CN1396111A - Process for preparing nano cubic niobium nitride powder - Google Patents
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- CN1396111A CN1396111A CN 02136245 CN02136245A CN1396111A CN 1396111 A CN1396111 A CN 1396111A CN 02136245 CN02136245 CN 02136245 CN 02136245 A CN02136245 A CN 02136245A CN 1396111 A CN1396111 A CN 1396111A
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Abstract
A process for preparing cubic niobium nitride nanometre powder from amorphous Nb2O5 powder as raw material features that the said amorphous Nb2O5 is directly nitrided at high temp. in a tubular reactor under ammonia atmosphere. Its advantages are controllable particle size (15-40 nm) by change of the process conditions, simple process and low cost.
Description
Technical Field
The invention relates to a preparation method of cubic phase nano niobium nitride powder, which can be used for preparing high-performance ceramics, wear-resistant materials and superconducting materials. Belongs to the field of nanometer material.
Background
Metal nitrides have high corrosion resistance and excellent high-temperature mechanical properties, and have recently received attention from material researchers and business persons. Due to its potential application prospect, the preparation technology of ultrafine particles of metal nitrides is regarded by people in various fields. Niobium nitride has high relative density (8.47), high melting point (2300 ℃), high hardness (Mohs hardness of 8 and microhardness of 14.3GPa), and superconductivity. As a new material, niobium nitride has wide application prospect.
The nano niobium nitride is a niobium nitride product with the grain size within 100nm, and the nano niobium nitride can be used for replacing micron-sized niobium nitride to reduce the sintering temperature and improve the sintering performance; the reinforcing phase can effectively improve the strength and the wear resistance of metal and ceramic matrixes; can also be used as a superAnd (3) conducting materials. Therefore, the nano niobium nitride has great practical value. Industrially, niobium nitride is generally produced by a direct method and a reduction method. The direct method is that metal niobium and nitrogen are used as raw materials, the crushed metal niobium is sent into a nitriding furnace, and then nitrogen is introduced to react for 1-2h at the temperature of 700-. The reduction method is to prepare niobium nitride by using niobium pentoxide and nitrogen as raw materials in the presence of carbon. Adding carbon powder into the crushed niobium pentoxide powder, fully mixing the powder, sending the mixture into a reduction furnace, introducing hydrogen and nitrogen, and carrying out reduction reaction for 2 hours at 1250 ℃ to obtain the niobium nitride. The biggest defects of the two reactions are that the preparation of the superfine powder is difficult, the reduction method needs secondary carbon removal, the process is complex, and the product contains a certain amount of impurities. In recent years, researchers at home and abroad have developed new methods for preparing nitride ultrafine powder. The ball milling technology is a process for fully mixing and refining raw materials under a certain atmosphere condition by powder of the raw materials, and therequired product material is finally obtained along with the progress of chemical reaction and the continuous formation of products in the process. Wuxue plumPp.40-46 in 1999 reported that the milling of pure metal powder was carried out under nitrogen atmosphere at a certain pressure by using a specially designed ball mill to prepare niobium nitride ultrafine powder, but the milling time was long, the abrasion of the milling medium had a certain influence on the product quality, the product contained a certain amount of impurities, and the production efficiency was low. Zhang et al reported in Journal of Materials Science Vol.26(1991) pp.3380-3385 that niobium nitride powder was prepared by combustion synthesis, but the particle size of the product was only in the micron range. The method for preparing the corresponding nano nitride powder by directly nitriding the nano oxide powder by ammonia gas is a new method for synthesizing the nano metal nitride powder. Recently we have reported in Journal of American Ceramic Society Vol.84(2001) No.11 pp.2710-2712 and Vol.85(2002) No.5 pp.1294-1296, respectively, as nano TiO2And Cr2O3Synthesizing nano TiN and CrN powder by using the raw materials. The preparation of nano NbN powder has been reported.
Disclosure of Invention
The invention aims to provide a method for preparing cubic-phase nano niobium nitride powder.
The object of the invention is thus achieved: firstly, taking niobium hydroxide as a starting raw material, dissolving the niobium hydroxide into concentrated sulfuric acid solution at a certain temperature, hydrolyzing to generate a precipitate, washing and drying to prepare niobium hydroxide powder, and calcining to obtain amorphous niobium pentoxide powder with a high specific surface area; then, the amorphous niobium pentoxide powder with highspecific surface area is nitrified in a tubular reaction furnace at high temperature under the condition of flowing ammonia gas to synthesize cubic phase nano niobium nitride powder.
It can be seen that the implementation can be divided into two major steps:
firstly, preparing amorphous niobium pentoxide powder with high specific surface area by a hydrolysis method; and secondly, nitriding the amorphous niobium pentoxide powder with high specific surface area to prepare cubic-phase nano niobium nitride powder. Now, the following are detailed respectively:
preparation of amorphous niobium pentoxide powder with high specific surface area
The invention takes niobium hydroxide as a starting material. Firstly, adding niobium hydroxide into a concentrated sulfuric acid solution with the acid water ratio of 3-5: 1, heating to dissolve the niobium hydroxide, and dropwise adding the niobium hydroxide into distilled water under the stirring of the rotation speed of 400-800 r/min to generate a precipitate. Filtering the precipitate, washing with distilled water to remove impurities until the pH value of the solution is close to 7; washing twice with absolute ethyl alcohol to remove water in the precipitate, avoiding the generation of hard agglomeration, obtaining amorphous niobium hydroxide powder with good dispersibility, drying and sieving the product, and calcining at the temperature of 300-500 ℃ for 1-2 hours to obtain the amorphous niobium pentoxide powder with high specific surface area. The precipitation temperature is 20-50 ℃, the precipitation time is 1-12 hours, the drying condition of the precipitation product is 100 ℃, the drying time is 12 hours, and the precipitation product is ground and sieved by a 200-mesh sieve.
Preparation of cubic phase nano niobium nitride powder
Putting the obtained amorphous niobium pentoxide powder with the high specific surface area into a quartz boat, putting the quartz boat into a tubular atmosphere furnace, introducing ammonia gas, heating to 650-800 ℃ at a flow rate of 0.5-5L/min, at a heating rate of 5-10 ℃/min, preserving the heat for 3-8 hours at the temperature, and naturally cooling to room temperature under flowing ammonia gas to obtain the nano niobium nitride powder. The grain diameter and the nitriding speed of the nano niobium nitride powder can be controlled by the reaction temperature; controlling the grain diameter of the nano niobium nitride powder by controlling the nitriding heat preservation time; the reaction time is shortened by controlling the flow rate of ammonia gas. Therefore, the selection of the three parameters has a crucial influence on the particle size and yield after reaction, and the reasonable selection of the three parameters is important for organic matching.
The reaction process is as follows: (2)
the preparation method of the nano niobium nitride powder provided by the invention is characterized by comprising the following steps:
1. the prepared nano niobium chromium nitride powder has small grain diameter, good dispersibility and purity of more than 95 percent.
2. The production process is simple, the required production equipment is simple, and the industrial production is easy to realize.
3. The ammonia gas is used as the nitriding agent in the production process, and the reaction is more facilitated and the safety is higher than that of using nitrogen gas and hydrogen gas as the nitriding agent.
Drawings
FIG. 1 is an X-ray diffraction chart of a niobium nitride powder obtained by nitriding at 650 ℃ for 8 hours.
FIG. 2 is a transmission electron micrograph of niobium nitride powder obtained by nitriding at 650 ℃ for 8 hours.
FIG. 3 is an X-ray diffraction chart of a niobium nitride powder obtained by nitriding at 700 ℃ for 3 hours.
FIG. 4 is a transmission electron micrograph of a niobium nitride powder obtained by nitriding at 700 ℃ for 3 hours.
FIG. 5 is an X-ray diffraction chart of a niobium nitride powder obtained by nitriding at 700 ℃ for 5 hours.
FIG. 6 is a transmission electron micrograph of a niobium nitride powder obtained by nitriding at 700 ℃ for 5 hours.
Detailed Description
Example 1
2.5g of niobium hydroxide was taken and dissolved in 100ml of a concentrated sulfuric acid solution having an acid water ratio of 3: 1 by heating. The solution was added dropwise to 2500ml of distilled water with stirring at 600 rpm, to produce a precipitate. Filtering the precipitate, washing with distilled water to remove anions, washing with anhydrous ethanol twice, drying the filter cake at 100 deg.C for 12 hr, grinding, sieving with 200 mesh sieve, calcining at 300 deg.C for 1 hr to obtain powder with specific surface area up to 191.8m2Amorphous niobium pentoxide powder per gram. Putting the prepared amorphous niobium pentoxide powder with high specific surface area into a quartz boat, putting the quartz boat into a tubular atmosphere furnace, introducing ammonia gas, heating to 650 ℃ at the flow rate of 1 liter/minute and the heating rate of 10 ℃/minute, preserving the heat for 8 hours at the temperature, and then naturally cooling to room temperature under flowing ammonia gas. Obtaining the nano niobium nitride powder. FIG. 1 is an X-ray diffraction diagram of the nano niobium nitride powder prepared in this example, which shows, in comparison with JCPDS card 38-1155: the powder is cubic phase niobium nitride, which shows that the high specific surface area amorphous niobium pentoxide powder is nitrided for 8 hours at 650 ℃ in ammonia gas flow, and the niobium nitride powder with the purity of more than 95 percent can be obtained, wherein three diffraction peaks in the figure are respectively the diffraction peaks of a niobium nitride (111) crystal face, a niobium nitride (200) crystal face and a niobium nitride (220) crystal face. FIG. 2 is a transmission electron micrograph showing that the particle size is about 15 nm.
Example 2
Amorphous niobium pentoxide powder with high specific surface area was prepared as described in example 1. Putting the prepared amorphous niobium pentoxide powder with high specific surface area into a quartz boat, putting the quartz boat into a tubular atmosphere furnace, introducing ammonia gas, heating to 700 ℃ at the flow rate of 1 liter/minute at the temperature of 10 ℃/minute, preserving the heat for 3 hours at the temperature, and naturally cooling to room temperature under flowing ammonia gas to obtain the nano niobium nitride powder. FIG. 3 is an X-ray diffraction pattern of the nano niobium nitride powder prepared in this example, which shows, in comparison with JCPDS card 38-1155: the powder is cubic phase niobium nitride, which shows that the high specific surface area amorphous niobium pentoxide powder is nitrided in ammonia gas flow at 700 ℃ for 3 hours to obtain the niobium nitride powder with the purity of more than 95 percent, wherein three diffraction peaks in the figure are respectively the diffraction peaks of a niobium nitride (111) crystal face, a niobium nitride (200) crystal face and a niobium nitride (220) crystal face. FIG. 4 is a transmission electron micrograph showing that the particle diameter is 15 to 20 nm.
Example 3
Amorphous niobium pentoxide powder with high specific surface area was prepared as described in example 1. Putting the prepared amorphous niobium pentoxide powder with high specific surface area into a quartz boat, putting the quartz boat into a tubular atmosphere furnace, introducing ammonia gas, heating to 700 ℃ at the flow rate of 1 liter/minute at the temperature of 10 ℃/minute, preserving the heat for 5 hours at the temperature, and naturally cooling to room temperature under flowing ammonia gas to obtain the nano niobium nitride powder. FIG. 5 is an X-ray diffraction pattern of the nano niobium nitride powder prepared in this example, which shows, in comparison with JCPDS card 38-1155: the powder is cubic phase niobium nitride, which shows that the amorphous niobium pentoxide powder with high specific surface area is nitrided for 5 hours at 700 ℃ in ammonia gas flow, the niobium nitride powder with the purity of more than 95 percent can be obtained, and three diffraction peaks in the figure are respectively the diffraction peaks of a niobium nitride (111) crystal face, a niobium nitride (200) crystal face and a niobium nitride (220) crystal face. FIG. 6 is a transmission electron micrograph showing that the particle diameter is about 25 nm.
Example 4
Amorphous niobium pentoxide powder with high specific surface area was prepared as described in example 1. Putting the prepared amorphous niobium pentoxide powder with high specific surface area into a quartz boat, putting the quartz boat into a tubular atmosphere furnace, introducing ammoniagas, heating to 750 ℃ at the flow rate of 1 liter/minute and the heating rate of 10 ℃/minute, preserving the heat for 3 hours at the temperature, and naturally cooling to room temperature under flowing ammonia gas to obtain the nano niobium nitride powder. X-ray diffraction studies showed that: the powder is cubic phase niobium nitride. The amorphous niobium pentoxide powder with high specific surface area is nitridized for 3 hours at 750 ℃ in ammonia gas flow, and the niobium nitride powder with the purity of more than 95 percent can be obtained. Transmission electron microscope observation shows that: the particle size is about 25 nm.
Example 5
Amorphous niobium pentoxide powder with high specific surface area was prepared as described in example 1. Putting the prepared amorphous niobium pentoxide powder with high specific surface area into a quartz boat, putting the quartz boat into a tubular atmosphere furnace, introducing ammonia gas, heating to 800 ℃ at the flow rate of 1 liter/minute at the temperature of 10 ℃/minute, preserving the heat for 3 hours at the temperature, and naturally cooling to room temperature under flowing ammonia gas to obtain the nano niobium nitride powder. X-ray diffraction studies showed that: the powder is cubic phase niobium nitride. The amorphous niobium pentoxide powder with high specific surface area is nitridized for 3 hours at 800 ℃ in ammonia gas flow, and the niobium nitride powder with the purity of more than 95 percent can be obtained. Transmission electron microscope observation shows that: the particle size is 30-40 nm.
Claims (7)
1. A method for preparing cubic phase nano niobium nitride is characterized by comprising the following steps:
(1) firstly, preparing amorphous niobium pentoxide powder withhigh specific surface area by a hydrolysis method;
(2) under the flowing ammonia atmosphere, the amorphous niobium pentoxide powder is directly nitrided to synthesize cubic phase nano niobium nitride powder with the granularity of 15-40 nm.
2. The method as claimed in claim 1, wherein the amorphous niobium pentoxide powder with high specific surface area is prepared by hydrolysis method by dissolving niobium hydroxide in concentrated sulfuric acid under normal pressure, adding dropwise into distilled water under stirring at 400-.
3. The method for preparing cubic nano niobium nitride as claimed in claim 2, wherein the precipitation temperature is 20 to 50 ℃ and the precipitation time is 1 to 12 hours; the drying temperature is 100 ℃, and the drying time is 12 hours.
4. The method for preparing cubic-phase nano niobium nitride as claimed in claim 2 or 3, wherein the acid water ratio of the concentrated sulfuric acid solution is 3-5: 1.
5. The method of claim 1, wherein the amorphous niobium pentoxide powder is directly nitrided under the following process parameters:
(1) the nitridation reaction temperature is controlled at 650-800 ℃;
(2) the flow of ammonia gas is 0.5-5L/min;
(3) nitriding and keeping the temperature for 3-8 hours.
6. The method for preparing cubic nano niobium nitride as claimed in claim 5, wherein the temperature rising rate of nitriding is 5 to 10 ℃/min; and naturally cooling to room temperature under flowing ammonia gas.
7. The method for preparing cubic phase nano niobium nitride as claimed in claim 5 or 6, wherein the particle size and nitriding speed of the nano niobium nitride powder are controlled by controlling the reaction temperature; controlling the particle size of the powder prepared by nitriding and preserving heat for a long time; the reaction time is shortened by controlling the flow rate of ammonia gas.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366538C (en) * | 2006-05-31 | 2008-02-06 | 中国科学院物理研究所 | Method for preparing lanthanide nitride using metal oxide |
| CN100383035C (en) * | 2006-05-31 | 2008-04-23 | 中国科学院物理研究所 | Method for preparing nitride using oxide |
| CN103107340A (en) * | 2013-01-24 | 2013-05-15 | 青岛克瑞化工有限公司 | Preparation method of lithium iron phosphate electric conduction agent |
| CN106315674A (en) * | 2016-08-17 | 2017-01-11 | 武汉科技大学 | Feather-like niobium pentoxide nanobelt as well as preparation method and application thereof |
| CN112746319A (en) * | 2019-10-29 | 2021-05-04 | 中国科学院福建物质结构研究所 | Porous niobium nitride single crystal material and preparation method and application thereof |
-
2002
- 2002-07-26 CN CNB021362459A patent/CN1166557C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366538C (en) * | 2006-05-31 | 2008-02-06 | 中国科学院物理研究所 | Method for preparing lanthanide nitride using metal oxide |
| CN100383035C (en) * | 2006-05-31 | 2008-04-23 | 中国科学院物理研究所 | Method for preparing nitride using oxide |
| CN103107340A (en) * | 2013-01-24 | 2013-05-15 | 青岛克瑞化工有限公司 | Preparation method of lithium iron phosphate electric conduction agent |
| CN106315674A (en) * | 2016-08-17 | 2017-01-11 | 武汉科技大学 | Feather-like niobium pentoxide nanobelt as well as preparation method and application thereof |
| CN106315674B (en) * | 2016-08-17 | 2017-10-27 | 武汉科技大学 | A kind of featheriness niobium pentoxide nano band and preparation method and application |
| CN112746319A (en) * | 2019-10-29 | 2021-05-04 | 中国科学院福建物质结构研究所 | Porous niobium nitride single crystal material and preparation method and application thereof |
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