CN103130506B - Method for preparing superfine titanium carbonitride - Google Patents

Method for preparing superfine titanium carbonitride Download PDF

Info

Publication number
CN103130506B
CN103130506B CN201310081551.0A CN201310081551A CN103130506B CN 103130506 B CN103130506 B CN 103130506B CN 201310081551 A CN201310081551 A CN 201310081551A CN 103130506 B CN103130506 B CN 103130506B
Authority
CN
China
Prior art keywords
temperature
titanium carbonitride
tio
particle size
carbon source
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.)
Active
Application number
CN201310081551.0A
Other languages
Chinese (zh)
Other versions
CN103130506A (en
Inventor
郭伟
周怡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changsha Wing High High-Tech New Materials Co ltd
Original Assignee
Changsha Wing High High-Tech New Materials Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changsha Wing High High-Tech New Materials Co ltd filed Critical Changsha Wing High High-Tech New Materials Co ltd
Priority to CN201310081551.0A priority Critical patent/CN103130506B/en
Publication of CN103130506A publication Critical patent/CN103130506A/en
Application granted granted Critical
Publication of CN103130506B publication Critical patent/CN103130506B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention belongs to the field of metal ceramic material preparation, and provides a method for preparing superfine titanium carbonitride. The method comprises the following steps of: firstly, ball-milling and mixing nano TiO2 with an organic carbon source, and preparing into a piece material in a cold pressing mode; feeding the piece material into a vacuum sensing furnace, vacuumizing till the pressure inside the furnace is less than or equal to 50Pa, increasing the temperature to 300-800 DEG C and preserving the temperature for 0.5-2h; subsequently increasing the temperature to be 1000-1900 DEG C and preserving the temperature for 0.5-2h, wherein vacuumizing is constantly performed in the temperature preservation process; stopping vacuumizing after the temperature preservation is accomplished, introducing nitrogen so as to make the pressure in the furnace be of 1.1-1.2 atmosphere pressures; preserving the temperature for 1-4h to sufficiently nitridize the raw material; and subsequently decreasing the temperature, taking out the piece material, crushing, ball-milling and grading so as to obtain the superfine titanium carbonitride of which the Fisher particle size is less than 1mm. A TiCN powder material prepared by using the method is high in purity, few in impurities, small in particle size, uniform in particle size distribution and spherical in morphology, and can be used as a raw material of a cutting tool, a metal ceramic, a spraying material and the like.

Description

A kind of method of preparing super fine titanium carbonitride
Technical field
The invention belongs to cermet material field, relate to a kind of method of preparing super fine titanium carbonitride.
Background technology
In recent years, because Ti (C, N) based ceramic metal has good wear resistance, high hot hardness, better oxidation-resistance and high temperature creep-resisting energy, be subject to people and more and more paid close attention to.In addition, the main raw material of making traditional Wimet is WC and Co, they are all rare strategic resources, and Ti (C, N) main raw material of based metal ceramic cutter material is Ti, Ti reserves are on earth W 70 times 131, therefore there is great cost and resources advantage compared with traditional Wimet.But the intensity of Ti (C, N) based ceramic metal and toughness but, lower than traditional WC-Co series hard metal, have seriously limited ceramic-metallic application.If we can, in the case of not reducing Ti (C, N) based ceramic metal premium properties, improve its intensity and toughness, Ti (C, N) based ceramic metal will become the good cutting material that substitutes of traditional WC-Co series hard metal so.Therefore, according to Hall-Petch formula, utilize ultrafine powder to prepare superfine Ti (C, N) based ceramic metal is more and more with the research of the obdurability of raising material, but the technology of current existing preparation TiCN powder is not that raw materials cost is high, equipment complexity is exactly that quality product is low, is difficult to obtain high, the even-grained high quality superfine Ti of purity CN powder.
At present, the method for preparing TiCN powder body material comprises: by carbodynamite at 1100 DEG C of pyrolytic decompositions; Utilize nano TiN and carbon black to react in the argon gas stream of 1300 DEG C; Adopt sodium Metal 99.5 at 600 DEG C of reduction C 3n 3cl 3and TiCl 4mixture; Combine sol-gel technique and the carbothermic reduction technology (1550 DEG C) of using; Utilize gac in the nitrogen of 900~1500 DEG C, to reduce TiO 2; Utilize titanium and carbon in nitrogen, to carry out self-propagating high-temperature reaction; Ball milling TiO in nitrogen for a long time 2, graphite and aluminium powder.And the method for the existing TiCN of preparation powder is all one section of reaction, and raw materials cost is high, and equipment complexity or quality product are low, is difficult to obtain that purity is high, granularity is little, the high quality TiCN powder of even particle size distribution.
Summary of the invention
For deficiency of the prior art, the present invention aims to provide a kind of method of preparing super fine titanium carbonitride, the principal feature of the method is to adopt organic carbon source, vacuum reducing carbonization fast in vacuum oven, prepared superfine Ti CN powder body material purity is high, impurity is few, granularity is less than 1 micron, and pattern is spherical, even particle size distribution, and cost is low, technique is simple.
For achieving the above object, the technical solution adopted in the present invention is:
Prepare a method for super fine titanium carbonitride, concrete steps are:
(1) by nano-TiO 2mix wherein nano-TiO with organic carbon source ball milling 2with the mass ratio of contained C in organic carbon source be 10:1~4.8, then cold pressing and make piece material;
(2) described block of material packed in vacuum induction furnace, be evacuated to furnace pressure and be less than or equal to 50Pa, be then warming up to 300 DEG C-800 DEG C with the heat-up rate of 5 DEG C/min-8 DEG C/min, insulation 0.5 h-3h; Be warming up to 1000 DEG C~1900 DEG C, insulation 0.5 h~3h, constantly vacuumizes in insulating process again;
After (3) (2) steps finish, pass into nitrogen, making furnace pressure is 1.1-1.2 normal atmosphere, continue to be incubated 1 h~4h at 1000 DEG C~1900 DEG C, make the abundant nitrogenize of raw material, be then cooled to 150 DEG C~350 DEG C, take out piece material, fragmentation, ball milling, classification, obtain the carbon titanium nitride powder material that Fisher particle size is less than 1 micron.
The described nano-TiO of step (1) 2preferred Fisher particle size is less than 100 nanometers, TiO 2content is greater than 99%.
The carbon source of the described carbon source of step (1) is selected from polyvinyl alcohol, sucrose, starch, tartrate, oxalic acid or glucose.
The described nano-TiO of step (1) 2be preferably 10:2~4 with the mass ratio of contained C in carbon source.
In preferred steps (2), described block of material packed in vacuum induction furnace, be evacuated to furnace pressure and be less than or equal to 50Pa, be then warming up to 350 DEG C-650 DEG C with the heat-up rate of 5 DEG C/min-8 DEG C/min, insulation 0.5 h-2h; Be warming up to again 1100 DEG C~1700 DEG C, insulation 0.5 h~2h.
The speed heating up again of step (2) does not have particular requirement, so that 3 DEG C/min-8 DEG C/min is better.
The described nitrogen gas purity of step (3) is preferably greater than 99%.
Below the present invention is further explained and is illustrated:
Principle of the present invention comprises decomposes coated, reduction and nitrogenize three phases: the 1st, and the decomposition of organic carbon source is coated, pack in vacuum induction furnace by described block of material, be evacuated to furnace pressure and be less than or equal to 50Pa, then be warming up to 300 DEG C-800 DEG C with the heat-up rate of 5 DEG C/min-8 DEG C/min, insulation 0.5 h-3h.The 2nd, step of reaction, is warming up to 1000 DEG C~1900 DEG C again, and insulation 0.5 h~3h, constantly vacuumizes in insulating process.The 3rd, the nitrogenize stage, i.e. insulation stops vacuumizing after finishing, and passes into nitrogen, and making furnace pressure is 1.1-1.2 normal atmosphere, and insulation 1 h~4h, makes the abundant nitrogenize of raw material, is then cooled to 150 DEG C~350 DEG C, takes out piece material.
In the coated stage of decomposition of organic carbon source, under vacuum state, organic carbon source melts, decomposes, and generates fine carbon black, is enclosed in uniformly TiO 2particle surface can play the effect of foaming in the time of organic carbon fusing, decomposition, is that material piece is loose, is conducive to the mass transfer of nitrogen; Organic carbon produces superfine carbon granule while decomposition, surround uniformly around Nanometer Titanium Dioxide particle, not only can make carbon react fully fast at lower temperature with titanium white, the more important thing is because the coating function of carbon makes can directly not contact between titanium white particle, thereby suppressed growing up of particle.
At reduction phase, be warming up to 1000 DEG C~1900 DEG C, by titanium white (TiO 2) fully reduction, excess carbon reduction TiO under 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.The CO simultaneously generating due to reaction is pumped rapidly, has also promoted carrying out rapidly and thoroughly of reaction, and O content is wherein reduced to and is less than 1%.
In the nitrogenize stage, work as TiO 2after fully being reduced by carbon, stop vacuumizing, pass into nitrogen, and make furnace pressure be slightly larger than a normal atmosphere, the metal Ti that at this moment reduction generates starts to react with nitrogen rapidly, generates titanium nitride, and its reaction formula is 2Ti+N 2=2TiN, the Ti that TiN generates with reduction phase again simultaneously (1-y)c x, wherein 0≤y≤1,, there is solid solution reaction, thereby generate single-phase TiCN material in 0≤x≤1.
Compared with prior art, advantage of the present invention is:
1, method of the present invention comprises and decomposes coated, reduction and nitrogenize three phases, the quality product obtaining is high, prepared superfine Ti CN powder body material purity is high is more than or equal to 99%, O content lower than 1%, few, the Fisher particle size of impurity is less than 1um, pattern is spherical, even particle size distribution.
2, 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.
Brief description of the drawings
Fig. 1 and Fig. 2 are the SEM figure of the prepared product of the embodiment of the present application 1;
Fig. 3 and Fig. 4 are the SEM figure of German Stratco Inc. like product.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
embodiment 1:
Prepare a method for super fine titanium carbonitride, adopt TiO 2with starch be raw material, by 100kg TiO 2evenly mix (wherein nano-TiO with 87.5kg starch 2mass ratio 10:3.85 with institute's carbon containing in organic carbon source), cold pressing and make piece material, pack in vacuum oven, speed with 5 DEG C/min heats up rapidly, and vacuumizes simultaneously, makes vacuum tightness be less than 50pa, when temperature rises to after 700 DEG C, insulation 1h, while then continuing to rise to 1500 DEG C, insulation 2h, then stops vacuumizing, and passes into continuously nitrogen, making furnace pressure is 1.1 normal atmosphere, 1500 DEG C time, after nitrogenize 2h, stop heating, make product furnace cooling.Product TiCN content is that 99.2%, O content is 0.9%, and Fisher particle size is 0.93um, and SEM pattern is spherical, and even particle size distribution is shown in Fig. 1, Fig. 2.Fig. 3 and Fig. 4 are the SEM figure of German Stratco Inc. like product.By Fig. 1 and Fig. 3 contrast, Fig. 2 and Fig. 4 contrast, known, the prepared product SEM pattern of the present invention is spherical, size-grade distribution is more even.
embodiment 2:
Prepare a method for super fine titanium carbonitride, adopt TiO 2with polyvinyl alcohol be raw material, by 100kg TiO 2evenly mix (wherein nano-TiO with containing 76.8kg polyvinyl alcohol 2mass ratio 10:4 with institute's carbon containing in organic carbon source), cold pressing and make piece material, pack in vacuum oven, speed with 5 DEG C/min heats up rapidly, and vacuumizes simultaneously, makes vacuum tightness be less than 50pa, when temperature rises to after 650 DEG C, insulation 1h, while then continuing to rise to 1520 DEG C, insulation 2h, then stops vacuumizing, and passes into continuously nitrogen, making furnace pressure is 1.1 normal atmosphere, after 1520 DEG C of nitrogenize 3h, stop heating, make product furnace cooling.Product TiCN content is that 99.1%, O content is 0.8%, and Fisher particle size is 0.96um.

Claims (5)

1. a method of preparing super fine titanium carbonitride, is characterized in that, concrete steps are:
(1) by nano-TiO 2mix wherein nano-TiO with organic carbon source ball milling 2with the mass ratio of contained C in organic carbon source be 10:1~4.8, then cold pressing and make piece material; Described organic carbon source is selected from polyvinyl alcohol, sucrose, starch, tartrate, oxalic acid or glucose;
(2) described block of material packed in vacuum induction furnace, be evacuated to furnace pressure and be less than or equal to 50Pa, be then warming up to 300 DEG C-800 DEG C with the heat-up rate of 5 DEG C/min-8 DEG C/min, insulation 0.5 h-3h; Be warming up to 1000 DEG C~1900 DEG C, insulation 0.5 h~3h, constantly vacuumizes in insulating process again;
After (3) (2) steps finish, pass into nitrogen, making furnace pressure is 1.1-1.2 normal atmosphere, continue to be incubated 1 h~4h at 1000 DEG C~1900 DEG C, make the abundant nitrogenize of raw material, be then cooled to 150 DEG C~350 DEG C, take out piece material, fragmentation, ball milling, classification, obtain the carbon titanium nitride powder material that Fisher particle size is less than 1 micron.
2. a kind of method of preparing super fine titanium carbonitride according to claim 1, is characterized in that the described nano-TiO of step (1) 2fisher particle size be less than 100 nanometers, TiO 2content is greater than 99%.
3. according to a kind of method of preparing super fine titanium carbonitride described in claim 1 or 2, it is characterized in that the described nano-TiO of step (1) 2with the mass ratio of contained C in carbon source be 10:2~4.
4. according to a kind of method of preparing super fine titanium carbonitride described in claim 1 or 2, it is characterized in that, in step (2), be warming up to 350 DEG C-650 DEG C with the heat-up rate of 5 DEG C/min-8 DEG C/min, insulation 0.5 h-2h; Be warming up to again 1100 DEG C~1700 DEG C, insulation 0.5 h~2h.
5. according to a kind of method of preparing super fine titanium carbonitride described in claim 1 or 2, it is characterized in that, the described nitrogen gas purity of step (3) is greater than 99%.
CN201310081551.0A 2013-03-15 2013-03-15 Method for preparing superfine titanium carbonitride Active CN103130506B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310081551.0A CN103130506B (en) 2013-03-15 2013-03-15 Method for preparing superfine titanium carbonitride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310081551.0A CN103130506B (en) 2013-03-15 2013-03-15 Method for preparing superfine titanium carbonitride

Publications (2)

Publication Number Publication Date
CN103130506A CN103130506A (en) 2013-06-05
CN103130506B true CN103130506B (en) 2014-07-09

Family

ID=48491017

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310081551.0A Active CN103130506B (en) 2013-03-15 2013-03-15 Method for preparing superfine titanium carbonitride

Country Status (1)

Country Link
CN (1) CN103130506B (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103387216B (en) * 2013-07-28 2016-03-02 桂林理工大学 With TiOSO 4the method that titanium source and carbon source prepare TiCN powder is respectively with starch
CN103387215B (en) * 2013-07-28 2016-03-02 桂林理工大学 The method that titanium source and carbon source prepare TiCN powder is respectively with tetrabutyl titanate and starch
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
CN103395753B (en) * 2013-08-04 2016-02-24 桂林理工大学 The method that titanium source and carbon source prepare TiCN powder is respectively with tetrabutyl titanate and tetramethylolmethane
CN103435355A (en) * 2013-08-28 2013-12-11 桂林理工大学 Method for preparing TiCN powder by respectively taking butyl titanate and sucrose as titanium source and carbon source
CN103449387A (en) * 2013-08-28 2013-12-18 桂林理工大学 Method for preparing TiCN powder by using TiOSO4 as titanium source and cane sugar as carbon source
CN103787407B (en) * 2013-12-25 2016-04-20 河北科技大学 Reaction ball milling legal system is for nano TiC N/Al 2o 3the method of composite powder
CN103979508B (en) * 2014-05-04 2015-07-08 华中科技大学 Preparation method of nano-Ti(C,N) solid solution powder
CN105621378A (en) * 2015-12-27 2016-06-01 北京工业大学 Preparation method for TiN (1-x) Cx daltonide powder
CN106430286B (en) * 2016-09-18 2018-01-12 河南师范大学 One kind prepares core shell structure ZnO/g C3N4The method of composite
CN108424147A (en) * 2018-02-12 2018-08-21 吉林长玉特陶新材料技术股份有限公司 A kind of method that Rapid Nitriding produces titanium carbonitride, nitrogenizes titanium valve
CN109437917B (en) * 2018-12-19 2020-06-12 北京科技大学 Method for producing titanium nitride and titanium carbonitride by two-stage reduction nitridation
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
CN110357639A (en) * 2019-07-29 2019-10-22 株洲红芯新材料科技有限公司 Super fine titanium carbonitride powder end and preparation method thereof
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
CN111547724A (en) * 2020-05-20 2020-08-18 蓬莱市超硬复合材料有限公司 Superfine titanium carbide powder and preparation method thereof
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5417952A (en) * 1994-05-27 1995-05-23 Midwest Research Institute Process for synthesizing titanium carbide, titanium nitride and titanium carbonitride
CN1944249A (en) * 2006-11-02 2007-04-11 沈阳理工大学 Super fine titanium carbonitride powder and its preparing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5417952A (en) * 1994-05-27 1995-05-23 Midwest Research Institute Process for synthesizing titanium carbide, titanium nitride and titanium carbonitride
CN1944249A (en) * 2006-11-02 2007-04-11 沈阳理工大学 Super fine titanium carbonitride powder and its preparing method

Also Published As

Publication number Publication date
CN103130506A (en) 2013-06-05

Similar Documents

Publication Publication Date Title
CN103130506B (en) Method for preparing superfine titanium carbonitride
CN102976759A (en) Method for preparing titanium carbonitride by use of vacuum reduction nitriding method
CN103924111B (en) The preparation method of a kind of Wimet nanometer particle size powder and high performance sintered block materials
CN105274375B (en) Based on the compound method for preparing high elastic modulus Ti sills of nano-ceramic particle
CN108557783B (en) Preparation method of high-purity nano titanium nitride powder
CN105499576A (en) Method for preparing porous titanium-aluminium alloy through powder metallurgy
CN105692642B (en) A kind of nano bar-shape zirconium boride powder and preparation method thereof
CN106670505A (en) Method for preparing tungsten-cobalt-carbon composite powder through spray pyrolysis method
CN110407213B (en) (Ta, nb, ti, V) C high-entropy carbide nano powder and preparation method thereof
CN109437203A (en) A kind of preparation method of high-purity one dimension SiC nano material
CN105692641A (en) Preparation method and application of tungsten boride
CN109079151B (en) Method for preparing ultra-coarse tungsten powder by high-temperature liquid-phase reduction of tungsten oxide
CN101863663B (en) Combustion method for preparing submicron grade titanium carbide polycrystal powder
CN110921639B (en) Preparation method of nano titanium carbonitride powder
CN106588018A (en) Method for preparing superhigh temperature carbonized hafnium ceramic nano-powder
CN109437917B (en) Method for producing titanium nitride and titanium carbonitride by two-stage reduction nitridation
CN102874809A (en) Silicon carbide composite powder and preparation process thereof
CN107285329B (en) Tungsten diboride hard material and preparation method and application thereof
CN108149127A (en) A kind of aluminum-base nano titanium carbonitride crystal seed alloy and preparation method thereof
CN102242341B (en) High-temperature-resistant titanium film super-hard composite material and production process thereof
CN105541345A (en) Method for preparing superfine hafnium carbide ceramic powder
CN107698264A (en) A kind of preparation method of modified alpha-phase silicon nitride powder
CN103962568B (en) A kind of method of microwave heating preparation reduction chromium powder
Li et al. Low-temperature synthesis of high-purity TiB2 via carbothermal reduction of metatitanic acid and H3BO3
Xiang et al. Reaction sequences and influence factors during preparation of Ti (C, N) powders

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent for invention or patent application
CB03 Change of inventor or designer information

Inventor after: Guo Wei

Inventor after: Zhou Yi

Inventor before: Guo Wei

Inventor before: Wang Jialiang

Inventor before: Zhou Yi

COR Change of bibliographic data

Free format text: CORRECT: INVENTOR; FROM: GUO WEI WANG JIALIANG ZHOU YI TO: GUO WEI ZHOU YI

C14 Grant of patent or utility model
GR01 Patent grant
CP03 Change of name, title or address

Address after: 410205 No. 38 Lugu Lutian Road, Changsha High-tech Development Zone, Hunan Province

Patentee after: Changsha Wei Hui hi tech new material Co., Ltd.

Address before: 410205 Hunan province Changsha City Lugu high tech Zone Lu Tin Road No. 38

Patentee before: Changsha Wing High High-tech New Materials Co.,Ltd.

CP03 Change of name, title or address