CN109721368B - Titanium carbonitride powder and method for preparing titanium carbonitride from hydrolyzable titanium source - Google Patents
Titanium carbonitride powder and method for preparing titanium carbonitride from hydrolyzable titanium source Download PDFInfo
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Abstract
The invention relates to titanium carbonitride powder and a method for preparing titanium carbonitride by using a hydrolyzable titanium source, wherein the hydrolyzable titanium source is used as the titanium source, carbon black is used as the carbon source, triton X-100 or hexadecyl trimethyl ammonium bromide is used as a surfactant, cyclohexane is used as a hydrolysis buffering agent, and ammonia water is used as a precipitator, and the preparation process flow is as follows: preparing emulsion → dropping ammonia water → pumping filtration and washing of suspension, drying → pretreatment of precursor powder → carbothermal nitridation reduction → titanium carbonitride. The method does not use ball milling mixing, can realize mass production, has the product particle size of 200-300 nm and the purity of more than 99 percent, has low preparation cost, and provides a new synthesis path for the titanium carbonitride.
Description
Technical Field
The invention relates to the technical field of ceramic powder preparation, in particular to a method for preparing titanium carbonitride from titanium carbonitride powder and a hydrolysable titanium source.
Background
WC-Co series hard alloy has high strength and good toughness, is widely used in modern manufacturing industry, but has slightly insufficient hardness and wear resistance, and is limited in certain applications. The titanium carbonitride based cermet material has high hardness, high red hardness and high wear resistance, and thus is an ideal material for replacing WC-Co hard alloy. However, in order to prepare a titanium carbonitride cermet material having excellent overall properties, it is necessary to prepare a titanium carbonitride ceramic powder having high purity, fine particle size and stable sintering properties.
The preparation method of the titanium carbonitride powder comprises a carbothermal nitridation reduction method, a chemical vapor deposition method, a mechanical alloying method and a chemical synthesis method. The carbothermic nitridation reduction method has lower cost, and can be used for large-scale production and has great advantages compared with other methods. The traditional carbothermal nitridation reduction method for synthesizing titanium carbonitride powder usually takes titanium dioxide and carbon black as raw materials, ball-milling and mixing the raw materials, and then carrying out carbothermal nitridation reduction reaction at high temperature. For example, chinese patent application CN 108424147 a discloses a method for producing titanium carbonitride and titanium nitride powder by rapid nitridation, which uses traditional titanium dioxide and carbon black raw materials, and high-energy ball milling and mixing, spray granulation and drying of slurry, and powder preparation by rapid nitridation device. The method realizes the mixing of the carbon and the titanium by a physical method, and the raw materials are difficult to be uniformly mixed due to the difference of the proportion and the polarity of the raw materials, so that incomplete reaction is easily caused.
Chinese patent application CN 101462701 a discloses a method for preparing titanium nitride ceramic powder, which uses a low-temperature combustion method to uniformly mix a titanium source and a carbon source to prepare precursor powder, but this method needs strong acid as an oxidant, has certain requirements on equipment, and is difficult to realize mass production. And the organic matter used is taken as a carbon source, the carbonization process of the organic matter is complex, and the content of carbon finally entering carbothermal nitridation reduction is difficult to quantify.
Chinese patent application CN 1559912A discloses a preparation method of titanium carbonitride ternary compound powder material, which adopts TiCl4Is a titanium source, CaC2Or CCl4As carbon source, NaN3Is used as a nitrogen source, and titanium carbonitride powder is generated by reaction in a high-temperature high-pressure stainless steel reaction kettle. Wherein the reactant CaC2Can react with water in the air, and can finish the weighing operation only in a water-free and oxygen-free glove box. NaN3Belongs to a highly toxic substance, is non-flammable but explosive, and increases the production risk. The synthesis temperature of the method is 450 ℃, the sintering temperature of the titanium carbonitride base metal ceramic is 1300-1450 ℃, the powder synthesis temperature is far lower than the use temperature, and the method is very easy to denitrify in practical application to cause material defects and has low use value. The reaction vessel of the method is a high-temperature high-pressure stainless steel reaction kettle, and mass production is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects of the existing titanium carbonitride preparation technology and provide a method for preparing titanium carbonitride by using a hydrolyzable titanium source.
The invention also protects the titanium carbonitride powder prepared according to the method and the application of the titanium carbonitride powder in preparing the titanium carbonitride base cermet material which is widely applied to the field of machining, such as cutting materials.
The main principle of the invention is that the hydrolyzable titanium source is utilized for hydrolysis, so that the carbon source and the titanium source are fully mixed, the mixing uniformity of the raw materials is increased, and the nano titanium dioxide is attached to the surface of the carbon black, so that the reaction activity can be improved, and the temperature required by the reaction can be reduced. The method can not only save the ball milling and mixing process of titanium dioxide and carbon black by the traditional carbothermic method, but also solve the problems of uneven mixing and overhigh reaction temperature and make up the defect that the existing chemical synthesis method cannot realize mass production.
Hydrolysis of hydrolyzable titanium sources involves multiple complex intermediate reaction products, and because the hydrolysis reaction is usually severe, agglomeration is easily caused, and the high-temperature carbothermic reaction fails. Therefore, when titanium tetrachloride, butyl titanate or the like is used as a titanium source, it is usually isolated from water by means of a glove box to avoid contact with water. The invention overcomes the prejudice of traditional titanium source selection, and tries to hydrolyze the hydrolyzable titanium source and uniformly combine the nano titanium dioxide with the carbon source by means of necessary control conditions. The selection of the carbon source is very critical, and only carbon black can meet the requirement of adsorption capacity through repeated tests. Cyclohexane is a hydrolysis buffering agent and has the function of slowing down the hydrolysis speed of the titanium source and preventing the product from agglomerating. The effect that titanium dioxide particles form a surrounding structure with carbon black as a core and form water-in-oil or oil-in-water particles under the action of ammonia precipitation can not be obtained only by reducing the hydrolysis reaction speed, and the effect that titanium dioxide uniformly precipitates on the surface of carbon black can be formed under the action of the dispersion of a surfactant.
In the solution A, a hydrolyzable titanium source is contacted with water to be immediately hydrolyzed to generate a large amount of white smoke, ethanol is used for replacing water, on one hand, the hydrolysis can be relieved, on the other hand, when the solution A meets the water, the ethanol is equivalent to an unstable emulsion formed by the water phase and the cyclohexane under the action of a surfactant, and in a precipitation stage, titanium dioxide powder with narrow particle size distribution and better dispersibility can be generated. In order to obtain better hydrolysis and precipitation effects, the volume ratio of cyclohexane to ethanol in the solution A is preferably 1: 0.5-2.
In the solution B, a large amount of white smoke is emitted by violent hydrolysis of the hydrolysable titanium source when meeting water, so that the hydrolysis degree of the titanium source can be effectively reduced by adding ethanol to the solution B to replace part of deionized water, and a better hydrolysis effect is obtained.
The surfactant is divided into two parts, the mass ratio of the surfactant in the solution A to the surfactant in the solution B is 0.5-1:1, and the surfactant has different effects in the solution A and the solution B: the surfactant is added into the solution A to help the solution to form an unstable emulsion, so that titanium dioxide powder with better performance is generated in the precipitation process, and the surfactant in the solution B is modified by carbon black to improve the dispersion stability of the carbon black. In order to take both effects into consideration, the inventor conducts repeated experiments, and finds that the surfactant is preferably triton or hexadecyl trimethyl ammonium bromide, the triton is liquid, and when the triton X-100 is adopted, the total amount (the adding amount of the liquid A plus the adding amount of the liquid B) is 1/(5-15) of the total volume of the emulsion; the cetyl trimethyl ammonium bromide is solid, and when the cetyl trimethyl ammonium bromide is adopted, the total amount (the addition amount in the solution A + the addition amount in the solution B) is 20-40 g/L, based on the total volume of the emulsion. When the surfactant is too little, the carbon black in the solution has poor dispersibility and is easy to agglomerate, so that the precursor carbon titanium is mixed unevenly. In the step 2 of the invention, the pH value is increased too fast due to too high concentration of ammonia water, the nucleation of titanium dioxide particles is faster, and the particle size distribution of the powder is widened. Therefore, the ammonia water is diluted to 6.5 mol/L-7.5 mol/L by deionized water, and the volatilization of the ammonia water can be relieved by diluting the ammonia water. Theoretically, the slower the amount of ammonia added, the better, but the reaction time increases, preferably from 6.5mol/L to 7.5mol/L, and a balance between the precipitation effect and the reaction time is obtained. In the process of dropwise adding the ammonia water, a relatively uniform precipitation effect can be obtained by means of high-speed stirring. And stopping dropwise adding ammonia water when the pH value of the solution is 7-8, and completely precipitating at the moment.
The specific scheme is as follows:
a method for preparing titanium carbonitride from a hydrolysable titanium source, comprising the steps of:
step 1: mixing cyclohexane, ethanol and a surfactant, adjusting the pH to 2-3, and adding a hydrolyzable titanium source to obtain a solution A; mixing deionized water, ethanol, a surfactant and carbon black to obtain a solution B; mixing the solution A and the solution B, and stirring to obtain emulsion;
step 2: adding ammonia water into the emulsion obtained in the step (1), stirring to obtain a suspension, filtering to obtain a solid, and drying to obtain precursor powder;
and step 3: after the precursor powder obtained in the step 2 is crushed, pretreating for 1-3 hours at the temperature of 400-800 ℃;
and 4, step 4: and (3) maintaining the pressure of nitrogen in the furnace at 500-4000 pa in a flowing nitrogen atmosphere at 1400-1580 ℃, and carrying out carbothermic reduction reaction for 1-4 hours to obtain the titanium carbonitride.
Further, the hydrolyzable titanium source is at least one of titanium tetrachloride, titanium sulfate, titanium tetrabromide and titanium acyl sulfate.
Further, the volume ratio of the cyclohexane to the ethanol in the step 1 is 1: 0.5-2;
optionally, the volume ratio of the deionized water to the ethanol in the step 1 is 0.3-2: 1;
optionally, the surfactant in the step 1 is triton or hexadecyl trimethyl ammonium bromide, and the mass ratio of the surfactant in the solution A to the surfactant in the solution B is 0.5-1: 1;
optionally, the addition of carbon black in step 1: the mass ratio of the hydrolyzable titanium source is 2.4-2.7-1.
Further, in the step 1, the total amount of the surfactant triton X-100 is 1/(5-15) of the total volume of the emulsion;
optionally, in the step 1, the total amount of the surfactant cetyl trimethyl ammonium bromide is 20-40 g/L.
Furthermore, the concentration of the ammonia water in the step 2 is 6.5 mol/L-7.5 mol/L.
Further, in step 2, ammonia water was added dropwise with stirring, and the addition of ammonia water was stopped when the pH of the solution became 7 to 8, to obtain a suspension.
Further, the pretreatment temperature in the step 3 is 500-600 ℃.
Further, the temperature of the carbothermic reduction reaction in the step 4 is 1480-1500 ℃, and the nitrogen pressure is 1000-2000 pa.
The invention also provides titanium carbonitride powder prepared by the method for preparing titanium carbonitride by using the hydrolyzable titanium source.
The invention also protects the application of the titanium carbonitride powder to the preparation of the titanium carbonitride-based cermet material.
Has the advantages that: the invention prepares titanium carbonitride by hydrolyzing a hydrolyzable titanium source, modifies carbon black by a surfactant, and forms a nucleus on the surface of the carbon black preferentially by hydrolyzing titanium dioxide particles generated by hydrolysis under the action of a hydrolysis buffer, ethanol and ammonia water, thereby achieving a better mixing effect. The method does not use ball milling mixing, can realize mass production, has the product particle size of 200-300 nm and the purity of more than 99 percent, has low preparation cost, and provides a new synthesis path for the titanium carbonitride.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is an SEM photograph of a precursor provided in accordance with one embodiment 1 of the present invention;
FIG. 2 is an XRD diffraction spectrum of a titanium carbonitride powder provided in accordance with one embodiment 1 of the present invention;
fig. 3 is an SEM photograph of the titanium carbonitride powder provided in one embodiment 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The test methods used below included:
and (4) SEM test: the equipment is Zeiss-sigma 500, and the test voltage is 15-20 KV.
XRD test: the X' Pert Powder type X-ray diffractometer of the Pasnaceae has a Cu target type, a tube pressure of 40Kv, a scanning range of 10-90 degrees and a scanning speed of 0.02 degree/s.
The ammonia water used in the examples is concentrated ammonia water with a concentration of 13-15 mol/L, and is diluted to 6.5-7.5 mol/L when in use.
Example 1
Titanium carbonitride was prepared according to the following steps:
(1) mixing 300ml of cyclohexane with 150ml of ethanol, adjusting the pH value to 2-3, adding 12g of hexadecyl trimethyl ammonium bromide, adjusting the pH value to 2-3, and slowly dripping 24ml of titanium tetrachloride under the condition of high-speed magnetic stirring to obtain solution A. 150ml of ethanol was mixed with 50ml of deionized water. Adding 18g of hexadecyl trimethyl ammonium bromide and 6.68g of carbon black, and stirring for 30min to obtain a solution B. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 150ml of ammonia water with 150ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) And drying the precipitate, heating to 600 ℃ in a vacuum tube furnace, and preserving heat for 2h to obtain the precursor.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1500 ℃ for 4 hours at the heating rate of 10 ℃/min and the nitrogen partial pressure of 2000 pa.
The titanium carbonitride powder prepared by the process has the particle size of 200-300 nm, the oxygen content of 0.62 percent (mass content), the purity of 99.38 percent (mass content), and the approximate chemical formulaTi(C0.57,N0.43)
Fig. 1 is an SEM photograph of the precursor in step (3), and it can be seen from fig. 1 that titanium dioxide forms tightly bound agglomerates with carbon black, fig. 2 is an XRD diffraction spectrum of the titanium carbonitride powder obtained by the preparation, and it can be seen from fig. 2 that the synthesized powder is a titanium carbonitride powder without a hetero phase, fig. 3 is an SEM photograph of the titanium carbonitride powder obtained by the preparation, and it can be seen from fig. 3 that the particle size of the titanium carbonitride powder reaches the nanometer level.
Example 2
Titanium carbonitride was prepared according to the following steps:
(1) mixing 600ml of cyclohexane with 300ml of ethanol, adjusting the pH value to 2-3, adding 20g of hexadecyl trimethyl ammonium bromide, adjusting the pH value to 2-3, and slowly dripping 48ml of titanium tetrachloride under the condition of high-speed magnetic stirring to obtain solution A. 300ml of ethanol was mixed with 200ml of deionized water. 25g of cetyltrimethylammonium bromide and 12.33g of carbon black were added thereto, and stirred for 30min to obtain solution B. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 250ml of ammonia water with 250ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 600 ℃ in a vacuum tube furnace and held for 2 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1500 ℃ for 2 hours at the heating rate of 10 ℃/min and the nitrogen partial pressure of 2000 pa.
The titanium carbonitride powder prepared by the process has the particle size of 200-300 nm, the oxygen content of 0.67 percent and the approximate chemical formula of Ti (C)0.43,N0.57) The purity was 99.33% (mass content).
Example 3
Titanium carbonitride was prepared according to the following steps:
(1) mixing 300ml of cyclohexane with 150ml of ethanol, adjusting the pH value to 2-3, adding 12g of hexadecyl trimethyl ammonium bromide, adjusting the pH value to 2-3, and slowly dripping 24ml of titanium tetrachloride under the condition of high-speed magnetic stirring to obtain solution A. 150ml of ethanol was mixed with 50ml of deionized water. 18g of cetyltrimethylammonium bromide and 6.68g of carbon black were added to obtain a B solution. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 150ml of ammonia water with 150ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 600 ℃ in a vacuum tube furnace and held for 2 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1500 ℃ for 4 hours at the heating rate of 10 ℃/min and the nitrogen partial pressure of 1000 pa.
The titanium carbonitride powder prepared by the process has the particle size of 200-300 nm, the oxygen content of 0.61 percent and the approximate chemical formula of Ti (C)0.58,N0.42) The purity was 99.39% (mass content).
Example 4
Titanium carbonitride was prepared according to the following steps:
(1) mixing 300ml of cyclohexane with 150ml of ethanol, adjusting the pH value to 2-3, adding 12g of hexadecyl trimethyl ammonium bromide, adjusting the pH value to 2-3, and slowly dripping 24ml of titanium tetrachloride under the condition of high-speed magnetic stirring to obtain solution A. 150ml of ethanol was mixed with 50ml of deionized water. Adding 18g of hexadecyl trimethyl ammonium bromide and 6.15g of carbon black, and stirring for 30min to obtain a solution B. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 150ml of ammonia water with 150ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 600 ℃ in a vacuum tube furnace and held for 2 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1400 ℃ for 2h at the heating rate of 10 ℃/min and the nitrogen partial pressure of 2000 pa.
The titanium carbonitride powder prepared by the process has the particle size of 200-300 nm, the oxygen content of 0.87 percent and the approximate chemical formula of Ti (C)0.45,N0.55) The purity was 99.13% (mass content).
Example 5
Titanium carbonitride was prepared according to the following steps:
(1) mixing 300ml of cyclohexane with 150ml of ethanol, adjusting the pH value to 2-3, adding 12g of hexadecyl trimethyl ammonium bromide, adjusting the pH value to 2-3, and slowly dripping 24ml of titanium tetrachloride under the condition of high-speed magnetic stirring to obtain solution A. 150ml of ethanol was mixed with 50ml of deionized water. 18g of cetyltrimethylammonium bromide and 6.15g of carbon black were added to obtain a B solution. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 150ml of ammonia water with 150ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 600 ℃ in a vacuum tube furnace and held for 2 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1500 ℃ for 4 hours at the heating rate of 10 ℃/min and the nitrogen partial pressure of 1000 pa.
The titanium carbonitride powder prepared by the process has the particle size of 200-300 nm, the oxygen content of 0.62 percent and the approximate chemical formula of Ti (C)0.53,N0.47) The purity was 99.38% (mass content).
Example 6
Titanium carbonitride was prepared according to the following steps:
(1) mixing 300ml of cyclohexane with 150ml of ethanol, adjusting the pH value to 2-3, adding 30ml of triton X-100, adjusting the pH value to 2-3, and adding 52.8g of titanium sulfate under the condition of high-speed magnetic stirring to obtain solution A. 150ml of ethanol was mixed with 50ml of deionized water. 30ml of Triton X-100 and 6.15g of carbon black were added to obtain solution B. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 150ml of ammonia water with 150ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 600 ℃ in a vacuum tube furnace and held for 2 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1500 ℃ for 4 hours at the heating rate of 10 ℃/min and the nitrogen partial pressure of 1000 pa.
The titanium carbonitride powder prepared by the process has the particle size of 200-300 nm, the oxygen content of 0.62 percent and the approximate chemical formula of Ti (C)0.53,N0.47) The purity was 99.38% (mass content).
Example 7
Titanium carbonitride was prepared according to the following steps:
(1) mixing 600ml of cyclohexane with 300ml of ethanol, adjusting the pH value to 2-3, adding 60ml of triton X-100, adjusting the pH value to 2-3, and slowly adding 160g of titanium tetrabromide under the condition of high-speed magnetic stirring to obtain solution A. 300ml of ethanol was mixed with 200ml of deionized water. 100ml of Triton X-100 and 13.5g of carbon black were added thereto, and the mixture was stirred for 30 minutes to obtain solution B. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 250ml of ammonia water with 250ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 400 ℃ in a vacuum tube furnace and held for 3 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1580 ℃ for 1h at the heating rate of 10 ℃/min and the nitrogen partial pressure of 4000pa to obtain the titanium carbonitride powder.
Example 8
Titanium carbonitride was prepared according to the following steps:
(1) mixing 600ml of cyclohexane with 300ml of ethanol, adjusting the pH value to 2-3, adding 100ml of triton X-100, adjusting the pH value to 2-3, and slowly adding 80g of titanyl sulfate under the condition of high-speed magnetic stirring to obtain solution A. 300ml of ethanol was mixed with 200ml of deionized water. 200ml of Triton X-100 and 14g of carbon black are added and stirred for 30min to obtain a solution B. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 250ml of ammonia water with 250ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 8. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 540 ℃ in a vacuum tube furnace and held for 2 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1460 ℃ for 2 hours at the heating rate of 10 ℃/min and the nitrogen partial pressure of 2000pa to obtain the titanium carbonitride powder.
Example 9
Titanium carbonitride was prepared according to the following steps:
(1) mixing 600ml of cyclohexane with 300ml of ethanol, adjusting the pH value to 2-3, adding 60ml of triton X-100, adjusting the pH value to 2-3, and slowly adding 160g of titanium tetrabromide under the condition of high-speed magnetic stirring to obtain solution A. 300ml of ethanol was mixed with 200ml of deionized water. 100ml of Triton X-100 and 13.5g of carbon black were added thereto, and the mixture was stirred for 30 minutes to obtain solution B. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 250ml of ammonia water with 250ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 600 ℃ in a vacuum tube furnace and held for 1 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, keeping the temperature at 1480 ℃ for 3 hours at the heating rate of 10 ℃/min and the nitrogen partial pressure of 1000pa to obtain the titanium carbonitride powder.
Example 10
Titanium carbonitride was prepared according to the following steps:
(1) mixing 600ml of cyclohexane with 300ml of ethanol, adjusting the pH value to 2-3, adding 50ml of triton X-100, adjusting the pH value to 2-3, and slowly adding 160g of titanium tetrabromide under the condition of high-speed magnetic stirring to obtain solution A. 300ml of ethanol was mixed with 200ml of deionized water. 70ml of Triton X-100 and 13.5g of carbon black were added thereto, and the mixture was stirred for 30 minutes to obtain solution B. Mixing the two solutions A and B, and stirring for 30 min.
(2) And (3) mixing 250ml of ammonia water with 250ml of deionized water, pouring into an infusion bottle, dripping the diluted ammonia water into the mixed solution obtained in the step (1) by using a 34G needle under the condition of high-speed magnetic stirring, and stopping dripping the ammonia water when the pH value is 7. And carrying out suction filtration on the suspension to obtain a precipitate.
(3) The precipitate was dried and heated to 500 ℃ in a vacuum tube furnace and held for 2 h.
(4) And (4) grinding the precursor in the step (3), putting the ground precursor into a vacuum degreasing furnace, and keeping the temperature at 1400 ℃ for 4 hours at the heating rate of 10 ℃/min and the nitrogen partial pressure of 500pa to obtain the titanium carbonitride powder.
Comparative example 1
Comparative 1 was prepared by following the procedure of example 1 except that the carbon black of example 1 was replaced with activated carbon. The test finds that: because the particle size of the activated carbon is far larger than that of the carbon black, the action of the surfactant is limited, and the solution A and the solution B are mixed and then stand to generate activated carbon precipitation; the product after the carbothermal nitridation reduction reaction can be seen as large blocks of unreacted activated carbon through a scanning electron microscope.
Comparative example 2
Comparative sample 2 was prepared by following the procedure of example 1 except that the amount of cetyltrimethylammonium bromide added in example 1 was reduced to 0, i.e., no cetyltrimethylammonium bromide was added to neither solution a nor solution B.
The test finds that: after the A liquid and the B liquid are mixed, titanium dioxide generated by titanium tetrachloride hydrolysis is obviously separated from carbon black, and cannot be combined, so that the experiment fails.
Comparative example 3
Comparative 2 was prepared by following the procedure of example 1 except that the amount of cyclohexane added in example 1 was reduced to 0, i.e., cyclohexane was not used in liquid A.
The test finds that: because cyclohexane is not added into the solution A, the solution A is difficult to prepare, and the hexadecyl trimethyl ammonium bromide is slowly dissolved; after the A liquid and the B liquid are mixed, because titanium tetrachloride is hydrolyzed to generate a large amount of white smoke, the precipitation speed is increased in the stage of dripping ammonia water, the particle size distribution of titanium dioxide powder obtained by hydrolysis is widened, the agglomeration condition is increased, and the titanium-carbon combination effect after the carbothermic nitridation reduction reaction is deteriorated.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A method for preparing titanium carbonitride from a hydrolysable titanium source, comprising the steps of:
step 1: mixing cyclohexane, ethanol and a surfactant, adjusting the pH to 2-3, and adding a hydrolyzable titanium source to obtain a solution A; mixing deionized water, ethanol, a surfactant and carbon black to obtain a solution B; mixing the solution A and the solution B, and stirring to obtain emulsion;
step 2: adding ammonia water into the emulsion obtained in the step (1), wherein the concentration of the ammonia water is 6.5-7.5 mol/L, stirring to obtain a suspension, filtering to obtain a solid, and drying to obtain precursor powder;
and step 3: after the precursor powder obtained in the step 2 is crushed, pretreating for 1-3 hours at the temperature of 400-800 ℃;
and 4, step 4: and (3) maintaining the pressure of nitrogen in the furnace at 500-4000 pa in a flowing nitrogen atmosphere at 1400-1580 ℃, and carrying out carbothermic reduction reaction for 1-4 hours to obtain the titanium carbonitride.
2. A process for preparing titanium carbonitride from a hydrolyzable titanium source as set forth in claim 1 characterized by: the hydrolyzable titanium source is at least one of titanium tetrachloride, titanium sulfate, titanium tetrabromide and titanium acyl sulfate.
3. A process for preparing titanium carbonitride from a hydrolyzable titanium source as set forth in claim 1 characterized by: the volume ratio of the cyclohexane to the ethanol in the step 1 is 1: 0.5-2.
4. A process for preparing titanium carbonitride from a hydrolyzable titanium source as set forth in claim 1 characterized by: the volume ratio of the deionized water to the ethanol in the step 1 is 0.3-2: 1.
5. a process for preparing titanium carbonitride from a hydrolyzable titanium source as set forth in claim 1 characterized by: in the step 1, the surfactant is triton or hexadecyl trimethyl ammonium bromide, and the mass ratio of the surfactant in the solution A to the surfactant in the solution B is 0.5-1: 1.
6. A process for preparing titanium carbonitride from a hydrolyzable titanium source as set forth in claim 1 characterized by: adding amount of carbon black in step 1: the mass ratio of the hydrolyzable titanium source is 2.4-2.7-1.
7. The method of preparing titanium carbonitride according to claim 5 characterized by the fact that: in the step 1, the total amount of the surfactant Triton X-100 is 1/(5-15) of the total volume of the emulsion.
8. The method of preparing titanium carbonitride according to claim 5 characterized by the fact that: in the step 1, the total amount of the surfactant cetyl trimethyl ammonium bromide is 20-40 g/L.
9. A process for preparing titanium carbonitride from a hydrolyzable titanium source as set forth in claim 1 characterized by: and (3) dropwise adding ammonia water while stirring in the step 2, and stopping dropwise adding the ammonia water when the pH value of the solution is 7-8 to obtain a suspension.
10. A process for preparing titanium carbonitride from a hydrolyzable titanium source as set forth in claim 1 characterized by: the pretreatment temperature in the step 3 is 500-600 ℃.
11. A process for preparing titanium carbonitride from a hydrolyzable titanium source as set forth in claim 1 characterized by: the temperature of the carbothermic reduction reaction in the step 4 is 1480-1500 ℃, and the nitrogen pressure is 1000-2000 pa.
12. A titanium carbonitride powder produced by the process for producing titanium carbonitride using the hydrolyzable titanium source as defined in any one of claims 1 to 11.
13. Use of the titanium carbonitride powder of claim 12 characterized by: is used for preparing the titanium carbonitride base cermet material.
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