CN108101009A - Titanium nitride nanopower high pressure liquid-phase synthesis process - Google Patents
Titanium nitride nanopower high pressure liquid-phase synthesis process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B21/0763—Preparation from titanium, zirconium or hafnium halides
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of titanium nitride nanopower high pressure liquid-phase synthesis process, belong to titanium nitride preparing technical field.The preparation method of the present invention comprises the following steps；Step A：Prepare reaction promoter, liquefied ammonia is added in into reaction promoter, treat liquefied ammonia with after reaction promoter layering, titanium tetrachloride being added in into reaction promoter, is chemically reacted under temperature A, pressure B, reaction is washed after terminating, and obtains nitridation titanium precursors；Step B：The nitridation titanium precursors that step A is obtained are roasted, obtain titanium nitride nanopower.Wherein：35 DEG C of ＜ temperature A≤30 DEG C, pressure B are 0.2MPa~1.5MPa.The preparation method of the present invention reduces energy consumption, and production cost is relatively low, the nitride powder purity of acquisition is high, particle uniformly, narrow particle size distribution, grain size be up to nanoscale.
Description
Technical field
The invention belongs to titanium nitride preparing technical field, more specifically to a kind of titanium nitride nanopower high pressure liquid
It is combined to method.
Background technology
Nitride powder is the base stock for preparing titanium nitride ceramic, is the key that influence titanium nitride ceramic performance, wherein
Nanoscale nitride powder is in black, and micron order nitride powder is in yellow.Titanium nitride has fusing point high, and chemical stability is good,
The good physicochemical properties such as hardness is big, and conductive, heat conduction and optical property are good, make it suffer from very important use in every field
On the way, especially in terms of cermet field and cash equivalent furnishing fields.Industry is more and more to the demand of titanium nitride powder,
Titanium nitride is not only cheap as coating price but also wear resistant corrosion resistant, its a lot of performances are better than vacuum coating.Titanium nitride ceramic is
A kind of high-performance ceramic, it has excellent physical and chemical performance, such as high intensity, high rigidity, high temperature resistant, wear-resistant, acid and alkali-resistance
It corrodes, in addition with series of advantages such as good electric conductivity, thermal conductivity, is widely used.
Nano titanium nitride powder refers to nitride powder of its crystallite dimension within 100 nanometers, and micron order is replaced with it
Nitride powder, which makees raw material, can reduce the sintering temperature of titanium nitride ceramic, improve sintering character；Enhancing phase is used it as, can be had
Effect improves metal, the intensity and toughness of ceramic matrix.Moreover, because particle is small, large specific surface area, can be dispersed in other materials
Conductive network is formed, greatly improves the electric conductivity of composite material.So Nano titanium nitride, which is one kind, has broad prospect of application
Material.
With the intensification both at home and abroad to titanium nitride research, the method for preparing titanium nitride is also more and more.Such as patent discloses
Number：CN 101298321A, publication date：On November 05th, 2008, invention and created name are：A kind of system of titanium nitride nanopower
Preparation Method, preparation method is passed through ammonia using nanotubed titanic acid as titanium source in tube furnace disclosed in this application, from room temperature
To 800-1000 DEG C of progress nitridation reaction 0.5-24H, up to titanium nitride nanopower after cooling.
At present, the preparation process of titanium nitride mainly has metallic titanium powder or TiH2Direct nitridation method, TiO2Carbothermal reduction-nitridation
Method, microwave carbothermal reduction method, chemical vapour deposition technique, self-propagating high-temperature synthesis, mechanical alloying method, SiCl4Liquid phase method etc..
Traditional solid phase method：Titanium nitride powder, this kind of method required temperature can be made in the processing of nitrogen high temperature in Titanium or titantium hydride
It is higher, and under high temperature titanium nitride reunite caking, particle is coarse, differed with the required nanoscale titanium nitride in present market compared with
Greatly, so also needing to Mechanical Crushing, total energy consumption is higher.Vapor phase method is the new technology to grow up nearest decades：With four chlorinations
Titanium, ammonia, hydrogen, nitrogen are raw material, carry out chemical reaction in the reactor and prepare titanium nitride powder, this kind of method reaction compared with
Soon, but reaction process is not easily controlled, and reaction temperature is higher, energy consumption is higher.
In conclusion the method that above method prepares nitride powder, all there are it is different degrees of the defects of, therefore need to research and develop
Go out a kind of preparation method of low-cost titanium nitride nanopower, to overcome drawbacks described above.
The content of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome above deficiency of the prior art, provide a kind of titanium nitride nanopower and its
Preparation method, the preparation method reduce energy consumption, and production cost is relatively low, the nitride powder purity of acquisition is high, particle uniformly, grain
Narrowly distributing, grain size are spent up to nanoscale.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention is：
The titanium nitride nanopower high pressure liquid-phase synthesis process of the present invention, comprises the following steps：
Step A：Prepare reaction promoter, liquefied ammonia is added in into reaction promoter, after treating the layering of liquefied ammonia and reaction promoter, to anti-
It answers and titanium tetrachloride is added in auxiliary agent, chemically reacted under temperature A, pressure B, reaction is washed after terminating, and obtains nitrogen
Change titanium precursors；
Step B：The nitridation titanium precursors that step A is obtained are roasted, obtain titanium nitride nanopower.
As further improvement of the present invention, the reaction promoter for nonpolar non-aromatic hydrocarbons or one kind in halogenated hydrocarbons or
The a variety of mixing of person.
As further improvement of the present invention, wherein, -35 DEG C of ＜ temperature A≤30 DEG C.
As further improvement of the present invention, the pressure B is 0.2MPa~1.5MPa.
As further improvement of the present invention, in step A chemical reaction start before, control titanium tetrachloride, liquefied ammonia and
The mass ratio of reaction promoter is 1：2~4：2~6.
As further improvement of the present invention, the temperature roasted in step B is 400 DEG C~1300 DEG C.
As further improvement of the present invention, the time roasted in step B is 400 DEG C~1300 DEG C.
As further improvement of the present invention, roasted in step B under protective atmosphere.
As further improvement of the present invention, the protective atmosphere is one kind in nitrogen, helium or argon gas.
As further improvement of the present invention, the reaction promoter is toluene or dichloromethane or toluene and dichloromethane
Mixture.
3. advantageous effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result：
(1) present invention is using the synthetically prepared titanium nitride nanopower of liquid phase method, and reaction is controllable, and reaction time is short, reaction temperature
Spend relatively mild, therefore energy consumption of reaction is relatively low, and technical process is simple and without large scale equipment, and production cost is relatively low, can industry greatly
Metaplasia is produced, and react gained nitride powder purity is high, particle uniformly, narrow particle size distribution, grain size up to nanoscale, future will
Progressively substitute traditional titanium nitride preparation method, there are bright prospects, and reaction promoter used in reacting, liquefied ammonia is recyclable follows
Ring uses.
(2) present invention is using one or more kinds of mixing in nonpolar non-aromatic hydrocarbons or halogenated hydrocarbons as reaction promoter, into
Titanium tetrachloride is dissolved in more than reaction promoter during row chemical reaction, and titanium tetrachloride can be prevented to be dissolved in other solvents and give birth to
Into similar to [(C6R6)TiCl3]+Complex, so as to avoid that titanium nitride nanopower purity is caused when introducing carbon to drop
The phenomenon that low；Further, when step A is chemically reacted, which can dissolve each other with titanium tetrachloride, and titanium tetrachloride can quilt
The reaction promoter wraps up, and the reaction promoter of titanium tetrachloride outer layer can inhibit growing up for titanium nitride precursor in chemical reaction, from
And be conducive to obtain nanoscale nitridation titanium valve.
(3) in the present invention, the chemical reaction of step A is carried out in -35 DEG C~30 DEG C of relatively mild temperature, at this time in liquefied ammonia
Ammonia it is readily volatilized (boiling point of liquefied ammonia be 33.42 DEG C), correspondingly, maintaining the high compression ring of 0.2MPa~1.5MPa in step A
Border so that the ammonia in liquefied ammonia is not volatile, so as to effectively maintain liquid-phase chemical reaction；Meanwhile the chemical reaction of step A
It is carried out in -35 DEG C~30 DEG C of relatively mild temperature, reduces to maintain the low temperature environment of the chemical reaction of step A and consume
The energy reduces energy consumption, reduces production cost.
Description of the drawings
It in order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of scope, for those of ordinary skill in the art, without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the flow chart of titanium nitride nanopower high pressure liquid-phase synthesis process in the present invention.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
Part of the embodiment of the present invention, instead of all the embodiments.Therefore, the embodiment of the present invention to providing in the accompanying drawings below
Detailed description be not intended to limit the scope of claimed invention, but be merely representative of the present invention selected embodiment.
Based on the embodiments of the present invention, what those of ordinary skill in the art were obtained without creative efforts is all
Other embodiment belongs to the scope of protection of the invention.
To further appreciate that present disclosure, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1
With reference to figure 1, a kind of titanium nitride nanopower high pressure liquid-phase synthesis process comprises the following steps：
Step A：Using toluene as reaction promoter, liquefied ammonia is added in into toluene, after treating that liquefied ammonia stablizes layering with toluene, to first
Titanium tetrachloride is added in benzene and is chemically reacted under conditions of -34 DEG C, 0.2MPa, reaction is washed after terminating, and is obtained
To nitridation titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is
1:2:6。
Step B：The nitridation titanium precursors that step A is obtained are roasted under nitrogen protective atmosphere, calcination temperature is
400 DEG C, roasting time control finally obtains titanium nitride nanopower in 150min, and titanium nitride nanopower is averaged after testing
Grain size is 40nm, average grain size 15nm.
In the present embodiment, step A chemical reactions are washed, purified after terminating, and are concretely comprised the following steps：It is anti-by liquefied ammonia
After backwashing washs filtering, extracts remaining ammonium chloride, filters out remaining reaction promoter, obtains pure nitridation titanium precursors；It is pure
Liquid phase after change is separated by distillation out pure ammonia, reaction promoter and ammonium chloride, recycles.
In the present invention, the chemical reaction of step A is specially TiCl4+6NH3=Ti (NH)2↓+4NH4Cl, in closed reaction
It is chemically reacted in container, displaces the air in reaction vessel repeatedly using protective gas, make to be in reaction vessel
Anhydrous and oxygen-free state, and it is 0.2MPa~1.5MPa to maintain pressure in reaction vessel, and temperature can be realized at -35 DEG C~30 DEG C
Effecting reaction effectively reduces the energy consumption.
Embodiment 2
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using toluene as reaction promoter, liquefied ammonia is added in into toluene, after treating that liquefied ammonia stablizes layering with toluene, to first
Titanium tetrachloride is added in benzene and is chemically reacted under conditions of -20 DEG C, 0.3Mpa, reaction is washed after terminating, and is obtained
To nitridation titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is
1:4:2。
Step B：The nitridation titanium precursors that step A is obtained are roasted under helium protective atmosphere, calcination temperature is
800 DEG C, roasting time is controlled in 60min, finally obtains titanium nitride nanopower, after testing the average grain of titanium nitride nanopower
Footpath is 70nm, average grain size 20nm.
Embodiment 3
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using toluene as reaction promoter, liquefied ammonia is added in into toluene, after treating that liquefied ammonia stablizes layering with toluene, to first
Titanium tetrachloride is added in benzene and is chemically reacted under conditions of -10 DEG C, 0.4MPa, reaction is washed after terminating, and is obtained
To nitridation titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is
1:3:5。
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1000 DEG C, roasting time control finally obtains titanium nitride nanopower in 60min, and titanium nitride nanopower is averaged after testing
Grain size is 200nm, average grain size 60nm.
Embodiment 4
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using toluene as reaction promoter, liquefied ammonia is added in into toluene, after treating that liquefied ammonia stablizes layering with toluene, to first
Titanium tetrachloride is added in benzene and is chemically reacted under conditions of 10 DEG C, 0.6MPa, reaction is washed after terminating, and is obtained
Nitrogenize titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is 1:
2.5:4。
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1200 DEG C, roasting time control finally obtains titanium nitride nanopower in 80min, and titanium nitride nanopower is averaged after testing
Grain size is 300nm, average grain size 100nm.
Embodiment 5
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using toluene as reaction promoter, liquefied ammonia is added in into toluene, after treating that liquefied ammonia stablizes layering with toluene, to first
Titanium tetrachloride is added in benzene and is chemically reacted under conditions of 20 DEG C, 1.5MPa, reaction is washed after terminating, and is obtained
Nitrogenize titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is 1:
3.5:3。
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1300 DEG C, roasting time control finally obtains titanium nitride nanopower in 60min, and titanium nitride nanopower is averaged after testing
Grain size is 350nm, average grain size 100nm.
Embodiment 6
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using dichloromethane as reaction promoter, liquefied ammonia is added in into dichloromethane, treats that liquefied ammonia is stablized with dichloromethane
After layering, titanium tetrachloride is added in into dichloromethane and is chemically reacted under conditions of -34 DEG C, 0.2MPa, reaction knot
It is washed after beam, obtains nitridation titanium precursors；Wherein, before chemical reaction starts, control titanium tetrachloride, liquefied ammonia and reaction
The mass ratio of auxiliary agent is 1:2:6.
Step B：The nitridation titanium precursors that step A is obtained are roasted under nitrogen protective atmosphere, calcination temperature is
800 DEG C, roasting time control finally obtains titanium nitride nanopower in 150min, and titanium nitride nanopower is averaged after testing
Grain size is 80nm, average grain size 40nm.
Embodiment 7
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using dichloromethane as reaction promoter, liquefied ammonia is added in into dichloromethane, treats that liquefied ammonia is stablized with dichloromethane
After layering, titanium tetrachloride is added in into dichloromethane and is chemically reacted under conditions of -20 DEG C, 0.3Mpa, reaction knot
It is washed after beam, obtains nitridation titanium precursors；Wherein, before chemical reaction starts, control titanium tetrachloride, liquefied ammonia and reaction
The mass ratio of auxiliary agent is 1:4:2.
Step B：The nitridation titanium precursors that step A is obtained are roasted under helium protective atmosphere, calcination temperature is
900 DEG C, roasting time control finally obtains titanium nitride nanopower in 120min, and titanium nitride nanopower is averaged after testing
Grain size is 100nm, average grain size 50nm.
Embodiment 8
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using dichloromethane as reaction promoter, liquefied ammonia is added in into dichloromethane, treats that liquefied ammonia is stablized with dichloromethane
After layering, titanium tetrachloride is added in into dichloromethane and is chemically reacted under conditions of -10 DEG C, 0.4MPa, reaction knot
It is washed after beam, obtains nitridation titanium precursors；Wherein, before chemical reaction starts, control titanium tetrachloride, liquefied ammonia and reaction
The mass ratio of auxiliary agent is 1:3:5.
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1000 DEG C, roasting time control finally obtains titanium nitride nanopower in 60min, and titanium nitride nanopower is averaged after testing
Grain size is 150nm, average grain size 80nm.
Embodiment 9
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using dichloromethane as reaction promoter, liquefied ammonia is added in into dichloromethane, treats that liquefied ammonia is stablized with dichloromethane
After layering, titanium tetrachloride is added in into dichloromethane and is chemically reacted under conditions of 10 DEG C, 0.8MPa, reaction terminates
It is washed afterwards, obtains nitridation titanium precursors；Wherein, before chemical reaction starts, control titanium tetrachloride, liquefied ammonia and reaction help
The mass ratio of agent is 1:2.5:4.
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1200 DEG C, roasting time control finally obtains titanium nitride nanopower in 60min, and titanium nitride nanopower is averaged after testing
Grain size is 160nm, average grain size 90nm.
Embodiment 10
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using dichloromethane as reaction promoter, liquefied ammonia is added in into dichloromethane, treats that liquefied ammonia is stablized with dichloromethane
After layering, titanium tetrachloride is added in into dichloromethane and is chemically reacted under conditions of 30 DEG C, 1.3MPa, reaction terminates
It is washed afterwards, obtains nitridation titanium precursors；Wherein, before chemical reaction starts, control titanium tetrachloride, liquefied ammonia and reaction help
The mass ratio of agent is 1:3.5:3.
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1300 DEG C, roasting time control finally obtains titanium nitride nanopower in 30min, and titanium nitride nanopower is averaged after testing
Grain size is 140nm, average grain size 80nm.
Embodiment 11
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using the mixture of toluene and dichloromethane as reaction promoter, add into the mixture of toluene and dichloromethane
Enter liquefied ammonia, after treating that liquefied ammonia is layered with the stabilized with mixture of toluene and dichloromethane, into the mixture of toluene and dichloromethane
It adds in titanium tetrachloride and is chemically reacted under conditions of -34 DEG C, 0.2MPa, reaction is washed after terminating, and obtains nitrogen
Change titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is 1:2:
6。
Step B：The nitridation titanium precursors that step A is obtained are roasted under nitrogen protective atmosphere, calcination temperature is
800 DEG C, roasting time control finally obtains titanium nitride nanopower in 150min, and titanium nitride nanopower is averaged after testing
Grain size is 100nm, average grain size 60nm.
Embodiment 12
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using the mixture of toluene and dichloromethane as reaction promoter, add into the mixture of toluene and dichloromethane
Enter liquefied ammonia, after treating that liquefied ammonia is layered with the stabilized with mixture of toluene and dichloromethane, into the mixture of toluene and dichloromethane
It adds in titanium tetrachloride and is chemically reacted under conditions of -20 DEG C, 0.3Mpa, reaction is washed after terminating, and obtains nitrogen
Change titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is 1:4:
2。
Step B：The nitridation titanium precursors that step A is obtained are roasted under helium protective atmosphere, calcination temperature is
900 DEG C, roasting time control finally obtains titanium nitride nanopower in 120min, and titanium nitride nanopower is averaged after testing
Grain size is 90nm, average grain size 55nm.
Embodiment 13
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using the mixture of toluene and dichloromethane as reaction promoter, add into the mixture of toluene and dichloromethane
Enter liquefied ammonia, after treating that liquefied ammonia is layered with the stabilized with mixture of toluene and dichloromethane, into the mixture of toluene and dichloromethane
It adds in titanium tetrachloride and is chemically reacted under conditions of -10 DEG C, 0.4MPa, reaction is washed after terminating, and obtains nitrogen
Change titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is 1:3:
5。
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1000 DEG C, roasting time control finally obtains titanium nitride nanopower in 100min, and titanium nitride nanopower is averaged after testing
Grain size is 160nm, average grain size 100nm.
Embodiment 14
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using the mixture of toluene and dichloromethane as reaction promoter, add into the mixture of toluene and dichloromethane
Enter liquefied ammonia, after treating that liquefied ammonia is layered with the stabilized with mixture of toluene and dichloromethane, into the mixture of toluene and dichloromethane
It adds in titanium tetrachloride and is chemically reacted under conditions of 10 DEG C, 0.5MPa, reaction is washed after terminating, and is nitrogenized
Titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is 1:2.5:
4。
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1200 DEG C, roasting time control finally obtains titanium nitride nanopower in 80min, and titanium nitride nanopower is averaged after testing
Grain size is 200nm, average grain size 90nm.
Embodiment 15
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprises the following steps：
Step A：Using the mixture of toluene and dichloromethane as reaction promoter, add into the mixture of toluene and dichloromethane
Enter liquefied ammonia, after treating that liquefied ammonia is layered with the stabilized with mixture of toluene and dichloromethane, into the mixture of toluene and dichloromethane
It adds in titanium tetrachloride and is chemically reacted under conditions of 30 DEG C, 1.5MPa, reaction is washed after terminating, and is nitrogenized
Titanium precursors；Wherein, before chemical reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is 1:3.5:
3。
Step B：The nitridation titanium precursors that step A is obtained are roasted under argon gas protective atmosphere, calcination temperature is
1300 DEG C, roasting time control finally obtains titanium nitride nanopower in 60min, and titanium nitride nanopower is averaged after testing
Grain size is 300nm, average grain size 95nm.
Schematically the present invention and embodiments thereof are described above, this describes no restricted, institute in attached drawing
What is shown is also one of embodiments of the present invention, and actual structure is not limited thereto.So if common skill of this field
Art personnel are enlightened by it, without departing from the spirit of the invention, are not inventively designed and the technical solution
Similar frame mode and embodiment, are within the scope of protection of the invention.
Claims (10)
1. titanium nitride nanopower high pressure liquid-phase synthesis process, which is characterized in that comprise the following steps：
Step A：Prepare reaction promoter, liquefied ammonia is added in into reaction promoter, treat liquefied ammonia with after reaction promoter layering, being helped to reaction
Titanium tetrachloride is added in agent, is chemically reacted under temperature A, pressure B, reaction is washed after terminating, and obtains titanium nitride
Presoma；
Step B：The nitridation titanium precursors that step A is obtained are roasted, obtain titanium nitride nanopower.
2. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 1, which is characterized in that the reaction helps
Agent is one or more kinds of mixing in nonpolar non-aromatic hydrocarbons or halogenated hydrocarbons.
3. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 1, which is characterized in that wherein, -35 DEG C
＜ temperature A≤30 DEG C.
4. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 3, which is characterized in that the pressure B
For 0.2MPa~1.5MPa.
5. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 4, which is characterized in that change in step A
Before reaction starts, the mass ratio for controlling titanium tetrachloride, liquefied ammonia and reaction promoter is 1：2~4：2~6.
6. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 5, which is characterized in that roasted in step B
The temperature of burning is 400 DEG C~1300 DEG C.
7. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 6, which is characterized in that roasted in step B
The time of burning is 20min~150min.
8. the titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 1~7 any one, feature exist
In being roasted in step B under protective atmosphere.
9. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 8, which is characterized in that the protectiveness
Atmosphere is one kind in nitrogen, helium or argon gas.
10. the titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 1~7 any one, feature exist
In the reaction promoter is toluene or dichloromethane or the mixture of toluene and dichloromethane.
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Cited By (1)
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| CN115246632A (en) * | 2020-11-02 | 2022-10-28 | 刘辉 | Method for preparing titanium nitride section bar by utilizing solid titanium tetrachloride and low-temperature liquid ammonia |
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| CN1312218A (en) * | 2001-03-23 | 2001-09-12 | 中国科学院上海硅酸盐研究所 | Titania nitriding process for preparing nanometer titanium nitride powder |
| CN1438172A (en) * | 2003-02-27 | 2003-08-27 | 北京科技大学 | Method for preparing titanium nitride fine powder by eiquid-phase reduction |
| CN101475151A (en) * | 2008-08-01 | 2009-07-08 | 北京科技大学 | Preparation of conductive titanium nitride/silicon nitride nano composite material |
| CN103864030A (en) * | 2012-12-11 | 2014-06-18 | 浙江海洋学院 | Nanometer titanium nitride powder preparation method |
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2018
- 2018-01-26 CN CN201810076302.5A patent/CN108101009B/en active Active
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| CN1312218A (en) * | 2001-03-23 | 2001-09-12 | 中国科学院上海硅酸盐研究所 | Titania nitriding process for preparing nanometer titanium nitride powder |
| CN1438172A (en) * | 2003-02-27 | 2003-08-27 | 北京科技大学 | Method for preparing titanium nitride fine powder by eiquid-phase reduction |
| CN101475151A (en) * | 2008-08-01 | 2009-07-08 | 北京科技大学 | Preparation of conductive titanium nitride/silicon nitride nano composite material |
| CN103864030A (en) * | 2012-12-11 | 2014-06-18 | 浙江海洋学院 | Nanometer titanium nitride powder preparation method |
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| HUGO TIZNADO ET AL.: "Surface Chemistry in the Atomic Layer Deposition of TiN Films from TiCl4 and Ammonia", 《J. PHYS. CHEM. B》 * |
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| CN115246632A (en) * | 2020-11-02 | 2022-10-28 | 刘辉 | Method for preparing titanium nitride section bar by utilizing solid titanium tetrachloride and low-temperature liquid ammonia |
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