CN112941357B - Preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry - Google Patents
Preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
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- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/12—Making non-ferrous alloys by processing in a semi-solid state, e.g. holding the alloy in the solid-liquid phase
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
Abstract
The invention provides a preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry, belonging to the technical field of metal material manufacturing. A preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry comprises the following steps: under the condition of casting, adding an aluminum-yttrium master alloy into a melt in batches, preserving heat for a period of time, then adding an aluminum-graphene intermediate precast block into the melt in batches by using high-energy ultrasound, then rapidly reducing the temperature to a semi-solid interval, continuing ultrasound, and then rapidly quenching with water to obtain a uniformly spheroidized semi-solid structure. The method has the advantages of stable process, environmental protection and safety, obviously refined structure of the prepared semi-solid slurry, good combination of the graphene and a matrix interface, and relatively uniform distribution of secondary phases.
Description
Technical Field
The invention belongs to the technical field of metal material manufacturing, and particularly relates to a preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry.
Background
With the development of society, new energy automobiles will become the mainstream of the automobile industry in the future. In order to realize light weight, most new energy automobile parts are made of aluminum alloy. However, the performance requirements cannot be completely satisfied by a simple aluminum alloy, and an aluminum matrix composite with excellent performance can be used. Graphene has excellent mechanical, electrical and thermal properties and is considered to be the most attractive nano reinforcing phase for developing high-performance metal matrix composites. Therefore, the aluminum matrix composite prepared by using the graphene as the nano reinforcement has extremely excellent performance. However, the performance improvement and popularization and application of the graphene reinforced aluminum matrix composite material are limited by the preparation processes (such as powder metallurgy, melt stirring and the like) widely applied at home and abroad at present for the following reasons: the graphene is agglomerated in a matrix, and the poor interface reaction and the preparation process are complex. Aiming at the problems, the research on novel casting preparation technology is developed, the homogenization composite integration process of graphene and aluminum alloy is explored, and the shortening of the cycle time of the preparation process and the forming of complex components are very important.
The semi-solid metal forming process was first proposed and developed by researchers in the 70's of the 20 th century, i.e., semi-solid forming, i.e., forming by utilizing the non-dendritic nature of the metal material during its transition from solid to liquid or from liquid to solid. Compared with the traditional casting and forging process, the metal semi-solid forming process has many advantages, such as stable mold filling, no turbulence and splashing, and less gas entrapment; the deformation resistance is small, the equipment investment is reduced, and the energy is saved; the forming temperature is low, and the service life of the die is long; the solidification shrinkage is small, the precision of the workpiece is high, the workpiece is almost formed in a near-net shape, and raw materials are saved; the internal structure of the formed part is compact, the hole defects are few, and the mechanical property is high; the solidification time is shortened, the production efficiency is high, and the like. The semi-solid processing technology is called as a new modern metallurgy technology and is known as the advanced metal processing technology of century. Therefore, the semi-solid forming process for researching the graphene reinforced aluminum matrix composite material has wide prospect. Semi-solid slurry making is one of the keys of semi-solid forming technology, and the core of the semi-solid slurry making is that metal grains must be refined and spheroidized.
The existing methods for preparing the semi-solid slurry mainly comprise an isothermal heat treatment method, a mechanical stirring method, an ultrasonic vibration method, an electromagnetic stirring method, a near liquid phase line method and the like. The mechanical stirring method has the following disadvantages: the molten metal is easily polluted and corroded by the stirrer, and gas and impurities are easily involved after a long time, so that a stirring dead zone exists, and the quality of the semi-solid blank is influenced. The isothermal heat treatment method has the following disadvantages: the technological parameters such as heating temperature, heat preservation time and the like are difficult to control. The electromagnetic stirring method has the following disadvantages: the equipment investment is large, the electromagnetic gap of the device is large, the magnetic flux leakage is serious, a large part of energy cannot be used for stirring the metal melt, and the production cost is greatly increased. The near liquid phase line method has the following disadvantages: the preparation period is long, and the pouring temperature of the melt is difficult to accurately control.
Disclosure of Invention
The invention provides a preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry aiming at the defects of the prior art. According to the invention, the effect of composite reinforcement of rare earth and graphene is realized by the methods of solution dispersion, vacuum sintering and ultrasonic fusion casting. The method has the advantages that: the inherent structure of graphene cannot be damaged by solution dispersion, and a good effect on pre-dispersion of graphene can be achieved; high-energy ultrasonic waves are introduced into the metal melt, the generated transient high temperature and high pressure change the local balance, the surface tension of the liquid surface is reduced, strong local impact is generated, and a strong scattering effect can be generated on an agglomerated phase; the addition of rare earth and graphene can spheroidize the crystal grains of the aluminum-silicon alloy.
The invention is realized by the following technical scheme:
a preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry comprises the following steps:
1) carrying out ultrasonic dispersion and mixing on graphene and aluminum powder to obtain a mixed solution;
2) magnetically stirring the mixed solution under the action of a constant-temperature heating magnetic stirrer, drying the stirred mixed solution in a vacuum drying oven, sintering the dried powder in a vacuum hot-pressing sintering furnace to obtain an aluminum graphene (Al-GNPs) intermediate precast block, cutting the precast block and an aluminum yttrium (Al-Y) intermediate alloy into small particles, and coating the small particles with aluminum foil paper for later use;
3) cutting Al-Si-Cu matrix alloy into small blocks, putting the small blocks into a graphite crucible, putting the crucible into a resistance furnace, heating to 740-760 ℃, preserving heat for 25-30min to completely melt the matrix alloy, then adding Al-Y intermediate alloy small particles into the crucible in batches, preserving heat for 20-25min, heating to 780-800 ℃, then adding Al-GNPs intermediate prefabricated block small particles into the crucible in batches at different angles, adding prefabricated blocks and simultaneously applying high-energy ultrasound, and then quickly reducing the melt temperature to 585-600 ℃ to obtain semi-solid slurry;
4) and (4) applying secondary ultrasound to the semi-solid slurry obtained in the step 3), wherein the ultrasound time is 60-90s, and immediately performing water quenching on the slurry obtained by the secondary ultrasound after finishing the ultrasound, so as to obtain a semi-solid structure with fine grains.
Further, the specific mixing step in the step 1) is to mix the graphene nanosheets and the absolute ethyl alcohol by mixing 2.5-3.5 g of graphene nanosheets into each 100ml of ethanol, then to place the mixture into an ultrasonic cleaning instrument for ultrasonic dispersion treatment for 100-150min, to mix the aluminum powder and the absolute ethyl alcohol by mixing 46.5-47.5 g of aluminum powder into each 150ml of ethanol for mechanical stirring for 100-150min at a stirring speed of 100-120r/min, to evenly pour the aluminum powder-ethanol mixed solution into the graphene nanosheet ethanol dispersion solution after the ultrasonic dispersion treatment, to continuously keep the same power and frequency ultrasonic dispersion treatment and to stir the same stirring speed for 60-80min to obtain the mixed solution.
Further, the graphene nanosheet is a graphene nanosheet with a thickness of 4-20nm, a microchip size of 5-10 μm and a layer number of less than 20, the purity of the aluminum powder is greater than or equal to 99.5%, and the particle size is 200-300 meshes.
Further, the ultrasonic power of the ultrasonic dispersion treatment is 400-480W, and the frequency is 35-45 kHz.
Further, the magnetic stirring heating temperature in the step 2) is 45-55 ℃, and the stirring speed is 1500-; in particular, to avoid delamination of the aluminum powder from the GNPs, the magnetic stirring was maintained until the ethanol mixture of Al-GNPs became pasty.
Further, the sintering temperature in the step 2) is 400-; particularly, the mass percent of GNPs in the intermediate precast block of Al-GNPs obtained after sintering is 5-7%, and the balance is Al.
Further, the mass percent of the rare earth Y in the Al-Y intermediate alloy in the step 2) is 8-10%, and the balance is Al.
A large number of researches show that the rare earth can refine alpha-Al phase and eutectic silicon phase of the aluminum-silicon alloy, and has obvious spheroidizing effect on crystal grains. In addition, the graphene has excellent heat-conducting property, so that the graphene can play a certain role in refining crystal grains, and the research on the preparation of the graphene and rare earth composite reinforced aluminum-silicon alloy semi-solid slurry has good potential value.
Further, the Al-Si-Cu matrix alloy in the step 3) comprises the following elements in percentage by mass: 9.5 to 11.0 percent of silicon, 2.5 to 3.0 percent of copper and the balance of aluminum.
Further, after the base alloy in the step 3) is completely melted, hexachloroethane accounting for 0.2-0.3 wt% of the total mass of the melt is added for refining and deslagging.
Further, the Al-Y master alloy is added in the step 3), wherein the addition amount of the rare earth Y accounts for 0.3-0.5wt% of the total weight of the alloy melt; the Al-GNPs intermediate prefabricated block small particles are added, wherein the addition amount of the GNPs accounts for 0.4-0.5wt% of the total weight of the alloy melt.
Further, the high-energy ultrasonic operation method in the step 3) is that an ultrasonic horn probe is extended into the melt for 3-5mm, the ultrasonic power is 2.1-2.8kW, the ultrasonic frequency is 18-22kHz, the time is 10-15min, and the horizontal position of the ultrasonic horn in the crucible is moved every 2-3min in the ultrasonic process; argon is filled in the whole ultrasonic process for protection.
Compared with other methods, the ultrasonic vibration method has less defects, can obtain an ideal non-dendritic crystal semi-solid structure in a short time, and really realizes high efficiency and low energy consumption. When the acoustic cavitation type high-temperature impact wave acts on a melt, acoustic cavitation and acoustic flow effects can be generated, and high-temperature high-pressure impact waves generated by the acoustic cavitation effect have very important effects on the aspects of breaking crystal grains, promoting nucleation, destroying a boundary layer and the like. Meanwhile, the graphene can be promoted to be uniformly dispersed in the matrix by an ultrasonic method, and the rare earth is uniformly degenerated in the matrix, which plays an important role in obtaining fine and round semi-solid crystal grains.
Further, the parameters of the secondary ultrasound except time in the step 4) are consistent with the ultrasound in the step 3); the water quenching temperature is 20-30 ℃, and the water quenched product is dried in a vacuum drying oven at 40-50 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the fine characteristics of rare earth and graphene are utilized to carry out composite refinement on the crystal grains of the aluminum-silicon alloy; (2) the high-energy ultrasound promotes the uniform dispersion of graphene in the melt, and meanwhile, the deterioration of rare earth can be more uniform; (3) the secondary ultrasonic energy further spheroidizes the semi-solid tissue of the slurry.
The method has the advantages of safe and environment-friendly operation, stable process and low energy consumption, the semi-solid structure of the prepared composite material is obviously refined, the interface of the graphene and the matrix alloy is well combined, and the distribution of the secondary phase is relatively uniform.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples. The process is conventional unless otherwise specified, and the starting materials are commercially available from a public source.
Example 1
A preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry comprises the following steps:
(1) mixing 3g of graphene nanosheets with the thickness of 4-20nm, the size of the nanosheets of 5-10 microns and the number of layers smaller than 20 with absolute ethyl alcohol in a beaker according to the proportion that each 100ml of the ethanol is mixed, and then putting the mixture into an ultrasonic cleaning instrument for ultrasonic dispersion treatment for 130min, wherein the ultrasonic power is 450W, and the frequency is 40 kHz; mixing aluminum powder with purity not less than 99.5%, particle size of 200-300 meshes and absolute ethanol in a beaker by mixing 47g of aluminum powder in each 150ml of ethanol through mechanical stirring at the stirring speed of 110r/min for 130 min; and then uniformly pouring an aluminum powder ethanol mixed solution into the graphene nanosheet ethanol dispersion liquid subjected to ultrasonic dispersion treatment, and continuously maintaining the ultrasonic dispersion treatment at the same power and frequency and stirring at the same stirring speed for 70min to obtain a mixed solution.
(2) Magnetically stirring the mixed solution under the action of a constant-temperature heating magnetic stirrer, wherein the heating temperature is 50 ℃, the stirring speed is 1800r/min, and the magnetic stirring is stopped until the Al-GNPs ethanol mixed solution is pasty in order to avoid the layering phenomenon of the aluminum powder and the GNPs; stirring and drying in a vacuum drying oven.
(3) And putting the dried powder into a vacuum hot-pressing sintering furnace for sintering, wherein the sintering temperature is 420 ℃, the hot-pressing pressure is 50MPa, and the pressure maintaining time is 2.5h to obtain an Al-6GNPs intermediate precast block (the mass percent of GNPs is 6%), putting the precast block and Al-9Y intermediate alloy (the mass percent of Y is 9%) into a vacuum drying oven for drying, cutting into small particles, and coating with aluminum foil paper for later use.
(4) Taking a matrix Al-Si-Cu alloy (the mass percent of Si in the alloy is 10.5%, the mass percent of Cu is 2.8%, and the balance is Al), cutting the matrix Al-Si-Cu alloy into small blocks, putting the small blocks into a graphite crucible, putting the graphite crucible into a resistance furnace, heating to 750 ℃, and preserving heat for 28min to completely melt the matrix alloy.
(5) After the alloy is completely melted, adding hexafluoroethane which accounts for 0.3 wt.% of the total mass of the melt for refining and deslagging; then, adding spare Al-Y intermediate alloy small particles into the crucible in batches, wherein the addition amount of the rare earth Y accounts for 0.4 wt% of the total weight of the alloy melt, and then, preserving heat for 24 min; after the heat preservation is finished, the temperature is raised to 790 ℃, then spare small particles of Al-GNPs intermediate precast blocks are added into the crucible in batches at different angles, the addition amount of the GNPs accounts for 0.4 wt.% of the total weight of the alloy melt, and high-energy ultrasound is applied while the precast blocks are added: extending an ultrasonic amplitude transformer probe into the melt for about 4mm, wherein the ultrasonic power is 2.8kW, the ultrasonic frequency is 20kHz, the ultrasonic time is 13min, and moving the horizontal position of the ultrasonic amplitude transformer in the crucible every 2min in the ultrasonic process; argon is filled in the whole ultrasonic process for protection.
(6) After the ultrasonic treatment is finished, applying secondary ultrasonic treatment to the semi-solid slurry when the temperature of the melt is rapidly reduced to 590 ℃, wherein the ultrasonic treatment time is 80s, and the rest ultrasonic parameters are the same as those in the step (5); and immediately carrying out water quenching on the slurry after the secondary ultrasonic treatment, wherein the water quenching temperature is 25 ℃, and after the water quenching, putting the slurry into a vacuum drying oven for drying (the drying temperature is 25 ℃) to obtain a semi-solid structure with fine grains.
The semi-solid state grain structure of the composite material prepared under the condition of the embodiment is fine and round, the average grain size is reduced by 53 percent compared with that of the matrix alloy under the same condition, and the average shape coefficient is improved by 32 percent compared with that of the matrix alloy under the same condition.
Example 2
A preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry comprises the following steps:
(1) mixing graphene nano sheets with the thickness of 4-20nm, the size of micro sheets of 5-10 microns and the number of layers less than 20 with absolute ethyl alcohol in a beaker according to the proportion that 2.5g of graphene nano sheets are mixed in each 100ml of ethanol, and then putting the mixture into an ultrasonic cleaning instrument for ultrasonic dispersion treatment for 100min, wherein the ultrasonic power is 400W, and the frequency is 35 kHz; mixing aluminum powder with purity not less than 99.5 percent and particle size of 200-300 meshes and absolute ethanol in a beaker by mixing 47.5g of aluminum powder into each 150ml of ethanol through mechanical stirring at the stirring speed of 100r/min for 100 min; and then uniformly pouring an aluminum powder ethanol mixed solution into the graphene nanosheet ethanol dispersion solution subjected to ultrasonic dispersion treatment, and continuously keeping the ultrasonic dispersion treatment at the same power and frequency and stirring at the same stirring speed for 60min to obtain a mixed solution.
(2) Magnetically stirring the mixed solution under the action of a constant-temperature heating magnetic stirrer, wherein the heating temperature is 50 ℃, the stirring speed is 1500r/min, and the magnetic stirring is required to be kept until the Al-GNPs ethanol mixed solution is pasty in order to avoid the layering phenomenon of the aluminum powder and the GNPs; stirring and drying in a vacuum drying oven.
(3) And putting the dried powder into a vacuum hot-pressing sintering furnace for sintering, wherein the sintering temperature is 400 ℃, the hot-pressing pressure is 40MPa, and the pressure maintaining time is 2 hours, so as to obtain an Al-5GNPs intermediate precast block (the mass percentage of GNPs is 5%), putting the precast block and Al-8Y intermediate alloy (the mass percentage of Y is 8%) into a vacuum drying oven for drying, cutting into small particles, and coating with aluminum foil paper for later use.
(4) Taking a matrix Al-Si-Cu alloy (the mass percent of Si in the alloy is 10.5%, the mass percent of Cu is 2.8%, and the balance is Al), cutting the matrix Al-Si-Cu alloy into small blocks, putting the small blocks into a graphite crucible, putting the graphite crucible into a resistance furnace, heating to 740 ℃, and preserving heat for 25min to completely melt the matrix alloy.
(5) After the alloy is completely melted, adding hexafluoroethane which accounts for 0.2 wt.% of the total mass of the melt for refining and deslagging; then, adding spare Al-Y intermediate alloy small particles into the crucible in batches, wherein the addition amount of the rare earth Y accounts for 0.3 wt% of the total weight of the alloy melt, and then, preserving heat for 20 min; after the heat preservation is finished, the temperature is raised to 780 ℃, then spare small particles of Al-GNPs intermediate precast blocks are added into the crucible in batches at different angles, the addition amount of the GNPs accounts for 0.4 wt% of the total weight of the alloy melt, and high-energy ultrasound is applied while the precast blocks are added: extending an ultrasonic amplitude transformer probe into the melt for about 3mm, wherein the ultrasonic power is 2.1kW, the ultrasonic frequency is 20kHz, the ultrasonic time is 10min, and moving the horizontal position of the ultrasonic amplitude transformer in the crucible every 2min in the ultrasonic process; argon is filled in the whole ultrasonic process for protection.
(6) After the ultrasonic treatment is finished, applying secondary ultrasonic treatment to the semi-solid slurry when the temperature of the melt is rapidly reduced to 585 ℃, wherein the ultrasonic treatment time is 60s, and the rest ultrasonic parameters are the same as those in the step (5); and immediately carrying out water quenching on the slurry after the secondary ultrasonic treatment, wherein the water quenching temperature is 20 ℃, and after the water quenching, putting the slurry into a vacuum drying oven for drying (the drying temperature is 40 ℃) to obtain a semi-solid structure with fine grains.
The semi-solid state crystal grain structure of the composite material prepared under the experimental condition is fine and round, the average crystal grain size is reduced by 48 percent compared with that of the matrix alloy under the same condition, and the average shape coefficient is improved by 26 percent compared with that of the matrix alloy under the same condition.
Example 3
A preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry comprises the following steps:
(1) mixing 3.5g of graphene nanosheets with the thickness of 4-20nm, the size of the nanosheets of 5-10 microns and the number of layers of less than 20 with absolute ethyl alcohol in a beaker according to the proportion that each 100ml of ethyl alcohol is mixed, and then placing the mixture into an ultrasonic cleaning instrument for ultrasonic dispersion treatment for 150min, wherein the ultrasonic power is 480W, and the frequency is 45 kHz; mixing aluminum powder with purity not less than 99.5 percent and particle size of 200-300 meshes and absolute ethanol in a beaker by mixing 46.5g of aluminum powder into each 150ml of ethanol through mechanical stirring at the stirring speed of 120r/min for 150 min; and then uniformly pouring an aluminum powder ethanol mixed solution into the graphene nanosheet ethanol dispersion liquid subjected to ultrasonic dispersion treatment, and continuously maintaining the ultrasonic dispersion treatment at the same power and frequency and stirring at the same stirring speed for 80min to obtain a mixed solution.
(2) Magnetically stirring the mixed solution under the action of a constant-temperature heating magnetic stirrer, wherein the heating temperature is 50 ℃, the stirring speed is 2000r/min, and the magnetic stirring is required to be kept until the Al-GNPs ethanol mixed solution is pasty in order to avoid the layering phenomenon of the aluminum powder and the GNPs; stirring and drying in a vacuum drying oven.
(3) And putting the dried powder into a vacuum hot-pressing sintering furnace for sintering, wherein the sintering temperature is 430 ℃, the hot-pressing pressure is 60MPa, and the pressure maintaining time is 3h to obtain an Al-7GNPs intermediate precast block (the mass percent of GNPs is 7%), putting the precast block and Al-10Y intermediate alloy (the mass percent of Y is 10%) into a vacuum drying oven for drying, cutting into small particles, and coating with aluminum foil paper for later use.
(4) Taking a matrix Al-Si-Cu alloy (the mass percent of Si in the alloy is 10.5%, the mass percent of Cu is 2.8%, and the balance is Al), cutting the matrix Al-Si-Cu alloy into small blocks, putting the small blocks into a graphite crucible, putting the graphite crucible into a resistance furnace, heating to 760 ℃, and preserving heat for 30min to completely melt the matrix alloy.
(5) After the alloy is completely melted, adding hexafluoroethane which accounts for 0.3 wt.% of the total mass of the melt for refining and deslagging; then, adding spare Al-Y intermediate alloy small particles into the crucible in batches, wherein the addition amount of the rare earth Y accounts for 0.5wt% of the total weight of the alloy melt, and then, preserving heat for 25 min; after the heat preservation is finished, the temperature is raised to 800 ℃, then spare small particles of Al-GNPs intermediate precast blocks are added into the crucible in batches at different angles, the addition amount of the GNPs accounts for 0.5 wt.% of the total weight of the alloy melt, and high-energy ultrasound is applied while the precast blocks are added: extending an ultrasonic amplitude transformer probe into the melt by about 5mm, wherein the ultrasonic power is 2.8kW, the ultrasonic frequency is 20kHz, the ultrasonic time is 15min, and moving the horizontal position of the ultrasonic amplitude transformer in the crucible every 3min in the ultrasonic process; argon is filled in the whole ultrasonic process for protection.
(6) After the ultrasonic treatment is finished, applying secondary ultrasonic treatment to the semi-solid slurry when the temperature of the melt is rapidly reduced to 600 ℃, wherein the ultrasonic treatment time is 90s, and the rest ultrasonic parameters are the same as those in the step (5); and immediately carrying out water quenching on the slurry after the secondary ultrasonic treatment, wherein the water quenching temperature is 30 ℃, and after the water quenching, putting the slurry into a vacuum drying oven for drying (the drying temperature is 50 ℃) to obtain a semi-solid structure with fine grains.
The semi-solid state crystal grain structure of the composite material prepared under the experimental condition is fine and round, the average crystal grain size is reduced by 51 percent compared with that of the matrix alloy under the same condition, and the average shape coefficient is improved by 29 percent compared with that of the matrix alloy under the same condition.
The above-described embodiments are only preferred embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made by one skilled in the art, and any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry is characterized by comprising the following steps:
1) carrying out ultrasonic dispersion and mixing on graphene and aluminum powder to obtain a mixed solution; mixing 2.5-3.5 g of graphene nanosheets with absolute ethyl alcohol per 100ml of ethanol, then placing the mixture into an ultrasonic cleaning instrument for ultrasonic dispersion treatment for 100-organic-solvent 150min, mechanically stirring and mixing aluminum powder and absolute ethyl alcohol per 150ml of ethanol with 46.5-47.5 g of aluminum powder for 100-organic-solvent 150min at the stirring speed of 100-organic-solvent 120r/min, and uniformly pouring an aluminum powder-ethanol mixed solution into the graphene nanosheet ethanol dispersion liquid after ultrasonic dispersion treatment to continuously keep the same power and frequency ultrasonic dispersion treatment and stir the same stirring speed for 60-80min to obtain a mixed solution;
2) magnetically stirring the mixed solution under the action of a constant-temperature heating magnetic stirrer, drying the mixed solution in a vacuum drying oven after stirring, sintering the dried powder in a vacuum hot-pressing sintering furnace to obtain an aluminum graphene intermediate precast block, cutting the precast block and aluminum yttrium intermediate alloy into small particles, and coating the small particles with aluminum foil paper for later use;
3) cutting Al-Si-Cu matrix alloy into small blocks, placing the small blocks into a graphite crucible, placing the crucible into a resistance furnace, heating to 740-;
4) applying secondary ultrasound to the semi-solid slurry obtained in the step 3), wherein the ultrasound time is 60-90s, and immediately performing water quenching on the slurry obtained by the secondary ultrasound after the ultrasound is finished to obtain a semi-solid structure with fine grains;
step 2), sintering at 400-430 ℃ under the condition of hot pressing pressure of 40-60MPa for 2-3h to obtain an aluminum graphene intermediate precast block after sintering, wherein the mass percent of graphene is 5% -7%, and the balance is aluminum;
step 3) the high-energy ultrasonic operation method comprises the steps of extending an ultrasonic horn probe into a melt for 3-5mm, wherein the ultrasonic power is 2.1-2.8kW, the ultrasonic frequency is 18-22kHz, the time is 10-15min, and the horizontal position of the ultrasonic horn in the crucible is moved every 2-3min in the ultrasonic process; argon is filled in the whole ultrasonic process for protection.
2. The preparation method of the graphene and rare earth composite reinforced aluminum alloy semi-solid slurry as claimed in claim 1, wherein the graphene nanoplatelets of step 1) are graphene nanoplatelets with a thickness of 4-20nm, a nanoplatelet size of 5-10 μm and a number of layers of less than 20, the purity of the aluminum powder is greater than or equal to 99.5%, and the particle size is 200-300 meshes; the ultrasonic power of the ultrasonic dispersion treatment is 400-480W, and the frequency is 35-45 kHz.
3. The preparation method of the graphene and rare earth composite reinforced aluminum alloy semi-solid slurry as claimed in claim 1, wherein the magnetic stirring heating temperature in the step 2) is 45-55 ℃, and the stirring speed is 1500-;
in order to avoid the layering phenomenon of the aluminum powder and the graphene, the magnetic stirring needs to be kept until the aluminum graphene ethanol mixed solution is pasty.
4. The preparation method of the graphene and rare earth composite reinforced aluminum alloy semi-solid slurry as claimed in claim 1, wherein the mass percent of rare earth yttrium in the aluminum-yttrium master alloy in the step 2) is 8% -10%, and the balance is aluminum.
5. The preparation method of the graphene and rare earth composite reinforced aluminum alloy semi-solid slurry as claimed in claim 1, wherein the Al-Si-Cu matrix alloy in the step 3) comprises the following elements in percentage by mass: 9.5 to 11.0 percent of silicon, 2.5 to 3.0 percent of copper and the balance of aluminum.
6. The method for preparing the graphene and rare earth composite reinforced aluminum alloy semi-solid slurry according to claim 1, wherein the addition amount of the rare earth yttrium in the step 3) is 0.3-0.5wt% of the total weight of the alloy melt; the addition amount of the graphene in the aluminum graphene intermediate prefabricated block small particles accounts for 0.4-0.5wt% of the total weight of the alloy melt.
7. The preparation method of the graphene and rare earth composite reinforced aluminum alloy semi-solid slurry according to claim 1, wherein the parameters of the secondary ultrasound except time in the step 4) are consistent with those of the ultrasound in the step 3); the water quenching temperature is 20-30 ℃, and the water quenched product is dried in a vacuum drying oven at 40-50 ℃.
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