CN114934206B - Multi-element aluminide reinforced aluminum-based composite material and preparation method and application thereof - Google Patents

Multi-element aluminide reinforced aluminum-based composite material and preparation method and application thereof Download PDF

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CN114934206B
CN114934206B CN202210592478.2A CN202210592478A CN114934206B CN 114934206 B CN114934206 B CN 114934206B CN 202210592478 A CN202210592478 A CN 202210592478A CN 114934206 B CN114934206 B CN 114934206B
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CN114934206A (en
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董勇
杨煜锋
姚泽强
胡永俊
章争荣
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Guangdong University of Technology
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • 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
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    • C22C1/00—Making non-ferrous alloys
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    • 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
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    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B14/00—Crucible or pot furnaces
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    • F27B14/10—Crucibles

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Abstract

The invention belongs to the technical field of metal matrix composite materials, and discloses a multi-element aluminide reinforced aluminum matrix composite material and a preparation method and application thereof. The multi-element aluminide reinforced phase contains five or more main elements, has higher strength and high-temperature thermal stability, and has higher bonding strength with an aluminum matrix. The preparation process of the multi-element aluminide reinforced aluminum-based composite material is simple, the multi-element high-entropy alloy crucible is utilized to perform in-situ diffusion on multi-atoms in pure aluminum or aluminum alloy metal liquid in a synergic mode, meanwhile, the mechanical stirring is applied, the element distribution uniformity and the diffusion speed are accelerated, and the preparation efficiency is greatly increased. The reinforcing phase of the multi-element aluminide reinforced aluminum-based composite material is distributed in an aluminum matrix in a superfine thin strip shape and a short rod shape, the volume percentage of the reinforcing phase can reach 7.7%, the normal-temperature and high-temperature mechanical properties are excellent, and the multi-element aluminide reinforced aluminum-based composite material has the characteristics of small density, good thermal stability and corrosion resistance and can be applied to the fields of aerospace, automobile manufacturing and the like.

Description

Multi-element aluminide reinforced aluminum-based composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal matrix composite materials, and particularly relates to a high-strength and high-plasticity multi-element aluminide reinforced aluminum matrix composite material as well as a preparation method and application thereof.
Background
With the continuous improvement of the industrial requirements on the material performance, the performance of a single material is difficult to meet the requirements, for example, in the application of automobile pistons, brake discs, aircraft landing gears and the like, the material is required to still maintain good mechanical properties in a high-temperature environment, and simultaneously, good wear resistance is also required. The composite material well solves the problems, and the advantages of the components can be combined by regulating and controlling the components and the content of the composite material, so that the comprehensive performance of the material is improved, and the multifunctional material is obtained. The aluminum alloy has the characteristics of low density, good processing performance, high specific strength, excellent heat conductivity and corrosion resistance and the like, and is widely applied to the fields of aerospace, marine industry, transportation and the like. The combination of the aluminum alloy and some reinforcements can retain the advantages of low density, good heat transfer property and corrosion resistance of the aluminum alloy, and simultaneously enhance the strength, wear resistance and thermal stability of the material.
Common reinforcements of aluminum matrix composites are SiC, graphene, intermetallic compounds, and the like. The intermetallic compound has the advantages of high strength, high modulus, high melting point, good thermal stability and the like, and has great application prospect in the field of high-temperature structural materials. However, intermetallic compounds have poor fracture toughness and are easily brittle, and have low ductility, which is disadvantageous for further processing. By adding the intermetallic compound into the aluminum matrix, the obtained aluminum matrix composite combines the advantages of the aluminum alloy and the intermetallic compound, is easy to process and low in density, and still maintains higher strength and creep resistance at high temperature. In order to obtain high strength and high plasticity and eliminate the phenomenon of plasticity reduction caused by introduction of intermetallic compounds, the invention provides a multi-element aluminide reinforced aluminum-based composite material and a preparation method thereof.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a multi-element aluminide reinforced aluminum-based composite material with light weight, good thermal stability and higher mechanical strength.
The invention also aims to provide a preparation method of the multi-element aluminide reinforced aluminum-based composite material, which is a diffusion couple in-situ diffusion method.
The invention also aims to provide application of the multi-element aluminide reinforced aluminum-based composite material.
The purpose of the invention is realized by the following technical scheme:
a multi-element aluminide reinforced aluminum-based composite material is composed of a reinforced phase multi-element aluminide and a matrix; the substrate is pure Al or Al alloy; the multi-element aluminide contains Al element and more than four elements of Co, cr, fe, ni, mn and Cu.
The preparation method of the multi-element aluminide reinforced aluminum matrix composite material comprises the following operation steps:
(1) Preparing a high-entropy alloy crucible cast ingot, wherein the height of the inside of the crucible is h mm, the diameter of the inside of the crucible is dmm, the thickness of the crucible is 10-50mm, and the high-entropy alloy crucible cast ingot is formed by mixing more than four elements of Co, cr, fe, ni, mn and Cu according to equal atomic ratio;
(2) Placing the high-entropy alloy crucible cast ingot in a muffle furnace for homogenizing annealing, heating to 1000-1200 ℃ at a heating rate of 10 ℃/min, preserving heat for 2-4 hours, cooling to 400 ℃ at a cooling rate of 3 ℃/min after heat preservation, and then cooling to room temperature along with the furnace;
(3) Milling the inner surface of the high-entropy alloy crucible cast ingot by machining, and removing an oxide film on the inner surface, wherein the surface roughness is Ra12.5 or below; then cleaning with alcohol and air drying for later use;
(4) Remelting pure Al or Al alloy, casting the remelted pure Al or Al alloy into a graphite crucible with the diameter of (d-2) mm to obtain a pure Al bar or an aluminum alloy bar with the length of (h + 3) mm or more, cleaning the surface of the bar by ultrasonic alcohol, removing water vapor, oil stain and an oxide layer on the surface, and air-drying for later use;
(5) Putting the bar material obtained in the step (4) into the high-entropy alloy crucible ingot obtained in the step (3), and forcibly pressing the part of the bar material, which is higher than the surface of the high-entropy alloy crucible ingot, into the high-entropy alloy crucible ingot by using a press machine to obtain a tightly-combined high-entropy alloy/pure Al diffusion couple or a high-entropy alloy/aluminum alloy diffusion couple;
(6) Putting the prepared high-entropy alloy/pure Al diffusion couple or high-entropy alloy/aluminum alloy diffusion couple into a heat treatment furnace, heating to 680-700 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2-6 hours; in the heat preservation process, mechanical stirring is applied to promote the synergistic diffusion and the distribution uniformity of multiple elements;
(7) And after the heat preservation stage is finished, removing dross on the surface of the aluminum liquid, casting the aluminum liquid into a steel mould, and air-cooling to room temperature to obtain the multi-element aluminide reinforced aluminum-based composite material.
The high-entropy alloy crucible ingot in the step (1) is made of an equiatomic ratio high-entropy alloy CoCrFeMnNi, coCrFeNi or CoCrCuFeNi.
The high-entropy alloy crucible cast ingot in the step (1) is obtained by machining the high-entropy alloy cast ingot or directly casting the high-entropy alloy cast ingot by a casting method.
The sources of the high-entropy alloy ingot in the step (1) and the pure Al or Al alloy in the step (4) are not particularly limited, and the high-entropy alloy ingot and the pure Al or Al alloy can be prepared according to a method well known by a person skilled in the art or can be a commercially available product.
And (2) selecting pure raw materials with the purity of more than 99.9wt% for Al, co, cr, fe, ni, mn or Cu used in the preparation process of the high-entropy alloy crucible ingot in the step (1).
The heating of the step (2) is heating to 1000 ℃; the time for heat preservation was 4 hours.
The heating in the step (6) is heating to 680 ℃.
The mechanical stirring is applied in a stirring mode in the conventional metal smelting process, a motor drives a stirring rod, and the other end of the stirring rod is connected with a turbine; the surfaces of the stirring rod and the turbine are coated with zirconia coatings.
The multi-element aluminide reinforced aluminum-based composite material is applied to the fields of aerospace and automobile manufacturing.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The conventional preparation method of the aluminum-based composite material is a powder sintering method, but the method can only prepare small-sized workpieces, which is greatly limited in industrial application.
(2) The method used by the invention belongs to a liquid diffusion synthesis method, and the aluminum-based composite material prepared by the currently common liquid synthesis method is prepared by adding reinforcing material particles after aluminum is melted, and then uniformly distributing the particles through stirring to form the aluminum-based composite material.
(3) The high-entropy alloy crucible in the preparation method can be repeatedly used, the material utilization rate is effectively improved, the resource waste is reduced, and the cost is saved.
(4) Compared with an aluminum matrix, the performance of the aluminum matrix composite material prepared by the invention is greatly improved, wherein the hardness is improved by nearly 100 percent, the yield strength is improved by nearly 100 to 400 percent, and meanwhile, the ductility is nearly consistent with that of the aluminum matrix, and good plasticity and toughness are still maintained; the multi-element aluminide has higher binding energy and thermal stability, and the usable temperature of the aluminum alloy is improved.
Drawings
FIG. 1 is a scanning electron micrograph of the multi-element aluminide-reinforced aluminum matrix composite prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the multi-element aluminide reinforced aluminum-based composite material prepared in example 1 of the present invention.
FIG. 3 shows the result of the spectrum analysis of the multi-element aluminide reinforced aluminum matrix composite prepared in example 1 of the present invention.
FIG. 4 is an engineering stress-strain curve measured by compression of the multi-element aluminide reinforced aluminum-based composite material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
(1) Preparing a CoCrFeMnNi high-entropy alloy crucible cast ingot, wherein the height of the inside of the crucible is 60mm, the diameter of the inside of the crucible is 40mm, the thickness of the crucible is 10mm, and the components of the high-entropy alloy crucible cast ingot are CoCrFeMnNi with equal atomic ratio;
(2) And (2) placing the high-entropy alloy crucible cast ingot in the step (1) in a muffle furnace for homogenizing annealing, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 4 hours, cooling to 400 ℃ at a cooling rate of 3 ℃/min after heat preservation, and then cooling to room temperature along with the furnace.
(3) Milling the inner surface of the high-entropy alloy crucible cast ingot by machining, and removing an oxide film on the inner surface, wherein the surface roughness is Ra12.5 or below; cleaning the crucible with alcohol and air-drying for later use;
(4) Remelting pure Al, casting the pure Al into a graphite crucible with the diameter of 38mm to obtain a bar with the length of 80mm, cutting off a top shrinkage cavity part, cleaning the surface of the bar with ultrasonic alcohol, removing water vapor, oil stain and an oxide layer on the surface, and air-drying for later use;
(5) Putting the bar material obtained in the step (4) into the high-entropy alloy crucible obtained in the step (3), and forcibly pressing the part of the bar material, which is higher than the surface of the high-entropy alloy crucible cast ingot, into the high-entropy alloy crucible cast ingot by using a press machine, wherein no gap exists between the bar material and the high-entropy alloy crucible cast ingot, so that a CoCrFeMnNi high-entropy alloy/pure Al diffusion couple which is tightly combined is obtained;
(6) Placing the prepared CoCrFeMnNi high-entropy alloy/pure Al diffusion couple into a heat treatment furnace, heating to 700 ℃ at the heating rate of 10 ℃/min, and preserving heat for 4 hours; in the heat preservation process, mechanical stirring is applied to promote the synergistic diffusion and the distribution uniformity of multiple elements;
(7) And after the heat preservation stage is finished, removing dross on the surface of the aluminum liquid, casting the aluminum liquid into a steel mould, and air-cooling to room temperature to obtain the multi-element aluminide reinforced aluminum-based composite material with a certain size and shape.
In the preparation process of the CoCrFeMnNi high-entropy alloy crucible ingot in the step (1), co, cr, fe, ni and Mn elements are all selected from pure raw materials with the purity of at least more than 99.9 wt%.
Example 2:
(1) Preparing a CoCrFeNi high-entropy alloy crucible cast ingot, wherein the height of the inside of the crucible is 50mm, the diameter of the inside of the crucible is 30mm, the thickness of the crucible is 10mm, and the components of the high-entropy alloy crucible cast ingot are CoCrFeNi with equal atomic ratio;
(2) And (2) placing the high-entropy alloy crucible cast ingot in the step (1) in a muffle furnace for homogenizing annealing, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 4 hours, cooling to 400 ℃ at a cooling rate of 3 ℃/min after heat preservation, and then cooling to room temperature along with the furnace.
(3) Milling the inner surface of the high-entropy alloy crucible cast ingot by machining, and removing an oxide film on the inner surface, wherein the surface roughness is Ra12.5 or below; cleaning the crucible with alcohol and air-drying for later use;
(4) Remelting pure Al, casting the pure Al into a graphite crucible with the diameter of 28mm to obtain a bar with the length of 70mm, cutting off a top shrinkage cavity part, cleaning the surface of the bar with ultrasonic alcohol, removing water vapor, oil stain and an oxide layer on the surface, and air-drying for later use;
(5) Putting the bar material obtained in the step (4) into the high-entropy alloy crucible obtained in the step (3), and forcibly pressing the part of the bar material, which is higher than the surface of the high-entropy alloy crucible cast ingot, into the high-entropy alloy crucible cast ingot by using a press machine, wherein no gap exists between the bar material and the high-entropy alloy crucible cast ingot, so that a CoCrFeNi high-entropy alloy/pure Al diffusion couple which is tightly combined is obtained;
(6) Placing the prepared CoCrFeNi high-entropy alloy/pure Al diffusion couple into a heat treatment furnace, heating to 680 ℃ at a heating rate of 10 ℃/min, and preserving heat for 6 hours; in the heat preservation process, mechanical stirring is applied to promote the synergistic diffusion and the distribution uniformity of multiple elements;
(7) And after the heat preservation stage is finished, removing dross on the surface of the aluminum liquid, casting the aluminum liquid into a steel mould, and air-cooling to room temperature to obtain the multi-element aluminide reinforced aluminum-based composite material with a certain size and shape.
In the preparation process of the CoCrFeNi high-entropy alloy crucible ingot in the step (1), co, cr, fe and Ni elements are selected from pure raw materials with the purity of at least more than 99.9 wt%.
Fig. 1 is a scanning electron microscope photograph of the multi-element aluminide-reinforced aluminum matrix composite prepared in example 1 of the present invention, and it can be seen from fig. 1 that the intermetallic compound reinforcing phases of the aluminum matrix composite are mostly distributed in thin strips in the aluminum matrix, and the area of the intermetallic compound phase is about 7.7% and the standard deviation is 0.6% when the statistics of different positions of the sample 20 is performed by using ImagePro software, which indicates that the intermetallic compound phases are uniformly distributed in the aluminum matrix.
FIG. 2 is an X-ray diffraction pattern of the multi-element aluminide reinforced aluminum-based composite material prepared in example 1, and it can be known from FIG. 2 that the phases existing in the aluminum-based composite material are mainly divided into an Al matrix and a phase structure similar to Al 9 Co 2 A multi-component intermetallic compound phase of (a).
FIG. 3 is the result of the spectrum analysis of the multi-element aluminide reinforced aluminum-based composite material prepared in example 1 of the present invention, and it can be known from FIG. 3 that the intermetallic compound in the aluminum-based composite material is formedThe material mainly consists of Al, fe, co and Ni, and also contains a small amount of Cr and Mn elements, wherein Al atoms occupy about 83%, and the atomic ratio of Fe, co and Ni is close to 1:1:1, the intermetallic compound phase is presumed to be Al by the X-ray diffraction pattern analysis of FIG. 2 9 (FeCoNi) 2 And (4) phase(s).
FIG. 4 is the engineering stress-strain curve measured by compression of the multi-element aluminide reinforced aluminum-based composite material prepared in example 1 of the present invention, and it can be known from FIG. 4 that the yield strength of the aluminum-based composite material is 119.8MPa, while the yield strength of the pure aluminum bar without reinforcement treatment is 30.9MPa, the yield strength is improved by nearly 400%, and a high elongation rate is still maintained.
The Vickers hardness of the multi-element aluminide reinforced aluminum-based composite material prepared in the embodiment 1 is HV49, and the Vickers hardness of pure aluminum is HV25 under the same test condition and environment, so that the hardness is improved by nearly 100%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. A multi-element aluminide reinforced aluminum matrix composite is characterized in that: the composite material consists of a reinforced phase multi-element aluminide and a matrix; the substrate is pure Al or Al alloy; the multi-element aluminide contains Al element, co, cr, fe, ni and Mn;
the preparation method of the multi-element aluminide reinforced aluminum matrix composite material comprises the following operation steps:
(1) Preparing a high-entropy alloy crucible ingot, wherein the height of the inside of the crucible is h mm, the diameter of the inside of the crucible is d mm, the thickness of the crucible is 10-50mm, and the high-entropy alloy crucible ingot is prepared by mixing Co, cr, fe, ni and Mn according to equal atomic ratio;
(2) Placing the high-entropy alloy crucible cast ingot in a muffle furnace for homogenizing annealing, heating to 1000-1200 ℃ at a heating rate of 10 ℃/min, preserving heat for 2-4 hours, cooling to 400 ℃ at a cooling rate of 3 ℃/min after heat preservation, and then cooling to room temperature along with the furnace;
(3) Milling the inner surface of the high-entropy alloy crucible cast ingot by machining, and removing an oxide film on the inner surface, wherein the surface roughness is less than Ra12.5; then cleaning with alcohol and air drying for later use;
(4) Remelting pure Al or Al alloy, casting the pure Al or Al alloy into a graphite crucible with the diameter of (d-2) mm to obtain a pure Al bar or an aluminum alloy bar with the length of more than (h + 3) mm, cleaning the surface of the bar by ultrasonic alcohol, removing surface water vapor, oil stain and an oxide layer, and air-drying for later use;
(5) Putting the bar material obtained in the step (4) into the high-entropy alloy crucible ingot obtained in the step (3), and forcibly pressing the part of the bar material, which is higher than the surface of the high-entropy alloy crucible ingot, into the high-entropy alloy crucible ingot by using a press machine to obtain a tightly-combined high-entropy alloy/pure Al diffusion couple or a high-entropy alloy/aluminum alloy diffusion couple;
(6) Putting the prepared high-entropy alloy/pure Al diffusion couple or high-entropy alloy/aluminum alloy diffusion couple into a heat treatment furnace, heating to 680-700 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2-6 hours; in the heat preservation process, mechanical stirring is applied to promote the synergistic diffusion and the distribution uniformity of multiple elements;
(7) And after the heat preservation stage is finished, removing dross on the surface of the aluminum liquid, casting the aluminum liquid into a steel mould, and air-cooling to room temperature to obtain the multi-element aluminide reinforced aluminum-based composite material.
2. The multi-aluminide reinforced aluminum-based composite material of claim 1, wherein: the high-entropy alloy crucible cast ingot in the step (1) is obtained by machining the high-entropy alloy cast ingot or directly casting the high-entropy alloy crucible cast ingot by a casting method.
3. The multi-aluminide reinforced aluminum-based composite material of claim 1, wherein: and (2) selecting pure raw materials with the purity of more than 99.9wt% for Al, co, cr, fe, ni or Mn used in the preparation process of the high-entropy alloy crucible ingot in the step (1).
4. The multi-aluminide reinforced aluminum-based composite material of claim 1, wherein: the heating of the step (2) is heating to 1000 ℃; the time for heat preservation was 4 hours.
5. The multi-aluminide reinforced aluminum-based composite material of claim 1, wherein: the heating in the step (6) is heating to 680 ℃.
6. The multi-aluminide reinforced aluminum-based composite material of claim 1, wherein: the mechanical stirring is applied in a stirring mode in the conventional metal smelting process, a motor drives a stirring rod, and the other end of the stirring rod is connected with a turbine; the surfaces of the stirring rod and the turbine are coated with zirconia coatings.
7. Use of the multi-aluminide reinforced aluminium-based composite material according to claim 1 in the fields of aerospace and automotive manufacturing.
CN202210592478.2A 2022-05-27 2022-05-27 Multi-element aluminide reinforced aluminum-based composite material and preparation method and application thereof Active CN114934206B (en)

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