CN109607559B - Method for synthesizing ternary layered compound by adopting metal powder fluxing agent - Google Patents
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- 239000000843 powder Substances 0.000 title claims abstract description 351
- 239000002184 metal Substances 0.000 title claims abstract description 95
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 95
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 74
- 150000001875 compounds Chemical class 0.000 title claims abstract description 45
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 36
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 53
- 230000001681 protective effect Effects 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 230000004907 flux Effects 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000010453 quartz Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 37
- 238000003786 synthesis reaction Methods 0.000 abstract description 37
- 238000001308 synthesis method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
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- 230000000052 comparative effect Effects 0.000 description 18
- 235000015895 biscuits Nutrition 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
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- 238000001816 cooling Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
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- 238000001914 filtration Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 229910033181 TiB2 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 238000011049 filling Methods 0.000 description 2
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- 229910052745 lead Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
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- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
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Abstract
The invention provides a method for synthesizing a ternary layered compound by adopting a metal powder fluxing agent, wherein the ternary layered compound is Ti3B2N, the method comprises reacting TiH2Stirring the powder, the amorphous B powder and the hexagonal BN powder into a mixture; adding metal powder into the mixture, heating in an inert protective atmosphere, and keeping the temperature to obtain a sample; under the inert protective atmosphere, after the sample is naturally cooled to the room temperature, the residual metal powder in the sample is removed by dilute hydrochloric acid to obtain Ti3B2And N is added. The metal powder fluxing agent is Al powder, Pb powder or Zn powder; heating to 700-1000 ℃ when Al powder is used, and keeping the temperature for 2-12 h; heating to 600-900 ℃ when the Pb powder is used, and keeping the temperature for 12-24 hours; and when the Zn powder is used, the temperature is 700-1000 ℃, and the heat is preserved for 1-6 h. The synthesis method provided by the invention can greatly reduce Ti3B2The synthesis temperature of N, the synthesis method is simple and easy to operate, is suitable for industrial large-scale production, and reduces the production cost.
Description
Technical Field
The invention belongs to the field of structural materials, and particularly relates to a method for synthesizing a ternary layered compound by adopting a metal powder fluxing agent.
Background
Ti3B2N is a novel ternary layered compound which has high modulus (Young modulus 430.22GPa, shear modulus 181.06GPa), high strength and the like. At the same time, Ti3B2N has a very low density (theoretical density 4.80 g/cm)3)。
Chinese patent application 2016100610872 discloses a novel ceramic crystal Ti3B2N and a preparation method thereof, which adopts a high-temperature solid-phase reaction method to synthesize Ti3B2N, but the synthesis temperature required by the application is higher than 1100-1200 ℃, which is not beneficial to the practical production of the product, and the high-temperature production cost is higher, and the synthesis technology disclosed by the application is not mature, and needs to be improved continuously.
Therefore, other synthesis methods were sought to lower the synthesis temperature for Ti3B2The practical application of the N material has good practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art that the material Ti is a new material3B2The problem of high synthesis temperature of N, and the proposed method adopts metal powder Al, Pb and Zn fluxing agent to synthesize Ti3B2And (N) in the same way. The synthesis method provided by the invention can greatly reduce Ti3B2The synthesis temperature of N is suitable for industrial large-scale production, and the production cost is reducedThe method is as follows.
In order to achieve the above purpose, the invention provides the following technical scheme:
method for synthesizing ternary layered compound by adopting metal powder fluxing agent, wherein the ternary layered compound is Ti3B2N, synthesizing the Ti3B2The method of N comprises:
firstly TiH2Mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder uniformly to obtain a mixture; adding metal powder serving as a fluxing agent into the mixture, uniformly mixing, tabletting, heating to a set temperature under an inert protective atmosphere, and keeping the temperature for a certain time to obtain a sample; finally, under the inert protective atmosphere, after the sample is naturally cooled to the room temperature, the residual metal powder fluxing agent in the sample is removed by adopting dilute hydrochloric acid to obtain Ti3B2N；
The metal powder fluxing agent is Al powder, Pb powder or Zn powder;
when the added metal powder fluxing agent is Al powder, heating to 700-1000 ℃ under an inert protective atmosphere and preserving heat for 2-12 hours;
when the added metal powder fluxing agent is Pb powder, tabletting, placing the obtained product into a quartz tube, heating the quartz tube to 600-900 ℃ under an inert protective atmosphere, and keeping the temperature for 12-24 hours;
when the added metal powder fluxing agent is Zn powder, the temperature is raised to 700-1000 ℃ under the inert protective atmosphere, and the temperature is kept for 1-6 h.
In the method for synthesizing the ternary layered compound by using the metal powder fluxing agent, preferably, the metal powder is added into the mixture in the following specific amount:
when the added metal powder fluxing agent is Al powder, metal Al powder with the weight ratio of 5-15% of the mixture is required to be added;
when the added metal powder fluxing agent is Pb powder, adding metal Pb powder accounting for 15-30% of the weight of the mixture;
when the added metal powder fluxing agent is Zn powder, metal Zn powder accounting for 5-15% of the mixture by weight needs to be added.
In the method for synthesizing the ternary layered compound by adopting the metal powder fluxing agent, preferably, when the added metal powder fluxing agent is Al powder, the temperature is raised to 700-1000 ℃ under the inert protective atmosphere, and the temperature is kept for 3-5 h or 7-11 h; preferably, the temperature is raised to 700-900 ℃ under the inert protective atmosphere, and the temperature is kept for 4-5 h or 7-11 h;
when the added metal powder fluxing agent is Pb powder, tabletting, placing the obtained product into a quartz tube, heating the quartz tube to 600-900 ℃ under an inert protective atmosphere, and keeping the temperature for 15-22 h; preferably, the temperature is increased to 700-900 ℃ and the temperature is kept for 15-20 h;
when the added metal powder fluxing agent is Zn powder, heating to 700-1000 ℃ under an inert protective atmosphere and preserving heat for 3-5 hours; preferably, the temperature is raised to 700-900 ℃ under the inert protective atmosphere, and the temperature is kept for 4-5 hours.
In the method for synthesizing the ternary layered compound by using the metal powder flux as described above, preferably, the TiH2The process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a reactor comprises the following steps: in TiH2Mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder, adding absolute ethyl alcohol, mixing and stirring uniformly, and then naturally drying;
preferably, the absolute ethyl alcohol is added, mixed and stirred for 5-30 hours, and then naturally dried.
In the method for synthesizing ternary layered compound by using metal powder fluxing agent, the anhydrous ethanol is preferably added in an amount which is enough to ensure that the liquid level of the anhydrous ethanol is completely submerged and exceeds TiH2Mixing the powder, the amorphous B powder and the hexagonal BN powder;
preferably, the absolute ethanol is added in an amount such that the absolute ethanol level completely submerges above the TiH2The material obtained by mixing the powder, the amorphous B powder and the hexagonal BN powder is 1-5 mm.
In the method for synthesizing the ternary layered compound by using the metal powder flux as described above, preferably, the TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝(2.5～3.5)：(0.7～1.3)：(0.7～1.3)。
In the method for synthesizing the ternary layered compound by using the metal powder flux as described above, preferably, the TiH2Three kinds of powder, the amorphous B powder and the hexagonal BN powderMolar ratio of starting materials TiH2：B：BN＝(2.5～3)：(1～1.3)：(1～1.3)；
Preferably, the TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝3：1：1。
In the method for synthesizing the ternary layered compound by using the metal powder fluxing agent, preferably, the temperature is increased at a rate of 5-10 ℃/min in an inert protective atmosphere;
preferably, the temperature is increased at the speed of 6-8 ℃/min under the inert protective atmosphere.
In the method for synthesizing a ternary layered compound by using a metal powder flux as described above, preferably, the inert gas in the inert protective atmosphere is argon or nitrogen;
preferably, the inert gas is argon.
In the method for synthesizing the ternary layered compound by using the metal powder fluxing agent, the concentration of the dilute hydrochloric acid is preferably 10-20%;
preferably, the time for soaking the sample in the dilute hydrochloric acid is 24-96 hours.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
1. the synthesis method provided by the invention can greatly reduce Ti3B2The synthesis temperature of N, the synthesis method is simple and easy to operate, is suitable for industrial large-scale production, and reduces the production cost.
2. In the invention, Al powder fluxing agent is added to successfully prepare Ti3B2The N synthesis temperature is reduced to 700-1000 ℃, and the Pb powder fluxing agent is added to successfully synthesize Ti3B2The N synthesis temperature is reduced to 600-900 ℃, and Ti is successfully synthesized by adding a Zn powder fluxing agent3B2The synthesis temperature of N is reduced to 700-1000 ℃; therefore, the three metal powders in the technical scheme of the invention can obviously reduce Ti3B2The synthesis temperature of N is very important for practical application.
Drawings
FIG. 1Ti3B2Theoretical XRD pattern of N compound.
FIG. 2 Ti prepared by using Al flux in the present invention as described in example 13B2XRD pattern of N sample.
FIG. 3 XRD pattern of comparative example 1 of the present invention.
FIG. 4 Ti prepared by using Pb flux in the present invention as described in example 23B2XRD pattern of N sample.
FIG. 5 XRD pattern of comparative example 2 of the present invention.
FIG. 6 Ti prepared by Zn flux in the present invention, example 33B2XRD pattern of N sample.
FIG. 7 XRD pattern of comparative example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The specific embodiment of the invention provides a method for synthesizing a ternary layered compound by adopting a metal powder fluxing agent, wherein the ternary layered compound is Ti3B2N, synthesis of Ti3B2The method of N comprises:
first, firstly, TiH2And uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder to obtain a mixture.
TiH2The process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a reactor comprises the following steps: in TiH2Mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder, adding absolute ethyl alcohol, mixing and stirring uniformly, and then naturally drying; preferably, the absolute ethyl alcohol is added, mixed and stirred for 5-30 hours, and then the mixture is naturally stirredAir drying
The absolute ethyl alcohol is added in an amount which is required to meet the condition that the liquid level of the absolute ethyl alcohol is completely submerged and exceeds TiH2Mixing the powder, the amorphous B powder and the hexagonal BN powder; preferably, the absolute ethanol is added in an amount such that the absolute ethanol level completely submerges above the TiH2The material obtained by mixing the powder, the amorphous B powder and the hexagonal BN powder is 1-5 mm (for example, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm and 4.8 mm).
TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2: b: BN ═ 2.5 to 3.5 (e.g., 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4): (0.7-1.3) (e.g., 0.7, 0.9, 1.0, 1.1, 1.15, 1.2, 1.25, 1.26, 1.27): (0.7-1.3) (e.g., 0.7, 0.9, 1.0, 1.1, 1.15, 1.2, 1.25, 1.26, 1.27). Preferably, TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2: b: BN ═ 2.5 to 3 (e.g., 2.65, 2.75, 2.85, 2.95): (1-1.3) (e.g., 1.1, 1.15, 1.2, 1.25, 1.26, 1.27): (1-1.3) (e.g., 1.1, 1.15, 1.2, 1.25, 1.26, 1.27); still more preferably, the TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝3：1：1。
And secondly, adding metal powder serving as a fluxing agent into the mixture, uniformly mixing, tabletting, heating to a set temperature under an inert protective atmosphere, and keeping the temperature for a certain time to obtain a sample.
In the invention, the metal powder fluxing agent is Al powder, Pb powder or Zn powder.
When the added metal powder fluxing agent is Al powder, the temperature is raised to 700-1000 ℃ (for example, 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃ and 990 ℃) under the inert protective atmosphere, and the temperature is preserved for 2-12 h (for example, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h and 11.5 h).
When Pb powder is used as the added metal powder fluxing agent, the Pb powder is tableted and then placed into a quartz tube, the temperature of the quartz tube is raised to 600-900 ℃ (for example 650 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃ and 890 ℃) under the inert protective atmosphere, and the quartz tube is kept warm for 12-24 h (for example 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, 21h, 22h and 23 h).
When the added metal powder fluxing agent is Zn powder, the temperature is raised to 700-1000 ℃ (for example, 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃ and 990 ℃) under the inert protective atmosphere, and the temperature is kept for 1-6 h (for example, 1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h and 5.8 h).
Further preferably, when the added metal powder fluxing agent is Al powder, the temperature is raised to 700-1000 ℃ (for example, 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃ and 990 ℃) under the inert protective atmosphere, and the temperature is kept for 3-5 hours or 7-11 hours; preferably, the temperature is raised to 700 to 900 ℃ (e.g., 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 870 ℃, 900 ℃) under an inert protective atmosphere and the temperature is kept for 4 to 5 hours or 7 to 11 hours.
When Pb powder is used as the added metal powder fluxing agent, tabletting, placing the obtained product into a quartz tube, heating the quartz tube to 600-900 ℃ (650 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃ and 890 ℃) in an inert protective atmosphere, and preserving heat for 15-22 hours; preferably, the temperature is raised to 700 to 900 ℃ (e.g., 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 870 ℃, 900 ℃) and the temperature is preserved for 15 to 20 hours.
When the added metal powder fluxing agent is Zn powder, heating to 700-1000 ℃ (for example 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃ and 990 ℃) in an inert protective atmosphere, and preserving heat for 3-5 hours; preferably, the temperature is raised to 700 to 900 ℃ (for example 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 870 ℃ and 900 ℃) in an inert protective atmosphere and the temperature is kept for 4 to 5 hours.
When the added metal powder fluxing agent is Al powder, metal Al powder with the weight ratio of 5-15% of the mixture is required to be added; when the added metal powder fluxing agent is Pb powder, metal Pb powder with the weight ratio of 15-30% (such as 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%) of the mixture needs to be added; when the added metal powder fluxing agent is Zn powder, 5-15% (such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%) of metal Zn powder by weight of the mixture is required to be added.
In the invention, the temperature is raised at the speed of 5-10 ℃/min (for example, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.5 ℃/min, 8 ℃/min, 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min) under the inert protective atmosphere; preferably, the temperature is raised at a rate of 6 to 8 ℃/min (e.g., 6.2 ℃/min, 6.5 ℃/min, 7.3 ℃/min, 7.6 ℃/min, 7.8 ℃/min) under an inert protective atmosphere.
In the invention, the inert gas under the inert protective atmosphere is argon or nitrogen; preferably, the inert gas is argon.
Thirdly, naturally cooling the sample to room temperature in an inert protective atmosphere, and removing residual metal powder fluxing agent in the sample by using dilute hydrochloric acid to obtain Ti3B2N。
Wherein the concentration of dilute hydrochloric acid is 10-20% (e.g., 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%); preferably, the sample is soaked in the diluted hydrochloric acid for 24-96 h (for example, 26h, 27h, 28h, 29h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h, 75h, 80h, 85h, 90h, 95 h). The specific soaking time depends on the content of the metal powder in the sample, and the present invention is not limited thereto.
In summary, the present invention synthesizes Ti by using Al, Pb and Zn flux3B2And (N) the method comprises the following steps: according to TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2: b: BN ═ 2.5-3.5: (0.7-1.3): (0.7-1.3), weighing TiH2Powder, amorphous B powder and hexagonal BN powder; weighing TiH2Powder, amorphous B powder, hexagonalUniformly mixing BN powder, adding metal powder as a fluxing agent, uniformly mixing, tabletting, heating under an inert protective atmosphere and preserving heat; after the reaction is finished, naturally cooling the sample to room temperature under the inert protective atmosphere; removing residual metal powder in the sample by using dilute hydrochloric acid to obtain Ti3B2N。
In the synthetic method of the invention, Al powder fluxing agent is added to successfully prepare Ti3B2The N synthesis temperature is reduced to 700-1000 ℃. Adopts Pb powder fluxing agent to successfully prepare Ti3B2The synthesis temperature of N is reduced to 600-900 ℃. Adopts the addition of Zn powder fluxing agent to successfully prepare Ti3B2The N synthesis temperature is reduced to 700-1000 ℃. The technical scheme of the invention can successfully reduce the synthesis temperature mainly because: the flux with lower melting point is adopted for melting at lower temperature, and the diffusion of the raw materials participating in the solid-phase reaction is promoted in the liquid environment, so that the reaction can be started at lower temperature. The method specifically comprises the following steps:
namely, the Al powder fluxing agent is selected by the invention: 1) the melting point of Al is 660 ℃; 2) although Al and B have binary phase compound AlB12Exist, but the synthesis temperature needs to be more than 1000 ℃; al and N exist in a binary phase compound AlN, but the synthesis temperature of the compound AlN needs to be over 1200 ℃; while the ternary compound of Al-B-N is absent. Therefore, the Al powder with lower melting point is used as the fluxing agent to effectively reduce the synthesis temperature.
Namely, the Pb powder fluxing agent is selected by the invention: 1) the melting point of Pb is 327 ℃ lower; 2) and no binary or ternary compound of Pb-B, Pb-N, Pb-B-N exists. Therefore, the Pb powder with lower melting point is used as the fluxing agent to effectively reduce the synthesis temperature.
Namely, the Zn powder fluxing agent is selected by the invention: 1) the melting point of Zn is 419 ℃; 2) meanwhile, binary or ternary compounds of Zn-B, Zn-N, Zn-B-N do not exist. Therefore, Zn powder with lower melting point is adopted as the fluxing agent, so that the synthesis temperature can be effectively reduced.
Therefore, the invention can obviously reduce Ti3B2The synthesis temperature of N is very important for practical application.
Zn powder, TiH in the following examples2The powder, the amorphous B powder and the hexagonal BN powder are all commercial products, and the purity is more than 99.9 percent.
Example 1
This example provides a process for synthesizing Ti using Al flux3B2Method of N, Synthesis of Ti3B2The method of N comprises the following steps:
1) separately weighing TiH2Powder, amorphous B powder and hexagonal BN powder for later use;
and TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝3：1：1；
2) TiH weighed in the step 1)2Putting the powder, the amorphous B powder and the hexagonal BN powder into a container, and uniformly mixing and stirring to obtain a mixture;
TiH2the process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a container is as follows: in TiH2And adding absolute ethyl alcohol into the powder, the amorphous B powder and the hexagonal BN powder, mixing and stirring for 18 hours, and naturally drying. Wherein, the addition amount of the absolute ethyl alcohol must meet the condition that the liquid level of the absolute ethyl alcohol is completely submerged and exceeds TiH2The material obtained by mixing the powder, the amorphous B powder and the hexagonal BN powder is 3 mm.
3) Adding metal Al powder accounting for 10% of the weight of the mixture into the mixture obtained in the step 2) as a fluxing agent, uniformly mixing in an agate mortar, tabletting (the pressure in the tabletting process needs to be 5MPa), and cold-pressing into a biscuit block; and (3) placing the biscuit block in a tube furnace, heating to 900 ℃ at the speed of 10 ℃/min under the inert protective atmosphere, and preserving heat for 3 h.
4) Obtaining a sample after the step 3) is finished; naturally cooling the sample to room temperature under the inert protective atmosphere; soaking the sample in 15% dilute hydrochloric acid for 48 hr to remove residual Al, diluting with distilled water, filtering, and centrifuging to obtain Ti3B2N black sample.
Ti prepared in this example3B2The XRD pattern of the N product is shown in figure 2. Due to Ti3B2N is a new synthetic substance, so the X-ray diffraction standard card library has not been included. Using a crystal XRD spectrumSimulation software poudrix, available Ti3B2The theoretical XRD pattern of N is shown in figure 1. Comparing FIG. 1 with FIG. 2, it can be determined that the main phase in the synthesized sample is Ti3B2And (3) an N compound. Meanwhile, the sample also contains a small amount of impure phase (TiN, JCPDS card number: 38-1420; TiB)2JCPDS card number: 35-0741).
Example 2
This example provides a process for synthesizing Ti using Al flux3B2Method of N, Synthesis of Ti3B2The method of N comprises the following steps:
1) separately weighing TiH2Powder, amorphous B powder and hexagonal BN powder for later use;
and TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝3.5：0.7：1；
2) TiH weighed in the step 1)2Putting the powder, the amorphous B powder and the hexagonal BN powder into a container, and uniformly mixing and stirring to obtain a mixture;
TiH2the process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a container is as follows: in TiH2And adding absolute ethyl alcohol into the powder, the amorphous B powder and the hexagonal BN powder, mixing and stirring for 30 hours, and naturally drying. The absolute ethyl alcohol is added in an amount which is required to meet the condition that the liquid level of the absolute ethyl alcohol is completely submerged and exceeds TiH2The material obtained by mixing the powder, the amorphous B powder and the hexagonal BN powder is 2 mm.
3) Adding metal Al powder accounting for 15% of the weight of the mixture into the mixture obtained in the step 2) as a fluxing agent, uniformly mixing in an agate mortar, tabletting (the pressure in the tabletting process needs to be 3MPa), and cold-pressing into a biscuit block; and (3) placing the biscuit block in a tube furnace, heating to 700 ℃ at the speed of 6 ℃/min under the inert protective atmosphere, and preserving heat for 4 h.
4) Obtaining a sample after the step 3) is finished; naturally cooling the sample to room temperature under the inert protective atmosphere; soaking the sample in 15% dilute hydrochloric acid for 30 hr to remove residual Al, diluting with distilled water, filtering, and centrifuging to obtain Ti3B2N black sample.
The XRD pattern of the product prepared in this example is not shown. This example contains Ti3B2N、TiB2And TiN, and Ti in the sample synthesized in this example3B2The content of N is similar to that in example 1.
Comparative example 1
The comparative example differs from example 1 in that: no Al flux was added. The other synthesis steps are the same as in example 1.
The XRD pattern of the product prepared in this comparative example is shown in FIG. 3. As can be seen from FIG. 3, in the case where this comparative example is identical to example 1 in other conditions, but no Al flux is added, Ti cannot be obtained in the comparative example3B2And (4) N phase.
Example 3
This example provides a method for synthesizing Ti using a Pb flux3B2Method of N, Synthesis of Ti3B2The method of N comprises the following steps:
1) separately weighing TiH2Powder, amorphous B powder and hexagonal BN powder for later use;
and TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝3：1：1；
2) TiH weighed in the step 1)2Putting the powder, the amorphous B powder and the hexagonal BN powder into a container, and uniformly mixing and stirring to obtain a mixture;
TiH2the process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a container is as follows: in TiH2And adding absolute ethyl alcohol into the powder, the amorphous B powder and the hexagonal BN powder, mixing and stirring for 18 hours, and naturally drying. Wherein, the addition amount of the absolute ethyl alcohol must meet the condition that the liquid level of the absolute ethyl alcohol is completely submerged and exceeds TiH2The material obtained by mixing the powder, the amorphous B powder and the hexagonal BN powder is 3 mm.
3) Adding 20% by weight of metal Pb powder serving as a fluxing agent into the mixture obtained in the step 2), uniformly mixing in an agate mortar, tabletting (the pressure in the tabletting process needs to be 5MPa), and cold-pressing into a biscuit block; placing the biscuit block in a quartz tube, vacuumizing and filling Ar gas, and sealing the quartz tube; the quartz tube was heated to 800 ℃ at a rate of 10 ℃/min and held for 18 h.
4) Obtaining a sample after the step 3) is finished; naturally cooling the sample to room temperature along with the furnace; soaking the sample in 15% dilute hydrochloric acid for 48 hr to remove residual Pb, diluting with distilled water, filtering, and centrifuging to obtain Ti3B2N black sample.
Ti prepared in this example3B2The XRD pattern of the N product is shown in figure 4. Due to Ti3B2N is a new synthetic substance, so the X-ray diffraction standard card library has not been included. Ti can be obtained by adopting crystal XRD spectrogram simulation software poudrix3B2The theoretical XRD pattern of N is shown in figure 1. Comparing FIG. 1 with FIG. 4, it can be determined that the main phase in the synthesized sample is Ti3B2And (3) an N compound. Meanwhile, the sample also contains a small amount of impure phase (TiN, JCPDS card number: 38-1420; TiB)2JCPDS card number: 35-0741).
Example 4
This example provides a method for synthesizing Ti using a Pb flux3B2Method of N, Synthesis of Ti3B2The method of N comprises the following steps:
1) separately weighing TiH2Powder, amorphous B powder and hexagonal BN powder for later use;
and TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝3：0.8：0.8；
2) TiH weighed in the step 1)2Putting the powder, the amorphous B powder and the hexagonal BN powder into a container, and uniformly mixing and stirring to obtain a mixture;
TiH2the process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a container is as follows: in TiH2And adding absolute ethyl alcohol into the powder, the amorphous B powder and the hexagonal BN powder, mixing and stirring for 25 hours, and naturally drying. The absolute ethyl alcohol is added in an amount which is required to meet the condition that the liquid level of the absolute ethyl alcohol is completely submerged and exceeds TiH2The material obtained by mixing the powder, the amorphous B powder and the hexagonal BN powder is 4 mm.
3) Adding 20% by weight of metal Pb powder serving as a fluxing agent into the mixture obtained in the step 2), uniformly mixing in an agate mortar, tabletting (the pressure in the tabletting process needs to be 8MPa), and cold-pressing into a biscuit block; placing the biscuit block in a quartz tube, vacuumizing and filling Ar gas, and sealing the quartz tube; the quartz tube was heated to 800 ℃ at a rate of 8 ℃/min and held for 17 h.
4) Obtaining a sample after the step 3) is finished; naturally cooling the sample to room temperature along with the furnace; soaking the sample in 12% dilute hydrochloric acid for 40 hr to remove residual Pb, diluting with distilled water, filtering, and centrifuging to obtain Ti3B2N black sample.
The XRD pattern of the product prepared in this example is not shown. This example contains Ti3B2N、TiB2And TiN, and Ti in the sample synthesized in this example3B2The content of N was similar to that in example 3.
Comparative example 2
The comparative example differs from example 3 in that: no Pb flux was added and no hydrochloric acid soak was performed. The other synthetic steps are the same as example 3.
The XRD pattern of the product prepared in this comparative example is shown in FIG. 5. As can be seen from FIG. 5, in the case where this comparative example was otherwise identical to example 3 except that no Pb flux was added, Ti could not be obtained in the comparative example3B2And (4) N phase.
Example 5
This example provides a process for the synthesis of Ti using a Zn flux3B2Method of N, Synthesis of Ti3B2The method of N comprises the following steps:
1) separately weighing TiH2Powder, amorphous B powder and hexagonal BN powder for later use;
and TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝3：1：1；
2) TiH weighed in the step 1)2Putting the powder, the amorphous B powder and the hexagonal BN powder into a container, and uniformly mixing and stirring to obtain a mixture;
TiH2the process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a container is as follows: in TiH2And adding absolute ethyl alcohol into the powder, the amorphous B powder and the hexagonal BN powder, mixing and stirring for 18 hours, and naturally drying. Wherein, the addition amount of the absolute ethyl alcohol must meet the condition that the liquid level of the absolute ethyl alcohol is completely submerged and exceeds TiH2The material obtained by mixing the powder, the amorphous B powder and the hexagonal BN powder is 3 mm.
3) Adding metal Zn powder accounting for 10 percent of the weight of the mixture into the mixture obtained in the step 2) as a fluxing agent, uniformly mixing in an agate mortar, tabletting (the pressure in the tabletting process needs to be 5MPa), and cold-pressing into a biscuit block; and (3) placing the biscuit block in a tube furnace, heating to 900 ℃ at the speed of 10 ℃/min under the inert protective atmosphere, and preserving heat for 3 h.
4) Obtaining a sample after the step 3) is finished; naturally cooling the sample to room temperature under the inert protective atmosphere; soaking the sample in 15% dilute hydrochloric acid for 48 hr to remove residual Zn, diluting with distilled water, filtering, and centrifuging to obtain Ti3B2N black sample.
Ti prepared in this example3B2The XRD pattern of the N product is shown in figure 6. Due to Ti3B2N is a new synthetic substance, so the X-ray diffraction standard card library has not been included. Ti can be obtained by adopting crystal XRD spectrogram simulation software poudrix3B2The theoretical XRD pattern of N is shown in figure 1. Comparing FIG. 1 with FIG. 6, it can be determined that the main phase in the synthesized sample is Ti3B2And (3) an N compound. Meanwhile, the sample also contains a small amount of impure phase (TiN, JCPDS card number: 38-1420; TiB)2JCPDS card number: 35-0741).
Example 6
This example provides a process for the synthesis of Ti using a Zn flux3B2Method of N, Synthesis of Ti3B2The method of N comprises the following steps:
1) separately weighing TiH2Powder, amorphous B powder and hexagonal BN powder for later use;
and TiH2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN＝2.5：1：1.3；
2) TiH weighed in the step 1)2Putting the powder, the amorphous B powder and the hexagonal BN powder into a container, and uniformly mixing and stirring to obtain a mixture;
TiH2the process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a container is as follows: in TiH2And adding absolute ethyl alcohol into the powder, the amorphous B powder and the hexagonal BN powder, mixing and stirring for 10 hours, and naturally drying. The absolute ethyl alcohol is added in an amount which is required to meet the condition that the liquid level of the absolute ethyl alcohol is completely submerged and exceeds TiH25mm of mixed material of the powder, the amorphous B powder and the hexagonal BN powder.
3) Adding 12% by weight of metal Zn powder serving as a fluxing agent into the mixture obtained in the step 2), uniformly mixing in an agate mortar, tabletting (the pressure in the tabletting process needs to be 4MPa), and cold-pressing into a biscuit block; and (3) putting the biscuit block into a tube furnace, heating to 850 ℃ at the speed of 7 ℃/min under the inert protective atmosphere, and preserving heat for 4.5 h.
4) Obtaining a sample after the step 3) is finished; naturally cooling the sample to room temperature under the inert protective atmosphere; soaking the sample in 16% dilute hydrochloric acid for 80 hr to remove residual Zn, diluting with distilled water, filtering, and centrifuging to obtain Ti3B2N black sample.
The XRD pattern of the product prepared in this example is not shown. This example contains Ti3B2N、TiB2And TiN, and Ti in the sample synthesized in this example3B2The content of N is similar to that in example 5.
Comparative example 3
The comparative example differs from example 5 in that: no Zn flux was added. The other synthesis steps were the same as in example 5.
The XRD pattern of the product prepared in this comparative example is shown in FIG. 7. As can be seen from FIG. 7, in the case where this comparative example is identical to example 5 in other conditions, but no Zn flux is added, Ti could not be obtained in the comparative example3B2And (4) N phase.
In summary, the present invention has the following technical effects:
1. the synthesis method provided by the invention can greatly reduce Ti3B2The synthesis temperature of N, the synthesis method is simple and easy to operate, is suitable for industrial large-scale production, and reduces the production cost.
2. In the invention, Al powder fluxing agent is added to successfully prepare Ti3B2The N synthesis temperature is reduced to 700-1000 ℃, and the Pb powder fluxing agent is added to successfully synthesize Ti3B2The N synthesis temperature is reduced to 600-900 ℃, and Ti is successfully synthesized by adding a Zn powder fluxing agent3B2The synthesis temperature of N is reduced to 700-1000 ℃; therefore, the three metal powders in the technical scheme of the invention can obviously reduce Ti3B2The synthesis temperature of N is very important for practical application.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (17)
1. A method for synthesizing a ternary layered compound by adopting a metal powder fluxing agent is characterized in that the ternary layered compound is Ti3B2N, synthesizing the Ti3B2The method of N comprises:
firstly TiH2Mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder uniformly to obtain a mixture; adding metal powder serving as a fluxing agent into the mixture, uniformly mixing, tabletting, heating to a set temperature under an inert protective atmosphere, and keeping the temperature for a certain time to obtain a sample; finally, under the inert protective atmosphere, after the sample is naturally cooled to the room temperature, the residual metal powder fluxing agent in the sample is removed by adopting dilute hydrochloric acid to obtain Ti3B2N；
The metal powder fluxing agent is Al powder, Pb powder or Zn powder;
when the added metal powder fluxing agent is Al powder, heating to 700 ~ 1000 ℃ under the inert protective atmosphere and preserving heat for 2 ~ 12 h;
when Pb powder is added as the metal powder fluxing agent, tabletting, putting into a quartz tube, heating the quartz tube to 600 ~ 900 ℃ under the inert protective atmosphere, and keeping the temperature for 12 ~ 24 h;
when the added metal powder fluxing agent is Zn powder, the temperature is raised to 700 ~ 1000 ℃ under the inert protective atmosphere, and the temperature is kept for 1 ~ 6 h.
2. The method for synthesizing a ternary layered compound using a metal powder flux as set forth in claim 1, wherein the amount of the metal powder added to the mixture is specifically as follows:
when the added metal powder fluxing agent is Al powder, metal Al powder with the weight ratio of 5 ~ 15% of the mixture is required to be added;
when the added metal powder fluxing agent is Pb powder, metal Pb powder which accounts for 15 ~ 30% of the weight of the mixture needs to be added;
when the added metal powder fluxing agent is Zn powder, metal Zn powder with the weight ratio of 5 ~ 15% of the mixture is required to be added.
3. The method for synthesizing a ternary layered compound using a metal powder flux according to claim 1,
when the added metal powder fluxing agent is Al powder, heating to 700 ~ 1000 ℃ under the inert protective atmosphere, and preserving heat for 3 ~ 5h or 7-11 h;
when Pb powder is added as the metal powder fluxing agent, tabletting, putting into a quartz tube, heating the quartz tube to 600 ~ 900 ℃ under the inert protective atmosphere, and keeping the temperature for 15 ~ 22 h;
when the added metal powder fluxing agent is Zn powder, the temperature is raised to 700 ~ 1000 ℃ under the inert protective atmosphere, and the temperature is kept for 3 ~ 5 hours.
4. The method of synthesizing a ternary layered compound using a metal powder flux as claimed in claim 1 wherein said TiH is2The process of uniformly mixing and stirring the powder, the amorphous B powder and the hexagonal BN powder in a reactor comprises the following steps: in TiH2And adding absolute ethyl alcohol into the powder, the amorphous B powder and the hexagonal BN powder, mixing and stirring uniformly, and naturally drying.
5.The method of claim 4 in which the absolute alcohol is added in an amount sufficient to completely submerge the absolute alcohol above the TiH level2Mixing the powder, the amorphous B powder and the hexagonal BN powder.
6. The method of synthesizing a ternary layered compound using a metal powder flux as claimed in claim 1 wherein said TiH is2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN=(2.5~3.5)：(0.7~1.3)：(0.7~1.3)。
7. The method of synthesizing a ternary layered compound using a metal powder flux as claimed in claim 6 wherein said TiH is2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN=(2.5~3)：(1~1.3)：(1~1.3) 。
8. The method for synthesizing a ternary layered compound using a metal powder flux as set forth in claim 1, wherein the temperature is raised at a rate of 5 ~ 10 ℃/min under an inert protective atmosphere.
9. The method for synthesizing a ternary layered compound using a metal powder flux according to claim 1, wherein the inert gas under an inert protective atmosphere is argon or nitrogen.
10. The method for synthesizing a ternary layered compound using a metal powder flux as set forth in claim 1, wherein the concentration of the dilute hydrochloric acid is 10 to 20%.
11. The method for synthesizing a ternary layered compound using a metal powder flux according to claim 3,
when the added metal powder fluxing agent is Al powder, heating to 700 ~ 900 ℃ under the inert protective atmosphere, and preserving heat for 4 ~ 5h or 7-11 h;
when Pb powder is added as the metal powder fluxing agent, tabletting, putting into a quartz tube, heating the quartz tube to 700 ~ 900 ℃ under the inert protective atmosphere, and keeping the temperature for 15 ~ 20 h;
when the added metal powder fluxing agent is Zn powder, the temperature is raised to 700 ~ 900 ℃ under the inert protective atmosphere, and the temperature is kept for 4 ~ 5 h.
12. The method for synthesizing a ternary layered compound using a metal powder flux as claimed in claim 4, wherein the anhydrous ethanol is added, mixed and stirred for 5 ~ 30 hours, and then naturally dried.
13. The method of claim 5 in which the absolute alcohol is added in an amount sufficient to completely submerge the absolute alcohol above the TiH level2The material obtained by mixing the powder, the amorphous B powder and the hexagonal BN powder is 1 ~ 5 mm.
14. The method of synthesizing a ternary layered compound using a metal powder flux as claimed in claim 7 wherein said TiH is2The molar ratio TiH of the powder, the amorphous B powder and the hexagonal BN powder2：B：BN=3：1：1。
15. The method for synthesizing a ternary layered compound using a metal powder flux as set forth in claim 8, wherein the temperature is raised at a rate of 6 ~ 8 ℃/min under an inert protective atmosphere.
16. A method for synthesizing a ternary layered compound using a metal powder flux as in claim 9 wherein the inert gas is argon.
17. A method for synthesizing a ternary layered compound with a metal powder flux as in claim 10 wherein the time for soaking the sample in the dilute hydrochloric acid is 24 ~ 96 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810169742.5A CN108328587A (en) | 2018-02-08 | 2018-02-08 | It is a kind of that Ti is synthesized using Al fluxing agents3B2The method of N |
| CN201810169741.0A CN108439989A (en) | 2018-02-08 | 2018-02-08 | It is a kind of that Ti is synthesized using Zn fluxing agents3B2The method of N |
| CN2018101697410 | 2018-02-08 | ||
| CN201810169743X | 2018-02-08 | ||
| CN2018101697425 | 2018-02-08 | ||
| CN201810169743.XA CN108275692A (en) | 2018-02-08 | 2018-02-08 | It is a kind of that Ti is synthesized using Pb fluxing agents3B2The method of N |
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| RU2070600C1 (en) * | 1993-07-19 | 1996-12-20 | Научно-производственное предприятие "Темп" | Superhard composition material |
| CN107021759A (en) * | 2016-01-29 | 2017-08-08 | 河南理工大学 | A kind of new ceramics crystal Ti3B2N and preparation method thereof |
| CN107663090A (en) * | 2016-07-28 | 2018-02-06 | 河南理工大学 | One kind synthesis high purity Ti3B2N method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2070600C1 (en) * | 1993-07-19 | 1996-12-20 | Научно-производственное предприятие "Темп" | Superhard composition material |
| CN107021759A (en) * | 2016-01-29 | 2017-08-08 | 河南理工大学 | A kind of new ceramics crystal Ti3B2N and preparation method thereof |
| CN107663090A (en) * | 2016-07-28 | 2018-02-06 | 河南理工大学 | One kind synthesis high purity Ti3B2N method |
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| Title |
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| 电弧离子镀制备TiBN 纳米复合涂层;田灿鑫等;《表面技术》;20170630;第46卷(第4期);第151-155页 * |
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