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CN118685670B - Heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material and preparation method thereof - Google Patents

Heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material and preparation method thereof Download PDF

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CN118685670B
CN118685670B CN202411199921.5A CN202411199921A CN118685670B CN 118685670 B CN118685670 B CN 118685670B CN 202411199921 A CN202411199921 A CN 202411199921A CN 118685670 B CN118685670 B CN 118685670B
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die
aluminum alloy
aluminum
casting
strength
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CN118685670A (en
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李法兵
赵光年
李柄霖
耿德敏
马晓涛
文晨旭
张浩波
吴中平
刘建路
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Shandong Haihua Group 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
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04—Modified aluminium-silicon alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
    • B22D1/002—Treatment with gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D43/00—Mechanical cleaning, e.g. skimming of molten metals
    • B22D43/001—Retaining slag during pouring molten metal
    • B22D43/004—Retaining slag during pouring molten metal by using filtering means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/06—Obtaining aluminium refining
    • C22B21/066—Treatment of circulating aluminium, e.g. by filtration
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
    • C22B9/055—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ while the metal is circulating, e.g. combined with filtration
    • 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
    • C22C1/026—Alloys based on aluminium
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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

Abstract

The invention discloses a heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material and a preparation method thereof, and belongs to the technical field of aluminum alloy materials. The weight percentage of each component in the die-casting aluminum alloy is Si：6.0～12%、Mg：0.1～0.45%、Mn：0.3～0.85%、Cr：0.05～0.2%、Sr：0.05～0.15%、Zr：0.05～0.12%、Ni：0.03～0.07%、Fe<0.2%,, the total amount of other impurities is less than or equal to 0.5 percent, and the balance is Al. The die-casting aluminum alloy phase comprises a matrix alpha-Al solid solution, si and ZrNi phases, wherein the ZrNi phases are uniformly distributed near a die-casting aluminum alloy grain boundary, have a hydrogen absorption equilibrium pressure of 5 multiplied by 10 ‑4 Pa and a hydrogen absorption capacity exceeding 200ml/g at 20 ℃, do not melt when heated to 1010 ℃, have the hydrogen content of the aluminum liquid of less than or equal to 0.04ml/100g Al and the slag content of less than or equal to 0.008mm 2/kg, and the prepared heat-treatment-free die-casting aluminum alloy has excellent toughness and high hydrogen embrittlement resistance.

Description

Heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material and preparation method thereof
Technical Field
The invention relates to the technical field of aluminum alloy materials, in particular to a heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material and a preparation method thereof.
Background
The development of high strength and toughness aluminum alloy die castings for automotive body structural members, typically all aluminum body frames of Audi A8 for the 1990 s, have been applied to critical joint portions of the body, and such body structural members are generally crash-safe members, which are connected by rivets, and require good toughness while maintaining good strength. With the rapid development of new energy automobiles, automobile structural members are rapidly developed toward the design and manufacturing directions of integration, light weight and high efficiency, such as an integrated die-cast automobile body, an integrated die-cast auxiliary frame and the like. As the die-casting aluminum alloy for the vacuum die-casting structural part of the automobile body widely used at present, the heat treatment process of the AlSi10MnMg alloy can cause the problems of deformation and surface foaming of the die casting, and particularly, along with the continuous upsizing of the die casting, the subsequent shaping difficulty and the rejection rate are greatly improved. therefore, the heat treatment-free die-casting aluminum alloy material can be directly used in an as-cast state to avoid the problems, and can also reduce the manufacturing cost of parts, so that development and application of the die-casting aluminum alloy material are gradually becoming research hot spots in recent years. The Chinese patent document with publication number CN117867333A discloses a high-strength heat-treatment-free aluminum alloy for high-pressure casting and a preparation method thereof, wherein the high-strength heat-treatment-free aluminum alloy comprises 5.0-15.0% of La, 1.5-4.5% of Er, 0.5-2.5% of Cu, 0.3-1.5% of Mg, 0.2-1.5% of Zn, 0.05-0.30% of Ag, 0.1-0.4% of Mn, 0.05-0.35% of Ti, 0.05-0.35% of Sc, 0.05-0.25% of Zr and 0.05-0.35% of Y, and the aluminum alloy is prepared by various methods, the heavy rare earth elements are matched for preparing the alloy with high casting formability, High strength and plasticity high strength heat treatment-free aluminum alloy, but excessive alloying elements increase the controllable difficulty of aluminum alloying, and excessive rare earth is added to cause the problem of high raw material cost, so that the industrial popularization and application are difficult to realize; the invention discloses a heat-treatment-free high-strength and toughness die-casting aluminum alloy and a preparation method thereof, wherein the aluminum alloy consists of 9.5-12.5% of Si, 0.3-0.6% of Mg, 0.5-1.5% of Cu, 0.2-0.5% of Mn, 0.1-0.2% of Ti, 0.01-0.05% of Sr, 0.005-0.015% of P, the content of Fe is not more than 0.25% and the balance of Al and impurities by refining coarse alpha-Al grains and Si phases. Hydrogen is the only gas which can be dissolved in the aluminum liquid in a large amount, has great harm to the performance of aluminum and aluminum alloy, is easy to be separated out from castings in the heat treatment process to form surface bubbles, and the rejection rate caused by the excessive hydrogen accounts for about half of all aluminum casting rejects. The hydrogen in aluminum not only causes macroscopic defects, but also affects the structure of the structure, and has influence on a series of performances such as strength, fatigue, toughness, corrosion resistance, anodic oxidation and the like. The heat-treatment-free aluminum alloy avoids the deformation of the die casting and the generation of surface bubbles caused by heat treatment, but if the hydrogen content in the heat-treatment-free aluminum alloy is too high, the fatigue life can be obviously reduced besides the toughness of the aluminum alloy die casting, and the occurrence of hydrogen embrittlement is caused under the induction action of external environments such as alternating stress, impact load, rainwater and sea water. The hydrogen content of aluminum and aluminum alloy is only about 0.1ml/100g Al, which is one to two orders of magnitude lower than the hydrogen content in steel and titanium alloy, so that the hydrogen content of aluminum liquid is controlled below 0.1ml/100g Al from the aluminum alloy casting stage to avoid the occurrence of extreme accidents such as brittle failure caused by hydrogen embrittlement in the full life cycle of heat treatment-free aluminum alloy die castings from casting, loading application and the like to scrapping. In addition, from the whole life cycle of the casting, under the induction of application scenes such as high-temperature high-humidity water vapor, alternating impact stress and the like, hydrogen in the external environment and supersaturated hydrogen atoms remained in the solid aluminum can be restless, once the hydrogen atoms are combined into hydrogen molecules, the hydrogen molecules are accompanied with rapid volume expansion, and the generated internal stress can reach 10 4 MPa, so that the aluminum alloy can be torn from the inside. In summary, the heat-treatment-free aluminum alloy substantially puts more stringent requirements on aluminum alloy materials and various links of processing and preparation, and only the effective control of the hydrogen content and the inclusion content in the aluminum alloy is realized, and meanwhile, the high-strength and toughness heat-treatment-free aluminum alloy materials manufactured by taking recovered waste aluminum with complex components and more impurities as raw materials are realized, so that the heat-treatment-free die-casting aluminum alloy materials can really reduce the cost and improve the efficiency of enterprises and promote the benign and healthy development of the heat-treatment-free die-casting aluminum alloy industry for automobile structural parts.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material and a preparation method thereof from the whole life cycle of the die-casting aluminum alloy. The heat-treatment-free high-strength and high-toughness die-casting aluminum alloy realizes effective control of hydrogen and slag content, has higher yield strength, tensile strength and elongation, and shows excellent toughness, and meanwhile, the prepared heat-treatment-free high-strength and high-toughness die-casting aluminum alloy has high hydrogen embrittlement resistance.
In order to achieve the purpose, the weight percentage of each component in the die-casting aluminum alloy is Si：6.0～12%、Mg：0.1～0.45%、Mn：0.3～0.85%、Cr：0.05～0.2%、Sr：0.05～0.15%、Zr：0.05～0.12%、Ni：0.03～0.07%、Fe<0.2%,, the total amount of other impurities is less than or equal to 0.5 percent, and the balance is Al.
The die-casting aluminum alloy phase comprises a matrix alpha-Al solid solution, si and ZrNi phases, wherein the ZrNi phases of an orthorhombic system are uniformly distributed in a die-casting aluminum alloy grain boundary region, the die-casting aluminum alloy phase has a hydrogen absorption equilibrium pressure of 5 multiplied by 10 -4 Pa and a hydrogen absorption capacity of more than 200ml/g at 20 ℃ and does not melt when heated to 1010 ℃, and the die-casting aluminum alloy has a die-casting tensile strength of 280-350 MPa, a yield strength of 150-198MPa and an elongation of 9-16%.
The preparation method of the invention comprises the following steps:
1) Adding an aluminum ingot, silicon, aluminum chromium and aluminum manganese intermediate alloy into a smelting furnace, heating to 750-780 ℃, and uniformly stirring for 15-30 min after the aluminum ingot is completely melted;
2) Heating the aluminum liquid to 710-730 ℃, uniformly spraying a refining agent into the aluminum liquid by using nitrogen load, keeping the temperature for 10-15 min, standing the aluminum liquid for 20-30 min after the spraying is finished, and deslagging after fully reacting and floating refining agent particles, wherein the spraying speed of the refining agent is 0.6-1.0 kg/min, and the nitrogen pressure is 0.35-0.8MPa;
3) After the alloy components are detected to be qualified, transferring the aluminum liquid to a heat preservation furnace, starting a rotary degassing machine in the middle of the heat preservation furnace, setting the rotary speed of a rotor to 400-450 r/min, setting the argon pressure to 0.2-0.35 MPa, setting the argon flow to 10-15L/min, degassing for 10-15 min, uniformly scattering a layer of slag removing agent on the surface of the degassed aluminum liquid to remove slag, standing for 10-20 min, controlling the temperature of the aluminum liquid to 660-690 ℃, and performing three-stage filtration to obtain aluminum liquid with the hydrogen content less than or equal to 0.04ml/100g Al and the slag content less than or equal to 0.008mm 2/kg, wherein the aluminum liquid enters a preheated ingot casting die through a distributor to obtain the heat-treatment-free die-casting aluminum alloy ingot.
The refining agent in the step 2) comprises, by mass, 30-50wt% of KCl, 5-10wt% of MgCl 2:30～55wt%;CaF2:5～10 wt%;BaCl2 -6wt% of ZrNi alloy, and powder particles with the particle size of 0.5-1 mu m prepared by repeatedly smelting the ZrNi alloy in a magnetic suspension smelting furnace for three times and then ball-milling the powder particles. The refining agent is prepared by mixing the components according to the corresponding percentages, loading the mixture into a ball mill with the rotating speed of 100-600 r/min, mixing the mixture into powder, and sieving the powder with a sieve of 30-60 meshes.
The slag removing agent in the step 3) is MgCl 2 and KCl with the weight ratio of 1 to 1.5, the third-stage filtration is that a glass fiber cloth flashboard is arranged at an aluminum liquid outlet of the heat preservation furnace to carry out first-stage filtration, then the slag removing agent flows through a foam ceramic filter sheet with the thickness of 8 to 20mm and the aperture of 20 to 80 meshes to carry out second-stage filtration, and finally the slag removing agent flows through an alumina gravel deep bed filter with the particle size of 2 to 10mm to carry out third-stage filtration.
The invention has the following beneficial effects:
The invention starts from the full life cycle of the heat-treatment-free die-casting aluminum alloy, introduces ZrNi alloy with extremely low hydrogen absorption equilibrium pressure and large hydrogen absorption amount into the field of die-casting aluminum alloy for the first time, and constructs a solid solution with a matrix alpha-Al, Si is a main alloying element of the die-casting aluminum alloy, si can improve the casting fluidity of the aluminum alloy in the die-casting aluminum alloy, the die is not stuck and is suitable for die casting, meanwhile, si and Mg can form Mg 2 Si strengthening phases to obviously enhance the strength of the die-casting aluminum alloy, the higher the content of Si is, the better the fluidity of the die-casting aluminum alloy is, the higher the strength is, but the higher the content of Si is, the plasticity of the die-casting aluminum alloy is reduced, mg is an important strengthening element of the die-casting aluminum alloy, mg and Si can form Mg 2 Si strengthening phases to obviously enhance the strength of the die-casting aluminum alloy, the higher the content of Mg is, but the higher the content of Mg is, the plasticity of the die-casting aluminum alloy is also reduced, in the actual production process, the atomic ratio of Mg/Si is about 1.73, mn element and matrix Al have the same potential as MnAl 6 and pure aluminum, the corrosion resistance of the aluminum alloy can be effectively improved, and the Mn can be used as a high-temperature crystallization strengthening phase to enhance the temperature of the die-casting aluminum alloy, the invention uses regenerated aluminum with higher impurity iron content as raw material to realize waste aluminum regeneration, and reduces cost, cr element is typical disperse phase forming element to inhibit alloy recrystallization and grain growth, trace element Cr is easy to form disperse phase with Fe to replace other harmful Fe-containing phase, and reduce the splitting effect of insoluble Fe-containing relative matrix. The Sr element is the most effective Si phase-change agent accepted by Al-Si alloy, has better refining and modifying effects on alpha-Al, greatly improves the mechanical property of the alloy, and takes Zr as a refined aluminum alloy structure, Trace elements with various effects of improving thermal stability and the like are widely applied to aluminum alloy, the ZrNi alloy has a hydrogen absorption equilibrium pressure of 5 multiplied by 10 -4 Pa and a hydrogen absorption capacity exceeding 200ml/g at room temperature (20 ℃), can quickly absorb hydrogen in aluminum liquid and external environment into aluminum alloy castings until the interior of the alloy is solidified into metal hydrogen, the ZrNi alloy is heated to 1010 ℃ and does not melt, the high thermal stability is achieved, the extremely low hydrogen content in the whole process of solidification processing of the aluminum liquid and the whole life cycle of die casting aluminum alloy is ensured, hydrogen embrittlement is avoided, in addition, 0.5-1 mu m of ZrNi alloy fine particles are uniformly distributed in a grain boundary area and serve as effective nucleation substrates, the grain structure is thinned, the segregation degree is reduced, and the refinement of eutectic Si and matrix alpha-Al solid solution phase is promoted, the homogenization, the three-stage filtration combined by the glass fiber cloth flashboard, the foam ceramic filter disc and the deep-bed filter and the low-temperature heat preservation standing sedimentation with the total duration of 30-50 min effectively reduce the slag content and the iron content introduced by the regenerated aluminum. the die-casting aluminum alloy has the yield strength of up to 198MPa, the tensile strength of up to 350MPa and the elongation of up to 16%, and the aluminum liquid hydrogen content is less than or equal to 0.04ml/100g Al and the slag content is less than or equal to 0.008mm 2/kg.
The invention has the advantages of sufficient reserves of raw material mineral resources, low raw material cost, complex components and capability of taking recovered waste aluminum containing more impurities as raw materials to manufacture the heat-treatment-free high-strength and high-toughness aluminum alloy, reduces the manufacturing cost, improves the production efficiency, can reduce the cost and increase the efficiency for enterprises, and promotes the benign and healthy development of the heat-treatment-free die-casting aluminum alloy industry for automobile structural parts.
Drawings
FIG. 1 is an XRD pattern of the ZrNi alloy used in examples 1 to 3;
FIG. 2 is an XRD pattern of the die-cast aluminum alloy obtained in example 3;
FIG. 3 is an image of a metallographic structure of the die-cast aluminum alloy prepared in example 2 at 1000 times magnification;
FIG. 4 is a secondary electron image of a 3000 times scanning electron microscope of the die-cast aluminum alloy prepared in example 2;
Fig. 5 is a secondary electron image of a 3000 x scanning electron microscope of the die-cast aluminum alloy prepared in example 3. (the sample was corroded with 4% nitric acid alcohol solution (volume fraction), the metallographic specimen was observed on a LEICA DM IRM-type Optical Microscope (OM) and a JEOL JXA-8100-type Scanning Electron Microscope (SEM) equipped with an OxFORD 7412-type spectrometer (EDS), the phase composition analysis was performed on a D/MAX-RC-type X-ray diffractometer (XRD) using a Cu target, and the plate-like tensile specimen was subjected to a room temperature (293K) tensile test on a DNS 200-type universal tester at a tensile speed of 2mm.min -1.)
Detailed Description
For a better understanding of the present invention, reference will now be made to the following description of the invention taken in conjunction with the accompanying drawings and examples, but the scope of the invention is not limited to the expression of the examples.
Example 1
The heat treatment-free high-strength and high-toughness die-casting aluminum alloy material comprises, by weight, 12% of Si, 0.1% of Mg, 0.3% of Mn, 0.05% of Cr, 0.15% of Sr, 0.05% of Zr, 0.03% of Ni, 0.12% of Fe, the total amount of other impurities and 0.5% of Al, and the balance of Al. The die-casting aluminum alloy phase comprises a matrix alpha-Al solid solution, si and ZrNi phases, wherein the ZrNi alloy is prepared by repeatedly smelting for three times by a magnetic suspension smelting furnace and then ball milling and sieving, and the grain size is 0.5 mu m as shown in figure 1. The ZrNi phase of the orthorhombic system is uniformly distributed in the grain boundary region of the die-casting aluminum alloy, has a hydrogen absorption equilibrium pressure of 5 multiplied by 10 -4 Pa and a hydrogen absorption capacity exceeding 200ml/g at 20 ℃ and does not melt when heated to 1010 ℃, and the die-casting aluminum alloy of the embodiment has the die-casting tensile strength of 350MPa, the yield strength of 198MPa and the elongation of 9 percent.
A preparation method of a heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material comprises the following steps:
1) Adding the regenerated aluminum ingot, silicon, aluminum chromium and aluminum manganese intermediate alloy into a smelting furnace, heating to 750 ℃, and uniformly stirring for 15min after the aluminum ingot is completely melted;
2) Heating aluminum liquid to 710 ℃, uniformly spraying a refining agent into the aluminum liquid by using nitrogen load, keeping the aluminum liquid for 10min, standing the aluminum liquid for 20min after the spraying is finished, and removing slag after fully reacting and floating refining agent particles, wherein the spraying speed of the refining agent is 0.6kg/min, the nitrogen pressure is 0.35MPa, the refining agent is prepared by mixing all components according to the corresponding percentage, loading the components into a ball mill with the rotating speed of 100r/min, mixing the components into powder, and sieving the powder with a 30-mesh sieve, wherein the percentages of all components forming the refining agent are MgCl 2:42 wt%,KCl:35 wt%,CaF2:10 wt%,BaCl2:10 wt percent, and the percentage of ZrNi alloy is 3wt%;
3) After the alloy component is detected to be qualified, transferring the aluminum liquid to a heat preservation furnace, starting a rotary degassing machine in the middle of the heat preservation furnace, setting the rotary speed of a rotor to 400r/min, setting the argon pressure to 0.2MPa, setting the argon flow to 10L/min, and degassing for 10min, uniformly scattering a layer of slag-removing agent consisting of MgCl 2 and KCl with the weight ratio of 1:1 on the surface of the degassed aluminum liquid, carrying out slag-removing, standing for 10min, controlling the temperature of the aluminum liquid to 660 ℃, setting a glass fiber cloth flashboard at an aluminum liquid outlet of the heat preservation furnace for primary filtering, then carrying out secondary filtering through a foamed ceramic filter sheet with the thickness of 8mm and the aperture of 20 meshes, and finally carrying out tertiary filtering through an alumina gravel deep bed filter with the particle size of 10 mm. The aluminum liquid with the hydrogen content of 0.04ml/100g Al and the slag content of 0.008mm 2/kg is prepared through three-stage filtration, and enters a preheated ingot casting die through a distributor, so that the prepared heat-treatment-free die casting aluminum alloy has excellent toughness and high hydrogen embrittlement resistance.
Example 2
The heat treatment-free high-strength and high-toughness die-casting aluminum alloy material comprises, by weight, 6.0% of Si, 0.45% of Mg, 0.85% of Mn, 0.2% of Cr, 0.05% of Sr, 0.12% of Zr, 0.07% of Ni, 0.15% of Fe, the total amount of other impurities and 0.4% of Al, and the balance of Al. The die-casting aluminum alloy phase comprises a matrix alpha-Al solid solution, si and ZrNi phases, as shown in a metallographic structure of FIG. 3 and a scanning electron microscope image of FIG. 4, wherein the metallographic structure of FIG. 3 clearly shows alpha-Al solid solution crystal grains with the grain size of about 10 mu m and eutectic silicon phases distributed among the alpha-Al solid solution crystal grains, and the scanning electron microscope image of FIG. 4 shows Al 4.01MnSi0.74 phases with the grain size of about 10 mu m, which are generated by the high Mn content of the die-casting aluminum alloy phase. The ZrNi alloy is prepared by repeatedly smelting for three times by a magnetic suspension smelting furnace and then ball milling and sieving, and the particle size is 1.0 mu m as shown in figure 1. The ZrNi phase of the orthorhombic system is uniformly distributed in the grain boundary region of the die-casting aluminum alloy, has a hydrogen absorption equilibrium pressure of 5 multiplied by 10 -4 Pa and a hydrogen absorption capacity exceeding 200ml/g at 20 ℃ and does not melt when heated to 1010 ℃, and the die-casting aluminum alloy of the embodiment has a die-casting tensile strength of 280MPa, a yield strength of 150MPa and an elongation of 16%.
A preparation method of a heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material comprises the following steps:
1) Adding the regenerated aluminum ingot, silicon, aluminum chromium and aluminum manganese intermediate alloy into a smelting furnace, heating to 780 ℃, and uniformly stirring for 30min after the aluminum ingot is completely melted;
2) Heating aluminum liquid to 730 ℃, uniformly spraying a refining agent into the aluminum liquid by using nitrogen load, keeping the aluminum liquid for 15min, standing the aluminum liquid for 30min after the spraying is finished, and allowing refining agent particles to fully react and float upwards to remove slag, wherein the spraying speed of the refining agent is 1.0kg/min, and the nitrogen pressure is 0.8MPa;
3) After the alloy component is detected to be qualified, transferring the aluminum liquid to a heat preservation furnace, starting a rotary degassing machine in the middle of the heat preservation furnace, setting the rotary speed of a rotor to 450r/min, setting the argon pressure to 0.35MPa, setting the argon flow to 15L/min, and degassing for 15min, uniformly scattering a layer of slag-forming agent consisting of MgCl 2 and KCl with the weight ratio of 1.5 on the surface of the degassed aluminum liquid, carrying out slag-forming, standing for 20min, controlling the temperature of the aluminum liquid to 690 ℃, setting a glass fiber cloth flashboard at an aluminum liquid outlet of the heat preservation furnace for primary filtration, carrying out secondary filtration through a foamed ceramic filter disc with the thickness of 20mm and the aperture of 80 meshes, and finally carrying out tertiary filtration through an alumina gravel deep bed filter with the particle size of 2mm. The aluminum liquid with the hydrogen content of 0.01ml/100g Al and the slag content of 0.004mm 2/kg is prepared through three-stage filtration, and enters a preheated ingot casting die through a distributor, so that the prepared heat-treatment-free die casting aluminum alloy has excellent toughness and high hydrogen embrittlement resistance.
Example 3
The heat treatment-free high-strength and high-toughness die-casting aluminum alloy material comprises, by weight, 9% of Si, 0.2% of Mg, 0.5% of Mn, 0.15% of Cr, 0.1% of Sr, 0.09% of Zr, 0.05% of Ni, 0.1% of Fe, the total amount of other impurities and 0.3% of Al, and the balance of Al. The die-casting aluminum alloy phase of the embodiment comprises a matrix alpha-Al solid solution, si and ZrNi phases, as shown in figure 2, wherein the ZrNi alloy is prepared by repeatedly smelting for three times by a magnetic suspension smelting furnace and then ball milling and sieving, as shown in figure 1, and the particle size of the ZrNi alloy is 0.75 mu m. The ZrNi phase of the orthorhombic system is uniformly distributed in the grain boundary region of the die-casting aluminum alloy, has a hydrogen absorption equilibrium pressure of 5 multiplied by 10 -4 Pa and a hydrogen absorption capacity exceeding 200ml/g at 20 ℃ and does not melt when heated to 1010 ℃, and due to the fact that the content of the ZrNi phase is too low, a corresponding diffraction peak does not appear on an XRD map, but ZrNi phase particles with the grain size of about 0.75 mu m can be clearly observed on a scanning electron microscope image amplified by 3000 times in FIG. 5, and are uniformly distributed in the eutectic Si phase region of the die-casting aluminum alloy, the eutectic Si grains are obviously thinned under the action of a ZrNi alloy grain refiner, the grain size of granular eutectic Si grains is about 1 mu m, and meanwhile, part of eutectic Si grains exist in a short bar shape. The die-cast aluminum alloy of the embodiment has the die-cast tensile strength of 310MPa, the yield strength of 174MPa and the elongation of 11.5 percent.
A preparation method of a heat-treatment-free high-strength and high-toughness die-casting aluminum alloy material comprises the following steps:
1) Adding the regenerated aluminum ingot, silicon, aluminum chromium and aluminum manganese intermediate alloy into a smelting furnace, heating to 760 ℃, and uniformly stirring for 25min after the aluminum ingot is completely melted;
2) Heating the aluminum liquid to 720 ℃, uniformly spraying a refining agent into the aluminum liquid by using nitrogen load, keeping the aluminum liquid for 13min, standing the aluminum liquid for 25min after the spraying is finished, and deslagging after fully reacting and floating refining agent particles, wherein the spraying speed of the refining agent is 0.8kg/min, the nitrogen pressure is 0.6MPa, and the refining agent consists of the following components in percentage by mass. The refining agent is prepared by mixing the components according to the corresponding percentages, loading the mixture into a ball mill with the rotating speed of 400r/min, grinding the mixture into powder, and sieving the powder with a 50-mesh sieve, wherein the percentages of the components constituting the refining agent are 5.5 percent by weight of MgCl 2：55wt%,KCl：30wt%,CaF2：5.5wt%,BaCl2 and 4.5 percent by weight of ZrNi alloy;
3) After the alloy component is detected to be qualified, transferring the aluminum liquid to a heat preservation furnace, starting a rotary degassing machine in the middle of the heat preservation furnace, setting the rotary speed of a rotor to 425r/min, setting the argon pressure to 0.3MPa, setting the argon flow to 13L/min, and degassing for 12min, uniformly scattering a layer of slag-forming agent consisting of MgCl 2 and KCl with the weight ratio of 1.25 on the surface of the degassed aluminum liquid, carrying out slag-forming, standing for 15min, controlling the temperature of the aluminum liquid to 675 ℃, setting a glass fiber cloth flashboard at an aluminum liquid outlet of the heat preservation furnace for primary filtration, carrying out secondary filtration through a foamed ceramic filter disc with the thickness of 14mm and the aperture of 60 meshes, and finally carrying out tertiary filtration through an alumina gravel deep bed filter with the particle size of 6 mm. The aluminum liquid with the hydrogen content of 0.02ml/100g Al and the slag content of 0.006mm 2/kg is prepared through three-stage filtration, and enters a preheated ingot casting die through a distributor, so that the prepared heat-treatment-free integrated die-casting aluminum alloy ingot has excellent toughness and high hydrogen embrittlement resistance.
Comparative example
The regenerated die-casting aluminum alloy comprises, by weight, 6.0% of Si, 0.45% of Mg, 0.85% of Mn, 0.2% of Cr, 0.05% of Sr, 0.15% of Fe, the total amount of other impurities and 0.4% of Al, and the balance of Al. The die-casting aluminum alloy phase of the embodiment comprises a matrix alpha-Al solid solution and a Mg 2 Si phase, wherein the die-casting aluminum alloy of the comparative example has die-casting tensile strength of 275MPa, yield strength of 132MPa and elongation of 5.74%.
The preparation method of the regenerated die-cast aluminum alloy comprises the following steps:
1) Adding the regenerated aluminum ingot, silicon, aluminum chromium and aluminum manganese intermediate alloy into a smelting furnace, heating to 780 ℃, and uniformly stirring for 30min after the aluminum ingot is completely melted;
2) Heating aluminum liquid to 730 ℃, uniformly spraying a refining agent into the aluminum liquid by using nitrogen load, keeping the aluminum liquid for 15min, standing the aluminum liquid for 30min after the spraying is finished, and allowing refining agent particles to fully react and float upwards to remove slag, wherein the spraying speed of the refining agent is 1.0kg/min, the nitrogen pressure is 0.8MPa, the refining agent is prepared by mixing the components according to the corresponding percentage, loading the components into a ball mill with the rotating speed of 600r/min, mixing the components into powder, and sieving the powder through a 60-mesh sieve, wherein the percentage of the components forming the refining agent is MgCl 2：40wt%,KCl：50wt%,CaF2：5wt%,BaCl2 wt%;
3) After the alloy component is detected to be qualified, transferring the aluminum liquid to a heat preservation furnace, starting a rotary degassing machine in the middle of the heat preservation furnace, setting the rotary speed of a rotor to 450r/min, setting the argon pressure to 0.35MPa, setting the argon flow to 15L/min, and degassing for 15min, uniformly scattering a layer of slag-forming agent consisting of MgCl 2 and KCl with the weight ratio of 1.5 on the surface of the degassed aluminum liquid, carrying out slag-forming, standing for 20min, controlling the temperature of the aluminum liquid to 690 ℃, setting a glass fiber cloth flashboard at an aluminum liquid outlet of the heat preservation furnace for primary filtration, carrying out secondary filtration through a foamed ceramic filter disc with the thickness of 20mm and the aperture of 80 meshes, and finally carrying out tertiary filtration through an alumina gravel deep bed filter with the particle size of 2 mm. Three-stage filtering to obtain aluminum liquid with hydrogen content of 0.18ml/100g Al and slag content of 0.012mm 2/kg, and feeding the aluminum liquid into preheated ingot mould by means of distributor to obtain die-casting aluminum alloy ingot.
Compared with the examples, the comparative example refining agent is not added with ZrNi alloy, so that the diffusion speed of hydrogen in the aluminum liquid is reduced, high-efficiency dehydrogenation and degassing cannot be realized even through the bubble floating and the refining treatment of the traditional refining agent, and the high hydrogen content in the aluminum liquid leads to the remarkable increase of the slag content and the remarkable reduction of the toughness of the prepared die-casting aluminum alloy. The hydrogen content and the slag content in the aluminum liquid are directly related, and the measures of reducing hydrogen and removing slag are integrated and inseparable, as shown by the comparison of the performance indexes in the table 1.

Claims (5)

1.一种免热处理高强韧压铸铝合金材料，其特征在于，所述压铸铝合金中各组分的重量百分比为Si：6.0～12%、Mg：0.1～0.45%、Mn：0.3～0.85%、Cr：0.05～0.2%、Sr：0.05～0.15%、Zr：0.05～0.12%、Ni：0.03～0.07%、Fe<0.2%，其他杂质总量和≤0.5%，余量为Al；1. A heat-treatment-free high-strength and tough die-casting aluminum alloy material, characterized in that the weight percentage of each component in the die-casting aluminum alloy is Si: 6.0-12%, Mg: 0.1-0.45%, Mn: 0.3-0.85%, Cr: 0.05-0.2%, Sr: 0.05-0.15%, Zr: 0.05-0.12%, Ni: 0.03-0.07%, Fe<0.2%, the total amount of other impurities is ≤0.5%, and the balance is Al; 所述压铸铝合金物相包括基体α-Al固溶体、Si及ZrNi相；ZrNi相属正交晶系，均布于压铸铝合金晶界附近区域，在20℃具有5×10-4Pa的吸氢平衡压及超过200ml/g的氢吸附容量，且加热至1010℃不发生熔化；所述压铸铝合金的压铸态抗拉强度为280～350MPa、屈服强度为150～198MPa、延伸率为9～16％。The die-cast aluminum alloy phases include matrix α-Al solid solution, Si and ZrNi phases; the ZrNi phase belongs to the orthorhombic crystal system, is evenly distributed in the area near the grain boundary of the die-cast aluminum alloy, has a hydrogen absorption equilibrium pressure of 5× 10-4 Pa and a hydrogen adsorption capacity of more than 200ml/g at 20°C, and does not melt when heated to 1010°C; the die-cast aluminum alloy has a die-cast tensile strength of 280-350MPa, a yield strength of 150-198MPa, and an elongation of 9-16%. 2.一种如权利要求1所述的免热处理高强韧压铸铝合金材料的制备方法，其特征在于包括以下步骤：2. A method for preparing a heat-treatment-free high-strength and toughness die-casting aluminum alloy material as claimed in claim 1, characterized in that it comprises the following steps: 1)将再生铝锭、硅、铝铬和铝锰中间合金投入熔炼炉，升温至750～780℃，铝锭完全熔解后均匀搅拌15～30min；随后待铝液降温至680～710℃加入镁锭和Al-Sr中间合金，将其压入熔液底部完全熔解并搅拌均匀；1) Put the recycled aluminum ingot, silicon, aluminum-chromium and aluminum-manganese master alloy into the melting furnace, raise the temperature to 750-780°C, stir evenly for 15-30 minutes after the aluminum ingot is completely melted; then wait until the aluminum liquid is cooled to 680-710°C, add the magnesium ingot and Al-Sr master alloy, press them into the bottom of the melt to completely melt and stir evenly; 2)将铝液升温至710～730℃，将精炼剂用氮气负载均匀喷吹到铝液中并保持10～15min，喷吹完毕后铝液静置20～30min，使精炼剂颗粒充分反应上浮后除渣；所述精炼剂的喷吹速度为0.6～1.0kg/min，氮气压力0.35～0.8MPa；所述的精炼剂由以下质量分数的各组分组成KCl: 30～50wt%；MgCl2:30～55wt%；CaF2:5～10 wt%；BaCl2:5～10 wt%；ZrNi合金:3～6 wt%；2) The aluminum liquid is heated to 710-730°C, and the refining agent is evenly sprayed into the aluminum liquid with nitrogen load and maintained for 10-15 minutes. After the spraying is completed, the aluminum liquid is allowed to stand for 20-30 minutes to allow the refining agent particles to fully react and float up before slag removal; the refining agent has a spraying speed of 0.6-1.0 kg/min and a nitrogen pressure of 0.35-0.8 MPa; the refining agent is composed of the following components in mass fractions: KCl: 30-50wt%; MgCl 2 :30-55wt%; CaF 2 :5-10 wt%; BaCl 2 :5-10 wt%; ZrNi alloy: 3-6 wt%; 3) 合金成分检测合格后，将铝液转至保温炉，开启保温炉中部的旋转除气机，转子旋转速度设置为400～450r/min，氩气压力0.2～0.35MPa，氩气流量10～15L/min，除气时间10～15min；向除气后的铝液表面均匀撒上一层打渣剂进行打渣，静置10～20min后，控制铝液温度660～690℃，经过三级过滤，制得氢含量≤0.04ml/100g Al、渣含量≤0.008mm2/kg的铝液；铝液通过分配器进入经预热的铸锭模具，制得免热处理压铸铝合金锭。3) After the alloy composition test is qualified, the aluminum liquid is transferred to the holding furnace, and the rotary degasser in the middle of the holding furnace is turned on. The rotor rotation speed is set to 400-450r/min, the argon pressure is 0.2-0.35MPa, the argon flow rate is 10-15L/min, and the degassing time is 10-15min; a layer of slag remover is evenly sprinkled on the surface of the degassed aluminum liquid for slag removal. After standing for 10-20min, the aluminum liquid temperature is controlled at 660-690℃. After three-stage filtration, the aluminum liquid with a hydrogen content of ≤0.04ml/100g Al and a slag content of ≤0.008mm2 /kg is obtained; the aluminum liquid enters the preheated ingot mold through a distributor to obtain a heat-free die-casting aluminum alloy ingot. 3. 根据权利要求2所述的免热处理高强韧压铸铝合金材料的制备方法，其特征在于，步骤3)中的打渣剂为重量比1: 1～1.5的MgCl2和KCl；所述三级过滤为在保温炉铝液出口处设置玻璃丝布闸板进行一级过滤，随后流经厚度8~20mm、20~80目孔径的泡沫陶瓷过滤片进行二级过滤，最后流经颗粒尺寸2~10mm的氧化铝砂砾深床过滤器进行第三级过滤。3. The method for preparing a heat-treatment-free high-strength and tough die-cast aluminum alloy material according to claim 2, characterized in that the slag remover in step 3) is MgCl2 and KCl in a weight ratio of 1:1-1.5; the three-stage filtration is to set a glass cloth gate at the outlet of the aluminum liquid in the insulation furnace for primary filtration, then flow through a foam ceramic filter with a thickness of 8-20 mm and an aperture of 20-80 meshes for secondary filtration, and finally flow through an alumina gravel deep bed filter with a particle size of 2-10 mm for third-stage filtration. 4.根据权利要求2所述的免热处理高强韧压铸铝合金材料的制备方法，其特征在于，所述精炼剂是将各组分按相应百分比配料并装入转速100~600r/min的球磨机混磨成粉后过30~60目筛制得。4. The method for preparing a heat-treatment-free high-strength and tough die-cast aluminum alloy material according to claim 2 is characterized in that the refining agent is prepared by mixing the components according to corresponding percentages and loading them into a ball mill with a rotation speed of 100-600 r/min, mixing and grinding them into powder, and then passing through a 30-60 mesh sieve. 5.根据权利要求2所述的免热处理高强韧压铸铝合金材料的制备方法，其特征在于，所述ZrNi合金为经磁悬浮熔炼炉反复熔炼三次后再经球磨过筛制得的粒径为0.5~1μm的粉末颗粒。5. The method for preparing a heat treatment-free high-strength and tough die-cast aluminum alloy material according to claim 2 is characterized in that the ZrNi alloy is a powder particle with a particle size of 0.5-1 μm obtained by repeatedly smelting three times in a magnetic suspension smelting furnace and then ball milling and sieving.
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