CN109721368A - A kind of method that carbon titanium carbonitride powder and hydrolyzable titanium source prepare titanium carbonitride - Google Patents
A kind of method that carbon titanium carbonitride powder and hydrolyzable titanium source prepare titanium carbonitride Download PDFInfo
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Abstract
The present invention relates to a kind of methods that carbon titanium carbonitride powder and hydrolyzable titanium source prepare titanium carbonitride, using hydrolyzable titanium source as titanium source, carbon black is carbon source, triton x-100 or cetyl trimethylammonium bromide are surfactant, hexamethylene is hydrolysis buffer, ammonium hydroxide is precipitating reagent, preparation process flow are as follows: configuration lotion → instillation ammonium hydroxide → suspension is filtered, washed, drying → precursor powder pretreatment → carbon tropical resources reduction → titanium carbonitride.This method does not use ball mill mixing, it can be achieved that producing in enormous quantities, and particle size is 200~300nm, and purity is greater than 99%, and preparation cost is low, provides a kind of new synthesis path for titanium carbonitride.
Description
Technical field
The present invention relates to ceramic powders preparation technical field, especially a kind of carbon titanium carbonitride powder and hydrolyzable titanium source system
The method of standby titanium carbonitride.
Background technique
WC-Co series hard metal has high-intensitive and good toughness, is widely used in modern manufacturing industry, but its hardness with
Wearability slightly has deficiency, is restricted in some applications.Base titanium carbonitride material is due to high rigidity, height
Red hardness, wearability become the ideal material of substitution WC-Co hard alloy.But to prepare the carbon nitridation of high comprehensive performance
Titanium ceramic material just has to prepare the stable titanium carbonitride ceramic powders of high-purity, fine granularity, sintering character.
The preparation method of carbon titanium carbonitride powder has carbon tropical resources reduction method, chemical vapour deposition technique, mechanical alloying method, change
Learn synthetic method.For carbon tropical resources reduction method since cost is relatively low, being produced on a large scale has great advantage compared to other methods.It passes
Carbon tropical resources reduction method synthesizing titanium carbonitride powder unite usually using titanium dioxide and carbon black as raw material, ball mill mixing is then in high temperature
Lower progress carbon tropical resources reduction reaction.Such as 108424147 A of Chinese patent application CN discloses a kind of Rapid Nitriding production carbon
The method of titanium nitride, titanium nitride powder, using traditional titanium dioxide and carbon black feed stock, high-energy ball milling mixing, mist projection granulating is dry
Dry slurry carries out powder preparation using Rapid Nitriding device.The method realizes that carbon titanium mixes using physical method, since raw material is matched
Than with polarity difference, raw material is difficult to be uniformly mixed, and be easy to cause reaction incomplete.
101462701 A of Chinese patent application CN discloses a kind of method for preparing titanium nitride ceramic powder, utilizes low temperature
Combustion method makes titanium source and carbon source is uniformly mixed with precursor powder, but the method need to use strong acid to make oxidant, to equipment
It there are certain requirements, it is difficult to realize and produce in enormous quantities.And the organic matter used, as carbon source, organic carbon process is complicated, finally
The carbon content restored into carbon tropical resources is difficult to quantify.
1559912 A of Chinese patent application CN discloses a kind of preparation side of three elemental compound powder material of titanium carbonitride
Method, using TiCl4For titanium source, CaC2Or CCl4For carbon source, NaN3For nitrogen source, life is reacted in high temperature and pressure stainless steel cauldron
At carbon titanium carbonitride powder.Wherein reactant CaC2Can react with the water in air, must in the glove box of anhydrous and oxygen-free ability it is complete
It is operated at weighing.NaN3Belong to extremely toxic substance, no combustibility, but have explosivity, increases the danger of production.The method synthesis temperature
Degree is 450 DEG C, and base titanium carbonitride sintering temperature is 1300~1450 DEG C, and powder synthesis temperature is far below its use
Temperature, easily denitrogenation leads to fault in material in practical applications, and use value is not high.This method reaction vessel be high temperature and pressure not
Become rusty steel reaction kettle, it is difficult to realize and produce in enormous quantities.
Summary of the invention
The purpose of the invention is to overcome the shortcomings of existing titanium carbonitride technology of preparing, a kind of hydrolyzable titanium is provided
The method that source prepares titanium carbonitride, this method pass through without ball milling, the inexpensive synthesizing titanium carbonitride powder of realization and control raw material
Carbon, titanium ratio and nitrogen flow can control the carbon-nitrogen ratio of powder in a certain range.
The present invention also protects the carbon titanium carbonitride powder being prepared according to the method and carbon titanium carbonitride powder for making
The purposes of standby base titanium carbonitride material, base titanium carbonitride material are widely used in field of machining,
Such as cutting material.
Cardinal principle of the invention is hydrolyzed using hydrolyzable titanium source, is sufficiently mixed carbon source with titanium source, increases raw material
Mixing uniformity, nano-titanium dioxide is attached to carbon blacksurface, can be improved reactivity reduce react required for temperature.
The method can save the ball milling mixing process of traditional carbothermic method titanium dioxide and carbon black, and can solve mixing not
, the excessively high problem of reaction temperature makes up the shortcomings that existing chemical synthesis can not be produced in enormous quantities.
The hydrolysis of hydrolyzable titanium source is related to the intermediate reaction product of multiple complexity, since hydrolysis is typically more violent,
It is easy to cause and reunite, high temperature carbon-thermal reduction is caused to fail.Therefore, with titanium tetrachloride, butyl titanate etc. be titanium source when, usually to keep away
Exempt to contact with water, be completely cut off by glove box.The present invention overcomes the prejudice of traditional titanium source selection, feels free to try by can water
The titanium source hydrolysis of solution property, by necessary control condition, combines nano-titanium dioxide equably with carbon source.Wherein, carbon source
Selection is very crucial, and by repetition test, only carbon black can satisfy adsorption capacity requirement.Hexamethylene is hydrolysis buffer, is made
With being to slow down titanium source hydrolysis rate, prevent product from reuniting.Only by hydrolysis speed is reduced, titanium dioxide can not be obtained
Titanium particle is karyomorphism at structure is surrounded using carbon black, also needs the peptizaiton of surfactant, forms " Water-In-Oil " or " water packet
The particle of oil " forms the effect that titanium dioxide homogeneously precipitates in carbon blacksurface under ammonia precipitation process effect.
In A liquid: hydrolyzable titanium source, which contacts to hydrolyze immediately with water, generates a large amount of white cigarettes, replaces water, a side using ethyl alcohol
Face can alleviate hydrolysis, and on the other hand, when A liquid encounters water, ethyl alcohol is equivalent under the action of water phase and surfactant and ring
Hexane forms unstable lotion, and in precipitate phase, it is relatively narrow to can be generated particle diameter distribution, the better titanium dioxide powder of dispersibility
End.In order to obtain preferable hydrolysis and sedimentation effect, the volume ratio of A liquid cyclohexane and ethyl alcohol is preferably 1:0.5-2.
In B liquid: hydrolyzable titanium source meets water and hydrolyzes a large amount of white cigarettes of emerging for violent, therefore ethyl alcohol substitution portion is added in B liquid
Divide deionized water, the hydrolysis degree of titanium source can be effectively reduced, obtain better hydrolysis effect.
Surfactant is divided into two parts in the present invention, and the mass ratio in A liquid and B liquid is 0.5-1:1, and surfactant exists
It is acted in A liquid and B liquid different: adding surfactant in A liquid and solution is helped to form unstable lotion, have in precipitation process
Conducive to performance more preferably titania powder is generated, surfactant is carbon black modified in B liquid, improves the stably dispersing of carbon black
Property.Both are acted in order to balance, inventor's repetition test, and discovery surfactant is preferably that Qula is logical or cetyl front three
Base ammonium bromide, Qula is led to for liquid, and when using triton x-100, total amount (dosage in dosage+B liquid in A liquid) is that lotion is total
1/ (5~15) of volume；Cetyl trimethylammonium bromide is solid, total when using cetyl trimethylammonium bromide
Measuring (dosage in dosage+B liquid in A liquid) is 20~40g/L, with the total volume meter of lotion.When surfactant is very few, charcoal in solution
Black dispersibility is bad easy to reunite, and it is uneven to will lead to the mixing of presoma carbon titanium.The excessive concentration of ammonium hydroxide will cause in step 2 of the present invention
PH rising is too fast, and faster, powder diameter distribution broadens TiO 2 particles forming core.Therefore, it is necessary to realize ammonia with deionized water
Water is diluted to 6.5mol/L~7.5mol/L, and ammonium hydroxide dilutes the volatilization that can alleviate ammonium hydroxide.Theoretically ammonium hydroxide additive amount it is more slow more
It is good, but the reaction time increases, preferably 6.5mol/L~7.5mol/L obtains the balance of sedimentation effect and reaction time.It is dripping
During adding ammonium hydroxide, more uniform sedimentation effect can be obtained by high-speed stirred.When pH value of solution is to 7~8, stop that ammonia is added dropwise
Water has precipitated completely at this time.
Concrete scheme is as follows:
A kind of method that hydrolyzable titanium source prepares titanium carbonitride, comprising the following steps:
Step 1: hexamethylene, ethyl alcohol and surfactant being mixed, adjusting pH is 2~3, and hydrolyzable titanium source is added, obtains
To A liquid；Deionized water, ethyl alcohol, surfactant and carbon black are mixed, B liquid is obtained；A liquid and B liquid are mixed, cream is stirred to get
Liquid；
Step 2: ammonium hydroxide is added into the lotion that step 1 obtains, stirs to get suspension, filters to take solid, is dried to obtain
Precursor powder；
Step 3: small in 400~800 DEG C of at a temperature of pretreatment 1~3 after the precursor powder that step 2 is obtained crushes
When；
Step 4: the product that step 3 obtains maintains nitrogen pressure in furnace in 1400 DEG C~1580 DEG C of flowing nitrogen atmosphere
For 500~4000pa, carries out carbothermic reduction reaction 1~4 hour, obtain titanium carbonitride.
Further, the hydrolyzable titanium source is titanium tetrachloride, at least one in titanium sulfate, titanium tetrabromide, titanium sulfate acyl
Kind.
Further, the volume ratio 1:0.5-2 of step 1 cyclohexane and ethyl alcohol；
Optional, deionized water and the volume ratio of ethyl alcohol are 0.3-2:1 in step 1；
Optional, surfactant described in step 1 leads to for Qula or cetyl trimethylammonium bromide, in A liquid and B liquid
In mass ratio be 0.5-1:1；
Optional, the dosage of carbon black in step 1: the mass ratio of the material=2.4 of hydrolyzable titanium source~2.7-1.
Further, in step 1 surfactant triton x-100 total amount be total emulsion volume 1/ (5~15)；
Optional, the total amount of surfactant cetyl trimethylammonium bromide is 20~40g/L in step 1.
Further, the concentration of ammonium hydroxide is 6.5mol/L~7.5mol/L in step 2.
Further, ammonium hydroxide is added dropwise while stirring in step 2, stops that ammonium hydroxide is added dropwise when pH value of solution=7-8, obtains suspended
Liquid.
Further, pretreatment temperature is 500~600 DEG C in step 3.
Further, in step 4 carbothermic reduction reaction temperature be 1480 DEG C~1500 DEG C, nitrogen pressure be 1000~
2000pa。
The present invention also protects a kind of carbon titanium carbonitride powder, the method system for preparing titanium carbonitride with the hydrolyzable titanium source
It is standby to obtain.
The present invention also protects the purposes of the carbon titanium carbonitride powder, is used to prepare base titanium carbonitride material.
The utility model has the advantages that the present invention prepares titanium carbonitride using hydrolyzable titanium source hydrolysis, by surfactant to carbon black
Play the role of modified effect, in conjunction with hydrolysis buffer, ethyl alcohol and ammonium hydroxide, hydrolysis is made to generate TiO 2 particles preferentially in carbon black
Surface forming core reaches preferable mixed effect.This method does not use ball mill mixing, it can be achieved that producing in enormous quantities, and particle size is
200~300nm, purity are greater than 99%, and preparation cost is low, provide a kind of new synthesis path for titanium carbonitride.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, attached drawing will be briefly described below, it should be apparent that,
The accompanying drawings in the following description merely relates to some embodiments of the present invention, rather than limitation of the present invention.
Fig. 1 is the SEM photograph for the presoma that one embodiment of the invention 1 provides；
Fig. 2 is the XRD diffraction spectra for the carbon titanium carbonitride powder that one embodiment of the invention 1 provides；
Fig. 3 is the SEM photograph for the carbon titanium carbonitride powder that one embodiment of the invention 1 provides.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.It is real
It applies and particular technique or condition person is not specified in example, according to the literature in the art described technology or conditions or according to product
Specification carries out.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.Under
In the embodiment in face, such as it is not known and illustrates, " % " refers both to weight percent.
Test method used below includes:
SEM test: equipment is Zeiss-sigma500, and test voltage is 15~20KV.
XRD test: Panaco X ' Pert Powder type X-ray diffractometer, target type are Cu target, and pipe presses 40Kv, scanning range
10 °~90 °, scanning speed is 0.02 °/s.
Ammonium hydroxide used in embodiment is all concentrated ammonia liquor, and concentration is 13mol/L~15mol/L, and when use is diluted to
6.5mol/L~7.5mol/L.
Embodiment 1
Titanium carbonitride is prepared according to the following steps:
(1) 300ml thiacyclohexane is mixed with 150ml ethyl alcohol, adjusts pH to 2~3,12g cetyl trimethyl bromine is added
Change ammonium, under the conditions of adjusting pH to 2~3, then high speed magnetic stirring, is slowly dropped into 24ml titanium tetrachloride and obtains A liquid.By 150ml second
Alcohol is mixed with 50ml deionized water.18g cetyl trimethylammonium bromide and 6.68g carbon black is added, stirring 30min obtains B
Liquid,.By A, the mixing of two liquid of B continues to stir 30min.
(2) 150ml ammonium hydroxide is mixed with 150ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 600 DEG C in vacuum tube furnace, keep the temperature 2h, obtain presoma.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
For 2000pa, in 1500 DEG C of heat preservation 4h.
By carbon titanium carbonitride powder prepared by process above, partial size is 200~300nm, and oxygen content is that 0.62% (quality contains
Amount), the purity of carbon titanium carbonitride powder is 99.38% (mass content), and approximate chemical formula is Ti (C0.57,N0.43)
Fig. 1 is the SEM photograph of presoma in step (3), and as can be seen from Figure 1 titanium dioxide and carbon black form combination
Close aggregate, Fig. 2 is the XRD diffraction spectra for the carbon titanium carbonitride powder being prepared, from figure 2 it can be seen that synthetic powder
It is carbon titanium carbonitride powder without miscellaneous phase, Fig. 3 is the SEM photograph for the carbon titanium carbonitride powder being prepared, as can be seen from Figure 3 carbon nitrogen
Change titanium powder partial size and reaches Nano grade.
Embodiment 2
Titanium carbonitride is prepared according to the following steps:
(1) 600ml thiacyclohexane is mixed with 300ml ethyl alcohol, adjusts pH to 2~3,20g cetyl trimethyl bromine is added
Change ammonium, under the conditions of adjusting pH to 2~3, then high speed magnetic stirring, is slowly dropped into 48ml titanium tetrachloride and obtains A liquid.By 300ml second
Alcohol is mixed with 200ml deionized water.25g cetyl trimethylammonium bromide and 12.33g carbon black is added, stirring 30min obtains B
Liquid.By A, the mixing of two liquid of B continues to stir 30min.
(2) 250ml ammonium hydroxide is mixed with 250ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 600 DEG C in vacuum tube furnace, keep the temperature 2h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
For 2000pa, in 1500 DEG C of heat preservation 2h.
By carbon titanium carbonitride powder prepared by process above, partial size is 200~300nm, oxygen content 0.67%, approximate chemical
Formula is Ti (C0.43,N0.57), purity is 99.33% (mass content).
Embodiment 3
Titanium carbonitride is prepared according to the following steps:
(1) 300ml thiacyclohexane is mixed with 150ml ethyl alcohol, adjusts pH to 2~3,12g cetyl trimethyl bromine is added
Change ammonium, under the conditions of adjusting pH to 2~3, then high speed magnetic stirring, is slowly dropped into 24ml titanium tetrachloride and obtains A liquid.By 150ml second
Alcohol is mixed with 50ml deionized water.18g cetyl trimethylammonium bromide is added and 6.68g carbon black obtains B liquid.By A, two liquid of B
Mixing continues to stir 30min.
(2) 150ml ammonium hydroxide is mixed with 150ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 600 DEG C in vacuum tube furnace, keep the temperature 2h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
For 1000pa, in 1500 DEG C of heat preservation 4h.
By carbon titanium carbonitride powder prepared by process above, partial size is 200~300nm, oxygen content 0.61%, approximate chemical
Formula is Ti (C0.58,N0.42), purity is 99.39% (mass content).
Embodiment 4
Titanium carbonitride is prepared according to the following steps:
(1) 300ml thiacyclohexane is mixed with 150ml ethyl alcohol, adjusts pH to 2~3,12g cetyl trimethyl bromine is added
Change ammonium, under the conditions of adjusting pH to 2~3, then high speed magnetic stirring, is slowly dropped into 24ml titanium tetrachloride and obtains A liquid.By 150ml second
Alcohol is mixed with 50ml deionized water.18g cetyl trimethylammonium bromide and 6.15g carbon black is added, obtains B after stirring 30min
Liquid.By A, the mixing of two liquid of B continues to stir 30min.
(2) 150ml ammonium hydroxide is mixed with 150ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 600 DEG C in vacuum tube furnace, keep the temperature 2h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
For 2000pa, in 1400 DEG C of heat preservation 2h.
By carbon titanium carbonitride powder prepared by process above, partial size is 200~300nm, oxygen content 0.87%, approximate chemical
Formula is Ti (C0.45,N0.55), purity is 99.13% (mass content).
Embodiment 5
Titanium carbonitride is prepared according to the following steps:
(1) 300ml thiacyclohexane is mixed with 150ml ethyl alcohol, adjusts pH to 2~3,12g cetyl trimethyl bromine is added
Change ammonium, under the conditions of adjusting pH to 2~3, then high speed magnetic stirring, is slowly dropped into 24ml titanium tetrachloride and obtains A liquid.By 150ml second
Alcohol is mixed with 50ml deionized water.18g cetyl trimethylammonium bromide is added and 6.15g carbon black obtains B liquid.By A, two liquid of B
Mixing continues to stir 30min.
(2) 150ml ammonium hydroxide is mixed with 150ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 600 DEG C in vacuum tube furnace, keep the temperature 2h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
For 1000pa, in 1500 DEG C of heat preservation 4h.
By carbon titanium carbonitride powder prepared by process above, partial size is 200~300nm, oxygen content 0.62%, approximate chemical
Formula is Ti (C0.53,N0.47), purity is 99.38% (mass content).
Embodiment 6
Titanium carbonitride is prepared according to the following steps:
(1) 300ml thiacyclohexane is mixed with 150ml ethyl alcohol, adjusts pH to 2~3,30ml triton x-100 is added, adjusted
Under the conditions of pH to 2~3, then high speed magnetic stirring, 52.8g titanium sulfate is added and obtains A liquid.By 150ml ethyl alcohol and 50ml deionization
Water mixing.30ml triton x-100 is added and 6.15g carbon black obtains B liquid.By A, the mixing of two liquid of B continues to stir 30min.
(2) 150ml ammonium hydroxide is mixed with 150ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 600 DEG C in vacuum tube furnace, keep the temperature 2h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
For 1000pa, in 1500 DEG C of heat preservation 4h.
By carbon titanium carbonitride powder prepared by process above, partial size is 200~300nm, oxygen content 0.62%, approximate chemical
Formula is Ti (C0.53,N0.47), purity is 99.38% (mass content).
Embodiment 7
Titanium carbonitride is prepared according to the following steps:
(1) 600ml thiacyclohexane is mixed with 300ml ethyl alcohol, adjusts pH to 2~3,60ml triton x-100 is added, adjusted
Under the conditions of pH to 2~3, then high speed magnetic stirring, it is slowly added to 160g titanium tetrabromide and obtains A liquid.By 300ml ethyl alcohol and 200ml
Deionized water mixing.100ml triton x-100 and 13.5g carbon black is added, stirring 30min obtains B liquid.By A, two liquid of B is mixed,
Continue to stir 30min.
(2) 250ml ammonium hydroxide is mixed with 250ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 400 DEG C in vacuum tube furnace, keep the temperature 3h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
Carbon titanium carbonitride powder is obtained in 1580 DEG C of heat preservation 1h for 4000pa.
Embodiment 8
Titanium carbonitride is prepared according to the following steps:
(1) 600ml thiacyclohexane is mixed with 300ml ethyl alcohol, adjusts pH to 2~3,100ml triton x-100 is added, adjusted
Under the conditions of saving pH to 2~3, then high speed magnetic stirring, it is slowly added to 80g titanium sulfate acyl and obtains A liquid.By 300ml ethyl alcohol and 200ml
Deionized water mixing.200ml triton x-100 and 14g carbon black is added, stirring 30min obtains B liquid.By A, two liquid of B is mixed, after
Continuous stirring 30min.
(2) 250ml ammonium hydroxide is mixed with 250ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 8.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 540 DEG C in vacuum tube furnace, keep the temperature 2h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
Carbon titanium carbonitride powder is obtained in 1460 DEG C of heat preservation 2h for 2000pa.
Embodiment 9
Titanium carbonitride is prepared according to the following steps:
(1) 600ml thiacyclohexane is mixed with 300ml ethyl alcohol, adjusts pH to 2~3,60ml triton x-100 is added, adjusted
Under the conditions of pH to 2~3, then high speed magnetic stirring, it is slowly added to 160g titanium tetrabromide and obtains A liquid.By 300ml ethyl alcohol and 200ml
Deionized water mixing.100ml triton x-100 and 13.5g carbon black is added, stirring 30min obtains B liquid.By A, two liquid of B is mixed,
Continue to stir 30min.
(2) 250ml ammonium hydroxide is mixed with 250ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 600 DEG C in vacuum tube furnace, keep the temperature 1h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
Carbon titanium carbonitride powder is obtained in 1480 DEG C of heat preservation 3h for 1000pa.
Embodiment 10
Titanium carbonitride is prepared according to the following steps:
(1) 600ml thiacyclohexane is mixed with 300ml ethyl alcohol, adjusts pH to 2~3,50ml triton x-100 is added, adjusted
Under the conditions of pH to 2~3, then high speed magnetic stirring, it is slowly added to 160g titanium tetrabromide and obtains A liquid.By 300ml ethyl alcohol and 200ml
Deionized water mixing.70ml triton x-100 and 13.5g carbon black is added, stirring 30min obtains B liquid.By A, two liquid of B is mixed, after
Continuous stirring 30min.
(2) 250ml ammonium hydroxide is mixed with 250ml deionized water, is poured into infusion bottle, using 34G syringe needle in high speed magnetic force
Under stirring condition, ammonium hydroxide after dilution is instilled in mixed solution obtained in (1), stops that ammonium hydroxide is added dropwise when pH is 7.It will be suspended
Liquid carries out suction filtration taking precipitate.
(3) it after drying precipitate, will be heated to 500 DEG C in vacuum tube furnace, keep the temperature 2h.
(4) it will be put into vacuum degreasing furnace after presoma grinding in (3), with the heating rate of 10 DEG C/min, nitrogen partial pressure
Carbon titanium carbonitride powder is obtained in 1400 DEG C of heat preservation 4h for 500pa.
Comparative example 1
Comparative sample 1 is prepared according to step in embodiment 1, the carbon black in embodiment 1 is only replaced with into active carbon.Test hair
Existing: since activated carbon particle size is much larger than carbon black, Action of Surfactant is limited, A, stands after the mixing of two liquid of B, it is heavy active carbon occur
It forms sediment；Product can see the unreacted active carbon of bulk by scanning electron microscope after carbon tropical resources reduction reaction.
Comparative example 2
Comparative sample 2 is prepared according to step in embodiment 1, only by the cetyl trimethylammonium bromide in embodiment 1
Dosage is reduced to 0, i.e., is all added without cetyl trimethylammonium bromide in A liquid and B liquid.
Test discovery: by A, after the mixing of two liquid of B, the titanium dioxide that titanium tetrachloride hydrolysis generates is clearly separated with carbon black, nothing
Method combines, the failure of an experiment.
Comparative example 3
Comparative sample 2 is prepared according to step in embodiment 1, the dosage of the thiacyclohexane in embodiment 1 is only reduced to 0, i.e. A
Thiacyclohexane is not used in liquid.
Test discovery: due to not adding hexamethylene in A liquid, the preparation of A liquid is become difficult, cetyl trimethylammonium bromide dissolution
Slowly；By A, after the mixing of two liquid of B, since titanium tetrachloride hydrolysis generates a large amount of white cigarettes, the ammonium hydroxide stage is added dropwise, settling rate becomes faster,
It hydrolyzes obtained titania powder particle diameter distribution to broaden, reunion situation aggravates, the titanium carbon after causing carbon tropical resources reduction reaction
It is deteriorated in conjunction with effect.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method that hydrolyzable titanium source prepares titanium carbonitride, comprising the following steps:
Step 1: hexamethylene, ethyl alcohol and surfactant being mixed, adjusting pH is 2~3, and hydrolyzable titanium source is added, obtains A
Liquid；Deionized water, ethyl alcohol, surfactant and carbon black are mixed, B liquid is obtained；A liquid and B liquid are mixed, lotion is stirred to get；
Step 2: ammonium hydroxide is added into the lotion that step 1 obtains, stirs to get suspension, filters to take solid, is dried to obtain forerunner
Body powder；
Step 3: after the precursor powder that step 2 is obtained crushes, 400~800 DEG C at a temperature of pre-process 1~3 hour；
Step 4: for the product that step 3 obtains in 1400 DEG C~1580 DEG C of flowing nitrogen atmosphere, maintaining nitrogen pressure in furnace is 500
~4000pa carries out carbothermic reduction reaction 1~4 hour, obtains titanium carbonitride.
2. the method that hydrolyzable titanium source prepares titanium carbonitride according to claim 1, it is characterised in that: the hydrolyzable
Titanium source is at least one of titanium tetrachloride, titanium sulfate, titanium tetrabromide, titanium sulfate acyl.
3. the method that hydrolyzable titanium source prepares titanium carbonitride according to claim 1, it is characterised in that: hexamethylene in step 1
The volume ratio 1:0.5-2 of alkane and ethyl alcohol；
Optional, deionized water and the volume ratio of ethyl alcohol are 0.3-2:1 in step 1；
Optional, surfactant described in step 1 leads to for Qula or cetyl trimethylammonium bromide, in A liquid and B liquid
Mass ratio is 0.5-1:1；
Optional, the dosage of carbon black in step 1: the mass ratio of the material=2.4 of hydrolyzable titanium source~2.7-1.
4. the method that hydrolyzable titanium source prepares titanium carbonitride according to claim 3, it is characterised in that: surface in step 1
The total amount of activating agent triton x-100 is 1/ (5~15) of total emulsion volume；
Optional, the total amount of surfactant cetyl trimethylammonium bromide is 20~40g/L in step 1.
5. the method that hydrolyzable titanium source prepares titanium carbonitride according to claim 1, it is characterised in that: ammonium hydroxide in step 2
Concentration be 6.5mol/L~7.5mol/L.
6. the method that hydrolyzable titanium source prepares titanium carbonitride according to claim 1, it is characterised in that: side is stirred in step 2
It mixes side and ammonium hydroxide is added dropwise, stop that ammonium hydroxide is added dropwise when pH value of solution=7-8, obtain suspension.
7. the method that hydrolyzable titanium source prepares titanium carbonitride according to claim 1, it is characterised in that: locate in advance in step 3
Managing temperature is 500~600 DEG C.
8. the method that hydrolyzable titanium source prepares titanium carbonitride according to claim 1, it is characterised in that: carbon heat in step 4
The temperature of reduction reaction is 1480 DEG C~1500 DEG C, and nitrogen pressure is 1000~2000pa.
9. a kind of carbon titanium carbonitride powder prepares the side of titanium carbonitride with any one of the claim 1-8 hydrolyzable titanium source
Method is prepared.
10. a kind of purposes of carbon titanium carbonitride powder described in claim 9, it is characterised in that: be used to prepare titanium carbide nitride based metal
Ceramic material.
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