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WO2019090963A1 - 一种车身用原位纳米强化铝合金挤压材及制备方法 - Google Patents

一种车身用原位纳米强化铝合金挤压材及制备方法 Download PDF

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WO2019090963A1
WO2019090963A1 PCT/CN2018/072036 CN2018072036W WO2019090963A1 WO 2019090963 A1 WO2019090963 A1 WO 2019090963A1 CN 2018072036 W CN2018072036 W CN 2018072036W WO 2019090963 A1 WO2019090963 A1 WO 2019090963A1
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aluminum alloy
temperature
vehicle body
preparing
situ
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PCT/CN2018/072036
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English (en)
French (fr)
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赵玉涛
陶然
陈刚
怯喜周
浦俭英
李其荣
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江苏大学
亚太轻合金(南通)科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/01—Extruding metal; Impact extrusion starting from material of particular form or shape, e.g. mechanically pre-treated
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/001—Extruding metal; Impact extrusion to improve the material properties, e.g. lateral extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/02—Making uncoated products
    • B21C23/04—Making uncoated products by direct extrusion
    • B21C23/08—Making wire, bars, tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C29/00—Cooling or heating work or parts of the extrusion press; Gas treatment of work
    • B21C29/003—Cooling or heating of work
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C31/00—Control devices, e.g. for regulating the pressing speed or temperature of metal; Measuring devices, e.g. for temperature of metal, combined with or specially adapted for use in connection with extrusion presses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/003—Aluminium alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/049—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds for direct chill casting, e.g. electromagnetic casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/055—Cooling the moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/11—Treating the molten metal
    • B22D11/114—Treating the molten metal by using agitating or vibrating means
    • 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
    • C22C1/10—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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • 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
    • C22C32/001—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 only oxides
    • C22C32/0015—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 only oxides with only single oxides as main non-metallic constituents
    • C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • 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
    • C22C32/0047—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 carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0073—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 carbides, nitrides, borides or silicides as the main non-metallic constituents only borides
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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
    • 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
    • C22F1/043—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 of alloys with silicon as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to an aluminum-based composite material, in particular to an in-situ nano-reinforced aluminum alloy extruded material for a vehicle body and a preparation method thereof.
  • Chinese Patent No. 20100199928.9 discloses a processing method for improving the stamping formability of a 6111 aluminum alloy automobile sheet.
  • the 6111 alloy ingot produced by semi-continuous casting is heat treated at 220 ° C - 425 ° C for 8 h - 15 h, and then homogenized with furnace heating. Then, hot rolling is performed to improve press formability and paint strength.
  • Chinese patent 201410800786.5 discloses a 6016 aluminum alloy sheet for automobile body and a production method thereof, and improves the yield strength and the stamping yield of the aluminum alloy sheet by the steps of smelting and casting, milling, hot rolling, cold rolling and heat treatment.
  • 200710190078.4 discloses a method for improving the bake hardening property of an aluminum alloy sheet with a low Cu content. After the solution is solidified and water quenched, the 6022 sheet is preheated in 1 h, and the treatment temperature is 60 to 200 ° C, and the treatment time is 2min ⁇ 30min, the plate bake hardenability is significantly improved.
  • the existing aluminum body technology and review literature mainly improve the overall performance of the vehicle body material, especially the forming performance, through the regulation of the heat treatment process.
  • nano-reinforcing body is in-situ nucleated and grown thermodynamically stable phase from the aluminum matrix by chemical reaction, the surface of the reinforcing body is non-polluting, and the compatibility with the matrix is avoided.
  • the problem is that the interface has high bonding strength, so it has high specific strength, specific modulus, excellent fatigue resistance, good heat resistance, corrosion resistance, etc., and can be directly synthesized by a melt reaction method, and the cost is large.
  • the advantages of reduced amplitude have become a breakthrough new material in the field of nanomaterials and aluminum matrix composites.
  • the object of the present invention is to develop a novel method for preparing an in-situ nano-reinforced aluminum alloy extruded material for a vehicle body according to the deficiencies of the prior art, and adopting a high-frequency pulse magnetic field and a high-energy ultrasonic field to regulate the preparation process thereof, and combined with optimization.
  • the semi-continuous casting technology and the extrusion forming forming technology can improve the alloy structure and realize the distribution of the nanoparticles in the crystal and the grain boundary, and significantly improve the strong plasticity, impact resistance and fatigue resistance of the body material.
  • the invention can effectively solve the shortcomings of the current 6-series aluminum alloy for the vehicle body, which is lower in strength and poor in formability, and the two major drawbacks determine whether the aluminum alloy lightweight body can replace the steel plate.
  • the in-situ generated nanoparticles are in-situ nucleated and grown thermodynamically stable phases from the aluminum matrix by chemical reaction. Therefore, the surface of the reinforcing body is non-polluting, the bonding strength is high, and the external field control technology is combined to promote the dispersion and nucleation of the reinforcing particles.
  • the rare earth microalloying technology is added to obtain a semi-continuous casting of a composite material which is uniformly distributed in the crystal and the grain boundary of the nano-reinforced phase and the nano-Al 3 Er, Al 3 Y precipitated phase.
  • the fine-grain strengthening, the nano-reinforcing toughening and the dispersion strengthening of the nano-precipitating phase, the damping effect and the refinement and metamorphism effect of the rare earth itself breaking the relationship of the strong plastic inversion and maximizing the material Its own strong plasticity, impact resistance and fatigue resistance.
  • an aluminum-based composite extruded material for the body which can replace the steel sheet is obtained.
  • the system of the invention adopts a melt direct reaction synthesis method, that is, the aluminum melt is first melted to a reaction temperature, and the reactants are mixed and added to the melt in proportion to react to form nano-sized particles.
  • the method has the following characteristics: (1) excellent thermodynamic stability; (2) smooth interface between the matrix and the reinforcing particles, and firm bonding; (3) small particle morphology and dispersion distribution.
  • the main steps include: melting the aluminum alloy raw material into a melt at 750-850 ° C, and then wrapping the dried in-situ reactant powder with high-purity aluminum foil and pressing it into the melt through a high-purity graphite bell.
  • the reaction is carried out for 20-60 min, and a physical field is applied during the reaction, and the first purification treatment is performed after the reaction is completed; the rare earth is added to the purified melt for 12-20 minutes, and then subjected to a second purification treatment to obtain a composite.
  • the material is semi-continuously casted, and then subjected to two-stage homogenization treatment, and the treated aluminum alloy cast rod is subjected to hot extrusion processing and subsequent heat treatment, and finally a body material extrusion member is prepared.
  • the dried treated in-situ reactant powder containing the ceramic phase reinforcing body element is:
  • Potassium fluorozirconate (K 2 ZrF 6 ) and potassium fluoroborate (KBF 4 ) react to form nano-in-situ ZrB 2 particles, potassium fluorozirconate (K 2 ZrF 6 ) and potassium fluoroborate (KBF 4 )
  • the weight ratio is 25-27:37-40 (in order to prevent the formation of Al 3 Zr, the potassium fluoroborate needs to be 20%-30% excess), the powder is added in an amount of 10-35% of the matrix, and the reaction formula is:
  • Borax Na 2 B 4 O 7
  • potassium fluorozirconate K 2 ZrF 6
  • Borax Na 2 B 4 O 7
  • potassium fluorozirconate K 2 ZrF 6
  • the mass ratio of borax to potassium fluorozirconate is: 5 -7:10-15 (In order to prevent the formation of Al 3 Zr, the borax needs to be 20%-50% excess), the powder is added in an amount of 15%-40% of the matrix, and the reaction formula is:
  • the present invention uses three reaction systems to prepare in situ nanoparticle reinforced aluminum matrix composites.
  • the temperature of the melt direct reaction method needs to be controlled at 780-870 °C.
  • the physics field is an acousto-magnetic coupling field, which is a high frequency pulsed magnetic field and a high energy ultrasonic field.
  • High-frequency pulsed magnetic field frequency is 15-30Hz, magnetic current is 180-240A; high-energy ultrasonic field, power is 1000-1500W, frequency is 15-22kHz;
  • acoustic-magnetic coupling field can generate sound flow in two directions, can avoid The phenomenon of the outer side of the particles caused by a single magnetic field and the acoustic flow of a single ultrasonic field cause the cavitation bubbles to be distributed along the axial direction of the horn; and the acoustic-magnetic coupling field ensures that the mass transfer heat transfer process of the entire metal melt is completely performed, so that The concentration of each region in the metal melt is uniform, and the growth of the particles is suppressed. Therefore, the acousto-magnetic coupling field can not only avoid the disadvantages of a single physics field, but also amplify the
  • the rare earth is Al-20Er and Al-10Y intermediate alloy, and the content thereof is 0.05-0.4 wt% and 0.1-0.5 wt% of the matrix, respectively.
  • the invention has the advantages that the crystal grains can be refined and the coarse precipitated phase can be refined and refined, on the other hand, the wettability can be improved, the particle distribution can be more uniform, and the agglomeration between the nanoparticles can be reduced; Improve its performance.
  • the composite semi-continuous cast rod is produced by direct water-cooled semi-continuous casting.
  • the two-stage homogenization treatment heats the cast rod to 460-495 ° C for 2-4 h, and then at 510-580 ° C for 16 h-22 h.
  • the hot extrusion treatment step is: placing the homogenized ingot in a resistance furnace for pre-heat treatment at a temperature of 300 ° C - 350 ° C for 0.5 h - 1 h. Then, the hot extrusion molding of the mold is carried out according to the extrusion temperature of 400 ° C to 450 ° C and the extrusion speed of 1-2 mm / min.
  • the heat treatment is T4P+ artificial aging, solution hardening: temperature 540-570 ° C, holding time 1.5 h-5 h, water quenching; pre-aging: temperature 130-170 ° C, holding time 10-30 min; natural aging: room temperature 15 -20 days; artificial aging: temperature 170-180 ° C, holding time 20-60 min. Finally, qualified extruded bar for the body is obtained.
  • the invention provides an in-situ nano-reinforced aluminum matrix composite extrusion for automobile body and a preparation method thereof, and obtains in-situ nanoparticles by in-situ synthesis technology, rare earth microalloying technology and application of physical field control technology. (50nm-200nm) In-situ reinforced aluminum matrix composite semi-continuous casting with uniform distribution, fine grain and precipitated phase.
  • the extruded member prepared by the invention has high yield strength, good toughness and plasticity, and strong impact resistance, and can be applied to the vehicle body to improve the safety performance of the whole vehicle. The risk of injury to passengers can be reduced in the event of a collision.
  • Figure 1 is a flow chart of the preparation process of the present invention
  • FIG. 2 is a view showing the structure of an in-situ nano-reinforced aluminum-based composite ingot for a vehicle body according to the present invention.
  • FIG 3 is a view showing the hot extruded structure of the in-situ nano-reinforced aluminum-based composite material for a vehicle body of the present invention.
  • Figure 4 is a topographical view of the nano-reinforced particles of the present invention.
  • Raw materials AA6111 aluminum alloy (Cu 0.7%, Mg 0.73%, Si 0.76%, Fe 0.2%, Mn 0.3%, Zn 0.1%, Cr 0.05%, the rest are Al and other unavoidable impurities, among which other unavoidable impurities The percentage should be ⁇ 0.12%).
  • Solid powder Industrial potassium fluorozirconate (K 2 ZrF 6 ) and potassium fluoroborate (KBF 4 ) powder having a purity of 98%.
  • the method for preparing the automobile body material comprises the following steps:
  • the surface scum was removed, and the temperature was lowered to 780 ° C, and the first purification treatment was carried out (the refining agent hexachloroethane was sprayed into the alloy liquid in batches for refining for 10 min, and the slag was slag).
  • the purified melt was again placed in a smelting furnace and heated to 780 ° C. 0.1% Al-20Er and 0.2% Al-10Y intermediate alloy were added, and the second purification treatment was carried out for 15 minutes (refining, and then adding 0.5%). Slag remover, perform light agitation, and finally slag.
  • the cast rod obtained in the step 2 was subjected to a cut-end milling surface to obtain a short cast rod having a length of 100 mm. Then, the cast rod was placed in a box type electric resistance furnace to be heated, heated to 460 ° C for 2 h, and then kept at 560 ° C for 22 h.
  • T4P+ artificial aging heat treatment of the bar after extrusion.
  • Solution quenching temperature 545 ° C, holding time 2 h, water quenching; pre-aging: temperature 150 ° C, holding time 10 min; natural aging: standing at room temperature for 20 days; artificial aging: temperature 170 ° C, holding time 30 min.
  • qualified extruded bar for the body is obtained.
  • Raw materials AA6111 aluminum alloy (Cu 0.7%, Mg 0.73%, Si 0.76%, Fe 0.2%, Mn 0.3%, Zn 0.1%, Cr 0.05%, the rest are Al and other unavoidable impurities, among which other unavoidable impurities The percentage should be ⁇ 0.12%).
  • Solid powder Industrial cerium carbonate (Ce 2 (CO 3 ) 3 ) powder having a purity of 99.9%.
  • the preparation method was basically the same as that in Example 1, except that the reaction system was different, and 3% vol Al 2 O 3 /AA6111 aluminum-based composite material was prepared by using cesium carbonate.
  • the strontium carbonate powder drying step drying at 250 ° C and mixing and grinding (particle size less than 100 ⁇ m, mass of barium carbonate is 180 g).
  • 2 two-stage homogenization heat up to 450 ° C for 2 h, then heat at 560 ° C for 22 h.
  • Raw materials AA6111 aluminum alloy (Cu 0.7%, Mg 0.73%, Si 0.76%, Fe 0.2%, Mn 0.3%, Zn 0.1%, Cr 0.05%, the rest are Al and other unavoidable impurities, among which other unavoidable impurities The percentage should be ⁇ 0.12%).
  • Solid powder Industrial potassium fluorozirconate (K 2 ZrF 6 ) and borax (Na 2 B 4 O 7 ) powder having a purity of 98%.
  • the preparation method was basically the same as that in Example 1, except that the reaction system was different, and 3% vol Al 2 O 3 + ZrB 2 /AA6111 aluminum-based composite material was prepared by using potassium fluorozirconate and borax.
  • the powder drying step drying and mixing grinding at 200 ° C (particle size less than 100 ⁇ m, borax mass 101 g, potassium fluorozirconate mass 240 g).
  • 2 two-stage homogenization heat up to 460 ° C for 2 h, and then heat at 570 ° C for 22 h.
  • 3 heat treatment process is different: solution hardening: temperature 560 ° C, holding time 2 h, water quenching; pre-aging: temperature 160 ° C, holding time 10 min; natural aging: room temperature for 20 days; artificial aging: temperature 170 ° C, holding time 30 min.
  • Raw materials AA6016 aluminum alloy (Cu 0.18%, Mg 0.5%, Si 1.12%, Fe 0.2%, Mn 0.15%, Zn 0.2%, Cr 0.05%, the rest are Al and other unavoidable impurities, among which other unavoidable impurities The percentage should be ⁇ 0.12%).
  • Solid powder Industrial potassium fluorozirconate (K 2 ZrF 6 ) and potassium fluoroborate (KBF 4 ) powder having a purity of 98%.
  • the method for preparing the automobile body material is the same as the steps (1) and (2) in the embodiment 1, except that the following steps are performed:
  • the cast rod obtained in the step (2) was subjected to a cut-end milling surface to obtain a short cast rod having a length of 100 mm. Then, the cast rod was placed in a box type electric resistance furnace to be heated, heated to 465 ° C for 4 h, and then kept at 560 ° C for 20 h.
  • T4P+ artificial aging heat treatment of the bar after extrusion.
  • Solution quenching temperature 550 ° C, holding time 4 h, water quenching; pre-aging: temperature 160 ° C, holding time 10 min; natural aging: 20 days at room temperature; artificial aging: temperature 180 ° C, holding time 30 min.
  • qualified extruded bar for the body is obtained.
  • Raw materials AA6016 aluminum alloy (Cu 0.18%, Mg 0.5%, Si 1.12%, Fe 0.2%, Mn 0.15%, Zn 0.2%, Cr 0.05%, the rest are Al and other unavoidable impurities, among which other unavoidable impurities The percentage should be ⁇ 0.12%).
  • Solid powder Industrial cerium carbonate (Ce 2 (CO 3 ) 3 ) powder having a purity of 99.9%.
  • the preparation method is basically the same as that in Example 4, except that: 1 different reaction system, 3% vol Al 2 O 3 /AA6016 aluminum-based composite material is prepared by using cerium carbonate, and the cerium carbonate powder drying step: drying at 250 ° C Dry and mixed grinding (particle size less than 100 ⁇ m, mass of barium carbonate 180 g).
  • 2 two-stage homogenization heat up to 470 ° C for 4 h, then heat at 565 ° C for 20 h.
  • 3 heat treatment process solid solution quenching: temperature 555 ° C, holding time 4 h, water quenching; pre-aging: temperature 160 ° C, holding time 15 min; natural aging: room temperature for 20 days; artificial aging: temperature 180 ° C, holding time 30 min.
  • Raw materials AA6016 aluminum alloy (Cu 0.18%, Mg 0.5%, Si 1.12%, Fe 0.2%, Mn 0.15%, Zn 0.2%, Cr 0.05%, the rest are Al and other unavoidable impurities, among which other unavoidable impurities The percentage should be ⁇ 0.12%).
  • Solid powder Industrial potassium fluorozirconate (K 2 ZrF 6 ) and borax (Na 2 B 4 O 7 ) powder having a purity of 98%.
  • the preparation method was basically the same as that in Example 4, except that: 1 The reaction system was different, and 3% vol Al 2 O 3 + ZrB 2 /AA6016 aluminum-based composite material was prepared by using potassium fluorozirconate and borax.
  • the powder drying step drying and mixing grinding at 200 ° C (particle size less than 100 ⁇ m, borax mass 101 g, potassium fluorozirconate mass 240 g).
  • 2 two-stage homogenization heat up to 480 ° C for 4 h, then heat at 570 ° C for 20 h.
  • 1, 2, and 3 are preparations of AA6111 nano reinforced composite extruded materials
  • 4, 5, and 6 are preparations of AA6016 nano reinforced composite extruded materials
  • specific mechanical properties are as follows:
  • the embodiments of the present invention have the following beneficial effects: the tensile strength and the yield strength are greatly improved, the elongation is large, the forming property is good, and it can be seen that the ZrB 2 particle reinforcement can significantly improve the strength but the elongation is not improved.
  • the enhancement of Al 2 O 3 particles can significantly improve the elongation but the strength is not improved obviously, but the performance of the binary particles is obviously improved, so the performance index of the embodiment of the present invention always shows that it is superior to the matrix alloy.
  • the performance and various mechanical properties can meet the requirements of automotive body materials.
  • the invention provides a novel nano-reinforced composite material extrusion profile for a vehicle body and a preparation method thereof, and combines the precise control of the process parameters of the preparation method and the selection of the reaction system to obtain a lightweight high-strength body material, In the future, the preparation of high-performance lightweight body materials provides a reference basis with broad market prospects and economic value.

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Abstract

一种车身用原位纳米强化铝合金挤压材的制备方法，以含生成陶瓷相增强体元素的混合粉剂作为反应物，通过施加声磁耦合场在铝熔体内原位合成制备纳米增强颗粒，并加入稀土中间合金，制得复合材料半连铸棒；然后对铸棒进行热挤压变形，再进行T4P+人工时效热处理，获得挤压型材。制得的挤压型材具有较高的强度、抗疲劳性和抗冲击性以及成形性能。

Description

一种车身用原位纳米强化铝合金挤压材及制备方法 技术领域
本发明涉及一种铝基复合材料，特指一种车身用原位纳米强化铝合金挤压材及制备方法。
背景技术
世界汽车工业正面临着越来越严峻的问题，主要涉及能源、环境和安全。世界节能与环境协会的研究报告指出：汽车自重每减少10％，燃油消耗可降低6％-8％，排放降低5％-6％。而燃油消耗每减少1升，CO 2排放量减少2.45kg。目前全球汽车的碳排放量已达到各种碳排放总量的25％。国际先进汽车企业已通过选用轻量化材料在实现整车轻量化方面取得巨大进展，而铝合金材料是目前首选的轻量化材料。6000系铝合金由于具有中高等强度，良好的成形性及耐蚀性，且焊接性好，烘烤后表面质量高，可进行热处理强化，是目前汽车车身轻量化的关键材料，以6016，6111，6022，6005A为代表的铝材已经在国外制造的汽车车身外板上得到了越来越广泛的应用。
中国专利20100199928.9公开了一种提高6111铝合金汽车板冲压成形性的加工处理方法，将半连续铸造产生的6111合金铸锭经220℃-425℃热处理8h-15h，然后随炉升温进行均匀化处理，再进行热轧，提高了冲压成形性及烤漆强度。中国专利201410800786.5公开了汽车车身用6016铝合金薄板及其生产方法，通过熔炼及铸造、铣面、热轧、冷轧、热处理工艺步骤，提高了铝合金板材的屈服强度和冲压式的成品率。中国专利200710190078.4公开了一种改善低Cu含量铝合金汽车板烘烤硬化性能的方法，将6022板材固溶水淬后，在1h内进行预热处理，处理温度为60～200℃，处理时间在2min～30min，使得板材烘烤硬化性得到显著提高。
目前，现有的铝车身技术和综述文献主要是通过对热处理工艺的调控来进一步提高车身材料的综合性能特别是成形性能。然而，通过这些技术依然存在着以下的缺点(1)依靠传统的合金析出强化难以摆脱强塑性倒置的关系，通常以牺牲强度的方法提高塑性；(2)热处理工艺温度高，时间长以及工艺复杂都不适合工业化批量连续化生产。因此急需开发一种新型的高强韧铝基新材料。
原位生成纳米颗粒增强铝基复合材料，由于其纳米增强体是通过化学反应从铝基体中原位形核、长大的热力学稳定相，因此增强体表面无污染，避免了与基体相容性不良的问题，界面结合强度高，因而其具有高的比强度、比模量，出色的抗疲劳能力，很好的耐热性、耐腐蚀性等，且可通过熔体反应法直接合成，成本大幅度降低等优点，已成 为近年来纳米材料与铝基复合材料交叉领域中具有突破性的新材料。但是，原位铝基纳米复合材料的制备比较困难，仍存在尚未突破的“瓶颈”：①生成的颗粒形态和大小不易控制，亚微米级尚能达到，纳米级难达到；②生成的纳米颗粒易团聚，分布不均匀问题。
发明内容
本发明的目的就在于针对现有技术的不足，开发一种新型车身用原位纳米强化铝合金挤压材的制备方法，采用高频脉冲磁场和高能超声场调控其制备过程，并结合优化的半连铸技术和挤压加工成形技术，在改善合金组织的同时，实现纳米颗粒在晶内和晶界均分布，显著提高车身材料的强塑性、抗冲击性和抗疲劳性能。
本发明能有效解决目前车身用6系铝合金相比于钢强度低、成型加工性差的缺点，这两大缺点决定铝合金轻量化车身能否代替钢板的关键。原位生成的纳米颗粒是通过化学反应从铝基体中原位形核、长大的热力学稳定相，因此增强体表面无污染，结合强度高，并结合外场调控技术促进增强颗粒的分散和形核，以及加入稀土微合金化技术，可获得均匀分布在晶内和晶界的纳米增强相和纳米Al 3Er、Al 3Y析出相的复合材料半连铸件。通过纳米颗粒的Orowan强化、细晶强化、纳米增强体增韧和纳米析出相的弥散强化、阻尼效应以及稀土本身的细化和变质效应的作用，打破强塑性倒置的关系，最大限度的提高材料本身的强塑性、抗冲击性和抗疲劳性。然后通过优化的半连铸技术和挤压加工成形技术，获得可代替钢板的车身用铝基复合材料挤压材。
本发明体系采用熔体直接反应合成法，即先将铝熔体熔化至反应温度，将反应物按比例混合加入至熔体中进行反应生成纳米级颗粒。该方法与其他复合材制备方法相比，具备以下特点：(1)极佳的热力学稳定性；(2)基体与增强颗粒界面光滑，结合牢固；(3)颗粒形貌小，弥散分布。
本发明的实施例是这样实现的：
主要步骤包括：将铝合金原料在750-850℃的条件下熔炼成熔体，然后将烘干处理过的原位反应物粉体用高纯铝箔包裹通过高纯石墨钟罩压入熔体中进行反应20-60min，同时在反应过程中施加物理场，反应结束后进行第一次净化处理；将稀土加入到净化后的熔体保温12-20min之后，进行第二次净化处理，制得复合材料半连续铸棒，然后进行双级均匀化处理，将处理后的铝合金铸棒进行热挤压加工和后续的热处理，最后制备出车身材料挤压件。
所述的烘干处理过的含生成陶瓷相增强体元素的原位反应物粉体为：
(1)氟锆酸钾(K 2ZrF 6)和氟硼酸钾(KBF 4)，反应生成纳米原位ZrB 2颗粒，其氟 锆酸钾(K 2ZrF 6)和氟硼酸钾(KBF 4)的重量比例为25-27：37-40(为了防止生成Al 3Zr，氟硼酸钾需过量20％-30％)，粉体加入量为基体的10-35％，反应式为：
3K 2ZrF 6+6KBF 4+10Al＝3ZrB 2+9KAlF 4+K3AlF 6。
(2)碳酸铈(Ce 2(CO 3) 3)，反应生成纳米原位Al 2O 3颗粒，其加入量为基体的5-20％，反应式为：
2Ce 2(CO 3) 3+4Al＝2Al 2O 3+4Ce+6CO 2；
(3)硼砂(Na 2B 4O 7)和氟锆酸钾(K 2ZrF 6)，反应生成二元纳米ZrB 2+Al 2O 3颗粒，硼砂与氟锆酸钾的质量比例为：5-7：10-15(为了防止生成Al 3Zr，硼砂需过量20％-50％)，粉体加入量为基体的15％-40％，反应式为：
9Na 2B 4O 7+30K 2ZrF 6+60Al＝12ZrO 2+18ZrB 2+13Al 2O 3+18K 2NaAlF 6+16AlF 3+24KF。因此本发明采用三种反应体系制备原位纳米颗粒增强铝基复合材料。
所述的熔体直接反应法的温度需控制在780-870℃。
所述的物理场为声磁耦合场，是高频脉冲磁场和高能超声场。高频脉冲磁场，频率为15-30Hz，磁力电流为180-240A；高能超声场，功率为1000-1500W，频率为15-22kHz；声磁耦合场可产生两种方向的声流运动，可避免单一磁场造成的颗粒偏聚外侧的现象和单一超声场的声流运动造成空化泡沿变幅杆轴向分布；并且声磁耦合场可保证整个金属熔体传质转热过程完全进行，使得金属熔体中各个区域浓度均匀，抑制颗粒的长大。因此声磁耦合场不仅可以避免单一物理场的缺点，还能放大单一物理场的优点。
所述的稀土为Al-20Er和Al-10Y中间合金，其含量分别为基体的0.05-0.4wt％和0.1-0.5wt％。其优点：一方面可细化晶粒以及对其粗大的析出相进行变质细化，另一方面，可改善其润湿性，使颗粒分布更均匀，减少纳米颗粒之间的团聚；从而有利于改善其性能。
所述的复合材料半连续铸棒是通过直接水冷半连续铸造制得。
所述的双级均匀化处理，将铸棒升温至460-495℃保温2-4h，再在510-580℃保温16h-22h。
所述的热挤压处理步骤为：将均匀化之后的铸锭放置在电阻炉中进行预热处理，温度300℃-350℃，时间0.5h-1h。然后按照挤压温度为400℃-450℃，挤压速度为1-2mm/min的工艺条件进行模具热挤压成形。
所述的热处理为T4P+人工时效，固溶淬火：温度540-570℃，保温时间1.5h-5h，水淬；预时效：温度130-170℃，保温时间10-30min；自然时效：常温放置15-20天；人工 时效：温度170-180℃，保温时间20-60min。最后得到合格的车身用挤压棒材。
本发明的有益效果是：
本发明提供了一种用于汽车车身用原位纳米增强铝基复合材料挤压件及其制备方法，通过原位合成技术、稀土微合金化技术以及施加物理场调控技术，获得原位纳米颗粒(50nm-200nm)分布均匀、晶粒和析出相细小的原位增强铝基复合材料半连铸件。再通过后期的热挤压成形，使得本发明制备的挤压件具有较高的屈服强度、良好的韧性和塑性，以及较强的抗冲击性，应用在车身上能够提高整车的安全性能，发生碰撞时能减少乘客受伤的风险。
附图说明
为了更清楚地说明本发明的技术方案，下面将对所需要使用的附图做简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明的制备工艺流程图
图2为本发明的车身用原位纳米增强铝基复合材料铸锭的组织结构图。
(a)ZrB 2增强铝基复合材料；(b)Al 2O 3增强铝基复合材料；(c)ZrB 2+Al 2O 3增强铝基复合材料。
图3为本发明的车身用原位纳米增强铝基复合材料的热挤压组织结构图。
(a)ZrB 2挤压材；(b)Al 2O 3挤压材；(c)ZrB 2+Al 2O 3挤压材。
图4为本发明的纳米增强颗粒的形貌图。
(a)ZrB 2颗粒；b)Al 2O 3颗粒；(c)ZrB 2+Al 2O 3颗粒。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下多获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
原材料：AA6111铝合金(Cu 0.7％，Mg 0.73％，Si 0.76％，Fe 0.2％，Mn 0.3％，Zn 0.1％， Cr 0.05％，其余为Al和其他不可避免的杂质，其中其他不可避免杂质的百分含量应≤0.12％)。
固体粉末：纯度为98％的工业用氟锆酸钾(K 2ZrF 6)和氟硼酸钾(KBF 4)粉剂。
汽车车身材料的制备方法包括以下步骤：
(1)铝合金的熔炼：在将1Kg铝合金原材料进行熔炼，当铝合金熔化成铝液温度达到850℃时，分批加入在200℃下烘干并混合研磨的粉体(粒度小于100μm，氟锆酸钾的质量为163g，氟硼酸钾为177g)，同时开启高频脉冲磁场和高能超声场的组合装置(磁场：频率20Hz，磁力电流200A；超声：功率1000W，频率20kHz)反应30min，反应结束将表面的浮渣去除，并待温度降至780℃，进行第一次净化处理(将精炼剂六氯乙烷分批喷入到合金液中进行精炼10min，扒渣)。将净化过的熔体再次放入熔炼炉中加热到780℃，加入0.1％Al-20Er和0.2％Al-10Y中间合金，保温15min，进行第二次净化处理(进行精炼，再加入0.5％的清渣剂，进行浅度搅拌，最后扒渣)。
(2)半连续铸造：待熔体温度在750℃的情况下，将熔体注入结晶器中，当熔体在石墨环处凝固结壳后，引锭头以30mm/min速度下降，同时开启冷却水进行冷却，水温25℃，水压为0.2MPa，铸造完成后，吊起铸棒，得到直径60mm的3％volZrB 2/AA6111铝基复合材料半连续铸棒。
(3)双级均匀化处理：将步骤2所得的铸棒进行切头切尾铣面，制得长度为100mm的短铸棒。然后将铸棒放入箱式电阻炉中加热，升温至460℃保温2h，再在560℃保温22h。
(4)棒材热挤压：将步骤3得到的棒材放置在电阻炉中进行预热处理，温度300℃，时间1h。然后将挤压温度设定为450℃，按照挤压速度为1mm/min进行模具热挤压成形，得到直径为20mm的挤压棒材。
(5)T4P+人工时效：将挤压之后的棒材进行热处理。固溶淬火：温度545℃，保温时间2h，水淬；预时效：温度150℃，保温时间10min；自然时效：常温放置20天；人工时效：温度170℃，保温时间30min。最后得到合格的车身用挤压棒材。
实施例2：
原材料：AA6111铝合金(Cu 0.7％，Mg 0.73％，Si 0.76％，Fe 0.2％，Mn 0.3％，Zn 0.1％，Cr 0.05％，其余为Al和其他不可避免的杂质，其中其他不可避免杂质的百分含量应≤0.12％)。
固体粉末：纯度为99.9％的工业用碳酸铈(Ce 2(CO 3) 3)粉末。
制备方法与实施例1中基本相同，不同之处在于，①反应体系不同，采用碳酸铈制备3％vol Al 2O 3/AA6111铝基复合材料。其碳酸铈粉末烘干步骤:250℃下烘干并混合研磨(粒度小于100μm，碳酸铈的质量为180g)。②双级均匀化：升温至450℃保温2h，再在560℃保温22h。③热处理工艺不同：固溶淬火：温度550℃，保温时间2h，水淬；预时效：温度160℃，保温时间10min；自然时效：常温放置20天；人工时效：温度170℃，保温时间30min。
实施例3：
原材料：AA6111铝合金(Cu 0.7％，Mg 0.73％，Si 0.76％，Fe 0.2％，Mn 0.3％，Zn 0.1％，Cr 0.05％，其余为Al和其他不可避免的杂质，其中其他不可避免杂质的百分含量应≤0.12％)。
固体粉末：纯度为98％的工业用氟锆酸钾(K 2ZrF 6)和硼砂(Na 2B 4O 7)粉剂。
制备方法与实施例1中基本相同，不同之处在于，①反应体系不同，采用氟锆酸钾和硼砂制备3％vol Al 2O 3+ZrB 2/AA6111铝基复合材料。其粉末烘干步骤:200℃下烘干并混合研磨(粒度小于100μm，硼砂的质量为101g，氟锆酸钾的质量为240g)。②双级均匀化：升温至460℃保温2h，再在570℃保温22h。③热处理工艺不同：固溶淬火：温度560℃，保温时间2h，水淬；预时效：温度160℃，保温时间10min；自然时效：常温放置20天；人工时效：温度170℃，保温时间30min。
实施例4：
原材料：AA6016铝合金(Cu 0.18％，Mg 0.5％，Si 1.12％，Fe 0.2％，Mn 0.15％，Zn 0.2％，Cr 0.05％，其余为Al和其他不可避免的杂质，其中其他不可避免杂质的百分含量应≤0.12％)。
固体粉末：纯度为98％的工业用氟锆酸钾(K 2ZrF 6)和氟硼酸钾(KBF 4)粉剂。
汽车车身材料的制备方法与实施例1中的步骤(1),(2)相同，不同之处在于后面的步骤：
(3)双级均匀化处理：将步骤(2)所得的铸棒进行切头切尾铣面，制得长度为100mm的短铸棒。然后将铸棒放入箱式电阻炉中加热，升温至465℃保温4h，再在560℃保温20h。
(4)棒材热挤压：将步骤(3)得到的棒材放置在电阻炉中进行预热处理，温度320℃，时间1h。然后将挤压温度设定为440℃，按照挤压速度为1.2mm/min进行模具热挤压成形，得到直径为20mm的挤压棒材。
(5)T4P+人工时效：将挤压之后的棒材进行热处理。固溶淬火：温度550℃，保温时间4h，水淬；预时效：温度160℃，保温时间10min；自然时效：常温放置20天；人工时效：温度180℃，保温时间30min。最后得到合格的车身用挤压棒材。
实施例5：
原材料：AA6016铝合金(Cu 0.18％，Mg 0.5％，Si 1.12％，Fe 0.2％，Mn 0.15％，Zn 0.2％，Cr 0.05％，其余为Al和其他不可避免的杂质，其中其他不可避免杂质的百分含量应≤0.12％)。
固体粉末：纯度为99.9％的工业用碳酸铈(Ce 2(CO 3) 3)粉末。
制备方法与实施例4中基本相同，不同之处在于：①反应体系不同，采用碳酸铈制备3％vol Al 2O 3/AA6016铝基复合材料，其碳酸铈粉末烘干步骤:250℃下烘干并混合研磨(粒度小于100μm，碳酸铈的质量为180g)。②双级均匀化：升温至470℃保温4h，再在565℃保温20h。③热处理工艺不同：固溶淬火：温度555℃，保温时间4h，水淬；预时效：温度160℃，保温时间15min；自然时效：常温放置20天；人工时效：温度180℃，保温时间30min。
实施例6：
原材料：AA6016铝合金(Cu 0.18％，Mg 0.5％，Si 1.12％，Fe 0.2％，Mn 0.15％，Zn 0.2％，Cr 0.05％，其余为Al和其他不可避免的杂质，其中其他不可避免杂质的百分含量应≤0.12％)。
固体粉末：纯度为98％的工业用氟锆酸钾(K 2ZrF 6)和硼砂(Na 2B 4O 7)粉剂。
制备方法与实施例4中基本相同，不同之处在于：①反应体系不同，采用氟锆酸钾和硼砂制备3％vol Al 2O 3+ZrB 2/AA6016铝基复合材料。其粉末烘干步骤:200℃下烘干并混合研磨(粒度小于100μm，硼砂的质量为101g，氟锆酸钾的质量为240g)。②双级均匀化：升温至480℃保温4h，再在570℃保温20h。③热处理工艺不同：固溶淬火：温度560℃，保温时间4h，水淬；预时效：温度160℃，保温时间20min；自然时效：常温放置20天；人工时效：温度180℃，保温时间30min。
实施例中，1、2、3是AA6111纳米增强复合材料挤压材的制备，4、5、6是AA6016纳米增强复合材料挤压材的制备，具体的机械性能见下表：
表1 各试试例提供的纳米增强复合材料挤压材的性能检测结果
Figure PCTCN2018072036-appb-000001
Figure PCTCN2018072036-appb-000002
综上，本发明实施例具有如下有益效果：拉伸强度、屈服强度有较大提高，延伸率很大，成形性能好，并且可以看出，ZrB 2颗粒增强可明显提高强度但是延伸率提高不明显，Al 2O 3颗粒增强可明显提高延伸率但是强度提高不明显，但是二元颗粒增强各项性能都有明显的提升，因此本发明的实施例的性能指标始终体现出比基体合金更加优异的性能，并且各项机械性能可以满足汽车车身材质的要求。
本发明提供了一种新型的车身用纳米增强复合材料挤压型材及其制备方法，并结合对制备方法工艺参数的精确控制和反应体系的选择，获得一种轻质高强韧的车身材料，为今后制备高性能的轻质车身材料提供了参考依据，具有广阔的市场前景和经济价值。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于：将含生成陶瓷相增强体元素的粉体作为反应物，采用熔体直接反应法并同时在反应过程中施加声磁耦合场合成纳米增强颗粒，然后加入中间合金，制得复合材料半连续铸棒，然后进行双级均匀化处理，将处理后的铝合金铸棒依次进行热挤压加工和后续的热处理，最后制备出车身材料挤压件。
  2. 如权利要求1所述的一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于：所述的含生成陶瓷相增强体元素的粉体为：(1)氟锆酸钾(K 2ZrF 6)和氟硼酸钾(KBF 4)，其质量比为：25-27：37-40，粉体加入量为铝合金基体重量的10-35％；(2)碳酸铈，粉体加入量为铝合金基体重量的5-20％或(3)硼砂和氟锆酸钾，其质量比为：5-7：10-15，粉体加入量为铝合金基体的15-40％。
  3. 如权利要求1所述的一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于：所述的熔体直接反应法的反应温度控制在780-870℃。
  4. 如权利要求1所述的一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于：所述的声磁耦合场，为高频脉冲磁场和高能超声场。高频脉冲磁场，频率为15-30Hz，磁力电流为180-240A；高能超声场，功率为1000-1500W，频率为15-22kHz。
  5. 如权利要求1所述的一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于：所述的稀土以Al-20Er和Al-10Y中间合金的形式加入，其加入含量分别为铝合金基体重量的0.05-0.4％和0.1-0.5％
  6. 如权利要求1所述的一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于，所述的双级均匀化处理，是将铸棒升温至460-495℃保温2-4h，再在510-580℃保温16h-22h。
  7. 如权利要求1所述的一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于，所述的热挤压处理步骤为：将均匀化之后的铸锭放置在电阻炉中进行预热处理，温度300℃-350℃，时间0.5h-1h；然后按照挤压温度为400℃-450℃，挤压速度为1-2mm/min的工艺条件进行模具热挤压成形。
  8. 如权利要求1所述的一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于，所述的热处理为T4P+人工时效，固溶淬火：温度540-570℃，保温时间1.5h-5h，水淬；预时效：温度130-170℃，保温时间10-30min；自然时效：常温放置15-20天；人工时效：温度170-180℃，保温时间20-60min。
  9. 如权利要求1所述的一种车身用原位纳米强化铝合金挤压材的制备方法，其特征在于，所述复合材料半连续铸棒是通过直接水冷半连续铸造制得。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113604691A (zh) * 2021-07-02 2021-11-05 福建省南平铝业股份有限公司 新能源汽车复杂腔体结构用6系铝合金及其制备方法
CN114101610A (zh) * 2020-08-26 2022-03-01 宝山钢铁股份有限公司 一种颗粒增强新型6xxx铝合金板带的制备方法
CN114990369A (zh) * 2022-07-28 2022-09-02 鼎镁新材料科技股份有限公司 一种再生铝制备铝合金自行车轮圈的方法
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CN115652230B (zh) * 2022-11-10 2024-12-20 魏桥(苏州)轻量化研究院有限公司 消除6系铝合金停放效应的方法及铝合金产品
CN116334459A (zh) * 2023-03-15 2023-06-27 北京工业大学 一种基于电致塑性的微纳级颗粒增强铝基线材及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040016318A1 (en) * 2002-07-23 2004-01-29 General Electric Company Method for making materials having artificially dispersed nano-size phases and articles made therewith
CN101391290A (zh) * 2008-11-05 2009-03-25 江苏大学 一种磁场与超声场耦合作用下熔体反应合成金属基复合材料的方法
CN101956120A (zh) * 2010-10-12 2011-01-26 江苏大学 一种纳米颗粒增强铝基复合材料的制备方法及装置
CN105018806A (zh) * 2015-07-23 2015-11-04 广西柳拖车辆有限公司 电动汽车车身用板材的制造方法
CN106702222A (zh) * 2016-12-16 2017-05-24 镇江创智特种合金科技发展有限公司 一种混合稀土参杂的（TiB2+ZrB2）/Al复合材料制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RO128216B1 (ro) * 2011-04-22 2017-07-28 Institutul Naţional De Cercetare-Dezvoltare Pentru Metale Neferoase Şi Rare - Imnr Procedeu de obţinere in situ a materialelor compozite de tipul al-si/al, şi instalaţie experimentală
CN104959395B (zh) * 2015-07-06 2017-04-26 广西大学 一种方管铝合金型材的等温挤压加工方法
CN106086530B (zh) * 2016-05-31 2018-01-16 江苏大学 一种原位铝基复合材料的制备方法及其装置
CN106834986B (zh) * 2017-03-07 2018-12-18 烟台南山学院 一种航空用铝合金均匀化热处理工艺
CN107893170A (zh) * 2017-11-13 2018-04-10 江苏大学 一种车身用原位纳米强化铝合金挤压材及制备方法
CN109504870B (zh) * 2018-11-21 2020-11-20 江苏大学 一种轻量化汽车防撞梁用原位纳米强化铝合金及制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040016318A1 (en) * 2002-07-23 2004-01-29 General Electric Company Method for making materials having artificially dispersed nano-size phases and articles made therewith
CN101391290A (zh) * 2008-11-05 2009-03-25 江苏大学 一种磁场与超声场耦合作用下熔体反应合成金属基复合材料的方法
CN101956120A (zh) * 2010-10-12 2011-01-26 江苏大学 一种纳米颗粒增强铝基复合材料的制备方法及装置
CN105018806A (zh) * 2015-07-23 2015-11-04 广西柳拖车辆有限公司 电动汽车车身用板材的制造方法
CN106702222A (zh) * 2016-12-16 2017-05-24 镇江创智特种合金科技发展有限公司 一种混合稀土参杂的（TiB2+ZrB2）/Al复合材料制备方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN115821179A (zh) * 2022-12-16 2023-03-21 西安交通大学 一种电磁耦合辅助加工金属材料的方法
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