CN111996410A - Graphene reinforced magnesium-based composite material and preparation method and application thereof - Google Patents
Graphene reinforced magnesium-based composite material and preparation method and application thereof Download PDFInfo
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- CN111996410A CN111996410A CN202010980907.4A CN202010980907A CN111996410A CN 111996410 A CN111996410 A CN 111996410A CN 202010980907 A CN202010980907 A CN 202010980907A CN 111996410 A CN111996410 A CN 111996410A
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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
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- 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
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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
- C22C1/1073—Infiltration or casting under mechanical pressure, e.g. squeeze casting
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- 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
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- 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
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Abstract
The invention relates to a graphene reinforced magnesium-based composite material and a preparation method and application thereof. Mixing the reinforcement, the magnesium matrix and the liquid compatilizer to obtain suspension; spray drying the obtained suspension to obtain dry powder; molding the obtained dry powder to obtain a block blank; and melting and mixing the block blank and the magnesium alloy blank, and casting to obtain the graphene reinforced magnesium-based composite material. The graphene nanoparticle reinforced magnesium-based composite material is prepared by a low-cost process, the dispersion and spreading of the agglomerated and wrinkled industrial graphene material can be realized by one-step mechanical stirring, the mechanical damage of the graphene material cannot be caused, and meanwhile, the preparation of the composite material has low requirements on equipment, low processing cost, high production efficiency and controllable interface structure, and has excellent industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of graphene reinforced magnesium-based composite materials, and particularly relates to a graphene reinforced magnesium-based composite material and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The magnesium alloy has low density, high specific strength and rigidity and excellent damping performance, is applied to the fields of automobiles, rail transit, aerospace and the like, and is an important structural material for realizing light weight. However, the magnesium alloy has low strength and poor plasticity, and the application of the magnesium alloy is limited. Improving the strength and the shaping of the magnesium alloy, and is a necessary way for expanding the application field of the magnesium alloy.
The research at present finds that the strength and the shaping of the magnesium matrix can be greatly improved by adding a very small amount of graphene into the magnesium matrix. The graphene has excellent mechanical properties, the elastic modulus of the graphene can reach 1TPa, the tensile strength can reach 125GPa, and the density of the graphene is only 2.23g/cm3It is an ideal magnesium alloy matrix strengthening phase. At present, the preparation process of the graphene reinforced magnesium-based composite material mainly comprises a solid forming method and a liquid forming method.
However, many problems still exist with current preparation techniques, such as: 1. the interface structure is not adjustable; 2. the process route is complicated, and high-efficiency industrial production is difficult to realize; 3. the process strengthens the damage of the phase structure and reduces the strengthening effect.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a graphene reinforced magnesium-based composite material and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a graphene reinforced magnesium-based composite material comprises the following specific steps:
mixing the reinforcement, the magnesium matrix and the liquid compatilizer to obtain suspension;
spray drying the obtained suspension to obtain dry powder;
molding the obtained dry powder to obtain a block blank;
carrying out hot extrusion molding on the block blank to obtain a graphene magnesium-based composite material preform;
melting and mixing the composite material preform and the magnesium alloy blank, and casting to obtain the graphene reinforced magnesium-based composite material;
and (3) preserving the temperature of the casting blank at a semi-solid temperature, and then carrying out die casting and extrusion casting to obtain the composite material part.
The mixing effect of the reinforcement, the magnesium matrix and the liquid compatilizer is that the shearing force generated by mechanical stirring is utilized to promote the further dispersion of the graphene powder, so that turbid liquid of the magnesium matrix and the graphene is obtained;
through the spray drying process, the long-time drying process is avoided, and the problem of agglomeration under the influence of interfacial tension due to solution evaporation is also avoided;
carrying out hot extrusion on the powder cold-pressed block, adding a hot extrusion bar into a magnesium alloy melt, obtaining a uniformly dispersed composite material melt by utilizing the self-stabilization effect of the nano particles in the melt, and casting to obtain a composite material casting blank;
and (3) performing semi-solid heat preservation on the casting blank, wherein the purpose of the semi-solid heat preservation is to regulate and control the solid-liquid phase component ratio and the graphene/magnesium matrix interface structure, and then performing die casting or extrusion casting on the semi-solid blank to obtain the magnesium-based composite material part.
In some embodiments of the invention, the magnesium matrix and the reinforcement are mixed in the following ratio: the mass fraction of the reinforcement is 0.1-5%; preferably 5%, the balance being magnesium matrix.
In some embodiments of the present invention, the reinforcement is graphene or graphene oxide, and has an average thickness of 1 to 30nm and an average plate diameter of 100nm to 100 μm.
In some embodiments of the present invention, the magnesium matrix is a pure magnesium powder or a magnesium alloy powder, and has an average particle size of 1 to 100 μm.
In some embodiments of the 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.
In some embodiments of the invention, the liquid compatibilizing agent comprises at least one of water, absolute ethanol, acetone.
Preferably, when the liquid compatibilizer is water, the mixing is performed by mechanical stirring, and the atmosphere in which the mechanical stirring is performed is air.
Preferably, when the liquid compatibilizer is absolute ethanol and/or acetone, the atmosphere in which the mechanical agitation is performed is an inert gas.
Further preferably, the mechanical stirring speed is 200-10000 r/min, and the stirring time is 0.5-20 h.
The mechanical stirring is matched with the liquid compatilizer to realize the mixing of the magnesium matrix and the reinforcement, and the dispersion of the agglomerated graphene and the spreading of the wrinkled graphene are realized by utilizing the shearing force generated by the mechanical stirring to obtain the suspension distributed in a dispersing way.
In some embodiments of the invention, the method of spray drying is: and spraying the suspension from the electrostatic spray gun by using a spray dryer under the condition of high-pressure hot air to obtain dry powder.
Preferably, the stirring speed of the suspension in the feeding tank of the spray dryer is 100 rpm-1000 rpm; preferably 700-900 rpm;
preferably, the output voltage of the electrostatic spray gun is 10-85 kv; preferably 60-70 kv.
The parameters of spray drying affect the particle size and uniformity, yield of the resulting dried powder. The yield of the dried powder was 97.9% by the spray drying method described above.
In some embodiments of the present invention, the graphene-reinforced magnesium-based composite material has a graphene mass content of 0.1 to 5%; preferably 0.5-2.5%.
In some embodiments of the invention, the method of forming the blank is cold press forming; preferred cold press forming conditions are: at room temperature, the pressure is 100-300MPa, and the pressure maintaining time is 4-6 min; preferably, the pressure is 200MPa and the dwell time is 5 min.
The condition of cold press molding is favorable for mixing the graphene and the magnesium matrix, the graphene is uniformly dispersed, agglomeration is avoided, metallurgical bonding of the graphene and the magnesium matrix is facilitated, and the bonding strength is higher.
In some embodiments of the invention, the inert gas in the melt mixing of the billet is SF6+CO2And (4) mixing the gases.
In some embodiments of the present invention, the magnesium alloy ingot and the bulk ingot are melted and then mechanically stirred at a mechanical stirring rate of 10rpm to 100rpm for a mechanical stirring time of 5min to 60 min.
In some embodiments of the invention, the casting temperature is 700 to 750 ℃; preferably 720 deg.c.
In a fourth aspect, a spray drying device comprises a drying tower, a power supply and a collecting device, wherein a positive electrode or a negative electrode of the power supply is respectively connected with the drying tower and the collecting device through leads, one ends of the two leads are respectively connected with conducting strips, the two conducting strips are respectively positioned at the top of the drying tower and in the collecting device, a discharge port is formed in the bottom of the drying tower, and the collecting device is positioned below the drying tower and is opposite to the discharge port.
In some embodiments of the present invention, the drying tower further comprises a feeding pipe, the feeding pipe is sequentially connected with the high pressure fan, the stirrer and the heater, the heater is located at one end close to the drying tower, one end of the feeding pipe extends into the drying tower, and the bottom of the end extending into the drying tower is provided with the high pressure nozzle.
In some embodiments of the invention, the power supply is a dc power supply.
In a third aspect, the graphene-reinforced magnesium-based composite material is obtained by the preparation method of the graphene-reinforced magnesium-based composite material.
Preferably, the mass fraction of the graphene is 0.1% to 5%, and more preferably, the mass fraction of the graphene is 0.5% to 2.5%. Within the range, the graphene has better fine-grain strengthening and dispersion strengthening effects.
In a fourth aspect, the 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 are provided.
In a fifth aspect, a component includes the graphene reinforced magnesium-based composite material.
In a sixth aspect, the method for preparing the component includes the steps of performing semi-solid heat preservation on the graphene reinforced magnesium-based composite material to obtain a composite material semi-solid blank, and then performing die-casting molding on the graphene reinforced magnesium-based composite material to obtain the component.
And (3) performing semi-solid heat preservation on the casting blank, wherein the purpose of the semi-solid heat preservation is to regulate and control the solid-liquid phase component ratio and the graphene/magnesium matrix interface structure, and then performing die casting or extrusion casting on the semi-solid blank to obtain the magnesium-based composite material part.
Preferably, the semi-solid heat preservation temperature is 595-615 ℃, and the heat preservation time is 30-120 min.
Preferably, the conditions for the die casting are as follows: the injection speed is 1-7 m/s, the injection specific pressure is 30-200 MPa, and the pressure maintaining time is 20-50 s.
The microstructure of the obtained semi-solid material is distributed evenly and refined through the semi-solid heat preservation treatment step.
One or more technical schemes of the invention have the following beneficial effects:
1. the graphene nanoparticle reinforced magnesium-based composite material is efficiently prepared by adopting a low-cost process, the dispersion and spreading of the agglomerated and wrinkled industrial-grade graphene material are realized by mechanical stirring, the graphene is introduced into the molten magnesium alloy by adopting a cold-pressing prefabricated blank, the oxidation and agglomeration phenomena of the graphene in the casting process can be effectively solved by utilizing the self-stabilization effect of the graphene nanoparticles, and the process is simple in flow, low in equipment requirement, low in processing cost, high in production efficiency and excellent in industrial application prospect.
2. The graphene and magnesium matrix powder turbid liquid is subjected to a spray drying method, so that a long-time drying process is avoided; the spraying method adopts direct current, and agglomeration in the drying process is avoided. Compared with the traditional drying method, the preparation efficiency is improved; compared with vacuum drying, freeze drying and supercritical drying, the method reduces the equipment cost.
3. The semi-solid heat preservation treatment is carried out on the as-cast blank, so that the regulation and control of the interface structure, the components, the primary phase particle size and morphology and the solid-liquid phase proportion are realized.
4. The semi-solid blank is thixomolded by adopting the technologies of die casting, extrusion casting and the like, and by utilizing the characteristics of high viscosity and low temperature of the semi-solid blank, compared with full-liquid molding, the method realizes laminar filling, avoids the defects of air entrainment, shrinkage porosity and the like, and realizes high-density casting.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a gold phase diagram of composite materials obtained by different graphene contents in examples 1 to 3 and comparative example 1; wherein a is comparative example 1, b is example 2, c is example 1, d is example 3;
FIG. 2 shows the interfaces of the composite materials obtained in examples 1 to 3 and comparative example 1; wherein a is comparative example 1, b is example 2, c is example 1, d is example 3;
fig. 3 is a graph showing hardness evolution of composite materials obtained from different graphene contents in examples 1 to 3 and comparative example 1.
FIG. 4 is a transmission electron micrograph of the composite material interface in example 1.
FIG. 5 shows the microstructure of the semi-solid insulation water quenched composite material of example 4.
Fig. 6 is a water-quenched structure diagram of a semi-solid billet of example 4.
Fig. 7 is a structural view of the spray drying apparatus.
The device comprises a high-pressure fan 1, a high-pressure fan 2, a stirrer 3, a heater 4, a drying tower 5, a high-pressure nozzle 6, a collecting device 7, a discharge hole 8 and a power supply.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. The invention will be further illustrated by the following examples
Example 1
A high-efficiency preparation method of a graphene nanoparticle reinforced magnesium-based composite material comprises the following steps:
(1) weighing 250g of a reinforcement (5%) and a magnesium matrix (95%) according to the mass fraction (wt.%), wherein the reinforcement is few-layer graphene, the thickness of the reinforcement is 3-10 nm, and the sheet diameter of the reinforcement is 5-10 μm; the magnesium matrix is AZ91 magnesium alloy powder, and the particle size is 1-2 μm.
(2) Respectively preparing the powder weighed in the step (1) into suspension by mechanical stirring and a liquid compatilizer, and specifically, the method comprises the following steps: and (3) putting the powder of each group into a mechanical stirrer, adding 500g of absolute ethyl alcohol, and mechanically stirring in an air environment at the stirring speed of 8000r/min for 3-60 min to obtain a suspension.
(3) Respectively preparing the suspension obtained in the step (2) into dry composite material powder by an electrostatic spray drying method, which comprises the following steps: and (3) placing the suspension in a feeding tank of a spray dryer, wherein the stirring speed in the feeding tank is 800rpm, spraying the suspension out of the electrostatic spray gun under the action of high-pressure hot air, and outputting a voltage of 60kv by the electrostatic spray gun to finally obtain the composite material powder after uniformly mixing the reinforcement and the matrix. Through the test: the yields of the above powders were 97.9%, respectively.
(4) Adding the composite material powder obtained in the step (3) into a self-made die for cold press forming, wherein the diameter of a cold preformed blank is 50mm, and the press forming conditions are as follows: room temperature, pressure 200MPa, dwell time 5 min.
(5) Weighing 500g of AZ91 magnesium alloy block and cold-pressed prefabricated blank according to the mass fraction (wt.%), wherein the mass content of graphene is 1.5%, and placing the AZ91 magnesium alloy block in SF6+CO2And (3) melting under the protection of mixed gas, heating to 780 ℃ after the alloy is melted, preserving heat for 30min, putting the block prefabricated blank in the step (4) into a crucible, mechanically stirring after the prefabricated blank is melted, wherein the mechanical stirring speed is 100rpm, and the mechanical stirring time is 15min, and casting at 740 ℃ to obtain the graphene nanoparticle reinforced magnesium-based composite material.
Example 2
Compared with example 1, the mass content of graphene in step (5) is 0.5%.
Example 3
Compared with example 1, the mass content of graphene in step (5) is 2.5%.
Comparative example 1
Compared with example 1, the mass content of graphene in step (5) is 0%. That is, no reinforcement was added in step (1) as compared to example 1. The other processing steps are the same as in example 1.
Specific compositions of example 1, example 2, example 3 and comparative example 1 are shown in table 1, and the mass contents of the four groups of materials, graphene, are 0, 0.5%, 1.5% and 2.5%, respectively.
TABLE 1 four groups of formulation
The results of observing the four graphene nanoparticle-reinforced magnesium-based composite materials prepared in the steps (5) of the examples 1 to 3 and the comparative example 1 by using a Zeiss Axio observer Alm type metallographic microscope are respectively shown in a graph a to a graph d in fig. 1. As can be seen from diagrams b to d in FIG. 1: the graphene is uniformly dispersed in the AZ91 magnesium matrix, the agglomeration phenomenon is avoided, and the concentration degree of the graphene in the composite material is obviously increased along with the increase of the content of the graphene.
The four graphene nanoparticle-reinforced mg-based composites prepared in examples 1 to 3 and comparative example 1 were subjected to T4 solid solution to detect the crystal grain size. The specific parameters are as follows: and (3) carrying out solution treatment at 435 ℃ and keeping the temperature for 2 h. The microstructure of the composite material after solution treatment was observed by the metallographic microscope, and the results are shown in fig. 2, a to d. As can be seen from diagrams b to d in FIG. 2: the introduction of the graphene can obviously refine the grain size of the AZ91 magnesium alloy matrix, and the grain size of the magnesium is refined from 176 mu m (graphene content is 0%) to 32 mu m (graphene content is 1.5 wt%).
The hardness of the composite material after the solution treatment was measured using an XHV-1000 type microhardness tester, and the results are shown in FIG. 3. As can be seen from FIG. 3, the addition of graphene can obviously improve the hardness of the composite material, the hardness of the material is increased from-66 HV (graphene content 0%) to-89 HV (graphene content 1.5 wt.%), and the increase is 35%, mainly due to the fine-grain strengthening and dispersion strengthening effects brought by the introduction of graphene.
The interface of the composite material of group C prepared in step (5) of example 1 was observed by a transmission electron microscope, and the result is shown in fig. 4. As can be seen from fig. 4: the interface of the graphene magnesium-based composite material has obvious transition layer and interface product generation, the transition layer and the interface product are combined into metallurgical bonding, and the bonding strength is high.
Example 4
A graphene nanoparticle reinforced magnesium-based composite material interface regulation method comprises the following steps:
(1) weighing 250g of a reinforcement (5%) and a magnesium matrix (95%) according to the mass fraction (wt.%), wherein the reinforcement is few-layer graphene, the thickness of the reinforcement is 3-10 nm, and the sheet diameter of the reinforcement is 5-10 μm; the magnesium matrix is AZ91 magnesium alloy powder, and the particle size is 1-2 μm.
(2) Respectively preparing the powder weighed in the step (1) into suspension by mechanical stirring and a liquid compatilizer, and specifically, the method comprises the following steps: and (3) putting the powder of each group into a mechanical stirrer, adding 500g of absolute ethyl alcohol, and mechanically stirring in an air environment at the stirring speed of 8000r/min for 1.0h to obtain a suspension.
(3) Respectively preparing the suspension obtained in the step (2) into dry composite material powder by an electrostatic spray drying method, which comprises the following steps: and (3) placing the suspension in a feeding tank of a spray dryer, wherein the stirring speed in the feeding tank is 800rpm, spraying the suspension out of the electrostatic spray gun under the action of high-pressure hot air, and outputting a voltage of 60kv by the electrostatic spray gun to finally obtain the composite material powder after uniformly mixing the reinforcement and the matrix. Through the test: the yields of the above powders were 97.9%, respectively.
(4) Adding the composite material powder obtained in the step (3) into a self-made die for cold press forming, wherein the diameter of a cold preformed blank is 50mm, and the press forming conditions are as follows: room temperature, pressure 200MPa, dwell time 5 min.
(5) Weighing 500g of AZ91 magnesium alloy block (99%) and cold-pressed preform (1%) in mass fraction (wt.%), and placing AZ91 magnesium alloy block in SF6+CO2And (3) melting under the protection of mixed gas, heating to 780 ℃ after the alloy is melted, preserving heat for 30min, putting the block prefabricated blank in the step (4) into a crucible, mechanically stirring after the prefabricated blank is melted, wherein the mechanical stirring speed is 100rpm, the mechanical stirring time is 15min, and casting at 740 ℃ to obtain the graphene nanoparticle reinforced magnesium-based composite material, namely the composite material as-cast blank.
(6) Performing semi-solid heat preservation on the composite material as-cast blank obtained in the step (5), wherein the specific parameters are as follows: 595 to 615 ℃, and the heat preservation time is 30 to 120 min. And obtaining the composite material semi-solid blank. The main purpose of the step is to realize the regulation and control of the solid-liquid phase proportion, the appearance and the size of primary phase particles and the interface structure of the composite material. The microstructure of the composite material after the semi-solid heat-preservation water quenching treatment is observed by adopting the metallographic microscope, and the results are respectively shown in a-d diagrams in fig. 5.
(7) And (4) transferring the semi-solid blank obtained in the step (6) into a die-casting die for die-casting forming. The specific parameters are as follows: the injection speed is 1-7 m/s, the injection specific pressure is 30-200 MPa, and the pressure maintaining time is 20-50 s. And obtaining the composite material semi-solid die-casting part.
The water-quenched sample obtained in step (6) was subjected to composition analysis by EDS, and the results are shown in table 2. As can be seen from the diagrams a and b in fig. 5 and table 2, the control of the primary phase morphology, the solid-liquid phase ratio and the solute element concentration thereof can be realized by adjusting the process parameters in the step (6).
TABLE 2 evolution of the composition of the semi-solid system
And (3) observing the interface of graphene/AZ 91D in the water-quenched structure of the semi-solid blank of the composite material prepared in the step (6) by using a transmission electron microscope, wherein the result is shown in FIG. 6. As can be seen from the diagrams a and b in fig. 6: and (4) regulating and controlling the interface configuration of the composite material by adjusting the process parameters in the step (6). The regulation mechanism is the changes of the temperature, the time and the solute element components, which result in the changes of the interface wettability, the interface product and the interface thickness.
Example 5
An efficient preparation method of an interface-adjustable graphene reinforced magnesium-based composite material comprises the following steps:
(1) weighing 250g of a reinforcement (5%) and a magnesium matrix (95%) according to the mass fraction (wt.%), wherein the reinforcement is few-layer graphene, the thickness of the reinforcement is 3-10 nm, and the sheet diameter of the reinforcement is 5-10 μm; the magnesium matrix is AZ91 magnesium alloy powder, and the particle size is 1-2 μm.
(2) Respectively preparing the powder weighed in the step (1) into suspension by mechanical stirring and a liquid compatilizer, and specifically, the method comprises the following steps: and (3) putting the powder of each group into a mechanical stirrer, adding 500g of absolute ethyl alcohol, and mechanically stirring in an air environment at the stirring speed of 8000r/min for 1.0h to obtain a suspension. The main purpose of the 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) Respectively preparing the suspension obtained in the step (2) into dry composite material powder by an electrostatic spray drying method, which comprises the following steps: and (3) placing the suspension in a feeding tank of a spray dryer, wherein the stirring speed in the feeding tank is 800rpm, spraying the suspension out of the electrostatic spray gun under the action of high-pressure hot air, and outputting a voltage of 60kv by the electrostatic spray gun to finally obtain the composite material powder after uniformly mixing the reinforcement and the matrix. Through the test: the yields of the above powders were 97.9%, respectively.
(4) Adding the composite material powder obtained in the step (3) into a self-made die for cold press forming, wherein the diameter of a cold preformed blank is 50mm, and the press forming conditions are as follows: room temperature, pressure 200MPa, dwell time 5 min.
(5) Weighing 500g of AZ91 magnesium alloy block (99%) and cold-pressed preform (1%) in mass fraction (wt.%), and placing AZ91 magnesium alloy block in SF6+CO2And (3) melting under the protection of mixed gas, heating to 780 ℃ after the alloy is melted, keeping the temperature for 30min, putting the block prefabricated blank in the step (4) into a crucible, mechanically stirring the melted prefabricated blank at the speed of 100rpm for 15min at 740 ℃, and casting to obtain the graphene nanoparticle reinforced magnesium-based composite material, wherein the content of graphene in the composite material is 0.1%.
Example 6
An efficient preparation method of an interface-adjustable graphene reinforced magnesium-based composite material comprises the following steps:
(1) weighing 250g of a reinforcement (5%) and a magnesium matrix (95%) according to the mass fraction (wt.%), wherein the reinforcement is few-layer graphene, the thickness of the reinforcement is 3-10 nm, and the sheet diameter of the reinforcement is 5-10 μm; the magnesium matrix is AZ91 magnesium alloy powder, and the particle size is 1-2 μm.
(2) Respectively preparing the powder weighed in the step (1) into suspension by mechanical stirring and a liquid compatilizer, and specifically, the method comprises the following steps: and (3) putting the powder of each group into a mechanical stirrer, adding 500g of absolute ethyl alcohol, and mechanically stirring in an air environment at the stirring speed of 8000r/min for 1.0h to obtain a suspension. The main purpose of the 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) Respectively preparing the suspension obtained in the step (2) into dry composite material powder by an electrostatic spray drying method, which comprises the following steps: and (3) placing the suspension in a feeding tank of a spray dryer, wherein the stirring speed in the feeding tank is 800rpm, spraying the suspension out of the electrostatic spray gun under the action of high-pressure hot air, and outputting a voltage of 60kv by the electrostatic spray gun to finally obtain the composite material powder after uniformly mixing the reinforcement and the matrix. Through the test: the yields of the above powders were 97.9%, respectively.
(4) Adding the composite material powder obtained in the step (3) into a self-made die for cold press forming, wherein the diameter of a cold preformed blank is 50mm, and the press forming conditions are as follows: room temperature, pressure 200MPa, dwell time 5 min.
(5) Weighing 500g of AZ91 magnesium alloy block (50%) and cold-pressed preform (50%) in mass fraction (wt.%), and placing AZ91 magnesium alloy block in SF6+CO2And (3) melting under the protection of mixed gas, heating to 780 ℃ after the alloy is melted, keeping the temperature for 30min, putting the block prefabricated blank in the step (4) into a crucible, mechanically stirring the melted prefabricated blank at the speed of 100rpm for 15min at 740 ℃, and casting to obtain the graphene nanoparticle reinforced magnesium-based composite material, wherein the content of graphene in the composite material is 5%.
As shown in fig. 7, a spray drying device comprises a drying tower 4, a power supply 8 and a collecting device 6, wherein the positive electrode or the negative electrode of the power supply 8 is respectively connected with the drying tower 4 and the collecting device 6 through wires, one end of each of the two wires is respectively connected with a conducting strip, the two conducting strips are respectively located at the top of the drying tower 4 and in the collecting device 6, a discharge hole 6 is formed in the bottom of the drying tower 4, and the collecting device 6 is located below the drying tower 4 and is opposite to the opening.
Compared with the existing drying tower 4, the power supply 8 is added, two poles of the power supply 8 are respectively connected with the leads, and the leads 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 conducting strips, and the powder is charged with the same kind of charges after entering the drying tower, so that the powder is mutually repelled to avoid agglomeration. And then attracted by the heterogeneous charge of the collection means. The powder yield is improved.
Still include the inlet pipe, the inlet pipe connects gradually high pressure positive blower 1, agitator 2, heater 3, and heater 3 is located 4 one ends near the drying tower, and the one end of inlet pipe stretches into drying tower 4, and the bottom of stretching into the end sets up high pressure nozzle 5. One end of the feed pipe extends from the feed inlet at the top of the drying tower 4. Two wires stretch into the top and the collection device of drying tower respectively, and collection device's top sets up uncovered, and uncovered is facing to the discharge gate, so two electrodes are relative.
The power supply 8 is a dc power supply.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a graphene reinforced magnesium-based composite material is characterized by comprising the following steps: the method comprises the following specific steps:
mixing the reinforcement, the magnesium matrix and the liquid compatilizer to obtain suspension;
spray drying the obtained suspension to obtain dry powder;
molding the obtained dry powder to obtain a block blank;
and melting and mixing the block blank and the magnesium alloy blank, and casting to obtain the graphene reinforced magnesium-based composite material.
2. The method for preparing a graphene-reinforced magnesium-based composite material according to claim 1, wherein: the mixing ratio of the magnesium matrix to the reinforcement is as follows: the mass fraction of the reinforcement is 0.1-5%, and the balance is magnesium matrix; preferably, the mass fraction of the reinforcement is 5%;
or the reinforcement is graphene or graphene oxide, the average thickness of the reinforcement is 1-30 nm, and the average sheet diameter is 100 nm-100 mu m;
or the magnesium matrix is pure magnesium powder or magnesium alloy powder, and the average grain diameter is 1-100 mu m;
or the ratio of the mass of the liquid compatilizer to the mass sum of the magnesium matrix and the reinforcement is 1-3: 1; preferably 2: 1.
3. The method for preparing a graphene-reinforced magnesium-based composite material according to claim 1, wherein: the liquid compatilizer comprises at least one of water, absolute ethyl alcohol and acetone;
preferably, when the liquid compatibilizer is water, the atmosphere in which the mechanical stirring is performed is an inert gas;
preferably, when the liquid compatilizer is absolute ethyl alcohol and/or acetone, the atmosphere environment in which the mechanical stirring is carried out is air;
further preferably, the mechanical stirring speed is 200-10000 r/min, and the stirring time is 0.5-20 h.
4. The method for preparing a graphene-reinforced magnesium-based composite material according to claim 1, wherein: the spray drying method comprises the following steps: spraying suspension from an electrostatic spray gun by using a spray dryer under the condition of high-pressure hot air to obtain dry powder;
preferably, the stirring speed of the suspension in the feeding tank of the spray dryer is 100 rpm-1000 rpm; preferably 700-900 rpm;
preferably, the output voltage of the electrostatic spray gun is 10-85 kv; preferably 60-70 kv.
5. The method for preparing a graphene-reinforced magnesium-based composite material according to claim 1, wherein: the forming treatment method of the blank is cold press forming; preferred cold press forming conditions are: at room temperature, the pressure is 100-300MPa, and the pressure maintaining time is 4-6 min; preferably, the pressure is 200MPa, and the pressure maintaining time is 5 min;
or the inert gas in the blank melting and mixing is SF6+CO2Mixing the gas;
or the inert gas in the blank melting and mixing is SF6+CO2Mixing the gas;
or, after the magnesium alloy blank and the block blank are melted, mechanically stirring at the speed of 10-8000 rpm for 5-60 min.
6. The method for preparing a graphene-reinforced magnesium-based composite material according to claim 4, wherein: the spray dryer comprises a drying tower, a power supply and a collecting device, wherein the positive pole or the negative pole of the power supply is respectively connected with the drying tower and the collecting device through leads, one ends of the two leads are respectively connected with conducting strips, the two conducting strips are respectively positioned at the top of the drying tower and in the collecting device, the bottom of the drying tower is provided with a discharge hole, and the collecting device is positioned below the drying tower and is opposite to the discharge hole;
preferably, the drying tower further comprises a feeding pipe, the feeding pipe is sequentially connected with a high-pressure fan, a stirrer and a heater, the heater is located at one end close to the drying tower, one end of the feeding pipe extends into the drying tower, and a high-pressure nozzle is arranged at the bottom of the extending end;
preferably, the power supply is a dc power supply.
7. A graphene-reinforced magnesium-based composite material obtained by the method for preparing a graphene-reinforced magnesium-based composite material according to any one of claims 1 to 6;
preferably, the mass fraction of the graphene is 0.1% to 5%, and more preferably, the mass fraction of the graphene is 0.5% to 2.5%.
8. A method of preparing the graphene-reinforced magnesium-based composite material as claimed in any one of claims 1 to 6 or the use of the graphene-reinforced magnesium-based composite material as claimed in claim 7 in the fields of automobiles, rail transit and aerospace.
9. A component, characterized by: comprising the graphene-reinforced magnesium-based composite material of claim 7.
10. The method of manufacturing a component part according to claim 9, wherein: the method comprises the steps of carrying out semi-solid heat preservation on the graphene reinforced magnesium-based composite material to obtain a composite material semi-solid blank, and then carrying out die-casting molding on the graphene reinforced magnesium-based composite material to obtain a part;
preferably, the semi-solid heat preservation temperature is 595-615 ℃, and the heat preservation time is 30-120 min;
preferably, the conditions for the die casting are as follows: the injection speed is 1-7 m/s, the injection specific pressure is 30-200 MPa, and the pressure maintaining time is 20-50 s.
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| WO2022057232A1 (en) * | 2020-09-17 | 2022-03-24 | 山东省科学院新材料研究所 | Graphene-reinforced magnesium-based composite material, preparation method for same, and applications thereof |
| CN114406271A (en) * | 2022-01-20 | 2022-04-29 | 山东省科学院新材料研究所 | Macroscopic preparation method, device and application of nanocarbon material-metal composite material |
| CN118497545A (en) * | 2024-07-17 | 2024-08-16 | 广州众山紧固件有限公司 | Preparation method of graphene reinforced magnesium alloy semi-solid slurry |
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| CN115608994A (en) * | 2022-09-22 | 2023-01-17 | 哈尔滨理工大学 | Preparation and forming process of magnesium-based composite material lath |
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| CN118497545A (en) * | 2024-07-17 | 2024-08-16 | 广州众山紧固件有限公司 | Preparation method of graphene reinforced magnesium alloy semi-solid slurry |
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