CN113480316B - Non-stoichiometric oxynitride nano powder and preparation method thereof - Google Patents

Non-stoichiometric oxynitride nano powder and preparation method thereof Download PDF

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CN113480316B
CN113480316B CN202110742071.9A CN202110742071A CN113480316B CN 113480316 B CN113480316 B CN 113480316B CN 202110742071 A CN202110742071 A CN 202110742071A CN 113480316 B CN113480316 B CN 113480316B
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CN113480316A (en
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李端
李俊生
曾良
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National University of Defense Technology
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Abstract

The invention discloses non-stoichiometric oxynitride nano powder and a preparation method thereof, wherein the preparation method comprises the steps of dissolving europium oxide powder, tantalum pentoxide powder and urea in absolute ethyl alcohol, carrying out ball milling to obtain mixed slurry, drying the mixed slurry to obtain mixed precursor powder, and calcining the mixed precursor powder in protective atmosphere to obtain EuTa (O, N)3Oxynitride nano-powder prepared from EuTa (O, N)3Carrying out ammoniation annealing treatment on the oxynitride nano powder in ammonia atmosphere to obtain non-stoichiometric oxynitride nano powder EuTaOaNbA is more than or equal to 1.5 and less than or equal to 2.5, b is more than or equal to 0.5 and less than or equal to 1.5, and a: b is not equal to 2: 1. The method has the advantages of low cost, simple process, high product purity and the like, and the prepared product has good dielectric property and magnetism.

Description

Non-stoichiometric oxynitride nano powder and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of high-performance dielectric ceramic materials, in particular to non-stoichiometric oxynitride nano powder and a low-cost preparation method thereof.
Background
The rare earth perovskite oxynitride is a novel functional material which is of great importance in the world in recent years. The oxynitride is obtained by introducing N atoms and rare earth metal cations into corresponding binary rare earth perovskite oxide ABOx, and the common type is AB (O, N)3,A2BO3N or A (B, B')1(O,N)3And the like, wherein A is a rare earth element (such as La, Nd, Pr, Eu and the like), and B/B' is a transition group metal element (such as Ta, Ti, Nb, Mo, Zr, W and the like). In the crystal structure, the B atom usually forms B (O, N) with the O/N atom6Octahedron and the B atom is located in the center of the octahedron. Due to the different arrangement of O/N atoms (cis and trans) and B (O, N)6The octahedron has different inclination degrees, and the oxynitrides have different crystal structures.
Since nitrogen atoms are higher in electronegativity and polarization than oxygen atoms, and the N-2p orbital level is higher than O-2p according to band theory, the introduction of N atoms in oxynitrides causes the band gap (band gap) between the conduction band and the valence band thereof to decrease. For example, the band gap of common perovskite oxides is typically higher than 3.0eV, while the band gap of their corresponding oxynitrides is between 1.5eV and 2.5 eV. This reduction in band gap results inThe microscopic electronic structure of the material is changed, and the optical properties of the material are changed. Meanwhile, due to the introduction of rare earth elements and the diversity of O/N distribution, the material also obtains a plurality of new functional characteristics. For example, La1-xSrxTiO2+ xN1-xThe dielectric constant is very high at room temperature; RTiO2N(R＝Ce，Pr，Nd)、NdVO2N and GdNbON2Has paramagnetism; LaTiO 22N and RTaON2(R ═ La, Ce and Pr) can be used as a visible light catalyst to crack water to produce hydrogen.
According to the relationship of material structure-process-performance, the preparation process is the key point for obtaining ideal microstructure and excellent comprehensive performance of the rare earth perovskite oxynitride material. At present, the mainstream method for synthesizing the oxynitride powder is to synthesize a composite oxide precursor containing a plurality of metal cations by adopting processes such as solid-phase calcination, sol-gel, polyol coprecipitation, hydrothermal method and the like, and then perform ammoniation treatment in a flowing ammonia atmosphere and at a high temperature. However, in the second ammoniation step, the gas-solid reaction is slow to diffuse, the reaction is often limited to the gas-solid contact surface, and the powder is ground in the middle of the reaction to improve the yield, so that the preparation time is greatly prolonged, and more efficient preparation and optimization processes are further researched.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the non-stoichiometric oxynitride nano powder with low cost, simple process, high purity and high dielectric constant and the preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing non-stoichiometric oxynitride nano powder comprises the following steps:
(1) dissolving europium oxide powder, tantalum pentoxide powder and urea in absolute ethyl alcohol, and performing ball milling to obtain mixed slurry;
(2) drying the mixed slurry obtained in the step (1) to obtain mixed precursor powder;
(3) mixing the mixed precursor obtained in the step (2)Calcining the powder in a protective atmosphere to obtain EuTa (O, N)3Oxynitride nanopowders;
(4) subjecting the EuTa (O, N) obtained in the step (3)3The oxynitride nano powder is subjected to ammoniation annealing treatment in ammonia atmosphere, namely the temperature is raised to 800-1500 ℃ at the heating rate of 1-50 ℃/min, the temperature is kept for 1-24 h, and the oxynitride nano powder is cooled to room temperature along with the furnace to obtain the non-stoichiometric oxynitride nano powder EuTaOaNbWherein a is more than or equal to 1.5 and less than or equal to 2.5, b is more than or equal to 0.5 and less than or equal to 1.5, and a: b is not equal to 2: 1.
In the method for preparing the non-stoichiometric oxynitride nano powder, in the step (1), the proportion of the europium trioxide powder, the tantalum pentoxide powder, the urea and the absolute ethyl alcohol is preferably 1 g-5 g: 2 g-8 g: 1 g-15 g: 5 mL-100 mL, and the ball milling time is preferably 1 h-24 h.
In the method for preparing the non-stoichiometric oxynitride nano powder, preferably, in the step (1), the europium trioxide, the tantalum pentoxide, the urea and the absolute ethyl alcohol are in a ratio of 2 g-4 g: 3 g-6 g: 2 g-10 g: 5 mL-50 mL, and the ball milling time is 2 h-12 h.
In the method for preparing the non-stoichiometric oxynitride nano powder, preferably, in the step (4), the temperature rise rate is 10-30 ℃/min, the temperature is increased to 900-1400 ℃, and the temperature is maintained for 1-12 h.
In the above method for preparing non-stoichiometric oxynitride nano powder, preferably, in step (3), the protective atmosphere is one or more of nitrogen, helium and argon, and the calcining process is: heating to 800-1400 ℃ at a heating rate of 50-500 ℃/min, preserving the heat for 0-30 min, and cooling to room temperature along with the furnace.
The preparation method of the non-stoichiometric oxynitride nano powder preferably comprises the steps of heating to 900-1300 ℃ and keeping the temperature for 1-10 min.
In the above method for preparing the non-stoichiometric oxynitride nanopowder, in the step (2), the drying temperature is preferably 30 to 120 ℃ and the drying time is preferably 1 to 72 hours.
In the above method for preparing the non-stoichiometric oxynitride nanopowder, the drying temperature is preferably 50 to 80 ℃ and the drying time is preferably 6 to 48 hours.
As a general technical concept, the present invention also provides a non-stoichiometric oxynitride nano powder, which is EuTaOaNbWherein a is more than or equal to 1.5 and less than or equal to 2.5, b is more than or equal to 0.5 and less than or equal to 1.5, and a: b is not equal to 2: 1.
Compared with the prior art, the invention has the advantages that:
1. the invention provides a preparation method of non-stoichiometric oxynitride nano powder by mixing EuTa (O, N)3The oxynitride is subjected to an ammoniation annealing treatment in an ammonia gas atmosphere to obtain non-stoichiometric oxynitride nanopowder because of NH3Directly prepared EuTa (O, N) with certain reducibility3Eu is in an intermediate valence state between +2 and +3, and NH is generated during the ammonia gas annealing treatment process3The content of O/N in the sample is changed by reducing the Eu element in the intermediate valence state, and finally the Eu element tends to be in a stable state. In the process, the phase change process of the sample occurs, and the process gradually evolves along with the temperature and time of the ammoniation process, namely the phase change process can be controlled by controlling the temperature and time of the ammoniation annealing process. The invention prepares EuTa (O, N) by using cheap urea as a nitrogen source and calcining at a lower temperature3Compared with the mainstream two-step method or one-step high-temperature synthesis method, the oxynitride has the advantages of low cost, short time consumption, simple and convenient operation, high product purity and good dielectric property, and can obtain non-stoichiometric oxynitride nano powder.
The invention adopts specific urea content during calcination, and the urea content in the mixed precursor powder is 2-15 times of the urea amount calculated by a chemical equation, so that a reaction system not only has a solid nitrogen source provided by urea in a reaction mixture, but also has gaseous nitrogen source provided by urea decomposed by heating, thereby greatly improving the nitriding efficiency. In addition, the ammonia gas can also effectively remove residual carbon generated by incomplete decomposition of urea in the reaction mixture, and the purity of the oxynitride product is greatly improved.
The method adopts a faster heating rate (50-500 ℃/min) when the mixed precursor powder is calcined, and the heating rate of the traditional method is generally 1-10 ℃/min. The urea can be decomposed at a lower temperature, so that the nitrogen source is lost in advance, the nitridation degree is low when the reaction system reaches a higher temperature for generating oxynitride, and the product purity is not high. The rapid temperature rise can inhibit the decomposition of urea from the aspect of chemical kinetics, and the temperature of a reaction system rapidly reaches the temperature required by the generation of oxynitride on the premise of keeping a large amount of nitrogen source, so that sufficient nitridation reaction occurs, the reaction time is greatly shortened, and the purity of the product is improved.
2. The invention provides non-stoichiometric oxynitride nano powder which is EuTaOaNbWherein a is more than or equal to 1.5 and less than or equal to 2.5, b is more than or equal to 0.5 and less than or equal to 1.5, and the specific stoichiometric ratio of O and N ensures that the oxynitride nano powder has good dielectric properties.
Drawings
FIG. 1 is an optical photograph and an XRD spectrum of the non-stoichiometric oxynitride nano-powder obtained in example 1 of the present invention.
FIG. 2 is a graph showing the magnetic susceptibility of the non-stoichiometric oxynitride nano-powder prepared in example 1 of the present invention.
FIG. 3 is a graph showing the dielectric characteristics of the non-stoichiometric oxynitride nano-powder obtained in example 1 of the present invention.
FIG. 4 is an SEM photograph of the change of the microstructure of the sample during the ammonification annealing treatment in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and the specific preferred embodiments, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
Example 1:
the invention relates to a preparation method of non-stoichiometric oxynitride nano powder, which comprises the following steps:
(1) adding 3g of europium oxide, 3.75g of tantalum pentoxide and 5.45g of urea into 50mL of absolute ethanol, and carrying out ball milling for 240min to obtain mixed slurry;
(2) drying the mixed slurry obtained in the step (1), wherein the drying process comprises the following steps: preserving the heat for 24 hours at the temperature of 60 ℃ to obtain mixed precursor powder;
(3) placing the mixed precursor powder obtained in the step (2) in a crucible, and then calcining in a nitrogen atmosphere, wherein the heating rate is 100 ℃/min, the temperature is 1100 ℃, and the heat preservation time is 1 min; finally, cooling to room temperature along with the furnace to obtain EuTa (O, N)3Oxynitride nanopowders;
(4) subjecting the EuTa (O, N) obtained in the step (3)3Performing ammoniation annealing treatment on the oxynitride nano powder in an ammonia atmosphere, namely heating to 1100 ℃ (annealing temperature) at a heating rate of 10 ℃/min, keeping the temperature for 6h, cooling to room temperature along with a furnace, and detecting that the obtained oxynitride is EuTaO1.96N1.04。
The phase composition and the micro-morphology of the non-stoichiometric oxynitride nanopowder of this example are shown in FIGS. 1 to 4, respectively: as can be seen from FIG. 1, the phase is almost pure phase EuTa (O, N)3(content 99.8%), black color, uniform shape and size of product, and crystal grain size of about 50-100 nm. EuTa (O, N) prepared in this example, as shown in FIGS. 2 and 33The oxynitride has a higher dielectric constant of 15845, the magnetic susceptibility of the sample in a temperature range of 10K-300K follows Curie-Weiss law, and the corresponding equation is as follows: χ is 7.75/T-3.32, and the effective magnetic moment is 7.82 μ B. As can be seen from fig. 4, in the ammonification annealing process, the microstructure of the sample is firstly changed from regular and uniform cubic particles of the original sample to cubic particles with smoother boundaries, then the sample is gradually changed from cubes to irregular spherical particles, and in the process, an obvious grain fusion phenomenon occurs, and finally irregular polyhedral particles are re-dispersed. The granularity and the distribution of the sample do not obviously change in the whole change process, and according to the shape change process of the sample, the phase change process of the sample can be inferred in the ammoniation annealing process, and the process gradually evolves along with the temperature and the time of the ammoniation process, namely the phase can be controlled by controlling the temperature and the time of the ammoniation annealing processAnd (6) changing the process.
Example 2:
the invention relates to a preparation method of non-stoichiometric oxynitride nano powder, which comprises the following steps:
(1) adding 3g of europium oxide powder, 3.75g of tantalum pentoxide powder and 5.45g of urea into 50mL of absolute ethanol, and carrying out ball milling for 240min to obtain mixed slurry;
(2) drying the mixed slurry obtained after ball milling in the step (1), wherein the drying process comprises the following steps: preserving the heat for 24 hours at the temperature of 60 ℃ to obtain mixed precursor powder;
(3) placing the mixed precursor powder obtained in the step (2) in a crucible, and then calcining in a nitrogen atmosphere, wherein the heating rate is 100 ℃/min, the temperature is 1100 ℃, and the heat preservation time is 1 min; finally, cooling to room temperature along with the furnace to obtain EuTa (O, N)3Oxynitride nanopowders;
(4) subjecting the EuTa (O, N) obtained in the step (3)3Performing ammoniation annealing treatment on the oxynitride nano powder in an ammonia atmosphere, namely heating to 1000 ℃ at the heating rate of 20 ℃/min, keeping the temperature for 6h, and detecting that the obtained oxynitride is EuTaO1.75N1.25。
Example 3:
the invention relates to a preparation method of non-stoichiometric oxynitride nano powder, which comprises the following steps:
(1) adding 3g of europium oxide powder, 3.75g of tantalum pentoxide powder and 5.45g of urea into 50mL of absolute ethanol, and carrying out ball milling for 240min to obtain mixed slurry;
(2) drying the mixed slurry obtained after ball milling in the step (1), wherein the drying process comprises the following steps: preserving the heat for 24 hours at the temperature of 60 ℃ to obtain mixed precursor powder;
(3) placing the mixed precursor powder obtained in the step (2) in a crucible, and then calcining in a nitrogen atmosphere, wherein the heating rate is 100 ℃/min, the temperature is 1100 ℃, and the heat preservation time is 1 min; finally, cooling to room temperature along with the furnace to obtain EuTa (O, N)3Oxynitride nanopowders;
(4) subjecting the EuTa (O, N) obtained in the step (3)3Oxynitride nano powder in ammonia atmospherePerforming ammoniation annealing treatment, namely heating to 1200 ℃ at the heating rate of 30 ℃/min, keeping the temperature for 15h, and detecting that the obtained oxynitride is EuTaO2.04N0.96。
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.

Claims (8)

1. A method for preparing non-stoichiometric oxynitride nano powder is characterized by comprising the following steps:
(1) dissolving europium oxide powder, tantalum pentoxide powder and urea in absolute ethyl alcohol, and performing ball milling to obtain mixed slurry;
(2) drying the mixed slurry obtained in the step (1) to obtain mixed precursor powder;
(3) calcining the mixed precursor powder obtained in the step (2) in a protective atmosphere to obtain EuTa (O, N)3Oxynitride nanopowders;
(4) subjecting the EuTa (O, N) obtained in the step (3)3The oxynitride nano powder is subjected to ammoniation annealing treatment in ammonia atmosphere, namely the temperature is raised to 800-1500 ℃ at the heating rate of 1-50 ℃/min, the temperature is kept for 1-24 h, and the oxynitride nano powder is cooled to room temperature along with the furnace to obtain the non-stoichiometric oxynitride nano powder EuTaOaNbWherein a is more than or equal to 1.5 and less than or equal to 2.5, b is more than or equal to 0.5 and less than or equal to 1.5, and a: b is not equal to 2: 1.
2. The method for preparing non-stoichiometric oxynitride nanopowder according to claim 1, wherein in step (1), the ratio of the europium trioxide powder to the tantalum pentoxide powder to the urea to the absolute ethyl alcohol is 1-5 g: 2-8 g: 1-15 g: 5-100 mL, and the ball milling time is 1-24 h.
3. The method for preparing non-stoichiometric oxynitride nanopowder according to claim 2, wherein in step (1), the europium trioxide, tantalum pentoxide, urea and absolute ethanol are in a ratio of 2g to 4 g: 3g to 6 g: 2g to 10 g: 5mL to 50mL, and the ball milling time is 2h to 12 h.
4. The method for preparing a non-stoichiometric oxynitride nanopowder according to claim 1 wherein in step (4), the temperature is raised to 900-1400 ℃ at a rate of 10-30 ℃/min and held for 1-12 h.
5. The method for preparing non-stoichiometric oxynitride nano powder according to any one of claims 1 to 4, wherein in the step (3), the protective atmosphere is one or more of nitrogen, helium and argon, and the calcining process is: heating to 800-1400 ℃ at a heating rate of 50-500 ℃/min, preserving the heat for 0-30 min, and cooling to room temperature along with the furnace.
6. The method for preparing a non-stoichiometric oxynitride nanopowder according to claim 5 wherein in step (3), the temperature is raised to 900-1300 ℃ and maintained for 1-10 min.
7. The method for producing a non-stoichiometric oxynitride nanopowder according to any one of claims 1 to 4, wherein in the step (2), the drying temperature is 30 ℃ to 120 ℃ and the drying time is 1h to 72 h.
8. The method for preparing non-stoichiometric oxynitride nano powder according to claim 7, wherein the drying temperature in step (2) is 50 to 80 ℃ and the drying time is 6 to 48 hours.
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