CN100422074C - Method for preparing nanometer titanium carbonitride powder - Google Patents
Method for preparing nanometer titanium carbonitride powder Download PDFInfo
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- CN100422074C CN100422074C CNB2005100423666A CN200510042366A CN100422074C CN 100422074 C CN100422074 C CN 100422074C CN B2005100423666 A CNB2005100423666 A CN B2005100423666A CN 200510042366 A CN200510042366 A CN 200510042366A CN 100422074 C CN100422074 C CN 100422074C
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Abstract
The present invention provides a method for preparing nanometer titanium carbonitride powder. The present invention is characterized in that the nanometer titanium carbonitride powder is prepared by one-step synthesis through the simultaneous reaction in the process of ball milling of titanium powder, carbon powder and nitrogen containing gas in a ball milling tank. The process of the present invention is carried out at normal temperature without heating, and the present invention has the advantages of simple process, easy control and high productivity. The proportion of carbon atoms and nitrogen atoms in titanium carbonitride can also be changed by adjusting the proportion of titanium powder and carbon powder in solid raw materials and the pressure of nitrogen containing gas, and the nanometer titanium carbonitride powder with different quality constants can be obtained.
Description
Affiliated technical field
The invention provides a kind of preparation method of nano-carbon titanium nitride powder, belong to preparation nano ceramics technical field.
Background technology
(Ti (C, N)) has high fusing point, hardness, thermal conductivity and specific conductivity, wear resistance and good chemical stability to titanium carbonitride, can be used for making wear parts, cutting tool, electrode and coating, is a kind of broad-spectrum novel material.C, N atomic ratio difference in the titanium carbonitride, its lattice parameter are also different, and with the increase of C/ (C+N) value, lattice parameter increases.The titanium carbonitride of different lattice constants, performance are slightly different.
The traditional method of producing titanium carbonitride mainly contains: (1) chemical reduction method, with carbon, nitrogen or the reduction of ammonia direct chemical titanium dioxide, titanium tetrachloride or titanium hydride; (2) solid-state diffusion method, at high temperature (1000～1500 ℃), by carbon and nitrogen simultaneously to the titanium valve solid-state diffusion, or the mixture by TiC and TiN mutually mutual diffusion obtain.The carbon titanium nitride particle size that adopts these methods to produce is all bigger, and size is more than micron order.
Because nano-carbon titanium nitride powder has some tangible advantages, and causes people's attention, some preparation nano-scale carbon titanium nitride novel methods have been developed.As passing through TiCl as reductive agent with sodium
4And C
3N
3Cl
3At the synthetic preparation of 600 ℃ of direct reaction nano-carbon titanium nitride, method is as follows: with analytically pure C
3N
3Cl
3(1g), excessive TiCl
4(5ml) and sodium (4g) put into the stainless cylinder of steel of high pressure of 30ml capacity, all operations all carries out in the glove box of nitrogen gas stream.Pressure pan sealing back naturally cools to room temperature then at 600 ℃ of insulation 10h in stove.Adopt raw spirit, distilled water and diluted acid to clean respectively the product of collecting and repeatedly remove impurity, dry 3 hours [Guozhen Shen, et al.A simple route to preparenanocrystalline titanium carbinitride.Materials Research Bulletin 37 (2002) 1207-1211] in 70 ℃ of vacuum at last.The another kind of method for preparing the nano-carbon titanium nitride ultrafine powder is: TiO (OH)
2At first hydrolysis in deionized water after colloidal sol and activated carbon mix, 60 ℃ of gelations, then gel is dried to constant weight at 120 ℃, the TiO2 powder that obtains, again the TiO2 powder that obtains is put into plumbago crucible, synthetic TiCl-xNx powder [Junhui Xiang in 1400～1600 ℃ of nitrogen gas stream, et al.Synthesis of Ti (C, N) ultralfine powders by carbothermal reduction of TiO2 derived from sol-gel process.Journal of theEuropean Ceramic Society.20 (2000) 933-938].Chinese patent communique disclosed application number on September 24th, 2003 is 02125986.0 patent of invention for another example: the plasma chemical gas phase synthesis method prepares the technology of titanium carbonitride ceramic powder, patentee: Bai Wanjie, its technical scheme is: utilize DC arc plasma to be thermal source, the gas N of the electric arc of flowing through
2-H
2-Ar be heated to 4800～5200 ℃ of high temperature with simultaneously through liquefied gas, the TiCl of vaporizer heating evaporation
4And NH
3Gas enters plasma reactor jointly and decomposes building-up reactions with titanium carbonitride fast, when the temperature of reaction in the reactor remains on 1200～1300 ℃, the titanium carbonitride that generates through the crystallization of extremely short time (Millisecond), grow up, cool off, obtain nano-carbon titanium nitride powder through gas solid separation then.These prepare the method for nano-carbon titanium nitride powder, complex process, loaded down with trivial details, and productivity is low, the cost height, application is restricted.
Summary of the invention
The object of the present invention is to provide the preparation method of the nano-carbon titanium nitride powder that a kind of technology is simple, productivity is high, its technical scheme is:
A kind of preparation method of nano-carbon titanium nitride powder, it is characterized in that: by reaction when the titanium valve in the ball grinder, carbon dust and nitrogenous gas are in mechanical milling process, one-step synthesis prepares nano-carbon titanium nitride powder, and wherein nitrogenous gas is meant mixed gas a kind of of nitrogen or ammonia or nitrogen, ammonia and rare gas element.
The preparation method of described nano-carbon titanium nitride powder, titanium valve and carbon dust by the proportioning of massfraction are in the ball grinder: the titanium valve component accounts for 85%～97.5%, the carbon dust component accounts for 2.5%～15%, the pressure of nitrogenous gas remains on 0.1MPa～0.6MPa in the ball grinder, and nitrogen element content is 0.4%～40% of titanium valve and a carbon dust total amount by massfraction.
The preparation method of described nano-carbon titanium nitride powder, carbon dust is Graphite Powder 99, carbon black, activated carbon powder or other carbonaceous material.
The preparation method of described nano-carbon titanium nitride powder contains in the nitrogen mixture gas, and the dividing potential drop of nitrogen or ammonia is greater than 0.1MPa.
Preparation process is: under the normal temperature titanium valve, carbon dust certain proportion are put into ball grinder and sealed, give in the jar again and charge into nitrogenous gas, make the pressure of preceding jar of interior nitrogenous gas of ball milling remain on 0.1MPa～10MPa, continuously ball milling for some time (behind about 50min～120min), the synthesis of nano carbon titanium nitride powder that reacts simultaneously of the nitrogen in titanium valve, carbon dust and the nitrogenous gas.
The present invention compared with prior art, have following conspicuous outstanding advantage: the method for preparing nano-carbon titanium nitride powder of the present invention is by titanium valve, carbon dust and the nitrogenous gas one-step synthesis that reacts simultaneously in mechanical milling process, carry out under the normal temperature, need not heating, technology is simple, be easy to control, the productivity height; The ratio by adjusting titanium valve and carbon dust in the solid material and the pressure of nitrogenous gas can also change the ratio of carbon atom and nitrogen-atoms in the titanium carbonitride, obtain the nano-carbon titanium nitride powder of different lattice constants.
Embodiment
Embodiment 1
Particle diameter is about the titanium valve 8g of 1 μ m and Graphite Powder 99 1.5g that particle diameter is about 250 μ m puts into the stainless steel jar mill that a volume is 100ml.Fill pure nitrogen gas in jar, nitrogen pressure was 0.40MPa when ball milling began.During ball milling 120min, titanium valve, Graphite Powder 99 and nitrogen react simultaneously and obtain titanium carbonitride, and behind the continuation ball milling 140min, the grain-size of titanium carbonitride is 30nm.Carbon, nitrogen-atoms ratio are about 45: 1 in the titanium carbonitride, and the lattice constant of titanium carbonitride is 0.4311nm.
Embodiment 2
Particle diameter is about the titanium valve 8g of 1 μ m and carbon black 1.0g that particle diameter is about 250 μ m puts into the stainless steel jar mill that a volume is 100ml.Fill pure nitrogen gas in jar, nitrogen pressure was 0.60MPa when ball milling began.During ball milling 85min, titanium valve, carbon black and nitrogen react simultaneously and obtain titanium carbonitride.After continuing ball milling 110min, the grain-size of titanium carbonitride is 20nm.Carbon, nitrogen-atoms ratio are about 1.9: 1 in the titanium carbonitride, and the lattice constant of titanium carbonitride is 0.4295nm.
Embodiment 3
Particle diameter is about the titanium valve 8g of 1 μ m and carbon black 0.5g that particle diameter is about 250 μ m puts into the stainless steel jar mill that a volume is 100ml.Fill pure ammonia in jar, ammonia pressure was 0.60MPa when ball milling began.Behind the ball milling 94min, titanium valve, carbon black and nitrogen react simultaneously and obtain titanium carbonitride.Continue ball milling to 120min, the grain-size of titanium carbonitride is 14nm, and carbon, nitrogen-atoms ratio are about 0.7: 1, and the lattice constant of titanium carbonitride is 0.4260nm.
Claims (4)
1. the preparation method of a nano-carbon titanium nitride powder, it is characterized in that: by reaction when the titanium valve in the ball grinder, carbon dust and nitrogenous gas are in mechanical milling process, one-step synthesis prepares nano-carbon titanium nitride powder, and wherein nitrogenous gas is meant mixed gas a kind of of nitrogen or ammonia or nitrogen, ammonia and rare gas element.
2. the preparation method of nano-carbon titanium nitride powder according to claim 1, it is characterized in that: titanium valve and carbon dust by the proportioning of massfraction are in the ball grinder: the titanium valve component accounts for 85%～97.5%, the carbon dust component accounts for 2.5%～15%, the pressure of nitrogenous gas remains on 0.1MPa～0.6MPa in the ball grinder, and nitrogen element content is 0.4%～40% of titanium valve and a carbon dust total amount by massfraction.
3. the preparation method of nano-carbon titanium nitride powder according to claim 1, it is characterized in that: carbon dust is Graphite Powder 99, carbon black, activated carbon powder or other carbonaceous material.
4. the preparation method of nano-carbon titanium nitride powder according to claim 1, it is characterized in that: contain in the nitrogen mixture gas, the dividing potential drop of nitrogen or ammonia is greater than 0.1MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100423666A CN100422074C (en) | 2005-01-13 | 2005-01-13 | Method for preparing nanometer titanium carbonitride powder |
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| CNB2005100423666A CN100422074C (en) | 2005-01-13 | 2005-01-13 | Method for preparing nanometer titanium carbonitride powder |
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| CN1803587A CN1803587A (en) | 2006-07-19 |
| CN100422074C true CN100422074C (en) | 2008-10-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565176B (en) * | 2009-05-31 | 2010-08-25 | 四川大学 | Method for dispersing nanometer TiN powder |
| CN110980667A (en) * | 2019-12-25 | 2020-04-10 | 株洲鸿达实业有限公司 | Micro-nano TiCN powder and preparation method and application thereof |
| CN113004048A (en) * | 2021-03-10 | 2021-06-22 | 滁州学院 | Preparation method of titanium oxycarbonitride ceramic powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055957A (en) * | 1991-04-20 | 1991-11-06 | 中国科学院电工研究所 | Ion plating technology for titanium carbonitride coatings |
| CN1443726A (en) * | 2002-08-08 | 2003-09-24 | 白万杰 | Process for preparing titanium carbonitride ceramic powder body by utilizing plasma chemial gas phase synthesis method |
| US20040207074A1 (en) * | 2003-04-16 | 2004-10-21 | The Regents Of The University Of California | Metal MEMS devices and methods of making same |
| US20040216559A1 (en) * | 2003-04-29 | 2004-11-04 | Kim Byoung Kee | Process for manufacturing ultra fine TiC-transition metal-based complex powder |
| CN1559912A (en) * | 2004-03-02 | 2005-01-05 | 山东大学 | Preparation process for three elemental compound powder material of titanium carbonitride |
-
2005
- 2005-01-13 CN CNB2005100423666A patent/CN100422074C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055957A (en) * | 1991-04-20 | 1991-11-06 | 中国科学院电工研究所 | Ion plating technology for titanium carbonitride coatings |
| CN1443726A (en) * | 2002-08-08 | 2003-09-24 | 白万杰 | Process for preparing titanium carbonitride ceramic powder body by utilizing plasma chemial gas phase synthesis method |
| US20040207074A1 (en) * | 2003-04-16 | 2004-10-21 | The Regents Of The University Of California | Metal MEMS devices and methods of making same |
| US20040216559A1 (en) * | 2003-04-29 | 2004-11-04 | Kim Byoung Kee | Process for manufacturing ultra fine TiC-transition metal-based complex powder |
| CN1559912A (en) * | 2004-03-02 | 2005-01-05 | 山东大学 | Preparation process for three elemental compound powder material of titanium carbonitride |
Non-Patent Citations (4)
| Title |
|---|
| Ti(CxN1-x)粉末SHS工艺 研究. 康志君等.硬质合金，第13卷第2期. 1996 |
| Ti(CxN1-x)粉末SHS工艺 研究. 康志君等.硬质合金，第13卷第2期. 1996 * |
| 在氮气中球磨Ti粉制备纳米TiNx. 周丽等.硅酸盐通报，第6期. 2004 |
| 在氮气中球磨Ti粉制备纳米TiNx. 周丽等.硅酸盐通报，第6期. 2004 * |
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