WO2020042948A1 - 球磨制备具有片层结构的纳米max相陶瓷粉体或料浆并调控粉体氧含量的方法 - Google Patents

球磨制备具有片层结构的纳米max相陶瓷粉体或料浆并调控粉体氧含量的方法 Download PDF

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WO2020042948A1
WO2020042948A1 PCT/CN2019/101340 CN2019101340W WO2020042948A1 WO 2020042948 A1 WO2020042948 A1 WO 2020042948A1 CN 2019101340 W CN2019101340 W CN 2019101340W WO 2020042948 A1 WO2020042948 A1 WO 2020042948A1
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ball
ball milling
powder
slurry
milling
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PCT/CN2019/101340
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French (fr)
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柏春光
谢曦
崔玉友
杨锐
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中国科学院金属研究所
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Priority to US17/272,339 priority Critical patent/US11975334B2/en
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Definitions

  • the invention relates to the field of ceramic materials, in particular to a method for preparing nano MAX phase ceramic powder or slurry having a lamellar structure by ball milling and regulating the oxygen content of the powder.
  • MAX phase ceramics are a class of processable ceramics with many unique and excellent properties. This ceramic has covalent, metal, and ionic bonds at the same time. With ceramic and metal properties. Such as: high melting point of ceramic materials, oxidation and corrosion resistance, metal conductivity, workability, damage tolerance, thermal shock resistance and other properties, nano-ceramic radiation damage resistance. The above characteristics make MAX phase ceramics expected to be applied in the fields of high temperature service parts, friction resistant parts, conductive elements, corrosion resistant parts, nuclear industry parts, protective coatings and other fields. However, as a structural ceramic material, most MAX phase ceramics have very coarse grains due to the high reaction synthesis temperature.
  • Nanocrystalline ceramics have excellent mechanical properties and some special functions due to the high proportion of grain boundaries and the special structure of interface atoms.
  • the main disadvantages of ordinary ceramics are poor toughness and low internal strength of many internal defects.
  • the nano-powder has a high activity and a large specific surface, which can significantly reduce the sintering temperature.
  • the density of the material is high, the composition uniformity is good, and the strength, toughness and superplasticity of the ceramic are greatly improved compared with ordinary ceramics. Therefore, the research and development of technology that can turn MAX phase ceramics into nano-ceramic powder is very important to improve the performance and application prospects of MAX phase ceramics.
  • Nano-multiphase ceramics due to the introduction of second-phase particles distributed at the grain boundaries, have deflection, absorption, and bridging effects on cracks, which help improve the toughness and high-temperature strength of ceramic materials.
  • the existing nano-multiphase ceramics are mainly toughened by adding external second-phase particles.
  • the performance of the nano-multiphase ceramics prepared by this method is far inferior to that of in-situ growth of nano-two-phase particles with phase interface matching on the nano-ceramic substrate. Strengthen and toughen ceramics.
  • Nano-powders of MAX phase ceramics are prepared by ball milling, and the surface oxygen content of the powders is adjusted during ball milling.
  • Nano-MAX / oxide composite ceramics with precise and adjustable content. This type of ceramics has excellent mechanical properties at room temperature and high temperature.
  • the precise and controllable content means that for different service environments of materials, the performance of materials can be optimized to meet different needs, the advantages of materials are effectively used, and the adaptability of service is improved.
  • MXenes sheet material such as a two-dimensional transition metal carbide, nitride, or carbonitride
  • the new transition metal carbide nanosheets MXenes came out with its excellent electrochemical properties, good water solubility, very large surface area, and lighter quality and stability, so it is expected to be as extensive as graphene in many fields.
  • Applications, such as: MXenes has good ion diffusion channels, conductivity and porous structure as electrode materials for lithium ion batteries. Because of its good electromagnetic coupling and loss characteristics, it is used as a light and high-strength absorbing material in various electronic equipment and weapon systems. MXenes also has good biological safety and has a large surface area and high chemical reaction sites. It has been reported as a catalyst carrier, water purification material, and medical material.
  • the size of the precursor powder determines the size of the accordion structure formed by the nanosheets.
  • the particles of MXenes material after etching and peeling are also micron, which completely limits the nano characteristics of nanosheet MXenes material as a functional material.
  • the MXenes material prepared directly by the nano-layer MAX phase powder etching has a unique small size effect. When the size of the layer is close to or smaller than the wavelength of the external energy source, the optical, electrical, magnetic, acoustic, and thermal Aspects of the physical properties have new effects.
  • the nano-sheet MAX phase powder has a large surface area, a large number of surface atoms, dense defects, high surface activity, and changes in the spectral characteristics of quantum dots, which are very conducive to peeling and etching or chemically modifying the surface to develop new materials.
  • the nano-sheet MAX phase powder used for MXenes materials generally requires very low oxygen content. Even the surface oxide film in the coarse powder contains only 0.01% mass fraction of oxygen atoms, which will affect the preparation and performance of MXenes materials. It has a very fatal effect, so it is required to remove oxygen at the same time during the ball milling to reduce the oxygen content to a very low level, so the regulation of the oxygen content of the powder is also very critical.
  • the purpose of the present invention is to provide a method for preparing nano-MAX phase ceramic powder or slurry having a lamellar structure by ball milling and regulating the oxygen content of the powder, and verifying the reliability and effectiveness of the technical route through various different ball milling methods. It is possible to obtain MAX phase ceramic nanosheet powders and slurries with different particle sizes, and different oxygen contents.
  • the method has simple process and can realize continuous and large-scale batch preparation.
  • a method for preparing nano MAX phase ceramic powder or slurry with a lamellar structure by ball milling and regulating the oxygen content of the powder is used as a raw material, and gas or Liquid gas, through the multi-dimensional action and adjustment of ball milling parameters and gas reaction, to obtain nano-sheet layered MAX phase ceramic powder or a slurry containing its components, while realizing the particle size adjustment and control of the powder, the surface composition of the powder and Regulation of the active state.
  • a ball milling device is used for ball milling the MAX phase ceramic coarse powder with a size of 1 to 5000 microns, while the ball milling Continuously pass gas or liquid gas with accurate chemical composition into the ball mill tank.
  • the method for preparing a nano-MAX phase ceramic powder or slurry having a lamellar structure by ball milling and regulating the oxygen content of the powder is During the ball milling process, depending on the target particle size and oxygen content requirements, ball milling equipment with or without temperature control is used; ball milling equipment It is a common planetary ball mill, high-energy ball mill, roller ball mill, stirring ball mill or vibration ball mill.
  • the ball milling method is wet ball milling or dry ball milling.
  • the particle size of the nanosheet powder obtained by different equipment, preparation methods and parameters is between 20 and 400 nanometers. Adjustable, the oxygen content is adjustable from 0.0001% to 20%.
  • the method for preparing nano MAX phase ceramic powder or slurry having a lamellar structure by ball milling and regulating the oxygen content of the powder is controlled by using a mixture of oxygen and an inert gas or a mixture of hydrogen and an inert gas; Integral meter, the ratio of oxygen or hydrogen to inert gas is greater than 0 to 1.
  • the method for preparing the nano-MAX phase ceramic powder or slurry having a lamellar structure by ball milling and regulating the oxygen content of the powder is realized by using a ball mill tank, a stirring ball mill or a vibration ball mill.
  • the ordinary planetary ball mill or high-energy ball mill passes the liquid medium outside the tank of the whole ball mill tank for temperature control; the ultra-low temperature cooling medium is cooled by low temperature liquid gas Agents: liquid argon, liquid nitrogen, liquid oxygen and polymer materials.
  • Other temperature control media are oil, water, alcohol, ketone, benzene or other liquid materials. The temperature control media can be adjusted from -200 ⁇ 300 °C between.
  • the method for preparing nano MAX phase ceramic powder or slurry having a lamellar structure by ball milling and regulating the oxygen content of the powder adopting wet ball milling to mix MAX phase ceramic powder, ball milling medium, and ball milling beads, and then ball milling.
  • the method for preparing a nano-MAX phase ceramic powder or slurry having a lamellar structure by ball milling and regulating the oxygen content of the powder is in the ball milling parameters.
  • the ball milling beads and the MAX-phase ceramic powder are in a 1: 1 to 100: 1 ball.
  • the material mass ratio is mixed; for wet ball milling, the amount of ball milling medium is between 10% and 500% of the total mass of the ball; for dry ball milling, the amount of surface dispersant is 0.01% of the total mass of the MAX phase ceramic powder ⁇ 10%; for roller ball mill, stirring ball mill, ordinary planetary ball mill, the ball milling speed is between 20 ⁇ 2000 rpm, and the ball milling time is 1 ⁇ 72 hours; for high energy ball mill, the ball milling speed is between 200 ⁇ 50,000 rpm. In the meantime, the ball milling time is 0.5 to 48 hours; for the vibration ball mill, the vibration frequency is between 5 to 5000 Hz, the amplitude is 1 to 50 mm, and the ball milling time is 2 to 180 hours.
  • the method for preparing a nano MAX phase ceramic powder or slurry with a lamellar structure by ball milling and regulating the oxygen content of the powder, the treatment of the ball milling product is determined by the use state of the required materials:
  • the slurry and ball mill beads obtained by wet ball milling can be sieved or filtered to obtain the slurry; for dry ball milling, the powder particle size reaches the target After the value is added, the ball milling medium required for the wet ball milling is added, and the ball slurry is milled for 5 to 1000 minutes to obtain a slurry with good dispersibility, and then the obtained slurry and ball mill beads are sieved or filtered through a sieve to obtain a slurry;
  • the slurry obtained by wet ball milling is dried or evaporated under reduced pressure under the protection of vacuum and argon, and the powder obtained by dry ball milling is Complete powder sieving in vacuum glove box and keep it sealed;
  • the method for preparing nano MAX phase ceramic powder or slurry with a lamellar structure by ball milling and regulating the oxygen content of the powder When the purity of the powder needs to be controlled, such as using acid-soluble metal balls and ball mill tanks, The powder is acid-washed; if alkali-soluble ceramic balls and ball mill tanks are used, alkali cooking is performed to remove ball mill impurities.
  • the design idea of the present invention is:
  • the flakes of the MAX phase directly cause fatigue microcracks or the interface between the flakes is detached by a ball milling method.
  • the gas is continuously introduced during the ball milling process.
  • the active ingredients in the gas will diffuse into the fresh surface through fatigue cracks and the fault plane between the sheets and react weakly with the highly active surface to accelerate the surface. Cleavage and cracking.
  • more cleavage and cracking of the surface further promotes the diffusion of the reactive gas, and finally the MAX phase ceramic particles are completely cracked and layered, and nano-sized sheets with a special surface state are obtained.
  • the degree of interface reaction in this process, the final size of the nanosheet layer and the oxygen content are multi-dimensionally controlled by factors such as ball milling parameters, ball milling ambient temperature, gas composition, and flow rate.
  • the invention and technical solution solve the preparation of MAX phase ceramic nanosheets And surface activity and functional regulation issues.
  • the technical method of the present invention can be implemented by almost all ball milling methods such as roller ball milling, stirring ball milling, vibration ball milling, ordinary planetary ball milling or high-energy ball milling, and has wide technical adaptability, simple and effective methods, and is suitable for large-scale continuous production.
  • the ball milling technical route of the present invention realizes the effective and cross-application of dry ball milling and wet ball milling alone, solves the problem of large differences in different technical routes, enhances the portability of technology, and the diversity of products.
  • the technology of the present invention realizes a variety of product morphologies. Depending on the final target product, powder and slurry morphologies can be obtained.
  • the technical method of the present invention is effective for almost all MAX-phase ceramics. Considering that there are more than 100 types of MAX-phase ceramics, the effective coverage of the preparation method is wide, and the design space for raw materials and different product properties is large.
  • the purity control of the product of the present invention can achieve the effectiveness and extensiveness of purity control by selecting multiple ball milling methods, ball milling parameters, ball milling materials, gas ratios, and post-processing steps, etc. to meet the requirements of different materials.
  • the particle size of the nano product powder of the final product of the present invention is adjustable between 20 and 400 nanometers, and the oxygen content is adjustable between 0.0001% and 20% by mass.
  • Figure 1 is a scanning electron microscope photograph of the MAX phase ceramic powder.
  • Figure 2 is a particle size measurement data curve using a ceramic powder laser particle size analyzer.
  • the abscissa Particle Size represents the granularity ( ⁇ m)
  • the ordinate Volume represents the volume percentage (%).
  • FIG. 3 is a scanning electron microscope image of a high-oxygen-content nanosheet powder.
  • FIG. 4 is a graph of measurement data of particle size or powder particle size in a slurry using a ceramic powder laser particle size analyzer.
  • the abscissa Particle Size represents the granularity ( ⁇ m)
  • the ordinate Volume represents the volume percentage (%).
  • the present invention uses micron-level MAX phase ceramic coarse powder as a raw material, and the ball mill can be passed into the ball mill tank with a special effect (special effect means: accelerated cleavage and cracking of the ceramic sheet layer, and the cracked sheet)
  • the layer interface has a weak reaction, which can increase or decrease the oxygen content on the surface of the sheet.)
  • nano-layered MAX phase ceramic powder or a material containing its components can be obtained. Pulp, to achieve the particle size adjustment control of the powder while realizing the control of the surface composition and active state of the powder.
  • the resulting powder or slurry can be used as a precursor to meet the needs of high-end MXenes material stripping and functionalization, or as a nano-material powder for MAX phase ceramics, and sintering to prepare in-situ in-situ nano-MAX phase with adjustable oxide content / Oxide composite ceramics, the specific process is as follows:
  • Ball milling device is used to ball mill MAX phase ceramic coarse powder with a size of 1 to 5000 microns (preferably 20 to 80 microns). During the ball milling, a gas or liquid gas with accurate chemical composition is continuously passed into the ball milling tank. .
  • the ball milling process depends on the target particle size and oxygen content requirements, with or without temperature controlled ball milling equipment.
  • Ball milling equipment can be any planetary ball mill, high-energy ball mill, roller ball mill, stirring ball mill, vibration ball mill and other arbitrary ball milling equipment.
  • the ball milling method can be wet ball milling and dry ball milling.
  • the particle size of the nanosheet powder obtained by different equipment, preparation methods and parameters is adjustable between 20 to 400 nm (preferably 100 to 200 nm), and the oxygen content is 0.0001% to 20% (preferably 0.02% to 10%). Adjustable quality score.
  • Gas content control adopts oxygen, inert gas or hydrogen and inert gas mixed ratio, and calculates oxygen (or hydrogen) by volume fraction: the ratio of inert gas ranges from 0 to 1 (preferably 0.1 to 0.3).
  • wet ball mill is used to mix MAX phase ceramic powder, ball milling medium, and ball milling beads after ball milling.
  • MAX phase ceramic powder, surface dispersant, and ball milling beads are mixed, and then ball milling is performed, or MAX phase ceramic powder and ball milling beads are mixed, and then ball milling is performed.
  • the ball-milling beads and ball-milling tanks can be acid-soluble metal balls and ball-milling tanks such as stainless steel, alkali-soluble ceramic balls and ball-milling tanks such as alumina and agate, and polymer-type ball-milling balls and ball-milling tanks.
  • Ball mill beads and ball mill cans of any material can be used.
  • Ball milling media can be volatile liquid solvents such as oil, water, alcohol, ketones, benzenes, etc.
  • the surface dispersant can be water-soluble and organic solvent-soluble Dispersant.
  • the temperature control is realized for the roller ball mill, the stirring ball mill or the vibration ball mill.
  • the ball mill tank is provided with a cover that can pass into the liquid medium, or the temperature control medium is directly passed into the tank.
  • a liquid medium is introduced outside the tank of the entire ball mill tank for temperature control.
  • Ultra-low temperature cooling medium adopts low-temperature liquid gas coolant: liquid argon, liquid nitrogen, liquid oxygen and polymer materials.
  • the ultra-low temperature cooling medium can be adjusted in the temperature range of -200 ⁇ -180 °C.
  • Other temperature control media can use oil, water, alcohol, ketones, benzenes, and other liquid substances.
  • the temperature control medium can be adjusted in the range of -50 to 300 ° C (preferably -10 to 100 ° C).
  • the ball milling beads and the MAX phase ceramic powder are mixed at a mass ratio of 1: 1 to 100: 1, and the amount of the wet ball milling ball milling medium is between 10% and 500% of the total mass of the ball. .
  • the dry ball milling surface dispersant is added in an amount of 0.01% to 10% of the total mass of the MAX phase ceramic powder.
  • the ball milling speed is between 20 and 2000 rpm, and the ball milling time is 1 to 72 hours.
  • the ball milling speed is between 200 and 50000 rpm, and the ball milling time is 0.5 to 48 hours.
  • the vibration frequency of the vibrating ball mill is between 5 and 5000 Hz, the amplitude is between 1 and 50 mm, and the ball milling time is 2 to 180 hours.
  • the processing of ball milling products is determined by the use state of the required materials. If you need to obtain slurry state materials, the slurry and ball mill beads obtained by wet ball milling can be screened or filtered to obtain the slurry, or the dry ball mill can be added after the powder particle size reaches the target value. The ball milling medium required for the wet ball milling is then ball milled for 5 to 1000 minutes to obtain a slurry with good dispersibility, and then the obtained slurry and ball mill beads are sieved or filtered through a sieve to obtain a slurry.
  • the slurry obtained by wet ball milling is dried or evaporated under reduced pressure under the protection of vacuum and argon, and the powder obtained by dry ball milling is vacuum gloves.
  • the powder is sieved in the box and sealed.
  • the slurry drying and powder screening processes can be completed in the atmospheric environment.
  • the method of preparing nano MAX phase ceramic powder or slurry with a lamellar structure by ball milling and regulating the oxygen content of the powder is as follows:
  • the oxygen content is 0.0002% by mass, which is far lower than the oxygen content of the raw material powder by 0.04%.
  • the particle size of the powder measured by a laser particle size analyzer is 100 nm, and the powder can be used as a precursor. It can meet the needs of high-end MXenes material stripping and etching.
  • the method of preparing nano MAX phase ceramic powder or slurry with a lamellar structure by ball milling and regulating the oxygen content of the powder is as follows:
  • the ceramic powder laser particle size analyzer measures a median diameter of 50 microns and uses liquid argon as a medium for ball milling.
  • the ball mill tank is installed on a roller ball mill, and liquid argon and liquid hydrogen are introduced into the ball mill tank.
  • the flow rate of the liquid argon gas is 2 liters / hour, and the flow rate of the liquid hydrogen gas is 0.5 liters / hour.
  • the ball milling process is completed at extremely low temperatures, and liquid gas is passed in for protection, the oxidation process of the material is effectively avoided.
  • the oxygen content of the powder after the ball milling is 0.01% by mass, which is slightly lower than the 0.02% oxygen content of the raw material powder.
  • the brittleness of the material is significantly increased.
  • the obtained nanosheet Nb 3 AlC 2 powder has a median diameter of 50 nm.
  • the powder can be used as a precursor to meet high-end MXenes Material peeling and etching requirements.
  • the method of preparing nano MAX phase ceramic powder or slurry with a lamellar structure by ball milling and regulating the oxygen content of the powder is as follows:
  • the ball mill tank is removed from the ball mill, the ball mill beads are sorted out in an indoor environment, and the obtained slurry is suction-filtered in a suction filtration device to obtain a usable slurry.
  • the slurry can be directly dried, which can be dried using an oven or a centrifugal spray dryer to obtain powder.
  • This method can be used to prepare directly shaped ceramic slurry or high oxygen content nanosheet powder (see Figure 3 for SEM images).
  • the oxygen content is 10% by mass, which is much higher than the oxygen content of the raw material powder by 0.03%.
  • the particle size or particle diameter of the slurry in the slurry measured by the laser particle size analyzer is 180 nm (particle size The measurement data results are shown in Figure 4).
  • the powder can be used as a precursor to meet the needs of high-end MXenes material stripping and etching. Powders and particles can absorb oxygen on the surface and highly oxygen, but the crystal structure and material are essentially nanosheet powders that have not changed.
  • the nano-alumina particles can be grown and precipitated in situ on the nano-Ti 2 AlC ceramic sheet.
  • the nano-Ti 2 AlC / Al 2 O 3 multi-phase ceramic obtained after densification has far exceeded Excellent performance of ordinary ceramics.

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Abstract

一种球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，采用微米级的MAX相陶瓷粗粉作为原料，球磨的同时往球磨罐中通入具有特殊效果的气体或液态气体，通过球磨参数和气体反应等多维作用和调节，得到纳米片层状的MAX相陶瓷粉体或含有其成分的料浆，实现粉体粒度调节控制的同时实现粉体表面成分和活性状态的调控。

Description

球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法 技术领域
本发明涉及陶瓷材料领域，具体为一种球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法。
背景技术
MAX相陶瓷(如：Ti 3SiC 2、Ti 2AlC、Nb 2AlC等)是一类具有众多独特优异性质的可加工陶瓷，这种陶瓷同时具有共价键、金属键、离子键，所以兼具陶瓷和金属的性质。如：陶瓷材料的高熔点、抗氧化和抗腐蚀能力、金属的导电性、可加工性、损伤容抗、抗热冲击等性能，纳米陶瓷的耐辐射损伤性。上述特点使得MAX相陶瓷有望在高温服役部件、耐摩擦部件、导电元件、耐蚀部件、核工业部件、保护性涂层等领域获得应用。然而作为结构陶瓷材料使用，大部分MAX相陶瓷由于反应合成温度很高，反应合成的晶粒非常粗大。而且作为可以自蔓延燃烧合成的材料，反应合成中放出大量的热，导致反应不可控，反应副产物多，晶粒大小控制非常困难，难以通过反应控制获得纳米晶陶瓷。而纳米晶陶瓷由于高比例的晶界及界面原子特殊结构，因而具有优良的力学性能和某些特殊的功能。普通陶瓷主要缺点是韧性差，内部缺陷多强度偏低。而纳米粉体由于活性高，比表面大可以显著降低烧结温度，烧结后材料的致密度高，成分均匀性好，陶瓷的强度、韧性和超塑性相比普通陶瓷而言均大幅提高。因而研发可以将MAX相陶瓷变成纳米陶瓷粉末的技术，对于提高MAX相陶瓷的性能和应用前景至关重要。
纳米复相陶瓷，由于引入分布于晶界的第二相颗粒，对裂纹有偏转、吸收、桥接等作用，有助于提高陶瓷材料的韧性以及高温强度。但是现有的纳米复相陶瓷主要通过添加外部的第二相颗粒强韧化，该方法制备的纳米复相陶瓷性能远远不及在纳米陶瓷基体上原位生长具有位相界面匹配的纳米二相颗粒强韧化陶瓷。通过球磨制备MAX相陶瓷的纳米粉体，同时在球磨时进行粉体表面氧含量调节，就能在烧结时在纳米MAX相陶瓷的基体里原位生长出细小弥散分布，化学亲和性极高，含量精确可调控的纳米MAX相/氧化物复相陶瓷，该类陶瓷具有极优异的室温及高温力学性能。含量精确可调控意味着针对材料不同的使役环境，可以对材料的性能进行优化设计满足不同需求，有效利用材料的优点，提高使役适应性。
通过使用氢氟酸刻蚀去除MAX相中的A原子金属层，就可以获得二维的MXenes片层材料(如：二维过渡金属碳化物、氮化物或碳氮化物)。新的过渡族金属碳化物纳米片MXenes一问世以其优异的电化学性能、良好的水溶性、非常大的表面积以及较轻的质量和稳定性，因而有望在诸多领域获得如石墨烯一样的广泛应用，如：MXenes具有良好离子扩散通道、导电性和多孔结构作为锂离子电池的电极材料应用。因其良好的电磁耦合及损耗特性，作为轻质高强的吸波材料，用于各种电子设备及武器系统。MXenes还具生物安全性好同时有大的表面积和高化学反应位点，作为催化剂载体，净水材料，医用材料已经被研究报道。
而对于作为功能材料使用的纳米片层的MXenes材料而言，前驱体粉体粒度的大小决定纳米 片层所构成的手风琴结构的尺度大小。如：作为前驱体的MAX相粉体材料是微米级的，则刻蚀剥离完后的MXenes材料颗粒也是微米级的，完全限制纳米片层的MXenes材料作为功能材料的纳米特性。而直接通过纳米片层MAX相粉体刻蚀制备的MXenes材料具有独特的小尺寸效应，当片层的大小与外部能量源的波长相近或更小时，在光学、电学、磁学、声学、热学方面的物理性质都有新的效果。同时，纳米片层MAX相粉体表面积大，表面原子数目多，缺陷密集，表面活性高，量子点的能谱特征变化，都非常有利于剥离刻蚀或进行化学修饰表面开发出新的材料。但是，用于MXenes材料的纳米片层MAX相粉体一般要求氧含量非常的低，即使是粗粉中表面氧化膜所含量的仅0.01％质量分数的氧原子，都会对MXenes材料的制备和性能产生非常致命的影响，所以要求球磨过程中同时除氧，把氧含量降低到非常低的地步，因而粉体的氧含量调控同样非常关键。
发明内容
本发明的目的在于提供一种球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，通过多种不同的球磨方法验证技术路线的可靠性和有效性，可以得到不同粒度尺寸，不同含氧量的MAX相陶瓷纳米片层粉体和料浆，该方法工艺简单，能实现连续和规模化批量制备。
本发明的技术方案是：
一种球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，采用微米级的MAX相陶瓷粗粉作为原料，球磨的同时往球磨罐中通入气体或液态气体，通过球磨参数和气体反应的多维作用和调节，得到纳米片层状的MAX相陶瓷粉体或含有其成分的料浆，实现粉体的粒度调节控制的同时，实现粉体表面成分和活性状态的调控。
所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，采用球磨装置对尺寸为1～5000微米的MAX相陶瓷粗粉进行球磨，球磨的同时连续往球磨罐中通入化学成分精确配比过的气体或液态气体。
所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，球磨过程视目标粒度和氧含量需求，使用或者不使用温度控制的球磨设备；球磨设备是普通行星球磨机、高能球磨机、滚筒球磨机、搅拌球磨机或振动球磨机，球磨方式是湿法球磨或干法球磨；不同设备、制备方法和参数获得的纳米片层粉体粒度在20～400纳米之间可调，氧含量在0.0001％～20％质量分数可调。
所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，气体含量控制采用氧气、惰性气体混合配比或氢气、惰性气体混合配比；按体积分比计，氧气或氢气与惰性气体比值范围为大于0至1。
所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，温度控制的实现是对滚筒球磨机、搅拌球磨机或振动球磨机，采用球磨罐外附加可通入液体介质的包套，或直接在罐体中通入温度控制介质；对普通行星球磨机或高能球磨机在整个球磨罐的罐仓外通入液态介质进行温度控制；超低温冷却介质采用低温液态气体冷却剂： 液氩、液氮、液氧和高分子材质包套，其他温度控制介质采用油、水、醇、酮、苯类或其他液态物，温度控制介质可调节温度范围为-200～300℃之间。
所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，采用湿法球磨将MAX相陶瓷粉体、球磨介质，球磨珠混合后进行球磨，采用干法球磨将MAX相陶瓷粉体、表面分散剂、球磨珠混合后，进行球磨或将MAX相陶瓷粉体、球磨珠混合后进行球磨；需要对粉体进行纯度控制时，球磨珠和球磨罐是不锈钢酸溶性金属球和球磨罐、氧化铝或玛瑙碱溶性陶瓷球和球磨罐，或者高分子类的球磨珠和球磨罐；不需要进行纯度和杂质控制时，则使用任意材质球磨珠和球磨罐，球磨介质是油、水、醇、酮或苯类可挥发液态溶剂，表面分散剂是水溶性及有机溶剂溶性分散剂。
所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，球磨参数中，球磨珠与MAX相陶瓷粉体按1:1～100:1的球料质量比进行混合；对湿法球磨，球磨介质加入量为球料总质量的10％～500％之间；对干法球磨，表面分散剂加入量为MAX相陶瓷粉体总质量的0.01％～10％之间；对滚筒球磨机、搅拌球磨机、普通行星球磨机，球磨转速在20～2000转/分钟之间，球磨时间1～72小时；对高能球磨机，球磨转速在200～50000转/分钟之间，球磨时间0.5～48小时；对振动球磨机，振动频率在5～5000Hz之间，振幅1～50mm之间，球磨时间2～180小时。
所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，球磨产物处理的处理由所需物料的使用状态决定：
(1)如需获得料浆状态物料，则将湿法球磨获得的料浆和球磨珠过筛网进行筛分或抽滤得到料浆即可；对于干法球磨，则在粉体粒度达到目标值后，加入湿法球磨所需球磨介质，再球磨5～1000分钟获得分散性好的料浆，然后对获得的料浆和球磨珠过筛网进行筛滤或抽滤得到料浆；
(2)如需获得氧含量低于5％质量分数粉体，则对湿法球磨获得的料浆在真空及氩气保护下进行烘干或减压蒸发，对干法球磨获得的粉体则在真空手套箱中完成粉体筛分并密封保存；
(3)对氧含量高于5％质量分数的粉体，在大气环境中完成料浆烘干及粉体筛分工艺。
所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，需对粉体进行杂质纯度控制时，如采用酸溶性金属球和球磨罐，则对粉体进行酸洗；如采用碱溶性陶瓷球和球磨罐，则进行碱煮去除球磨杂质。
本发明的设计思想是：
本发明通过球磨的方法使得MAX相的片层直接产生疲劳微裂纹，或片层间的界面脱离。同时在球磨的过程中连续不断的通入气体，气体中的有效成分会在球磨过程中通过疲劳裂纹、片层之间的层错面扩散进入新鲜表面并与高活性表面微弱反应，加速表面的解理和开裂。同时更多表面的解理和开裂进一步促进反应气体的扩散，最终使得MAX相陶瓷颗粒完全裂解和片层化，获得纳米状的同时具有特殊表面状态的片层。该过程的界面反应程度，纳米片层 的最终尺寸大小和氧含量多少，受球磨参数、球磨环境温度、气体成分和流速等因素多维控制，该发明和技术方案解决MAX相陶瓷纳米片层的制备和表面活性和功能调控问题。
本发明具有以下优点及有益效果：
(1)本发明技术方法可以通过滚筒球磨、搅拌球磨、振动球磨、普通行星球磨或高能球磨等几乎所有球磨方式实现，技术适应性广，方法简单有效，适合大批量连续化生产。
(2)本发明球磨技术路线实现干法球磨和湿法球磨单独有效或交叉应用，解决不同技术路线差异性大的问题，增强技术的可移植性，以及产物的多样性。
(3)本发明技术实现产物形态多种多样，视最终目标产物可获得粉体和料浆多种形态。
(4)本发明技术方法对几乎所有MAX相陶瓷均有效，考虑到MAX相陶瓷的种类超过一百多种，其可制备方法的有效覆盖性广，原料和需求不同产品性能可设计空间大。
(5)本发明产品的纯度控制能通过选择合适的球磨方式、球磨参数、球磨材质、气体配比、后处理步骤等多重调控，实现纯度控制的有效性和广泛性，满足不同的材料需求。
(6)本发明最终产物纳米片层粉体粒度在20～400纳米之间可调，氧含量在0.0001％～20％质量分数可调。
附图说明
图1为MAX相陶瓷粉体的扫描电镜照片。
图2为使用陶瓷粉激光粒度仪的粒度测量数据曲线。图中，横坐标Particle Size代表粒度(μm)，纵坐标Volume代表体积百分比(％)。
图3为高氧含量纳米片层粉体的扫描电镜图片。
图4为使用陶瓷粉激光粒度仪的料浆中颗粒物或粉体粒度测量数据曲线。图中，横坐标Particle Size代表粒度(μm)，纵坐标Volume代表体积百分比(％)。
具体实施方式
在具体实施过程中，本发明采用微米级的MAX相陶瓷粗粉作为原料，球磨的同时往球磨罐中通入具有特殊效果(特殊效果是指：加速陶瓷片层解理开裂，与开裂的片层界面微弱反应，能增加或减少片层表面氧含量)的气体或液态气体，通过球磨参数和气体反应等多维作用和调节，得到纳米片层状的MAX相陶瓷粉体或含有其成分的料浆，实现粉体的粒度调节控制的同时实现粉体表面成分和活性状态的调控。最终获得的粉体或料浆可作为前驱体，满足高端的MXenes材料剥离和功能化等需求，或作为MAX相陶瓷的纳米原料粉体，烧结制备氧化物含量可调控的原位自生纳米MAX相/氧化物复相陶瓷，具体过程如下：
1、采用球磨装置对尺寸为1～5000微米(优选为20～80微米)的MAX相陶瓷粗粉进行球磨，球磨的同时连续往球磨罐中通入化学成分精确配比过的气体或液态气体。球磨过程视目标粒度和氧含量需求，使用或者不使用温度控制的球磨设备。球磨设备可以是普通行星球磨机、高能球磨机、滚筒球磨机、搅拌球磨机、振动球磨机等任意球磨设备，球磨方式可以是湿法球磨和干法球磨。不同设备、制备方法和参数获得的纳米片层粉体粒度在20～400纳米(优选为100～200纳米)之间可调，氧含量在0.0001％～20％(优选为0.02％～10％) 质量分数可调。
2、气体含量控制采用氧气、惰性气体或氢气、惰性气体混合配比，体积分数计算氧气(或氢气)：惰性气体比值范围为0～1(优选为0.1～0.3)之间。
3、采用湿法球磨将MAX相陶瓷粉体、球磨介质，球磨珠混合后进行球磨。采用干法球磨则将MAX相陶瓷粉体、表面分散剂、球磨珠混合后，进行球磨或将MAX相陶瓷粉体、球磨珠混合后进行球磨。需要对粉体进行纯度控制时，球磨珠和球磨罐可以是不锈钢等酸溶性金属球和球磨罐，氧化铝、玛瑙等碱溶性陶瓷球和球磨罐，高分子类的球磨珠和球磨罐。不需要进行纯度和杂质控制则任意材质球磨珠和球磨罐都可以使用，球磨介质可以是油、水、醇、酮、苯类等可挥发液态溶剂，表面分散剂可以是水溶性及有机溶剂溶性分散剂。
4、温度控制的实现是对滚筒球磨机、搅拌球磨机或振动球磨机，采用球磨罐外附加可通入液体介质的包套，或直接在罐体中通入温度控制介质；对普通行星球磨机或高能球磨机在整个球磨罐的罐仓外通入液态介质进行温度控制。超低温冷却介质采用低温液态气体冷却剂：液氩、液氮、液氧和高分子材质包套，超低温冷却介质可调节温度范围为-200～-180℃之间。其他温度控制介质可以采用油、水、醇、酮、苯类及其他液态物，温度控制介质可调节温度范围为-50～300℃(优选为-10～100℃)之间。
5、球磨参数中球磨珠与MAX相陶瓷粉体按1:1～100:1的球料质量比进行混合，对湿法球磨球磨介质加入量为球料总质量的10％～500％之间。对干法球磨表面分散剂加入量为MAX相陶瓷粉体总质量的0.01％～10％之间。对滚筒球磨机、搅拌球磨机、普通行星球磨机球磨转速在20～2000转/分钟之间，球磨时间1～72小时。对高能球磨机球磨转速在200～50000转/分钟之间，球磨时间0.5～48小时。对振动球磨机振动频率在5～5000Hz之间，振幅1～50mm之间，球磨时间2～180小时。
6、球磨产物处理的处理由所需物料的使用状态决定。如需获得料浆状态物料，则将湿法球磨获得的料浆和球磨珠过筛网进行筛分或抽滤得到料浆即可，或对干法球磨则在粉体粒度达到目标值后加入湿法球磨所需球磨介质，再球磨5～1000分钟获得分散性好的料浆，然后对获得的料浆和球磨珠过筛网进行筛滤或抽滤得到料浆。如需获得氧含量低于5％质量分数粉体，则对湿法球磨获得的料浆在真空及氩气保护下进行烘干或减压蒸发，对干法球磨获得的粉体则在真空手套箱中完成粉体筛分并密封保存。对氧含量高于5％质量分数的粉体，可在大气环境中完成料浆烘干及粉体筛分工艺。需对粉体进行杂质纯度控制时，如采用酸溶性金属球和球磨罐，则对粉体进行酸洗；如采用碱溶性陶瓷球和球磨罐，则进行碱煮去除球磨杂质。
由于本发明涵盖技术方法和路线广泛，最终产物调节控制范围广泛，为有助于进一步理解本发现的目的、方案和优点先结合具体实例进行进一步清晰完整的描述。同时需要指出的是下面所描述的实例仅仅是作为列举的部分工作和实施方案，并非全部的可以实施方案。凡是使用本发明权利要求范围内的技术方法，均应属于本发明的保护范围。
实施例1
本实施例中，球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法如下：
(1)称取品名为Ti 3AlC 2的MAX相陶瓷粉50克，该陶瓷粉激光粒度仪测量粒度中径为100微米，称取分散剂聚甲基丙烯酸钠0.2克。
(2)将Ti 3AlC 2陶瓷粉，分散剂装入容积为500mL可通入气体的不锈钢球磨罐中，放入400克不锈钢球。
(3)将球磨罐安装在可连续通入气体的行星球磨机上，开始通入氢气和氩气体积比为1:5的混合气体，气体流速为5升/小时，保持气体通入直至球磨罐温度降至设定值。
(4)设定球磨环境温度为室温，即不通入其他温度控制介质。启动球磨机，以600转/分钟的转速球磨12小时。
(5)球磨结束后，启动球磨仓冷却系统，等待球磨罐温度降至0℃，关闭气体通入，密封球磨罐，关闭球磨机机和球磨机冷却系统。
(6)将球磨罐从球磨机上取下，和粉末筛网，粉末包装机，放入真空手套箱中。启动真空手套箱的真空系统，至真空度降至10 -3Pa关闭抽真空系统，然后往手套箱通入氩气。再在手套箱中分拣出球磨珠，筛分粉体，并将粉体真空封装保存。
该方法得到的粉体经化学分析，氧含量在0.0002％质量分数，远低于原料粉体0.04％的含氧量，激光粒度仪测量粉体粒度中径为100纳米，粉体可作为前驱体可满足高端的MXenes材料剥离和刻蚀等需求。
实施例2
本实施例中，球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法如下：
(1)称取品名为Nb 3AlC 2的MAX相陶瓷粉500克，该陶瓷粉激光粒度仪测量粒度中径为50微米，采用液态氩气作为介质进行球磨。
(2)将Nb 3AlC 2陶瓷粉，装入容积为10L可通入气体或液体的聚氨酯球磨罐中，放入8千克聚氨酯包覆的铁球。
(3)将球磨罐安装在滚筒球磨机上，开始往球磨罐中通入液态氩气和液态氢气，液态氩气流速为2升/小时，液态氢气流速为0.5升/小时。
(4)维持液态气体的通入，直至球磨罐内温度维持在-150℃下恒定，启动球磨机，设置滚筒转速100转/分钟，球磨72小时。
(5)球磨结束后，关闭液态气体通入，密封球磨罐，关闭球磨机，并将罐体从球磨机上取下。
(6)将球磨罐从球磨机上取下，和粉末筛网，粉末包装机，放入真空手套箱中。启动真空手套箱的真空系统，至真空度降至10 -3Pa关闭抽真空系统，然后往手套箱通入氩气。再在手套箱中分拣出球磨珠，筛分粉体，并将粉体真空封装保存。
由于球磨过程在极端低温下完成，同时通入液态气体进行保护，有效避免材料的氧化过 程。经化学分析测定，球磨完成后粉体氧含量在0.01％质量分数，略低于原料粉体0.02％的含氧量。同时极端低温条件和液态氢气的作用下，材料的脆性明显增加，球磨完成后，获得的纳米片层Nb 3AlC 2粉体粒度中径为50纳米，粉体可作为前驱体可满足高端的MXenes材料剥离和刻蚀等需求。
实施例3
本实施例中，球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法如下：
(1)称取品名为Ti 2AlC的MAX相陶瓷粉500克，粉体扫描电镜照片见图1。该陶瓷粉激光粒度仪测量粒度中径为80微米(粒度测量数据结果见图2)，量取液态甲苯1000毫升。
(2)将Ti 2AlC陶瓷粉，去离子水装入容积为5L可通入气体的真空玛瑙磨搅拌罐中，放入4千克玛瑙球。
(3)将球磨罐安装在带温控介质包套控温的搅拌球磨机上，开始通入氧气和氮气体积比为1:4的混合气体，气体流速为10升/小时，保持气体通入直至球磨结束。
(4)将温控介质甘油通入温控介质包套，启动加热系统。待球罐温度恒定在150℃后。启动球磨机，以1000转/分钟的转速球磨24小时。
(5)球磨结束后，启动球磨仓冷却系统，等待球磨罐温度降至0℃，关闭气体通入，密封球磨罐，关闭球磨机和球磨机冷却系统。
(6)将球磨罐从球磨机上取下，在室内环境下分拣出球磨珠后，将获得的料浆在抽滤装置中抽滤，获得可供使用的料浆。
(7)如果需要获得粉体则可直接对料浆进行烘干，既可以使用烘箱进行干燥，也可以使用离心雾化干燥机进行干燥，最终获得粉体。
该方法既可以用于制备直接成型陶瓷的料浆也可以用于制备高氧含量纳米片层粉体(扫描电镜图片见图3)。对得到的粉体经化学分析，氧含量在10％质量分数，远高于原料粉体0.03％的含氧量，激光粒度仪测量料浆中颗粒物或粉体粒度中径均为180纳米(粒度测量数据结果见图4)，粉体可作为前驱体可满足高端的MXenes材料剥离和刻蚀等需求。粉体和颗粒物可表面吸氧高度吸氧，但晶体结构和材料本质是未发生改变的纳米片层粉体。该粉体在烧结过程中，能在纳米的Ti 2AlC陶瓷片层上原位生长和析出纳米氧化铝颗粒，致密化后得到的纳米的Ti 2AlC/Al 2O 3复相陶瓷具有远超普通陶瓷的优异性能。

Claims (9)

  1. 一种球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，采用微米级的MAX相陶瓷粗粉作为原料，球磨的同时往球磨罐中通入气体或液态气体，通过球磨参数和气体反应的多维作用和调节，得到纳米片层状的MAX相陶瓷粉体或含有其成分的料浆，实现粉体的粒度调节控制的同时，实现粉体表面成分和活性状态的调控。
  2. 按照权利要求1所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，采用球磨装置对尺寸为1～5000微米的MAX相陶瓷粗粉进行球磨，球磨的同时连续往球磨罐中通入化学成分精确配比过的气体或液态气体。
  3. 按照权利要求1所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，球磨过程视目标粒度和氧含量需求，使用或者不使用温度控制的球磨设备；球磨设备是普通行星球磨机、高能球磨机、滚筒球磨机、搅拌球磨机或振动球磨机，球磨方式是湿法球磨或干法球磨；不同设备、制备方法和参数获得的纳米片层粉体粒度在20～400纳米之间可调，氧含量在0.0001％～20％质量分数可调。
  4. 按照权利要求3所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，气体含量控制采用氧气、惰性气体混合配比或氢气、惰性气体混合配比；按体积分比计，氧气或氢气与惰性气体比值范围为大于0至1。
  5. 按照权利要求3所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，温度控制的实现是对滚筒球磨机、搅拌球磨机或振动球磨机，采用球磨罐外附加可通入液体介质的包套，或直接在罐体中通入温度控制介质；对普通行星球磨机或高能球磨机在整个球磨罐的罐仓外通入液态介质进行温度控制；超低温冷却介质采用低温液态气体冷却剂：液氩、液氮、液氧和高分子材质包套，其他温度控制介质采用油、水、醇、酮、苯类或其他液态物，温度控制介质可调节温度范围为-200～300℃之间。
  6. 按照权利要求4所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，采用湿法球磨将MAX相陶瓷粉体、球磨介质，球磨珠混合后进行球磨，采用干法球磨将MAX相陶瓷粉体、表面分散剂、球磨珠混合后，进行球磨或将MAX相陶瓷粉体、球磨珠混合后进行球磨；需要对粉体进行纯度控制时，球磨珠和球磨罐是不锈钢酸溶性金属球和球磨罐、氧化铝或玛瑙碱溶性陶瓷球和球磨罐，或者高分子类的球磨珠和球磨罐；不需要进行纯度和杂质控制时，则使用任意材质球磨珠和球磨罐，球磨介质是油、水、醇、酮或苯类可挥发液态溶剂，表面分散剂是水溶性及有机溶剂溶性分散剂。
  7. 按照权利要求6所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，球磨参数中，球磨珠与MAX相陶瓷粉体按1:1～100:1的球料质量比进行混合；对湿法球磨，球磨介质加入量为球料总质量的10％～500％之间；对干法球磨，表面分散剂加入量为MAX相陶瓷粉体总质量的0.01％～10％之间；对滚筒球磨机、搅拌球磨机、普通行星球磨机，球磨转速在20～2000转/分钟之间，球磨时间1～72小时； 对高能球磨机，球磨转速在200～50000转/分钟之间，球磨时间0.5～48小时；对振动球磨机，振动频率在5～5000Hz之间，振幅1～50mm之间，球磨时间2～180小时。
  8. 按照权利要求6所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，球磨产物处理的处理由所需物料的使用状态决定：
    (1)如需获得料浆状态物料，则将湿法球磨获得的料浆和球磨珠过筛网进行筛分或抽滤得到料浆即可；对于干法球磨，则在粉体粒度达到目标值后，加入湿法球磨所需球磨介质，再球磨5～1000分钟获得分散性好的料浆，然后对获得的料浆和球磨珠过筛网进行筛滤或抽滤得到料浆；
    (2)如需获得氧含量低于5％质量分数粉体，则对湿法球磨获得的料浆在真空及氩气保护下进行烘干或减压蒸发，对干法球磨获得的粉体则在真空手套箱中完成粉体筛分并密封保存；
    (3)对氧含量高于5％质量分数的粉体，在大气环境中完成料浆烘干及粉体筛分工艺。
  9. 按照权利要求6所述的球磨制备具有片层结构的纳米MAX相陶瓷粉体或料浆并调控粉体氧含量的方法，其特征在于，需对粉体进行杂质纯度控制时，如采用酸溶性金属球和球磨罐，则对粉体进行酸洗；如采用碱溶性陶瓷球和球磨罐，则进行碱煮去除球磨杂质。
PCT/CN2019/101340 2018-08-31 2019-08-19 球磨制备具有片层结构的纳米max相陶瓷粉体或料浆并调控粉体氧含量的方法 WO2020042948A1 (zh)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113044842A (zh) * 2021-01-12 2021-06-29 辽宁中色新材科技有限公司 一种高纯碳化铝钛的生产工艺
CN113402270A (zh) * 2021-06-15 2021-09-17 兰州大学 一种多相纳米晶陶瓷复合材料的制备方法
CN113526506A (zh) * 2020-04-17 2021-10-22 北京化工大学 一种采用蚀刻-球磨法制备TiO2/Ti3C2复合纳米材料的方法
CN114804883A (zh) * 2021-01-27 2022-07-29 中国科学院金属研究所 一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法
WO2023013864A1 (ko) * 2021-08-05 2023-02-09 전북대학교산학협력단 저산소 맥스 상 제조방법 및 장치
CN117772382A (zh) * 2024-02-28 2024-03-29 中科雅丽科技有限公司 一种玻璃微珠研磨粉体细度精控调整方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109289995B (zh) * 2018-08-31 2020-09-18 中国科学院金属研究所 球磨制备具有片层结构的纳米max相陶瓷粉体或料浆并调控粉体氧含量的方法
CN112875703A (zh) * 2021-01-08 2021-06-01 北京航空航天大学 高熵二维材料、高熵max相材料及其制备方法
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KR102555516B1 (ko) * 2022-10-05 2023-07-13 대가파우더시스템 주식회사 다공성 세라믹 필터 제조방법
CN116920024A (zh) * 2023-01-31 2023-10-24 百草边大生物科技(青岛)有限公司 一种含无患子提取物的大生物功能剂

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102633505A (zh) * 2012-03-14 2012-08-15 中国科学院宁波材料技术与工程研究所 一种高纯度max相陶瓷粉体的制备方法
KR20130042270A (ko) * 2011-10-18 2013-04-26 한국원자력연구원 고속 기계적 밀링장치와 밀링조제를 이용한 세라믹 나노 분말 제조방법 및 이에 의해 제조된 세라믹 나노 분말
CN107117616A (zh) * 2017-05-27 2017-09-01 陕西科技大学 一种利用三元MAX材料制备层状MXenes材料的方法
US20180201512A1 (en) * 2017-01-16 2018-07-19 Winsky Technology Hong Kong Limited Yolk-shell-structured material, anode material, anode, battery, and method of forming same
CN109289995A (zh) * 2018-08-31 2019-02-01 中国科学院金属研究所 球磨制备具有片层结构的纳米max相陶瓷粉体或料浆并调控粉体氧含量的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942455A (en) * 1995-11-14 1999-08-24 Drexel University Synthesis of 312 phases and composites thereof
CN100506692C (zh) * 2007-04-27 2009-07-01 武汉理工大学 一种高纯Ti2AlC粉体材料的制备方法
CN106699184A (zh) * 2017-01-12 2017-05-24 盐城工学院 一种Ti3SnC2陶瓷粉末的制备方法及其制得的陶瓷粉末
CN106824406B (zh) * 2017-02-09 2018-10-23 许昌学院 一种陶瓷浆料的制备装置
CN207153900U (zh) * 2017-08-18 2018-03-30 连云港龙塔研磨材料有限公司 一种用于制备纳米陶瓷磨料的原料处理系统

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130042270A (ko) * 2011-10-18 2013-04-26 한국원자력연구원 고속 기계적 밀링장치와 밀링조제를 이용한 세라믹 나노 분말 제조방법 및 이에 의해 제조된 세라믹 나노 분말
CN102633505A (zh) * 2012-03-14 2012-08-15 中国科学院宁波材料技术与工程研究所 一种高纯度max相陶瓷粉体的制备方法
US20180201512A1 (en) * 2017-01-16 2018-07-19 Winsky Technology Hong Kong Limited Yolk-shell-structured material, anode material, anode, battery, and method of forming same
CN107117616A (zh) * 2017-05-27 2017-09-01 陕西科技大学 一种利用三元MAX材料制备层状MXenes材料的方法
CN109289995A (zh) * 2018-08-31 2019-02-01 中国科学院金属研究所 球磨制备具有片层结构的纳米max相陶瓷粉体或料浆并调控粉体氧含量的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG, W.: "Preparation of nanosized Ti3A1C2/Cu Compositee Powders and the Fabrication of the Bulk Composites", BEIJING JIAOTONG UNIVERSITY DOCTORAL DISSERTATION, 30 June 2017 (2017-06-30), pages 31 - 44 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113526506A (zh) * 2020-04-17 2021-10-22 北京化工大学 一种采用蚀刻-球磨法制备TiO2/Ti3C2复合纳米材料的方法
CN113044842A (zh) * 2021-01-12 2021-06-29 辽宁中色新材科技有限公司 一种高纯碳化铝钛的生产工艺
CN113044842B (zh) * 2021-01-12 2022-05-17 辽宁中色新材科技有限公司 一种高纯碳化铝钛的生产工艺
CN114804883A (zh) * 2021-01-27 2022-07-29 中国科学院金属研究所 一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法
CN114804883B (zh) * 2021-01-27 2023-11-10 中国科学院金属研究所 一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法
CN113402270A (zh) * 2021-06-15 2021-09-17 兰州大学 一种多相纳米晶陶瓷复合材料的制备方法
CN113402270B (zh) * 2021-06-15 2022-05-27 兰州大学 一种多相纳米晶陶瓷复合材料的制备方法
WO2023013864A1 (ko) * 2021-08-05 2023-02-09 전북대학교산학협력단 저산소 맥스 상 제조방법 및 장치
KR20230021247A (ko) * 2021-08-05 2023-02-14 전북대학교산학협력단 저산소 맥스 상 제조방법 및 장치
KR102569313B1 (ko) * 2021-08-05 2023-08-21 전북대학교산학협력단 저산소 맥스 상 제조방법 및 장치
CN117772382A (zh) * 2024-02-28 2024-03-29 中科雅丽科技有限公司 一种玻璃微珠研磨粉体细度精控调整方法

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