CN113416078B - Non-stoichiometric titanium boride and high-entropy boride ceramic prepared from same - Google Patents
Non-stoichiometric titanium boride and high-entropy boride ceramic prepared from same Download PDFInfo
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Abstract
A non-stoichiometric titanium boride and a high-entropy boride ceramic prepared by using the same belong to the technical field of preparation of special compounds. The invention provides a non-stoichiometric titanium boride with a chemical formula of TiB X Wherein X is more than or equal to 1 and less than or equal to 1.8, and a preparation method thereof. On the other hand, the high-entropy boride ceramic contains TiB X Also includes a compound of formula (I) and (II) with X The diboride with equal molar mass is prepared by two or more than two combinations through mechanical alloying and sintering processes, the sintering temperature is 1500-1900 ℃, and the preparation method thereof. The invention has simple process, low requirement on equipment, low energy consumption and low cost. Prepared TiB X After sintering at 1500-1800 ℃, the obtained hardness can reach 26.5GPa and the toughness can reach 6.4 MPa.m 1/2 . The prepared high-entropy boride ceramic has high toughness and low requirement on sintering temperature.
Description
Technical Field
The invention belongs to the technical field of preparation of special compounds. In particular to nonstoichiometric titanium boride and high-entropy boride ceramic prepared by utilizing the nonstoichiometric titanium boride.
Background
TiB 2 Has high melting pointPoint, high hardness, excellent mechanical property and physical and chemical stability, but the strong interaction and the lattice structure of the material make the melting point and the low diffusion coefficient of the material high and difficult to process by the traditional technology. TiB 2 Is a gray black powder, which is the most stable crystalline compound formed in the boron titanium element combination. TiB of hexagonal structure 2 The structure is a metalloid compound with a C32 type structure, the space point group is P6/mmm, in the crystal structure, a boron atom surface and a titanium atom surface alternately appear to form a two-dimensional network structure, the titanium atom is positioned at the vertex angle position and the bottom center position of a hexagonal prism, and the boron atom is positioned at the center position of a triangular prism formed by the titanium atom. TiB 2 Similar to the graphite structure, the conductive graphite has good conductive performance and metal luster; TiB 2 Simultaneously has ionic bond and covalent bond, and ionic bond (Ti-B) between the titanium atom surface and the boron atom surface, so that the alloy has high hardness and brittleness characteristics; the boron atom surface covalent bond (B-B) makes it have high melting point, and the sintering temperature is generally above 2000 ℃. However, studies have shown that single phase TiB 2 Flexural strength (300MPa) and fracture toughness (3.5MPa. m) of the material 1/2 ) Both are low and the sintering properties of TiB2 ceramic are poor, limiting its applications. Based on the above facts, titanium boride produced industrially has generally been used as an additive for decades. Or the sintering aid or the toughening additive is added to ensure that the titanium boride has application value, but the inherent excellent performances of high hardness, heat resistance and the like of the titanium boride are lost to a certain extent. And with the development of aerospace, TiB 2 The characteristics of high hardness, high temperature resistance and the like are taken into consideration, but the weakness of the characteristics also limits the practical application.
With the demand of aerospace, researchers have focused on transition metal high-entropy borides. In 2016, Gild, Harrington, Zhang and the like apply a high-entropy concept to transition metal boride ceramics for the first time, and MA and SPS are utilized to prepare a series of transition metal boride high-entropy ceramics with single-phase hexagonal crystal structures. They found that the transition metal atoms in these single phase borides are randomly distributed at the atomic level on the metal corresponding lattice sites. Secondly, the hardness of the high-entropy boride ceramics is higher than the average hardness of the corresponding five single-component transition metal boride ceramics, and the oxidation resistance of the high-entropy boride ceramics is also improved. At the same time, the sintering temperature of the high-entropy boride is too high and the obvious brittleness causes the application of the boride to be limited.
Therefore, the invention uses TiB 2 The powder and Ti powder are used as basic raw materials, and Mechanical Alloying (MA) is used for preparing the alloy capable of retaining TiB at different times 2 Crystal structure and high hardness, and can lower sintering temperature and raise toughness. And with TiB X (X is more than or equal to 1 and less than or equal to 1.8) is used as a component, and the sintering temperature of the prepared high-entropy boride is 1500-1900 ℃ under the same MA and SPS sintering conditions, and the toughness reaches 6.2 MPa.m 1/2 。
Disclosure of Invention
In view of the problems in the prior art, the invention aims to design and provide non-stoichiometric titanium boride and high-entropy boride ceramic prepared by using the non-stoichiometric titanium boride. The non-stoichiometric TiBx is prepared by a mechanical alloying method, so that the brittleness of the titanium boride is improved, and the sintering temperature is reduced. With Ti and TiB 2 As a raw material, Ti atoms are made to enter TiB by mechanical alloying 2 In the method, part of B atoms are subjected to 'vacancy', so that Ti-B bonds (ionic bonds) and B-B bonds (covalent bonds) which cause high hardness and brittleness are reduced, and Ti-Ti bonds (metal bonds) are increased, so that the sintering temperature can be reduced, and the toughness can be improved. The high-entropy boride prepared by taking the non-stoichiometric titanium boride as a component has high hardness and high toughness, greatly reduces the sintering temperature, and has low requirements on the purity of equipment and raw materials, low energy consumption and low cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a non-stoichiometric titanium boride, characterized in that the titanium boride has the chemical formula of TiB X Wherein X is more than or equal to 1 and less than or equal to 1.8.
The non-stoichiometric titanium boride is characterized in that the titanium boride has a single close-packed hexagonal crystal structure.
A preparation method of the nonstoichiometric titanium boride is characterized by comprising the following steps:
(1) mixing Ti powder less than 10 μm with TiB 2 Mixing the powder according to a molar ratio of 1: 1-9, and filling the mixture and grinding balls into a ball milling tank under an argon environment;
(2) and (2) mounting the ball milling tank obtained in the step (1) on a ball mill, stopping the ball milling reaction, opening the tank in an argon environment, and taking out to obtain the titanium boride.
The preparation method is characterized in that in the step (1), the grinding ball is made of stainless steel or hard alloy, the ball milling tank is made of stainless steel or hard alloy, and the ball-material ratio is 10-20: 1.
The preparation method is characterized in that the ball mill in the step (2) comprises a planetary ball mill, and the ball milling reaction time is 20-60 hours.
A high-entropy boride ceramic is characterized in that the component contains any one of the TiB X Also includes the said TiB X Equimolar mass of TiB 2 、TaB 2 、NbB 2 、VB 2 、HfB 2 、MoB 2 、WB 2 、ZrB 2 The high-entropy boride ceramic contains three or more transition group metal atoms of Ti, Zr, Nb, V, Hf, Ta, Mo and W.
The high-entropy boride ceramic is characterized in that the high-entropy boride ceramic is of a single-phase single covalent bond close-packed hexagonal crystal structure and is prepared through mechanical alloying and sintering processes, and the sintering temperature is 1500-1900 ℃.
The preparation method of the high-entropy boride ceramic is characterized by comprising the following steps of:
(1) mixing: weighing the TiB with equal molar mass X Uniformly mixing with covalent bond diboride with a close-packed hexagonal structure, and sealing the mixture in a ball milling tank together with grinding balls in a glove box filled with argon;
(2) preparing a mixture: mounting the ball milling tank obtained in the step (1) on a ball mill, stopping the ball milling tank in an argon environment after ball milling, and taking out a mixture;
(3) pre-pressing and forming: putting the mixture into a die for prepressing and forming, maintaining the pressure for 5-10 min, and then relieving the pressure and demoulding to prepare a blank;
(4) hot-pressing and sintering: and (3) putting the blank into a mold, putting the mold on a sintering machine for hot-pressing sintering, naturally cooling to below 60 ℃, and taking out to obtain a sample.
The preparation method is characterized in that the covalent bond diboride with the close-packed hexagonal structure in the step (1) is TiB 2 、TaB 2 、NbB 2 、VB 2 、HfB 2 、MoB 2 、WB 2 、ZrB 2 The grinding balls are stainless steel or hard alloy, the ball milling tank is stainless steel or hard alloy, and the ball-material ratio is 10-20: 1.
The preparation method is characterized in that the ball milling time in the step (2) is 20-60 hours, and the prepressing formation condition is as follows: room temperature and pressure of 100-200 MPa; the technological parameters of the hot-pressing sintering in the step (3) are as follows: the sintering chamber is in vacuum or argon atmosphere with a vacuum degree of 3 multiplied by 10 1 ～3×10 -3 Pa, the pressure of the sintering machine is 30-50 MPa, the sintering temperature is 1500-1900 ℃, and the heat preservation time is 10-30 min.
The invention adopts a non-stoichiometric titanium boride reaction ball milling method to prepare TiB X The ball mill can be a planetary ball mill or other ball milling equipment with different forms which can achieve the same effect, and the purpose is to utilize mechanical energy to enable TiB to be in a ball milling process 2 Fully mixing with Ti, crushing and activating to improve the reaction capability, so that the mixture reacts spontaneously in the ball milling process for 20-60 hours to form non-stoichiometric ratio TiB X . TiB obtained X Made up of a single TiB X Having a structure with TiB 2 The same close-packed hexagonal crystal structure, the average grain size is less than 10 nm.
The preparation method of the high-entropy boride ceramic is realized by mechanical ball milling, and the adopted ball mill can be a planetary ball mill or other ball milling equipment with different forms which can achieve the same effect, and aims to fully mix, crush and activate all participating components by utilizing mechanical energy in the ball milling process and improve the reaction capability.
Compared with the prior art, the invention has the following beneficial effects:
(1) the non-stoichiometric titanium boride has simple process, the purity of the used raw materials is more than 99.5 percent, the granularity is less than 10 mu m, the requirement on equipment is low, the energy consumption is low, the cost is low, and the prepared sintered body has high hardness and high toughness.
(2) TiB product of the invention X The hardness and toughness of the block obtained after sintering at 1500-1800 ℃ are improved, and the sintering temperature is greatly reduced. The hardness obtained after sintering reaches 26.5GPa, and the toughness reaches 6.4 MPa.m 1/2 。
(3) The high-entropy boride ceramic has simple process, and can reach sintering temperature of 1500-1900 ℃ and toughness of 6.2 MPa.m 1/2 Low energy consumption and low cost.
Drawings
FIG. 1 shows the mixing of TiB powder at different times 1.0 (molar ratio Ti: TiB) 2 1:1) XRD pattern;
FIG. 2 shows the TiB powder mixture at different times 1.5 XRD pattern of (a);
FIG. 3 shows TiB as a powder mixture at different times 1.8 XRD pattern of (a);
FIG. 4 shows 60h of TiB at different temperatures 1.8 A hardness and toughness data chart of the powder sintered body;
FIG. 5 shows the sintered TiB at 1900 deg.C 1.5 -TaB 2 -NbB 2 -VB 2 XRD pattern of composite sintered body.
Detailed Description
The invention will be further illustrated by the following examples and figures.
Example 1:
(1) ti powder with the granularity of less than 10 mu m and TiB are mixed according to the calculated amount 2 Mixing the powder according to a molar ratio of 1:1, loading the mixture into a hard alloy ball milling tank under an argon environment, and selecting the same hard alloy grinding balls with a ball-to-material ratio of 20: 1;
(2) and (3) installing the ball milling tank in the step (1) on a planetary ball mill, performing ball milling for 40 and 60 hours, and stopping taking materials. Taking materials under the condition of an argon environment;
(3) a small amount of the resulting material was taken out and subjected to XRD analysis, and the results are shown in FIG. 1.
As can be seen from FIG. 1, the molar ratio of Ti to TiB is 2 After the mixture ratio of 1:1 is matched, the single-phase TiB is obtained after ball milling for 40 to 60 hours X (X＝1.0)。
Example 2:
(1) ti powder with the granularity of less than 10 mu m and TiB are mixed according to the calculated amount 2 Mixing the powder according to a molar ratio of 1:3, loading the mixture into a hard alloy ball milling tank under an argon environment, and selecting the same hard alloy grinding balls with a ball-to-material ratio of 20: 1;
(2) and (3) installing the ball milling tank in the step (1) on a planetary ball mill, performing ball milling for 40 and 60 hours, and stopping taking materials. Taking materials under the condition of an argon environment;
(3) a small amount of the material was taken out from the prepared material and subjected to XRD analysis, and the result was shown in FIG. 2.
As can be seen from FIG. 2, the molar ratio of Ti to TiB is 2 After the mixture ratio of 1:3 is matched, single-phase TiB is obtained after ball milling for 20, 40 and 60 hours X (X＝1.5)。
Example 3:
(1) ti powder with the granularity of less than 10 mu m and TiB are mixed according to the calculated amount 2 Mixing the powder according to a molar ratio of 1:9, loading the mixture into a hard alloy ball milling tank under an argon environment, and selecting the same hard alloy grinding balls with a ball-to-material ratio of 10: 1;
(2) and (3) installing the ball milling tank in the step (1) on a planetary ball mill, performing ball milling for 40 and 60 hours, and stopping taking materials. Taking materials under the condition of an argon environment;
(3) taking out a small amount of the prepared material, carrying out XRD analysis (the result is shown in figure 3), and sintering the rest;
(4) the bulk samples sintered at 1600, 1700 and 1800 ℃ on the spark plasma sintering machine were polished and XRD analyzed again (the results are shown in fig. 3), and performance was checked. The results are shown in FIG. 4.
As can be seen from FIG. 3, the molar ratio of Ti to TiB is 2 After the mixture ratio of 1:9 is matched, the single-phase TiB is obtained after ball milling for 20, 40 and 60 hours X (X ═ 1.8). As can be seen from FIG. 4, the molar ratio of Ti to TiB is 2 After the mixture ratio of 1:9 is finished, ball milling is carried out for 60 hours, and then sintering is carried out at 1500-1800 ℃ to obtain single-phase TiB X (X ═ 1.8), the hardness of which is up to 26.5GPa, and the toughness of which is 6.4MPa 1/2 。
Example 4:
(1) mixing TiB according to an equimolar ratio 1.5 、TaB 2 、NbB 2 、VB 2 Weighing the calculated mass, and uniformly mixing; and sealing the mixture and the hard alloy grinding balls in a hard alloy ball milling tank in a glove box filled with argon at a ball-to-material ratio of 10: 1.
(2) And (2) mounting the ball milling tank in the step (1) on a planetary ball mill, performing ball milling for 40 hours, stopping the ball milling machine, and taking materials in an argon environment glove box.
(3) And (3) putting the mixture prepared in the step (2) into a die for prepressing and forming, wherein the room temperature and the pressure are 200 MPa. Keeping for 5-10 min, then decompressing and demoulding to prepare a blank.
(4) And (4) putting the blank prepared in the step (3) into a die, and putting the die on a sintering press for hot-pressing sintering. The technological parameters are as follows: sintering the chamber in argon atmosphere; the pressure of the sintering machine is 50MPa, the sintering temperature is 1900 ℃, the heat preservation time is 10min, then the temperature is naturally cooled to be below 60 ℃, and a sample is taken out.
After polishing, XRD detection shows that the result is shown in figure 5. The hardness is 26.3GPa and the toughness is 6.2 MPa.m 1/2 。
Example 5:
(1) mixing TiB according to an equimolar ratio 1.5 、TaB 2 、NbB 2 、VB 2 Weighing the calculated mass, and uniformly mixing; and sealing the mixture and the hard alloy grinding balls in a hard alloy ball milling tank in a glove box filled with argon at a ball-to-material ratio of 10: 1.
(2) And (2) installing the ball milling tank in the step (1) on a proper ball mill, performing ball milling for 60 hours, stopping the ball milling machine, and taking materials under the argon environment condition.
(3) And (3) putting the mixture prepared in the step (2) into a die for prepressing and forming, wherein the room temperature and the pressure are 100 MPa. Keeping for 5-10 min, then decompressing and demoulding to prepare a blank.
(4) And (4) putting the blank prepared in the step (3) into a die, and putting the die on a sintering press for hot-pressing sintering. The technological parameters are as follows: sintering chamber argon atmosphere; the pressure of the sintering machine is 30MPa, the sintering temperature is 1800 ℃, the heat preservation time is 30min, then the sample is naturally cooled to below 60 ℃, and the sample is taken out.
After polishing, the hardness is 26.8GPa and the toughness is 6.0 MPa.m 1/2 。
Example 6:
(1) mixing TiB according to an equimolar ratio 1.8 、TaB 2 、NbB 2 、VB 2 、MoB 2 、WB 2 And ZrB 2 、HfB 2 Weighing the calculated mass, and uniformly mixing; and sealing the mixture in a hard alloy ball milling tank together with hard alloy grinding balls in a glove box filled with argon, wherein the ball-to-material ratio is 20: 1.
(2) And (2) mounting the ball milling tank in the step (1) on a planetary ball mill, performing ball milling for 20 hours, stopping the ball milling machine, and taking materials under the argon environment condition.
(3) And (3) putting the mixture prepared in the step (2) into a die for prepressing and forming, wherein the room temperature and the pressure are 200 MPa. Keeping for 5-10 min, then decompressing and demoulding to prepare a blank.
(4) And (4) putting the blank prepared in the step (3) into a die, and putting the die on a sintering press for hot-pressing sintering. The technological parameters are as follows: vacuum degree of sintering chamber 3X 10 -1 Pa; the pressure of the sintering machine is 50MPa, the sintering temperature is 1600 ℃, the heat preservation time is 30min, then the temperature is naturally cooled to below 60 ℃, and the sample is taken out.
After grinding, the hardness is 25.9GPa and the toughness is 6.4 MPa.m 1/2 。
Example 7:
(1) mixing TiB according to an equimolar ratio 1.0 、TaB 2 、NbB 2 、VB 2 、HfB 2 Weighing the calculated mass, and uniformly mixing; and sealing the mixture in a hard alloy ball milling tank together with hard alloy grinding balls in a glove box filled with argon, wherein the ball-to-material ratio is 20: 1.
(2) And (2) mounting the ball milling tank in the step (1) on a planetary ball mill, performing ball milling for 40 hours, stopping the ball milling machine, and taking materials under the argon environment condition.
(3) And (3) putting the mixture prepared in the step (2) into a die for prepressing and forming, wherein the room temperature and the pressure are 100 MPa. Keeping for 5-10 min, then decompressing and demoulding to prepare a blank.
(4) And (4) putting the blank prepared in the step (3) into a die, and putting the die on a sintering press for hot-pressing sintering. The technological parameters are as follows: sintering the chamber in argon atmosphere; the pressure of the sintering machine is 50MPa, the sintering temperature is 1900 ℃, the heat preservation time is 30min, then the temperature is naturally cooled to below 60 ℃, and the sample is taken out.
After polishing, the hardness is 26.6GPa and the toughness is 5.7 MPa.m 1/2 。
Example 8:
(1) mixing TiB according to an equimolar ratio 1.5 、TaB 2 、NbB 2 、VB 2 、ZrB 2 Weighing the calculated mass, and uniformly mixing; and sealing the mixture in a hard alloy ball milling tank together with hard alloy grinding balls in a glove box filled with argon, wherein the ball-to-material ratio is 20: 1.
(2) And (2) mounting the ball milling tank in the step (1) on a planetary ball mill, performing ball milling for 40 hours, stopping the ball milling machine, and taking materials under the argon environment condition.
(3) And (3) putting the mixture prepared in the step (2) into a die for prepressing and forming, wherein the room temperature and the pressure are 100 MPa. Keeping for 5-10 min, then decompressing and demoulding to prepare a blank.
(4) And (4) putting the blank prepared in the step (3) into a die, and putting the die on a sintering press for hot-pressing sintering. The technological parameters are as follows: sintering chamber argon atmosphere; the pressure of the sintering machine is 50MPa, the sintering temperature is 1800 ℃, the heat preservation time is 30min, then the sample is naturally cooled to below 60 ℃, and the sample is taken out.
After grinding, the hardness is 24.6GPa, the toughness is 5.9 MPa.m 1/2 。
Claims (8)
1. The high-entropy boride ceramic is characterized in that the components contain nonstoichiometric titanium boride, and the chemical formula of the nonstoichiometric titanium boride is TiB X Wherein X is more than or equal to 1 and less than or equal to 1.8, the titanium boride has a single close-packed hexagonal crystal structure, and the method further comprisesTiB X Equimolar mass of TiB 2 、TaB 2 、NbB 2 、VB 2 、HfB 2 、MoB 2 、WB 2 、ZrB 2 The high-entropy boride ceramic contains three or more transition group metal atoms of Ti, Zr, Nb, V, Hf, Ta, Mo and W.
2. A high entropy boride ceramic according to claim 1 wherein the process for the preparation of non-stoichiometric titanium boride comprises the steps of:
(1) mixing Ti powder less than 10 μm with TiB 2 Mixing the powder according to a molar ratio of 1: 1-9, and filling the mixture and grinding balls into a ball milling tank under an argon environment;
(2) and (2) installing the ball milling tank obtained in the step (1) on a ball mill, stopping the ball milling tank after the ball milling reaction is carried out, opening the tank and taking out the ball milling tank under an argon environment, thus obtaining the titanium boride.
3. The high-entropy boride ceramic of claim 2, wherein in step (1), the grinding balls are stainless steel or cemented carbide, the ball milling pot is stainless steel or cemented carbide, and the ball-to-material ratio is 10-20: 1.
4. The high-entropy boride ceramic of claim 2 wherein the ball mill in step (2) comprises a planetary ball mill and the ball milling reaction time is 20 to 60 hours.
5. The high-entropy boride ceramic of claim 1 wherein the high-entropy boride ceramic is a single phase single covalent bond close packed hexagonal crystal structure prepared by mechanical alloying and sintering processes and the sintering temperature is 1500 to 1900 ℃.
6. A method of preparing a high entropy boride ceramic according to any one of claims 1 to 5, comprising the steps of:
(1) mixing: weighing the TiB with equal molar mass X Uniformly mixing with covalent bond diboride with a close-packed hexagonal structure, and sealing the mixture in a ball milling tank together with grinding balls in a glove box filled with argon;
the covalent bond diboride with the close-packed hexagonal structure is TiB 2 、TaB 2 、NbB 2 、VB 2 、HfB 2 、MoB 2 、WB 2 、ZrB 2 Two or more of (a);
(2) preparing a mixture: mounting the ball milling tank obtained in the step (1) on a ball mill, stopping the ball milling tank in an argon environment after ball milling, and taking out a mixture;
(3) pre-pressing and forming: putting the mixture into a die for prepressing and forming, maintaining the pressure for 5-10 min, and then relieving the pressure and demoulding to prepare a blank;
(4) hot-pressing and sintering: and (3) putting the blank into a mold, putting the mold on a sintering machine for hot-pressing sintering, naturally cooling to below 60 ℃, and taking out to obtain a sample.
7. The preparation method according to claim 6, wherein in the step (1), the grinding balls are made of stainless steel or hard alloy, the ball milling pot is made of stainless steel or hard alloy, and the ball-to-material ratio is 10-20: 1.
8. The method according to claim 6, wherein the ball milling time in the step (2) is 20 to 60 hours; the conditions of the pre-pressing molding in the step (3) are as follows: room temperature and pressure of 100-200 MPa; the technological parameters of the hot-pressing sintering in the step (4) are as follows: the sintering chamber is in vacuum or argon atmosphere with a vacuum degree of 3 multiplied by 10 1 ~3×10 -3 Pa, the pressure of the sintering machine is 30-50 MPa, the sintering temperature is 1500-1900 ℃, and the heat preservation time is 10-30 min.
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