CN111286634B - Preparation method of cerium oxide-coated graphene oxide aluminum material semi-solid blank - Google Patents
Preparation method of cerium oxide-coated graphene oxide aluminum material semi-solid blank Download PDFInfo
- Publication number
- CN111286634B CN111286634B CN202010125952.1A CN202010125952A CN111286634B CN 111286634 B CN111286634 B CN 111286634B CN 202010125952 A CN202010125952 A CN 202010125952A CN 111286634 B CN111286634 B CN 111286634B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- aluminum
- ultrasonic
- graphene
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C22C1/12—Making non-ferrous alloys by processing in a semi-solid state, e.g. holding the alloy in the solid-liquid phase
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- 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
Abstract
A preparation method of a cerium oxide coated graphene oxide aluminum product semi-solid blank comprises the steps of adding cerium nitrate into a graphene oxide suspension for adsorption, then adding urea and ammonia water for reaction, and carrying out heat treatment on a precipitate to obtain cerium oxide coated graphene oxide; ultrasonically mixing the obtained powder and aluminum powder in ethanol, drying, and performing cold extrusion molding; reheating and extruding to obtain a bar stock; reheating and then cooling the furnace; and then heating to a solid fraction of 25-40%, continuously performing ultrasonic treatment, casting and cooling to obtain a semi-solid blank with a spherical structure. The invention can further improve the utilization of the coating layer on the basis of improving the wetting, increase the associativity and reduce the incidence rate of agglomeration; the occurrence rate of dangerous events in the preparation process is reduced. The grain structure is refined; the graphene coating reduces the generation of an interface brittle phase Al4C3 of carbon and aluminum; the dispersibility is ensured; the graphene floating defect caused by the problems of density difference and the like is avoided.
Description
Technical Field
The invention belongs to the technical field of material preparation.
Background
Graphene Oxide (GO) belongs to a member of Graphene (GNSs) family and is formed by sp2A two-dimensional material of a thickness of monoatomic layers composed of hybridized carbon atoms. The physical properties of the graphene are close to those of graphene, the modulus of the graphene is close to that of diamond, and the theoretical mechanical properties of the graphene are slightly lower than those of GNSs. However, the chemical stability and temperature resistance are reduced due to a large number of carboxyl groups and hydroxyl group bonds attached to the surface. Limiting their use in composite materials. GO also has similar drawbacks of the carbon materials used in metal matrices, GO shows very poor mutual wetting with metallic aluminum and its integrity in metal matrices is difficult to guarantee. This weakens the shear-lag strengthening effect of GO reinforced aluminum-based material during stress, and GO is extremely largeThe specific surface area also seriously affects its dispersibility in the metal matrix. Therefore, how to reduce the agglomeration of GO in the metal forming process and improve the wettability of GO with the matrix becomes a key to prepare GO reinforced metal matrix composites with excellent performance. It is preferable to use oxygen radicals on the surface.
A large number of carboxyl or hydroxyl bonds are attached to the surface of the graphene oxide, so that the graphene oxide has good reaction activity. The metal ions can be directly attracted by using the root bonds and then reduced into a transition layer superior to the wettability of graphite and a metal material, so that the aims of increasing the binding property and reducing the dispersion difficulty of GO in metal can be fulfilled. In addition, the strong oxidizing acid treatment process of the common graphene before coating treatment is avoided. The danger and the preparation difficulty in the coating process are reduced.
Common nano-coating layers can be roughly divided into two types, namely metal simple substances or metal oxides, such as titanium oxide, nickel oxide, copper and the like. Based on the purpose of enhancing the mechanical properties of the composite material and improving the dispersion and interface bonding of the nanocarbon material, the similarity between the lattice structure of the coating and the matrix and the reactive wetting are generally used for judgment. In order to play the role of the plating layer to a greater extent and improve the interface bonding, in practice, a coating layer and a base material are often required to have a trace amount of reactive wetting, such as copper or titanium simple substance.
In published patent No. 103361637a, the name is: the preparation method of the chemical nickel plating graphene. The method is a typical chemical plating method, the success rate is relatively high, however, the steps are extremely complex, activation, sensitization and the like are required, the reagent usually has certain toxicity and poor controllability, suspended products are easy to be prevented from appearing on the surface of graphene in the reaction and mixed into the final coated graphene powder, the pH value of the reaction solution is difficult to control, so that the problems of large waste, pollution and the like of the plating solution are caused, and the method has certain limitations.
The preparation of graphene aluminum-based composite materials by a stirring casting method and a powder metallurgy method is common. However, the two methods have obvious defects, under the casting condition, the density difference between graphene and aluminum is large above the liquidus line of the aluminum alloy, so that the graphene is easy to seriously agglomerate and float along with the flowing of a melt, so that the strengthening failure is caused, powder metallurgy is taken as a popular research direction, the temperature is usually set below a solidus line or close to a solid phase, and the problems of interface bonding and compactness become more serious on the premise of adding the graphene with poor wettability.
In the published patent No. CN 108085524A, entitled "a preparation method of graphene reinforced aluminum-based composite material", conventional powder metallurgy methods such as mixing, ball milling, cold pressing and hot extrusion are adopted to prepare the graphene reinforced aluminum-based composite material, the method has stronger referential significance, and the interface bonding of the material prepared by the method needs to be optimized to promote the exertion of load-bearing reinforcement.
In the published patent No. CN106513621A, entitled "a method for preparing graphene/aluminum composite material", mixed powder and semi-solid interval molding is adopted to make graphene more uniform and improve material compactness to a certain extent, but impurities of conventional chemical plating are difficult to control and the effect of a plating layer on a substrate is more concentrated on corrosion rather than strength improvement.
In the patent publication No. CN 107675028A, entitled "single-layer graphene/aluminum composite material and preparation method thereof", powder is heated and then put into a melt forming process to prepare the graphene reinforced aluminum-based composite material. The method is similar to the process angle provided by the text and has better reference significance. However, graphene above the liquidus line is likely to be agglomerated again due to problems such as poor wettability and poor density, and the final performance-enhancing effect is likely to be reduced.
Therefore, an economical and effective preparation method of the semi-solid GO reinforced aluminum material blank is still lacked at present.
Disclosure of Invention
The invention aims to provide a novel method for improving the mechanical property of an aluminum matrix composite material by utilizing the synergy of a graphene oxide/rare earth oxide coating and other reinforcing phases. On the basis of a semi-solid preparation process, modified GO is added into an aluminum alloy, and oxygen radicals contained in GO are utilized to combine with rare earth oxide, so that reactive wettability of a coating layer and a matrix is promoted to disperse GO, the dispersity and the associativity of GO are improved, and the problems of reaction burning loss of graphene oxide and other substances at high temperature and the like are solved. By utilizing the characteristic that rare earth can be used as a modifier and the reducibility of cerium oxide and aluminum, the grain structure is refined, the Si phase morphology at a crystal boundary is improved, and the trace reaction of rare earth oxide and a matrix can achieve the effects of auxiliary optimization of the structure and wetting increase based on the modification effect.
CeO2+Al=Ce+Al2O3 （1）
∆GT = -51 963.7 + 15.28T （2）
In a semi-solid temperature range, the incidence rate of floating and uneven distribution of graphene caused by problems of poor density, nonwetting and the like can be effectively reduced by controlling the solid fraction and improving the wettability. The method has the advantages of high controllability, strong customization, good combination performance and lower cost theoretically. Meanwhile, the formed rare earth oxide transition layer is generated in situ, and the bonding performance is good.
The invention is realized by the following technical scheme.
The invention relates to a preparation method of a semi-solid blank coated with cerium oxide and graphene oxide aluminum material, which comprises the following steps.
(1) Adding Graphene Oxide (GO) into an absolute ethyl alcohol solution, and carrying out ultrasonic treatment for 10-15 min, wherein the ultrasonic power is not less than 150W, so as to obtain an ethyl alcohol suspension of GO.
(2) According to the formula of cerium nitrate (Ce (NO)3)3) The molar ratio of the Ce (NO) to the absolute ethyl alcohol is 1: 5-1: 83)3Adding the solution into absolute ethyl alcohol for ultrasonic dissolution, then dropwise adding the solution into the GO ethanol solution obtained in the step (1), and continuously performing ultrasonic treatment during the addition process to obtain GO and Ce (NO)3)3The molar ratio is controlled to be 1: 0.35-1: 0.85, and the ultrasonic treatment is continued for 3-5 hours after the addition.
(3) Mixing urea (CO (NH)2)2) Adding the crystal into absolute ethyl alcohol, and then dropwise adding GO and Ce (NO) obtained in the step (2)3)3And carrying out ultrasonic treatment for 10-30 min after suspension liquid is obtained. Wherein the mole ratio of GO to urea is 1: 0.7-1: 1.6, the process is carried out in a magnetic stirrer, and the stirring speed is 200-300 r/min.
(4) Adding ammonia water (NH)3•H20) Dropwise adding GO and Ce (NO) obtained in step (3)3)3In the suspension, stirring is kept during the addition of ammonia water, the pH value is controlled to be kept between 8 and 9, and the reaction is carried out for 7 to 12 hours.
(5) And (3) sealing the solution obtained in the step (4) in a TFM sealing tank, heating for 2-3 h at 150-200 ℃, then air-cooling at room temperature, and obtaining a precipitate by using a centrifugal device. And finally, repeatedly cleaning the prefabricated material by using absolute ethyl alcohol, and drying the prefabricated material in a vacuum furnace to obtain the prefabricated material.
(6) And (3) putting the prefabricated material obtained in the step (5) into a corundum crucible, putting the corundum crucible into a vacuum tube furnace, heating to 400 ℃, keeping the temperature for 30min, then heating to 450-600 ℃, and roasting at high temperature for 1-3 h, wherein the corundum crucible must be tightly covered to prevent the GO from splashing due to heating reduction. Finally obtaining cerium oxide (CeO)2) Coated GO.
(7) The CeO obtained in the step (6)2And putting the coated GO and aluminum alloy powder into ethanol, stirring for assisting ultrasonic premixing, wherein the mass of the GO is 7-12 wt% of the total mixed powder, the volume ratio of the ethanol to the total mixed powder is 1.5: 1-1: 1, and the time is controlled to be 30 min. The resulting powder was then vacuum dried.
(8) The CeO obtained in the step (7)2The coated GO and aluminum alloy powder mixture is put into a pure aluminum flat pocket for sealing. And (3) carrying out cold extrusion treatment, wherein the extrusion pressure is 10-18 MPa, the pressure is maintained for about 5-10 min, then carrying out hot extrusion treatment, the temperature is 400-450 ℃, and the extrusion ratio is about 12-20, so as to obtain the foamed aluminum bar, and cutting the foamed aluminum bar according to the length of 6-12 mm.
(9) And (4) selecting the foam structure aluminum rods with the same length in the step (8), stacking the foam structure aluminum rods in the graphite crucible, compacting the foam structure aluminum rods, adding aluminum alloy ingots with the same volume ratio, and putting the aluminum alloy ingots into a vacuum infiltration furnace. Vacuumizing to 5-20 Pa, then discharging the vacuum, and vacuumizing again and circulating for 2-3 times to remove impurities. Then, the temperature is raised to 773K at 5-10K/min, and the temperature is raised to 1073-1200K at 2-4K/min after 30min of heat preservation. And slowly filling gas for pressurization to provide infiltration pressure, wherein the filling pressure is within the range of 1-4 MPa, the pressure maintaining time is 7-15 min, and after infiltration is finished, the sample is cooled along with the furnace.
(10) And (4) putting the composite material obtained in the step (9) into a graphite crucible again for heating, determining the temperature according to the solid phase rate, controlling the solid phase rate to be 25-40%, and then carrying out high-energy ultrasonic vibration for 10-16 min for re-dispersion, wherein the power is controlled to be 0.3-1.2 Kw. The whole process is protected by argon and the temperature is required to be constant. The diameter of the graphite crucible is about 1-3 times of the diameter of the probe, and the graphite crucible is in a wide-mouth structure type with a large upper end diameter and a small lower end diameter so as to reduce the attenuation rate of ultrasound.
(11) And (4) casting the semi-solid composite material obtained in the step (10) into a die preheated to 500 ℃, wherein the bottom end of the die is connected with an ultrasonic probe. And (3) keeping 500-1200W of ultrasound in the semisolid solidification process, and continuously cooling under the condition of 20KHz to keep a spherical structure.
The invention uses aluminum alloy as casting aluminum, such as ZL101, ZL105 and other aluminum alloy.
The invention has the following uniqueness: (1) according to the method, rare earth oxide can be coated on GO, the utilization of a coating layer can be further improved on the basis of improving wetting, the associativity is increased, the agglomeration occurrence rate is reduced, and (2) the coating process utilizes the bond of GO, so that the common high-concentration acid washing process is avoided, and the occurrence rate of dangerous events in the preparation process is reduced. (3) The grain structure is refined by the replacement reaction of rare earth oxide and aluminum. (4) The graphene coating can reduce the generation of an interface brittle phase Al4C3 of carbon and aluminum to a certain extent. (5) The rare earth oxide is dispersed along with the graphene, and the dispersity of the graphene is guaranteed due to the extremely small size of the graphene. (6) The dispersion process is to add aluminum matrix by mixed powder extrusion and infiltration processes and then prepare a semi-solid state by an ultrasonic process, so that the defect of floating of graphene caused by the problems of density difference and the like is avoided.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1.
Ce(NO3)3Adding the dried graphene nanosheets serving as raw materials into absolute ethyl alcohol, and performing ultrasonic treatment for 40min at a power of 150W; wherein Ce (NO)3)3Mols with anhydrous ethanolIn a ratio of 1: 7. Then, this solution was added dropwise to the preformed GO ethanol solution, with the addition process sonicating continuously, and finally Ce (NO)3)3The addition amount is determined by the molar ratio of GO to Ce (NO)3)3Controlling the molar ratio to be 1:0.5, and continuing to perform ultrasonic treatment for 3 hours after adding; adding appropriate amount of CO (NH)2)2Adding into anhydrous ethanol, adding the suspension dropwise, and performing ultrasonic treatment for 10 min. Wherein GO and CO (NH)2)2The molar ratio is 1:0.8, the process is carried out in a magnetic stirrer, and the stirring speed is 200-300 r/min. Then obtaining a reaction precursor. And (3) dropwise adding ammonia water into the GO turbid liquid, keeping stirring in the ammonia water adding process, controlling the pH value to be 8, and keeping the reaction time to be about 7 h. Sealing the obtained solution in a TFM sealing tank, heating for 3h, controlling the temperature to be 150 ℃, and cooling in air at room temperature. The precipitate was obtained by centrifugation. And finally, repeatedly cleaning the prefabricated material by using absolute ethyl alcohol, and drying the prefabricated material in a vacuum furnace to obtain the prefabricated material. Putting the obtained powder into a corundum crucible, putting the corundum crucible into a vacuum tube furnace, heating to 400 ℃, keeping the temperature for 30min, then heating to 450 ℃, and roasting at high temperature for 3h, wherein the corundum crucible must be tightly covered to prevent the graphene oxide from splashing due to heating reduction. Finally obtaining rare earth oxide CeO2Coated GO.
CeO with the mass fraction of 9 percent of aluminum alloy powder2The @ GO and the aluminum powder are put into ethanol to be stirred and assisted with ultrasonic premixing, wherein the volume ratio of the ethanol to the composite powder is 2:1, the time is controlled to be 30min, and then the obtained powder is dried in vacuum for later use. The obtained CeO2Adding the @ GO aluminum powder mixture into a pure aluminum flat pocket and sealing. Performing cold extrusion treatment under 50MPa for 5 min. The extruded powder was then hot extruded without unsealing at a temperature of 450 ℃ at an extrusion ratio of about 12. The resulting bar was cut to length of about 9 mm.
Selecting foamed aluminum bars with the same height to form a stacking structure, placing the stacking structure into a graphite crucible for compaction, adding aluminum alloy ingots with the same volume ratio, and placing the aluminum alloy ingots into a vacuum infiltration furnace. Vacuumizing to 5-20 Pa, then discharging the vacuum, and vacuumizing again and circulating for two to three times to remove impurities. And then heating to 773K at 5K/min, preserving heat for 30min, and then heating to 1073-1200K at the speed of 2K/min. And then slowly filling gas for pressurization to provide infiltration pressure, wherein the filling pressure is within 1MPa, the pressure maintaining time is 7-15 min, and after infiltration is finished, the sample is cooled along with the furnace. And putting the obtained composite material into a graphite crucible again for heating, specifically controlling the temperature to be 25-40% according to the solid phase rate, and then carrying out high-energy ultrasonic vibration for 10min for re-dispersion, wherein the power is controlled to be 0.6 Kw. The whole process is protected by argon and the temperature is required to be constant. Casting the semi-solid into a die preheated to about 500 ℃, wherein the bottom end of the die is connected with an ultrasonic probe. The ultrasonic wave is kept at 500W in the semi-solid solidification process, and the process is continued under the condition of 20KHz until the cooling is carried out.
Example 2.
Adding cerium nitrate and GO serving as raw materials into absolute ethyl alcohol, and carrying out ultrasonic treatment at a power of 150W for 40 min; wherein Ce (NO)3)3The molar ratio of the ethanol to the absolute ethyl alcohol is 1: 8. Then, this solution was added dropwise to the resulting GO ethanol solution, with the addition process sonicating continuously, and finally Ce (NO)3)3The addition amount is determined by the molar ratio of GO to Ce (NO)3)3Controlling the molar ratio to be 1:0.6, and continuing to perform ultrasonic treatment for 3 hours after adding; adding appropriate amount of CO (NH)2)2Adding into anhydrous ethanol, adding the suspension dropwise, and performing ultrasonic treatment for 20 min. Wherein GO and CO (NH)2)2The molar ratio is 1:1, the process is carried out in a magnetic stirrer, and the stirring speed is 200-300 r/min. And (3) dropwise adding ammonia water into the GO turbid liquid, keeping stirring in the ammonia water adding process, controlling the pH value to be 9, and keeping the reaction time to be about 7 hours. Sealing the obtained solution in a TFM sealing tank, heating for 2h, controlling the temperature to be 200 ℃, and cooling in air at room temperature. The precipitate was obtained by centrifugation. And finally, repeatedly cleaning the prefabricated material by using absolute ethyl alcohol, and drying the prefabricated material in a vacuum furnace to obtain the prefabricated material. And putting the obtained powder into a corundum crucible, putting the corundum crucible into a vacuum tube furnace, heating to 400 ℃, keeping the temperature for 30min, then heating to 500 ℃, and roasting at high temperature for 1-3 h, wherein the corundum crucible is required to be tightly covered to prevent the graphene oxide from splashing due to heating reduction. Finally obtaining rare earth oxide CeO2Coated GO.
CeO with the mass fraction of 9 percent of aluminum alloy powder2Stirring the @ GO and the aluminum powder in ethanol for auxiliary ultrasonic premixing, wherein the volume ratio of the ethanol to the composite powder is 2:1, the time is controlled to be 30min, and thenAnd drying the obtained powder in vacuum for later use. The obtained CeO2Adding the @ GO aluminum powder mixture into a pure aluminum flat pocket and sealing. Performing cold extrusion treatment under 50MPa for 10 min. The extruded powder was then hot extruded without unsealing at a temperature of 430 ℃ with an extrusion ratio of about 12. The resulting foamed bar stock was cut to length of about 8 mm.
Selecting foamed aluminum bars with the same height to form a stacking structure, placing the stacking structure into a graphite crucible for compaction, adding aluminum alloy ingots with the same volume ratio, and placing the aluminum alloy ingots into a vacuum infiltration furnace. Vacuumizing to 10Pa, then discharging the vacuum, and vacuumizing again for two to three times to remove impurities. Then the temperature is raised to 773K at 5K/min, and the temperature is raised to 1100K at the speed of 2K/min after 30min of heat preservation. And then slowly filling gas for pressurization to provide infiltration pressure, wherein the filling pressure is within 1MPa, the pressure maintaining time is 8min, and after the infiltration is finished, the sample is cooled along with the furnace. The obtained composite material is put into a graphite crucible again for heating, the solid phase rate is controlled to be about 30 percent, and then the composite material is dispersed again by high-energy ultrasonic vibration for 10min, and the power is controlled to be 1.2 Kw. The whole process is protected by argon and the temperature is required to be constant. Casting the semi-solid into a die preheated to about 500 ℃, wherein the bottom end of the die is connected with an ultrasonic probe. Ultrasonic wave is kept at 600W in the semi-solid solidification process, and the process is continued under the condition of 20KHz until cooling.
Claims (2)
1. A preparation method of a semi-solid blank coated with cerium oxide and graphene oxide aluminum material is characterized by comprising the following steps:
(1) adding graphene oxide into an absolute ethanol solution, and carrying out ultrasonic treatment for 10-15 min at the ultrasonic power of more than or equal to 150W to obtain an ethanol suspension of the graphene oxide;
(2) adding cerium nitrate into absolute ethyl alcohol according to the molar ratio of 1: 5-1: 8 of cerium nitrate to the absolute ethyl alcohol for ultrasonic dissolution, then dropwise adding the solution into the graphene oxide ethanol solution obtained in the step (1), carrying out uninterrupted ultrasonic treatment in the adding process, controlling the molar ratio of the graphene oxide to the cerium nitrate to be 1: 0.35-1: 0.85, and continuing ultrasonic treatment for 3-5 hours after adding;
(3) adding urea crystals into absolute ethyl alcohol, then dropwise adding the suspension of the graphene oxide and the cerium nitrate obtained in the step (2), and performing ultrasonic treatment for 10-30 min; wherein the molar ratio of the graphene oxide to the urea is 1: 0.7-1: 1.6, the process is carried out in a magnetic stirrer, and the stirring speed is 200-300 r/min;
(4) dropwise adding ammonia water into the suspension of the graphene oxide and the cerium nitrate in the step (3), keeping stirring in the ammonia water adding process, controlling the pH value to be 8-9, and reacting for 7-12 h;
(5) sealing the solution obtained in the step (4) in a TFM sealing tank, heating for 2-3 h at 150-200 ℃, then air-cooling at room temperature, obtaining a precipitate by using a centrifugal device, finally repeatedly cleaning by using absolute ethyl alcohol, and drying by using a vacuum furnace to obtain a prefabricated material;
(6) putting the prefabricated material obtained in the step (5) into a corundum crucible, covering the corundum crucible tightly, putting the corundum crucible into a vacuum tube furnace, heating to 400 ℃, keeping the temperature for 30min, then heating to 450-600 ℃, and roasting at high temperature for 1-3 h to finally obtain cerium oxide coated graphene oxide;
(7) stirring the cerium oxide coated graphene oxide and aluminum alloy powder obtained in the step (6) in ethanol to assist ultrasonic premixing, wherein the mass of the graphene oxide is 7-12 wt% of the total mixed powder, the volume ratio of the ethanol to the total mixed powder is 1.5: 1-1: 1, the time is controlled to be 30min, and then drying the obtained powder in vacuum;
(8) sealing the mixture of the cerium oxide coated graphene oxide and the aluminum alloy powder obtained in the step (7) in a pure aluminum flat pocket, performing cold extrusion treatment at the extrusion pressure of 10-18 MPa and the pressure maintaining time of 5-10 min, and then performing hot extrusion treatment at the temperature of 400-450 ℃ and the extrusion ratio of 12-20 to obtain a foam structure aluminum bar, and cutting the foam structure aluminum bar according to the length of 6-12 mm;
(9) selecting the foam structure aluminum rods with the same length in the step (8), stacking the foam structure aluminum rods in a graphite crucible, compacting, adding aluminum alloy ingots with the same volume ratio, putting the aluminum alloy ingots in a vacuum infiltration furnace, vacuumizing to 5-20 Pa, then discharging the vacuum, and vacuumizing again for 2-3 times to remove impurities; then heating to 773K at 5-10K/min, keeping the temperature for 30min, and then heating to 1073-1200K at 2-4K/min; then slowly filling gas for pressurization to provide infiltration pressure, wherein the filling pressure is within the range of 1-4 MPa, the pressure maintaining time is 7-15 min, and after infiltration is finished, the sample is cooled along with a furnace;
(10) putting the composite material obtained in the step (9) into a graphite crucible again for heating, determining the temperature according to the solid phase rate, controlling the solid phase rate to be 25-40%, then carrying out high-energy ultrasonic vibration for 10-16 min for re-dispersion, controlling the power to be 0.3-1.2 Kw, and keeping the temperature constant in the whole process under the protection of argon; the diameter of the graphite crucible is 1-3 times of the diameter of the probe, and the graphite crucible is in a wide-mouth structure type with a large upper end diameter and a small lower end diameter;
(11) and (3) casting the semi-solid composite material obtained in the step (10) into a die preheated to 500 ℃, connecting the bottom end of the die with an ultrasonic probe, keeping the ultrasonic wave at 500-1200W in the semi-solid solidification process, and continuously cooling under the condition of 20KHz to keep the spherical structure.
2. The method of preparing a semi-solid billet of aluminum material coated with cerium oxide and graphene oxide according to claim 1, wherein the aluminum alloy is cast aluminum ZL101 or ZL 105.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010125952.1A CN111286634B (en) | 2020-02-27 | 2020-02-27 | Preparation method of cerium oxide-coated graphene oxide aluminum material semi-solid blank |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010125952.1A CN111286634B (en) | 2020-02-27 | 2020-02-27 | Preparation method of cerium oxide-coated graphene oxide aluminum material semi-solid blank |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111286634A CN111286634A (en) | 2020-06-16 |
| CN111286634B true CN111286634B (en) | 2021-03-16 |
Family
ID=71022908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010125952.1A Active CN111286634B (en) | 2020-02-27 | 2020-02-27 | Preparation method of cerium oxide-coated graphene oxide aluminum material semi-solid blank |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111286634B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112941357B (en) * | 2021-01-11 | 2022-09-13 | 高安市璐克斯机械有限公司 | Preparation method of graphene and rare earth composite reinforced aluminum alloy semi-solid slurry |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102716734B (en) * | 2012-06-15 | 2015-02-04 | 浙江师范大学 | Preparation method for cerium oxide/graphene oxide nanocomposite |
| CN104073674B (en) * | 2014-06-20 | 2016-03-30 | 哈尔滨翔科新材料有限公司 | A kind of preparation method of Graphene aluminum matrix composite |
| CN106219590B (en) * | 2016-08-16 | 2017-12-12 | 南昌大学 | A kind of preparation method of rare earth oxide/graphene nanocomposite material |
| CN106399872B (en) * | 2016-09-09 | 2018-01-12 | 南昌大学 | A kind of preparation method of the whisker carbon nanotubes-aluminum composites semi-solid blank of coating alumina |
| CN106350695B (en) * | 2016-09-09 | 2018-05-04 | 南昌大学 | A kind of preparation method of simple substance copper clad multi-walled carbon nanotube/aluminum matrix composite semi-solid blank |
| CN106881466B (en) * | 2017-03-23 | 2018-11-30 | 江西理工大学 | The preparation method of rare earth modified grapheme enhancing metal-based compound bar |
| US10829677B2 (en) * | 2017-06-27 | 2020-11-10 | Ge Aviation Systems Limited | Graphene doped aluminum composite and method of forming |
| CN108060321B (en) * | 2017-12-07 | 2019-06-11 | 中北大学 | A kind of preparation method of graphene reinforced aluminum matrix composites |
| CN108796397A (en) * | 2018-07-11 | 2018-11-13 | 兰州交通大学 | A kind of preparation method of graphene/carbon SiClx/aluminium composite material |
| CN109207782B (en) * | 2018-09-17 | 2020-07-14 | 南昌大学 | Preparation method of titanium oxide/graphene oxide coated reinforced silicon-phase aluminum-based composite material |
| CN109182821B (en) * | 2018-09-17 | 2020-07-14 | 南昌大学 | Die casting method for graphene-reinforced ADC12 aluminum alloy |
| CN110453113B (en) * | 2019-09-16 | 2020-10-27 | 宜春学院 | Method for reinforcing aluminum alloy composite material by cesium oxide modified graphene |
-
2020
- 2020-02-27 CN CN202010125952.1A patent/CN111286634B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111286634A (en) | 2020-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111363945B (en) | Preparation and interface optimization method of modified graphene nanosheet magnesium-aluminum material | |
| CN108559864B (en) | In-situ nano reinforced aluminum alloy hub for new energy automobile and manufacturing method | |
| WO2019090963A1 (en) | In-situ nanoreinforced aluminum alloy extrusion for car body and preparation method | |
| CN111363942B (en) | Preparation method of rare earth oxide @ graphene nanosheet/aluminum-based blank | |
| CN109692964A (en) | A kind of reinforced aluminum matrix composites and preparation method thereof | |
| CN112481519B (en) | Preparation method of high-damping CuAlMn shape memory alloy | |
| CN106350695B (en) | A kind of preparation method of simple substance copper clad multi-walled carbon nanotube/aluminum matrix composite semi-solid blank | |
| CN111286634B (en) | Preparation method of cerium oxide-coated graphene oxide aluminum material semi-solid blank | |
| CN1195088C (en) | Reaction and ball grinding process to prepare in-situ reinforced Mg-based composite material | |
| CN110129624B (en) | SiC-Al3Preparation method of Ti reinforced aluminum matrix composite material | |
| CN103695673B (en) | A kind of intermetallic compound particle Al 3the preparation method of-M reinforced aluminum matrix composites | |
| WO2022246888A1 (en) | High-strength and toughness, high-thermal-conductivity, and easy-to-weld aluminum-based composite material for 5g base station and preparation method therefor | |
| CN109266893B (en) | Method for reinforcing magnesium alloy composite material by coating zinc oxide graphene | |
| CN106350753B (en) | A kind of preparation method of simple substance copper clad whisker carbon nanotube/magnesium-base composite material semi-solid state blank | |
| CN111996407B (en) | Preparation method of graphene reinforced aluminum matrix composite material with dual-mode structure | |
| CN111676384B (en) | Reinforced magnesium-based composite material and preparation method thereof | |
| CN111304482B (en) | Method for improving elastic modulus of particle reinforced aluminum matrix composite | |
| CN114000015A (en) | In-situ multiphase particle coupling reinforced aluminum matrix composite material and preparation method thereof | |
| CN108118183A (en) | Abrasion-resistant cast copper alloy and preparation method with high rigidity | |
| CN106367696A (en) | Preparation method for crystal whisker carbon nano tubes coated with aluminum oxide/magnesium matrix composite semi-solid billets | |
| CN108517449B (en) | Ti (C, N) -304 stainless steel cermet and preparation process thereof | |
| CN113088743B (en) | Method for preparing carbon nano tube reinforced AZ61 magnesium alloy semi-solid slurry | |
| CN113088744B (en) | Preparation method of modified carbon nanotube reinforced aluminum alloy semi-solid slurry | |
| CN111349834B (en) | Micro-nano dual-phase hybrid particle reinforced magnesium-lithium-based composite material and preparation method thereof | |
| CN101712069B (en) | Grain refinement method for Mg-Mn as-cast magnesium alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |