CN110357633B - Method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature - Google Patents

Method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature Download PDF

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CN110357633B
CN110357633B CN201910625528.0A CN201910625528A CN110357633B CN 110357633 B CN110357633 B CN 110357633B CN 201910625528 A CN201910625528 A CN 201910625528A CN 110357633 B CN110357633 B CN 110357633B
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aluminum
titanium
powder
graphene
room temperature
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郝巍
倪娜
肖巍伟
赵晓峰
姜娟
范晓慧
郭芳威
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Shanghai Jiaotong University
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Abstract

The invention relates to a method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature, which comprises the steps of dissolving graphene oxide in deionized water, adding L-ascorbic acid, stirring, controlling the temperature to be 80-120 ℃, fully performing reduction reaction to form graphene hydrogel with a uniform structure, and drying and dehydrating to obtain graphene aerogel; uniformly mixing graphene aerogel, titanium powder and aluminum powder; pressing the obtained mixed powder into a blank, taking a platinum sheet as an electrode and a graphite column as a pressurizing contact, and carrying out flash sintering treatment to obtain compact and uniform titanium-aluminum-carbon ceramic. Compared with the prior art, the titanium-aluminum-carbon ceramic with high density, high purity and uniform grain size is prepared by adopting the graphene-assisted flash firing technology, and the preparation method is simple in preparation process, high in efficiency and capable of being completed at room temperature.

Description

Method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature
Technical Field
The invention relates to a method for preparing ceramics, in particular to a method for rapidly preparing titanium-aluminum-carbon ceramics at room temperature.
Background
Mn+1AXnWhere M is a transition group element, e.g. V, Ti, Ta, etc., A is predominantly a group III or IV element, e.g. Si, Al, Ga, Ge, etc., X is C or N, N is 1, 2, 3, 4, 5, each of which may be referred to as 211 phase (Ti, Ta, etc.) (for short)2AlC,Cr2AlC,Ta2AlC, etc.), 312 phase (Ti)3AlC2,Ti3SiC2) 413 phase and 523 phase. Mn+1The AXn compound has a similar hexagonal crystal structure and a spatial structure of P63And/mmc. These compounds are thermodynamically stable layered compounds and have a wide range of applications. For example, Ti3AlC2The unit cell parameters of (1) are a, b and c, 0.30753nm and 1.8578nm, and the theoretical density is 4.25g/cm3. Ti (1) and Ti (2) occupy positions 2a and 2f, respectively, with the Al atom in the 2b position and the C atom in the 2b (z ═ 0.5701) position. Ti3AlC2The structural features can be interpreted as: the Al atoms are arranged in layers and are separated by Ti which is tightly packed6C octahedron, both in a direction perpendicular to the a axisIn a periodic stacking arrangement with C atoms in the center of the octahedron and two Ti atoms per unit cell3AlC2. Titanium aluminum carbon (Ti)3AlC2,Ti2AlC, etc.) contains three bonding modes of ionic bonding, covalent bonding and metallic bonding, which is the reason that the ceramic material has both metallic and ceramic properties. The Ti-C bond is a covalent bond, and the bonding force is strong, so that the titanium-aluminum-carbon has high elastic modulus (300 GPa) and strength (760 MPa). However, the Ti-Al bonds and the Al atomic layers are bonded by metal bonds, and the bonding between the layers is similar to the van der Waals force bonding mode between graphite layers, so that the titanium-aluminum-carbon has the self-lubricating characteristic of a laminated structure. Meanwhile, the titanium-aluminum-carbon has excellent high-temperature oxidation resistance, and can form Al below 1200 DEG C2O3And TiO2At higher temperatures, Al is formed2TiO5. The coefficient of thermal expansion of titanium-aluminum-carbon is-9.0X 10-6V. DEG C, with formation of aluminum oxide film (Al)2O3, 9.3×10-6/° c), the bonding force of the oxide layer can be improved, and the oxidation protection can be further performed on the base material. And the titanium aluminum carbon has special bonding characteristics, so that the atomic displacement damage can be recovered, and the titanium aluminum carbon also has good tolerance to radiation damage. May be applied to future nuclear industry nuclear fuel cladding materials. Therefore, the preparation and synthesis of titanium-aluminum-carbon become one of the hot spots of domestic and foreign research in recent years. The simple and rapid synthesis method is provided, and has important significance for the application of the method in the future high-temperature field.
To date, a wide variety of methods have been used to prepare titanium-aluminum-carbon ceramics, such as the carbonization reaction [ N.C. Ghosh, S.P. Harimkar, Consolidation and synthesis of MAX phases by Spark Plasma Sintering (SPS): a review, Advances in science and technology of Mn+1AXn phases,Woodhead Publishing Limited,Oklahoma State University,USA,2012.]Hot press reaction sintering process [ Jae-Ho Han, Sung-Sic Hwang, Dongyun Lee, Sangg-Whan Park, Synthesis and mechanical properties of Ti3AlC2by hot pressing TiCx/Al powder mixture,Journal of the European Ceramic Society 28(2008)979–988.]Discharge plasma sintering method [ Ludi Xu, Degui Zhu, Yunlong Liu, Tohru S. Suzuki, Byung-nam Kim, Yoshio Sakka, Salvator grass, Chunfeng Hu, Effect of texture on oxidation resistance of Ti3AlC2,Journal of the European Ceramic Society 38(2018)3417– 3423.]Mechanical alloying method [ Bilge Yaman Islak, Erhan ayas3SiC2and Ti3SiC2/SiC composites.Ceramics International 45(2019)12297–12306.]And high temperature self-propagating reaction methods [ Maryam Akhlaghi, second Ali Taybifard, Esmaeil Salahi, Mehdi Shahedi Ashi, Gert Schmidt. self-propagating high-temperature synthesis of Ti3AlC2MAX phase from mechanically-activated Ti/Al/graphite powder mixture,Ceramics International 44(2018)9671–9678.]The above processes are all carried out at high temperature, and the carbothermic method is generally used for preparing Ti by a two-step method3AlC2The ceramic is prepared by preparing ceramic powder under the high-temperature condition by a carbothermic method and then preparing the final ceramic by sintering, so that the time period is long, the process is complex, and the grain size and microstructure of the ceramic cannot be regulated and controlled by controlling the particle size of the powder. The hot-pressing sintering method needs to sinter the ceramic under a higher temperature condition, so that the abnormal growth of ceramic grains is easily caused, and the performance of the ceramic at the later stage is influenced; the discharge plasma sintering method can rapidly sinter ceramics, but still has higher temperature and higher requirement on equipment; meanwhile, the mechanical alloying for preparing the titanium-aluminum-carbon ceramic also needs high-temperature reaction sintering at a later stage to obtain a final target product; the titanium aluminum carbon ceramic prepared by the high-temperature self-propagating reaction method also needs a material system to provide a synthesis reaction at a higher temperature, the composition and the grain size of the material are difficult to control, the ceramic sintering densification is difficult to realize, and meanwhile, due to the existence of local thermal stress in the material system, the defects of cracks and the like exist in the ceramic, so that the later-period performance of the ceramic is not good.
Disclosure of Invention
The invention aims to overcome the defects of the prior art that the high-temperature synthesis and sintering of the titanium-aluminum-carbon ceramic have high requirements on equipment and the process is complex and difficult to control, and provides a method for rapidly preparing the titanium-aluminum-carbon ceramic at room temperature.
The purpose of the invention can be realized by the following technical scheme:
a method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature comprises the following steps:
dissolving graphene oxide in deionized water, adding L-ascorbic acid, stirring, controlling the temperature to be 80-120 ℃, and fully performing a reduction reaction to form graphene hydrogel with a uniform structure;
drying and dehydrating the graphene hydrogel to obtain a porous and loose graphene aerogel with a large specific surface area;
uniformly mixing graphene aerogel, titanium powder and aluminum powder;
pressing the obtained mixed powder into a blank, taking a platinum sheet as an electrode and a graphite column as a pressurizing contact, and carrying out flash sintering treatment to obtain compact and uniform titanium-aluminum-carbon ceramic.
Further, the electric field intensity is controlled to be 50-300V/cm and the current density is controlled to be 80-500mA/mm during the flash sintering treatment2The sintering pressure is 10-50MPa, and the vacuum degree is controlled at 1-15 Pa.
Further, during the flash sintering treatment, the electric field intensity is controlled to be 80-200V/cm, and the current density is controlled to be 80-180mA/mm2The sintering pressure is 20-40MPa, and the vacuum degree is controlled at 1-6 Pa.
The technical parameters related to the present application, such as the preparation process of the graphene aerogel, the particle size of the powder, the proportion, the parameters of the ball milling process, and the electric field intensity, the current density, the sintering applied pressure, the vacuum degree and the like adopted in the flash sintering technology sintering are results summarized through a large number of experiments and based on the chemical thermodynamics of materials and the kinetic reaction mechanism. Firstly, in the flash process, there are multiple physical processes such as electric field, thermal field and coupling action thereof. Therefore, its sintering mechanism may also be based on a combination of these physical processes. Only under the technical parameter range, the preparation process of the graphene aerogel, the particle size of the powder, the proportion, the ball milling and the flash firing process can be carried out under the conditions of the flash firing process to carry out rapid carbonization reaction sintering to prepare the compact titanium-aluminum-carbon ceramic. On the contrary, the preparation process parameters, the particle size and the proportion of the graphene aerogel are not the parameters, the strength of a flash firing electric field is overlarge, the current density is overlarge, the sintering applied pressure is overlarge, the energy of a ceramic system is higher, the flash firing is violent, so that the carbonization is incomplete, and simultaneously, the abnormal growth of crystal grains is caused, so that the structure and the performance of the ceramic are deteriorated; in addition, the degree of vacuum is too high, which does not cause oxidation of the material, but does not facilitate the generation of joule heat in the ceramic material under the action of current. Similarly, the strength of the flash firing electric field is too small, the current density is too small, the energy in the ceramic and at the grain boundary is too low due to too small applied pressure, the flash firing process cannot be initiated due to too low current, and further sufficient energy cannot be provided for the crystal grains and the inside of the grain boundary to induce diffusion sintering reaction densification, that is, the joule heat at the reactant and the interface is not enough to provide the energy required for sintering, so that the carbonization reaction in the ceramic material is incomplete, the defects are many, the density is low, the second phase at the grain boundary is relatively complex, and the structure and the performance of the ceramic material are poor; in addition, the vacuum degree is low, and under the driving of high energy and joule heat, the oxygen content in the internal material and at the interface of the material is high, so that oxidation is easily caused, the internal carbonization reaction of the ceramic material is prevented, sintering densification is avoided, and the target titanium-aluminum-carbon ceramic material cannot be normally obtained.
Furthermore, the solid content of the graphene oxide solution is 3-10 g/L.
Furthermore, the concentration of the L-ascorbic acid in the graphene oxide solution is 0.5-5 g/L.
Further, the graphene hydrogel is dried and dehydrated for 4-12h at the temperature of 50-80 ℃.
Further, the particle size of the titanium powder is 1-10 μm, and the particle size of the aluminum powder is 1-10 μm.
Furthermore, the molar ratio of the graphene aerogel to the titanium powder to the aluminum powder is (1-10) to (1-20) to (1-10).
Further, a planetary ball mill is adopted for ball milling, so that the graphene aerogel, the titanium powder and the aluminum powder are uniformly mixed.
Furthermore, the mass ratio of the mixed powder of the graphene aerogel, the titanium powder and the aluminum powder to the pebbles in the ball mill is 1: 8-20, the rotating speed of the ball mill is 200-500 turns, and the ball milling time is 6-24 hours.
The titanium-aluminum-carbon ceramic is prepared by sintering through a reduced graphene oxide auxiliary flash firing technology, and the composition and microstructure of the titanium-aluminum-carbon ceramic can be flexibly regulated and controlled to optimize and improve the microstructure and performance of the titanium-aluminum-carbon ceramic. Firstly, mixing activated powder by high-energy ball milling by using prepared graphene aerogel as a carbon source and aluminum powder and titanium powder as an aluminum source and a titanium source respectively, and then performing cold isostatic pressing to form a prefabricated blank; and then in the flash sintering process, the graphene, aluminum powder and titanium powder are subjected to carbonization reaction, and pressure is applied under the action of a room-temperature electric field to rapidly sinter and densify the formed titanium-aluminum-carbon ceramic. The titanium-aluminum-carbon ceramic prepared by sintering is compact and high in purity, and the grain size is small and controllable, so that the problems that the grain growth and microstructure of the ceramic are difficult to control by high-temperature sintering in the traditional method for preparing the sintered titanium-aluminum-carbon ceramic, the process is complex, the requirement on equipment is high and the like are solved.
The flash firing technology is a method capable of sintering and densifying the electrolyte ceramic in a very short time and at a lower temperature. The electrolyte ceramic powder is first dry-pressed into shape and then connected to an electric circuit, a fixed initial voltage is applied to the electrolyte sample, and the electrolyte ceramic green body is placed in a furnace to be heated or at room temperature. When the furnace temperature reaches a fixed value, the current in the circuit rises sharply and instantly. Thus, the electrolyte ceramic can be sintered to be dense in a few seconds. Because of the sharply rising current and the starting point of sintering, the following advantages are obtained: (1) the sintering temperature is low; (2) the sintering rate is high; (3) the constant-temperature sintering time is short; (4) can compact some electrolytes which are difficult to compact in traditional high-temperature sintering, such as BZY; (5) no sintering aid is required to be added; (6) the device is simple and convenient. In the flash process, there are many physical processes such as electric field, thermal field and coupling action thereof. Therefore, its sintering mechanism may also be based on a combination of these physical processes. The current mainstream academic view mainly comprises the theory and speed of the joule heat effectThe rapid temperature rise promotes densification theory, particle contact point local thermal effect theory, defect action theory and the like. Comprises ion conductor (such as 3YSZ, 8YSZ, etc. cubic and tetragonal zirconia phase), insulator (Al)2O3) Semiconductor (BaTiO)3ZnO, SiC, etc.) and metalloid conductive ceramics (Co)2MnO4And ZrB2) And the like. 8YSZ can realize densification under the action of an electric field of 120V/cm and at the temperature of 750 ℃ which is far lower than that of the traditional sintering material.
According to the invention, the titanium-aluminum-carbon ceramic with high density, high purity and uniform grain size is prepared by adopting a graphene auxiliary flash firing technology, so that on one hand, reduced graphene oxide is taken as a carbon source, and flash firing in-situ synthesis at room temperature is realized to prepare a titanium-aluminum-carbon MAX phase; on the other hand, under the action of an electric field, certain pressure is provided at the same time, so that the ceramic can be sintered and densified at room temperature, and the method for synthesizing and preparing the ceramic at room temperature can be provided, and the composition, the structure and the performance of the ceramic can be flexibly and effectively regulated.
Compared with the prior art, the invention has the following advantages:
(1) reduced graphene oxide aerogel is used as a carbon source, and meanwhile, the titanium-aluminum-carbon MAX-phase ceramic with controllable sintering components is prepared by an auxiliary flash-firing technology under the room temperature condition.
(2) Simultaneously, the flash firing technology is adopted, the titanium-aluminum-carbon MAX phase ceramic is prepared by an in-situ reaction sintering one-step method, and the prepared ceramic is compact, has good crystallinity, is uniform in grain size distribution and has a controllable structure.
(3) The method for preparing the titanium-aluminum-carbon MAX phase ceramic has the advantages of low preparation temperature, simple and controllable process, high reaction sintering efficiency and low requirement on equipment.
(4) The titanium-aluminum-carbon MAX phase ceramic prepared by the method has a uniform structure and the compactness can reach 92-100%.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature comprises the following steps:
(1) dissolving graphene oxide (the diameter is 0.5-10 mu m, the number of layers is 1-5) in deionized water, preparing solid content to be 3-10g/L, carrying out ultrasonic oscillation for 30-100min, then carrying out magnetic stirring for 1-12h to fully dissolve the graphene oxide in the deionized water to form a uniform solution, then adding L-ascorbic acid into the solution, controlling the concentration to be 0.5-5g/L, carrying out magnetic stirring for 1-12h, and standing in an oven at 80-120 ℃ to fully carry out reduction reaction to form graphene hydrogel with a uniform structure;
(2) putting the graphene hydrogel obtained in the step 1 into an electrothermal blowing drying oven at the temperature of 50-80 ℃ for drying and dehydrating for 4-12h to obtain porous and loose graphene aerogel with large specific surface area;
(3) taking the graphene aerogel obtained in the step 2, micron-level titanium powder (Ti) (1-10 microns) and micron-level aluminum powder (Al) (1-10 microns), and mixing the materials according to a molar ratio of: mixing graphene aerogel, Ti and Al in a ratio of (1-10) to (1-20) to (1-10), and ball-milling by using a planetary ball mill to uniformly mix the graphene aerogel, titanium powder and aluminum powder, controlling the mass ratio of the mixed powder to the ball stone to be 1: 8-20, and ball-milling at the rotating speed of 200 and 500 revolutions for 6-24 hours to obtain uniformly mixed powder.
(4) Performing cold isostatic pressing on the mixed powder in the step 3 to form a cylindrical blank (the diameter is 5-30 mm, the height is 1-10mm), then performing flash sintering by using a platinum sheet as an electrode and a graphite column as a pressurizing contact, and controlling the electric field intensity of the sample to be 50-300V/cm and the current density to be 80-500mA/mm2The sintering pressure is 10-50MPa, the vacuum degree is controlled at 1-15Pa, and the compact and uniform titanium-aluminum-carbon ceramic can be obtained, and the compactness can reach 92-100%.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
In the particular embodiment of the present invention that is employed,
the graphene oxide powder is produced by Shanghai carbon source Huogu new material science and technology company, and has the diameter: 0.5-10 μm, number of layers: 1-5 layers, the single-layer rate is more than 99 percent, and the purity is more than or equal to 99.9 percent.
L-ascorbic acid is produced by Shanghai Michelin Biotechnology Limited, and has a purity of not less than 99.0%.
The titanium powder is produced by Shanghai ultramicro nanotechnology Limited company, and the purity is more than or equal to 99.0 percent.
The aluminum powder is produced by Shanghai ultramicro nanotechnology Limited company, and the purity is more than or equal to 99.0 percent.
The power of the ultrasonic generator is 500-1500W, the oscillation time is 10-100 min, and the ultrasonic generator is produced by ultrasonic instruments Limited company in Kunshan city.
The ball milling process adopts a planetary ball mill which is manufactured by Nanjing university and has model number QM-3SP 4.
The cold isostatic pressing equipment is a manual split type cold isostatic pressing machine of model YLJ-CIP-20B, which is produced by Anhui Hefei Crystal Material technology Limited.
The AC constant voltage and current power supply is an ALP-1000V 1A power supply produced by Yangzhou Dinghua electronics Limited of Jiangsu.
The flash burning equipment is a vacuum high-temperature tube furnace, which is a VBF-1200X-HB tube furnace produced by Anhui fertilizer material technology Limited.
The drying adopts an electric heating air blast drying oven which is DHG-9075A produced by Shanghai-Hengscientific instruments Co.
Example 1:
a method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature comprises the following steps:
(1) dissolving graphene oxide (the diameter is 0.5-10 mu m, the number of layers is 1-5) in deionized water, preparing the solid content to be 3g/L, carrying out ultrasonic oscillation for 40min, then carrying out magnetic stirring for 3h to fully dissolve the graphene oxide in the deionized water to form a uniform solution, then adding L-ascorbic acid into the solution, controlling the concentration to be 1g/L, carrying out magnetic stirring for 3h, and standing in an oven at 80 ℃ to fully carry out reduction reaction to form graphene hydrogel with a uniform structure;
(2) putting the graphene hydrogel obtained in the step 1 into an electrothermal blowing drying oven at 50 ℃ for drying and dehydrating for 4 hours to obtain porous and loose graphene aerogel with large specific surface area;
(3) taking the graphene aerogel obtained in the step 2, micron-level titanium powder (Ti) (1 mu m) and micron-level aluminum powder (Al) (1 mu m), and mixing the materials according to the molar ratio: mixing graphene aerogel, Ti and Al in a ratio of 2: 3: 1, and ball-milling by using a planetary ball mill to uniformly mix the graphene aerogel, titanium powder and aluminum powder, controlling the mass ratio of the mixed powder to the ball stone to be 1: 10, and controlling the rotating speed of the ball mill to be 300 revolutions, so as to obtain uniformly mixed powder after ball milling for 8 hours.
(4) Performing cold isostatic pressing on the mixed powder in the step 3 to form a cylindrical blank (the diameter is 10mm, the height is 3mm), then performing flash sintering by using a platinum sheet as an electrode and a graphite column as a pressurizing contact, and controlling the electric field intensity of the sample to be 120V/cm and the current density to be 200mA/mm2The sintering pressure is 30MPa, the vacuum degree is controlled to be 2Pa, and the compact and uniform titanium-aluminum-carbon ceramic can be obtained, and the compactness can reach 95%.
Example 2:
a method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature comprises the following steps:
(1) dissolving graphene oxide (the diameter is 0.5-10 mu m, the number of layers is 1-5) in deionized water, preparing 5g/L of solid content, carrying out ultrasonic oscillation for 60min, then carrying out magnetic stirring for 5h to fully dissolve the graphene oxide in the deionized water to form a uniform solution, then adding L-ascorbic acid into the solution, controlling the concentration to be 2g/L, carrying out magnetic stirring for 8h, and standing in a 90 ℃ oven to fully carry out reduction reaction to form graphene hydrogel with a uniform structure;
(2) putting the graphene hydrogel obtained in the step 1 into an electrothermal blowing drying oven at 60 ℃ for drying and dehydrating for 8 hours to obtain porous and loose graphene aerogel with large specific surface area;
(3) taking the graphene aerogel obtained in the step 2, micron-level titanium powder (Ti) (2 microns) and micron-level aluminum powder (Al) (2 microns), and mixing the materials according to a molar ratio: mixing graphene aerogel, Ti and Al in a ratio of 1: 2: 1, and ball-milling by using a planetary ball mill to uniformly mix the graphene aerogel, titanium powder and aluminum powder, controlling the mass ratio of the mixed powder to the ball stone to be 1: 12, and ball-milling at the rotating speed of 400 revolutions for 12 hours to obtain uniformly mixed powder.
(4) Performing cold isostatic pressing on the mixed powder in the step 3 to form a cylindrical blank (the diameter is 20 mm, the height is 5mm), then performing flash sintering by using a platinum sheet as an electrode and a graphite column as a pressurizing contact, and controlling the electric field intensity of the sample to be 240V/cm and the current density to be 400mA/mm2The sintering pressure is 40MPa, the vacuum degree is controlled to be 5Pa, and the compact and uniform titanium-aluminum-carbon ceramic can be obtained, and the compactness can reach 97%.
Example 3:
a method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature comprises the following steps:
(1) dissolving graphene oxide (the diameter is 0.5-10 mu m, the number of layers is 1-5) in deionized water, preparing solid content to be 3g/L, carrying out ultrasonic oscillation for 100min, then carrying out magnetic stirring for 10h to fully dissolve the graphene oxide in the deionized water to form a uniform solution, then adding L-ascorbic acid into the solution, controlling the concentration to be 0.5g/L, carrying out magnetic stirring for 10h, and standing in an oven at 80 ℃ to fully carry out reduction reaction to form graphene hydrogel with a uniform structure;
(2) putting the graphene hydrogel obtained in the step 1 into an electrothermal blowing drying oven at 50 ℃ for drying and dehydrating for 12 hours to obtain porous and loose graphene aerogel with large specific surface area;
(3) taking the graphene aerogel obtained in the step 2, micron-level titanium powder (Ti) (1 mu m) and micron-level aluminum powder (Al) (1 mu m), and mixing the materials according to the molar ratio: mixing graphene aerogel, Ti and Al in a ratio of 1: 1, and ball-milling by using a planetary ball mill to uniformly mix the graphene aerogel, titanium powder and aluminum powder, controlling the mass ratio of the mixed powder to the ball stone to be 1: 8, and ball-milling at the rotating speed of 200 revolutions for 24 hours to obtain uniformly mixed powder.
(4) Performing cold isostatic pressing on the mixed powder in the step 3 to form a cylindrical blank (the diameter is 30 mm, the height is 8mm), then performing flash sintering by using a platinum sheet as an electrode and a graphite column as a pressurizing contact, and controlling the electric field intensity of the sample to be 50V/cm and the current density to be 500mA/mm2The sintering pressure is 40MPa, the vacuum degree is controlled at 15Pa, and the compact and uniform titanium-aluminum-carbon ceramic can be obtained, and the compactness can reach 95%.
Example 4:
a method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature comprises the following steps:
(1) dissolving graphene oxide (the diameter is 0.5-10 mu m, the number of layers is 1-5) in deionized water, preparing a solid content of 10g/L, carrying out ultrasonic oscillation for 60min, then carrying out magnetic stirring for 5h to fully dissolve the graphene oxide in the deionized water to form a uniform solution, then adding L-ascorbic acid into the solution, controlling the concentration to be 5g/L, carrying out magnetic stirring for 8h, and standing in a 100 ℃ oven to fully carry out reduction reaction to form graphene hydrogel with a uniform structure;
(2) putting the graphene hydrogel obtained in the step 1 into an electrothermal blowing drying oven at 80 ℃ for drying and dehydrating for 4 hours to obtain porous and loose graphene aerogel with large specific surface area;
(3) taking the graphene aerogel obtained in the step 2, micron-level titanium powder (Ti) (5 microns) and micron-level aluminum powder (Al) (8 microns), and mixing the materials according to a molar ratio: mixing graphene aerogel, Ti and Al in a ratio of 5: 20: 3, and ball-milling by using a planetary ball mill to uniformly mix the graphene aerogel, titanium powder and aluminum powder, controlling the mass ratio of the mixed powder to the ball stones to be 1: 20, and carrying out ball milling at the rotating speed of the ball mill of 300 revolutions for 18 hours to obtain uniformly mixed powder.
(4) Performing cold isostatic pressing on the mixed powder in the step 3 to form a cylindrical blank (the diameter is 20 mm, the height is 5mm), then performing flash sintering by using a platinum sheet as an electrode and a graphite column as a pressurizing contact,the electric field intensity of the sample is controlled to be 200V/cm, and the current density is controlled to be 180mA/mm2The sintering pressure is 20MPa, the vacuum degree is controlled to be 1Pa, and the compact and uniform titanium-aluminum-carbon ceramic can be obtained, and the compactness can reach 96%.
Example 5:
a method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature comprises the following steps:
(1) dissolving graphene oxide (the diameter is 0.5-10 mu m, the number of layers is 1-5) in deionized water, preparing 5g/L of solid content, carrying out ultrasonic oscillation for 60min, then carrying out magnetic stirring for 5h to fully dissolve the graphene oxide in the deionized water to form a uniform solution, then adding L-ascorbic acid into the solution, controlling the concentration to be 2g/L, carrying out magnetic stirring for 8h, and standing in a 90 ℃ oven to fully carry out reduction reaction to form graphene hydrogel with a uniform structure;
(2) putting the graphene hydrogel obtained in the step 1 into an electrothermal blowing drying oven at 60 ℃ for drying and dehydrating for 8 hours to obtain porous and loose graphene aerogel with large specific surface area;
(3) taking the graphene aerogel obtained in the step 2, micron-level titanium powder (Ti) (2 microns) and micron-level aluminum powder (Al) (2 microns), and mixing the materials according to a molar ratio: mixing graphene aerogel, Ti and Al in a ratio of 1: 2: 1, and ball-milling by using a planetary ball mill to uniformly mix the graphene aerogel, titanium powder and aluminum powder, controlling the mass ratio of the mixed powder to the ball stone to be 1: 12, and ball-milling at the rotating speed of 400 revolutions for 12 hours to obtain uniformly mixed powder.
(4) Performing cold isostatic pressing on the mixed powder in the step 3 to form a cylindrical blank (the diameter is 20 mm, the height is 5mm), then performing flash sintering by using a platinum sheet as an electrode and a graphite column as a pressurizing contact, and controlling the electric field intensity of the sample to be 240V/cm and the current density to be 400mA/mm2The sintering pressure is 40MPa, the vacuum degree is controlled to be 5Pa, and the compact and uniform titanium-aluminum-carbon ceramic can be obtained, and the compactness can reach 97%.
Example 6:
(1) dissolving graphene oxide (the diameter is 0.5-10 mu m, the number of layers is 1-5) in deionized water, preparing a solid content of 6g/L, carrying out ultrasonic oscillation for 60min, then carrying out magnetic stirring for 5h to fully dissolve the graphene oxide in the deionized water to form a uniform solution, then adding L-ascorbic acid into the solution, controlling the concentration to be 1g/L, carrying out magnetic stirring for 8h, and standing in an oven at 80 ℃ to fully carry out reduction reaction to form graphene hydrogel with a uniform structure;
(2) putting the graphene hydrogel obtained in the step 1 into an electrothermal blowing drying oven at 60 ℃ for drying and dehydrating for 8 hours to obtain porous and loose graphene aerogel with large specific surface area;
(3) taking the graphene aerogel obtained in the step 2, micron-level titanium powder (Ti) (10 microns) and micron-level aluminum powder (Al) (10 microns), and mixing the materials according to a molar ratio of: mixing graphene aerogel, Ti and Al in a ratio of 10: 1: 10, and ball-milling by using a planetary ball mill to uniformly mix the graphene aerogel, titanium powder and aluminum powder, controlling the mass ratio of the mixed powder to the ball stone to be 1: 10, and controlling the rotating speed of the ball mill to be 400 revolutions, and obtaining uniformly mixed powder after ball milling for 12 hours.
(4) Performing cold isostatic pressing on the mixed powder in the step 3 to form a cylindrical blank (the diameter is 20 mm, the height is 5mm), then performing flash sintering by using a platinum sheet as an electrode and a graphite column as a pressurizing contact, and controlling the electric field intensity of the sample to be 300V/cm and the current density to be 80mA/mm2The sintering pressure is 10MPa, the vacuum degree is controlled at 5Pa, and the compact and uniform titanium-aluminum-carbon ceramic can be obtained, and the compactness can reach 98%.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (8)

1. A method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature is characterized by comprising the following steps:
dissolving graphene oxide in deionized water, adding L-ascorbic acid, stirring, controlling the temperature to be 80-120 ℃, and fully performing a reduction reaction to form graphene hydrogel with a uniform structure;
drying and dehydrating the graphene hydrogel to obtain a porous and loose graphene aerogel with a large specific surface area;
uniformly mixing graphene aerogel, titanium powder and aluminum powder;
pressing the obtained mixed powder into a blank, taking a platinum sheet as an electrode and a graphite column as a pressurizing contact, and carrying out flash sintering treatment to obtain compact and uniform titanium-aluminum-carbon ceramic;
controlling the electric field intensity to be 50-300V/cm and the current density to be 80-500mA/mm during flash sintering treatment2Sintering applied pressure is 10-50MPa, and vacuum degree is controlled to be 1-15 Pa;
the molar ratio of the graphene aerogel to the titanium powder to the aluminum powder is (1-10) to (1-20) to (1-10).
2. The method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature according to claim 1, wherein the electric field intensity is controlled to be 80-200V/cm and the current density is controlled to be 80-180mA/mm during the flash sintering treatment2The sintering pressure is 20-40MPa, and the vacuum degree is controlled at 1-6 Pa.
3. The method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature according to claim 1, wherein the solid content in the graphene oxide solution is 3-10 g/L.
4. The method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature according to claim 1, wherein the concentration of L-ascorbic acid in the graphene oxide solution is 0.5-5 g/L.
5. The method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature according to claim 1, wherein the graphene hydrogel is dried and dehydrated for 4-12h at 50-80 ℃.
6. The method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature according to claim 1, wherein the particle size of the titanium powder is 1-10 μm, and the particle size of the aluminum powder is 1-10 μm.
7. The method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature according to claim 1 or 6, wherein a planetary ball mill is used for ball milling, so that the graphene aerogel, titanium powder and aluminum powder are uniformly mixed.
8. The method for rapidly preparing titanium-aluminum-carbon ceramic at room temperature as claimed in claim 7, wherein the mass ratio of the mixed powder of graphene aerogel, titanium powder and aluminum powder to the ball stone in the ball mill is 1: 8-20, the rotation speed of the ball mill is 200-.
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