CN109504870B - In-situ nano reinforced aluminum alloy for lightweight automobile anti-collision beam and preparation method thereof - Google Patents
In-situ nano reinforced aluminum alloy for lightweight automobile anti-collision beam and preparation method thereof Download PDFInfo
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- CN109504870B CN109504870B CN201811392237.3A CN201811392237A CN109504870B CN 109504870 B CN109504870 B CN 109504870B CN 201811392237 A CN201811392237 A CN 201811392237A CN 109504870 B CN109504870 B CN 109504870B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
- C22C1/1052—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
Abstract
The invention relates to an aluminum-based composite material, in particular to an in-situ nano reinforced aluminum alloy for a lightweight automobile anti-collision beam and a preparation method thereof. By using the in-situ synthesis technology, the composite material of the uniformly distributed nano enhanced phase cluster and the fine crystal structure is obtained by taking the mixed powder of zirconium carbonate, potassium fluoborate and potassium fluotitanate as reactants, applying a acousto-magnetic coupling field in the reaction process and applying the acousto-magnetic coupling field in the solidification stage. And then, by means of an optimized hot extrusion technology and an optimized quenching technology, the defects of the material are reduced, the dynamic recrystallization of the subgrain the material is promoted, fine recrystallized grains are obtained, the strength, the plasticity, the impact resistance and the corrosion resistance of the material are improved, the collision energy absorption effect is improved to the maximum extent, and the qualified aluminum-based composite material profile for the automobile anti-collision beam is obtained.
Description
Technical Field
The invention relates to an aluminum-based composite material, in particular to an in-situ nano reinforced aluminum alloy for a lightweight automobile anti-collision beam and a preparation method thereof.
Background
Energy conservation and emission reduction, environmental protection and traffic safety are three major topics in the current automobile industry, and the light weight of automobiles is one of measures capable of achieving the goals. Research shows that the oil consumption per hundred kilometers can be reduced by 0.3 liter and the carbon dioxide discharged per kilometer can be reduced by 7.5-12.5 g when the automobile mass is reduced by 100 kg. Therefore, the light weight of the automobile is a research hotspot at present, one important way is to adopt a light-weight high-strength material, and the aluminum alloy is a light-weight material with excellent performance and is widely used for automobile structural parts nowadays. The automobile anti-collision beam is one of automobile body structural parts and one of the most important safety parts of an automobile, and mainly has the functions of absorbing and relieving external impact force in vehicle collision and protecting the safety of an automobile body and passengers in a collision accident of the automobile. At present, aluminum alloy extrusion materials for the automobile anti-collision beam are mainly 6082, 6061 and 6005A extrusion materials.
With the continuous improvement of global regulations on the aspect of vehicle quantity safety and the continuous improvement of people's understanding on the safety of automobile driving, higher requirements are put forward on the performance of the aluminum alloy material for the automobile anti-collision beam. Chinese patent 201410213392.X discloses an Al-Zn-Mg-Cu aluminum alloy for an automobile anti-collision beam and a manufacturing method of the Al-Zn-Mg-Cu aluminum alloy, and a new alloy formula is designed to improve the strength and the toughness of an aluminum alloy extruded material. Chinese patent 201710682641.3 discloses a high-performance low-cost aluminum alloy for an automobile anti-collision beam and a preparation process thereof, wherein the designed Al-Si-Mg-Cu alloy is subjected to 440-480 ℃ hot extrusion, and then local linear water mist treatment and shaping are performed at an outlet to obtain an extrusion material for the anti-collision beam.
According to the prior art and the patent, the comprehensive performance of the anti-collision collar is improved mainly by changing the components of the aluminum alloy and the extrusion process. However, the performance of the material is still improved by the traditional alloy precipitation strengthening through designing the components of the aluminum alloy, and the inversion relation of strong plasticity is difficult to get rid of; the temperature of the extrusion process is increased, and the process is changed to make the process complicated, so that the method is not suitable for industrial batch continuous production. Therefore, it is urgently needed to develop a novel lightweight high-strength and high-toughness anti-collision beam material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention develops an in-situ nano reinforced aluminum alloy for a lightweight automobile anti-collision beam by adopting an in-situ direct melt reaction technology and a preparation method thereof, and combines an acoustic-magnetic coupling field to regulate and control an in-situ reaction process (melt), a solidification process (semi-solid state) and a subsequent extrusion processing and forming technology, thereby obviously improving the strong plasticity and the impact resistance of the anti-collision beam.
According to the in-situ nano aluminum alloy for the light automobile anti-collision beam and the preparation method thereof, the mixed powder of zirconium carbonate, potassium fluoborate and potassium fluotitanate is used as a reactant through an in-situ synthesis technology, and zirconium carbonate is decomposed into zirconium oxide and can react with Al and Mg elements in an aluminum alloy matrix to generate magnesium aluminate spinel which is adsorbed at the interface between particles and the matrix, so that the growth and agglomeration of the particles can be prevented, the bonding strength between the particles and the interface is increased, and the nano particles are obtained. The acoustic magnetic coupling field is applied in the reaction process, so that the heat released by the decomposition of the zirconium carbonate can be more uniformly distributed in the melt, the yield of the particles is improved, the acoustic magnetic coupling field can change the relation of the interfacial energy between the particles and aluminum, the contact angle between the particles and the interface is smaller than 90 degrees, the particles are captured by the interface, and the nano particle clusters are uniformly distributed in the matrix. And applying an acoustic-magnetic coupling field in a solidification stage, wherein because the melt viscosity is high, applying a coupling field with higher strength can effectively break coarse precipitated phases, improve the nucleation rate in the solidification process of the melt, and finally obtain the composite material of uniformly distributed nano enhanced phase clusters and fine crystal structures. And then, by means of an optimized hot extrusion technology and an optimized quenching technology, the defects of the material are reduced, the dynamic recrystallization of the subgrain the material is promoted, fine recrystallized grains are obtained, the strength, the plasticity, the impact resistance and the corrosion resistance of the material are improved, the collision energy absorption effect is improved to the maximum extent, and the qualified aluminum-based composite material profile for the automobile anti-collision beam is obtained.
An in-situ nano reinforced aluminum alloy for a lightweight automobile anti-collision beam comprises the following aluminum alloy matrix components in percentage by mass: 1 to 1.2 portions of Si, 0.8 to 1 portion of Mg, 0.2 to 0.3 portion of Cu, 0.4 to 0.8 portion of Mn, 0.03 to 0.05 portion of Cr, 0.01 to 0.02 portion of Ti and the balance of Al.
The preparation method comprises the following steps:
putting an aluminum alloy matrix into a high-purity graphite crucible, melting at 750-780 ℃, preserving heat for 5-10min, then heating the melt to 830-870 ℃, pressing in dried reaction powder wrapped by high-purity aluminum foil into the melt, simultaneously applying a sound-magnetic coupling field for the first time in the reaction process, and carrying out refining and slagging-off treatment for the first time after reacting for 20-40 min; then the material is put into a resistance furnace to reduce the temperature to 600-660 ℃, the temperature is kept, the acousto-magnetic coupling field is applied for 10-20min for the second time, then the second time of refining and slag removing treatment is carried out, and the material is poured into a copper mold to obtain the composite material cast rod. And then carrying out homogenization treatment, and carrying out hot extrusion deformation processing and subsequent heat treatment on the treated aluminum alloy cast rod to finally obtain the in-situ nano reinforced aluminum alloy extrusion piece for the anti-collision beam.
The reaction powder wrapped by the high-purity aluminum foil is zirconium carbonate (Zr (CO)3)2) Potassium fluoroborate (KBF)4) And potassium fluotitanate (K)2TiF6) Reacting to generate in-situ nano ZrB2，TiB2And Al2O3Particles of potassium fluoroborate (KBF) having a particle size of 50-100nm4) Zirconium carbonate (Zr (CO)3)2) And potassium fluotitanate (K)2TiF6) The weight ratio of 10-12:3-5:5-6, and the adding amount of the reaction powder is 30-50% of the melt. ZrB with volume fraction of 1-3% can be obtained2,1-3％TiB2And 1-3% of Al2O3The nanoparticles of (1).
The first acousto-magnetic coupling field applied in the reaction process is a low-frequency magnetic field and a high-energy ultrasonic field. A low-frequency magnetic field with the frequency of 5-10Hz and the magnetic current of 50-100A; the power of the high-energy ultrasonic field is 800-; the application of the acoustic-magnetic coupling field in the high-temperature reaction process can promote the reaction, improve the yield of the particles, improve the wettability of the particles and the matrix, uniformly distribute the particles in the matrix, ensure the uniform concentration of each area in the melt, inhibit the growth of the particles and refine the particles.
The acoustic magnetic coupling field applied for the second time is a high-frequency pulse magnetic field and a high-energy ultrasonic field. High-frequency pulse with frequency of 15-22Hz and magnetic current of 200-250A; the power of the high-energy ultrasonic field is 1000-1500W, and the frequency is 20-25 kHz; because the acousto-magnetic coupling field is applied under the semi-solid state, because the melt viscosity is higher, the strong collision and scouring force generated by the magnetic field and the ultrasound can effectively break the coarse precipitated phase and the particle cluster, the morphology of the precipitated phase and the distribution of the particles are further improved, and meanwhile, the particles are mutually rubbed and collided by the intense turbulence generated on the magnetic field and the ultrasound, on one hand, the edges and corners of the particles are ground to be spheroidized, on the other hand, the larger collision force and shearing force between the particles can enable the defective positions between the particles to generate cracks, so that the particles are crushed, and finer particles are obtained. The application of the acousto-magnetic coupling field during the solidification process can further improve the microstructure of the material.
The homogenization treatment refers to heating the casting rod to 520-570 ℃, preserving the temperature for 20-24h, and then cooling the casting rod to room temperature in air.
The hot extrusion deformation processing technology comprises the following steps: processing the homogenized cast ingot into a bar material for extrusion according to the required size, feeding the bar material into a resistance furnace, heating the bar material to 450-DEG C and preserving the heat for 0.5-1h, then heating an extrusion die to 400-DEG C and preserving the heat for 10-30min, and carrying out hot extrusion at the extrusion speed of 2-5 mm/s.
The heat treatment is T6 heat treatment, and solid solution: the temperature is 510-540 ℃, and the heat preservation time is 2-5 h. The quenching adopts on-line water mist quenching and water penetration quenching, the temperature of the extruded material after the water mist quenching is 350-400 ℃, and the temperature after the water penetration quenching is 15-25 ℃. Artificial aging: the temperature is 170 ℃ and 190 ℃, and the heat preservation time is 4-8 h.
The invention has the beneficial effects that:
the invention provides an in-situ nano reinforced aluminum alloy for a lightweight automobile anti-collision beam and a preparation method thereof, wherein the reaction process and the solidification process are regulated and controlled by an in-situ direct melt reaction technology and an acousto-magnetic coupling field technology to obtain in-situ nano (ZrB)2+TiB2+Al2O3) The in-situ reinforced aluminum-based composite material ingot with uniformly distributed particles (50-100nm) and fine grains. The in-situ nano reinforced composite material prepared by the invention has higher strong plasticity and impact resistance through hot extrusion forming and T6 heat treatment, and the nano particles prepared by the invention can effectively improve the resistance of the materialThe corrosion property can achieve the effect of collision energy absorption, and the application of the anti-collision beam on the automobile can improve the safety of the automobile body and passengers in a collision accident.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings which are needed to be used will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of the preparation process of the present invention
FIG. 2 is a structural diagram of an in-situ nano reinforced aluminum matrix composite ingot for an anti-collision beam according to the present invention
FIG. 3 is a structural view of a hot extrusion tissue of the in-situ nano reinforced aluminum-based composite material for an anti-collision beam according to the present invention
FIG. 4 is a schematic diagram of the multi-component nano-reinforcing particles of the present invention
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments which can be obtained by a person skilled in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
Example 1:
(1) aluminum alloy casting: putting 1Kg of aluminum alloy into a high-purity graphite crucible, melting at 780 ℃ and preserving heat for 10min, then heating the melt to 870 ℃, adding the dried reaction powder (the granularity is less than 100 mu m, the mass of zirconium carbonate is 38g, the mass of potassium fluoborate is 69g, and the mass of potassium fluotitanate is 75g) coated by the high-purity aluminum foil into the melt in batches, simultaneously starting a combination device of a low-frequency magnetic field and a high-energy ultrasonic field (the magnetic field is 5Hz, the magnetic current is 50A, the ultrasonic power is 800W, and the frequency is 15kHz), reacting for 20min, and reactingRemoving scum on the surface of the melt after finishing, and spraying hexachloroethane into the solution for refining; then the mixture is put into a resistance furnace to reduce the temperature to 660 ℃ and keep the temperature, a combined device of a high-frequency pulse magnetic field and a high-energy ultrasonic field (the magnetic field: the frequency is 20Hz, the magnetic current is 250A; the ultrasonic wave: the power is 1500W, the frequency is 25kHz) is started for 15min, then secondary refining and slag skimming treatment are carried out (after the refining, 0.5 percent of slag striking agent is added, the slag is skived after stirring), and the mixture is poured into a copper mold to prepare (1 percent ZrB by volume)2+1vol％TiB2+1vol％Al2O3) An aluminum matrix composite cast rod.
(2) Homogenizing: and (4) performing head cutting, tail cutting and face milling on the cast rod obtained in the step (1) to obtain the cast rod with the length of 80 mm. Then the cast rod is put into a box type resistance furnace to be heated to 550 ℃ and insulated for 24 hours.
(3) Hot extrusion treatment: and processing the homogenized cast ingot into an extrusion ingot blank according to the required size, feeding the extrusion ingot blank into a resistance furnace, heating to 450 ℃, preserving heat for 0.5h, then heating an extrusion die to 450 ℃, preserving heat for 15min, and carrying out hot extrusion at the extrusion speed of 2mm/s to obtain an extrusion bar with the diameter of 15 mm.
(4) T6 heat treatment: and (4) carrying out heat treatment on the extruded bar obtained in the step (3). Solid solution: the temperature is 540 ℃, and the holding time is 2 h. The quenching adopts on-line water mist quenching and water penetration quenching, the temperature of the extruded material after the water mist quenching is 350 ℃, and the temperature after the water penetration quenching is 25 ℃. Artificial aging: the temperature is 170 ℃, and the holding time is 4 h. Finally obtaining the qualified in-situ particle reinforced aluminum matrix composite extrusion piece for the anti-collision beam.
Example 2:
the preparation method is basically the same as that in example 1, except that: the reaction substances were varied in mass, 77g zirconium carbonate, 138g potassium fluoroborate and 142g potassium fluorotitanate (2 vol% ZrB)2+2vol％TiB2+2vol％Al2O3) An aluminum matrix composite cast rod.
Example 3:
the preparation method is basically the same as that in example 1, except that: the reaction mass was varied, and the reaction mass was 115g of zirconium carbonate, 206g of potassium fluoroborate and 210g of potassium fluorotitanate (3 vol% ZrB)2+3vol％TiB2+3vol％Al2O3) An aluminum matrix composite cast rod.
Each example is a composite of in-situ nanoparticles with different volume fractions, and the specific mechanical properties are shown in the following table:
table 1 shows the results of testing the properties of the extruded materials of the nano-reinforced composite materials
Tests prove that the automobile anti-collision beam has the following outstanding advantages and effects compared with the traditional automobile anti-collision beam: the tensile strength, the yield strength and the elongation are greatly improved, and the deformation amount is 60-85% in a quasi-static crushing test, so that the sample has no obvious cracks. However, the comparison of examples 2 and 3 shows that the volume fraction of the particles is not too high, and the volume fraction of the particles exceeds 6 vol%, and the content of the particles is too high, so that the particles are re-agglomerated, the distribution and the matrix structure of the particles are deteriorated, and the performance of the material is reduced. (2 vol% ZrB) prepared by the invention2+2vol％TiB2+2vol％Al2O3) The aluminum-based composite material has higher performance, can meet the requirement of mechanical performance of automobile anti-collision beam materials, and achieves the effect of collision energy absorption.
The invention provides an in-situ nano reinforced aluminum alloy for a lightweight automobile anti-collision beam and a preparation method thereof, and combines the precise control of the technological parameters of the preparation method and the selection of the particle volume fraction to obtain a light high-strength and high-toughness automobile anti-collision beam material, thereby providing a reference basis for preparing a high-performance light automobile anti-collision beam material in the future and having wide market prospect and economic value.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A preparation method of in-situ nano reinforced aluminum alloy for a lightweight automobile anti-collision beam is characterized in that an aluminum alloy matrix is placed in a high-purity graphite crucible to be melted at 750-780 ℃ and is subjected to heat preservation for 5-10min, then the temperature of the melt is raised to 830-870 ℃, dried reaction powder wrapped by high-purity aluminum foil is pressed into the melt, meanwhile, an acousto-magnetic coupling field is applied for the first time in the reaction process, and the first refining and slagging-off treatment are carried out after the reaction is carried out for 20-40 min; then placing the aluminum alloy into a resistance furnace, reducing the temperature to 600-; the reaction powder wrapped by the high-purity aluminum foil is zirconium carbonate (Zr (CO)3)2) Potassium fluoroborate (KBF)4) And potassium fluotitanate (K)2TiF6) Reacting to generate in-situ nano ZrB2，TiB2And Al2O3Particles of potassium fluoroborate (KBF) having a particle size of 50-100nm4) Zirconium carbonate (Zr (CO)3)2) And potassium fluotitanate (K)2TiF6) The weight ratio of the reaction powder is 10-12:3-5:5-6, the addition amount of the reaction powder is 30-50% of the melt, and ZrB with the volume fraction of 1-3% can be obtained2,1-3％TiB2And 1-3% of Al2O3The nanoparticles of (1); the first acousto-magnetic coupling field applied in the reaction process is a low-frequency magnetic field and a high-energy ultrasonic field; a low-frequency magnetic field with the frequency of 5-10Hz and the magnetic current of 50-100A; the power of the high-energy ultrasonic field is 800-; the acoustic magnetic coupling field applied for the second time is a high-frequency pulse magnetic field and a high-energy ultrasonic field; high-frequency pulse with frequency of 15-22Hz and magnetic current of 200-250A; the power of the high-energy ultrasonic field is 1000-1500W, and the frequency is 20-25 kHz.
2. The method for preparing in-situ nano reinforced aluminum alloy for the lightweight automobile anti-collision beam as recited in claim 1, wherein the homogenization treatment is heating the cast rod to 520-570 ℃ and keeping the temperature for 20-24h, and then air-cooling to room temperature.
3. The preparation method of the in-situ nano reinforced aluminum alloy for the lightweight automobile anti-collision beam as recited in claim 1, wherein the hot extrusion deformation processing technology comprises the following steps: processing the homogenized cast ingot into a bar material for extrusion according to the required size, feeding the bar material into a resistance furnace, heating the bar material to 450-DEG C and preserving the heat for 0.5-1h, then heating an extrusion die to 400-DEG C and preserving the heat for 10-30min, and carrying out hot extrusion at the extrusion speed of 2-5 mm/s.
4. The method for preparing the in-situ nano reinforced aluminum alloy for the light weight automobile anti-collision beam as recited in claim 1, wherein the heat treatment is T6 heat treatment, and the steps of dissolving: the temperature is 510-; the quenching adopts on-line water mist quenching and water penetration quenching, the temperature of the extruded material after the water mist quenching is 350-400 ℃, and the temperature after the water penetration quenching is 15-25 ℃; artificial aging: the temperature is 170 ℃ and 190 ℃, and the heat preservation time is 4-8 h.
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| CN110273087A (en) * | 2019-06-25 | 2019-09-24 | 昆明理工大学 | Regulate and control the method for hypereutectic aluminum-silicon alloy casting overall performance |
| CN111206166B (en) | 2019-12-10 | 2021-09-10 | 江苏大学 | Preparation method of in-situ ternary nanoparticle reinforced aluminum matrix composite |
| CN114351000B (en) * | 2021-12-20 | 2023-04-18 | 江苏大学 | Preparation method of in-situ nano-particle and rare earth coupling reinforced aluminum-based composite material |
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