阅读说明：本技术 一种TixAlCy/TiCz/TiaAlb多元复相陶瓷粉末及其低温快速制备方法 (TixAlCy/TiCz/TiaAlb multi-component complex-phase ceramic powder and low-temperature rapid preparation method thereof ) 是由 丁健翔 丁宽宽 张凯歌 张骁 夏欣欣 程宇泽 汪恬昊 查余辉 黄培艳 孙正明 于 2021-01-15 设计创作，主要内容包括：本发明公开一种Ti-xAlC-y/TiC-z/Ti-aAl-b多元复相陶瓷粉末及其低温快速制备方法,所述Ti-xAlC-y/TiC-z/Ti-aAl-b为多元组分的金属性陶瓷粉末(x＝2-3,y＝1-2,z＝0.625-1.020,a＝1-3,b＝1-5)；制备原料为Ti粉、TiC粉、Al粉、石墨粉,配比为xTi-yTiC-zAl-C(x＝2-2.2,y＝1-1.3,z＝0.9-1.2)；本发明通过结合冷冻干燥和二步快速降温技术在较低温度下高效制备出的所述Ti-xAlC-y/TiC-z/Ti-aAl-b多元复相陶瓷粉末,具有良好的导电、导热和力学性能,在结构、导电、导热、摩擦、复合等材料的开发和应用上具有广泛前景。(The invention discloses a Ti x AlC y /TiC z /Ti a Al b The multi-element multi-phase ceramic powder and the low temperature fast preparation method thereof, the Ti x AlC y /TiC z /Ti a Al b A metallic ceramic powder as a multicomponent component (x ═ 2-3, y ═ 1-2, z ═ 0.625-1.020, a ═ 1-3, b ═ 1-5); the preparation raw materials comprise Ti powder, TiC powder, Al powder and graphite powder, and the mixture ratio is xTi-yTiC-zAl-C (x is 2-2.2, y is 1-1.3, and z is 0.9-1.2); the Ti is efficiently prepared at a lower temperature by combining freeze drying and a two-step rapid cooling technology x AlC y /TiC z /Ti a Al b The multi-element multi-phase ceramic powder has good electric conductivity, heat conductivity and mechanical properties, and has wide prospects in development and application of materials such as structures, electric conductivity, heat conductivity, friction, composites and the like.)

1. Ti_xAlC_y/TiC_z/Ti_aAl_bThe multi-component multi-phase ceramic powder has a multi-component multi-phase structure, and is characterized in that x is 2-3, y is 1-2, z is 0.625-1.020, a is 1-3, and b is 1-5.

2. The Ti of claim 1_xAlC_y/TiC_z/Ti_aAl_bThe multi-element multi-phase ceramic powder is characterized in that the synthetic raw materials comprise Ti powder, TiC powder, Al powder and graphite powder, and the mixture ratio is xTi-yTiC-zAl-C, wherein x is 2-2.2, y is 1-1.3, and z is 0.9-1.2.

3. A method as claimed in any one of claims 1 to 2One kind of Ti_xAlC_y/TiC_z/Ti_aAl_bThe preparation method of the multi-element multi-phase ceramic powder is characterized by comprising the following steps:

s1, weighing Ti powder, TiC powder, Al powder and graphite powder, and placing the powder in a beaker;

s2, adding deionized water into the beaker in the step S1, and placing the beaker in an ultrasonic machine for dispersion;

s3, placing the mixed solution obtained in the step S2 in a freeze dryer for treatment;

s4: placing the mixed solid sample in the step S3 in a vacuum drying oven for drying;

s5, putting the dried powder in the step S4 into an atmosphere tube furnace, and raising the temperature to a first temperature point at a certain speed;

s6, cooling the powder obtained in the step S5 to a second temperature point, and preserving heat for a certain time;

and S7, cooling the powder in the step S6 to room temperature in a tube furnace.

4. A Ti according to claim 3_xAlC_y/TiC_z/Ti_aAl_bThe preparation method of the multi-component multi-phase ceramic powder is characterized in that the particle sizes of Ti powder, TiC powder, Al powder and graphite powder weighed in the step S1 are 10-20 mu m.

5. A Ti according to claim 3_xAlC_y/TiC_z/Ti_aAl_bThe preparation method of the multi-component complex-phase ceramic powder is characterized in that deionized water and the powder are added in the step S2 according to the mass ratio of (5-3) to 1, and the ultrasonic dispersion time is 10-30 min.

6. A Ti according to claim 3_xAlC_y/TiC_z/Ti_aAl_bThe preparation method of the multi-element multi-phase ceramic powder is characterized in that the temperature of the freeze-drying treatment in the step S3 is-40 to-30 ℃, and the time is 5 to 10 hours.

7. A process as claimed in claim 3Seed of Ti_xAlC_y/TiC_z/Ti_aAl_bThe preparation method of the multi-component complex-phase ceramic powder is characterized in that in the step S4, the vacuum drying temperature is 70-120 ℃, and the heat preservation time is 2 hours.

8. A Ti according to claim 3_xAlC_y/TiC_z/Ti_aAl_bThe preparation method of the multi-component multi-phase ceramic powder is characterized in that in the step S5, the atmosphere is Ar or N₂The temperature rise rate is 3-5 ℃/min, and the first temperature point is 1200-1300 ℃.

9. A Ti according to claim 3_xAlC_y/TiC_z/Ti_aAl_bThe preparation method of the multi-component complex phase ceramic powder is characterized in that in the step S6, the cooling rate is-15 to-25 ℃/min, the second temperature point is 800 to 900 ℃, and the heat preservation time is 2 hours.

10. A Ti according to claim 3_xAlC_y/TiC_z/Ti_aAl_bThe preparation method of the multi-element multi-phase ceramic powder is characterized in that the temperature reduction rate in the step S7 is-5 to-10 ℃/min.

Technical Field

The invention belongs to the technical field of ceramic powder materials, and particularly relates to Ti_xAlC_y/TiC_z/Ti_aAl_bA multi-element multi-phase ceramic powder and its low-temp. quick preparing process are disclosed.

Background

The Ti-Al-C system ceramic has wide application prospect in the fields of electric conduction, heat conduction, friction, structure and the like, but the pure Ti-Al-C system ceramic material (Ti-Al-C system ceramic material)₃AlC₂、Ti₃AlC、Ti₂AlC) and other materials have advantages in electric conduction but have defects in hardness, heat conduction, friction and the like. TiC of multiple carbides of titanium_xThe composite material has the characteristic of high hardness, and has a function of improving the overall strength of the composite material; and titanium-aluminum intermetallic compound (Ti)_aAl_b) Has good deformation, electric conduction and heat conduction performances, and has remarkable advantages in the aspects of electric conduction, heat conduction and processing after being compounded with other materials. If the advantages of the materials can be combined to prepare a multi-element complex-phase metallic ceramic material, the material will show potential in the application field of functional composite materials in the future. However, no efficient, rapid and low-cost technology for preparing the multi-component complex-phase ceramic material is available at present. Therefore, how to realize the rapid low-temperature preparation and the practical component regulation of the multi-element complex phase material of the system is a key problem to be solved urgently at present.

In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.

Disclosure of Invention

The invention aims to solve the problems of rapid low-temperature preparation and realistic component regulation of a Ti-Al-C system multi-element complex phase material, and provides a Ti-Al-C system multi-element complex phase material_xAlC_y/TiC_z/Ti_aAl_bA multi-element multi-phase ceramic powder and its low-temp. quick preparing process are disclosed.

In order to achieve the purpose, the invention discloses the following technical scheme: ti_xAlC_y/TiC_z/Ti_aAl_bThe multi-component multi-phase ceramic powder has a multi-component multi-phase structure, wherein x is 2-3, y is 1-2, z is 0.625-1.020, a is 1-3, and b is 1-5.

Preferably, such Ti_xAlC_y/TiC_z/Ti_aAl_bThe multi-element complex phase ceramic powder is prepared from Ti powder, TiC powder, Al powder and graphite powder in a ratio of xTi-yTiC-zAl-C, wherein x is 2-2.2, y is 1-1.3 and z is 0.9-1.2.

The invention also discloses the Ti_xAlC_y/TiC_z/Ti_aAl_bThe low temperature fast preparation process of multiple complex phase ceramic powder includes the following steps:

s1, weighing Ti powder, TiC powder, Al powder and graphite powder, and placing the powder in a beaker;

s2, adding deionized water into the beaker in the step S1, and placing the beaker in an ultrasonic machine for dispersion;

s3, placing the mixed solution obtained in the step S2 in a freeze dryer for treatment;

s4: placing the mixed solid sample in the step S3 in a vacuum drying oven for drying;

s5, putting the dried powder in the step S4 into an atmosphere tube furnace, and raising the temperature to a first temperature point at a certain speed;

s6, cooling the powder obtained in the step S5 to a second temperature point, and preserving heat for a certain time;

and S7, cooling the powder in the step S6 to room temperature in a tube furnace.

In the step S1, the particle sizes of the raw materials of Ti powder, TiC powder, Al powder and graphite powder are 10-20 μm.

In the step S2, deionized water and powder are added according to the mass ratio of (5-3) to 1, and the ultrasonic dispersion time is 10-30 min.

The temperature of the freeze-drying treatment in the step S3 is-40 to-30 ℃, and the time is 5 to 10 hours.

In the step S4, the vacuum drying temperature is 70-120 ℃, and the heat preservation time is 2 h.

The atmosphere in the step S5 is Ar or N₂The temperature rise rate is 3-5 ℃/min, and the first temperature point is 1200-1300 ℃.

In the step S6, the cooling rate is-15 to-25 ℃/min, the second temperature point is 800 to 900 ℃, and the heat preservation time is 2 hours.

The cooling rate in the step S7 is-5 to-10 ℃/min.

Compared with the prior art, the invention has the beneficial effects that: the invention adopts Ti powder, TiC powder, Al powder and graphite powder which are easy to obtain, selects reasonable raw material mixing ratio, and combines a freeze drying technology and a two-step rapid cooling process to obtain Ti with adjustable components_xAlC_y/TiC_z/Ti_aAl_bThe process of the multi-element multi-phase ceramic powder has the characteristics of low cost, high efficiency, good practicability and the like, the defects of low electric conduction, heat conduction, hardness and other properties of pure Ti-Al-C system ceramic powder are avoided, the multi-element multi-phase ceramic powder has low resistivity (the resistivity is 0.30-0.35 mu omega. m) and high heat conductivity (45-50 W.m)^-1·k^-1) The alloy has high hardness (4.6-4.9 GPa) and good processability, and has great application potential in the directions of structure, electricity, heat, friction and the like in the future.

Drawings

FIG. 1 shows Ti obtained in example 5₃AlC₂/Ti₂AlC/TiC_0.625SEM image of complex phase ceramic powder;

FIG. 2 shows Ti obtained in example 5₃AlC₂/Ti₂AlC/TiC_0.625Complex phase ceramic powder XRD result;

FIG. 3 shows Ti obtained in example 6₃AlC₂/Ti₂AlC/Ti₃AlC/TiC_0.625/TiAl₂Multiphase ceramic powder SEMA drawing;

FIG. 4 shows Ti obtained in example 6₃AlC₂/Ti₂AlC/Ti₃AlC/TiC_0.625/TiAl₂Complex phase ceramic powder XRD result.

Detailed Description

The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.

Ti of the invention_xAlC_y/TiC_z/Ti_aAl_bThe multi-component multi-phase ceramic powder has a multi-component multi-phase structure, wherein x is 2-3, y is 1-2, z is 0.625-1.020, a is 1-3, and b is 1-5.

Example 1

The particle size of raw materials of Ti powder, TiC powder, Al powder and graphite powder is 10 mu m, the molar ratio of Ti to TiC to Al to C is 2:1:0.9:1, the mixed powder is added into deionized water, the mass ratio is 1:3, ultrasonic dispersion is carried out for 10 minutes, then the mixed solution is put into a freeze dryer for treatment at-30 ℃ for 5 hours, then the mixed solution is dried in a vacuum drying box at 70 ℃ for 2 hours, the dried mixed powder is put into a tube furnace, the temperature is raised to 1200 ℃ at the heating rate of 3 ℃/min under the protection of Ar atmosphere without heat preservation, the mixed powder is immediately cooled to 800 ℃ at the cooling rate of-15 ℃/min, the temperature is preserved for 2 hours, and finally the mixed powder is cooled to room temperature at the cooling rate of-5 ℃/min to obtain Ti powder₃AlC₂/Ti₂AlC/Ti₃AlC/TiC_1.020/Ti₃Al₅Complex phase ceramic powder (Ti)₃AlC₂97.6% of Ti₂AlC 0.91%, Ti₃AlC 0.65%, TiC_1.0200.19% of Ti₃Al₅0.64% by weight).

Example 2

The particle size of raw materials of Ti powder, TiC powder, Al powder and graphite powder is 12 mu m, the molar ratio of Ti to TiC to Al to C is 2.1:1.1:0.9:1, the mixed powder is added into deionized water, the mass ratio is 1:4, ultrasonic dispersion is carried out for 12 minutes, then the mixed solution is put into a freeze dryer for treatment at-34 ℃ for 7 hours, then drying is carried out in a vacuum drying box at 88 ℃ for 2 hours, the dried mixed powder is put into a tube furnace, and the temperature is raised to a temperature of 4 ℃/min under the protection of Ar atmosphere at the heating rate of 4 ℃/minCooling to 860 deg.C at-18 deg.C/min without heat preservation at 1250 deg.C, preserving heat for 2h, and cooling to room temperature at-6 deg.C/min to obtain Ti₃AlC₂/Ti₂AlC/Ti₃AlC/TiC_0.989/Ti₂Al₅Complex phase ceramic powder (Ti)₃AlC₂98.0% of Ti₂AlC 0.81%, Ti₃AlC 0.59%, TiC_0.9890.16% of Ti₂Al₅0.44% is accounted for).

Example 3

The particle size of raw materials of Ti powder, TiC powder, Al powder and graphite powder is 14 mu m, the molar ratio of Ti to TiC to Al to C is 2.2:1.2:1:1, the mixed powder is added into deionized water with the mass ratio of 1:3, ultrasonic dispersion is carried out for 18 minutes, then the mixed solution is put into a freeze dryer for processing 8 hours at minus 38 ℃, then drying is carried out for 2 hours at 104 ℃ in a vacuum drying box, the dried mixed powder is put into a tube furnace and placed in an N tube furnace₂Under the protection of atmosphere, raising the temperature to 1280 ℃ at the heating rate of 5 ℃/min, immediately cooling to 870 ℃ at the cooling rate of-22 ℃/min without heat preservation, preserving heat for 2h, and finally cooling to room temperature at the cooling rate of-7 ℃/min to obtain Ti₃AlC₂/Ti₂AlC/Ti₃AlC/TiC_0.957/Ti_3.3Al complex phase ceramic powder (Ti)₃AlC₂98.1% of Ti₂AlC 0.77%, Ti₃AlC 0.58%, TiC_0.9570.14% of Ti_3.3Al 0.41%).

Example 4

The particle size of raw materials of Ti powder, TiC powder, Al powder and graphite powder is 20 mu m, the molar ratio of Ti to TiC to Al to C is 2.2:1.3:1.2:1, the mixed powder is added into deionized water, the mass ratio is 1:5, ultrasonic dispersion is carried out for 26 minutes, then the mixed solution is put into a freeze dryer for processing 10 hours at minus 37 ℃, then drying is carried out for 2 hours at 120 ℃ in a vacuum drying box, the dried mixed powder is put into a tube furnace and is put into an N tube furnace₂Under the protection of atmosphere, heating to 1270 ℃ at a heating rate of 5 ℃/min, immediately cooling to 880 ℃ at a cooling rate of-23 ℃/min without heat preservation, preserving heat for 2h, and finally cooling to room temperature at a cooling rate of-9 ℃/min to obtain Ti₃AlC₂/Ti₂AlC/Ti₃AlC/TiC_0.649/Ti₃Al complex phase ceramic powder (Ti)₃AlC₂98.3% of Ti₂AlC 0.73%, Ti₃AlC 0.59%, TiC_0.6490.15% of Ti₃Al 0.23%).

Example 5

The particle size of raw materials of Ti powder, TiC powder, Al powder and graphite powder is 11 mu m, the molar ratio of Ti to TiC to Al to C is 2.1:1.2:0.9:1, the mixed powder is added into deionized water, the mass ratio of the mixed powder to C is 1:4, ultrasonic dispersion is carried out for 15 minutes, then the mixed solution is put into a freeze dryer for treatment at-35 ℃ for 6 hours, then drying is carried out in a vacuum drying box for 2 hours at 90 ℃, the dried mixed powder is put into a tubular furnace, under the protection of Ar atmosphere, the temperature is increased to 1260 ℃ at the heating rate of 5 ℃/min without heat preservation, the temperature is immediately cooled to 900 ℃ at the cooling rate of-20 ℃/min, the temperature is preserved for 2 hours, and finally the temperature is cooled to room temperature at the cooling rate of-8 ℃/min to obtain Ti powder₃AlC₂/Ti₂AlC/TiC_0.625Complex phase ceramic powder (Ti)₃AlC₂99.1% of Ti₂0.71% of AlC and TiC_0.6250.19% by weight).

Example 6

The particle size of raw materials of Ti powder, TiC powder, Al powder and graphite powder is 18 mu m, the molar ratio of Ti to TiC to Al to C is 2.1:1.1:1.2:1, the mixed powder is added into deionized water, the mass ratio of the mixed powder to C is 1:5, ultrasonic dispersion is carried out for 30 minutes, then the mixed solution is put into a freeze dryer for processing for 10 hours at the temperature of minus 40 ℃, then drying is carried out for 2 hours at the temperature of 115 ℃ in a vacuum drying box, the dried mixed powder is put into a tube furnace, under the protection of Ar atmosphere, the temperature is increased to 1300 ℃ at the heating rate of 5 ℃/min, heat preservation is not carried out, the mixed powder is immediately cooled to 900 ℃ at the cooling rate of minus 25 ℃/min, heat preservation is carried out for 2 hours, and finally the mixed powder is cooled to the room temperature at the cooling₃AlC₂/Ti₂AlC/Ti₃AlC/TiC_0.625/TiAl₂Complex phase ceramic powder (Ti)₃AlC₂98.5% of Ti₂AlC 0.75%, Ti₃AlC 0.57%, TiC_0.6250.13% of TiAl₂Accounting for 0.05 percent.

Ti obtained in examples 1 to 6_xAlC_y/TiC_z/Ti_aAl_bMulticomponent complex phase ceramic powder and pure Ti-Al-C system ceramic powder (Ti) as comparative examples 1, 2₃AlC₂、Ti₂AlC) were compared and the results are shown in table 1:

TABLE 1 comparison of the Properties of examples 1 to 6 and comparative examples 1 and 2

As can be seen from the table 1, the adjustable Ti with different components is prepared by selecting reasonable raw material mixing ratio and combining the freeze drying technology and the two-step rapid cooling process_xAlC_y/TiC_z/Ti_aAl_bThe properties of the multi-element complex phase ceramic powder, such as electric conductivity, heat conductivity, hardness and the like, are obviously superior to those of pure Ti-Al-C system ceramic powder, and the multi-element complex phase ceramic powder has huge potential in future application.

The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.