CN103864030A - Nanometer titanium nitride powder preparation method - Google Patents
Nanometer titanium nitride powder preparation method Download PDFInfo
- Publication number
- CN103864030A CN103864030A CN201210537399.8A CN201210537399A CN103864030A CN 103864030 A CN103864030 A CN 103864030A CN 201210537399 A CN201210537399 A CN 201210537399A CN 103864030 A CN103864030 A CN 103864030A
- Authority
- CN
- China
- Prior art keywords
- titanium nitride
- colloid
- preparation
- urea
- nitride powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a nanometer titanium nitride preparation method, which is characterized by comprising the following steps: 1) preparing titanium tetrachloride and a dehydrated alcohol solvent into a titanium compound alcohol solution according to a molar ratio of 1:10-1:1; 2) adding the titanium compound alcohol solution to a certain proportion of urea to prepare a colloid, wherein a molar ratio of the urea to the titanium tetrachloride is 2:1-10:1; and 3) aging the colloid formed from the urea and the titanium compound, and treating the aged colloid for 2-10 h at a temperature of 600-1000 DEG C under a protection atmosphere to obtain the nanometer titanium nitride powder. Compared with the conventional preparation method, the preparation method of the present invention has advantages of wide synthesis raw material source, low cost, simple preparation process, low synthesis temperature and the like, and has wide application prospects in the industrial production. In addition, the prepared nanometer titanium nitride powder has characteristics of average particle size of 3-20 nm, narrow particle size distribution and good dispersity.
Description
Technical field
The present invention relates to nano-powder preparing technical field, specifically relate to the technique that a kind of colloid method is prepared Nano titanium nitride powder.
Background technology
Titanium nitride is a kind of broad-spectrum superhard material, and the block TiN of desirable stoichiometric ratio belongs to isometric system, is golden yellow, and has metalluster, and density is 5.22g/cm
3, 2930 DEG C of fusing points, microhardness is about 21GPa, and Young's modulus is about 590GPa, and linear expansivity is 9.35 × 10
-6/ DEG C (20～1000/ DEG C), thermal conductivity is 19.3W/ (mK) (20 DEG C), resistivity is 25.0 μ Ω cm, water insoluble, sour, is slightly soluble in hot chloroazotic acid and hydrofluoric acid mixed solution.Because it has high strength, high rigidity, high temperature resistant, acid resistance corrodes, the wear-resistant and good series of advantages such as electroconductibility, thermal conductivity, be all widely used at wear-resistant coating and the various metal parts of machining tool, cutlery, various forming materials mould and wear parts.
The method of preparing at present nitride powder has the methods such as direct nitridation method, titanium dioxide carbothermal reduction-nitridation method, vapor phase process, self propagating high temperature synthesis method, mechanical alloying method.Direct nitridation method is with titanium valve or TiH
2powder is raw material, and the condition existing at hydrogen and nitrogen or ammonia gas react generate nitrogenize titanium valve, and synthesis temperature is 1000～1400 DEG C.Direct nitridation method technique is simple, and synthetic titanium nitride nitrogen content is high, but direct nitridation method taking metal as raw material will experience high-temperature fusion process, and long reaction time, easily produces sintering phenomenon.Titanium dioxide nitriding is that carbothermal reduction-nitridation titanium dioxide is prepared titanium nitride under nitrogen or ammonia existence condition.Titanium dioxide nitriding is raw material owing to using titanium dioxide, needs to be reduced into through titanic the process of titanous, the temperature that this process need is higher.Vapor phase process refers to by titanium tetrachloride and nitrogen or the temperature of reaction of cracked ammonium more than 1300 DEG C prepares high-purity titanium nitride powder, also can use gas phase sodium or magnesium as obtaining the then synthetic titanium nitride of nitrogenize of nano level titanium valve after reductive agent reduction titanium tetrachloride.Nitride powder particle diameter prepared by this method is little, and oxygen level is low, has higher activity.But owing to using gas phase sodium and magnesium, this method preparation efficiency is low, cost is high.Self propagating high temperature synthesis method refers to that using pure metal powder or titanium dioxide and metal powder is raw material, burns synthetic under nitrogen atmosphere.This method is owing to being used high-purity titanium valve or need to add metal powder to reduce titanium dioxide as reductive agent, and preparation cost is higher.Machine-alloying is with titanium valve high-energy ball milling under nitrogen or ammonia atmosphere, the method for synthesis of nano nitride powder, and this method is owing to adopting ball milled, and the diameter of particle of preparation is larger, and size distribution is inhomogeneous.
In sum, above method is prepared the method for nitride powder, all has defect in various degree, such as: adopt ammonia as nitrogenous source, the corrosion resistance nature of equipment is had to higher requirement; Synthesis temperature is higher; The nitride powder size ratio of preparing is larger; Technique is loaded down with trivial details etc.Therefore need to develop that a kind of technique is simple, with low cost, synthesis temperature is low, the preparation method of the little and Nano titanium nitride powder that is evenly distributed of particle diameter, overcomes above-mentioned defect.
Summary of the invention
Technical problem to be solved by this invention is to provide for the above-mentioned state of the art that a kind of technique is simple, with low cost, synthesis temperature is low, the preparation method of the little and Nano titanium nitride powder that is evenly distributed of particle diameter.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of Nano titanium nitride powder, is characterized in that step is:
1) titanium tetrachloride and anhydrous alcoholic solvent are formulated as titanium compound alcoholic solution for 1:10 ~ 1:1 in molar ratio;
2) add a certain proportion of urea to be prepared into colloid titanium compound alcoholic solution, wherein the mol ratio of urea and titanium tetrachloride is 2:1 ~ 10:1;
3) colloid urea and titanium compound being formed, after ageing, is placed in baking oven inner drying and removes excess ethyl alcohol;
4) colloid is dried as after glass state material, moves in tube furnace, and under protective atmosphere, at 600 ~ 1000 DEG C of temperature, 2 ~ 10 hours treatment times can obtain Nano titanium nitride powder.
As improvement, described step 3) in the digestion time of colloid be 2 ~ 30 hours.
Improve again described step 3) in dry the temperature inside the box be 55 ~ 65 DEG C, be 46 ~ 50 hours time of drying.
Finally, described step 4) in protective atmosphere be preferably the one in nitrogen, helium or argon gas, the flow of protective atmosphere is 35 ~ 45sccm.
Compared with prior art, the invention has the advantages that: adopt colloid method to be prepared, use titanium salt is presoma, and alcoholic solution is solvent, and urea is nitrogenous source and reductive agent, low for equipment requirements, and technique is simple, and raw material is easy to get, with low cost, easily suitability for industrialized production; And the present invention is oxide-free intermediate in preparation process, and oxygen level is few, the Nano titanium nitride powder median size prepared by this method is 3 ~ 20nm, narrow diameter distribution, favorable dispersity.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of gained titanium nitride nanopower in embodiment 1;
Fig. 2 is the X-ray diffractogram of gained titanium nitride nanopower in embodiment 2;
Fig. 3 is the X-ray diffractogram of gained titanium nitride nanopower in embodiment 3;
Fig. 4 is the X-ray diffractogram of gained titanium nitride nanopower in embodiment 4.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment 1
10ml titanium tetrachloride carefully adds in 20ml dehydrated alcohol, after titanium tetrachloride and ethanol vigorous reaction, obtains settled solution.Gained solution is slowly added to 18g urea while stirring, after urea is dissolved in titanium tetrachloride and ethanolic soln completely, stop stirring, under gained colloid room temperature and ageing 24 hours.After 24 hours, above-mentioned colloid is placed in to baking oven inner drying and removes excess ethyl alcohol, drying the temperature inside the box is 60 DEG C, and be 48 hours time of drying.Colloid is glass state material after drying, and above-mentioned glass state material is transferred in tube furnace, and adjusting nitrogen flow is 40sccm, after logical 1 hour nitrogen, tube furnace is warming up to 900 DEG C with the temperature rise rate of 5 DEG C/min in advance, and 900 DEG C of insulations 2 hours.After insulation, tube furnace naturally cools to room temperature.After tube furnace is cooled to room temperature, gained sample is without further processing and be Nano titanium nitride powder.Fig. 1 has provided the X-ray diffractogram of gained Nano titanium nitride powder, and its diffraction peak is titanium nitride characteristic peak, the oxide-free peak of mixing, and turning out to be powder is titanium nitride, calculating Nano titanium nitride powder grain size by Scherrer formula is 12.4 nanometers.
Embodiment 2
10ml titanium tetrachloride carefully adds in 50ml dehydrated alcohol, after titanium tetrachloride and ethanol vigorous reaction, obtains settled solution.Gained solution is slowly added to 34g urea while stirring, after urea is dissolved in titanium tetrachloride and ethanolic soln completely, stop stirring, under gained colloid room temperature and ageing 24 hours.After 24 hours, above-mentioned colloid is placed in to baking oven inner drying and removes excess ethyl alcohol, drying the temperature inside the box is 60 DEG C, and be 48 hours time of drying.Colloid is glass state material after drying, and above-mentioned glass state material is transferred in tube furnace, and adjusting nitrogen flow is 40sccm, after logical 1 hour nitrogen, tube furnace is warming up to 900 DEG C with the temperature rise rate of 5 DEG C/min in advance, and 900 DEG C of insulations 2 hours.After insulation, tube furnace naturally cools to room temperature.After tube furnace is cooled to room temperature, gained sample is without further processing and be Nano titanium nitride powder.Fig. 1 has provided the X-ray diffractogram of gained Nano titanium nitride powder, and its diffraction peak is titanium nitride characteristic peak, the oxide-free peak of mixing, and turning out to be powder is titanium nitride, calculating Nano titanium nitride powder grain size by Scherrer formula is 12 nanometers.Fig. 2 has provided the X-ray diffractogram of gained Nano titanium nitride powder, and its diffraction peak is titanium nitride characteristic peak, the oxide-free peak of mixing, and turning out to be powder is titanium nitride, calculating Nano titanium nitride powder grain size by Scherrer formula is 12.3 nanometers.
Embodiment 3
10ml titanium tetrachloride carefully adds in 5ml dehydrated alcohol, after titanium tetrachloride and ethanol vigorous reaction, obtains settled solution.Gained solution is slowly added to 18g urea while stirring, after urea is dissolved in titanium tetrachloride and ethanolic soln completely, stop stirring, under gained colloid room temperature and ageing 2 hours.After 2 hours, above-mentioned colloid is placed in to baking oven inner drying and removes excess ethyl alcohol, drying the temperature inside the box is 60 DEG C, and be 48 hours time of drying.Colloid is glass state material after drying, and above-mentioned glass state material is transferred in tube furnace, and adjusting nitrogen flow is 40sccm, after logical 1 hour nitrogen, tube furnace is warming up to 650 DEG C with the temperature rise rate of 5 DEG C/min in advance, and 650 DEG C of insulations 2 hours.After insulation, tube furnace naturally cools to room temperature.After tube furnace is cooled to room temperature, gained sample is without further processing and be Nano titanium nitride powder.Fig. 3 has provided the X-ray diffractogram of gained Nano titanium nitride powder, and its diffraction peak is titanium nitride characteristic peak, the oxide-free peak of mixing, and turning out to be powder is titanium nitride, calculating Nano titanium nitride powder grain size by Scherrer formula is 3.76 nanometers.
Embodiment 4
10ml titanium tetrachloride carefully adds in 10ml dehydrated alcohol, after titanium tetrachloride and ethanol vigorous reaction, obtains settled solution.Gained solution is slowly added to 34g urea while stirring, after urea is dissolved in titanium tetrachloride and ethanolic soln completely, stop stirring, under gained colloid room temperature and ageing 24 hours.After 24 hours, above-mentioned colloid is placed in to baking oven inner drying and removes excess ethyl alcohol, drying the temperature inside the box is 60 DEG C, and be 48 hours time of drying.Colloid is glass state material after drying, and above-mentioned glass state material is transferred in tube furnace, and adjusting nitrogen flow is 40sccm, after logical 1 hour nitrogen, tube furnace is warming up to 800 DEG C with the temperature rise rate of 5 DEG C/min in advance, and 600 DEG C of insulations 2 hours.After insulation, tube furnace naturally cools to room temperature.After tube furnace is cooled to room temperature, gained sample is without further processing and be Nano titanium nitride powder.Fig. 4 has provided the X-ray diffractogram of gained Nano titanium nitride powder, and its diffraction peak is titanium nitride characteristic peak, the oxide-free peak of mixing, and turning out to be powder is titanium nitride, calculating Nano titanium nitride powder grain size by Scherrer formula is 11.7 nanometers.
Claims (4)
1. a preparation method for Nano titanium nitride powder, is characterized in that step is:
1) titanium tetrachloride and anhydrous alcoholic solvent are formulated as titanium compound alcoholic solution for 1:10 ~ 1:1 in molar ratio;
2) add a certain proportion of urea to be prepared into colloid titanium compound alcoholic solution, wherein the mol ratio of urea and titanium tetrachloride is 2:1 ~ 10:1;
3) colloid urea and titanium compound being formed, after ageing, is placed in baking oven inner drying and removes excess ethyl alcohol;
4) colloid is dried as after glass state material, moves in tube furnace, and under protective atmosphere, at 600 ~ 1000 DEG C of temperature, 2 ~ 10 hours treatment times can obtain Nano titanium nitride powder.
2. preparation method according to claim 1, is characterized in that described step 3) in the digestion time of colloid be 2 ~ 30 hours.
3. preparation method according to claim 1, is characterized in that described step 3) in dry the temperature inside the box be 55 ~ 65 DEG C, be 46 ~ 50 hours time of drying.
4. preparation method according to claim 1, is characterized in that described step 4) in protective atmosphere be the one in nitrogen, helium or argon gas, the flow of protective atmosphere is 35 ~ 45sccm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210537399.8A CN103864030A (en) | 2012-12-11 | 2012-12-11 | Nanometer titanium nitride powder preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210537399.8A CN103864030A (en) | 2012-12-11 | 2012-12-11 | Nanometer titanium nitride powder preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103864030A true CN103864030A (en) | 2014-06-18 |
Family
ID=50903134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210537399.8A Pending CN103864030A (en) | 2012-12-11 | 2012-12-11 | Nanometer titanium nitride powder preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103864030A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108059135A (en) * | 2018-01-26 | 2018-05-22 | 安徽工业大学 | Titanium nitride nanopower and preparation method thereof |
| CN108101009A (en) * | 2018-01-26 | 2018-06-01 | 安徽工业大学 | Titanium nitride nanopower high pressure liquid-phase synthesis process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05170411A (en) * | 1991-12-24 | 1993-07-09 | Showa Denko Kk | Production of ultra-fine pulverized titanium nitride |
| CN101462701A (en) * | 2009-01-09 | 2009-06-24 | 北京科技大学 | Method for preparing titanium nitride ceramic powder |
-
2012
- 2012-12-11 CN CN201210537399.8A patent/CN103864030A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05170411A (en) * | 1991-12-24 | 1993-07-09 | Showa Denko Kk | Production of ultra-fine pulverized titanium nitride |
| CN101462701A (en) * | 2009-01-09 | 2009-06-24 | 北京科技大学 | Method for preparing titanium nitride ceramic powder |
Non-Patent Citations (1)
| Title |
|---|
| 祝国强: ""过渡金属氮化物的合成与表征"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 8, 15 August 2012 (2012-08-15), pages 014 - 1 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108059135A (en) * | 2018-01-26 | 2018-05-22 | 安徽工业大学 | Titanium nitride nanopower and preparation method thereof |
| CN108101009A (en) * | 2018-01-26 | 2018-06-01 | 安徽工业大学 | Titanium nitride nanopower high pressure liquid-phase synthesis process |
| CN108101009B (en) * | 2018-01-26 | 2019-06-25 | 安徽工业大学 | Titanium nitride nanopower high pressure liquid-phase synthesis process |
| CN108059135B (en) * | 2018-01-26 | 2019-06-25 | 安徽工业大学 | Titanium nitride nanopower and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103130506B (en) | Method for preparing superfine titanium carbonitride | |
| Ha et al. | Hydrothermal synthesis and characterization of self-assembled h-WO3 nanowires/nanorods using EDTA salts | |
| CN103864030A (en) | Nanometer titanium nitride powder preparation method | |
| CN102190299B (en) | Preparation method of tungsten carbide nanopowder | |
| CN102491328A (en) | Titanium carbide powder and preparation method thereof | |
| CN102350508B (en) | Method for preparing doped-tungsten-based composite powder | |
| CN110227826A (en) | A method of preparing high-purity nm molybdenum powder | |
| Ramdani et al. | Synthesis and thermal behavior of Cu2O flower-like, Cu2O-C60 and Al/Cu2O-C60 as catalysts on the thermal decomposition of ammonium perchlorate | |
| Lin et al. | Using a cobalt activator to synthesize titanium carbide (TiC) nanopowders | |
| CN101704552A (en) | Molybdenum disulfide nano tube and preparation method thereof | |
| Loghman-Estarki et al. | Large scale synthesis of non-transformable tetragonal Sc2O3, Y2O3 doped ZrO2 nanopowders via the citric acid based gel method to obtain plasma sprayed coating | |
| Wang et al. | Mesoporous SiO2-derived g-C3N4@ CdS core-shell heteronanostructure for efficient and stable photocatalytic H2 production | |
| Johnson et al. | Iodine-rich biocidal reactive materials | |
| Wu et al. | Photocatalytic active titania nanowire arrays on Ti substrates | |
| CN103658677A (en) | Nanometer tungsten carbide powder preparing method | |
| EP2566814B1 (en) | Method of manufacturing silica nanopowders with fungicidal properties, especially for polymer composites | |
| Yang et al. | Hysteretic phase transformation of two-dimensional TiO2 | |
| Nuñez‐Briones et al. | Synthesis, structural characterization, and photocatalytic activity of Bi‐based nanoparticles | |
| Ramdani et al. | Synthesis, characterization and kinetic computations of fullerene (C60)–CuO on the mechanism decomposition of ammonium perchlorate | |
| CN108083808B (en) | Nano hafnium carbide ceramic organic precursor and preparation method thereof | |
| CN108298595B (en) | Method for preparing copper-cobalt sulfide microspheres | |
| CN107935598B (en) | Low-temperature sintering method of high-performance silicon carbide ceramic material | |
| CN101475151A (en) | Preparation of conductive titanium nitride/silicon nitride nano composite material | |
| CN107043260A (en) | A kind of novel tertiary osmium rhenium diboride (Os1 xRexB2) hard material and preparation method thereof | |
| Chand et al. | Study of CuO nanoparticles synthesized by sol‐gel method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140618 |