the modifier to the aluminum melt at the same time and continuing to melt to obtain a third homogeneously mixed melt;
  • Step S312 adding the refining agent into the third homogeneously mixed melt and continuing to smelt to obtain the complex rare earth alloy.
  • the rare earth aluminum alloy and the aluminum-strontium master alloy as a modifier are added together, and after it is completely melted and homogenized, the refiner is added therein.
  • the refining agent is added after refining.
  • the step S3 includes:
  • Step S321 adding the modifier to the aluminum melt and continuing to melt to obtain the fourth homogeneously mixed melt
  • Step S322 adding the rare earth aluminum alloy into the fourth homogeneously mixed melt and continuing to smelt to obtain a fifth homogeneously mixed melt;
  • Step S323 adding the refining agent into the fifth homogeneously mixed melt and continuing to smelt to obtain the complex rare earth alloy.
  • the modificator is firstly added, and after being completely melted and homogenized, the rare earth aluminum alloy is added, and after being further completely melted and homogenized, the aluminum-titanium intermediate as the refiner is finally added. Alloy/Al-Ti-B Master Alloy.
  • the refining in any of the above steps that is, the refining in the process of purifying the aluminum melt, the refining in the process of preparing the rare earth aluminum alloy, and the refining of each melt in step S3, can be carried out in the following manner:
  • the refining includes:
  • the added amount of the refining agent accounts for 0.1-0.3% of the mass of the added melt
  • the added amount of the slag remover accounts for 0.1-0.3% of the added mass of the melt
  • the components of the refining agent contain by mass:
  • the components of the slag remover contain by mass:
  • test the density of the melt when the density of the melt is less than 2.65g/ cm3 , then carry out the refining treatment; when the density of the melt is greater than or equal to 2.65g/ cm3 , that is, the refining process is not performed or the refining process is terminated.
  • the hydrogen content is estimated by testing the density of the melt. It is generally believed that the higher the density, the less the hydrogen content. As a standard, when the density reaches 2.65g/cm 3 , it can be considered that the hydrogen content is up to the standard, no need further refining. Of course, due to higher quality requirements, the density standard can also be set to 2.67g/cm 3 or higher.
  • the composite rare earth alloy for aluminum alloy modification according to the embodiment of the second aspect of the present invention contains strontium, titanium or titanium boron, and a rare earth metal, wherein, 1:(0.1-1.2):(0.1-1.2), the rare earth metal One or more selected from lanthanum, cerium, and yttrium.
  • Raw material high-purity aluminum ingot (purchased from Chinalco, composition: Al (99.99%), Fe ⁇ 0.1%, impurity ⁇ 0.05%)
  • Pretreatment Use a grinder to clean the scale and surface of the high-purity aluminum surface.
  • Ultrasonic cleaning Put the pretreated high-purity aluminum ingot into the cleaning agent for ultrasonic treatment.
  • Drying Put the high-purity aluminum ingot after ultrasonic cleaning into an oven and bake at 60-100°C for 30-60 minutes.
  • Refining treatment is performed after the high-purity aluminum is melted. Specifically: Refining the molten high-purity aluminum through the Ar+graphite automatic degassing stirring rod. Refining by blowing Ar at 740-760°C for 5-10 minutes, the amount of refining being blown in is 0.1-0.3% of the melt, and kept for 3-5 minutes. After that, let it stand for 10-20 minutes, put 0.1-0.3% scum remover in it to make it evenly disperse, and remove the scum on the surface.
  • Rare earth alloy melting and treatment adjust the temperature of the high-purity aluminum obtained in the above 1) to 780-820°C, and after heating and melting completely, add rare earth to the rare earth aluminum alloy with a lanthanum content of 0.2 ⁇ 0.02wt% according to the set mass percentage Aluminum-lanthanum alloy (purchased from Baotou Rare Earth Research Institute, composition: Al-10La, Fe ⁇ 0.05, impurity content ⁇ 0.15). Under the protection of argon atmosphere, heat it at 780-820°C to make it melt completely.
  • Refining treatment The whole process is under the protection of argon atmosphere, and the refining treatment is performed after the rare earth aluminum-lanthanum alloy is melted. Feed the Ar+graphite automatic degassing stirring rod to refine the melted one. In 5-10 minutes at 760-780°C, use Ar to blow into the refining agent, the refining dosage is 0.3wt% of the melt, and there should be no boiling bubbles on the upper surface of the aluminum liquid during the refining process. Removal of scum on the surface of the melt: After refining for 15-20 minutes, add 0.2wt% slag remover to evenly disperse and remove the scum on the surface.
  • Casting Quickly cast the above melt into the mold to ensure uniform composition of each part. This process uses full water cooling to cool it down.
  • Aluminum-strontium master alloy obtained from Nantong Angshen Metal Material Co., Ltd., composition: Al-10Sr, Fe ⁇ 0.05, impurity content ⁇ 0.15.
  • Pretreatment Use a grinder to clean the scale and surface of the Al-Sr master alloy.
  • Ultrasonic cleaning put the pretreated aluminum-strontium master alloy into an ultrasonic cleaning tank for ultrasonic treatment.
  • Drying put the cleaned aluminum-strontium master alloy into an oven and bake at 60-100°C for 30-60 minutes.
  • Refining treatment After the aluminum-strontium master alloy is melted, it is refined. The molten high-purity aluminum is refined by feeding the Ar+graphite automatic degassing stirring rod. Refining with Ar blowing at 730-750°C for 5-10 minutes, the amount of refining being blown in is 0.1-0.3% of the melt, and kept at 3-5 minutes. During the refining process, there should be no boiling bubbles on the upper surface of the aluminum liquid.
  • Al-Ti-B master alloy purchased from Nantong Angshen Metal Materials Co., Ltd. (composition and content: Ti: 5%, B: 1%, the rest: Al)
  • the aluminum melt, the rare earth aluminum alloy, the aluminum strontium master alloy, and the aluminum titanium boron master alloy are respectively prepared, and then mixed and smelted to obtain a composite rare earth alloy as a product.
  • the rare earth aluminum alloy is firstly added to the aluminum melt, then the aluminum strontium alloy is added, and finally the aluminum titanium alloy is added. details as follows:
  • Step 1 Ingredients: Preheat the high-purity aluminum, aluminum-titanium-boron master alloy, aluminum-strontium master alloy, and rare earth aluminum alloy obtained above according to the required mass percentage.
  • high-purity aluminum 4.8 parts
  • aluminum-titanium-boron master alloy 0.2 parts
  • aluminum-strontium master alloy 60 parts
  • rare earth aluminum alloy 35 parts
  • Step 2 Add and melt the rare earth aluminum alloy: for the above aluminum melt, first heat the rare earth aluminum alloy to 780-820°C to soften before melting, then control the overall temperature of the aluminum melt at 760-780°C, and put the rare earth Aluminum alloy is added to the aluminum melt for heat preservation.
  • the whole process adopts the protection of argon atmosphere and melts the rare earth aluminum alloy.
  • Step 3 After the rare earth aluminum alloy is completely melted, the temperature is controlled at 750-770° C. and stirred for 5-10 minutes.
  • the whole process is protected by an argon atmosphere, and the stirring rod is made of graphite material and preheated to 400-500°C before stirring.
  • Step 4 heat-preserve the melted melt at 740-760° C. and control the heat-retaining time within 5-20 minutes. In this stage, an alloying reaction occurs.
  • Step 5 After the heat preservation is completed, refining, degassing and slag removal are carried out. 0.3% refining agent is blown into the melt by argon, and the aeration time is controlled at 3 to 8 minutes; after that, further add 0.2% slag remover, stir for 5 minutes and let stand to remove the slag and impurities on the surface of the melt . The whole process is protected by argon atmosphere.
  • the aluminum melt is sampled before and during refining and its density is determined to estimate the hydrogen content.
  • the measurement method adopts the density method (compared with the theoretical value of aluminum of 2.70g/cm 3 ), the closer the measured sample is to 2.7g/cm 3 , the lower the internal hydrogen content of aluminum. Generally, it cannot reach 2.7g/cm 3 normally; the density test of the sample is approximately equal to 2.65g/cm 3 to estimate the hydrogen content. During the process, it must be vacuumized. If the hydrogen content is unqualified, further refining, that is, adding refining agent repeatedly , The deslagging agent is refined again.
  • Step 6 Stand still: put the melt that has been added with the rare earth aluminum alloy and refined for 3-5 minutes, and the temperature is controlled at 740-760 degrees.
  • Step 7 Adding and melting the aluminum-strontium master alloy: adding the above-mentioned refined aluminum-strontium master alloy into the melt in step 6, and controlling the temperature at 780-820° C. to completely melt the aluminum-strontium master alloy. The whole process is protected by argon atmosphere, and the aluminum-strontium master alloy is melted.
  • Step 8 After the aluminum-strontium master alloy is melted, control the temperature at 740-760° C. and stir for 3-8 minutes to achieve homogenization. The whole process is protected by an argon atmosphere, and the stirring rod is made of graphite material, which is preheated to 400-500°C before stirring.
  • Step 9 heat preservation treatment is carried out at 725-750°C.
  • the heat preservation time is controlled at 15-30 minutes.
  • Step 10 Refining, degassing and slag removal: After the heat preservation of the melt is completed, blow in 0.3% of the refining agent into the aluminum-rare-earth composite melt after argon gas is introduced, and the ventilation time is controlled at 5 to 10 minutes; put in 0.2% of Put the slag removal agent into the aluminum melt, stir for 5 minutes and remove the slag and impurities on the surface of the aluminum-rare-earth composite melt. The whole process is protected by argon atmosphere.
  • the aluminum melt is sampled before and during refining to determine the hydrogen content. (Hydrogen content requirement: greater than or equal to 2.65g/cm 3 ;) During the hydrogen measurement process, it must be vacuumized. If the hydrogen content is unqualified, then further refining, that is, adding refining agents and slag removers to refine again.
  • Step 11 Add Al-Ti-B master alloy: Add Al-Ti-B master alloy to the melt treated in Step 10 above, heat to melt completely, and stir evenly for 3-5 minutes to homogenize.
  • Step 12 heat preservation: after stirring, heat the melt for 8-12 minutes, and control the temperature at 715-725°C.
  • Step 13 Refining, degassing and slag removal: After the heat preservation of the melt is completed, blow in 0.3% of the refining agent into the aluminum-rare-earth composite melt after argon gas is introduced, and the ventilation time is controlled at 5 to 10 minutes; put in 0.2% of Put the slag removal agent into the aluminum melt, stir for 5 minutes and remove the slag and impurities on the surface of the aluminum-rare-earth composite melt. The whole process is protected by argon atmosphere.
  • the aluminum melt is sampled before and during refining to determine the hydrogen content. (Hydrogen content requirement: greater than or equal to 2.65g/cm 3 ;) Vacuum treatment must be performed during the hydrogen measurement process. If the hydrogen content is unqualified, further refining is carried out, that is, refining agents and slag removers are added repeatedly until it is qualified.
  • Step 14 casting: the mold is preheated at 300-400°C.
  • the temperature of the composite rare earth alloy melt obtained in step 13 above is controlled at 715-725° C. for casting.
  • the oxides on the surface of the aluminum-rare-earth composite melt are filtered through a glass fiber filter; before each casting, the surface of the aluminum-rare-earth composite melt is filtered before casting.
  • the cooling control of the casting mold adopts a water cooling method to cool the aluminum-rare-earth composite melt cast into the mold.
  • the solidification speed of the aluminum melt is controlled at 50-100°C/s, and the solidification method is sequential solidification.
  • the mass ratio of the rare earth metal:strontium:titanium or titanium boron weight is 1:(0.1-1.2):(0.1-1.2). That is to say, the content of modificator and refiner can be increased, and they can fully function.
  • FIG. 1 shows the metallographic structure of the aluminum alloy before modification
  • FIG. 2 shows the metallographic structure after modification.
  • Figure 1 and Figure 2 shows the metallographic structure of the aluminum alloy before modification
  • Figure 1 and Figure 2 shows the metallographic structure of the aluminum alloy before modification
  • Figure 1 and Figure 2 shows that the metallographic structure of the aluminum alloy before modification (Figure 1) can be seen that the coarse primary ⁇ -Al phase presents the structure of dendrites, and the diameter and length of the secondary dendrites and dendrites The crystal spacing is relatively large.
  • a large number of rose-like ⁇ -Al phases and rounder spherical ⁇ -Al phases also increased, the primary ⁇ -Al phase was significantly refined, and the number of dendrites decreased. . That is to say, after modification, the grains are sufficiently refined and the microstructure is uniform.
  • Example 1 the mechanical properties of the modified A356 aluminum alloy were evaluated using the composite rare earth aluminum alloy obtained in this example.
  • the evaluation results (referred to as Example 1) are shown in Table 1 below.
  • the test results of the unmodified A356 aluminum alloy (recorded as before modification) are given at the same time.
  • the test results of A356 aluminum alloy modified by adding modifier and refiner in exactly the same proportion instead of the composite rare earth aluminum alloy of this embodiment are also listed (referred to as comparative example 1).
  • Step 1 Ingredients: Preheat the high-purity aluminum, aluminum-titanium-boron master alloy, aluminum-strontium master alloy, and rare earth aluminum alloy obtained above according to the required mass percentage.
  • high-purity aluminum 4.8 parts
  • aluminum-titanium-boron master alloy 0.2 parts
  • aluminum-strontium master alloy 60 parts
  • rare earth aluminum alloy 35 parts
  • Step 2 Adding and melting the rare earth aluminum alloy & aluminum strontium master alloy: In the above aluminum melt, control the temperature at 760-780°C, and add the rare earth alloy material & aluminum strontium master alloy into the aluminum melt together.
  • the whole process is protected by an argon atmosphere, and the rare earth aluminum alloy is melted when the temperature is controlled at 780-820°C.
  • Step 3 After the rare earth aluminum alloy & aluminum-strontium intermediate alloy are completely melted, the temperature is controlled at 750-770° C. and stirred for 10 minutes. The whole process is protected by an argon atmosphere, and the stirring rod is made of graphite material, which is preheated to 450°C before stirring.
  • Step 4 heat-preserve the melted melt at 740-760° C. and control the heat-retaining time to 10 minutes.
  • Step 5 After the heat preservation is completed, refining, degassing and slag removal are carried out. 0.3wt% refining agent is blown into the melt by argon, and the aeration time is controlled at 5 minutes; thereafter, 0.2wt% slag remover is further added, stirred for 5 minutes, and the slag and impurities on the surface of the melt are removed. The whole process is protected by argon atmosphere.
  • the aluminum melt is sampled before and during refining to estimate the hydrogen content. (Requirement for melt density: greater than or equal to 2.65g/cm 3 .) During the hydrogen measurement process, it must be vacuumized. If the hydrogen content is unqualified, further refining is carried out, that is, refining agent and slag removal agent are added repeatedly for further refining.
  • Step 6 Stand still: put the melt that has been added with the rare earth aluminum alloy and refined for 3-5 minutes, and the temperature is controlled at 740-760 degrees.
  • the aluminum-titanium-boron master alloy is further added for smelting.
  • the experimental results show that the composite rare earth aluminum alloy obtained according to this embodiment can also effectively improve the mechanical strength of the aluminum alloy and achieve better refinement and modification effects.
  • the detailed data thereof are omitted here.
  • Step 1 Adding and melting the aluminum-strontium master alloy: adding the above-mentioned refined aluminum-strontium master alloy into the aluminum melt, and controlling the temperature at 780-820° C. to completely melt the aluminum-strontium master alloy. The whole process is protected by argon atmosphere, and the aluminum-strontium master alloy is melted.
  • Step 2 After the aluminum-strontium master alloy is melted, control the temperature at 740-760° C. and stir for 3-8 minutes to achieve homogenization. The whole process is protected by argon atmosphere, the stirring rod is made of graphite material, and it is preheated to 400-500°C before stirring.
  • Step 3 heat preservation treatment is carried out at 725-750°C.
  • the heat preservation time is controlled at 15-30 minutes.
  • Step 4 refining, degassing and slag removal: After the heat preservation of the melt is completed, 0.3wt% of refining agent is blown into the aluminum-rare-earth composite melt after passing through argon, and the ventilation time is controlled at 10 minutes; put in 0.2wt% Put the slag remover into the aluminum melt, stir for 5 minutes and salvage the slag and impurities on the surface of the aluminum-rare-earth composite melt. The whole process is protected by argon atmosphere.
  • the aluminum melt is sampled before and during refining to determine the hydrogen content. (Hydrogen content requirement: greater than or equal to 2.65g/cm 3 ;) During the hydrogen measurement process, it must be vacuumized. If the hydrogen content is unqualified, then further refining, that is, adding refining agents and slag removers to refine again.
  • Step 5 Adding and melting the rare earth aluminum alloy: the temperature of the melt in the above step 4 is controlled at 760-780° C., and the rare earth alloy material is added into the melt.
  • the whole process is protected by an argon atmosphere, and the rare earth aluminum alloy is melted when the temperature is controlled at 780-820°C.
  • Step 6 After the rare earth aluminum alloy is completely melted, control the temperature at 750-770° C. and stir for 10 minutes. The whole process is protected by argon atmosphere, the stirring rod is made of graphite material, and it is preheated to 400-500°C before stirring.
  • Step 7 heat preservation treatment is performed on the melted melt at 740-760° C. and the heat preservation time is controlled at 10 minutes.
  • Step 8 Refining: After the heat preservation is completed, refining, degassing and slag removal are carried out. 0.3wt% refining agent is blown into the melt by argon, and the aeration time is controlled at 5 minutes; after that, further add 0.2wt% slag remover, stir for 5 minutes and let stand to remove slag and impurities on the surface of the melt . The whole process is protected by argon atmosphere.
  • the aluminum melt is sampled before and during refining to estimate the hydrogen content. (Requirement for melt density: greater than or equal to 2.65g/cm 3 .) During the hydrogen measurement process, it must be vacuumized. If the hydrogen content is unqualified, further refining is carried out, that is, refining agent and slag removal agent are added repeatedly for further refining.
  • Step 9 standing still: the melt added with the rare earth aluminum alloy and refined is left standing for 3-5 minutes, and the temperature is controlled at 740-760°C.
  • the aluminum-titanium-boron master alloy is further added for smelting.
  • the experimental results show that the composite rare earth aluminum alloy obtained according to this embodiment can also effectively improve the mechanical strength of the aluminum alloy and achieve better refinement and modification effects.
  • the detailed data thereof are omitted here.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un alliage composite de terres rares pour la modification d'alliage d'aluminium et son procédé de préparation. Le procédé de préparation comprend les étapes suivantes : étape S1, fourniture d'une masse fondue d'aluminium ; étape S2, fourniture d'un modificateur, d'un raffineur et d'un alliage d'aluminium et de terres rares, un métal de terres rares dans l'alliage d'aluminium et de terres rares étant choisi parmi un ou plusieurs éléments parmi le lanthane, le cérium et l'yttrium ; et étape S3, dans une atmosphère de gaz inerte, ajout du modificateur, du raffineur et de l'alliage d'aluminium et de terres rares dans la masse fondue d'aluminium, puis sa fusion, et ainsi obtention de l'alliage composite de terres rares pour la modification d'alliage d'aluminium. Selon le procédé de préparation de l'alliage composite de terres rares utilisé pour la modification d'alliage d'aluminium dans les exemples de la présente invention, par introduction du métal de terres rares, l'effet d'empoisonnement mutuel entre le modificateur et le raffineur est considérablement surmonté, la quantité d'ajout du modificateur et du raffineur peut être augmentée, et en outre les effets de modification et d'affinage peuvent être améliorés.
PCT/CN2022/141281 2021-12-27 2022-12-23 Alliage composite de terres rares pour modification d'alliage d'aluminium et son procédé de préparation WO2023125263A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115896508A (zh) * 2022-12-09 2023-04-04 北京机科国创轻量化科学研究院有限公司 一种适于亚共晶铝硅合金的高效细化变质方法及压铸件

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114214534A (zh) * 2021-12-27 2022-03-22 上海耀鸿科技股份有限公司 改性铝合金及其制备方法
CN114277272A (zh) * 2021-12-27 2022-04-05 上海耀鸿科技股份有限公司 铝合金改性用复合稀土合金及其制备方法
CN114959369B (zh) * 2022-06-09 2023-05-12 江苏宏德特种部件股份有限公司 一种熵工程共晶型铝稀土铸造合金及其制备方法
CN115133012A (zh) * 2022-07-22 2022-09-30 合肥综合性国家科学中心能源研究院(安徽省能源实验室) 锂离子电池负极用珊瑚状纳米硅粉、负极材料及制备方法
CN116083762B (zh) * 2022-12-29 2023-11-14 华劲新材料研究院(广州)有限公司 一种适合一体化压铸铝合金材料

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6217141A (ja) * 1985-07-15 1987-01-26 Sumitomo Light Metal Ind Ltd Ａｌ−Ｓｉ系合金における共晶Ｓｉの微細化方法
CN101591746A (zh) * 2009-03-26 2009-12-02 广州钢铁企业集团有限公司 一种铝、铝合金用晶粒细化变质中间合金及其制备方法
CN103146944A (zh) * 2013-03-19 2013-06-12 新昌县国威铝制品辅助材料有限公司 一种铝或铝合金熔液清渣剂
CN108130443A (zh) * 2017-11-21 2018-06-08 包头稀土研究院 稀土铝钛硼合金及其制备方法
CN109234553A (zh) * 2018-09-25 2019-01-18 全球能源互联网研究院有限公司 一种Al-Zr-Sc-B耐热合金单丝及其制备方法
CN111349822A (zh) * 2020-03-20 2020-06-30 永城金联星铝合金有限公司 一种铝-钛-硼-锶-稀土合金线材及制备方法
CN114277272A (zh) * 2021-12-27 2022-04-05 上海耀鸿科技股份有限公司 铝合金改性用复合稀土合金及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108103363B (zh) * 2017-12-11 2019-10-29 南昌大学 一种用于亚共晶铝硅铸造合金的细化-变质剂及其制备方法和应用
WO2020002813A1 (fr) * 2018-06-25 2020-01-02 C-Tec Constellium Technology Center Procede de fabrication d'une piece en alliage d'aluminium
CN109439976B (zh) * 2019-01-09 2019-12-24 广东省材料与加工研究所 一种铸造铝硅合金的复合变质方法
CN112143945B (zh) * 2020-09-23 2021-12-17 上海耀鸿科技股份有限公司 一种多种复合稀土元素的高强韧性铸造铝硅合金及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6217141A (ja) * 1985-07-15 1987-01-26 Sumitomo Light Metal Ind Ltd Ａｌ−Ｓｉ系合金における共晶Ｓｉの微細化方法
CN101591746A (zh) * 2009-03-26 2009-12-02 广州钢铁企业集团有限公司 一种铝、铝合金用晶粒细化变质中间合金及其制备方法
CN103146944A (zh) * 2013-03-19 2013-06-12 新昌县国威铝制品辅助材料有限公司 一种铝或铝合金熔液清渣剂
CN108130443A (zh) * 2017-11-21 2018-06-08 包头稀土研究院 稀土铝钛硼合金及其制备方法
CN109234553A (zh) * 2018-09-25 2019-01-18 全球能源互联网研究院有限公司 一种Al-Zr-Sc-B耐热合金单丝及其制备方法
CN111349822A (zh) * 2020-03-20 2020-06-30 永城金联星铝合金有限公司 一种铝-钛-硼-锶-稀土合金线材及制备方法
CN114277272A (zh) * 2021-12-27 2022-04-05 上海耀鸿科技股份有限公司 铝合金改性用复合稀土合金及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115896508A (zh) * 2022-12-09 2023-04-04 北京机科国创轻量化科学研究院有限公司 一种适于亚共晶铝硅合金的高效细化变质方法及压铸件
CN115896508B (zh) * 2022-12-09 2023-10-10 北京机科国创轻量化科学研究院有限公司 一种适于亚共晶铝硅合金的高效细化变质方法及压铸件

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