CN108101009B - Titanium nitride nanopower high pressure liquid-phase synthesis process - Google Patents
Titanium nitride nanopower high pressure liquid-phase synthesis process Download PDFInfo
- Publication number
- CN108101009B CN108101009B CN201810076302.5A CN201810076302A CN108101009B CN 108101009 B CN108101009 B CN 108101009B CN 201810076302 A CN201810076302 A CN 201810076302A CN 108101009 B CN108101009 B CN 108101009B
- Authority
- CN
- China
- Prior art keywords
- titanium nitride
- titanium
- reaction
- nanopower
- liquefied ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of titanium nitride nanopower high pressure liquid-phase synthesis process, belong to titanium nitride preparation technical field.Preparation method of the invention includes the following steps；Step A: preparing reaction promoter, liquefied ammonia be added into reaction promoter, after liquefied ammonia and reaction promoter layering, titanium tetrachloride is added into reaction promoter, is chemically reacted under Yu Wendu A, pressure B, and reaction is washed after terminating, and obtains nitridation titanium precursors；Step B: the nitridation titanium precursors that step A is obtained are roasted, titanium nitride nanopower is obtained.Wherein: -35 DEG C of < temperature A≤30 DEG C, pressure B are 0.2MPa~1.5MPa.Preparation method of the invention reduces energy consumption, and lower production costs, the nitride powder of acquisition is with high purity, particle is uniform, narrow particle size distribution, partial size are up to nanoscale.
Description
Technical field
The invention belongs to titanium nitride preparation technical fields, more specifically to a kind of titanium nitride nanopower high pressure liquid
It is combined to method.
Background technique
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, thermally conductive and optical property is 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.Demand of the industry to titanium nitride powder is more and more,
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 there are the series of advantages such as good electric conductivity, thermal conductivity, be widely used.
Nano titanium nitride powder refers to nitride powder of its crystallite dimension within 100 nanometers, replaces micron order with it
Nitride powder, which makees raw material, can reduce the sintering temperature of titanium nitride ceramic, improve sintering character；Reinforced phase is used it as, can be had
Effect improves the intensity and toughness of metal, ceramic matrix.Moreover, because particle is small, large specific surface area, can be dispersed in other materials
Conductive network is formed, the electric conductivity of composite material is greatly improved.So Nano titanium nitride is a kind of with 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 disclosure
Number: CN 101298321A, publication date: on November 05th, 2008, invention and created name are as follows: a kind of system of titanium nitride nanopower
Preparation Method, preparation method disclosed in this application are passed through ammonia, from room temperature using nanotubed titanic acid as titanium source in tube furnace
To 800-1000 DEG C of progress nitridation reaction 0.5-24H, up to titanium nitride nanopower after cooling.
Currently, 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, such methods 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 agglomeration, particle is coarse, differed with the required nanoscale titanium nitride in present market compared with
Greatly, so also needing 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, such methods reaction compared with
Fastly, 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 have the defects that different degrees of, therefore needs to research and develop
A kind of preparation method of low-cost titanium nitride nanopower out, to overcome drawbacks described above.
Summary of the invention
1. technical problems to be solved by the inivention
It is in the prior art above insufficient it is an object of the invention to overcome, provide a kind of titanium nitride nanopower and its
Preparation method, the preparation method reduce energy consumption, and lower production costs, the nitride powder of acquisition is with high purity, particle is uniform, grain
Narrowly distributing, partial size are spent up to nanoscale.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
Titanium nitride nanopower high pressure liquid-phase synthesis process of the invention, comprising the following steps:
Step A: preparing reaction promoter, liquefied ammonia be added into reaction promoter, after liquefied ammonia and reaction promoter layering, to anti-
It answers and titanium tetrachloride is added in auxiliary agent, chemically reacted under Yu Wendu 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, titanium nitride nanopower is obtained.
As further improvement of the present invention, the reaction promoter be one of nonpolar non-aromatic hydrocarbons or 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 under protective atmosphere in step B.
As further improvement of the present invention, the protective atmosphere is one of nitrogen, helium or argon gas.
As further improvement of the present invention, the reaction promoter is toluene or methylene chloride or toluene and methylene chloride
Mixture.
3. beneficial effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result:
(1) present invention is synthetically prepared titanium nitride nanopower using liquid phase method, and reaction is controllable, and reaction time is short, reaction temperature
Spend relatively mild, therefore energy consumption of reaction is lower, and technical process is simple and is not necessarily to large scale equipment, lower production costs, can big industry
Metaplasia produces, and react gained nitride powder purity is high, particle uniformly, narrow particle size distribution, partial size up to nanoscale, future will
Gradually replace traditional titanium nitride preparation method, there are bright prospects, and reaction promoter used in reaction, liquefied ammonia can be recycled and follows
Ring uses.
(2) present invention is using the mixing of one or more of nonpolar non-aromatic hydrocarbons or halogenated hydrocarbons as reaction promoter, into
Titanium tetrachloride is dissolved in the above reaction promoter when row chemical reaction, and titanium tetrachloride can be prevented to be dissolved in other solvents and give birth to
At similar to [(C6R6)TiCl3]+Complex, to avoid causing because introducing carbon titanium nitride nanopower purity from dropping
Low phenomenon；Further, when step A is chemically reacted, which can dissolve each other with titanium tetrachloride, and titanium tetrachloride can quilt
The reaction promoter of reaction promoter package, titanium tetrachloride outer layer can inhibit growing up for titanium nitride precursor in chemical reaction, from
And it help 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, 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 the low temperature environment to maintain the chemical reaction of step A and consume
The energy reduces energy consumption, reduces production cost.
Detailed description of the invention
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 range 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
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Therefore, below to the embodiment of the present invention provided in the accompanying drawings
Detailed description be not intended to limit the range of claimed invention, but be merely representative of selected embodiment of the invention.
Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts all
Other embodiments shall fall within the protection scope of the present invention.
To further appreciate that the contents of the present invention, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1
With reference to Fig. 1, a kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using toluene as reaction promoter, liquefied ammonia being added into toluene, after stablizing layering to liquefied ammonia and 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 of control 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, maturing temperature is
400 DEG C, calcining time is controlled in 150min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 40nm, average grain size 15nm.
In the present embodiment, step A chemical reaction is washed, is purified after terminating, the specific steps are that: 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 maintaining pressure in reaction vessel is 0.2MPa~1.5MPa, it is at -35 DEG C~30 DEG C that temperature, which may be implemented,
Effecting reaction effectively reduces the energy consumption.
Embodiment 2
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using toluene as reaction promoter, liquefied ammonia being added into toluene, after stablizing layering to liquefied ammonia and 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 of control 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, maturing temperature is
800 DEG C, calcining time is controlled in 60min, finally obtains titanium nitride nanopower, through the average grain for detecting titanium nitride nanopower
Diameter is 70nm, average grain size 20nm.
Embodiment 3
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using toluene as reaction promoter, liquefied ammonia being added into toluene, after stablizing layering to liquefied ammonia and 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 of control 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, maturing temperature is
1000 DEG C, calcining time is controlled in 60min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 200nm, average grain size 60nm.
Embodiment 4
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using toluene as reaction promoter, liquefied ammonia being added into toluene, after stablizing layering to liquefied ammonia and 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 of control 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, maturing temperature is
1200 DEG C, calcining time is controlled in 80min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 300nm, average grain size 100nm.
Embodiment 5
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using toluene as reaction promoter, liquefied ammonia being added into toluene, after stablizing layering to liquefied ammonia and 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 of control 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, maturing temperature is
1300 DEG C, calcining time is controlled in 60min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 350nm, average grain size 100nm.
Embodiment 6
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using methylene chloride as reaction promoter, liquefied ammonia being added into methylene chloride, stablizes to liquefied ammonia and methylene chloride
After layering, titanium tetrachloride is added into methylene chloride 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, maturing temperature is
800 DEG C, calcining time is controlled in 150min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 80nm, average grain size 40nm.
Embodiment 7
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using methylene chloride as reaction promoter, liquefied ammonia being added into methylene chloride, stablizes to liquefied ammonia and methylene chloride
After layering, titanium tetrachloride is added into methylene chloride 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, maturing temperature is
900 DEG C, calcining time is controlled in 120min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 100nm, average grain size 50nm.
Embodiment 8
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using methylene chloride as reaction promoter, liquefied ammonia being added into methylene chloride, stablizes to liquefied ammonia and methylene chloride
After layering, titanium tetrachloride is added into methylene chloride 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, maturing temperature is
1000 DEG C, calcining time is controlled in 60min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 150nm, average grain size 80nm.
Embodiment 9
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using methylene chloride as reaction promoter, liquefied ammonia being added into methylene chloride, stablizes to liquefied ammonia and methylene chloride
After layering, titanium tetrachloride is added into methylene chloride and is chemically reacted under conditions of 10 DEG C, 0.8MPa, reaction terminates
It is washed later, obtains nitridation titanium precursors；Wherein, before chemical reaction starts, control titanium tetrachloride, liquefied ammonia and reaction are helped
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, maturing temperature is
1200 DEG C, calcining time is controlled in 60min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 160nm, average grain size 90nm.
Embodiment 10
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using methylene chloride as reaction promoter, liquefied ammonia being added into methylene chloride, stablizes to liquefied ammonia and methylene chloride
After layering, titanium tetrachloride is added into methylene chloride and is chemically reacted under conditions of 30 DEG C, 1.3MPa, reaction terminates
It is washed later, obtains nitridation titanium precursors；Wherein, before chemical reaction starts, control titanium tetrachloride, liquefied ammonia and reaction are helped
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, maturing temperature is
1300 DEG C, calcining time is controlled in 30min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 140nm, average grain size 80nm.
Embodiment 11
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using the mixture of toluene and methylene chloride as reaction promoter, add in the mixture of toluene and methylene chloride
Enter liquefied ammonia, after the layering of the stabilized with mixture of liquefied ammonia and toluene and methylene chloride, in the mixture of toluene and methylene chloride
Titanium tetrachloride is added 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 of control 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, maturing temperature is
800 DEG C, calcining time is controlled in 150min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 100nm, average grain size 60nm.
Embodiment 12
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using the mixture of toluene and methylene chloride as reaction promoter, add in the mixture of toluene and methylene chloride
Enter liquefied ammonia, after the layering of the stabilized with mixture of liquefied ammonia and toluene and methylene chloride, in the mixture of toluene and methylene chloride
Titanium tetrachloride is added 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 of control 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, maturing temperature is
900 DEG C, calcining time is controlled in 120min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 90nm, average grain size 55nm.
Embodiment 13
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using the mixture of toluene and methylene chloride as reaction promoter, add in the mixture of toluene and methylene chloride
Enter liquefied ammonia, after the layering of the stabilized with mixture of liquefied ammonia and toluene and methylene chloride, in the mixture of toluene and methylene chloride
Titanium tetrachloride is added 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 of control 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, maturing temperature is
1000 DEG C, calcining time is controlled in 100min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 160nm, average grain size 100nm.
Embodiment 14
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using the mixture of toluene and methylene chloride as reaction promoter, add in the mixture of toluene and methylene chloride
Enter liquefied ammonia, after the layering of the stabilized with mixture of liquefied ammonia and toluene and methylene chloride, in the mixture of toluene and methylene chloride
Titanium tetrachloride is added 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 of control 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, maturing temperature is
1200 DEG C, calcining time is controlled in 80min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 200nm, average grain size 90nm.
Embodiment 15
A kind of titanium nitride nanopower high pressure liquid-phase synthesis process, comprising the following steps:
Step A: using the mixture of toluene and methylene chloride as reaction promoter, add in the mixture of toluene and methylene chloride
Enter liquefied ammonia, after the layering of the stabilized with mixture of liquefied ammonia and toluene and methylene chloride, in the mixture of toluene and methylene chloride
Titanium tetrachloride is added 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 of control 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, maturing temperature is
1300 DEG C, calcining time is controlled in 60min, finally obtains titanium nitride nanopower, through being averaged for detection titanium nitride nanopower
Partial size is 300nm, average grain size 95nm.
Schematically the present invention and embodiments thereof are described above, description is not limiting, institute in attached drawing
What is shown is also one of embodiments of the present invention, and actual structure is not limited to this.So if the 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 (6)
1. titanium nitride nanopower high pressure liquid-phase synthesis process, which comprises the following steps:
Step A: preparing reaction promoter, liquefied ammonia be added into reaction promoter, and after liquefied ammonia and reaction promoter layering, Xiang Fanying is helped
Titanium tetrachloride is added in agent, is chemically reacted under Yu Wendu A, pressure B, reaction is washed after terminating, and obtains titanium nitride
Presoma；
The reaction promoter is the mixing of one or more of nonpolar non-aromatic hydrocarbons or halogenated hydrocarbons；
Wherein, -35 DEG C of < temperature A≤30 DEG C；The pressure B is 0.2MPa~1.5MPa；
Before chemical reaction starts in step A, control titanium tetrachloride, liquefied ammonia and reaction promoter mass ratio be 1:2~4:2~
6；
Step B: the nitridation titanium precursors that step A is obtained are roasted, titanium nitride nanopower is obtained.
2. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 1, which is characterized in that roasted in step B
The temperature of burning is 400 DEG C~1300 DEG C.
3. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 2, which is characterized in that roasted in step B
The time of burning is 20min~150min.
4. titanium nitride nanopower high pressure liquid-phase synthesis process according to any one of claims 1 to 3, feature exist
In being roasted under protective atmosphere in step B.
5. titanium nitride nanopower high pressure liquid-phase synthesis process according to claim 4, which is characterized in that the protectiveness
Atmosphere is one of nitrogen, helium or argon gas.
6. titanium nitride nanopower high pressure liquid-phase synthesis process according to any one of claims 1 to 3, feature exist
In the reaction promoter is the mixture of toluene or methylene chloride or toluene and methylene chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810076302.5A CN108101009B (en) | 2018-01-26 | 2018-01-26 | Titanium nitride nanopower high pressure liquid-phase synthesis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810076302.5A CN108101009B (en) | 2018-01-26 | 2018-01-26 | Titanium nitride nanopower high pressure liquid-phase synthesis process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108101009A CN108101009A (en) | 2018-06-01 |
| CN108101009B true CN108101009B (en) | 2019-06-25 |
Family
ID=62221302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810076302.5A Active CN108101009B (en) | 2018-01-26 | 2018-01-26 | Titanium nitride nanopower high pressure liquid-phase synthesis process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108101009B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2018
- 2018-01-26 CN CN201810076302.5A patent/CN108101009B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Surface Chemistry in the Atomic Layer Deposition of TiN Films from TiCl4 and Ammonia;Hugo Tiznado et al.;《J. Phys. Chem. B》;20060617;第110卷;第13491-13498页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108101009A (en) | 2018-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10364193B2 (en) | Method for synthesizing high-purity ultrafine ZrC—SiC composite powder | |
| KR100747805B1 (en) | Powder mixture or composite powder, a method for production thereof and the use thereof in composite materials | |
| Wu et al. | Preparation technology of ultra-fine tungsten carbide powders: an overview | |
| Xiang et al. | Synthesis of Ti (C, N) ultrafine powders by carbothermal reduction of TiO2 derived from sol–gel process | |
| Yang et al. | Synthesis of Y2O3-doped WC-Co powders by wet chemical method and its effect on the properties of WC-Co cemented carbide alloy | |
| CN108557783B (en) | Preparation method of high-purity nano titanium nitride powder | |
| Wang et al. | Effect of ZrO2 content on microstructure and mechanical properties of W alloys fabricated by spark plasma sintering | |
| US10441941B2 (en) | Preparation method of alumina supported cerium oxide powder material | |
| WO2020186752A1 (en) | Method for preparing superfine grain wc-co hard alloy by means of plasma ball milling | |
| Wu et al. | Synthesis of high purity nano-sized transition-metal carbides | |
| CN108129151A (en) | A kind of graphene/carbon SiClx nano composite structure layered ceramic and preparation method thereof | |
| WO2019227811A1 (en) | Ultrafine transition-metal boride powder, and preparation method therefor and application thereof | |
| CN108543952A (en) | A kind of method of precursor process synthesis WC base nano composite powders | |
| CN108101009B (en) | Titanium nitride nanopower high pressure liquid-phase synthesis process | |
| Xu et al. | Properties and microstructure of oxide dispersion strengthened tungsten alloy prepared by liquid-phase method: a review | |
| Ishigaki | Synthesis of functional oxide nanoparticles through RF thermal plasma processing | |
| CN108585876A (en) | The preparation method of titanium nitride nanopower | |
| CN110078120B (en) | Preparation method of yttria-stabilized zirconia powder based on supercritical dispersion roasting | |
| CN108059135B (en) | Titanium nitride nanopower and preparation method thereof | |
| CN106944628B (en) | A kind of scrap hard alloy recycling prepares superfine WC-Co composite powder method | |
| CN108928822B (en) | Method for preparing molybdenum carbide by gaseous reduction of molybdenum oxide | |
| Yin et al. | Mechanism and experimental study on preparation of high-quality vanadium nitride by one-step vacuum carbothermal reduction nitridation method | |
| KR20040060182A (en) | Process for manufacturing WC based powder by vaper reaction under vacuum pressure | |
| Liu et al. | In-situ fabrication of ZrB2-ZrC-SiCnws hybrid nanopowders with tuneable morphology SiCnws | |
| Wang et al. | Preparation of spherical α‐Al2O3 nanoparticles by microwave hydrothermal synthesis and addition of nano‐Al seeds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |