Multi-component carbide reinforced MAX phase ceramic material and preparation method thereof
By introducing multi-component carbides into MAX phase ceramics and solid-solubilizing elements such as Ti, Ta, Nb, Hf, and V, M2AlC-MC composite ceramics are formed, which solves the problem of insufficient hardness and strength of traditional MAX phase ceramics, improves their mechanical properties, and expands their application range.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANGHAI INST OF CERAMIC CHEM & TECH CHINESE ACAD OF SCI
- Filing Date
- 2024-11-11
- Publication Date
- 2026-05-12
AI Technical Summary
Traditional MAX phase ceramics have relatively low hardness and strength, which limits their application in engineering practice.
Multi-component carbide-reinforced MAX phase ceramic materials are prepared by solid-solution of transition metal elements such as Ti, Ta, Nb, Hf, and V at the M site, utilizing the high entropy effect and introducing multi-component metal carbides to form a two-phase ceramic, thus preparing M2AlC-MC composite ceramic materials.
This improved the hardness and fracture toughness of MAX phase ceramics, achieving excellent mechanical properties and expanding their application in engineering practice.
Smart Images
Figure CN122010569A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of structural ceramics technology, specifically relating to a multi-component carbide-reinforced MAX phase ceramic material and its preparation method. Background Technology
[0002] MAX phase materials are a class of ternary layered carbides or nitrides with a hexagonal lattice structure, where M and A correspond to transition metals and main group elements in the periodic table, respectively, and X is carbon or nitrogen. The traditional structural formula for MAX phases can be represented by M... n+1 AX n Based on the value of n, MAX phases can be classified into 211 phases (M2AX), 312 phases (M3AX2), and 413 phases (M4AX3), etc. MAX phases are characterized by alternating layers of A and MX atoms along the c-axis. Covalent and ionic bonds exist between M and X atoms, and the strength of these two types of chemical bonds is much greater than the covalent and metallic bonds between M and A atoms. Furthermore, the M atoms are connected by metallic bonds, which have low strength. Therefore, the bonding between the MX and A layers is very weak, making the MAX phase a unique nanolayered structure. Due to this unique layered structure of alternating MX and A layers, the MAX phase combines the excellent properties of both metals and ceramics, including low density, high modulus, good electrical and thermal conductivity, and machinability. Some MAX phases (Cr2AlC, Ti2AlC, and Ti3AlC2, etc.) also exhibit good oxidation resistance, corrosion resistance, and wear resistance. Studies show that several typical MAX phases (such as Ti3SiC2, Ti2AlC and Ti3AlC2) also have excellent resistance to neutron, electron and heavy ion irradiation damage, so they have good application prospects in high temperature and nuclear industry fields, and are expected to be used in high temperature structural materials, nuclear fuel cladding materials, new generation electrode brush materials, and bearings and seals that work in strong acid and strong alkali environments.
[0003] However, compared to ceramic materials, traditional MAX phase ceramics have relatively low hardness and strength, which greatly limits their application in engineering practice. Therefore, there is an urgent need to improve their mechanical properties. Typically, the mechanical properties of MAX phases are improved through strengthening methods such as solid solution strengthening, second-phase particle strengthening, and texture strengthening.
[0004] In 2004, Cantor, Yeh, and others proposed the concept of high-entropy alloys. High-entropy alloys possess unique high-entropy effects, lattice distortion effects, hysteresis diffusion effects, and cocktail effects, endowing them with excellent properties such as high strength, high hardness, oxidation resistance, and corrosion resistance. The equimolar ratio multi-component high-entropy alloy design concept breaks away from the traditional single-component composition design concept. "High entropy" has received widespread attention as a new materials design theory, thus extending to other materials fields. Furthermore, metal carbides possess high melting points, high hardness, and excellent mechanical properties and chemical stability, and are considered or have been applied in ultra-high temperature and nuclear fields. Based on the above, this invention employs entropy-increasing element solid solution design at the M site of the MAX phase, utilizing the "high-entropy effect" of multi-component materials and introducing multi-component metal carbides to form a dual-phase ceramic, thereby enhancing MAX phase ceramic materials and expanding their applications in engineering practice. Summary of the Invention
[0005] To address the issue of low strength and hardness in traditional MAX phase ceramics, the present invention aims to further improve the mechanical properties of MAX phase ceramics by providing a multi-component carbide-reinforced MAX phase ceramic material and its preparation method.
[0006] In a first aspect, the present invention provides a multi-component carbide-reinforced MAX phase ceramic material, wherein the chemical composition of the multi-component carbide-reinforced MAX phase ceramic material is M2AlC-MC, where M = at least three of Ti, Ta, Nb, Hf, and V, and the atomic percentage of each metal atom at the M site is between 5% and 35%.
[0007] Preferably, the phase composition of the multi-component carbide-reinforced MAX phase ceramic material includes M2AlC phase and MC phase; Preferably, based on the total mass of the multi-component carbide-reinforced MAX phase ceramic material as 100%, the mass percentage of the M2AlC phase is 60-80%, and the mass percentage of the MC phase is 20-40%.
[0008] Preferably, the Vickers hardness of the multi-component carbide-reinforced MAX phase ceramic material is 5.3-12.5 GPa, and the fracture toughness is 3.7-5.9 MPa·m. 1 / 2 .
[0009] Secondly, the present invention provides a method for preparing the above-mentioned multi-component carbide-reinforced MAX phase ceramic material, the preparation method comprising the following steps: (1) According to the chemical composition of the above multi-component carbide-reinforced MAX phase ceramic material, weigh the elemental powder of transition metal M, 10% excess aluminum powder and 10% deficiency carbon powder respectively, mix them by ball milling and sieve to obtain raw material mixed powder. (2) The raw material mixed powder is loaded into a graphite mold for pre-pressing, and then subjected to reactive hot pressing sintering. After sintering, the pressure is reduced by cooling to obtain the multi-component carbide-reinforced MAX phase ceramic material.
[0010] Preferably, in step (1), the ball-to-material ratio of the ball milling mixture is 4-6:1, the ball milling speed is 200-400 rpm, the ball milling time is 6-12 h, and the grinding media is ZrO.
[0011] Preferably, in step (1), the mesh size of the sieve is 200-250 mesh.
[0012] Preferably, in step (2), the pre-compression process is: holding the pressure at 20MPa for 5-10 minutes.
[0013] Preferably, in step (2), the graphite mold is coated with BN coating on its inner wall and the surface of the pressure head before the sample is loaded.
[0014] Preferably, in step (2), the reactive hot pressing sintering is carried out in an Ar atmosphere or a vacuum, and the vacuum degree of the vacuum atmosphere is controlled to be not less than 10. 1 Pa; heating rate is 5-12℃ / min, preferably 10℃ / min; sintering temperature is 1600-1700℃, preferably 1700℃; holding time is 1-3h, preferably 2h; during heating, holding at 600-800℃ for 0.5-1h, preferably at 600℃ for 1h; sintering pressure is 30-50MPa, preferably 40MPa.
[0015] Preferably, in step (2), the cooling and pressure reduction method is to cool the furnace to room temperature.
[0016] Beneficial effects This invention addresses the relatively low hardness and strength of traditional MAX phase ceramics by using transition metal elemental powders, aluminum powder, and carbon powder as raw materials. Through reactive hot pressing sintering, multiple transition metal elements (Ti, Ta, Nb, Hf, V) are successfully dissolved at the M position of the MAX phase. The "high entropy effect" of the multi-component system and the introduction of multi-component metal carbides to form a dual-phase ceramic are used to enhance the MAX phase ceramic material. The prepared M2AlC-MC (M = Ti, Ta, Nb, Hf, V) composite ceramic material has excellent mechanical properties. This invention enriches the MAX phase ceramic material system and is beneficial to the further research and development of high-entropy MAX phase composite materials. The preparation method provided by this invention is simple and has a short process cycle. Attached Figure Description
[0017] Figure 1The XRD patterns of the M2AlC-MC (M = Ti, Ta, Nb, Hf, V) composite ceramic materials prepared in Examples 8-11 of this invention are shown. Figure 2 SEM images of the M2AlC-MC (M = Ti, Ta, Nb, Hf, V) composite ceramic materials prepared in Examples 8-11 of the present invention, where: a is Example 8, b is Example 9, c is Example 10, and d is Example 11; Figure 3 The images show the XRD patterns of the multiphase ceramic materials prepared in Comparative Examples 1-3 of this invention. Detailed Implementation
[0018] The present invention will be further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.
[0019] First, this invention provides a multi-component carbide-reinforced MAX phase ceramic material. The chemical composition of the multi-component carbide-reinforced MAX phase ceramic material can be M2AlC-MC, where M = at least three of Ti, Ta, Nb, Hf, and V, and the atomic percentage of each metal atom at the M site is between 5% and 35%.
[0020] In some embodiments, the phase composition of the multi-component carbide-reinforced MAX phase ceramic material may include M2AlC phase and MC phase; preferably, based on the total mass of the multi-component carbide-reinforced MAX phase ceramic material as 100%, the mass proportion of M2AlC phase may be 60-80%, and the mass proportion of MC phase may be 20-40%.
[0021] The multi-component carbide-reinforced MAX phase ceramic material provided by this invention is prepared through metallurgical bonding under reactive hot pressing sintering, exhibiting a two-phase uniform distribution in its structural composition. It is also important to note that the ceramic material provided by this invention utilizes solid solution strengthening aided by the introduction of in-situ generated multi-component metal carbides for material reinforcement, which is significantly different from conventional material reinforcement methods such as second-phase particle reinforcement and texture strengthening. Second-phase particle reinforcement involves introducing second-phase particles such as TiC, SiC, Al2O3, TiB2, Y4Al2O9, and ZrC into the MAX phase matrix. The second phase introduced in this way is generally not in-situ generated and typically has a low proportion. Texture strengthening, on the other hand, improves performance by achieving preferred grain orientation and does not involve the introduction of a second phase for strengthening.
[0022] In addition, in the multi-component carbide-reinforced MAX phase ceramic material provided by the present invention, if the proportion of MC phase is too high, the material hardness will increase, but the fracture toughness will decrease to a certain extent; if the proportion of MC phase is too low, the material hardness will decrease, but the fracture toughness will increase to a certain extent.
[0023] In some embodiments, the Vickers hardness of the multi-component carbide-reinforced MAX phase ceramic material can be 5.3-12.5 GPa, and the fracture toughness can be 3.7-5.9 MPa·m. 1 / 2 .
[0024] The following is an exemplary description of a method for preparing a multi-component carbide-reinforced MAX phase ceramic material provided by the present invention. The preparation method may include the following steps: (1) According to the chemical composition of the above multi-component carbide-reinforced MAX phase ceramic material, weigh the elemental powder of metal M, 10% excess aluminum powder and 10% deficiency carbon powder respectively, mix them by ball milling and sieve to obtain raw material mixed powder. (2) The raw material mixed powder is loaded into a graphite mold for pre-pressing, and then subjected to reactive hot pressing sintering. After sintering, the pressure is reduced by cooling to obtain the multi-component carbide-reinforced MAX phase ceramic material.
[0025] In step (1), adding an extra 10% aluminum powder can compensate for the loss of aluminum during subsequent sintering, and reducing the addition of 10% carbon powder can balance the replenishment of free carbon during subsequent sintering, thereby reducing the generation of miscellaneous items.
[0026] In some embodiments, in step (1), the ball-to-material ratio of the ball milling mixture can be 4-6:1 (e.g., 5:1), the ball milling speed can be 200-400 rpm (250 rpm), the ball milling time can be 6-12 h, preferably 8 h, and the grinding media can be ZrO.
[0027] In some implementations, in step (1), the mesh size of the sieve can be 200-250 mesh.
[0028] In some embodiments, in step (2), the pre-pressing process can be: holding the pressure at 20 MPa for 5-10 minutes. Before the formal reaction hot pressing sintering, pre-pressing can effectively avoid the gas in some pores not being able to be expelled in time due to rapid pressurization during the sintering process, which would cause the sintering to be incomplete, thereby effectively reducing the porosity of the sample and achieving the effect of improving the densification of the ceramic sample.
[0029] In some embodiments, in step (2), the graphite mold may be coated with BN coating on its inner wall and the surface of the pressure head before loading the sample.
[0030] In some embodiments, in step (2), the reactive hot pressing sintering can be carried out in an Ar atmosphere or a vacuum, and the vacuum degree of the vacuum atmosphere can be controlled to be not less than 10. 1 Pa; the heating rate can be 5-12℃ / min, preferably 10℃ / min; the sintering temperature can be 1600-1700℃, preferably 1700℃; the holding time can be 1-3h, preferably 2h; during the heating process, the temperature can be held at 600-800℃ for 0.5-1h, preferably at 600℃ for 1h; the sintering pressure can be 30-50MPa, preferably 40MPa.
[0031] If the sintering temperature is too low, a large number of unreacted intermediate phases such as Nb2Al, Ta2Al, Nb2C, and Ta2C will exist in the ceramic material, which will also lead to the deterioration of the density and mechanical properties of the sintered ceramic material; if the sintering temperature is too high, the MAX phase generated in the ceramic material will decompose.
[0032] In some implementations, in step (2), the cooling and depressurization can be carried out by cooling the furnace to room temperature.
[0033] The preparation method disclosed in this invention introduces multi-component carbides and achieves solid solution of at least three elements among Ti, Ta, Nb, Hf, and V at the M position of the MAX phase ceramic in terms of structure. The prepared M2AlC-MC (M = Ti, Ta, Nb, Hf, V) composite ceramic material has excellent mechanical properties, providing a new approach to solving the problem of relatively low strength and hardness of traditional MAX phase ceramics.
[0034] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values in the examples below. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
[0035] Example 1
[0036] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment includes the following steps: (1) Weigh Ti powder, Ta powder, Nb powder, Al powder and C powder according to the molar ratio of Ti:Ta:Nb:Al:C=1:1:1:1.1:1.8, and mix them by ball milling. The ball milling process is as follows: ball-to-material ratio is 5:1, rotation speed is 250 rpm, ball milling time is 8 h, grinding media is ZrO, and the mixture is sieved to obtain raw material mixed powder. (2) The raw material mixture obtained in step (1) is loaded into a graphite mold and pre-pressed under a pressure of 20 MPa for 5-10 min. In a hot press furnace, the temperature is raised to 1600℃ at 10℃ / min and held for 2 h. During the heating process, the temperature is held at 600℃ for 1 h. Then, the temperature is cooled to room temperature with the furnace. During the sintering process, a pressure of 40 MPa is applied to obtain M2AlC-MC (M=Ti,Ta,Nb) composite ceramic material.
[0037] Example 2
[0038] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 1, with the main difference being: In step (2), the sintering temperature is 1700℃.
[0039] Example 3
[0040] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, Al powder and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:Al:C = 0.95:0.95:0.95:0.15:1.1:1.8.
[0041] Example 4
[0042] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, Al powder and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:Al:C = 0.9:0.9:0.9:0.3:1.1:1.8.
[0043] Example 5
[0044] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, Al powder and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:Al:C = 0.85:0.85:0.85:0.45:1.1:1.8.
[0045] Example 6
[0046] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, Al powder and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:Al:C = 0.8:0.8:0.8:0.6:1.1:1.8.
[0047] Example 7
[0048] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, Al powder and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:Al:C = 0.75:0.75:0.75:0.75:1.1:1.8.
[0049] Example 8
[0050] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, V powder, Al powder, and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:V:Al:C = 0.7125:0.7125:0.7125:0.7125:0.15:1.1:1.8.
[0051] Example 9
[0052] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, V powder, Al powder, and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:V:Al:C = 0.675:0.675:0.675:0.675:0.3:1.1:1.8.
[0053] Example 10
[0054] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, V powder, Al powder, and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:V:Al:C = 0.6375:0.6375:0.6375:0.6375:0.45:1.1:1.8.
[0055] Example 11
[0056] The preparation method of the multi-component carbide-reinforced MAX phase ceramic material provided in this embodiment is the same as that in Example 2, with the main difference being: In step (1), Ti powder, Ta powder, Nb powder, Hf powder, V powder, Al powder and C powder are weighed out according to the ratio of Ti:Ta:Nb:Hf:V:Al:C = 0.6:0.6:0.6:0.6:0.6:1.1:1.8.
[0057] Comparative Example 1
[0058] The preparation method of the multiphase ceramic material provided in this comparative example is the same as that in Example 1, with the main difference being: In step (2), the sintering temperature is 1200℃.
[0059] Comparative Example 2
[0060] The preparation method of the multiphase ceramic material provided in this comparative example is the same as that in Example 1, with the main difference being: In step (2), the sintering temperature is 1400℃.
[0061] Comparative Example 3
[0062] The preparation method of the multiphase ceramic material provided in this comparative example is the same as that in Example 1, with the main difference being: In step (2), the sintering temperature is 1500℃.
[0063] The performance results of the M2AlC-MC composite ceramic materials prepared in Examples 1-11 of this invention are shown in Figure 1 below:
[0064] Figure 1 The figures show the XRD patterns of the M2AlC-MC (M = Ti, Ta, Nb, Hf, V) composite ceramic materials prepared in Examples 8-11 of this invention. As can be seen from the figures, the composite ceramic materials prepared in Examples 8-11 are all two-phase materials consisting of M2AlC and MC.
[0065] Figure 2The images show SEM images of the M2AlC-MC (M = Ti, Ta, Nb, Hf, V) composite ceramic materials prepared in Examples 8-11 of this invention, where: a represents Example 8, b represents Example 9, c represents Example 10, and d represents Example 11. As can be seen from the images, the SEM images of Examples 8-11 all show two phases, gray and white, which are basically uniformly distributed. The gray phase represents M2AlC, and the white phase represents the MC phase.
[0066] Figure 3 The images show the XRD patterns of the multiphase ceramic materials prepared in Comparative Examples 1-3 of this invention. As can be seen from the images, due to the excessively low sintering temperature, unreacted intermediate phases are present in all the multiphase ceramics prepared in Comparative Examples 1-3.
[0067] Although the present invention has been described in detail through the preferred embodiments above, it should be understood that the above description should not be considered as a limitation of the present invention. Various modifications and substitutions to the present invention will be apparent to those skilled in the art after reading the above description. Therefore, the scope of protection of the present invention should be defined by the appended claims.
Claims
1. A multi-component carbide-reinforced MAX phase ceramic material, characterized in that, The chemical composition of the multi-component carbide-reinforced MAX phase ceramic material is M2AlC-MC, where M = at least three of Ti, Ta, Nb, Hf, and V, and the atomic percentage of each metal atom at the M site is between 5% and 35%.
2. The multi-component carbide-reinforced MAX phase ceramic material according to claim 1, characterized in that, The phase composition of the multi-component carbide-reinforced MAX phase ceramic material includes M2AlC phase and MC phase; Preferably, based on the total mass of the multi-component carbide-reinforced MAX phase ceramic material as 100%, the mass percentage of the M2AlC phase is 60-80%, and the mass percentage of the MC phase is 20-40%.
3. The multi-component carbide-reinforced MAX phase ceramic material according to claim 1 or 2, characterized in that, The Vickers hardness of the multi-component carbide-reinforced MAX phase ceramic material is 5.3-12.5 GPa, and the fracture toughness is 3.7-5.9 MPa·m. 1 / 2 .
4. A method for preparing a multi-component carbide-reinforced MAX phase ceramic material according to any one of claims 1-3, characterized in that, The preparation method includes the following steps: (1) According to the chemical composition of the above multi-component carbide-reinforced MAX phase ceramic material, weigh the elemental powder of transition metal M, 10% excess aluminum powder and 10% deficiency carbon powder respectively, mix them by ball milling and sieve to obtain raw material mixed powder. (2) The raw material mixed powder is loaded into a graphite mold for pre-pressing, and then subjected to reactive hot pressing sintering. After sintering, the pressure is reduced by cooling to obtain the multi-component carbide-reinforced MAX phase ceramic material.
5. The preparation method according to claim 4, characterized in that, In step (1), the ball-to-material ratio of the ball milling mixture is 4-6:1, the ball milling speed is 200-400 rpm, the ball milling time is 6-12 h, and the grinding media is ZrO.
6. The preparation method according to claim 4 or 5, characterized in that, In step (1), the mesh size of the sieve is 200-250 mesh.
7. The preparation method according to any one of claims 4-6, characterized in that, In step (2), the pre-compression process is as follows: hold the pressure at 20MPa for 5-10 minutes.
8. The preparation method according to any one of claims 4-7, characterized in that, In step (2), the graphite mold is coated with BN coating on its inner wall and the surface of the pressure head before the sample is loaded.
9. The preparation method according to any one of claims 4-8, characterized in that, In step (2), the reactive hot pressing sintering is carried out in an Ar atmosphere or a vacuum, and the vacuum degree of the vacuum atmosphere is controlled to be no less than 10. 1 Pa; heating rate is 5-12℃ / min, preferably 10℃ / min; sintering temperature is 1600-1700℃, preferably 1700℃; holding time is 1-3h, preferably 2h; during heating, holding at 600-800℃ for 0.5-1h, preferably at 600℃ for 1h; sintering pressure is 30-50MPa, preferably 40MPa.
10. The preparation method according to any one of claims 4-9, characterized in that, In step (2), the cooling and pressure reduction method is to cool the furnace to room temperature.