A liquid-phase preparation process realizes preparation of graphene-oriented arrangement aluminum matrix composite wire
By using liquid-phase preparation process and hot-pressing sintering technology, the directional arrangement of graphene in aluminum-based composite filaments was achieved, which solved the problem of disordered graphene in existing technologies, improved the electrical and mechanical properties of the material, and reduced the preparation difficulty and cost.
Patent Information
- Application Number
- CN202410983894.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-22
- Publication Date
- 2026-02-10
- Estimated Expiration
- 2044-07-22
AI Technical Summary
Existing technologies make it difficult to achieve directional arrangement of graphene in aluminum-based composite filaments, leading to a decrease in the material's electrical and mechanical properties, and the preparation process is complex.
A liquid-phase preparation process is adopted, in which graphene is uniformly dispersed in aluminum powder by high-energy mechanical ball milling, and AlN interface layer is generated by hot pressing sintering in a mixed atmosphere of ammonia and argon. Graphene/aluminum composite filaments are prepared by combining flat nozzle tubes to achieve the directional alignment of graphene, and then rapidly cooled and shaped in a coolant.
The high-orientation alignment of graphene/aluminum composite filaments was achieved, which improved electrical conductivity and mechanical properties, reduced preparation costs, and provided excellent tensile strength and elongation, making it suitable for large-scale production.
Smart Images
Figure CN118875284B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing graphene-aluminum-based composite filaments. Background Technology
[0002] Metal matrix composite filaments are composite fiber materials composed of a metal matrix and other non-metallic materials. They combine the high strength, heat resistance, and electrical conductivity of metals with the lightweight and corrosion resistance of other materials, resulting in a variety of excellent properties. Graphene, a non-metallic material, possesses extremely high theoretical properties, with tensile strength exceeding 100 GPa and an elastic modulus as high as 1 TPa, attracting widespread attention since its inception. As a novel high-performance reinforcing agent, graphene has a very broad application prospect in the field of composite materials.
[0003] Graphene, with its unique two-dimensional strengthening properties, is frequently used in metal matrix materials to enhance the performance of metal matrix composite filaments. Oriented graphene sheets can significantly improve the electrical and thermal conductivity of composites and increase their strength. However, current mainstream hot-pressing and sintering processes cannot control the arrangement of graphene in graphene / aluminum composites, resulting in random dispersion of graphene within the matrix. This leads to a disordered and unordered arrangement of graphene sheets, resulting in numerous defects and incomplete boundaries in the graphene / aluminum composite. This reduces the incompleteness and discontinuity of electron transport paths, thus affecting the electron transport capacity and reducing the material's electrical conductivity. Furthermore, the disordered arrangement of graphene also leads to poor mechanical properties in graphene / aluminum composites, affecting strength, toughness, and tensile properties, and complicating the fabrication process. Therefore, a fabrication process that enables the oriented arrangement of graphene in graphene / aluminum composite filaments is urgently needed. Summary of the Invention
[0004] To address the problem of disordered graphene arrangement in composite materials and to achieve directional arrangement of graphene in graphene / aluminum composite filaments, this invention proposes a liquid-phase preparation process for preparing aluminum-based composite filaments with directional graphene arrangement.
[0005] The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process of this invention is carried out according to the following steps:
[0006] I. Weighing Materials
[0007] Weigh out 0.5% to 2% of graphene and the remainder of aluminum metal powder as raw materials by mass fraction;
[0008] II. Preparation of graphene / aluminum powder precursors
[0009] The graphene and aluminum metal powder weighed in step one are mixed and added to a ball mill jar for high-energy mechanical ball milling to obtain graphene-aluminum powder. High-energy mechanical ball milling enables graphene to be uniformly dispersed on the surface of aluminum powder and enables strong mechanical bonding between graphene and aluminum metal powder, resulting in a composite material powder with strong physical bonding of graphene and aluminum. The obtained graphene-aluminum powder is separated from the ball milling balls, and then the graphene-aluminum powder is loaded into a steel mold and compacted using a hydraulic press to obtain a graphene / aluminum precursor with oriented graphene.
[0010] III. Sintering of graphene / aluminum precursors under a protective atmosphere
[0011] The graphene / aluminum precursor from step two is placed in an atmosphere furnace, which is then sealed and evacuated. Ammonia or a mixture of ammonia and argon is then introduced into the furnace, and hot pressing sintering is performed to obtain a quasi-oriented graphene / aluminum preform ingot. The ammonia or a mixture of ammonia and argon can form AlN at the graphene-aluminum interface. AlN has a hexagonal structure, which facilitates interlayer slip. The AlN bonded at the graphene-aluminum matrix interface helps coordinate the deformation of graphene and promotes the oriented arrangement of graphene.
[0012] The hot pressing sintering process is as follows: the furnace is heated to 600-650°C at a heating rate of 5-10°C / min, then a pressure of 100-150MPa is applied to the preform and hot pressing is performed for 240-300 minutes. Finally, after the temperature of the atmosphere furnace drops to room temperature, a composite ingot of quasi-oriented graphene / aluminum is obtained.
[0013] The volume fraction of ammonia in the mixed atmosphere of ammonia and argon is 50%. Ammonia and argon can better protect the material and prevent other mixed gases from contaminating the composite material.
[0014] IV. Preparation of directionally arranged graphene / aluminum composite filaments
[0015] The liquid graphene / aluminum composite material obtained by heating the quasi-oriented graphene / aluminum preform ingot prepared in step three is added to a syringe. The nozzle of the syringe is placed in a molding coolant, and the liquid graphene / aluminum composite material is extruded by the syringe and cooled and shaped in the molding coolant to obtain a composite material filament containing highly oriented graphene. The nozzle of the syringe is a flat nozzle or a circular nozzle.
[0016] The solute in the molding coolant is Na2CO3;
[0017] V. Annealing treatment
[0018] The composite filaments containing highly oriented graphene obtained in step four are then annealed. Annealing is used to eliminate residual stress in the filaments after cooling, stabilize the grain size in the composite filaments, reduce deformation and cracking tendency, and improve material properties.
[0019] The invention, its advantageous principles, and its beneficial effects:
[0020] 1. This invention involves densifying and hot-pressing graphene / aluminum precursors in an ammonia-containing atmosphere to obtain quasi-oriented graphene / aluminum preform ingots. Ammonia decomposes at high temperature to release active nitrogen atoms, generating a nano-interface layer of AlN and CN amorphous compounds at the graphene-aluminum interface. AlN, with its hexagonal structure and strong basal-plane slip properties, assists graphene in coordinated deformation during subsequent deformation processes, better aiding in the oriented alignment of graphene. The CN amorphous compounds suppress interfacial reactions, fill voids and defects at the interface, thereby improving the electrical conductivity of the composite material and enabling the preparation of high-quality, highly oriented graphene / aluminum composite filaments.
[0021] 2. This invention utilizes a liquid-phase process to prepare oriented graphene / aluminum composite filaments. The graphene / aluminum composite ingot is melted to a molten liquid state, then loaded into a syringe and extruded to form filaments. The equipment uses a flat spinneret, which can induce the two-dimensional graphene to be extruded parallel along the flat spinneret, so that the graphene sheets will be regularly and uniformly oriented, thereby improving the orientation degree of the graphene sheets.
[0022] 3. The preparation of the composite material filament of the present invention does not require large plastic deformation treatment. The manufacturing equipment used is simple, convenient, and low in cost, which can realize the low-cost manufacturing of graphene / aluminum composite material filament.
[0023] 4. In the extrusion process of the graphene / aluminum composite filament prepared by this invention, the syringe nozzle is immersed in a cold cooling liquid, which rapidly cools the graphene / aluminum composite material, achieving a quenching effect. This inhibits the growth of aluminum grains during slow cooling, realizes the fine grain strengthening of the matrix in the composite material, and further enhances the mechanical properties of the graphene / aluminum composite filament.
[0024] 5. In this invention, a 5% Na2CO3 molding coolant is used to rapidly cool the graphene / aluminum molten filament extruded from the syringe nozzle, thereby achieving material shaping. The solvent of the molding coolant has a large specific heat capacity and does not react with molten aluminum, which can achieve safe and efficient cooling of the aluminum filament. At the same time, the Na2CO3 solution is alkaline, and the alkaline substances in it can chemically react with the aluminum on the surface of the composite material, thereby forming a corrosion-resistant passivation film on the surface of the filament, which improves the corrosion resistance of the composite filament.
[0025] 6. The composite filaments prepared by this invention have excellent properties, with tensile strength reaching 550-700 MPa and elongation reaching 13%-16%; the process is stable, the equipment is simple, there is no pollution, and large-scale production can be achieved. Attached Figure Description
[0026] Figure 1 This is a schematic diagram of the syringe structure;
[0027] Figure 2 This is a schematic diagram of the flat nozzle tube of a syringe;
[0028] Figure 3 This is a schematic diagram of the circular nozzle tube of a syringe;
[0029] Figure 4 Metallographic image of the composite material filament prepared in Example 1 at 100x magnification;
[0030] Figure 5 XRD pattern of the composite filament prepared in Example 1;
[0031] Figure 6 Macroscopic photograph of the composite filaments prepared in Example 1;
[0032] Figure 7 Macroscopic photograph of the composite filaments prepared in Example 2. Detailed Implementation
[0033] The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any reasonable combination of the specific embodiments.
[0034] Specific Implementation Method 1: The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process in this implementation method is carried out according to the following steps:
[0035] I. Weighing Materials
[0036] Weigh out 0.5% to 2% of graphene and the remainder of aluminum metal powder as raw materials by mass fraction;
[0037] II. Preparation of graphene / aluminum powder precursors
[0038] The graphene and aluminum metal powder weighed in step one are mixed and added to a ball mill jar for high-energy mechanical ball milling to obtain graphene-aluminum powder; the obtained graphene-aluminum powder is separated from the ball milling balls, and then the graphene-aluminum powder is loaded into a steel mold and compacted using a hydraulic press to obtain a graphene / aluminum precursor with oriented graphene.
[0039] III. Sintering of graphene / aluminum precursors under a protective atmosphere
[0040] The graphene / aluminum precursor from step two is placed in an atmosphere furnace, the atmosphere furnace is sealed and evacuated, and then ammonia or a mixture of ammonia and argon is introduced into the atmosphere furnace for hot pressing sintering to obtain a quasi-oriented graphene / aluminum preform ingot.
[0041] The hot pressing sintering process is as follows: the furnace is heated to 600-650°C at a heating rate of 5-10°C / min, then a pressure of 100-150MPa is applied to the preform and hot pressing is performed for 240-300 minutes. Finally, after the temperature of the atmosphere furnace drops to room temperature, a composite ingot of quasi-oriented graphene / aluminum is obtained.
[0042] The volume fraction of ammonia in the mixed atmosphere of ammonia and argon is 50%.
[0043] IV. Preparation of directionally arranged graphene / aluminum composite filaments
[0044] The liquid graphene / aluminum composite material obtained by heating the quasi-oriented graphene / aluminum preform ingot prepared in step three is added to a syringe. The nozzle of the syringe is placed in a molding coolant, and the liquid graphene / aluminum composite material is extruded by the syringe and cooled and shaped in the molding coolant to obtain a composite material filament containing highly oriented graphene. The nozzle of the syringe is a flat nozzle or a circular nozzle.
[0045] The solute in the molding coolant is Na2CO3;
[0046] V. Annealing treatment
[0047] The composite filament containing highly oriented graphene obtained in step four is annealed.
[0048] This embodiment has the following beneficial effects:
[0049] 1. In this embodiment, a graphene / aluminum precursor is densified by hot-pressing sintering in an ammonia-containing atmosphere to obtain a quasi-oriented graphene / aluminum preform ingot. The ammonia decomposes at high temperature to release active N atoms, generating a nano-interface layer of AlN and CN amorphous compounds at the graphene-aluminum interface. AlN has a hexagonal structure and strong basal plane slip properties, which can assist graphene in coordinated deformation during subsequent deformation and better assist graphene in orientation. CN amorphous compounds can suppress interfacial reactions and fill voids and defects at the interface, thereby improving the electrical conductivity of the composite material and realizing the preparation of high-quality, highly oriented graphene / aluminum composite filaments.
[0050] 2. In this embodiment, a liquid-phase process is used to prepare oriented graphene / aluminum composite filaments. The graphene / aluminum composite ingot is melted to a molten liquid state and then loaded into a syringe to be extruded to form filaments. The equipment uses a flat spinneret, which can induce the two-dimensional graphene to be extruded parallel along the flat spinneret, so that the graphene sheets will be regularly and uniformly oriented, thereby improving the orientation degree of the graphene sheets.
[0051] 3. The preparation of composite filaments in this embodiment does not require large plastic deformation treatment. The manufacturing equipment used is simple, convenient, and low-cost, enabling low-cost manufacturing of graphene / aluminum composite filaments.
[0052] 4. In this embodiment, the graphene / aluminum composite filament is prepared by immersing the syringe nozzle in a cold coolant during the extrusion process, which rapidly cools the graphene / aluminum composite material and achieves a quenching effect. This inhibits the growth of aluminum grains during slow cooling, realizes fine grain strengthening of the matrix in the composite material, and further enhances the mechanical properties of the graphene / aluminum composite filament.
[0053] 5. In this embodiment, a 5% Na2CO3 molding coolant is used to rapidly cool the graphene / aluminum molten filament extruded from the syringe nozzle to achieve material shaping. The solvent of the molding coolant has a large specific heat capacity and does not react with molten aluminum, which can achieve safe and efficient cooling of the aluminum filament. At the same time, the Na2CO3 solution is alkaline, and the alkaline substances in it can chemically react with the aluminum on the surface of the composite material, thereby forming a corrosion-resistant passivation film on the surface of the filament, which improves the corrosion resistance of the composite filament.
[0054] 6. The composite filaments prepared in this embodiment have excellent properties, with tensile strength reaching 550-700 MPa and elongation reaching 13%-16%; the process is stable, the equipment is simple, there is no pollution, and large-scale production can be achieved.
[0055] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the aluminum metal powder mentioned in step one is one or a combination of several of the following: Al-Si alloy, Al-Si-Cu alloy, Al-Mg-Si alloy, Al-Cu-Mg alloy, Al-Zn-Cu alloy, Al-Zn-Mg-Cu alloy, and Al-Si-Cu-Mg alloy.
[0056] The mass fraction of Si in Al-Si alloys is 2% to 25%;
[0057] In Al-Mg-Si alloys, the mass fraction of Si is 0.5% to 25%, and the mass fraction of Mg is 0.5% to 50%.
[0058] In Al-Si-Cu alloys, the mass fraction of Si is 0.5% to 25%, and the mass fraction of Cu is 0.5% to 53%.
[0059] In Al-Cu-Mg alloys, the mass fraction of Cu is 0.5%–53%, and the mass fraction of Mg is 0.5%–38%.
[0060] In Al-Zn-Cu alloys, the mass fraction of Zn is 0.5%–55%, and the mass fraction of Cu is 0.5%–53%.
[0061] In Al-Zn-Mg-Cu alloys, the mass fraction of Zn is 0.5%–55%, the mass fraction of Mg is 0.5%–38%, and the mass fraction of Cu is 0.5%–53%.
[0062] In Al-Si-Cu-Mg alloys, the mass fraction of Si is 0.5%–25%, the mass fraction of Cu is 0.5%–53%, and the mass fraction of Mg is 0.5%–38%.
[0063] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 1 or 2 in that the compaction process described in step 2 is as follows: apply a longitudinal pressure of 60-80KN and hold the pressure for 10-20 minutes.
[0064] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that: the ball-to-material ratio in the high-energy mechanical ball milling process described in step two is (8-15):1; the ball milling speed is 200-300 r / min; and the ball milling time is 4-6 h. A larger ball-to-material ratio can make the graphene distribution more uniform.
[0065] Specific Implementation Method 5: This implementation method differs from Specific Implementation Methods 1 to 4 in that the graphene described in step 2 is few-layer graphene with an average sheet diameter of 150nm to 25μm and an average thickness of 0.5 to 25nm.
[0066] Specific Implementation Method Six: This implementation method differs from one of Specific Implementation Methods One to Five in that the solvent in the molding coolant described in step four is diesel oil or a mixed solvent obtained by mixing alkanes, cycloalkanes and aromatics in any proportion.
[0067] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that: the number of carbon atoms in the alkanes, cycloalkanes, or aromatics in the mixed solvent described in step four is 9 to 18; the number of carbon atoms in the alkanes, cycloalkanes, or aromatics contained in the diesel fuel is 9 to 18.
[0068] Specific Implementation Method Eight: This implementation method differs from one of Specific Implementation Methods One to Seven in that the mass fraction of Na2CO3 in the molding coolant described in step four is 2-5%.
[0069] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that the heating temperature of the quasi-oriented graphene / aluminum preform ingot in step four is 700-800℃.
[0070] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One to Nine in that: the syringe described in step four consists of a syringe tube (1), a piston (2), a nozzle tube (3), and septa (4); the piston (2) is located inside the syringe tube (1), and the nozzle tube (3) is located at the lower end of the syringe tube (1); the nozzle tube (3) is a flat nozzle tube or a circular nozzle tube, and multiple parallel septa (4) are provided inside the circular nozzle tube to divide the circular nozzle tube into multiple flat small nozzles. This can improve the efficiency of filament formation and reduce the process requirements for the syringe equipment;
[0071] Specific Implementation Method Eleven: This implementation method differs from Specific Implementation Methods One through Ten in that the annealing process described in step five is: holding at 300°C for 1 hour, followed by furnace cooling.
[0072] Example 1:
[0073] The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process in this embodiment is carried out according to the following steps:
[0074] I. Weighing Materials
[0075] Weigh out 1% graphene and the remainder 6061 aluminum metal powder by mass fraction as raw materials.
[0076] II. Preparation of graphene / aluminum powder precursors
[0077] The graphene and aluminum metal powder weighed in step one are mixed and added to a ball mill jar for high-energy mechanical ball milling to obtain graphene-aluminum powder; the obtained graphene-aluminum powder is separated from the ball milling balls, and then the graphene-aluminum powder is loaded into a steel mold and compacted using a hydraulic press to obtain a graphene / aluminum precursor with oriented graphene.
[0078] The compaction process is as follows: apply a longitudinal pressure of 70KN and hold the pressure for 20 minutes;
[0079] The ball-to-material ratio in the high-energy mechanical ball milling process is 10:1; the ball milling speed is 200 r / min and the ball milling time is 6 h; the ball milling process adopts forward rotation-stop-reverse rotation-stop, with forward or reverse rotation time of 10 min and stop time of 20 min;
[0080] The graphene is few-layer graphene with an average sheet diameter of 5 μm and an average thickness of 5 nm.
[0081] III. Sintering of graphene / aluminum precursors under a protective atmosphere
[0082] The graphene / aluminum precursor from step two is placed in an atmosphere furnace, the atmosphere furnace is sealed and evacuated, and then ammonia is introduced into the atmosphere furnace for hot pressing sintering to obtain a quasi-oriented graphene / aluminum preform ingot.
[0083] The hot pressing sintering process is as follows: the furnace is heated to 650°C at a heating rate of 10°C / min, then a pressure of 100MPa is applied to the preform and hot pressing is performed for 300 minutes. Finally, after the temperature of the atmosphere furnace drops to room temperature, a composite ingot of quasi-oriented graphene / aluminum is obtained.
[0084] IV. Preparation of directionally arranged graphene / aluminum composite filaments
[0085] The liquid graphene / aluminum composite material obtained by heating the quasi-oriented graphene / aluminum preform ingot prepared in step three is added to a syringe. The nozzle of the syringe is placed in the molding coolant. The liquid graphene / aluminum composite material is extruded by the syringe and cooled and shaped in the molding coolant to obtain a composite material filament containing highly oriented graphene.
[0086] The solute in the molding coolant is Na2CO3, and the solvent is diesel oil; the mass fraction of the molding coolant is 3%.
[0087] The number of carbon atoms in the alkanes, cycloalkanes or aromatics contained in the diesel fuel is 9 to 18.
[0088] The heating temperature of the quasi-oriented graphene / aluminum preform ingot is 750°C;
[0089] The nozzle of the syringe is a flat nozzle.
[0090] The syringe consists of a syringe tube (1), a piston (2), a nozzle tube (3), and a partition (4); the piston (2) is located inside the syringe tube (1), and the nozzle tube (3) is located at the lower end of the syringe tube (1); the nozzle tube (3) is a flat nozzle tube.
[0091] V. Annealing treatment
[0092] The composite filament containing highly oriented graphene obtained in step four is subjected to annealing treatment; the annealing process is as follows: heat treatment at 300℃ for 1 hour, followed by furnace cooling.
[0093] Figure 4 Metallographic image of the composite material filament prepared in Example 1 at 100x magnification. Figure 1 It can be seen that the graphene in the material is oriented and has a dense structure; Figure 5XRD pattern of the composite filament prepared in Example 1. Figure 5 An AlN interface layer can be seen formed at the interface. The graphene-aluminum composite fiber with oriented graphene arrangement prepared in this embodiment has a tensile strength of 577 MPa and an elongation of 14.1%, and the fiber material exhibits good corrosion resistance; the composite fiber as a whole exhibits good performance.
[0094] Example 2
[0095] The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process in this embodiment is carried out according to the following steps:
[0096] I. Weighing Materials
[0097] Weigh out 2% graphene and the remainder 6061 aluminum metal powder by mass fraction as raw materials.
[0098] II. Preparation of graphene / aluminum powder precursors
[0099] The graphene and aluminum metal powder weighed in step one are mixed and added to a ball mill jar for high-energy mechanical ball milling to obtain graphene-aluminum powder; the obtained graphene-aluminum powder is separated from the ball milling balls, and then the graphene-aluminum powder is loaded into a steel mold and compacted using a hydraulic press to obtain a graphene / aluminum precursor with oriented graphene.
[0100] The compaction process is as follows: apply a longitudinal pressure of 75KN and hold the pressure for 15 minutes;
[0101] The ball-to-material ratio in the high-energy mechanical ball milling process is 15:1; the ball milling speed is 300 r / min and the ball milling time is 4 h; the ball milling process adopts forward rotation-stop-reverse rotation-stop, with forward or reverse rotation time of 15 min and stop time of 15 min;
[0102] The graphene is few-layer graphene with an average sheet diameter of 5 μm and an average thickness of 5 nm.
[0103] III. Sintering of graphene / aluminum precursors under a protective atmosphere
[0104] The graphene / aluminum precursor from step two is placed in an atmosphere furnace, the atmosphere furnace is sealed and evacuated, and then a mixed atmosphere of ammonia and argon is introduced into the atmosphere furnace for hot pressing sintering to obtain a quasi-oriented graphene / aluminum preform ingot.
[0105] The volume fraction of ammonia in the mixed atmosphere of ammonia and argon is 50%.
[0106] The hot pressing sintering process is as follows: the furnace is heated to 600°C at a heating rate of 5°C / min, then a pressure of 150MPa is applied to the preform and hot pressing is performed for 300 minutes. Finally, after the temperature of the atmosphere furnace drops to room temperature, a composite ingot of quasi-oriented graphene / aluminum is obtained.
[0107] IV. Preparation of directionally arranged graphene / aluminum composite filaments
[0108] The liquid graphene / aluminum composite material obtained by heating the quasi-oriented graphene / aluminum preform ingot prepared in step three is added to a syringe. The nozzle of the syringe is placed in the molding coolant. The liquid graphene / aluminum composite material is extruded by the syringe and cooled and shaped in the molding coolant to obtain a composite material filament containing highly oriented graphene.
[0109] The solute in the molding coolant is Na2CO3, and the solvent is diesel oil; the mass fraction of the molding coolant is 3%.
[0110] The number of carbon atoms in the alkanes, cycloalkanes or aromatics contained in the diesel fuel is 9 to 18.
[0111] The heating temperature of the quasi-oriented graphene / aluminum preform ingot is 700°C;
[0112] The nozzle of the syringe is a flat nozzle.
[0113] The syringe consists of a syringe tube (1), a piston (2), a nozzle tube (3), and a partition (4); the piston (2) is located inside the syringe tube (1), and the nozzle tube (3) is located at the lower end of the syringe tube (1); the nozzle tube (3) is a flat nozzle tube.
[0114] V. Annealing treatment
[0115] The composite filament containing highly oriented graphene obtained in step four is subjected to annealing treatment; the annealing process is as follows: heat treatment at 300℃ for 1 hour, followed by furnace cooling.
[0116] The graphene-aluminum composite fiber with oriented graphene arrangement prepared in this embodiment has a tensile strength of 618 MPa and an elongation of 13.6%; the composite fiber exhibits good tensile properties and elongation.
Claims
1. A method for preparing aluminum-based composite filaments with oriented graphene arrangement using a liquid-phase preparation process, characterized in that: The method for preparing aluminum-based composite filaments with oriented graphene arrangement using a liquid-phase preparation process is carried out according to the following steps: I. Weighing Materials Weigh out 0.5% to 2% of graphene and the remainder of aluminum metal powder as raw materials by mass fraction; II. Preparation of graphene / aluminum powder precursors The graphene and aluminum metal powder weighed in step one are mixed and added to a ball mill jar for high-energy mechanical ball milling to obtain graphene-aluminum powder; the obtained graphene-aluminum powder is separated from the ball milling balls, and then the graphene-aluminum powder is loaded into a steel mold and compacted using a hydraulic press to obtain a graphene / aluminum precursor with oriented graphene. III. Sintering of graphene / aluminum precursors under a protective atmosphere The graphene / aluminum precursor from step two is placed in an atmosphere furnace, the atmosphere furnace is sealed and evacuated, and then ammonia or a mixture of ammonia and argon is introduced into the atmosphere furnace for hot pressing sintering to obtain a quasi-oriented graphene / aluminum preform ingot. The hot pressing sintering process is as follows: the furnace is heated to 600-650°C at a heating rate of 5-10°C / min, then a pressure of 100-150MPa is applied to the preform and hot pressing is performed for 240-300 minutes. Finally, after the temperature of the atmosphere furnace drops to room temperature, a composite ingot of quasi-oriented graphene / aluminum is obtained. The volume fraction of ammonia in the mixed atmosphere of ammonia and argon is 50%. IV. Preparation of directionally arranged graphene / aluminum composite filaments The liquid graphene / aluminum composite material obtained by heating the quasi-oriented graphene / aluminum preform ingot prepared in step three is added to a syringe. The nozzle of the syringe is placed in a molding coolant, and the liquid graphene / aluminum composite material is extruded by the syringe and cooled and shaped in the molding coolant to obtain a composite material filament containing highly oriented graphene. The nozzle of the syringe is a flat nozzle or a circular nozzle. The solute in the molding coolant is Na2CO3; The mass fraction of Na2CO3 in the molding coolant is 2-5%; V. Annealing treatment The composite filament containing highly oriented graphene obtained in step four is annealed.
2. The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process according to claim 1, characterized in that: The aluminum metal powder mentioned in step one is one or a combination of several of the following: Al-Si alloy, Al-Si-Cu alloy, Al-Mg-Si alloy, Al-Cu-Mg alloy, Al-Zn-Cu alloy, Al-Zn-Mg-Cu alloy, and Al-Si-Cu-Mg alloy. The mass fraction of Si in Al-Si alloys is 2% to 25%; In Al-Mg-Si alloys, the mass fraction of Si is 0.5%~25%, and the mass fraction of Mg is 0.5%~50%. In Al-Si-Cu alloys, the mass fraction of Si is 0.5%~25%, and the mass fraction of Cu is 0.5%~53%. In Al-Cu-Mg alloys, the mass fraction of Cu is 0.5%~53%, and the mass fraction of Mg is 0.5%~38%. In Al-Zn-Cu alloys, the mass fraction of Zn is 0.5%~55%, and the mass fraction of Cu is 0.5%~53%. In Al-Zn-Mg-Cu alloys, the mass fraction of Zn is 0.5%~55%, the mass fraction of Mg is 0.5%~38%, and the mass fraction of Cu is 0.5%~53%. In Al-Si-Cu-Mg alloys, the mass fraction of Si is 0.5%~25%, the mass fraction of Cu is 0.5%~53%, and the mass fraction of Mg is 0.5%~38%.
3. The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process according to claim 1, characterized in that: The compaction process described in step two is as follows: apply a longitudinal pressure of 60~80KN and hold the pressure for 10~20 minutes.
4. The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process according to claim 1, characterized in that: In step two, the ball-to-material ratio in the high-energy mechanical ball milling process is (8~15):1; the ball milling speed is 200~300 r / min, and the ball milling time is 4~6 h.
5. The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process according to claim 1, characterized in that: The graphene described in step two is few-layer graphene with an average sheet diameter of 150 nm to 25 μm and an average thickness of 0.5 to 25 nm.
6. The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process according to claim 1, characterized in that: The solvent in the molding coolant described in step four is diesel oil or a mixed solvent obtained by mixing alkanes, cycloalkanes and aromatics in any proportion.
7. The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process according to claim 1, characterized in that: The alkanes, cycloalkanes, or aromatics in the mixed solvent described in step four all have 9 to 18 carbon atoms; the alkanes, cycloalkanes, or aromatics in the diesel fuel all have 9 to 18 carbon atoms.
8. The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process according to claim 1, characterized in that: The heating temperature of the quasi-oriented graphene / aluminum preform ingot in step four is 700~800℃.
9. The method for preparing aluminum-based composite filaments with oriented graphene arrangement using the liquid-phase preparation process according to claim 1, characterized in that: The syringe described in step four consists of a syringe tube (1), a piston (2), a nozzle tube (3), and a diaphragm (4); The piston (2) is located inside the injector tube (1), and the nozzle tube (3) is located at the lower end of the syringe tube (1). The nozzle tube (3) is a flat nozzle tube or a circular nozzle tube. The circular nozzle tube is provided with multiple parallel partitions (4) to divide the circular nozzle tube into multiple flat small nozzles.
Citation Information
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