CN108163821B - Preparation method of spherical titanium nitride - Google Patents
Preparation method of spherical titanium nitride Download PDFInfo
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- CN108163821B CN108163821B CN201810089384.7A CN201810089384A CN108163821B CN 108163821 B CN108163821 B CN 108163821B CN 201810089384 A CN201810089384 A CN 201810089384A CN 108163821 B CN108163821 B CN 108163821B
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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
- C01B21/076—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 titanium or zirconium or hafnium
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Abstract
the invention relates to a preparation method of spherical titanium nitride, in particular to a method for preparing spherical titanium nitride by utilizing radio frequency plasma powder production equipment. The invention aims to provide a preparation method of spherical titanium nitride with high nodularity. The method adopts radio frequency plasma equipment as a reaction device, titanium hydride powder as a raw material and nitrogen as a reaction gas, prepares the titanium nitride powder in one step, has short process flow and extremely short reaction time, greatly improves the production efficiency, has no impurity pollution to the obtained product, has simple preparation process and lower requirement on the raw material, and lays a foundation for realizing the industrial production of the spherical titanium nitride powder. The spherical titanium nitride powder prepared by the method has high spheroidization rate and nitridation rate. The preparation raw materials do not need to be crushed greatly, and the particle size of the product is small.
Description
Technical Field
the invention relates to a preparation method of spherical titanium nitride, in particular to a method for preparing spherical titanium nitride by utilizing radio frequency plasma powder production equipment.
Background
The metal compound TiN has many excellent physical and chemical properties, excellent corrosion resistance, wear resistance and oxidation resistance, and has high melting point (3205 ℃) and hardness 1990 (x 9.8N/mm)2). TiN deposited on jewelry and lamps can achieve the beautiful effect and enhance the wear resistance, is a potential material for replacing the WC widely used at present, and can greatly reduce the cost of material application. The TiN compound has higher biocompatibility and also has high application value in the aspects of clinical medicine and oral medicine. Furthermore, TiN can be used for manufacturing crucibles, cutting tools, additives, etc. The application range and depth of TiN powder are not matched with the excellent performance of TiN powder, and the TiN powder is to be researched and developed by people, so that the TiN powder can be used as a new material in the century.
With the continuous and deep research on TiN, more and more methods are used for preparing TiN powder. The conventional TiN powder preparation method comprises the following steps: TiN powder obtained by a metal titanium powder nitriding method, a titanium dioxide carbothermic reduction nitriding method, a gas phase method and the like has irregular shapes, poor flowability, great discount on service performance, low nitriding rate, long nitriding time, wide particle size range and high energy consumption. To date, there has been no effective solution covering the above problems.
Compared with non-spherical titanium nitride powder, the mechanical properties of spherical titanium nitride are the same in all directions, and products with excellent properties are more easily obtained in powder metallurgy and 3D printing. Therefore, a preparation method of spherical titanium nitride with simple preparation process and high spheroidization rate is urgently needed.
Patent 200410072553.4 discloses a method for reactive plasma spraying of nanocrystalline titanium nitride powder, which uses a plasma spray gun for spraying, and specifically comprises the following main steps: titanium powder is filled into a powder feeder, mixed ion gas is fed, nitrogen is introduced into a reaction chamber, the titanium powder is fed into flame flow, and the flame flow is sprayed and collected into a container containing water. The preparation process is complex and the equipment requirement is high. More importantly, pure titanium powder is easily oxidized in the air to form titanium oxide. This is disadvantageous for nitriding. In addition, the spontaneous combustion danger of the pure titanium powder is great, and the production safety requirement is higher. Titanium powder is fed into flame flow, and energy loss is large in the process of spraying and collecting the titanium powder into a container containing water. And the sphericity of the obtained titanium nitride is not good, and the spheroidization rate needs to be further improved.
Disclosure of Invention
Aiming at the defects, the technical problem to be solved by the invention is to provide a preparation method of spherical titanium nitride, which has simple preparation process and high nodularity.
The preparation method of the spherical titanium nitride is prepared by adopting radio frequency plasma equipment, and specifically comprises the following steps:
a. Arcing: argon is used as ionized gas for arc starting, and nitrogen is introduced from a protective gas inlet of the radio frequency plasma equipment; controlling the working voltage of the radio frequency plasma equipment to be 5-15 kV, and controlling the power to be 30-200 kW;
b. Feeding: and after the arc is stabilized, controlling the flow ratio of the introduced argon to the introduced nitrogen to be 1: 20-10: 1, and then feeding titanium hydride powder by a feeding device to obtain the spherical titanium nitride.
Preferably, in the step a, after the arc is stabilized, the ionized gas is changed into a mixed gas of argon and nitrogen.
Preferably, in the mixed gas of argon and nitrogen, the volume ratio of argon to nitrogen is 1: 5-10: 1.
Further preferably, in the mixed gas of argon and nitrogen, the volume ratio of argon to nitrogen is preferably 1:2 to 3: 1.
Preferably, in the step b, the particle size of the titanium hydride powder is 10-400 μm.
Preferably, the titanium hydride powder is fed in a vibration mode, and the amplitude of the titanium hydride powder is 10-80%.
Compared with the prior art, the invention has the following beneficial effects:
The invention adopts radio frequency plasma equipment as a reaction device, titanium hydride powder as a raw material and nitrogen as a reaction gas to prepare the titanium nitride powder in one step, has short process flow and extremely short reaction time, greatly improves the production efficiency, has no impurity pollution to the obtained product, has simple preparation process and lower requirement on the raw material, and lays a foundation for realizing the industrial production of the spherical titanium nitride powder.
The spherical titanium nitride powder prepared by the method has high spheroidization rate and nitridation rate. The preparation raw materials do not need to be crushed greatly, and the particle size of the product is small.
the method is not only suitable for preparing the spherical titanium nitride powder, but also suitable for preparing the spherical zirconium nitride powder and other nitride ball powder.
drawings
FIG. 1 is an XRD pattern of titanium nitride prepared according to the present invention.
FIG. 2 is an SEM image of titanium nitride prepared according to the present invention.
Detailed Description
The preparation method of the spherical titanium nitride is prepared by adopting radio frequency plasma equipment, and specifically comprises the following steps:
a. Arcing: argon is used as ionized gas for arc starting, and nitrogen is introduced from a protective gas inlet of the radio frequency plasma equipment; controlling the working voltage of the radio frequency plasma equipment to be 5-15 kV, and controlling the power to be 30-200 kW;
b. Feeding: after the arc is stabilized, controlling the flow ratio of the introduced argon to the introduced nitrogen to be 1: 20-10: 1, then feeding titanium hydride powder by a feeding device, and directly nitriding the titanium hydride powder while dehydrogenating and spheroidizing the titanium hydride powder in a plasma torch to obtain semi-molten titanium nitride;
c. Spheroidizing: the semi-molten titanium nitride is cooled and solidified into a spherical shape under the action of surface tension.
The spheroidizing technology of the radio frequency plasma powder is the prior art, and the principle is that under the action of a high-frequency power supply, inert gas is ionized to form stable high-temperature inert gas plasma; the raw material with irregular shape is fed into a plasma torch through a feeding device, absorbs a large amount of heat in high-temperature plasma, the surface of the raw material is rapidly melted, the raw material enters a reactor at a very high speed, the raw material is rapidly cooled in an inert atmosphere, and the raw material is cooled and solidified into spherical powder under the action of surface tension. The invention realizes dehydrogenation and spheroidization of titanium hydride powder in the plasma torch and direct nitridation at the same time by controlling the voltage and power of the radio frequency plasma device and parameters such as specific gas, specific gas flow and the like, so as to obtain the spherical titanium nitride. The reaction principle is as follows:
TiH2＝Ti+H2
2Ti+N2＝2TiN
in the method, the two reactions are carried out in one step under the condition of a radio frequency plasma high-temperature field in which argon and nitrogen are introduced. Firstly, argon is introduced from the center of the radio frequency plasma device, namely an ionized gas inlet, and nitrogen is introduced from the edge of the radio frequency plasma device, namely a protective gas inlet. Thus, the argon flow is easy to generate plasma flow to decompose the titanium hydride material at high temperature. The nitrogen is introduced from the edge of the radio frequency plasma powder production equipment, so that the nitridation reaction is more complete. The titanium nitride obtained by the method has high spheroidization rate and nitridation rate, and spheroidization and nitridation are carried out simultaneously, so that the production efficiency is greatly improved.
In order to improve the spheroidization rate, preferably, in the step a, argon is used as ionized gas for arc starting to obtain argon arc, after the argon arc is stabilized, the ionized gas is changed into mixed gas of argon and nitrogen, and at this time, an argon-nitrogen arc is formed. Nitrogen ionization in the plasma torch is used as a reaction heat source and a reactant, and the nitrogen ionization and the titanium powder react at high temperature to directly obtain spherical titanium nitride powder, so that the reaction energy consumption can be saved, and the product purity and the spheroidization rate can be improved.
More preferably, in the mixed gas of argon and nitrogen, the volume ratio of argon to nitrogen is 1: 5-10: 1, and more preferably, the volume ratio of argon to nitrogen is 1: 2-3: 1. When the ionized gas is mixed gas, the flow ratio of the total introduced argon to the total introduced nitrogen still needs to be controlled to be 1: 20-10: 1. In the invention, the unit of flow is m no matter nitrogen or argon3/h。
The particle size of the titanium hydride powder is suitable for the invention, preferably, in the step b, the particle size of the titanium hydride powder is 40-100 μm.
Preferably, the titanium hydride powder is fed in a vibration mode, the amplitude of the vibration is 10-80%, so that the reaction of the titanium hydride powder is more complete, and the nitridation rate is improved.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
example 1
And producing the spherical titanium nitride powder by adopting radio frequency plasma powder production equipment. The amplitude of a feeding device of the radio frequency plasma powder production equipment is set to be 20%, the working voltage is 10.5kV, and the power is 48 kW. Introducing nitrogen into the side gas (namely a protective gas inlet), introducing argon into the middle gas (namely an ionized gas inlet), starting arc, introducing mixed gas of the argon and the nitrogen after the arc is stabilized, controlling the ratio of the nitrogen flow to the argon flow to be 2:1, feeding, reacting for 5min, and collecting to obtain the spherical titanium nitride powder. The XRD spectrum is shown in figure 1, and the SEM spectrum is shown in figure 2. The spheroidization rate reaches 80 percent, and the nitridation rate is 83 percent.
Wherein, the spheroidization rate is obtained by observing the spheroidization quantity of the appearance by adopting a scanning electron microscope. And the nitridation rate is obtained by measuring the surface of the sample by an energy spectrometer and combining the analysis result of an X-ray diffractometer.
Example 2
And producing the spherical titanium nitride powder by adopting radio frequency plasma powder production equipment. The amplitude of a feeding device of the radio frequency plasma powder production equipment is set to be 22%, the working voltage is 11.5kV, and the power is 55 kW. Nitrogen was introduced "as a side gas" (i.e., the shielding gas inlet), argon was introduced as a middle gas "(i.e., the ionized gas inlet) to initiate an arc, and the ratio of the nitrogen flow to the argon flow was 1: 1. and (3) after the arc is stabilized, feeding titanium hydride, reacting for 5min, and collecting, wherein the mass of the titanium nitride powder is measured to be 27 g. The XRD pattern is similar to that of figure 1, and the SEM pattern is similar to that of figure 2. The spheroidization rate reaches 82 percent, and the nitridation rate is 76 percent.
Example 3
And producing the spherical titanium nitride powder by adopting radio frequency plasma powder production equipment. The amplitude of a feeding device of the radio frequency plasma powder production equipment is set to be 24%, the working voltage is 8kV, and the power is 40 kW. Introducing nitrogen into the side gas (namely a protective gas inlet), introducing argon into the middle gas (namely an ionized gas inlet) for arc striking, introducing mixed gas of the argon and the nitrogen after the arc is stabilized, wherein the ratio of the nitrogen flow to the argon flow is 3:2, feeding, reacting for 5min, and collecting, wherein the mass of the titanium nitride powder is 28 g. The XRD pattern is similar to that of figure 1, and the SEM pattern is similar to that of figure 2. The spheroidization rate reaches 88 percent, and the nitridation rate is 78 percent.
Example 4
And producing the spherical titanium nitride powder by adopting radio frequency plasma powder production equipment. The amplitude of a feeding device of the radio frequency plasma powder production equipment is set to be 10%, the working voltage is 15kV, and the power is 200 kW. Introducing nitrogen into the side gas (namely a protective gas inlet), introducing argon into the middle gas (namely an ionized gas inlet) for arc striking, introducing mixed gas of the argon and the nitrogen after the arc is stabilized, wherein the ratio of the nitrogen flow to the argon flow is 3:20, feeding, reacting for 5min, and collecting, wherein the mass of the titanium nitride powder is 19 g. The XRD pattern is similar to that of figure 1, and the SEM pattern is similar to that of figure 2. The spheroidization rate reaches 91 percent, and the nitridation rate is 56 percent.
Example 5
and producing the spherical titanium nitride powder by adopting radio frequency plasma powder production equipment. The amplitude of a feeding device of the radio frequency plasma powder production equipment is set to be 80%, the working voltage is 12kV, and the power is 60 kW. Introducing nitrogen into the side gas (namely a protective gas inlet), introducing argon into the middle gas (namely an ionized gas inlet), starting arc, introducing mixed gas of the argon and the nitrogen after the arc is stabilized, wherein the ratio of the nitrogen flow to the argon flow is 9:10, feeding, reacting for 5min, and collecting, wherein the mass of the titanium nitride powder is 42 g. The XRD pattern is similar to that of figure 1, and the SEM pattern is similar to that of figure 2. The spheroidization rate reaches 81 percent, and the nitridation rate is 68 percent.
Claims (5)
1. The preparation method of the spherical titanium nitride is characterized by comprising the following steps: the preparation method is prepared by adopting radio frequency plasma equipment, and specifically comprises the following steps:
a. Arcing: argon is used as ionized gas for arc starting, and nitrogen is introduced from a protective gas inlet of the radio frequency plasma equipment; controlling the working voltage of the radio frequency plasma equipment to be 5-15 kV, and controlling the power to be 30-200 kW;
b. Feeding: after the arc is stabilized, controlling the flow ratio of the introduced argon to the introduced nitrogen to be 1: 20-10: 1, and then feeding titanium hydride powder by a feeding device to obtain spherical titanium nitride, wherein the titanium hydride powder is fed in a vibration mode, and the amplitude of the titanium hydride powder is 10-80%.
2. The method for preparing spherical titanium nitride according to claim 1, wherein: and a, after the arc is stabilized, changing the ionized gas into a mixed gas of argon and nitrogen.
3. The method for preparing spherical titanium nitride according to claim 2, wherein: in the mixed gas of argon and nitrogen, the volume ratio of argon to nitrogen is 1: 5-10: 1.
4. The method for preparing spherical titanium nitride according to claim 3, wherein: in the mixed gas of argon and nitrogen, the volume ratio of argon to nitrogen is 1: 2-3: 1.
5. the method for producing spherical titanium nitride according to any one of claims 1 to 4, characterized in that: in the step b, the particle size of the titanium hydride powder is 10-400 μm.
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| CN110157937B (en) * | 2019-04-09 | 2021-03-26 | 中国科学院金属研究所 | Method for preparing titanium nitride block with controllable components |
| CN111620313B (en) * | 2020-06-09 | 2022-09-06 | 合肥中航纳米技术发展有限公司 | Process for preparing nano titanium nitride powder by chemical vapor deposition method |
| CN114920218B (en) * | 2022-04-28 | 2024-01-05 | 湖南天际智慧材料科技有限公司 | Preparation process of nitride nano or submicron powder material |
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