CN102976759A - Method for preparing titanium carbonitride by use of vacuum reduction nitriding method - Google Patents
Method for preparing titanium carbonitride by use of vacuum reduction nitriding method Download PDFInfo
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- CN102976759A CN102976759A CN2012105472442A CN201210547244A CN102976759A CN 102976759 A CN102976759 A CN 102976759A CN 2012105472442 A CN2012105472442 A CN 2012105472442A CN 201210547244 A CN201210547244 A CN 201210547244A CN 102976759 A CN102976759 A CN 102976759A
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- titanium carbonitride
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Abstract
The invention belongs to the field of metal ceramic material preparation, and provides a method for preparing titanium carbonitride by use of a vacuum reduction nitriding method. The method comprises the following steps of: (1) ball-milling and mixing TiO2 and a carbon source, and performing cold pressing to obtain a block material; (2) putting the block material into a vacuum induction furnace, vacuumizing until the pressure in the furnace is lower than or equal to 50Pa, heating to 1,000-1,900 DEG C, and preserving heat for 0.5-2 hours while vacuumizing continuously; and (3) after the heat preservation, stopping vacuumizing, introducing nitrogen until the pressure in the furnace is 1.1-1.2 atmospheric pressures, preserving heat for 1-4 hours so that the raw material is sufficiently nitrided, then cooling, taking out the block material, breaking, ball-milling and grading to obtain the titanium carbonitride powder material. Through the invention, the prepared TiCN powder material has high purity, low content of O, few impurities and single phase composition, and can be used as a raw material of a cutting tool, a metal ceramic, a spraying material and the like.
Description
Technical field
The invention belongs to the cermet material field, relate to a kind of preparation method of TiCN powder body material.
Background technology
The binary carbide TiC of Ti element, binary nitride TiN have good performance and purposes widely.TiC has high fusing point (3260 ℃), high hardness, lower density (4.93g/cm
3) and high heat resistanceheat resistant, oxidation-resistance;
TiN has the hardness height, and good toughness resistance to wears, high-melting-point (2950 ℃), and high chemical stability and thermostability, good electrical and thermal conductivity, this bi-material has been widely used in machinery, chemical industry and microelectronic industry.The Ti-C-N ternary compound then has the premium properties of TiC and TiN concurrently, hot strength is high, heat-resisting, wear-resisting, the chemical water good stability, it simultaneously is again the good conductor of heat and electricity, can be used as wear part, cutting tool, electrode and coated material, have broad application prospects in fields such as machinery, electronics, chemical industry, automobile making, aerospace.
At present, the method for preparing the TiCN powder body material comprises: by polymerization too oxygen base carbodynamite at 1100 ℃ of pyrolytic decompositions; Utilize nano TiN and carbon black in 1300 ℃ argon gas stream, to react; Adopt sodium Metal 99.5 at 600 ℃ of reduction C
3N
3Cl
3And TiCl
4Mixture; Unite sol-gel technique and the carbothermic reduction technology (1550 ℃) used; Utilize gac in 900～1500 ℃ nitrogen, to reduce TiO
2Utilize titanium and carbon in nitrogen, to carry out the self-propagating high-temperature reaction; Long-time ball milling TiO in nitrogen
2, graphite and aluminium powder.And the existing method that prepare the TiCN powder all is one section reaction, and the raw materials cost height, and equipment complexity or quality product are low, is difficult to obtain purity height, high quality TiCN powder that phase composition is single.
Summary of the invention
For deficiency of the prior art, the present invention aims to provide the method that a kind of vacuum reducing nitriding prepares titanium carbonitride, and the principal feature of the method is a minute two-stage reaction, and prepared TiCN powder body material purity is high, O content is low, impurity is few, phase composition is single, and cost is low, and technique is simple.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of vacuum reducing nitriding prepares the method for titanium carbonitride, and concrete steps are:
(1) with TiO
2Mix with the carbon source ball milling, wherein TiO
2With the mass ratio of contained C in the carbon source be 10:1～4.8, then cold pressing and make the piece material;
(2) described block of material packed in the vacuum induction furnace, be evacuated to furnace pressure less than or equal to 50Pa, then the heat-up rate with 5 ℃/min-8 ℃/min is warming up to 1000 ℃～1900 ℃, and is incubated 0.5～2h, constantly vacuumizes in the insulating process;
(3) insulation stops to vacuumize after finishing, and passes into nitrogen, and making furnace pressure is 1.1-1.2 normal atmosphere, and insulation 1～4h makes the abundant nitrogenize of raw material, then is cooled to 450 ℃～550 ℃, takes out the piece material, and fragmentation, ball milling, classification get the carbon titanium nitride powder material.
The described TiO of step (1)
2Preferred Fisher particle size is less than 10 microns, TiO
2Content is greater than 99%.
The ash content of the described carbon source of step (1) is preferably less than 0.5%, and described carbon source is selected from coke, hard coal, carbon black, starch or glucose.
The described TiO of step (1)
2Be preferably 10:2～4 with the mass ratio of contained C in the carbon source.
Be warming up to 1600 ℃～1650 ℃ in the step (2), and insulation 2h.
The described nitrogen gas purity of step (3) is preferably greater than 98%.
Below the present invention will be further explained and the explanation:
Principle of the present invention is:
The present invention first under vacuum state by excessive carbon source with TiO
2Fully reduction, excess carbon reduction TiO under the vacuum state
2Chemical equation be TiO
2+ (2+x) C=Ti
y+ Ti
(1-y)C
x+ 2CO, wherein 0≤y≤1,0≤x≤1.Because under the vacuum state, the CO that reaction generates is pumped rapidly, thereby reaction is finished rapidly and thoroughly, O content wherein can be low to moderate 0.1%.Work as TiO
2After fully being reduced by carbon, stop to vacuumize, pass into nitrogen, and make furnace pressure be slightly larger than a normal atmosphere, the metal Ti that at this moment reduction generates begins rapidly and the nitrogen reaction, the generation titanium nitride, and its reaction formula is 2Ti+N
2The Ti that=2TiN, TiN generate with reduction phase again simultaneously
(1-y)C
x, wherein solid solution reaction occurs, thereby generates single-phase TiCN material in 0≤y≤1,0≤x≤1.
Compared with prior art, advantage of the present invention is:
1, method technique of the present invention is simple, and equipment requirements is low, cost is low, energy expenditure is less, be convenient to the advantage of large-scale commercial production.
2, method of the present invention is divided two-stage reaction, and the quality product that obtains is high, prepared TiCN powder body material purity tall and big in equal 99%, O content is lower than 0.1%, impurity is few, phase composition is single.
Description of drawings
Fig. 1 is the XRD figure of the prepared product of the embodiment of the present application 1;
Fig. 2 is the XRD figure of the prepared product of the embodiment of the present application 2.
Embodiment
The present invention is described further below in conjunction with embodiment.
Embodiment 1:
A kind of vacuum reducing nitriding prepares the method for titanium carbonitride, adopts TiO
2With the C(carbon black) be raw material, with 100kg TiO
2Cold pressing after evenly mixing with the 38.5kg carbon black and make the piece material, in the vacuum oven of packing into, heat up rapidly with the speed of 5 ℃/min, and vacuumize simultaneously, make vacuum tightness less than 50pa, when temperature rises to 1650 ℃, insulation 2h, then stop to vacuumize, pass into continuously nitrogen, making furnace pressure is 1.1 normal atmosphere, behind the nitrogenize 2h, stopped heating makes the product furnace cooling.Product TiCN content is that 99.2%, O content is that 0.06%, XRD phase composition is single, sees Fig. 1.
Embodiment 2:
A kind of vacuum reducing nitriding prepares the method for titanium carbonitride, adopts TiO
2With the C(carbon black) be raw material, with 100kg TiO
2Cold pressing after evenly mixing with the 41.5kg carbon black and make the piece material, in the vacuum oven of packing into, heat up rapidly with the speed of 5 ℃/min, and vacuumize simultaneously, make vacuum tightness less than 50pa, when temperature rises to 1600 ℃, insulation 2.5h, then stop to vacuumize, pass into continuously nitrogen, making furnace pressure is 1.1 normal atmosphere, behind the nitrogenize 2h, stopped heating makes the product furnace cooling.Product TiCN content is that 99.1%, O content is that 0.08%, XRD phase composition is single, sees Fig. 2.
Claims (6)
1. a vacuum reducing nitriding prepares the method for titanium carbonitride, and it is characterized in that concrete steps are: (1) is with TiO
2Mix with the carbon source ball milling, wherein TiO
2With the mass ratio of contained C in the carbon source be 10:1～4.8, then cold pressing and make the piece material;
(2) described block of material packed in the vacuum induction furnace, be evacuated to furnace pressure less than or equal to 50Pa, then the heat-up rate with 5 ℃/min-8 ℃/min is warming up to 1000 ℃～1900 ℃, and is incubated 0.5～2h, constantly vacuumizes in the insulating process;
(3) insulation stops to vacuumize after finishing, and passes into nitrogen, and making furnace pressure is 1.1-1.2 normal atmosphere, and insulation 1～4h makes the abundant nitrogenize of raw material, then is cooled to 450 ℃～550 ℃, takes out the piece material, and fragmentation, ball milling, classification get the carbon titanium nitride powder material.
2. described vacuum reducing nitriding prepares the method for titanium carbonitride according to claim 1, it is characterized in that the described TiO of step (1)
2Fisher particle size less than 10 microns, TiO
2Content is greater than 99%.
3. described vacuum reducing nitriding prepares the method for titanium carbonitride according to claim 1 and 2, it is characterized in that the ash content of the described carbon source of step (1) is less than 0.5%, and described carbon source is selected from coke, hard coal, carbon black, starch or glucose.
4. described vacuum reducing nitriding prepares the method for titanium carbonitride according to claim 1 and 2, it is characterized in that the described TiO of step (1)
2With the mass ratio of contained C in the carbon source be 10:2～4.
5. described vacuum reducing nitriding prepares the method for titanium carbonitride according to claim 1 and 2, it is characterized in that, is warming up to 1600 ℃～1650 ℃ in the step (2), and insulation 2h.
6. described vacuum reducing nitriding prepares the method for titanium carbonitride according to claim 1 and 2, it is characterized in that the described nitrogen gas purity of step (3) is greater than 98%.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193231A (en) * | 2013-04-01 | 2013-07-10 | 攀枝花学院 | Method for preparing titanium carbide or titanium carbonitride |
| CN103395755A (en) * | 2013-08-04 | 2013-11-20 | 桂林理工大学 | Method used for preparing TiCN powder by using tetrabutyl titanate as titanium source and phenolic resin as carbon source |
| CN105621378A (en) * | 2015-12-27 | 2016-06-01 | 北京工业大学 | Preparation method for TiN (1-x) Cx daltonide powder |
| CN108892140A (en) * | 2018-09-20 | 2018-11-27 | 成都美奢锐新材料有限公司 | A kind of method that vacuum method prepares carbon titanium carbonitride powder |
| CN109399585A (en) * | 2018-11-24 | 2019-03-01 | 冯良荣 | A method of preparing titanium carbonitride |
| CN109437917A (en) * | 2018-12-19 | 2019-03-08 | 北京科技大学 | A kind of method that two sections of reduction nitridations produce titanium nitride and titanium carbonitride |
| CN109536811A (en) * | 2018-12-26 | 2019-03-29 | 河源普益硬质合金厂有限公司 | A kind of Ti(CN) base TN18 cermet and its preparation process |
| CN109590480A (en) * | 2018-12-26 | 2019-04-09 | 河源普益硬质合金厂有限公司 | A kind of Ti(CN) base TN18 cermet making apparatus |
| CN110357637A (en) * | 2019-07-29 | 2019-10-22 | 株洲红日新材料科技有限公司 | Super fine titanium carbonitride powder end and preparation method thereof |
| CN110921639A (en) * | 2019-11-29 | 2020-03-27 | 江苏大学 | Preparation method of nano titanium carbonitride powder |
| CN115093233A (en) * | 2022-07-12 | 2022-09-23 | 吉林长玉特陶新材料技术股份有限公司 | Preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production |
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| CN1935742A (en) * | 2005-09-23 | 2007-03-28 | 四川大学 | High-temperature carbonitriding preparation method of nano crystal titanium carbonitride ceramic ultrafine powder |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193231A (en) * | 2013-04-01 | 2013-07-10 | 攀枝花学院 | Method for preparing titanium carbide or titanium carbonitride |
| CN103193231B (en) * | 2013-04-01 | 2015-12-09 | 攀枝花学院 | Prepare the method for titanium carbide or titanium carbonitride |
| CN103395755A (en) * | 2013-08-04 | 2013-11-20 | 桂林理工大学 | Method used for preparing TiCN powder by using tetrabutyl titanate as titanium source and phenolic resin as carbon source |
| CN103395755B (en) * | 2013-08-04 | 2015-09-23 | 桂林理工大学 | The method that titanium source and carbon source prepare TiCN powder is respectively with tetrabutyl titanate and resol |
| CN105621378A (en) * | 2015-12-27 | 2016-06-01 | 北京工业大学 | Preparation method for TiN (1-x) Cx daltonide powder |
| CN108892140A (en) * | 2018-09-20 | 2018-11-27 | 成都美奢锐新材料有限公司 | A kind of method that vacuum method prepares carbon titanium carbonitride powder |
| CN109399585A (en) * | 2018-11-24 | 2019-03-01 | 冯良荣 | A method of preparing titanium carbonitride |
| CN109437917A (en) * | 2018-12-19 | 2019-03-08 | 北京科技大学 | A kind of method that two sections of reduction nitridations produce titanium nitride and titanium carbonitride |
| CN109536811A (en) * | 2018-12-26 | 2019-03-29 | 河源普益硬质合金厂有限公司 | A kind of Ti(CN) base TN18 cermet and its preparation process |
| CN109590480A (en) * | 2018-12-26 | 2019-04-09 | 河源普益硬质合金厂有限公司 | A kind of Ti(CN) base TN18 cermet making apparatus |
| CN110357637A (en) * | 2019-07-29 | 2019-10-22 | 株洲红日新材料科技有限公司 | Super fine titanium carbonitride powder end and preparation method thereof |
| CN110921639A (en) * | 2019-11-29 | 2020-03-27 | 江苏大学 | Preparation method of nano titanium carbonitride powder |
| CN110921639B (en) * | 2019-11-29 | 2023-10-10 | 江苏大学 | Preparation method of nano titanium carbonitride powder |
| CN115093233A (en) * | 2022-07-12 | 2022-09-23 | 吉林长玉特陶新材料技术股份有限公司 | Preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production |
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Inventor after: Guo Wei Inventor after: Li Ziqiang Inventor before: Guo Wei Inventor before: Wang Jialiang Inventor before: Li Ziqiang |
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Application publication date: 20130320 |