CN101462701A - Method for preparing titanium nitride ceramic powder - Google Patents
Method for preparing titanium nitride ceramic powder Download PDFInfo
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- CN101462701A CN101462701A CNA200910076143XA CN200910076143A CN101462701A CN 101462701 A CN101462701 A CN 101462701A CN A200910076143X A CNA200910076143X A CN A200910076143XA CN 200910076143 A CN200910076143 A CN 200910076143A CN 101462701 A CN101462701 A CN 101462701A
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Abstract
The invention relates to a method for preparing titanium nitride ceramic powder, which belongs to the field of the preparation of ceramic powder. A titanium source comprises soluble titanium salt, namely titanium tetrachloride or titanium tetrabromide, and a carbon source comprises glucose, sucrose, citric acid and soluble starch. Nitric acid is used as an oxidizing agent, and urea is used as a fuel; and ammonium nitrate is used as a preparing agent. The mol ratio Ti ;C of the titanium source to the carbon source is 1 to (4-16), and the mol ratio of the nitric acid with the ammonium nitrate to the urea with the ammonium nitrate is (1-12) ;2. Various raw materials are dissolved in water and then are heated at a temperature of between 100 and 600 DEG C, and a solution undergoes a combustion reaction to generate precursors; the precursors are pulverized and then are pretreated for 0 to 10 hours at a temperature of between 200 and 800 DEG C, and then a carbon thermal reduction is carried out for 1 to 10 hours in the atmosphere of flowing nitrogen at a temperature of between 800 and 1,800 DEG C. Follow-up treatment is carried out on products to obtain titanium nitride powder. The titanium source and the carbon source in the precursors of the invention have fine granularity and are uniformly mixed; therefore, the method has good reaction activity and also has the advantages of lowering the temperature of the carbon thermal reduction reaction and improving the reaction rate. The method can prepare nanometer-level non-oxidized ceramic powder with good decentrality.
Description
Technical field
The invention belongs to the ceramic powder preparing technical field, a kind of method for preparing the Nano titanium nitride ceramic powder particularly is provided.
Background technology
Titanium nitride (TiN) pottery has high strength, high rigidity, high temperature resistant, series of advantages such as acid and alkali-resistance corrodes, wear-resistant and good electrical conductivity, thermal conductivity, be widely used in preparation sintering metal, cutting tool, smelting metal with crucible, fused salt electrolysis metal with the coating material of lining material, electrical contact and the metallic surface of electrode etc.
High-quality powder stock is the prerequisite that obtains premium quality product, the stupalith of processability excellence, often needs at first to prepare high purity, fine granularity, the good powder stock of sintering character.The preparation method of titanium nitride ceramic powder has carbothermic method, the direct nitrogenize of metal, chemical Vapor deposition process etc. multiple; wherein the powder of carbothermic method preparation has greater advantage at purity, granularity and aspects such as pattern, sintering character; in addition; this method cost is lower, suitability for scale production.The conventional carbon hot reducing method prepares titanium nitride powder, and to adopt titanium dioxide and carbon black usually be raw material, but because proportion and polarity difference, the two is difficult to mix, cause reaction not exclusively easily, in addition, the temperature of reaction height, long reaction time, therefore, this method remains further to be improved.
Summary of the invention
The object of the invention is to increase raw material blended homogeneity, simultaneously can make two kinds of littler direct contact reactss of subparticle of granularity, improves reactive behavior, synthesis of high purity, fine-grained ceramic powder under than the low reaction temperatures condition; Solving conventional carbon hot reducing method employing titanium dioxide and carbon black is the feedstock production titanium nitride powder, the problem of batch mixing inequality, temperature of reaction height, long reaction time.
The mixed precursor for preparing titanium dioxide and carbon by chemical process is one of effective way of improving carbothermic reduction condition and preparation fine granularity ceramic powder, its principle is can improve tradition and directly be raw material with titanium dioxide ceramic powder and carbon dust by chemical process the time, increase raw material blended homogeneity, simultaneously can make two kinds of littler direct contact reactss of subparticle of granularity, improve reactive behavior, synthesis of high purity, fine-grained ceramic powder under than the low reaction temperatures condition.
Low-temperature burning is synthetic to be a kind of combustion synthesis reaction in the liquid phase, its essence is the redox thermopositive reaction between oxygenant and the fuel.Normally adopting metal nitrate (or soluble substance of nitric acid+containing metal element) is oxygenant, urea is reductive agent (fuel), because the nitrogen element is-3 valencys in the urea, it can play the effect of reductive agent, with nitrate radical (the nitrogen element in the nitrate radical is+5 valencys, is oxygenant) redox reaction takes place, they are heated to certain temperature, the two combustible gas that decomposes is out known from experience the combustion reactions that non-explosion type takes place, and emits a large amount of heats and gas.
A kind of method for preparing titanium nitride ceramic powder, its characteristics are the low-temperature burning synthetic technology is applied to the preparation of titanium oxide and carbon mixed precursor, characteristics are that water-soluble organic carbon source such as glucose, sucrose, Zulkovsky starch, citric acid etc. are joined in the mixing solutions of metal nitrate (or soluble substance+nitric acid of other metal-salts) and organic-fuel, in liquid phase with behind each component uniform mixing solution being heated, between oxygenant and the fuel combustion reactions takes place.The combustion reactions liberated heat makes organic carbon source generation pyrolysis and charing, metal-salt then is converted into the superfine oxide ceramic powder of granularity, and be dispersed in the carbon source that forms behind the organic matter carbonizing, a large amount of gases of emitting in the combustion reactions process make the precursor that obtains become very fluffy foam-like material, can effectively prevent the reunion of powder particle in the precursor, help preparing the non-oxide ceramics powder of good dispersion property.
The present invention realizes by following steps:
1. raw material: the titanium source of being adopted comprises solubility titanium salt titanium tetrachloride, titanium tetrabromide.Carbon source is water-soluble organic carbon source, comprises glucose, sucrose, citric acid, Zulkovsky starch.The oxygenant that is adopted is a nitric acid.Fuel is urea.Ammonium nitrate is blender.
2. the preparation of precursor: the proportioning of titanium salt titanium tetrachloride or titanium tetrabromide and organic carbon source (glucose, sucrose, citric acid, Zulkovsky starch) is according to mol ratio Ti:C=1:(4～16); When not adding blender, the mol ratio of nitric acid and urea is (1～12): 1; When adding blender, it is (1～12) with the mol ratio that urea adds ammonium nitrate that nitric acid adds ammonium nitrate: 2, i.e. and { n
Nitric acid+ n
Ammonium nitrate}/{ 2n
Urea+ n
Ammonium nitrate}=(1～12): 2.With various raw materials water-soluble after, under 100～600 ℃ of temperature, heat, solution in experience volatilization, concentrate, after a series of processes such as bubbling, combustion reactions take place, obtain precursor.
3. the pre-treatment of precursor: after the precursor pulverizing with gained, pre-treatment is 0～10 hour under 200～800 ℃ temperature.
4. the carbothermic reduction reaction of precursor: the precursor that step 3 is obtained carbothermic reduction 1～10 hour in 800～1800 ℃ flowing nitrogen atmosphere, nitrogen flow is 1～20l/min, reaction product obtains titanium nitride powder through subsequent disposal.
Utilize the synthetic preparation of low-temperature burning precursor, overcome fully that traditional the two is difficult to the blended shortcoming when directly being raw material with oxide ceramic powder and carbon dust, can realize the oxide particle that granularity is more tiny and the homodisperse and the mixing of carbon source particle, therefore, precursor has good reactive behavior.With this precursor is that the prepared using carbothermic method prepares the non-oxide ceramics powder, can improve reaction conditions greatly, reduces temperature of reaction, improves speed of reaction.
The invention has the advantages that:
1. the low-temperature burning synthetic technology is used the preparation of titanium nitride ceramic powder, possessed the advantage of wet chemistry method, after various raw materials are water-soluble, in solution, realize metal titanium salt and the uniform mixing of carbon source on atom or molecular level easily.
2. made full use of synthetic easy, quick, the characteristic of low energy consumption of low-temperature burning; A large amount of gases that combustion reactions is emitted make precursor be fluffy spumescence, can effectively prevent to reunite, and help preparing the titanium nitride ceramic powder of good dispersion property.
In the precursor titanium source and carbon source granularity tiny, mix, reactive behavior is good, reduces the carbothermic reduction reaction temperature greatly, improves speed of reaction, can prepare the nanoscalar non-oxidic ceramic powder of good dispersion property.
Embodiment
Embodiment 1:
Take by weighing 0.1 mole of titanium tetrachloride, 0.1 mole of glucose, 0.2 mole in nitric acid, 0.1 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 300 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 1 hour in 400 ℃ air.Be reaction 1 hour under the condition of 3l/min at 1400 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 2:
Take by weighing 0.09 mole of titanium tetrachloride, 0.06 mole of citric acid, 1.5 moles in nitric acid, 0.5 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 200 ℃ the temperature controllable electric furnace and heat, solution in the experience volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 2 hours in 200 ℃ air.Be reaction 10 hours under the condition of 1l/min at 1200 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 3:
Take by weighing 0.09 mole of titanium tetrachloride, 0.06 mole of sucrose, 5 moles in nitric acid, 0.5 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 400 ℃ the temperature controllable electric furnace and heat, solution through volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 1 hour in 600 ℃ air.Be reaction 8 hours under the condition of 5l/min at 1600 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 4:
Take by weighing 0.09 mole of titanium tetrachloride, 0.15 mole of glucose, 2 moles in nitric acid, 0.5 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 200 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 2 hours in 500 ℃ air.Be reaction 5 hours under the condition of 10l/min at 1500 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 5:
Take by weighing 0.09 mole of titanium tetrachloride, 0.21 mole of glucose, 3 moles in nitric acid, 0.5 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 300 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 3 hours in 300 ℃ air.Be reaction 6 hours under the condition of 2l/min at 1100 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 6:
Take by weighing 0.1 mole of titanium tetrachloride, 0.15 mole of glucose, 1.5 moles in nitric acid, 0.5 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 400 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 5 hours in 400 ℃ air.Be reaction 4 hours under the condition of 3l/min at 1200 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 7:
Take by weighing 0.1 mole of titanium tetrachloride, 0.15 mole of glucose, 2.5 moles in nitric acid, 0.5 mole on urine rope.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 200 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, reaction obtains precursor.Precursor is pulverized the back to be handled 4 hours in 500 ℃ air.Be reaction 2 hours under the condition of 151/min at 1500 ℃, nitrogen flow with the gained material, the gained reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 8:
Take by weighing 0.1 mole of titanium tetrabromide, 0.15 mole of citric acid, 1.5 moles in nitric acid, 1 mole in ammonium nitrate.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 200 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, reaction obtains precursor.Precursor is pulverized the back to be handled 4 hours in 500 ℃ air.Be reaction 2 hours under the condition of 5l/min at 1500 ℃, nitrogen flow with the gained material, the gained reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 9:
Take by weighing 0.1 mole of titanium tetrachloride, 0.075 mole of sucrose, 0.5 mole in nitric acid, 0.5 mole in ammonium nitrate.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 200 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, reaction obtains precursor.Precursor is pulverized the back to be handled 6 hours in 500 ℃ air.Be reaction 2 hours under the condition of 51/min at 1500 ℃, nitrogen flow with the gained material, the gained reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 10:
Take by weighing 0.09 mole of titanium tetrabromide, 0.21 mole of glucose, 3 moles in nitric acid, 0.5 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 300 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 3 hours in 300 ℃ air.Be reaction 6 hours under the condition of 2l/min at 1800 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 11:
Take by weighing 0.1 mole of titanium tetrachloride, 0.05 mole of sucrose, 0.2 mole in nitric acid, 0.1 mole in urea, 0.1 mole in ammonium nitrate.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 300 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 3 hours in 400 ℃ air.Be reaction 1 hour under the condition of 3l/min at 1400 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 12:
Take by weighing 0.09 mole of titanium tetrachloride, 0.12 mole of glucose, 1.5 moles in nitric acid, 0.5 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 200 ℃ the temperature controllable electric furnace and heat, solution in the experience volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 2 hours in 200 ℃ air.Be reaction 10 hours under the condition of 1l/min at 1800 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Embodiment 13:
Take by weighing 0.1 mole of titanium tetrachloride, Zulkovsky starch ((C
6H
10O
5)
n) 0.1 mole (during n=1), 0.2 mole in nitric acid, 0.1 mole in urea.Above-mentioned various materials are dissolved in the distilled water of 100ml, are mixed with solution, solution is placed on 250 ℃ the temperature controllable electric furnace and heat, solution in volatilization, concentrate, combustion reactions take place after a series of processes such as bubbling, obtain precursor.Precursor is pulverized the back to be handled 1 hour in 400 ℃ air.Be reaction 4 hours under the condition of 7l/min at 1700 ℃, nitrogen flow with the gained material, reaction product obtains titanium nitride powder through subsequent disposal.
Claims (1)
1. method for preparing titanium nitride ceramic powder is characterized in that: concrete technology is:
A. raw material: the titanium source of being adopted comprises solubility titanium salt titanium tetrachloride, titanium tetrabromide; Carbon source is water-soluble organic carbon source, comprises glucose, sucrose, citric acid, Zulkovsky starch; The oxygenant that is adopted is a nitric acid, and fuel is urea; Ammonium nitrate is blender;
B. the preparation of precursor: the proportioning of titanium salt titanium tetrachloride or titanium tetrabromide and organic carbon source is according to mol ratio Ti:C=1:(4～16); When not adding blender, the mol ratio of nitric acid and urea is (1～12): 1; When adding blender, it is (1～12) with the mol ratio that urea adds ammonium nitrate that nitric acid adds ammonium nitrate: 2, i.e. and (n
Nitric acid+ n
Ammonium nitrate)/(2n
Urea+ n
Ammonium nitrate)=(1～12): 2; With various raw materials water-soluble after, under 100～600 ℃ of temperature, heat, obtain precursor after the solution generation combustion reactions;
C. the pre-treatment of precursor, after the precursor pulverizing with gained, pre-treatment is 0～10 hour under 200～800 ℃ temperature;
D. the carbothermic reduction 1～10 hour in 800～1800 ℃ flowing nitrogen atmosphere of the carbothermic reduction reaction of precursor, the precursor that step c is obtained, nitrogen flow is 1～20l/min, reaction product obtains titanium nitride powder through subsequent disposal.
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| CN200910076143XA CN101462701B (en) | 2009-01-09 | 2009-01-09 | Method for preparing titanium nitride ceramic powder |
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| CN200910076143XA CN101462701B (en) | 2009-01-09 | 2009-01-09 | Method for preparing titanium nitride ceramic powder |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864030A (en) * | 2012-12-11 | 2014-06-18 | 浙江海洋学院 | Nanometer titanium nitride powder preparation method |
| CN106115638A (en) * | 2016-06-22 | 2016-11-16 | 江汉大学 | The preparation method of a kind of titanium nitride, titanium nitride and application thereof |
| CN107215851A (en) * | 2016-03-22 | 2017-09-29 | 纳琳威纳米科技（上海）有限公司 | A kind of high heat insulation nano ceramic powder and its production and use |
| CN107777673A (en) * | 2017-11-13 | 2018-03-09 | 武汉科技大学 | A kind of cube zirconium nitride powder based on low-temperature reduction and preparation method thereof |
| CN107892329A (en) * | 2017-11-23 | 2018-04-10 | 北京科技大学 | A kind of high flux conbustion synthesis powder body material preparation facilities and preparation method |
-
2009
- 2009-01-09 CN CN200910076143XA patent/CN101462701B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864030A (en) * | 2012-12-11 | 2014-06-18 | 浙江海洋学院 | Nanometer titanium nitride powder preparation method |
| CN107215851A (en) * | 2016-03-22 | 2017-09-29 | 纳琳威纳米科技（上海）有限公司 | A kind of high heat insulation nano ceramic powder and its production and use |
| CN106115638A (en) * | 2016-06-22 | 2016-11-16 | 江汉大学 | The preparation method of a kind of titanium nitride, titanium nitride and application thereof |
| CN107777673A (en) * | 2017-11-13 | 2018-03-09 | 武汉科技大学 | A kind of cube zirconium nitride powder based on low-temperature reduction and preparation method thereof |
| CN107892329A (en) * | 2017-11-23 | 2018-04-10 | 北京科技大学 | A kind of high flux conbustion synthesis powder body material preparation facilities and preparation method |
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| CN101462701B (en) | 2011-05-04 |
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