WO2022057232A1 - Graphene-reinforced magnesium-based composite material, preparation method for same, and applications thereof - Google Patents

Graphene-reinforced magnesium-based composite material, preparation method for same, and applications thereof Download PDF

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WO2022057232A1
WO2022057232A1 PCT/CN2021/083342 CN2021083342W WO2022057232A1 WO 2022057232 A1 WO2022057232 A1 WO 2022057232A1 CN 2021083342 W CN2021083342 W CN 2021083342W WO 2022057232 A1 WO2022057232 A1 WO 2022057232A1
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graphene
composite material
magnesium
based composite
reinforced magnesium
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PCT/CN2021/083342
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French (fr)
Chinese (zh)
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张素卿
于欢
孙翠翠
马百常
吴建华
周吉学
王西涛
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山东省科学院新材料研究所
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    • 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
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/007—Semi-solid pressure die casting
    • 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
    • C22C1/1073—Infiltration or casting under mechanical pressure, e.g. squeeze casting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • 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
    • C22C32/0084—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 carbon or graphite as the main non-metallic constituent

Definitions

  • the invention belongs to the technical field of graphene-reinforced magnesium-based composite materials, and in particular relates to a graphene-reinforced magnesium-based composite material and a preparation method and application thereof.
  • Magnesium alloys have low density, high specific strength ratio stiffness, and excellent damping performance. They have been used in automobiles, rail transit, aerospace and other fields, and are important structural materials for achieving lightweight. However, magnesium alloys have low strength properties and poor plasticity, which limit the application of magnesium alloys. Improving its strength and shaping is a necessary way to expand the application field of magnesium alloys.
  • the purpose of the present invention is to provide a graphene-reinforced magnesium-based composite material and a preparation method and application thereof.
  • the technical scheme of the present invention is:
  • a preparation method of graphene reinforced magnesium-based composite material, the concrete steps are:
  • the obtained suspension is spray-dried to obtain dry powder;
  • the obtained dry powder is subjected to a molding process to obtain a block blank
  • the block blank is hot-extruded to obtain a graphene-magnesium-based composite material preform
  • the composite material preform and the magnesium alloy billet are melted and mixed, and the graphene-reinforced magnesium-based composite material is obtained by casting;
  • the casting billet is kept at a semi-solid temperature, followed by die casting and extrusion casting to obtain composite parts.
  • the effect of mixing the reinforcing body, the magnesium matrix and the liquid compatibilizer is to use the shear force generated by mechanical stirring to promote the further dispersion of the graphene powder to obtain a suspension of the magnesium matrix and the graphene;
  • the powder cold briquette is hot extruded, and the hot extruded bar is added to the magnesium alloy melt, and the self-stabilizing effect of nanoparticles in the melt is used to obtain a uniformly dispersed composite material melt, and the composite material cast is obtained after casting. blank;
  • the casting billet is subjected to semi-solid heat preservation.
  • the purpose of semi-solid heat preservation is to control the composition ratio of solid and liquid phases and the interface structure of graphene/magnesium matrix, and then the semi-solid billet is subjected to die casting or extrusion casting to obtain magnesium matrix composite parts.
  • the mixing ratio of the magnesium matrix and the reinforcing body is: the mass fraction of the reinforcing body is 0.1-5%; preferably, it is 5%, and the balance is the magnesium matrix.
  • the reinforcing body is graphene or graphene oxide with an average thickness of 1-30 nm and an average sheet diameter of 100 nm-100 ⁇ m.
  • the magnesium matrix is pure magnesium powder or magnesium alloy powder, and the average particle size is 1-100 ⁇ m.
  • the ratio of the mass of the liquid compatibilizer to the sum of the mass of the magnesium matrix and the reinforcement is 1-3:1; preferably 2:1.
  • the liquid compatibilizer includes at least one of water, absolute ethanol, and acetone.
  • the liquid compatibilizer is water
  • mechanical stirring is performed for mixing, and the atmosphere in which the mechanical stirring is located is air.
  • the atmosphere in which the mechanical stirring is located is an inert gas.
  • the speed of mechanical stirring is 200-10000r/min, and the stirring time is 0.5-20h.
  • Mechanical stirring and liquid compatibilizer are used to achieve the mixing of magnesium matrix and reinforcement, and the shear force generated by mechanical stirring is used to realize the dispersion of agglomerated graphene and the spreading of wrinkled graphene to obtain a dispersed suspension.
  • the spray drying method is as follows: using a spray dryer, under the condition of high pressure hot air, an electrostatic spray gun sprays the suspension to obtain dry powder.
  • the stirring speed of the suspension in the feeding tank of the spray dryer is 100rpm-1000rpm; preferably 700-900rpm;
  • the output voltage of the electrostatic spray gun is 10-85kv; preferably 60-70kv.
  • the parameters of spray drying affect the particle size, uniformity, and yield of the resulting dried powder.
  • the yield of dry powder reached 97.9%.
  • the mass content of graphene in the graphene-reinforced magnesium-based composite material is 0.1-5%; preferably 0.5-2.5%.
  • the forming treatment method of the blank is cold pressing; the preferred cold pressing conditions are: at room temperature, the pressure is 100-300MPa, and the pressure holding time is 4-6min; preferably, the pressure is 200MPa, the holding time is 5min.
  • the conditions of cold pressing are helpful for the mixing of graphene and magnesium matrix, graphene is dispersed evenly, agglomeration is avoided, it is beneficial to the metallurgical bonding of graphene and magnesium matrix, and the bonding strength is higher.
  • the inert gas in the melt mixing of the billet is a mixed gas of SF 6 +CO 2 .
  • the magnesium alloy billet and the bulk billet are melted and then mechanically stirred, the mechanical stirring rate is 10 rpm to 100 rpm, and the mechanical stirring time is 5 min to 60 min.
  • the casting temperature is 700-750°C; preferably 720°C.
  • a spray drying device comprising a drying tower, a power supply, and a collection device, the positive electrode or the negative electrode of the power supply is respectively connected to the drying tower and the collection device through wires, one end of the two wires is respectively connected to a conductive sheet, and the two conductive sheets are respectively connected. It is located at the top of the drying tower and in the collecting device. The bottom of the drying tower is provided with a discharge port, and the collecting device is located below the drying tower and is opposite to the discharge port.
  • the present invention also includes a feed pipe, the feed pipe is connected to the high-pressure fan, agitator, and heater in sequence, the heater is located at one end close to the drying tower, and one end of the feed pipe extends into the drying tower, and extends into the drying tower. The bottom of the end is provided with a high-pressure nozzle.
  • the power source is a DC power source.
  • a graphene-reinforced magnesium-based composite material obtained by the above-mentioned preparation method of a graphene-reinforced magnesium-based composite material.
  • the mass fraction of graphene is 0.1%-5%, and further preferably, the mass fraction of graphene is 0.5-2.5%. Within this range, graphene has better fine-grain strengthening and dispersion strengthening.
  • a component includes the above-mentioned graphene-reinforced magnesium-based composite material.
  • the preparation method of the above-mentioned parts is, the graphene-reinforced magnesium-based composite material is subjected to semi-solid heat preservation to obtain a semi-solid blank of the composite material, and then the graphene-reinforced magnesium-based composite material is die-casted to obtain zero. part.
  • the casting billet is subjected to semi-solid heat preservation.
  • the purpose of semi-solid heat preservation is to control the composition ratio of solid and liquid phases and the interface structure of graphene/magnesium matrix, and then the semi-solid billet is subjected to die casting or extrusion casting to obtain magnesium matrix composite parts.
  • the temperature of the semi-solid heat preservation is 595 to 615° C.
  • the time of the heat preservation is 30 to 120 minutes.
  • the die-casting conditions are as follows: the injection speed is 1-7 m/s, the injection specific pressure is 30-200 MPa, and the pressure holding time is 20-50 s.
  • the microstructure distribution of the obtained semi-solid material is uniform and refined.
  • the present invention adopts a low-cost process to efficiently prepare graphene nano-particle-reinforced magnesium-based composite materials, realizes the dispersion and spreading of agglomerated, wrinkled industrial-grade graphene materials by mechanical stirring, and adopts the mode of cold-pressed preform to introduce graphene into In the molten magnesium alloy, the self-stabilization effect of graphene nanoparticles can effectively solve the phenomenon of graphene oxidation and agglomeration in the casting process.
  • the process is simple, requires low equipment, low processing costs, high production efficiency, and has excellent Prospects for industrial application.
  • the suspension of graphene and magnesium matrix powder is spray-dried to avoid a long drying process; the spray method uses direct current to avoid agglomeration during the drying process.
  • the preparation efficiency is improved; compared with vacuum drying, freeze drying, and supercritical drying, the equipment cost is reduced.
  • the semi-solid heat preservation treatment of the as-cast billet realizes the controllability of the interface structure, composition, particle size and morphology of the primary phase, and the ratio of solid and liquid phases.
  • the semi-solid billet is thixoformed by techniques such as die casting and squeeze casting.
  • Fig. 1 is the metallographic diagram of the composite material obtained with different graphene contents in Example 1-Example 3 and Comparative Example 1; wherein a is Comparative Example 1, b is Example 2, c is Example 1, and d is an example 3;
  • Figure 2 shows the interface of the composite material obtained in Example 1-Example 3 and Comparative Example 1; wherein a is Comparative Example 1, b is Example 2, c is Example 1, and d is Example 3;
  • Example 3 is a graph of the hardness evolution of composite materials obtained with different graphene contents in Example 1-Example 3 and Comparative Example 1.
  • FIG. 4 is a transmission electron microscope image of the interface of the composite material in Example 1.
  • FIG. 4 is a transmission electron microscope image of the interface of the composite material in Example 1.
  • FIG. 5 is the microstructure of the composite material after the semi-solid heat preservation water quenching treatment of Example 4.
  • FIG. 6 is a water quenching structure diagram of the semi-solid billet of Example 4.
  • FIG. 7 is a structural diagram of a spray drying apparatus.
  • a kind of high-efficiency preparation method of graphene nano-particle reinforced magnesium-based composite material comprising the following steps:
  • step (2) the powder taken in step (1) is prepared into a suspension by mechanical stirring and a liquid compatibilizer respectively, and the specific steps are as follows: each group of powders is loaded into a mechanical mixer, and 500g of dehydrated alcohol is added in the air. Mechanical stirring is carried out in the environment, the stirring speed is 8000 r/min, and the mechanical stirring time is 3-60 min, and a suspension liquid is obtained after completion.
  • step (3) the suspension obtained in step (2) is prepared into dry composite powder by electrostatic spray drying method, the details are as follows: the suspension is placed in the feeding tank of the spray dryer, and the stirring speed in the feeding tank is At 800rpm, the suspension is sprayed from the electrostatic spray gun under the action of high-pressure hot air, and the output voltage of the electrostatic spray gun is 60kv, and finally the composite material powder after uniform mixing of the reinforcement and the matrix is obtained. After testing: the yields of the above powders were 97.9% respectively.
  • step (3) (4) adding the composite material powder obtained in step (3) into a self-made mold for cold pressing, the diameter of the cold preform is 50 mm, and the pressing and forming conditions are: room temperature, pressure 200 MPa, and pressure holding time 5 min.
  • the mass content of graphene in step (5) is 0.5%.
  • the mass content of graphene in step (5) is 2.5%.
  • Example 1 Compared with Example 1, the mass content of graphene in step (5) is 0%. That is, compared with Example 1, no enhancer was added in step (1). Other processing steps are the same as in Example 1.
  • Example 1 The specific compositions of Example 1, Example 2, Example 3 and Comparative Example 1 are shown in Table 1, and the graphene mass contents of the four groups of materials are 0, 0.5%, 1.5%, and 2.5%, respectively.
  • Example 1-Example 3 and Comparative Example 1 The four groups of graphene nanoparticle-reinforced magnesium-based composite materials prepared in Example 1-Example 3 and Comparative Example 1 were subjected to T4 solid solution, and the grain size was detected.
  • the specific parameters are as follows: solution treatment at 435°C for 2h.
  • the microstructure of the composite material after solution treatment was observed by the above-mentioned metallographic microscope, and the results are respectively shown in a to d in FIG. 2 . It can be seen from the pictures b to d in Figure 2 that the introduction of graphene can significantly refine the grain size of the AZ91 magnesium alloy matrix, and the magnesium grain size is refined from ⁇ 176 ⁇ m (graphene content 0%) to ⁇ 32 ⁇ m ( Graphene content 1.5 wt.%).
  • the hardness of the composites after solution treatment was tested by XHV-1000 microhardness tester, and the results are shown in Figure 3.
  • the addition of graphene can significantly improve the hardness of the composite material, and the material hardness increases from ⁇ 66HV (graphene content 0%) to ⁇ 89HV (graphene content 1.5wt.%), an increase of 35%, It is mainly attributable to the fine-grain strengthening and dispersion strengthening brought about by the introduction of graphene.
  • a method for regulating and controlling the interface of a graphene nanoparticle reinforced magnesium-based composite material comprising the following steps:
  • step (2) the powder taken in step (1) is prepared into a suspension by mechanical stirring and a liquid compatibilizer respectively, and the specific steps are as follows: each group of powders is loaded into a mechanical mixer, and 500g of dehydrated alcohol is added in the air. Mechanical stirring is carried out in the environment, the stirring speed is 8000r/min, and the mechanical stirring time is 1.0h, and a suspension liquid is obtained after completion.
  • step (3) the suspension obtained in step (2) is prepared into dry composite powder by electrostatic spray drying method, the details are as follows: the suspension is placed in the feeding tank of the spray dryer, and the stirring speed in the feeding tank is At 800rpm, the suspension is sprayed from the electrostatic spray gun under the action of high-pressure hot air, and the output voltage of the electrostatic spray gun is 60kv, and finally the composite material powder after uniform mixing of the reinforcement and the matrix is obtained. After testing: the yields of the above powders were 97.9% respectively.
  • step (3) (4) adding the composite material powder obtained in step (3) into a self-made mold for cold pressing, the diameter of the cold preform is 50 mm, and the pressing and forming conditions are: room temperature, pressure 200 MPa, and pressure holding time 5 min.
  • step (6) Semi-solid heat preservation is performed on the as-cast composite material obtained in step (5), the specific parameters are: 595-615° C., and the heat preservation time is 30-120 minutes. That is, the composite material semi-solid billet is obtained.
  • the main purpose of this step is to control the ratio of solid to liquid phase, the morphology and size of primary phase particles, and the interface structure of the composite material.
  • the above-mentioned metallographic microscope was used to observe the microstructure of the composite material after the semi-solid heat preservation water quenching treatment, and the results are shown in Figures a to d in FIG.
  • step (6) Transfer the semi-solid billet obtained in step (6) into a die-casting mold for die-casting.
  • the specific parameters are: injection speed 1-7m/s, injection specific pressure 30-200MPa, pressure holding time 20-50s. That is, the composite material semi-solid die-casting parts are obtained.
  • EDS was used to analyze the composition of the water quenched sample in step (6), and the results are shown in Table 2. It can be seen from Figures a and b in Figure 5 and Table 2 that by adjusting the process parameters of step (6), the morphology of the primary phase, the ratio of solid to liquid phase and the concentration of solute elements can be regulated.
  • An efficient preparation method of interface-regulated graphene reinforced magnesium-based composite material comprising the following steps:
  • step (2) the powder taken in step (1) is prepared into a suspension by mechanical stirring and a liquid compatibilizer respectively, and the specific steps are as follows: each group of powders is loaded into a mechanical mixer, and 500g of dehydrated alcohol is added in the air. Mechanical stirring is carried out in the environment, the stirring speed is 8000r/min, and the mechanical stirring time is 1.0h, and a suspension liquid is obtained after completion.
  • the main purpose of this step is to realize the dispersion of the agglomerated graphene, the spreading of the wrinkled graphene, and the uniform distribution of the spread graphene in the magnesium alloy powder.
  • step (3) the suspension obtained in step (2) is prepared into dry composite powder by electrostatic spray drying method, the details are as follows: the suspension is placed in the feeding tank of the spray dryer, and the stirring speed in the feeding tank is At 800rpm, the suspension is sprayed from the electrostatic spray gun under the action of high-pressure hot air, and the output voltage of the electrostatic spray gun is 60kv, and finally the composite material powder after uniform mixing of the reinforcement and the matrix is obtained. After testing: the yields of the above powders were 97.9% respectively.
  • step (3) (4) adding the composite material powder obtained in step (3) into a self-made mold for cold pressing, the diameter of the cold preform is 50 mm, and the pressing and forming conditions are: room temperature, pressure 200 MPa, and pressure holding time 5 min.
  • An efficient preparation method of interface-regulated graphene reinforced magnesium-based composite material comprising the following steps:
  • step (2) the powder taken in step (1) is prepared into a suspension by mechanical stirring and a liquid compatibilizer respectively, and the specific steps are as follows: each group of powders is loaded into a mechanical mixer, and 500g of dehydrated alcohol is added in the air. Mechanical stirring is carried out in the environment, the stirring speed is 8000r/min, and the mechanical stirring time is 1.0h, and a suspension liquid is obtained after completion.
  • the main purpose of this step is to realize the dispersion of the agglomerated graphene, the spreading of the wrinkled graphene, and the uniform distribution of the spread graphene in the magnesium alloy powder.
  • step (3) the suspension obtained in step (2) is prepared into dry composite powder by electrostatic spray drying method, the details are as follows: the suspension is placed in the feeding tank of the spray dryer, and the stirring speed in the feeding tank is At 800rpm, the suspension is sprayed from the electrostatic spray gun under the action of high-pressure hot air, and the output voltage of the electrostatic spray gun is 60kv, and finally the composite material powder after uniform mixing of the reinforcement and the matrix is obtained. After testing: the yields of the above powders were 97.9% respectively.
  • step (3) (4) adding the composite material powder obtained in step (3) into a self-made mold for cold pressing, the diameter of the cold preform is 50 mm, and the pressing and forming conditions are: room temperature, pressure 200 MPa, and pressure holding time 5 min.
  • a spray drying device includes a drying tower 4, a power supply 8, and a collection device 6.
  • the positive electrode or the negative electrode of the power supply 8 is respectively connected to the drying tower 4 and the collection device 6 through wires, and one end of the two wires is connected respectively.
  • Conductive sheet, the two conductive sheets are respectively located at the top of the drying tower 4 and in the collecting device 6.
  • the bottom of the drying tower 4 is provided with a discharge port 6, and the collecting device 6 is located below the drying tower 4 and is opposite to the opening.
  • a power source 8 is added, and the two poles of the power source 8 are respectively connected with wires, and the wires are respectively extended into the drying tower and the collecting device 6 .
  • the bottom of the drying tower 4 is opened, so that an electric field is formed between the two conductive sheets. After the powder enters the drying tower, it is charged with the same charge, so it repels each other and avoids agglomeration. It is then attracted by the heterogeneous charges of the collection device. Improve powder yield.
  • the feeding pipe is connected to the high-pressure fan 1, the agitator 2, and the heater 3 in turn.
  • the heater 3 is located at one end of the drying tower 4.
  • One end of the feeding pipe extends into the drying tower 4, and the bottom of the extending end is provided with High pressure nozzle 5.
  • One end of the feed pipe extends into the feed port at the top of the drying tower 4 .
  • the two wires extend into the top of the drying tower and the collecting device respectively.
  • the top of the collecting device is provided with an opening, and the opening faces the discharge port, so the two electrodes are opposite.
  • the power source 8 is a DC power source.

Abstract

The present invention relates to a graphene-reinforced magnesium-based composite material, a preparation method for same, and applications thereof. A reinforcer, a magnesium substrate, and a liquid-phase solvent are mixed to produce a suspension; the suspension produced is spray dried to produce a dry powder; the dry powder produced undergoes a molding treatment to produce a block blank; the block blank and a magnesium alloy blank are melted, mixed, and casted to produce the graphene-reinforced magnesium-based composite material. An inexpensive process is employed to prepare the graphene nanoparticle-reinforced magnesium-based composite material, the dispersion and spreading of an agglomerated and pleated industrial-grade graphene material can be implemented by means of one-step mechanical stirring, no mechanical damage is incurred on the graphene material, at the same time, the preparation of the composite material has low requirements on equipment, processing is inexpensive, the production efficiency is high, an interface structure is controllable, and excellent industrial application prospects are provided.

Description

一种石墨烯增强镁基复合材料及其制备方法和应用A kind of graphene-reinforced magnesium-based composite material and its preparation method and application 技术领域technical field
本发明属于石墨烯增强镁基复合材料技术领域，具体涉及一种石墨烯增强镁基复合材料及其制备方法和应用。The invention belongs to the technical field of graphene-reinforced magnesium-based composite materials, and in particular relates to a graphene-reinforced magnesium-based composite material and a preparation method and application thereof.
背景技术Background technique
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
镁合金密度低、比强度比刚度高、阻尼性能优异，已经应用于汽车、轨道交通和航空航天等领域，是实现轻量化的重要结构材料。然而，镁合金强度性能较低，塑性较差，限制了镁合金的应用。提高其强度、塑形，是拓展镁合金应用领域的必要途径。Magnesium alloys have low density, high specific strength ratio stiffness, and excellent damping performance. They have been used in automobiles, rail transit, aerospace and other fields, and are important structural materials for achieving lightweight. However, magnesium alloys have low strength properties and poor plasticity, which limit the application of magnesium alloys. Improving its strength and shaping is a necessary way to expand the application field of magnesium alloys.
目前的研究发现，镁基体中添加极少量的石墨烯，可使其强度、塑形大幅提升。石墨烯具有优异的力学性能，其弹性模量可达到1TPa，拉伸强度可达到125GPa，其密度仅为2.23g/cm 3，是非常理想的镁合金基体强化相。目前，石墨烯增强镁基复合材料的制备工艺主要可分为固态成形法及液态成形两大类。 The current research found that adding a very small amount of graphene to the magnesium matrix can greatly improve its strength and shape. Graphene has excellent mechanical properties, its elastic modulus can reach 1TPa, its tensile strength can reach 125GPa, its density is only 2.23g/cm 3 , and it is an ideal magnesium alloy matrix strengthening phase. At present, the preparation process of graphene-reinforced magnesium matrix composites can be mainly divided into two categories: solid-state forming method and liquid forming method.
然而，目前的制备技术仍存在很多问题，例如：1、界面结构不可调控；2、工艺路线繁琐，难以实现高效工业生产；3、工艺过程强化相结构损伤，降低强化效果。However, there are still many problems in the current preparation technology, such as: 1. The interface structure cannot be controlled; 2. The process route is cumbersome and it is difficult to achieve efficient industrial production; 3. The process strengthens the phase structure damage and reduces the strengthening effect.
发明内容SUMMARY OF THE INVENTION
针对上述现有技术中存在的问题，本发明的目的是提供一种石墨烯增强镁基复合材料及其制备方法和应用。In view of the problems existing in the above-mentioned prior art, the purpose of the present invention is to provide a graphene-reinforced magnesium-based composite material and a preparation method and application thereof.
为了解决以上技术问题，本发明的技术方案为：In order to solve the above technical problems, the technical scheme of the present invention is:
一种石墨烯增强镁基复合材料的制备方法，具体步骤为：A preparation method of graphene reinforced magnesium-based composite material, the concrete steps are:
将增强体、镁基体与液体相容剂混合得到悬浊液；Mix the reinforcing body, the magnesium matrix and the liquid compatibilizer to obtain a suspension;
将得到的悬浊液通过喷雾干燥得到干燥粉末；The obtained suspension is spray-dried to obtain dry powder;
将得到的干燥粉末进行成型处理得到块体坯料；The obtained dry powder is subjected to a molding process to obtain a block blank;
将块体坯料进行热挤压成形，得到石墨烯镁基复合材料预制棒；The block blank is hot-extruded to obtain a graphene-magnesium-based composite material preform;
将复合材料预制棒和镁合金坯料进行熔化混合，浇铸得到石墨烯增强镁基复合材料；The composite material preform and the magnesium alloy billet are melted and mixed, and the graphene-reinforced magnesium-based composite material is obtained by casting;
将铸坯在半固态温度保温，后续进行压铸、挤压铸造，得到复合材料零部件。The casting billet is kept at a semi-solid temperature, followed by die casting and extrusion casting to obtain composite parts.
增强体、镁基体与液体相容剂混合的作用是，利用机械搅拌产生的剪切力，促进石墨烯粉体的进一步分散，得到镁基体与石墨烯的悬浊液；The effect of mixing the reinforcing body, the magnesium matrix and the liquid compatibilizer is to use the shear force generated by mechanical stirring to promote the further dispersion of the graphene powder to obtain a suspension of the magnesium matrix and the graphene;
通过喷雾干燥过程，避免了长时间的干燥过程，同时避免了由于溶液蒸发，在界面张力的影响下的团聚问题；Through the spray drying process, the long drying process is avoided, and the problem of agglomeration under the influence of interfacial tension due to the evaporation of the solution is avoided at the same time;
将粉末冷压块进行热挤压，将热挤压棒材加入镁合金熔体中，利用纳米颗粒在熔体中的自稳定效应，得到均匀弥散的复合材料熔体，浇铸后得到复合材料铸坯；The powder cold briquette is hot extruded, and the hot extruded bar is added to the magnesium alloy melt, and the self-stabilizing effect of nanoparticles in the melt is used to obtain a uniformly dispersed composite material melt, and the composite material cast is obtained after casting. blank;
将铸坯进行半固态保温，半固态保温的目的是调控固液相成分比例，以及石墨烯/镁基体界面结构，随后将半固态坯料进行压铸或挤压铸造，得到镁基复合材料零部件。The casting billet is subjected to semi-solid heat preservation. The purpose of semi-solid heat preservation is to control the composition ratio of solid and liquid phases and the interface structure of graphene/magnesium matrix, and then the semi-solid billet is subjected to die casting or extrusion casting to obtain magnesium matrix composite parts.
在本发明的一些实施方式中，镁基体与增强体的混合比例为：增强体质量分数为0.1-5％；优选为5％，余量为镁基体。In some embodiments of the present invention, the mixing ratio of the magnesium matrix and the reinforcing body is: the mass fraction of the reinforcing body is 0.1-5%; preferably, it is 5%, and the balance is the magnesium matrix.
在本发明的一些实施方式中，增强体为石墨烯或氧化石墨烯，其平均厚度1～30nm，平均片径100nm～100μm。In some embodiments of the present invention, the reinforcing body is graphene or graphene oxide with an average thickness of 1-30 nm and an average sheet diameter of 100 nm-100 μm.
在本发明的一些实施方式中，镁基体为纯镁粉末或镁合金粉末，平均粒径为1～100μm。In some embodiments of the present invention, the magnesium matrix is pure magnesium powder or magnesium alloy powder, and the average particle size is 1-100 μm.
在本发明的一些实施方式中，液体相容剂的质量与镁基体与增强体的质量和的比为1-3:1；优选为2:1。In some embodiments of the present invention, the ratio of the mass of the liquid compatibilizer to the sum of the mass of the magnesium matrix and the reinforcement is 1-3:1; preferably 2:1.
在本发明的一些实施方式中，液体相容剂包括水、无水乙醇、丙酮中至少一种。In some embodiments of the present invention, the liquid compatibilizer includes at least one of water, absolute ethanol, and acetone.
优选的，当液体相容剂为水时，混合进行机械搅拌，机械搅拌所处的气氛环境为空气。Preferably, when the liquid compatibilizer is water, mechanical stirring is performed for mixing, and the atmosphere in which the mechanical stirring is located is air.
优选的，当液体相容剂为无水乙醇和/或丙酮时，机械搅拌所处的气氛环境为惰性气体。Preferably, when the liquid compatibilizer is anhydrous ethanol and/or acetone, the atmosphere in which the mechanical stirring is located is an inert gas.
进一步优选的，机械搅拌的速率为200～10000r/min，搅拌时间为0.5～20h。Further preferably, the speed of mechanical stirring is 200-10000r/min, and the stirring time is 0.5-20h.
机械搅拌与液体相容剂配合实现镁基体和增强体的混合，利用机械搅拌产生的剪切力，实现团聚石墨烯的分散、褶皱状石墨烯的铺展，获得弥散分布的悬浊液。Mechanical stirring and liquid compatibilizer are used to achieve the mixing of magnesium matrix and reinforcement, and the shear force generated by mechanical stirring is used to realize the dispersion of agglomerated graphene and the spreading of wrinkled graphene to obtain a dispersed suspension.
在本发明的一些实施方式中，喷雾干燥的方法为：利用喷雾干燥机，在高压热风的条件下，静电喷枪喷出悬浊液得到干燥粉末。In some embodiments of the present invention, the spray drying method is as follows: using a spray dryer, under the condition of high pressure hot air, an electrostatic spray gun sprays the suspension to obtain dry powder.
优选的，悬浊液在喷雾干燥机的加料罐中的搅拌速度为100rpm～1000rpm；优选为700-900rpm；Preferably, the stirring speed of the suspension in the feeding tank of the spray dryer is 100rpm-1000rpm; preferably 700-900rpm;
优选的，静电喷枪的输出电压为10-85kv；优选为60-70kv。Preferably, the output voltage of the electrostatic spray gun is 10-85kv; preferably 60-70kv.
喷雾干燥的参数影响得到的干燥粉末的粒径和均匀度、收率。通过上述的喷雾干燥方法，干燥粉末的收率达到97.9％。The parameters of spray drying affect the particle size, uniformity, and yield of the resulting dried powder. By the spray drying method described above, the yield of dry powder reached 97.9%.
在本发明的一些实施方式中，石墨烯增强镁基复合材料中石墨烯的质量含量为 0.1-5％；优选为0.5-2.5％。In some embodiments of the present invention, the mass content of graphene in the graphene-reinforced magnesium-based composite material is 0.1-5%; preferably 0.5-2.5%.
在本发明的一些实施方式中，坯料的成型处理方法为冷压成型；优选的冷压成型的条件为：室温下，压力为100-300MPa，保压时间为4-6min；优选的，压力为200MPa，保压时间为5min。In some embodiments of the present invention, the forming treatment method of the blank is cold pressing; the preferred cold pressing conditions are: at room temperature, the pressure is 100-300MPa, and the pressure holding time is 4-6min; preferably, the pressure is 200MPa, the holding time is 5min.
冷压成型的条件，有助于石墨烯和镁基体的混合，石墨烯分散均匀，避免团聚，有利于石墨烯和镁基体的冶金结合，结合强度更高。The conditions of cold pressing are helpful for the mixing of graphene and magnesium matrix, graphene is dispersed evenly, agglomeration is avoided, it is beneficial to the metallurgical bonding of graphene and magnesium matrix, and the bonding strength is higher.
在本发明的一些实施方式中，坯料熔化混合中的惰性气体为SF 6+CO 2混合气体。 In some embodiments of the present invention, the inert gas in the melt mixing of the billet is a mixed gas of SF 6 +CO 2 .
在本发明的一些实施方式中，镁合金坯料和块体坯料熔化后进行机械搅拌，机械搅拌速率为10rpm～100rpm，所述机械搅拌时间为5min～60min。In some embodiments of the present invention, the magnesium alloy billet and the bulk billet are melted and then mechanically stirred, the mechanical stirring rate is 10 rpm to 100 rpm, and the mechanical stirring time is 5 min to 60 min.
在本发明的一些实施方式中，浇铸的温度为700-750℃；优选为720℃。In some embodiments of the invention, the casting temperature is 700-750°C; preferably 720°C.
第四方面，一种喷雾干燥装置，包括干燥塔和电源、收集装置，电源的正极或负极分别通过导线与干燥塔、收集装置连接，两个导线的一端分别连接导电片，两个导电片分别位于干燥塔的顶部、收集装置中，干燥塔的底部设置出料口，收集装置位于干燥塔的下方与出料口相对。A fourth aspect, a spray drying device, comprising a drying tower, a power supply, and a collection device, the positive electrode or the negative electrode of the power supply is respectively connected to the drying tower and the collection device through wires, one end of the two wires is respectively connected to a conductive sheet, and the two conductive sheets are respectively connected. It is located at the top of the drying tower and in the collecting device. The bottom of the drying tower is provided with a discharge port, and the collecting device is located below the drying tower and is opposite to the discharge port.
在本发明的一些实施方式中，还包括进料管，进料管依次连接高压风机、搅拌器、加热器，加热器位于靠近干燥塔的一端，进料管的一端伸入干燥塔，伸入端的底部设置高压喷嘴。In some embodiments of the present invention, it also includes a feed pipe, the feed pipe is connected to the high-pressure fan, agitator, and heater in sequence, the heater is located at one end close to the drying tower, and one end of the feed pipe extends into the drying tower, and extends into the drying tower. The bottom of the end is provided with a high-pressure nozzle.
在本发明的一些实施方式中，电源为直流电源。In some embodiments of the invention, the power source is a DC power source.
第三方面，上述石墨烯增强镁基复合材料的制备方法得到的石墨烯增强镁基复合材料。In a third aspect, a graphene-reinforced magnesium-based composite material obtained by the above-mentioned preparation method of a graphene-reinforced magnesium-based composite material.
优选的，石墨烯质量分数为0.1％～5％，进一步优选的，石墨烯质量分数为0.5-2.5％。在这个范围内，石墨烯具有更好的细晶强化和弥散强化作用。Preferably, the mass fraction of graphene is 0.1%-5%, and further preferably, the mass fraction of graphene is 0.5-2.5%. Within this range, graphene has better fine-grain strengthening and dispersion strengthening.
第四方面，上述的石墨烯增强镁基复合材料的制备方法和石墨烯增强镁基复合材料在汽车、轨道交通和航空航天等领域中的应用。In the fourth aspect, the above-mentioned preparation method of the graphene-reinforced magnesium-based composite material and the application of the graphene-reinforced magnesium-based composite material in the fields of automobiles, rail transit, aerospace and the like.
第五方面，一种零部件，包括上述的石墨烯增强镁基复合材料。In a fifth aspect, a component includes the above-mentioned graphene-reinforced magnesium-based composite material.
第六方面，上述零部件的制备方法，所述方法为，将石墨烯增强镁基复合材料进行半固态保温，得到复合材料半固态坯料，然后将石墨烯增强镁基复合材料进行压铸成型得到零部件。The sixth aspect, the preparation method of the above-mentioned parts, the method is, the graphene-reinforced magnesium-based composite material is subjected to semi-solid heat preservation to obtain a semi-solid blank of the composite material, and then the graphene-reinforced magnesium-based composite material is die-casted to obtain zero. part.
将铸坯进行半固态保温，半固态保温的目的是调控固液相成分比例，以及石墨烯/镁基体界面结构，随后将半固态坯料进行压铸或挤压铸造，得到镁基复合材料零部件。The casting billet is subjected to semi-solid heat preservation. The purpose of semi-solid heat preservation is to control the composition ratio of solid and liquid phases and the interface structure of graphene/magnesium matrix, and then the semi-solid billet is subjected to die casting or extrusion casting to obtain magnesium matrix composite parts.
优选的，半固态保温的温度为595～615℃，保温的时间为30～120min。Preferably, the temperature of the semi-solid heat preservation is 595 to 615° C., and the time of the heat preservation is 30 to 120 minutes.
优选的，压铸成型的条件为：压射速度1～7m/s，压射比压30～200MPa，保压时间20～50s。Preferably, the die-casting conditions are as follows: the injection speed is 1-7 m/s, the injection specific pressure is 30-200 MPa, and the pressure holding time is 20-50 s.
通过半固态保温的处理步骤，得到的半固态材料的微观组织分布均匀、细化。Through the treatment step of semi-solid heat preservation, the microstructure distribution of the obtained semi-solid material is uniform and refined.
本发明一个或多个技术方案具有以下有益效果：One or more technical solutions of the present invention have the following beneficial effects:
1、本发明采用低成本工艺高效制备石墨烯纳米颗粒增强镁基复合材料，通过机械搅拌实现团聚、褶皱状的工业级石墨烯材料的分散与铺展，采用冷压预制坯的方式将石墨烯引入熔融的镁合金中，利用石墨烯纳米颗粒自稳定效应，能够有效解决铸造过程中石墨烯的氧化及团聚现象，该工艺流程简单，对设备要求低，加工成本低，生产效率高，具有优良的工业化应用前景。1. The present invention adopts a low-cost process to efficiently prepare graphene nano-particle-reinforced magnesium-based composite materials, realizes the dispersion and spreading of agglomerated, wrinkled industrial-grade graphene materials by mechanical stirring, and adopts the mode of cold-pressed preform to introduce graphene into In the molten magnesium alloy, the self-stabilization effect of graphene nanoparticles can effectively solve the phenomenon of graphene oxidation and agglomeration in the casting process. The process is simple, requires low equipment, low processing costs, high production efficiency, and has excellent Prospects for industrial application.
2、采用石墨烯、镁基体粉末悬浊液采取喷雾干燥方法，避免了长时间的干燥过程；喷雾方法采用直流电，避免了干燥过程中的团聚。相比传统干燥方法，提高了制备效率；相比真空干燥、冷冻干燥、超临界法干燥，降低了设备成本。2. The suspension of graphene and magnesium matrix powder is spray-dried to avoid a long drying process; the spray method uses direct current to avoid agglomeration during the drying process. Compared with the traditional drying method, the preparation efficiency is improved; compared with vacuum drying, freeze drying, and supercritical drying, the equipment cost is reduced.
3、对铸态坯料进行半固态保温处理，实现了界面结构、成分，以及初生相颗粒大小、形貌，固液相比例的可调控。3. The semi-solid heat preservation treatment of the as-cast billet realizes the controllability of the interface structure, composition, particle size and morphology of the primary phase, and the ratio of solid and liquid phases.
4、半固态坯料采用压铸、挤压铸造等技术触变成形，利用半固态坯料黏度高、温度低的特点，与全液态成形相比，实现层流充型，避免卷气、缩松等缺陷，实现高致密度铸造。4. The semi-solid billet is thixoformed by techniques such as die casting and squeeze casting. By utilizing the characteristics of high viscosity and low temperature of the semi-solid billet, compared with full liquid forming, laminar filling can be realized, avoiding entrainment, shrinkage, etc. defects to achieve high-density casting.
附图说明Description of drawings
构成本发明的一部分的说明书附图用来提供对本申请的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The accompanying drawings forming a part of the present invention are used to provide further understanding of the present application, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention.
图1为实施例1-实施例3、对比例1中不同石墨烯含量得到的复合材料金相图；其中a为对比例1，b为实施例2，c为实施例1，d为实施例3；Fig. 1 is the metallographic diagram of the composite material obtained with different graphene contents in Example 1-Example 3 and Comparative Example 1; wherein a is Comparative Example 1, b is Example 2, c is Example 1, and d is an example 3;
图2为实施例1-实施例3、对比例1中得到的复合材料界面；其中a为对比例1，b为实施例2，c为实施例1，d为实施例3；Figure 2 shows the interface of the composite material obtained in Example 1-Example 3 and Comparative Example 1; wherein a is Comparative Example 1, b is Example 2, c is Example 1, and d is Example 3;
图3为实施例1-实施例3、对比例1中不同石墨烯含量得到的复合材料硬度演变图。3 is a graph of the hardness evolution of composite materials obtained with different graphene contents in Example 1-Example 3 and Comparative Example 1.
图4为实施例1中复合材料界面透射电镜图。FIG. 4 is a transmission electron microscope image of the interface of the composite material in Example 1. FIG.
图5为实施例4的半固态保温水淬处理后复合材料的微观组织。FIG. 5 is the microstructure of the composite material after the semi-solid heat preservation water quenching treatment of Example 4. FIG.
图6为实施例4的半固态坯料水淬组织图。FIG. 6 is a water quenching structure diagram of the semi-solid billet of Example 4. FIG.
图7为喷雾干燥装置的结构图。FIG. 7 is a structural diagram of a spray drying apparatus.
其中，1、高压风机，2、搅拌器，3、加热器，4、干燥塔，5、高压喷嘴，6、收集装置，7、出料口，8、电源。Among them, 1. High-pressure fan, 2. Stirrer, 3. Heater, 4. Drying tower, 5. High-pressure nozzle, 6. Collection device, 7. Discharge port, 8. Power supply.
具体实施方式detailed description
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is exemplary and intended to provide further explanation of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, devices, components and/or combinations thereof.
下面结合实施例对本发明进一步说明Below in conjunction with embodiment, the present invention is further described
实施例1Example 1
一种石墨烯纳米颗粒增强镁基复合材料高效制备方法，包括如下步骤：A kind of high-efficiency preparation method of graphene nano-particle reinforced magnesium-based composite material, comprising the following steps:
(1)按质量分数(wt.％)，称取增强体(5％)和镁基体(95％)共250g，其中，所述增强体为少层石墨烯，厚度介于3～10nm，片径介于5～10μm；所述镁基体为AZ91镁合金粉末，粒径介于1～2μm。(1) According to the mass fraction (wt.%), weigh the reinforcing body (5%) and the magnesium matrix (95%) in a total of 250 g, wherein the reinforcing body is few-layer graphene, the thickness is between 3 and 10 nm, and the sheet The diameter is between 5-10 μm; the magnesium matrix is AZ91 magnesium alloy powder, and the particle size is between 1-2 μm.
(2)分别将步骤(1)称取的粉末通过机械搅拌和液体相容剂制备成悬浊液，具体步骤如下：将各组粉末装入机械搅拌机中，并加入500g的无水乙醇在空气环境中进行机械搅拌，搅拌转速为8000r/min，机械搅拌时间为3～60min，完成后得到悬浊液。(2) the powder taken in step (1) is prepared into a suspension by mechanical stirring and a liquid compatibilizer respectively, and the specific steps are as follows: each group of powders is loaded into a mechanical mixer, and 500g of dehydrated alcohol is added in the air. Mechanical stirring is carried out in the environment, the stirring speed is 8000 r/min, and the mechanical stirring time is 3-60 min, and a suspension liquid is obtained after completion.
(3)将步骤(2)得到悬浊液通过静电喷雾干燥法分别制备成干燥的复合材料粉末，具体如下：将所述悬浊液置于喷雾干燥机的加料罐中，加料罐内搅拌速度为800rpm，悬浊液在高压热风的作用下从静电喷枪中喷出，静电喷枪输出电压60kv，最终获得增强体与基体的均匀混合后的复合材料粉末。经过测试：上述粉末的收率分别为97.9％。(3) the suspension obtained in step (2) is prepared into dry composite powder by electrostatic spray drying method, the details are as follows: the suspension is placed in the feeding tank of the spray dryer, and the stirring speed in the feeding tank is At 800rpm, the suspension is sprayed from the electrostatic spray gun under the action of high-pressure hot air, and the output voltage of the electrostatic spray gun is 60kv, and finally the composite material powder after uniform mixing of the reinforcement and the matrix is obtained. After testing: the yields of the above powders were 97.9% respectively.
(4)将步骤(3)得到复合材料粉末加入自制模具进行冷压成形，冷预制坯直径50mm，压制成形条件为：室温，压力200MPa，保压时间5min。(4) adding the composite material powder obtained in step (3) into a self-made mold for cold pressing, the diameter of the cold preform is 50 mm, and the pressing and forming conditions are: room temperature, pressure 200 MPa, and pressure holding time 5 min.
(5)按质量分数(wt.％)，称取AZ91镁合金块体和冷压预制坯500g，石墨烯质量含量分别为1.5％，将AZ91镁合金块体在SF 6+CO 2混合气体保护下进行熔化，合金熔化后，升温至780℃，保温30min，将步骤(4)所述块体预制坯料放入坩埚，预制坯料熔化后进行机械搅拌，机械搅拌速率为100rpm，机械搅拌时间为15min在740℃浇铸得石墨烯纳米颗粒增强镁基复合材料，即得。 (5) According to the mass fraction (wt.%), 500 g of AZ91 magnesium alloy block and cold-pressed preform were weighed, and the mass content of graphene was 1.5%, respectively, and the AZ91 magnesium alloy block was protected by SF 6 +CO 2 mixed gas. After the alloy is melted, the temperature is raised to 780° C., and the temperature is kept for 30 minutes. The block prefabricated billet described in step (4) is put into the crucible, and the prefabricated billet is melted and then mechanically stirred. The mechanical stirring speed is 100 rpm, and the mechanical stirring time is 15min. Casting at 740 ° C to obtain graphene nanoparticles reinforced magnesium matrix composite material, that is, obtained.
实施例2Example 2
相比于实施例1，步骤(5)中石墨烯的质量含量为0.5％。Compared with Example 1, the mass content of graphene in step (5) is 0.5%.
实施例3Example 3
相比于实施例1，步骤(5)中石墨烯的质量含量为2.5％。Compared with Example 1, the mass content of graphene in step (5) is 2.5%.
对比例1Comparative Example 1
相比于实施例1，步骤(5)中石墨烯的质量含量为0％。即相比于实施例1，步骤(1)中没有加入增强体。其它处理步骤和实施例1相同。Compared with Example 1, the mass content of graphene in step (5) is 0%. That is, compared with Example 1, no enhancer was added in step (1). Other processing steps are the same as in Example 1.
实施例1、实施例2、实施例3和对比例1的具体组成如表1所示，四组材料石墨烯质量含量分别为0、0.5％、1.5％、2.5％。The specific compositions of Example 1, Example 2, Example 3 and Comparative Example 1 are shown in Table 1, and the graphene mass contents of the four groups of materials are 0, 0.5%, 1.5%, and 2.5%, respectively.
表1四组配比情况Table 1 The four groups of ratios
组别group A组Group A B组Group B C组Group C D组Group D
AZ91镁合金/％AZ91 magnesium alloy/% 100100 9090 7070 5050
冷压预制坯/％Cold-pressed preforms/% 00 1010 3030 5050
复合材料石墨烯含量/％Composite graphene content/% 00 0.50.5 1.51.5 2.52.5
采用Zeiss Axio observer Alm型金相显微镜对实施例1-实施例3、对比例1的步骤(5)制备的四组石墨烯配比的石墨烯纳米颗粒增强镁基复合材料进行观察，结果分别如图1中的a图～d图所示。从图1中的b图～d图可以看出：石墨烯在AZ91镁基体中均匀弥散分布，没有团聚现象，随着石墨烯含量的增加，复合材料中石墨烯的密集程度明显增加。Using Zeiss Axio observer Alm type metallographic microscope to observe four groups of graphene nanoparticle reinforced magnesium matrix composites prepared in step (5) of Example 1-Example 3 and Comparative Example 1, the results are as follows: Figure 1 shows a to d. It can be seen from the pictures b to d in Figure 1 that the graphene is uniformly dispersed and distributed in the AZ91 magnesium matrix without agglomeration. With the increase of the graphene content, the density of graphene in the composite material increases significantly.
将实施例1-实施例3、对比例1制备的四组石墨烯配比的石墨烯纳米颗粒增强镁基复合材料进行T4固溶，检测晶粒大小。具体参数如下：435℃下固溶处理保温2h。采用上述金相显微镜对固溶处理后复合材料的微观组织进行观察，结果分别如图2的中的a图～d图所示。从图2中的b图～d图可以看出：石墨烯的引入能够明显细化AZ91镁合金基体晶粒尺寸，镁晶粒尺寸从～176μm(石墨烯含量0％)细化到～32μm(石墨烯含量1.5wt.％)。The four groups of graphene nanoparticle-reinforced magnesium-based composite materials prepared in Example 1-Example 3 and Comparative Example 1 were subjected to T4 solid solution, and the grain size was detected. The specific parameters are as follows: solution treatment at 435°C for 2h. The microstructure of the composite material after solution treatment was observed by the above-mentioned metallographic microscope, and the results are respectively shown in a to d in FIG. 2 . It can be seen from the pictures b to d in Figure 2 that the introduction of graphene can significantly refine the grain size of the AZ91 magnesium alloy matrix, and the magnesium grain size is refined from ~176 μm (graphene content 0%) to ~32 μm ( Graphene content 1.5 wt.%).
采用XHV-1000型显微硬度仪对固溶处理后复合材料的硬度进行检测，结果如图3所示。从图3中可以看出，石墨烯的加入能明显提高复合材料硬度，材料硬度从～66HV(石墨烯含量0％)增加到～89HV(石墨烯含量1.5wt.％)，提高了35％，主要归因于石墨烯引入带来的细晶强化和弥散强化作用。The hardness of the composites after solution treatment was tested by XHV-1000 microhardness tester, and the results are shown in Figure 3. As can be seen from Figure 3, the addition of graphene can significantly improve the hardness of the composite material, and the material hardness increases from ~66HV (graphene content 0%) to ~89HV (graphene content 1.5wt.%), an increase of 35%, It is mainly attributable to the fine-grain strengthening and dispersion strengthening brought about by the introduction of graphene.
采用透射电镜对实施例1步骤(5)制备的C组复合材料界面进行观察，结果图4所示。从图4可以看出：石墨烯镁基复合材料界面有明显的过渡层和界面产物产生，两者结合为冶金结合，结合强度高。The interface of the composite material of group C prepared in step (5) of Example 1 was observed by transmission electron microscope, and the result is shown in FIG. 4 . It can be seen from Figure 4 that there are obvious transition layers and interface products at the interface of the graphene-magnesium matrix composite material, and the combination of the two is a metallurgical bond with high bond strength.
实施例4Example 4
一种石墨烯纳米颗粒增强镁基复合材料界面调控方法，包括如下步骤：A method for regulating and controlling the interface of a graphene nanoparticle reinforced magnesium-based composite material, comprising the following steps:
(1)按质量分数(wt.％)，称取增强体(5％)和镁基体(95％)共250g，其中，所述增强体为少层石墨烯，厚度介于3～10nm，片径介于5～10μm；所述镁基体为AZ91镁合金粉末，粒径介于1～2μm。(1) According to the mass fraction (wt.%), weigh the reinforcing body (5%) and the magnesium matrix (95%) in a total of 250 g, wherein the reinforcing body is few-layer graphene, the thickness is between 3 and 10 nm, and the sheet The diameter is between 5-10 μm; the magnesium matrix is AZ91 magnesium alloy powder, and the particle size is between 1-2 μm.
(2)分别将步骤(1)称取的粉末通过机械搅拌和液体相容剂制备成悬浊液，具体步骤如下：将各组粉末装入机械搅拌机中，并加入500g的无水乙醇在空气环境中进行机械搅拌，搅拌转速为8000r/min，机械搅拌时间为1.0h，完成后得到悬浊液。(2) the powder taken in step (1) is prepared into a suspension by mechanical stirring and a liquid compatibilizer respectively, and the specific steps are as follows: each group of powders is loaded into a mechanical mixer, and 500g of dehydrated alcohol is added in the air. Mechanical stirring is carried out in the environment, the stirring speed is 8000r/min, and the mechanical stirring time is 1.0h, and a suspension liquid is obtained after completion.
(3)将步骤(2)得到悬浊液通过静电喷雾干燥法分别制备成干燥的复合材料粉末，具体如下：将所述悬浊液置于喷雾干燥机的加料罐中，加料罐内搅拌速度为800rpm，悬浊液在高压热风的作用下从静电喷枪中喷出，静电喷枪输出电压60kv，最终获得增强体与基体的均匀混合后的复合材料粉末。经过测试：上述粉末的收率分别为97.9％。(3) the suspension obtained in step (2) is prepared into dry composite powder by electrostatic spray drying method, the details are as follows: the suspension is placed in the feeding tank of the spray dryer, and the stirring speed in the feeding tank is At 800rpm, the suspension is sprayed from the electrostatic spray gun under the action of high-pressure hot air, and the output voltage of the electrostatic spray gun is 60kv, and finally the composite material powder after uniform mixing of the reinforcement and the matrix is obtained. After testing: the yields of the above powders were 97.9% respectively.
(4)将步骤(3)得到复合材料粉末加入自制模具进行冷压成形，冷预制坯直径50mm，压制成形条件为：室温，压力200MPa，保压时间5min。(4) adding the composite material powder obtained in step (3) into a self-made mold for cold pressing, the diameter of the cold preform is 50 mm, and the pressing and forming conditions are: room temperature, pressure 200 MPa, and pressure holding time 5 min.
(5)按质量分数(wt.％)，称取AZ91镁合金块体(99％)和冷压预制坯(1％)500g，将AZ91镁合金块体在SF 6+CO 2混合气体保护下进行熔化，合金熔化后，升温至780℃，保温30min，将步骤(4)所述块体预制坯料放入坩埚，预制坯料熔化后进行机械搅拌，机械搅拌速率为100rpm，机械搅拌时间为15min在740℃浇铸得石墨烯纳米颗粒增强镁基复合材料，即得复合材料铸态坯料。 (5) According to the mass fraction (wt.%), weigh 500 g of AZ91 magnesium alloy bulk (99%) and cold-pressed preform (1%), and put the AZ91 magnesium alloy bulk under the protection of SF 6 +CO 2 mixed gas After melting, the alloy is heated to 780 ° C and kept for 30 minutes. The block prefabricated billet described in step (4) is put into the crucible, and the prefabricated billet is melted and then mechanically stirred. The mechanical stirring speed is 100rpm, and the mechanical stirring time is 15min. Casting at 740° C. to obtain the graphene nanoparticle reinforced magnesium matrix composite material, that is, to obtain the as-cast blank of the composite material.
(6)将步骤(5)得到复合材料铸态坯料进行半固态保温，具体参数为：595～615℃，保温时间30～120min。即得复合材料半固态坯料。本步骤的主要目的是实现固液相比例、初生相颗粒形貌及大小、复合材料界面结构调控。采用上述金相显微镜对半固态保温水淬处理后复合材料的微观组织进行观察，结果分别如图5中的a图～d图所示。(6) Semi-solid heat preservation is performed on the as-cast composite material obtained in step (5), the specific parameters are: 595-615° C., and the heat preservation time is 30-120 minutes. That is, the composite material semi-solid billet is obtained. The main purpose of this step is to control the ratio of solid to liquid phase, the morphology and size of primary phase particles, and the interface structure of the composite material. The above-mentioned metallographic microscope was used to observe the microstructure of the composite material after the semi-solid heat preservation water quenching treatment, and the results are shown in Figures a to d in FIG.
(7)将步骤(6)得到半固态坯料转入压铸模具进行压铸成形。具体参数为：压射速度1～7m/s，压射比压30～200MPa，保压时间20～50s。即得复合材料半固态压铸零部件。(7) Transfer the semi-solid billet obtained in step (6) into a die-casting mold for die-casting. The specific parameters are: injection speed 1-7m/s, injection specific pressure 30-200MPa, pressure holding time 20-50s. That is, the composite material semi-solid die-casting parts are obtained.
采用EDS对步骤(6)水淬样品进行成分分析，结果如表2所示。通过图5中的a图和b图及表2可以看出，通过调整步骤(6)工艺参数可实现初生相形貌、固液相比例及其溶质元素浓度的调控。EDS was used to analyze the composition of the water quenched sample in step (6), and the results are shown in Table 2. It can be seen from Figures a and b in Figure 5 and Table 2 that by adjusting the process parameters of step (6), the morphology of the primary phase, the ratio of solid to liquid phase and the concentration of solute elements can be regulated.
表2半固态体系成分演变Table 2 Composition evolution of semi-solid system
Figure PCTCN2021083342-appb-000001
Figure PCTCN2021083342-appb-000001
采用透射电镜对步骤(6)制备复合材料半固态坯料水淬组织中，石墨烯/AZ91D界面进行观察，结果图6所示。从图6中的a图和b图可以看出：通过调整步骤(6)工艺参数可实现复合材料界面构型的调控。其调控的机理在于保温温度、保温时间、溶质元素成分的变化，导致的界面润湿性、界面产物、界面厚度的变化。Transmission electron microscopy was used to observe the graphene/AZ91D interface in the water-quenched structure of the semi-solid billet of the composite material prepared in step (6), and the results are shown in FIG. 6 . It can be seen from the pictures a and b in Figure 6 that the interface configuration of the composite material can be regulated by adjusting the process parameters of step (6). The mechanism of its regulation lies in the changes of holding temperature, holding time, and composition of solute elements, which lead to changes in interface wettability, interface products, and interface thickness.
实施例5Example 5
一种界面可调控石墨烯增强镁基复合材料的高效制备方法，包括如下步骤：An efficient preparation method of interface-regulated graphene reinforced magnesium-based composite material, comprising the following steps:
(1)按质量分数(wt.％)，称取增强体(5％)和镁基体(95％)共250g，其中，所述增强体为少层石墨烯，厚度介于3～10nm，片径介于5～10μm；所述镁基体为AZ91镁合金粉末，粒径介于1～2μm。(1) According to the mass fraction (wt.%), weigh the reinforcing body (5%) and the magnesium matrix (95%) in a total of 250 g, wherein the reinforcing body is few-layer graphene, the thickness is between 3 and 10 nm, and the sheet The diameter is between 5-10 μm; the magnesium matrix is AZ91 magnesium alloy powder, and the particle size is between 1-2 μm.
(2)分别将步骤(1)称取的粉末通过机械搅拌和液体相容剂制备成悬浊液，具体步骤如下：将各组粉末装入机械搅拌机中，并加入500g的无水乙醇在空气环境中进行机械搅拌，搅拌转速为8000r/min，机械搅拌时间为1.0h，完成后得到悬浊液。本步骤的主要目的是实现团聚石墨烯的分散、褶皱状石墨烯的铺展、及铺展态石墨烯在镁合金粉末中的均匀分布。(2) the powder taken in step (1) is prepared into a suspension by mechanical stirring and a liquid compatibilizer respectively, and the specific steps are as follows: each group of powders is loaded into a mechanical mixer, and 500g of dehydrated alcohol is added in the air. Mechanical stirring is carried out in the environment, the stirring speed is 8000r/min, and the mechanical stirring time is 1.0h, and a suspension liquid is obtained after completion. The main purpose of this step is to realize the dispersion of the agglomerated graphene, the spreading of the wrinkled graphene, and the uniform distribution of the spread graphene in the magnesium alloy powder.
(3)将步骤(2)得到悬浊液通过静电喷雾干燥法分别制备成干燥的复合材料粉末，具体如下：将所述悬浊液置于喷雾干燥机的加料罐中，加料罐内搅拌速度为800rpm，悬浊液在高压热风的作用下从静电喷枪中喷出，静电喷枪输出电压60kv，最终获得增强体与基体的均匀混合后的复合材料粉末。经过测试：上述粉末的收率分别为97.9％。(3) the suspension obtained in step (2) is prepared into dry composite powder by electrostatic spray drying method, the details are as follows: the suspension is placed in the feeding tank of the spray dryer, and the stirring speed in the feeding tank is At 800rpm, the suspension is sprayed from the electrostatic spray gun under the action of high-pressure hot air, and the output voltage of the electrostatic spray gun is 60kv, and finally the composite material powder after uniform mixing of the reinforcement and the matrix is obtained. After testing: the yields of the above powders were 97.9% respectively.
(4)将步骤(3)得到复合材料粉末加入自制模具进行冷压成形，冷预制坯直径50mm，压制成形条件为：室温，压力200MPa，保压时间5min。(4) adding the composite material powder obtained in step (3) into a self-made mold for cold pressing, the diameter of the cold preform is 50 mm, and the pressing and forming conditions are: room temperature, pressure 200 MPa, and pressure holding time 5 min.
(5)按质量分数(wt.％)，称取AZ91镁合金块体(99％)和冷压预制坯(1％)500g，将AZ91镁合金块体在SF 6+CO 2混合气体保护下进行熔化，合金熔化后，升温至780℃，保温30min，将步骤(4)所述块体预制坯料放入坩埚，预制坯料熔化后进行机械搅拌，机械搅拌速率为100rpm，机械搅拌时间为15min在740℃浇铸得石墨烯纳米颗粒增强镁基复合材料，复合材料中石墨烯含量为0.1％，即得。 (5) According to the mass fraction (wt.%), weigh 500 g of AZ91 magnesium alloy bulk (99%) and cold-pressed preform (1%), and put the AZ91 magnesium alloy bulk under the protection of SF 6 +CO 2 mixed gas After melting, the alloy is heated to 780 ° C and kept for 30 minutes. The block prefabricated billet described in step (4) is put into the crucible, and the prefabricated billet is melted and then mechanically stirred. The mechanical stirring speed is 100rpm, and the mechanical stirring time is 15min. The graphene nano-particle reinforced magnesium-based composite material is obtained by casting at 740° C., and the graphene content in the composite material is 0.1%.
实施例6Example 6
一种界面可调控石墨烯增强镁基复合材料的高效制备方法，包括如下步骤：An efficient preparation method of interface-regulated graphene reinforced magnesium-based composite material, comprising the following steps:
(1)按质量分数(wt.％)，称取增强体(5％)和镁基体(95％)共250g，其中，所述增强体为少层石墨烯，厚度介于3～10nm，片径介于5～10μm；所述镁基体为AZ91镁合金粉末，粒径介于1～2μm。(1) According to the mass fraction (wt.%), weigh the reinforcing body (5%) and the magnesium matrix (95%) in a total of 250 g, wherein the reinforcing body is few-layer graphene, the thickness is between 3 and 10 nm, and the sheet The diameter is between 5-10 μm; the magnesium matrix is AZ91 magnesium alloy powder, and the particle size is between 1-2 μm.
(2)分别将步骤(1)称取的粉末通过机械搅拌和液体相容剂制备成悬浊液，具体步骤如下：将各组粉末装入机械搅拌机中，并加入500g的无水乙醇在空气环境中进行机械搅拌，搅拌转速为8000r/min，机械搅拌时间为1.0h，完成后得到悬浊液。本步骤的主要目的是实现团聚石墨烯的分散、褶皱状石墨烯的铺展、及铺展态石墨烯在镁合金粉末中的 均匀分布。(2) the powder taken in step (1) is prepared into a suspension by mechanical stirring and a liquid compatibilizer respectively, and the specific steps are as follows: each group of powders is loaded into a mechanical mixer, and 500g of dehydrated alcohol is added in the air. Mechanical stirring is carried out in the environment, the stirring speed is 8000r/min, and the mechanical stirring time is 1.0h, and a suspension liquid is obtained after completion. The main purpose of this step is to realize the dispersion of the agglomerated graphene, the spreading of the wrinkled graphene, and the uniform distribution of the spread graphene in the magnesium alloy powder.
(3)将步骤(2)得到悬浊液通过静电喷雾干燥法分别制备成干燥的复合材料粉末，具体如下：将所述悬浊液置于喷雾干燥机的加料罐中，加料罐内搅拌速度为800rpm，悬浊液在高压热风的作用下从静电喷枪中喷出，静电喷枪输出电压60kv，最终获得增强体与基体的均匀混合后的复合材料粉末。经过测试：上述粉末的收率分别为97.9％。(3) the suspension obtained in step (2) is prepared into dry composite powder by electrostatic spray drying method, the details are as follows: the suspension is placed in the feeding tank of the spray dryer, and the stirring speed in the feeding tank is At 800rpm, the suspension is sprayed from the electrostatic spray gun under the action of high-pressure hot air, and the output voltage of the electrostatic spray gun is 60kv, and finally the composite material powder after uniform mixing of the reinforcement and the matrix is obtained. After testing: the yields of the above powders were 97.9% respectively.
(4)将步骤(3)得到复合材料粉末加入自制模具进行冷压成形，冷预制坯直径50mm，压制成形条件为：室温，压力200MPa，保压时间5min。(4) adding the composite material powder obtained in step (3) into a self-made mold for cold pressing, the diameter of the cold preform is 50 mm, and the pressing and forming conditions are: room temperature, pressure 200 MPa, and pressure holding time 5 min.
(5)按质量分数(wt.％)，称取AZ91镁合金块体(50％)和冷压预制坯(50％)500g，将AZ91镁合金块体在SF 6+CO 2混合气体保护下进行熔化，合金熔化后，升温至780℃，保温30min，将步骤(4)所述块体预制坯料放入坩埚，预制坯料熔化后进行机械搅拌，机械搅拌速率为100rpm，机械搅拌时间为15min在740℃浇铸得石墨烯纳米颗粒增强镁基复合材料，复合材料中石墨烯含量为5％，即得。 (5) According to the mass fraction (wt.%), weigh 500 g of AZ91 magnesium alloy block (50%) and cold-pressed preform (50%), and put the AZ91 magnesium alloy block under the protection of SF 6 +CO 2 mixed gas After melting, the alloy is heated to 780 ° C and kept for 30 minutes. The block prefabricated billet described in step (4) is put into the crucible, and the prefabricated billet is melted and then mechanically stirred. The mechanical stirring speed is 100rpm, and the mechanical stirring time is 15min. The graphene nano-particle reinforced magnesium-based composite material is obtained by casting at 740° C., and the graphene content in the composite material is 5%.
如图7所示，一种喷雾干燥装置，包括干燥塔4和电源8、收集装置6，电源8的正极或负极分别通过导线与干燥塔4、收集装置6连接，两个导线的一端分别连接导电片，两个导电片分别位于干燥塔4的顶部、收集装置6中，干燥塔4的底部设置出料口6，收集装置6位于干燥塔4的下方与开口相对。As shown in FIG. 7 , a spray drying device includes a drying tower 4, a power supply 8, and a collection device 6. The positive electrode or the negative electrode of the power supply 8 is respectively connected to the drying tower 4 and the collection device 6 through wires, and one end of the two wires is connected respectively. Conductive sheet, the two conductive sheets are respectively located at the top of the drying tower 4 and in the collecting device 6. The bottom of the drying tower 4 is provided with a discharge port 6, and the collecting device 6 is located below the drying tower 4 and is opposite to the opening.
与现有的干燥塔4相比，增加了电源8，电源8的两极分别连接导线，并分别将导线伸入到干燥塔和收集装置6中。干燥塔4的底部开口，这样两个导电片之间形成了电场，粉末进入干燥塔后，带上了同种电荷，所以相互排斥，避免团聚。然后被收集装置的异种电荷吸引。提高得粉率。Compared with the existing drying tower 4 , a power source 8 is added, and the two poles of the power source 8 are respectively connected with wires, and the wires are respectively extended into the drying tower and the collecting device 6 . The bottom of the drying tower 4 is opened, so that an electric field is formed between the two conductive sheets. After the powder enters the drying tower, it is charged with the same charge, so it repels each other and avoids agglomeration. It is then attracted by the heterogeneous charges of the collection device. Improve powder yield.
还包括进料管，进料管依次连接高压风机1、搅拌器2、加热器3，加热器3位于靠近干燥塔的4一端，进料管的一端伸入干燥塔4，伸入端的底部设置高压喷嘴5。进料管的一端从干燥塔4顶部的进料口伸入。两个导线分别伸入干燥塔的顶部和收集装置，收集装置的顶部设置敞口，敞口对着出料口，所以两个电极相对。It also includes a feeding pipe. The feeding pipe is connected to the high-pressure fan 1, the agitator 2, and the heater 3 in turn. The heater 3 is located at one end of the drying tower 4. One end of the feeding pipe extends into the drying tower 4, and the bottom of the extending end is provided with High pressure nozzle 5. One end of the feed pipe extends into the feed port at the top of the drying tower 4 . The two wires extend into the top of the drying tower and the collecting device respectively. The top of the collecting device is provided with an opening, and the opening faces the discharge port, so the two electrodes are opposite.
电源8为直流电源。The power source 8 is a DC power source.
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。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种石墨烯增强镁基复合材料的制备方法，其特征在于：具体步骤为：A preparation method of graphene reinforced magnesium-based composite material, characterized in that: the concrete steps are:
    将增强体、镁基体与液体相容剂混合得到悬浊液；Mix the reinforcing body, the magnesium matrix and the liquid compatibilizer to obtain a suspension;
    将得到的悬浊液通过喷雾干燥得到干燥粉末；The obtained suspension is spray-dried to obtain dry powder;
    将得到的干燥粉末进行成型处理得到块体坯料；The obtained dry powder is subjected to a molding process to obtain a block blank;
    将块体坯料和镁合金坯料进行熔化混合，浇铸得到石墨烯增强镁基复合材料。The bulk billet and the magnesium alloy billet are melted and mixed, and cast to obtain a graphene-reinforced magnesium-based composite material.
  2. 如权利要求1所述的石墨烯增强镁基复合材料的制备方法，其特征在于：镁基体与增强体的混合比例为：增强体质量分数为0.1-5％，余量为镁基体；优选的，增强体质量分数为5％；The method for preparing a graphene-reinforced magnesium-based composite material according to claim 1, wherein the mixing ratio of the magnesium matrix and the reinforcement is: the mass fraction of the reinforcement is 0.1-5%, and the remainder is the magnesium matrix; preferably , the enhanced body mass fraction is 5%;
    或，增强体为石墨烯或氧化石墨烯，其平均厚度1～30nm，平均片径100nm～100μm；Or, the reinforcing body is graphene or graphene oxide, the average thickness of which is 1-30 nm, and the average sheet diameter is 100 nm-100 μm;
    或，镁基体为纯镁粉末或镁合金粉末，平均粒径为1～100μm；Or, the magnesium matrix is pure magnesium powder or magnesium alloy powder, and the average particle size is 1-100 μm;
    或，液体相容剂的质量与镁基体与增强体的质量和的比为1-3:1；优选为2:1。Or, the ratio of the mass of the liquid compatibilizer to the mass sum of the magnesium matrix and the reinforcing body is 1-3:1; preferably 2:1.
  3. 如权利要求1所述的石墨烯增强镁基复合材料的制备方法，其特征在于：液体相容剂包括水、无水乙醇、丙酮中至少一种；The method for preparing a graphene-reinforced magnesium-based composite material according to claim 1, wherein the liquid compatibilizer comprises at least one of water, dehydrated alcohol, and acetone;
    优选的，当液体相容剂为水时，机械搅拌所处的气氛环境为惰性气体；Preferably, when the liquid compatibilizer is water, the atmosphere in which the mechanical stirring is located is an inert gas;
    优选的，当液体相容剂为无水乙醇和/或丙酮时，机械搅拌所处的气氛环境为空气；Preferably, when the liquid compatibilizer is absolute ethanol and/or acetone, the atmosphere in which the mechanical stirring is located is air;
    进一步优选的，机械搅拌的速率为200～10000r/min，搅拌时间为0.5～20h。Further preferably, the speed of mechanical stirring is 200-10000r/min, and the stirring time is 0.5-20h.
  4. 如权利要求1所述的石墨烯增强镁基复合材料的制备方法，其特征在于：喷雾干燥的方法为：利用喷雾干燥机，在高压热风的条件下，静电喷枪喷出悬浊液得到干燥粉末；The preparation method of graphene reinforced magnesium-based composite material as claimed in claim 1, it is characterized in that: the method of spray drying is: utilize spray dryer, under the condition of high pressure hot air, electrostatic spray gun sprays suspension liquid to obtain dry powder ;
    优选的，悬浊液在喷雾干燥机的加料罐中的搅拌速度为100rpm～1000rpm；优选为700-900rpm；Preferably, the stirring speed of the suspension in the feeding tank of the spray dryer is 100rpm-1000rpm; preferably 700-900rpm;
    优选的，静电喷枪的输出电压为10-85kv；优选为60-70kv。Preferably, the output voltage of the electrostatic spray gun is 10-85kv; preferably 60-70kv.
  5. 如权利要求1所述的石墨烯增强镁基复合材料的制备方法，其特征在于：坯料的成型处理方法为冷压成型；优选的冷压成型的条件为：室温下，压力为100-300MPa，保压时间为4-6min；优选的，压力为200MPa，保压时间为5min；The preparation method of graphene-reinforced magnesium-based composite material according to claim 1, characterized in that: the forming treatment method of the blank is cold pressing; The pressure holding time is 4-6min; preferably, the pressure is 200MPa, and the pressure holding time is 5min;
    或，坯料熔化混合中的惰性气体为SF 6+CO 2混合气体； Or, the inert gas in the billet melting and mixing is SF 6 +CO 2 mixed gas;
    或，坯料熔化混合中的惰性气体为SF 6+CO 2混合气体； Or, the inert gas in the billet melting and mixing is SF 6 +CO 2 mixed gas;
    或，镁合金坯料和块体坯料熔化后进行机械搅拌，机械搅拌速率为10rpm～8000rpm，所述机械搅拌时间为5min～60min。Or, the magnesium alloy billet and the bulk billet are melted and then mechanically stirred, the mechanical stirring speed is 10 rpm to 8000 rpm, and the mechanical stirring time is 5 min to 60 min.
  6. 如权利要求4所述的石墨烯增强镁基复合材料的制备方法，其特征在于：喷雾干 燥机包括干燥塔和电源、收集装置，电源的正极或负极分别通过导线与干燥塔、收集装置连接，两个导线的一端分别连接导电片，两个导电片分别位于干燥塔的顶部、收集装置中，干燥塔的底部设置出料口，收集装置位于干燥塔的下方与出料口相对；The preparation method of graphene-enhanced magnesium-based composite material as claimed in claim 4, characterized in that: the spray dryer comprises a drying tower, a power supply, and a collection device, and the positive electrode or the negative electrode of the power supply is connected to the drying tower and the collection device through wires, respectively, One ends of the two wires are respectively connected to the conductive sheets, and the two conductive sheets are respectively located at the top of the drying tower and in the collecting device. The bottom of the drying tower is provided with a discharge port, and the collecting device is located below the drying tower and is opposite to the discharge port;
    优选的，还包括进料管，进料管依次连接高压风机、搅拌器、加热器，加热器位于靠近干燥塔的一端，进料管的一端伸入干燥塔，伸入端的底部设置高压喷嘴；Preferably, it also includes a feed pipe, the feed pipe is sequentially connected to a high-pressure fan, an agitator, and a heater, the heater is located at one end close to the drying tower, one end of the feed pipe extends into the drying tower, and a high-pressure nozzle is arranged at the bottom of the extended end;
    优选的，电源为直流电源。Preferably, the power source is a DC power source.
  7. 权利要求1-6任一所述的石墨烯增强镁基复合材料的制备方法得到的石墨烯增强镁基复合材料；The graphene-reinforced magnesium-based composite material obtained by the preparation method of any described graphene-reinforced magnesium-based composite material of claims 1-6;
    优选的，石墨烯质量分数为0.1％～5％，进一步优选的，石墨烯质量分数为0.5-2.5％。Preferably, the mass fraction of graphene is 0.1%-5%, and further preferably, the mass fraction of graphene is 0.5-2.5%.
  8. 权利要求1-6任一所述的石墨烯增强镁基复合材料的制备方法或权利要求7所述的石墨烯增强镁基复合材料在汽车、轨道交通和航空航天领域中的应用。The preparation method of the graphene-reinforced magnesium-based composite material described in any one of claims 1-6 or the application of the graphene-reinforced magnesium-based composite material according to claim 7 in the fields of automobiles, rail transit and aerospace.
  9. 一种零部件，其特征在于：包括权利要求7所述的石墨烯增强镁基复合材料。A component, characterized in that it comprises the graphene-reinforced magnesium-based composite material of claim 7.
  10. 权利要求9所述的零部件的制备方法，其特征在于：所述方法为，将石墨烯增强镁基复合材料进行半固态保温，得到复合材料半固态坯料，然后将石墨烯增强镁基复合材料进行压铸成型得到零部件；The preparation method of the part according to claim 9, characterized in that: the method is to carry out semi-solid heat preservation of the graphene-reinforced magnesium-based composite material to obtain a semi-solid blank of the composite material, and then the graphene-reinforced magnesium-based composite material is Die-casting to obtain parts;
    优选的，半固态保温的温度为595～615℃，保温的时间为30～120min；Preferably, the temperature of the semi-solid heat preservation is 595 to 615°C, and the time of the heat preservation is 30 to 120 minutes;
    优选的，压铸成型的条件为：压射速度1～7m/s，压射比压30～200MPa，保压时间20～50s。Preferably, the die-casting conditions are as follows: the injection speed is 1-7 m/s, the injection specific pressure is 30-200 MPa, and the pressure holding time is 20-50 s.
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