CN109835875B - Method for preparing nano titanium nitride powder by normal pressure chemical vapor deposition method - Google Patents

Method for preparing nano titanium nitride powder by normal pressure chemical vapor deposition method Download PDF

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CN109835875B
CN109835875B CN201910276334.4A CN201910276334A CN109835875B CN 109835875 B CN109835875 B CN 109835875B CN 201910276334 A CN201910276334 A CN 201910276334A CN 109835875 B CN109835875 B CN 109835875B
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titanium nitride
titanium
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chemical vapor
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CN109835875A (en
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葛万银
常哲
焦思怡
徐美美
张塨凡
施金豆
高文兴
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Shenzhen Wanzhida Technology Co ltd
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a method for preparing nano titanium nitride powder by a normal pressure chemical vapor deposition method, which comprises the steps of fully mixing a titanium source and a nitrogen source and grinding; and then putting the ground powder into a tubular furnace, heating the tubular furnace to a specified temperature in an inert atmosphere and a reducing atmosphere, preserving the heat, and cooling to room temperature after the reaction is finished to obtain gray black powder, namely the target product TiN. The invention adopts the chemical vapor deposition method to synthesize the high-purity nano titanium nitride powder, avoids the reaction process with high temperature and high time consumption, requires less raw materials for the preparation method, has less synthesis steps, and is convenient and simple to operate in the whole related process, low in cost and easy for large-scale production.

Description

Method for preparing nano titanium nitride powder by normal pressure chemical vapor deposition method
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a method for preparing nano titanium nitride powder by using a normal-pressure chemical vapor deposition method.
Background
Nitrogen is the most abundant element in air, but since nitrogen is chemically very stable, it is difficult to chemically react, but under some specific conditions, it may form nitrides with some transition elements, such as titanium nitride, vanadium nitride, zirconium nitride, etc., among which titanium nitride is studied and paid much attention. Titanium nitride has many excellent physical and chemical properties, such as high melting point (2950 ℃), high hardness, 8-9 mohs hardness, high thermochemical stability and excellent heat conduction and electrical conductivity, and in addition, titanium nitride also has excellent magnetic and optical properties, and based on the excellent properties of titanium nitride, titanium nitride is widely applied to various fields, mainly applied to the fields of high temperature resistance, wear resistance, electrode materials in the photoelectric industry, the field of catalysis and the like.
At present, there are many methods for preparing titanium nitride, including (1) direct nitridation of metallic titanium powder and (2) microwave carbon nitridationA thermal reduction method, (3) a titanium oxide reduction nitridation method, (4) a self-propagating high-temperature synthesis method, (5) a solvothermal synthesis method, (6) a mechanical alloying method, (7) a sol-gel method, and (8) a chemical vapor deposition method. All the preparation methods have respective advantages and disadvantages, but in general, no preparation method can quickly and simply prepare the titanium nitride nano powder, so that the search for a quick and simple preparation method is very important. The direct titanium powder nitriding method is characterized in that titanium powder reacts with nitrogen or ammonia gas to generate titanium nitride, the reaction temperature is 1200-1400 ℃, the method is relatively simple to operate, but the method has the defects that the reaction time is too long, about 30 hours is needed, and the powder sintering phenomenon is easily generated in the reaction process. The microwave carbothermic process is an oxidation-reduction reaction carried out at a relatively high temperature using inorganic carbon as a reducing agent, and has the advantages of low reaction temperature and short synthesis period. The titanium oxide reduction nitridation method is TiO2As raw material, reducing agent is carbon graphite in N2TiN is generated by reaction under the atmosphere, but the TiN prepared by the method has low purity, higher contents of O and C, higher reaction temperature and longer reaction time. The self-propagating high-temperature synthesis method is to ignite titanium powder (blank) and ammonia gas under certain pressure to obtain titanium nitride. The solvent thermal synthesis method is to add reactants and organic solvent into a closed system and control the reaction temperature and pressure to obtain the product. The method prepares titanium nitride as TiH2And NH4Cl is used as a raw material and is added into H at 500-800 DEG C2And N2The mixed gas is reacted to obtain the titanium nitride. The mechanical alloying method is to put titanium powder in ammonia gas and nitrogen gas atmosphere, and then ball milling is carried out by using a high-energy ball mill to obtain the nano titanium nitride. The sol-gel method is that the compound containing high chemical activity component is used as precursor, these raw materials are uniformly mixed in liquid phase, and undergone the processes of hydrolysis and condensation chemical reaction to form stable transparent sol system in the solution, the sol is undergone the process of ageing and slow polymerization between colloidal particles to form gel with three-dimensional network structure, then the gel is undergone the process of gelation treatmentThe material with molecular or even nano-substructure can be prepared by drying, sintering and curing. Zheng Yajie et al use this method to prepare titanium nitride powder. The chemical vapor deposition method is to generate titanium nitride with higher purity at 1100-1500 ℃ by taking titanium tetrachloride and ammonia gas as raw materials under hydrogen reduction. The existing scheme is that titanium dioxide, metal soluble chloride or hydrate thereof and melamine are mixed and ball-milled according to a certain mass, and then the mixture is put into a tubular furnace to react for 1-4 hours at 900-1400 ℃ to obtain the flaky titanium nitride nano material. The method has over-high reaction temperature and over-long reaction time, so that the method is particularly important for preparing the titanium nitride nano material with lower cost and simpler operation method.
At present, the preparation of TiN nano-materials by using a chemical vapor deposition method has two technical difficulties. First, Ti is easily oxidized to titanium dioxide at high temperature, which requires the reaction system to be in an oxygen-free condition, and usually requires the reaction to be carried out in an inert atmosphere. Secondly, although the melamine is synthesized by chemical vapor deposition, the reactant melamine can be decomposed at high temperature to generate highly toxic cyanide gas, which is not good for the health of experimenters.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing nano titanium nitride powder by using an atmospheric pressure chemical vapor deposition method, which has the advantages of low cost, less required raw materials, less synthesis steps, short time and easy large-scale production, and aims to overcome the defects in the prior art.
The invention adopts the following technical scheme:
a method for preparing nanometer titanium nitride powder by normal pressure chemical vapor deposition method comprises mixing titanium source and nitrogen source thoroughly and grinding; and then putting the ground powder into a tubular furnace, heating the tubular furnace to 600-1200 ℃ in an inert atmosphere and a reducing atmosphere, preserving the heat for 20-60 min, and cooling to room temperature after the reaction is finished to obtain the target gray-black TiN powder.
Specifically, the titanium source is titanium powder, and the nitrogen source is ammonium chloride.
Further, the mass ratio of the titanium source to the nitrogen source is 1: (8-15).
Specifically, the vacuum degree in the tube furnace is lower than 100 Pa.
Specifically, the heating rate of the tubular furnace is 2-10 ℃/min.
Specifically, the inert gas is high-purity argon, and the flow rate is 50-400 sccm.
Specifically, the reducing gas is hydrogen, and the flow rate is 20-80 sccm.
Specifically, the size of the prepared TiN powder particles is 20-200 nm.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention adopts a chemical vapor deposition method to fully mix and grind a titanium source and a nitrogen source; then putting the ground powder into a tube furnace, and vacuumizing the tube furnace; and heating the tube furnace to a specified temperature in an inert atmosphere and a reducing atmosphere, preserving heat, and cooling to room temperature after the reaction is finished to obtain black powder, namely the target product TiN. Compared with the conventional synthesis method, the method for synthesizing the high-purity titanium nitride nanopowder by adopting the chemical vapor deposition method is simpler, more efficient and safer, has the great advantage of avoiding a high-temperature and high-time-consuming reaction process, is convenient and simple to operate in the whole process, and only needs to keep the temperature at 600-1200 ℃ for 20-60 min, and is short in time and high in repeatability in the whole experimental process.
Furthermore, titanium powder has high activity at high temperature, and is easy to generate nitridation reaction to generate titanium nitride; and the titanium powder is an important industrial raw material, and the raw material is easy to obtain, thereby laying a foundation for subsequent batch production. The ammonium chloride is used as a nitrogen source, so that the price is low, and the cost is reduced for subsequent chemical industrial production; and the ammonium chloride is easily decomposed at high temperature to react with the titanium powder.
Further, the vacuum degree is lower than 100Pa, so that the oxygen content in the furnace is reduced, and the titanium powder and the residual oxygen can be effectively prevented from reacting at high temperature to generate titanium dioxide.
Furthermore, high-purity argon is used as inert gas, so that oxygen in the atmosphere is prevented from entering the furnace, and the titanium powder and the residual oxygen are effectively prevented from reacting at high temperature.
Furthermore, hydrogen is used as reducing gas, so that titanium oxide with partially oxidized surface can be effectively reduced into simple substance titanium, and titanium nitride with higher purity can be obtained. The flow rate is set so that the reduction of the surface titanium oxide cannot be achieved by a too low flow rate, and the flow rate is set so that the cost is increased and the risk factor is increased.
In conclusion, the method for synthesizing the high-purity titanium nitride nanopowder by adopting the chemical vapor deposition method is simpler, more efficient and safer.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is an XRD pattern of the product produced in example 1 of the present invention;
FIG. 2 is an SEM image of a product prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of the product prepared in example 2 of the present invention;
FIG. 4 is an SEM image of a product prepared in example 2 of the present invention;
FIG. 5 is an XRD pattern of the product prepared in example 3 of the present invention;
FIG. 6 is an SEM image of a product prepared in example 3 of the present invention;
FIG. 7 is an XRD pattern of the product prepared in example 4 of the present invention;
FIG. 8 is an SEM image of a product prepared according to example 4 of the present invention;
FIG. 9 is an XRD pattern of the product prepared in example 5 of the present invention;
FIG. 10 is an SEM image of a product prepared in example 4 of the present invention.
Detailed Description
The invention provides a method for preparing nano titanium nitride powder by a normal pressure chemical vapor deposition method, which comprises the steps of fully mixing a titanium source and a nitrogen source and grinding; and then putting the ground powder into a tubular furnace, heating the tubular furnace to 600-1200 ℃ in an inert atmosphere and a reducing atmosphere, preserving the heat for 20-60 min, and cooling to room temperature after the reaction is finished to obtain gray black powder, namely the target product TiN. The invention adopts the chemical vapor deposition method to synthesize the high-purity nano titanium nitride powder, avoids the reaction process with high temperature and high time consumption, requires less raw materials for the preparation method, has less synthesis steps, and is convenient and simple to operate in the whole related process, low in cost and easy for large-scale production.
The invention relates to a method for preparing nano titanium nitride powder by a normal pressure chemical vapor deposition method, which comprises the following steps:
s1, fully mixing and grinding a titanium source and a nitrogen source, wherein the titanium source is titanium powder, the nitrogen source is ammonium chloride, and the mass ratio of the titanium source to the nitrogen source is 1: (8-15);
s2, putting the ground powder into a tube furnace, and vacuumizing the tube furnace to ensure that the tube furnace is in an oxygen-free environment, wherein the vacuumizing vacuum degree of the tube furnace is lower than 100 Pa;
s3, introducing inert gas and reducing gas into the tube furnace, heating to 600-1200 ℃ at a heating rate of 2-10 ℃/min, and preserving heat for 20-60 min;
the inert gas is high-purity argon with the flow rate of 50-400 sccm, and the reducing gas is hydrogen with the flow rate of 20-80 sccm.
And S4, cooling to room temperature after heat preservation is finished, and obtaining the high-purity nano titanium nitride powder.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Firstly, fully mixing 1mmol of titanium powder and 15mmol of ammonium chloride, grinding, putting the ground powder into a tube furnace, and vacuumizing the tube furnace for 20 min;
then, introducing argon and hydrogen, wherein the flow of the argon is 50sccm, the flow of the hydrogen is 20sccm, heating the tube furnace to 1200 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 20min to finish the growth of the nanocrystalline, then stopping heating, and cooling to room temperature to obtain black powder, namely the target product.
Fig. 1 is an X-ray diffraction spectrum of TiN nanopowder grown according to example 1, without impurity peaks appearing, indicating that the product is pure TiN.
FIG. 2 is an SEM image of TiN nanopowder grown according to example 1, showing that the size of TiN particles is 100-200 nm and agglomeration occurs between the particles.
Example 2
Firstly, fully mixing 1mmol of titanium powder and 8mmol of ammonium chloride, grinding, putting the ground powder into a tube furnace, and vacuumizing the tube furnace for 20 min;
then, introducing argon and hydrogen, wherein the flow of the argon is 400sccm, the flow of the hydrogen is 80sccm, heating the tubular furnace to 900 ℃ at the heating rate of 3 ℃/min, preserving the temperature for 60min to finish the growth of the nanocrystalline, then stopping heating, and cooling to room temperature to obtain black powder, namely the target product.
Fig. 3 is an X-ray diffraction spectrum of TiN nano-powder grown according to example 2, and it can be seen that the main component of the product is TiN and the crystallinity is good.
FIG. 4 is an SEM image of TiN nanopowder grown according to example 2, and it can be seen that TiN particle size is 50-100 nm.
Example 3
Firstly, fully mixing 1mmol of titanium powder and 10mmol of ammonium chloride, grinding, putting the ground powder into a tube furnace, and vacuumizing the tube furnace for 20 min;
then, introducing argon and hydrogen, wherein the flow of the argon is 200sccm, the flow of the hydrogen is 40sccm, heating the tubular furnace to 800 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 30min to finish the growth of the nanocrystalline, then stopping heating, and cooling to room temperature to obtain black powder, namely the target product.
Fig. 5 is an X-ray diffraction spectrum of TiN nano-powder grown according to example 3, and it can be seen that the main component of the product is TiN and the crystallinity is good.
FIG. 6 is an SEM image of TiN nanopowder grown according to example 3, showing that the TiN particle size is 50-100 nm and agglomeration occurs between particles.
Example 4
Firstly, fully mixing 1mmol of titanium powder and 11mmol of ammonium chloride, grinding, putting the ground powder into a tube furnace, and vacuumizing the tube furnace for 20 min;
then, introducing argon and hydrogen, wherein the flow of the argon is 200sccm, the flow of the hydrogen is 40sccm, heating the tube furnace to 700 ℃ at the heating rate of 8 ℃/min, preserving the temperature for 30min to finish the growth of the nanocrystalline, then stopping heating, and cooling to room temperature to obtain black powder, namely the target product.
Fig. 7 is an X-ray diffraction spectrum of TiN nanopowder grown in accordance with example 4, without impurity peaks appearing, indicating that the product is pure TiN.
FIG. 8 is an SEM image of TiN nanopowder grown according to example 4, showing that the size of TiN particles is 20-50 nm and agglomeration occurs between particles.
Example 5
Firstly, fully mixing 1mmol of titanium powder and 13mmol of ammonium chloride, grinding, putting the ground powder into a tube furnace, and vacuumizing the tube furnace for 20 min;
then, introducing argon and hydrogen, wherein the flow of the argon is 200sccm, the flow of the hydrogen is 40sccm, heating the tubular furnace to 600 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 30min to finish the growth of the nanocrystalline, then stopping heating, and cooling to room temperature to obtain black powder, namely the target product.
FIG. 9 is an X-ray diffraction pattern of TiN nano-powder grown according to example 5, and it can be seen that TiN is a main component of the product and that agglomeration occurs between particles.
Fig. 10 is an SEM morphology photograph of TiN nano-powder grown according to example 5, and it can be seen that the TiN particles were seriously agglomerated.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (1)

1. A method for preparing nanometer titanium nitride powder by normal pressure chemical vapor deposition is characterized in that 1mmol of titanium source and 11mmol of nitrogen source are fully mixed and ground, the titanium source is titanium powder, and the nitrogen source is ammonium chloride; and putting the ground powder into a tubular furnace, vacuumizing the tubular furnace for 20min, heating the tubular furnace to 700 ℃ in an inert atmosphere and a reducing atmosphere, wherein the vacuum degree in the tubular furnace is lower than 100Pa, the heating rate of the tubular furnace is 8 ℃/min, the inert gas is high-purity argon, the flow rate is 200sccm, the reducing gas is hydrogen, the flow rate is 40sccm, the temperature is kept for 30min, cooling to room temperature after the reaction is finished, and obtaining a gray-black target product TiN powder, wherein the particle size of the TiN powder is 20 nm.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101759163A (en) * 2009-12-29 2010-06-30 山东大学 Process for preparing porous titanium nitride at low temperature
CN102910910A (en) * 2012-11-16 2013-02-06 四川理工学院 Method for preparing micro-nano titanium carbonitride powder with controllable carbon-nitrogen ratio by adopting solid state nitrogen source

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US6451692B1 (en) * 2000-08-18 2002-09-17 Micron Technology, Inc. Preheating of chemical vapor deposition precursors
JP2010084181A (en) * 2008-09-30 2010-04-15 Tokyo Electron Ltd Exhaust system structure of film deposition device, film deposition device and method for treating exhaust gas
CN106586984B (en) * 2016-11-25 2018-06-19 湖北工程学院 The method that chemical vapour deposition technique prepares sheet titanium nitride nano material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101759163A (en) * 2009-12-29 2010-06-30 山东大学 Process for preparing porous titanium nitride at low temperature
CN102910910A (en) * 2012-11-16 2013-02-06 四川理工学院 Method for preparing micro-nano titanium carbonitride powder with controllable carbon-nitrogen ratio by adopting solid state nitrogen source

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