CN110872191A - Nb-shaped alloy4AlC3Preparation method of porous ceramic - Google Patents

Nb-shaped alloy4AlC3Preparation method of porous ceramic Download PDF

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CN110872191A
CN110872191A CN201810998243.7A CN201810998243A CN110872191A CN 110872191 A CN110872191 A CN 110872191A CN 201810998243 A CN201810998243 A CN 201810998243A CN 110872191 A CN110872191 A CN 110872191A
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黄政仁
蔡平
刘学建
姚秀敏
杨丽慧
魏玉全
王晓洁
孟祥玮
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a Nb4AlC3A method of preparing a porous ceramic, comprising: mixing niobium powder, aluminum powder and carbon powder to obtain mixed powder; molding the obtained mixed powder, and then placing the mixed powder in a protective atmosphere for pressureless sintering at 1400-1750 ℃ for 1-720 minutes to obtain the Nb4AlC3A porous ceramic.

Description

Nb-shaped alloy4AlC3Preparation method of porous ceramic
Technical Field
The invention relates to a preparation method of MAX phase porous ceramic, in particular to Nb4AlC3A preparation method of porous ceramics, in particular to the field of porous ceramics preparation.
Background
Ternary lamellar ceramic MAX phases are an emerging ceramic family, commonly referred to as Mn+1AXnAnd (N-1, 2, 3 …), wherein M is an early transition metal element, a is a main group element (iiia-via), and X is C or N. They have consistent crystal structure characteristics: that is, adjacent closed M atomic layers are periodically separated by A atomic layer in c-axis direction, and X atoms are filled in octahedral gap of M atoms to form M6Structural form of X. The bonding force between the M atom and the X atom is a strong covalent bond, the M atom and the A atom layer are weak bonding similar to the Van der Waals force between the layered graphites, and the M atoms are bonded by a metal bond. Due to the coexistence of various chemical bonds, the ternary layered ceramic material combines the advantages of metal and ceramic in performance. The ceramic has the advantages of good ductility, good electric and heat conducting properties and good machinability like metal, high melting point, high thermal stability, corrosion resistance and the like. Thereby receiving wide attention of scientific research personnel.
Nb4AlC3Is a MAX phase ceramic newly synthesized in recent years, and the unit cell lattice constant thereof
Figure BDA0001782361790000011
Figure BDA0001782361790000012
Theoretical density of 7.06g/cm3. At present, to Nb4AlC3The research reports mainly focus on bulk ceramic and powder materials. Week (week)Yanchun et al [ J.Am.Ceram.Soc.,91,2258-]Niobium powder, aluminum powder and carbon powder are taken as raw materials by adopting an in-situ reaction-hot pressing process, and heat preservation is carried out for 1h at 1700 ℃ and under the pressure of 30MPa to successfully prepare Nb4AlC3A single phase bulk ceramic material. Hexadong et al (Chinese patent application No. 200910073098.2)]Report a kind of Nb4AlC3The ceramic powder is prepared by adopting a self-propagating high-temperature synthesis technology and taking niobium powder, aluminum powder and carbon powder as raw materials to prepare loose Nb4AlC3The block is subjected to subsequent crushing, grinding, sieving and drying to obtain high-purity Nb4AlC3The ceramic powder material can provide high-quality powder raw materials for preparing ceramic devices and related composite materials thereof with certain sizes, shapes and specifications. Excellent combination property enables to Nb4AlC3The deep research of the method is very important to prepare Nb with other structures4AlC3Ceramic materials will also expand their field of application. Nb is not yet known4AlC3A preparation method of porous ceramics.
Disclosure of Invention
Therefore, the invention provides Nb4AlC3A method of preparing a porous ceramic, comprising:
mixing niobium powder, aluminum powder and carbon powder to obtain mixed powder;
molding the obtained mixed powder, and then placing the mixed powder in a protective atmosphere to perform pressureless sintering at 1400-1750 ℃ for 1-720 min to obtain the Nb4AlC3A porous ceramic.
Preferably, the molar ratio of the niobium powder, the aluminum powder and the carbon powder is 4 (0.8-1.7) to 2.5-3.2, and preferably 4 (1.1-1.5) to 2.6-2.9).
Preferably, the carbon powder is graphite powder and/or carbon black powder.
Preferably, the niobium powder has a particle size of 30 to 80 μm, the aluminum powder has a particle size of 75 to 150 μm, and the carbon powder has a particle size of 1 to 10 μm.
Preferably, the mixing mode is ball milling mixing, and the parameters of the ball milling mixing include: the mass ratio of the ball material is (4-12) 1, the revolution speed is 100-500 rpm, the rotation speed is 100-600 rpm, and the time is 1-24 h; preferably, the parameters of ball milling mixing include: the mass ratio of the ball material is (6-10): 1, the revolution speed is 200-400 rpm, the rotation speed is 200-500 rpm, and the time is 3-16 h.
Preferably, the forming treatment comprises pre-pressing forming and cold isostatic pressing treatment, wherein the pre-pressing forming is forming under 10-60 MPa for 0-2 min; the cold isostatic pressing treatment is completed under 100-300 MPa for 2-5 min.
Preferably, the protective atmosphere is argon or a mixed gas of hydrogen and argon with the mass percent of hydrogen being less than 10%.
Preferably, the temperature rise rate of the pressureless sintering is 1-10 ℃/min, and preferably 3-5 ℃/min.
Preferably, the pressureless sintering temperature is 1500-1700 ℃, and the time is 3-240 min.
In another aspect, the present invention also provides a Nb prepared according to the above-described preparation method4AlC3Porous ceramic of said Nb4AlC3The porosity of the porous ceramic is 23.2-58.1%, and the purity is 48.9-99.7 wt%.
The invention has the beneficial effects that:
under the condition of lower energy consumption, a ball milling-pressureless sintering preparation method with a simple process is adopted, niobium, aluminum and carbon simple substance powder are used as raw materials, and the high-purity Nb with the porosity adjustable between 23.2 and 58.1 percent is prepared by designing the raw material proportion, ball milling process parameters (ball milling rotating speed, ball milling time and ball material ratio) and the pressureless sintering process (temperature rise rate, sintering temperature and heat preservation time)4AlC3A porous ceramic material. Is expected to be used in the fields of environmental protection, chemical industry, petroleum, smelting and the like. The method has the characteristics of energy conservation, environmental protection, simple process, high production efficiency and suitability for large-scale industrial production.
Drawings
FIG. 1 shows Nb prepared in example 12 of the present invention4AlC3XRD pattern of porous ceramic;
FIG. 2 shows Nb prepared in example 12 of the present invention4AlC3Scanning topography of the porous ceramic section;
FIG. 3 shows Nb prepared in comparative example 1 of the present invention4AlC3XRD pattern of porous ceramic;
FIG. 4 shows Nb prepared in comparative example 1 of the present invention4AlC3Macroscopic view of porous ceramics.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention provides a Nb4AlC3Porous ceramic of said Nb4AlC3The porous ceramic has high purity (48.9-99.7 wt%) and adjustable porosity between 23.2-58.1%.
In the present invention, Nb4AlC3The preparation method of the porous ceramic has the characteristics of simple process, safety, reliability, low cost, high production efficiency and suitability for large-scale industrial production. Prepared Nb4AlC3The porous ceramic has high purity and adjustable porosity of 23.2-58.1%, and is expected to be used in the fields of environmental protection, chemical industry, petroleum, smelting and the like. Nb is exemplarily illustrated below4AlC3A preparation method of porous ceramics.
Niobium powder, aluminum powder and carbon powder are mixed to obtain mixed powder. Wherein the carbon powder is graphite powder or/and carbon black powder. The mixing may be by ball milling. For example, niobium powder, aluminum powder, and carbon powder are put into a ball mill pot in which a protective gas is introduced, and ball-milled, and naturally cooled to room temperature to obtain a mixed powder. The molar ratio of the niobium powder to the aluminum powder can be 4 (0.8-1.7), and is preferably 4 (1.1-1.5). The molar ratio of the niobium powder to the carbon powder can be 4 (2.5-3.2), and is preferably 4 (2.6-2.9). The ball mill pot lining and ball material may be an oxide (e.g., ZrO)2、Al2O3Etc.), nitrides (e.g. Si3N4Etc.), carbides (such as WC, etc.), or alloy materials. The mass ratio of ball materials of the ball milling can be (4-12): 1, and preferably (6-10): 1. The revolution speed during ball milling can be 100-500 rpm, preferably 200-400 rpm; the rotation speed may be 100 to 600rpm, preferably 200 to 500 rpm. The ball milling time can be 1-24 h, and the optimization is carried outIs 3-16 h. Wherein, the grain diameter of the niobium powder can be 30-80 μm, the grain diameter of the aluminum powder can be 75-150 μm, and the grain diameter of the carbon powder can be 1-10 μm.
And molding the mixed powder to obtain a biscuit. Then the biscuit is put into an atmosphere furnace, pressureless sintering is carried out at high temperature, and Nb is obtained after furnace cooling4AlC3A porous ceramic. Wherein the forming treatment comprises pre-pressing forming and cold isostatic pressing treatment, and the pre-pressing forming is forming under 10-60 MPa for 0-2 min; the cold isostatic pressing treatment is completed under 100-300 MPa for 2-5 min. The atmosphere of the atmosphere furnace may be argon gas, or a mixed gas of hydrogen gas and argon gas in which the mass percentage of hydrogen gas is less than 10%. The temperature rise rate of the pressureless sintering can be 1-10 ℃/min, and preferably 3-5 ℃/min. The temperature of the pressureless sintering can be 1400-1750 ℃, and is preferably 1500-1700 ℃. The heat preservation time of the pressureless sintering can be 1-720 min, preferably 3-240 min.
The Nb is measured by adopting an Archimedes drainage method4AlC3The porosity of the porous ceramic is 23.2-58.1%. The prepared Nb is measured by adopting an XRD internal standard method4AlC3The purity of the porous ceramic is greater than 48 wt%, preferably greater than 99 wt%.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., a person skilled in the art can make a selection within suitable ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples, unless otherwise specified, the niobium powder, the aluminum powder and the graphite powder are all commercially available products, and the purity is greater than 98 wt%, wherein the niobium powder has a particle size of 30-80 μm, the aluminum powder has a particle size of 75-150 μm, and the carbon powder has a particle size of 1-10 μm.
Example 1:
55.75g of niobium powder, 4.45g of aluminum powder and 4.86g of graphite powder are weighed and poured into a zirconia ball millIn the jar, 520g of zirconia ball mill was added and mixed for 3 hours to obtain a uniformly mixed powder. Wherein, the revolution speed of the ball mill is 300rpm, and the rotation speed is 300 rpm. Weighing 10g of mixed powder, loading into a pre-pressing grinding tool, keeping the pressure at 10MPa for 2min for pre-pressing and forming, and keeping the pressure at 250MPa for 5min for cold isostatic pressing to obtain a biscuit. Then, the prepared biscuit is put into a corundum boat, the corundum boat is put into a high-temperature furnace, 95 wt% argon and 5 wt% hydrogen are introduced into the corundum boat, the temperature is raised to 1700 ℃ at the speed of 5 ℃/min and is kept for 20min, and Nb is obtained after furnace cooling4AlC3A porous ceramic;
nb prepared in this example4AlC3The purity of the porous ceramic was 78.6 wt%, and the porosity was 31.1%.
Example 2:
the difference between the embodiment and the embodiment 1 is that the ball milling time is 8h, and the pressureless sintering heat preservation time is 10 min. Other steps and parameters were the same as in example 1;
nb prepared in this example4AlC3The purity of the porous ceramic was 85.4 wt%, and the porosity was 29.4%.
Example 3:
the difference between this embodiment and example 1 is that the ball milling time is 8h, the pressureless sintering temperature is 1500 ℃, and the holding time is 240 min. Other steps and parameters were the same as in example 1;
nb prepared in this example4AlC3The purity of the porous ceramic was 77.9 wt%, and the porosity was 35.9%.
Example 4:
the difference between the embodiment and the embodiment 1 is that the ball milling time is 12h, the pressureless sintering temperature is 1500 ℃, and the heat preservation time is 360 min. Other steps and parameters were the same as in example 1;
nb prepared in this example4AlC3The purity of the porous ceramic was 69.1 wt%, and the porosity was 26.6%.
Example 5:
the difference between the embodiment and the embodiment 1 is that the ball milling time is 12h, the pressureless sintering temperature is 1680 ℃, and the heat preservation time is 30 min. Other steps and parameters were the same as in example 1;
nb prepared in this example4AlC3The purity of the porous ceramic was 90.7 wt%, and the porosity was 28.3%.
Example 6:
55.75g of niobium powder, 5.26g of aluminum powder and 4.86g of graphite powder are weighed and poured into a zirconia ball mill pot, 527g of zirconia ball mill is added for ball milling and mixing for 8 hours, and then uniformly mixed powder is obtained. Wherein, the revolution speed of the ball mill is 300rpm, and the rotation speed is 300 rpm. Weighing 10g of mixed powder, loading into a pre-pressing grinding tool, keeping the pressure at 10MPa for 2min for pre-pressing and forming, and keeping the pressure at 250MPa for 5min for cold isostatic pressing to obtain a biscuit. Then, the prepared biscuit is put into a corundum boat, the corundum boat is put into a high-temperature furnace, 95 wt% argon and 5 wt% hydrogen are introduced into the corundum boat, the temperature is raised to 1680 ℃ at the speed of 3 ℃/min and is kept for 60min, and Nb is obtained after furnace cooling4AlC3A porous ceramic;
nb prepared in this example4AlC3The purity of the porous ceramic was 91.2 wt%, and the porosity was 36.5%.
Example 7:
the present embodiment is different from example 6 in that the pressure of the cold isostatic pressing treatment is 100 MPa. The other steps and parameters were the same as in example 6;
nb prepared in this example4AlC3The purity of the porous ceramic was 92.6 wt%, and the porosity was 42.7%.
Example 8:
the difference between this embodiment and example 6 is that the pressure of the cold isostatic pressing treatment was 200MPa, and the temperature rise rate of pressureless sintering was 5 ℃/min. The other steps and parameters were the same as in example 6;
nb prepared in this example4AlC3The purity of the porous ceramic was 89.5 wt%, and the porosity was 34.2%.
Example 9:
the difference between this embodiment and example 6 is that the pressure of the cold isostatic pressing treatment is 300MPa, the temperature rise rate of the pressureless sintering is 5 ℃/min, and the holding time of the pressureless sintering is 45 min. The other steps and parameters were the same as in example 6;
nb prepared in this example4AlC3The purity of the porous ceramic was 76.5 wt%, and the porosity was 25.1%.
Example 10:
the difference between this embodiment and example 6 is that the ball milling time was 16 hours, and the temperature rise rate of pressureless sintering was 5 ℃/min. The sintering temperature is 1700 ℃, and the heat preservation time is 5 min. The other steps and parameters were the same as in example 6;
nb prepared in this example4AlC3The purity of the porous ceramic was 85.4 wt%, and the porosity was 23.2%.
Example 11:
55.75g of niobium powder, 6.07g of aluminum powder and 4.86g of graphite powder are weighed and poured into a zirconia ball mill pot, 533g of zirconia ball mill is added for ball milling and mixing for 4 hours, and then uniformly mixed powder is obtained. Wherein, the revolution speed of the ball mill is 300rpm, and the rotation speed is 300 rpm. Weighing 10g of mixed powder, loading into a pre-pressing grinding tool, keeping the pressure at 10MPa for 2min for pre-pressing and forming, and keeping the pressure at 250MPa for 5min for cold isostatic pressing to obtain a biscuit. Then, the prepared biscuit is put into a corundum boat, the corundum boat is put into a high-temperature furnace, 95 wt% argon and 5 wt% hydrogen are introduced into the corundum boat, the temperature is raised to 1680 ℃ at the speed of 3 ℃/min and is kept for 10min, and Nb is obtained after furnace cooling4AlC3A porous ceramic;
nb prepared in this example4AlC3The purity of the porous ceramic was 87.9 wt%, and the porosity was 39.8%.
Example 12:
this embodiment is different from example 11 in that the ball milling time was 8 hours. The other steps and parameters were the same as in example 11;
the Nb4AlC3 porous ceramic produced in this example had a purity of 99.7wt% and a porosity of 35.8%.
The XRD pattern of the material is shown in figure 1, and the phase of the prepared porous ceramic is Nb4AlC3(ii) a The scanning topography of the cross section is shown in FIG. 2, and the prepared Nb4AlC3The porous ceramic material containing continuous throughPores, Nb4AlC3The grains are in a typical lamellar structure.
Example 13:
the difference between this embodiment and example 11 is that the ball milling time was 8 hours, the pressure of cold isostatic pressing treatment was 300MPa, and the temperature rise rate of pressureless sintering was 5 ℃/min. The other steps and parameters were the same as in example 11;
nb prepared in this example4AlC3The purity of the porous ceramic was 94.2 wt%, and the porosity was 32.2%.
Example 14:
the difference between this embodiment and example 11 is that the ball milling time was 8 hours, the pressure of cold isostatic pressing treatment was 200MPa, and the temperature rise rate of pressureless sintering was 5 ℃/min. The other steps and parameters were the same as in example 11;
nb prepared in this example4AlC3The purity of the porous ceramic was 91.3 wt%, and the porosity was 39.6%.
Example 15:
the difference between this embodiment and embodiment 11 is that the ball milling time is 8h, the pressure of cold isostatic pressing treatment is 100MPa, the temperature rise rate of pressureless sintering is 5 ℃/min, the temperature of pressureless sintering is 1700 ℃, and the heat preservation time is 10 min. The other steps and parameters were the same as in example 11;
nb prepared in this example4AlC3The purity of the porous ceramic was 86.8 wt%, and the porosity was 40.5%.
Example 16:
55.75g of niobium powder, 6.07g of aluminum powder and 4.86g of graphite powder are weighed and poured into a zirconia ball mill pot, 533g of zirconia ball mill is added for ball milling and mixing for 6 hours, and then uniformly mixed powder is obtained. Wherein, the revolution speed of the ball mill is 400rpm, and the rotation speed is 300 rpm. Weighing 10g of mixed powder, loading into a pre-pressing grinding tool, keeping the pressure at 10MPa for 2min for pre-pressing and forming, and keeping the pressure at 200MPa for 5min for cold isostatic pressing to obtain a biscuit. Then, the prepared biscuit is put into a corundum boat, the corundum boat is put into a high-temperature furnace, 95 wt% argon and 5 wt% hydrogen are introduced into the high-temperature furnace, the temperature is raised to 1600 ℃ at the speed of 3 ℃/min, the temperature is kept for 120min, and the biscuit is cooled along with the furnaceObtaining Nb4AlC3A porous ceramic;
nb prepared in this example4AlC3The purity of the porous ceramic was 77.6 wt%, and the porosity was 36.7%.
Example 17:
55.75g of niobium powder, 6.07g of aluminum powder and 4.86g of graphite powder are weighed and poured into a zirconia ball mill pot, 533g of zirconia ball mill is added for ball milling and mixing for 3 hours, and then uniformly mixed powder is obtained. Wherein, the revolution speed of the ball mill is 200rpm, and the rotation speed is 500 rpm. Weighing 10g of mixed powder, loading into a pre-pressing grinding tool, keeping the pressure at 10MPa for 2min for pre-pressing and forming, and keeping the pressure at 200MPa for 5min for cold isostatic pressing to obtain a biscuit. Then, the prepared biscuit is put into a corundum boat, the corundum boat is put into a high-temperature furnace, 95 wt% argon and 5 wt% hydrogen are introduced into the corundum boat, the temperature is raised to 1680 ℃ at the speed of 3 ℃/min, the temperature is kept for 30min, and Nb is obtained after furnace cooling4AlC3A porous ceramic;
nb prepared in this example4AlC3The purity of the porous ceramic was 89.7 wt%, and the porosity was 45.0%.
Example 18:
55.75g of niobium powder, 6.07g of aluminum powder and 4.86g of graphite powder are weighed and poured into a zirconia ball mill pot, 400g of zirconia ball mill is added for ball milling and mixing for 8 hours, and then uniformly mixed powder is obtained. Wherein, the revolution speed of the ball mill is 300rpm, and the rotation speed is 400 rpm. Weighing 10g of mixed powder, loading into a pre-pressing grinding tool, keeping the pressure at 10MPa for 2min for pre-pressing and forming, and keeping the pressure at 200MPa for 5min for cold isostatic pressing to obtain a biscuit. Then, the prepared biscuit is put into a corundum boat, the corundum boat is put into a high-temperature furnace, 95 wt% argon and 5 wt% hydrogen are introduced into the corundum boat, the temperature is raised to 1680 ℃ at the speed of 3 ℃/min, the temperature is kept for 30min, and Nb is obtained after furnace cooling4AlC3A porous ceramic;
nb prepared in this example4AlC3The purity of the porous ceramic was 91.6 wt%, and the porosity was 34.2%.
Example 19:
55.75g of niobium powder, 6.07g of aluminum powder and 4.86g of graphite powder were weighedPouring the mixture into a zirconia ball milling tank, adding 667g of zirconia ball mill, and ball milling and mixing for 20h to obtain uniformly mixed powder. Wherein, the revolution speed of the ball mill is 300rpm, and the rotation speed is 200 rpm. Weighing 10g of mixed powder, loading into a pre-pressing grinding tool, keeping the pressure at 10MPa for 2min for pre-pressing and forming, and keeping the pressure at 200MPa for 5min for cold isostatic pressing to obtain a biscuit. Then, the prepared biscuit is put into a corundum boat, the corundum boat is put into a high-temperature furnace, 95 wt% argon and 5 wt% hydrogen are introduced into the corundum boat, the temperature is raised to 1700 ℃ at the speed of 3 ℃/min and is kept for 3min, and Nb is obtained after furnace cooling4AlC3A porous ceramic;
nb prepared in this example4AlC3The purity of the porous ceramic was 85.1 wt%, and the porosity was 25.4%.
Examples 20 to 29:
nb for examples 20 to 294AlC3See tables 1 and 2 for the preparation parameters of the porous ceramics.
To illustrate the present invention in detail, Table 1 further lists the Nb of the present invention4AlC3Preparation parameters of the porous ceramic:
Figure BDA0001782361790000071
Figure BDA0001782361790000081
to illustrate the present invention in detail, Table 2 further lists the Nb of the present invention4AlC3Preparation conditions and corresponding purities and porosities of the porous ceramics:
Figure BDA0001782361790000082
Figure BDA0001782361790000091
comparative example 1:
55.75g of niobium powder and 5.26g of aluminum powder were weighedAnd 4.86g of graphite powder are poured into a zirconia ball-milling tank, 132g of zirconia ball mill is added for ball-milling and mixing for 2 hours, and then uniformly mixed powder is obtained. And the revolution rate of the ball mill is 300rpm, the rotation rate is 0rpm, 10g of mixed powder is weighed and loaded into a pre-pressing grinding tool, the mixed powder is kept for 2min under the pressure of 10MPa for pre-pressing forming, and then kept for 5min under the pressure of 200MPa for cold isostatic pressing treatment to obtain the biscuit. Then, the prepared biscuit is put into a corundum boat, the corundum boat is put into a high-temperature furnace, 95 wt% argon and 5 wt% hydrogen are introduced into the corundum boat, the temperature is raised to 1680 ℃ at the speed of 5 ℃/min and is kept for 60min, and Nb is obtained after furnace cooling4AlC3A porous ceramic;
nb prepared by this comparative example4AlC3The purity of the porous ceramic was 32.7 wt%.
The XRD pattern of the material is shown in figure 3, and the phase of the prepared porous ceramic is formed by Nb4AlC3NbC and Nb2AlC composition; the macroscopic view of the porous ceramic is shown in fig. 4, a large number of cracks exist on the surface of the prepared porous ceramic, and powder on the surface is easy to fall off.
As is clear from the above tables 1,2 and comparative example 1, Nb4AlC3The purity and porosity of the porous ceramic varies widely, e.g., the purity of the porous ceramic prepared in example 12 is as high as 99.7wt%, example 26 is as low as 48.9 wt%, and the Nb prepared in comparative example 14AlC3The purity of the porous ceramic is only 32.7 wt%, which shows that besides the raw material proportion and the pressureless sintering process are factors influencing the purity of the porous ceramic, the ball milling process is also a key factor influencing the purity of the porous ceramic. Further, it is understood from examples 2, 3, 6 and 7 that Nb is influenced4AlC3The main factors of porosity of porous ceramics are the pressureless sintering process and the forming pressure.
Finally, it should be noted that although the present invention uses only planetary ball mills, zirconia ball mill pot liners and grinding balls for ball milling, it is necessary to note that other forms of ball mills (e.g., swing ball mills, etc.), other material ball mill pots, such as other oxides (e.g., Al), may be used2O3Etc.), nitrides (e.g. Si3N4Etc.), carbide (such as WC, etc.) or alloy, niobium powder, aluminum powder of different grain sizesAnd carbon powder as raw materials, and Nb with high purity and controllable porosity can be prepared by adjusting the experimental parameters of raw material proportion, ball milling, molding treatment, pressureless sintering and the like4AlC3A porous ceramic material. Accordingly, non-essential modifications and adaptations of the present invention as described above will occur to those skilled in the art and are within the scope of the present invention.

Claims (10)

1. Nb-shaped alloy4AlC3The preparation method of the porous ceramic is characterized by comprising the following steps:
mixing niobium powder, aluminum powder and carbon powder to obtain mixed powder;
molding the obtained mixed powder, and then placing the mixed powder in a protective atmosphere for pressureless sintering at 1400-1750 ℃ for 1-720 minutes to obtain the Nb4AlC3A porous ceramic.
2. The preparation method according to claim 1, wherein the molar ratio of the niobium powder, the aluminum powder and the carbon powder is 4 (0.8-1.7) to (2.5-3.2), preferably 4 (1.1-1.5) to (2.6-2.9).
3. The method according to claim 1 or 2, wherein the carbon powder is graphite powder and/or carbon black powder.
4. The method according to any one of claims 1 to 3, wherein the niobium powder has a particle size of 30 to 80 μm, the aluminum powder has a particle size of 75 to 150 μm, and the carbon powder has a particle size of 1 to 10 μm.
5. The method for preparing the nano-particles according to any one of claims 1 to 4, wherein the mixing manner is ball milling mixing, and parameters of the ball milling mixing comprise: the mass ratio of the ball material is (4-12): 1, the revolution speed is 100-500 rpm, the rotation speed is 100-600 rpm, and the time is 1-24 hours; preferably, the parameters of ball milling mixing include: the mass ratio of the ball material is (6-10): 1, the revolution speed is 200-400 rpm, the rotation speed is 200-500 rpm, and the time is 3-16 hours.
6. The preparation method according to any one of claims 1 to 5, wherein the forming treatment comprises pre-pressing forming and cold isostatic pressing treatment, and the pre-pressing forming is forming under 10-60 MPa for 0-2 minutes; the cold isostatic pressing treatment is completed under 100-300 MPa for 2-5 minutes.
7. The method according to any one of claims 1 to 6, wherein the protective atmosphere is argon gas or a mixed gas of hydrogen gas and argon gas in which the mass percentage of hydrogen gas is less than 10%.
8. The method according to any one of claims 1 to 7, wherein the pressureless sintering is carried out at a temperature rise rate of 1 to 10 ℃/min, preferably 3 to 5 ℃/min.
9. The method of any one of claims 1-8, wherein the pressureless sintering is performed at a temperature of 1500-1700 ℃ for 3-240 minutes.
10. Nb prepared by the production method according to any one of claims 1 to 94AlC3Porous ceramic, characterized in that said Nb4AlC3The porosity of the porous ceramic is 23.2-58.1%, and the purity is 48.9-99.7 wt%.
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