CN108424147A - A kind of method that Rapid Nitriding produces titanium carbonitride, nitrogenizes titanium valve - Google Patents
A kind of method that Rapid Nitriding produces titanium carbonitride, nitrogenizes titanium valve Download PDFInfo
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- CN108424147A CN108424147A CN201810547772.5A CN201810547772A CN108424147A CN 108424147 A CN108424147 A CN 108424147A CN 201810547772 A CN201810547772 A CN 201810547772A CN 108424147 A CN108424147 A CN 108424147A
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Abstract
The invention discloses the methods of a kind of Rapid Nitriding production titanium carbonitride, nitridation titanium valve, including：Step 1：It is according to mass ratio：Titanium dioxide powder:Carbon black=2.0~3.2:1 weighs raw material；Step 2：By the raw material by solid solution ratio 3:7 ratio is individually ground into the slurry being uniformly mixed after particle size is 45nm~90nm；Step 3：By the slurry spray granulating and drying, make powder material particle diameter distribution in 9 μm~53 μ ms；Step 4：The dried material is filled into the reactor in reacting furnace, is proceeded as follows and parameter setting：S1：It adjusts vacuum degree in reacting furnace and is not more than 30Pa, be warming up to 900 DEG C~1000 DEG C；S2：It is passed through nitrogen, it is 4kPa~6kPa to keep nitrogen air inlet partial pressure, and control furnace pressure is in 1~1.01 atmospheric pressure；S3：1300 DEG C~1500 DEG C are warming up to, control soaking time is 10~60min；S4：Nitrogen is closed, is vacuumized, vacuum degree in reacting furnace is made to be not more than 30Pa, fast cooling to room temperature.The present invention produces titanium carbonitride, the nitridation titanium valve of high-purity by the control of parameter.
Description
Technical field
The present invention relates to field of new material preparation more particularly to a kind of Rapid Nitriding production titanium carbonitride, nitrogenize titanium valve
Method.
Background technology
In recent years, due to titanium carbonitride, titanium nitride based ceramic metal have high-melting-point, high rigidity, low friction wearing character,
Be widely used in preparing cermet, cutting element, smelting metal crucible, molten-salt electrolysis metal electrode lining material,
Electric contact and the lining material etc. of metal surface have larger application value.Especially in terms of cutting tool, titanium carbonitride,
Titanium nitride based ceramic metal becomes the material for substituting WC-Co hard alloy with its high rigidity, high red hardness, wearability.In addition it makes
The W and Co for making conventional rigid alloy are the strategic resources of country, in the crucible of melting high temperature alloy, bullet resistant material, digging shield
There is important value with the first-class field of Missile Body, and over nearly 5 years, the cost of material of W and Co are respectively to be often close on 20% He
100% speed skyrockets, and in metal cutting process, and titanium carbonitride, titanium nitride base ceramet tool bit can generate higher
Free enthalpy increases it and resists the formation of cut tumor, peeling and cratering, in high speed grinding roughing, the size essence of half workpieces processing
Degree and machined surface quality are better than the workpiece that WC-Co hard alloy cutter is processed.Therefore, in cutting tool field, seek
Alternative materials become a main trend, but the research and development of China's titanium carbonitride, titanium nitride based ceramic metal are started late, only a small number of factories
Quotient has production capacity, and the performance of product compares same kind of products at abroad, also there is larger gap.Therefore, high-purity is researched and developed, quality is steady
Fixed controllable, titanium carbonitride, the titanium nitride based ceramic metal haveing excellent performance have larger value.
But the titanium carbonitride of high comprehensive performance, titanium nitride based ceramic metal are prepared, one of key seeks to close
At going out stable high-purity, fine granularity, narrow particle size distribution, performance, the good titanium carbonitride of sintering character, titanium nitride ceramic powder.
The powder raw material of high quality is the prerequisite for obtaining premium quality product, prepares titanium carbonitride, titanium nitride ceramic powder both at home and abroad
Method be concentrated mainly on carbothermic method, chemical vapour deposition technique, self-propagating high-temperature synthesis (SHS), mechanical alloying
(MA), it is a variety of to induce self-propagating reaction (MSR), chemical synthesis etc. for machinery, wherein because of self-propagating high-temperature synthesis (SHS), machine
Tool alloying (MA), machinery induction self-propagating reaction (MSR), chemical synthesis cost of material are higher, and impurity is difficult to remove, equipment
The reasons such as complexity, yield is relatively low, and reaction process is difficult to accurately control, it is difficult to large-scale production, for example, the Qu Xuan of University of Science ＆ Technology, Beijing
Brightness invention " a method of preparing titanium nitride ceramic powder " (101462701 B of Chinese patent Authorization Notice No. CN) patent
Using chemical synthesis can not large-scale production, and equipment requirement is high.Powder prepared by carbothermic method is in purity, granularity and shape
Looks, sintering character etc. have greater advantage, and this method cost is relatively low, suitable for scale production.But traditional carbothermic method
Titanium nitride powder generally use is prepared to realize the mode that raw material is laid on material boat continuously by open type carbon shirt-circuiting furnace high-temperature region
Nitridation production, although the method can be with continuous production, the powder nitriding rate produced is low, is readily incorporated oxygen impurities, equipment accounts for
It is big etc. with space, the inventions such as Guo Wei of Changsha Wing High High-tech New Materials Co., Ltd. it is " a kind of to prepare ultra-fine carbon nitridation
The method of titanium " (103130506 A of China Patent Publication No. CN) patent is easy to cause that internal nitriding rate is low to be made by briquetting nitridation
At powder quality unevenness, carbon source selection is also easily introduced excessive impurity；In addition Sichuan University invents " nanocrystalline to road equality
Patent description is excessively for the high temperature carbonization and nitrification the preparation method of TiCN ceramic ultrafine powder " (1935742 A of China Patent Publication No. CN)
Simply and the production time is long, and nitriding rate is uneven；The soup love inventions such as great waves of University Of Chongqing " ilmenite prepares titanium carbonitride powder C/N
Control method " (102021462 A of China Patent Publication No. CN) although patent cost of material is low, product impurity is more and goes
Except difficulty；In addition, Wang Li of University of Science ＆ Technology, Beijing et al. inventions " utilize fluidization ordinary pressure continuous synthesizing silicon nitride powder
Method " (Chinese patent grant number be CN 100351170C) improved by equipment and carry out carbothermic method, although can also use
Produce titanium carbonitride, titanium nitride, but high temperature fluidized difficulty, it complete equipment need to be purchased and manufacturing technology difficulty is high, and nitrogenizes
Time it is short need to repeat nitrogenize；Therefore, these methods all remain to be further improved.
Invention content
The present invention provides the methods of a kind of Rapid Nitriding production titanium carbonitride, nitridation titanium valve, pass through the control of parameter, raw
Titanium carbonitride, the nitridation titanium valve of production of high purity.
Technical solution provided by the invention is：A kind of method that Rapid Nitriding produces titanium carbonitride, nitrogenizes titanium valve, feature
It is, including：
Step 1：It is according to mass ratio：Titanium dioxide powder:Carbon black=2.0~3.2:1 weighs raw material；
Step 2：By the raw material by solid solution ratio 3:7 ratio is individually ground into after particle size is 45nm~90nm and mixes
Close uniform slurry；
Step 3：By the slurry spray granulating and drying, make powder material particle diameter distribution in 9 μm~53 μ ms；
Step 4：The dried material is filled into the reactor in reacting furnace, is proceeded as follows and parameter
Setting：
S1：It adjusts vacuum degree in reacting furnace and is not more than 30Pa, be warming up to 900 DEG C~1000 DEG C；
S2：It is passed through nitrogen, it is 4kPa~6kPa to keep nitrogen air inlet partial pressure, and control furnace pressure is in 1~1.01 air
Pressure；
S3：1300 DEG C~1500 DEG C are warming up to, control soaking time is 10~60min；
S4：Nitrogen is closed, is vacuumized, vacuum degree in reacting furnace is made to be not more than 30Pa, fast cooling to room temperature.
Preferably,
It is uniformly mixed after being individually ground to raw material using the method for high-energy ball milling in the step 2.
Preferably,
Reactor is using Rapid Nitriding device in the step 4；
The Rapid Nitriding device includes the reactor for loading powder and the fluid distributor for being passed through nitrogen, the fluid point
Cloth device is mounted on reactor bottom.
Preferably,
Heating control is at 1000 DEG C in the S1.
Preferably,
Heating rate is 20 DEG C/min in the S1.
Preferably,
Reacting furnace in the step 4 is atmosphere sintering furnace.
Preferably,
Reacting furnace in the step 4 is carbothermic reduction furnace.
Preferably,
Dispersing depolymerization auxiliary agent is added in process of lapping in the step 2.
Preferably,
Carbon/nitrogen the ratio for regulating and controlling product titanium carbonitride by controlling the soaking time in the S3, nitrogenizing titanium valve.
Preferably,
The purity of the raw material titanium dioxide powder and carbon black is more than or equal to 98%.
Preferably, further include：
Preferably,
Advantageous effect of the present invention：1) ingredient requirement used is not high, and cost is relatively low；2) high-energy ball milling, which substitutes, passes
System ball milling, shortens powder milling time and high efficiency；3) spray granulating and drying slurry is used so that drying efficiency substantially rises
Height, and dry powder size tunable narrow distribution range, pattern is spherical shape, while improving the mobility of powder；4) using quick
Nitridation device makes powder amount of fill increase, and nitrogen comes into full contact with powder, improves efficiency of nitridation, when shortening high-temperature region reaction
Between, and powder purity height is nitrogenized, carbon/nitrogen is than controllable；5) the Rapid Nitriding device used haves no need to change existing furnace structure, work
Skill is simply low for equipment requirements.
Description of the drawings
Fig. 1 produces Ti (C by the embodiment of the present invention one0.79,N0.21) powder XRD spectrum.
Fig. 2 produces Ti (C by the embodiment of the present invention one0.79,N0.21) powder SEM photograph.
Fig. 3 is the Rapid Nitriding apparatus structure schematic diagram used in the embodiment of the present invention.
Specific implementation mode
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art with reference to specification text
Word can be implemented according to this.
A kind of method that Rapid Nitriding produces titanium carbonitride, nitrogenizes titanium valve, including：
Step 1：It is according to mass ratio：Titanium dioxide powder:Carbon black=2.0~3.2:1 weighs raw material；
Step 2：By the raw material by solid solution ratio 3:7 ratio is individually ground into after particle size is 45nm~90nm and mixes
Close uniform slurry；
Step 3：By the slurry spray granulating and drying, make powder material particle diameter distribution in 9 μm~53 μ ms；
Step 4：The dried material is filled into the reactor in reacting furnace, is proceeded as follows and parameter
Setting：
S1：It adjusts vacuum degree in reacting furnace and is not more than 30Pa, be warming up to 900 DEG C~1000 DEG C；
S2：It is passed through nitrogen, it is 4kPa~6kPa to keep nitrogen air inlet partial pressure, and control furnace pressure is in 1~1.01 air
Pressure；
S3：1300 DEG C~1500 DEG C are warming up to, control soaking time is 10~60min；
S4：Nitrogen is closed, is vacuumized, vacuum degree in reacting furnace is made to be not more than 30Pa, fast cooling to room temperature.
It is uniformly mixed, and is grinding after being individually ground to raw material using the method for high-energy ball milling in the step 2
The dispersing depolymerization auxiliary agent that addition mass ratio is 1% in the process；It is adopted as shown in Figure 3 using Rapid Nitriding device in above-mentioned steps four
With making powder fluidized principle design and develop, it is used for atmosphere sintering furnace or carbothermic reduction furnace, the Rapid Nitriding device to include filling out
It fills the reactor 110 of powder and is passed through 120 two parts of fluid distributor of nitrogen, it is characterised in that fluid distributor 120 is installed
In 110 bottom of reactor, a large amount of stomatas are distributed in every pipeline 121, and pressure control device is equipped in line entry.Using fast
Fast nitridation device has amount of fill big, is not required to consider to load bed of material thickness, and powder comes into full contact with nitrogen in carbothermic reduction process,
The high-temperature region time can be shortened.Preferably, temperature is 1000 DEG C of degree in S1, and heating rate is 20 DEG C/min；In the S3
Heating control is at 1350 DEG C.The purity of the raw material titanium dioxide powder and carbon black is more than or equal to 98%.It is used in step 4
It is atmosphere sintering furnace or carbothermic reduction furnace.
In embodiment one, a kind of method that Rapid Nitriding produces titanium carbonitride, nitrogenizes titanium valve, by 26.5Kg titanium dioxide
Powder, 12.5Kg carbon powders are with high-energy ball milling by solid solution ratio 3:7 ratio is individually ground into the slurry within the scope of 50nm~100nm,
And the dispersant of mass ratio 1% is added in process of lapping, two kinds of slurries are uniformly mixed again after the completion of grinding, use mist projection granulating
Slurry is dried, control rate of drying makes diameter of particle be distributed in 10 μm~30 μ ms, and pattern is spherical shape, will be dried
Powder be filled into the reaction of Rapid Nitriding device, then Rapid Nitriding device is put into carbothermic reduction furnace, connects nitrogen
Pipeline will be evacuated to vacuum degree≤30Pa in stove, be warming up to 1000 DEG C with the rate of 20 DEG C/min, open Rapid Nitriding device fluid
The pressure control device of distributor, it is 5kPa to keep nitrogen air inlet partial pressure, control furnace pressure in 1~1.01 atmospheric pressure, after
It is continuous to be warming up to 1350 DEG C, 10min is kept the temperature, closes nitrogen, suction≤30Pa in stove, fast cooling to room temperature.Product is taken
XRD material phase analysis such as Fig. 1 is carried out after going out, is single-phase titanium carbonitride, and no second phase exists.It is measured using carbon oxygen, nitrogen oxygen analyzer
Carbon/nitrogen ratio is 0.79:0.21, O content is less than 0.4%, determines that production powder is Ti (C0.79,N0.21).Impurity is carried out using XRF
Elemental analysis, products obtained therefrom purity are more than 99.5%, and impurity and content are as shown in table 1, SEM such as Fig. 2, and pattern is spherical shape, granularity
In 10 μm~30 μ ms.
Table 1.Ti (C0.79,N0.21) powder impurity and content
| Impurity element | Mass fraction (%) |
| O | 0.319 |
| Na | 0.031 |
| Al | 0.007 |
| K | 0.009 |
| Ca | 0.009 |
| Fe | 0.02 |
| Zr | 0.016 |
| Ba | 0.028 |
| W | 0.031 |
In embodiment two, by 26.2Kg titanium dioxide powders, 10.1Kg carbon powders with high-energy ball milling by solid solution ratio 3:7 ratio
Example is individually ground into the slurry within the scope of 50nm~100nm, and the dispersant of mass ratio 1% is added in process of lapping, has ground
Two kinds of slurries are uniformly mixed by Cheng Houzai, and slurry is dried using mist projection granulating, and control rate of drying makes diameter of particle exist
10 μm~30 μ ms be distributed, pattern be spherical shape, dried powder is filled into the reaction of Rapid Nitriding device, then
Rapid Nitriding device is put into carbothermic reduction furnace, and nitrogen pipeline is connected, and vacuum degree≤30Pa will be evacuated in stove, with 20 DEG C/min's
Rate is warming up to 1000 DEG C, opens the pressure control device of Rapid Nitriding device fluid distributor, keeps nitrogen air inlet to divide and is
5kPa, control furnace pressure are continuously heating to 1350 DEG C in 1~1.01 atmospheric pressure, keep the temperature 30min, close nitrogen, are taken out in stove
Vacuum degree≤30Pa, fast cooling to room temperature.It is 0.51 to measure carbon/nitrogen ratio using carbon oxygen, nitrogen oxygen analyzer after product is taken out:
0.49, determine that production powder is Ti (C0.51,N0.49).Impurities analysis, gained Ti (C are carried out using XRF0.51,N0.49) purity
More than 99.6%, O content is less than 0.3%, and impurity and content are as shown in table 2.
Table 2.Ti (C0.51,N0.49) powder impurity and content
It, will be by 25.8Kg titanium dioxide powders, 7.99Kg carbon powder high-energy ball millings by solid solution ratio 3 in embodiment three:7
Ratio is individually ground into the slurry within the scope of 50nm~100nm, and the dispersant of mass ratio 1%, grinding are added in process of lapping
Two kinds of slurries are uniformly mixed again after the completion, slurry is dried using mist projection granulating, control rate of drying makes diameter of particle
It is distributed in 20 μm~40 μ ms, pattern is spherical shape, dried powder is filled into the reaction of Rapid Nitriding device, then
Rapid Nitriding device is put into carbothermic reduction furnace, nitrogen pipeline is connected, vacuum degree≤30Pa will be evacuated in stove, with 20 DEG C/min
Rate be warming up to 1000 DEG C, open the pressure control device of Rapid Nitriding device fluid distributor, keep nitrogen air inlet partial pressure
For 5kPa, control furnace pressure is continuously heating to 1350 DEG C in 1~1.01 atmospheric pressure, keeps the temperature 60min, closes nitrogen, in stove
Suction≤30Pa, fast cooling to room temperature.It is 0 to measure carbon/nitrogen ratio using carbon oxygen, nitrogen oxygen analyzer after product is taken out:
1, determine that production powder is TiN.Impurities analysis is carried out using XRF, products obtained therefrom TiN purity is more than 98.9%, and O content is small
In 1%, impurity and content are as shown in table 3.
The impurity and content of table 3.TiN powders
| Impurity element | Mass fraction (%) |
| O | 0.902 |
| Na | 0.021 |
| Al | 0.010 |
| K | 0.006 |
| Ca | 0.007 |
| Fe | 0.026 |
| Zr | 0.013 |
| Ba | 0.018 |
| W | 0.026 |
In example IV, by 26.1Kg titanium dioxide powders, 9.5Kg carbon powders with high-energy ball milling by solid solution ratio 3:7 ratio
Example is individually ground into the slurry within the scope of 50nm~100nm, and the dispersant of mass ratio 1% is added in process of lapping, has ground
Two kinds of slurries are uniformly mixed by Cheng Houzai, and slurry is dried using mist projection granulating, and control rate of drying makes diameter of particle exist
20 μm~50 μ ms be distributed, pattern be spherical shape, dried powder is filled into the reaction of Rapid Nitriding device, then
Rapid Nitriding device is put into carbothermic reduction furnace, and nitrogen pipeline is connected, and vacuum degree≤30Pa will be evacuated in stove, with 20 DEG C/min's
Rate is warming up to 1000 DEG C, opens the pressure control device of Rapid Nitriding device fluid distributor, keeps nitrogen air inlet to divide and is
5kPa, control furnace pressure are continuously heating to 1400 DEG C in 1~1.01 atmospheric pressure, keep the temperature 40min, close nitrogen, are taken out in stove
Vacuum degree≤30Pa, fast cooling to room temperature.It is 0.34 to measure carbon/nitrogen ratio using carbon oxygen, nitrogen oxygen analyzer after product is taken out:
0.66, determine that production powder is Ti (C0.34,N0.66), impurities analysis, gained Ti (C are carried out using XRF0.34,N0.66) purity
More than 99.1%, O content is less than 0.8%, and impurity and content are as shown in table 4.
Table 4.Ti (C0.34,N0.66) powder impurity and content
| Impurity element | Mass fraction (%) |
| O | 0.742 |
| Na | 0.032 |
| Al | 0.007 |
| K | 0.010 |
| Ca | 0.008 |
| Fe | 0.025 |
| Zr | 0.018 |
| Ba | 0.026 |
| W | 0.030 |
In embodiment five, by 26.0Kg titanium dioxide powders, 8.8Kg carbon powders with high-energy ball milling by solid solution ratio 3:7 ratio
Example is individually ground into the slurry within the scope of 50nm~100nm, and the dispersant of mass ratio 1% is added in process of lapping, has ground
Two kinds of slurries are uniformly mixed by Cheng Houzai, and slurry is dried using mist projection granulating, and control rate of drying makes diameter of particle exist
10 μm~30 μ ms be distributed, pattern be spherical shape, dried powder is filled into the reaction of Rapid Nitriding device, then
Rapid Nitriding device is put into carbothermic reduction furnace, and nitrogen pipeline is connected, and vacuum degree≤30Pa will be evacuated in stove, with 20 DEG C/min's
Rate is warming up to 1000 DEG C, opens the pressure control device of Rapid Nitriding device fluid distributor, keeps nitrogen air inlet to divide and is
5kPa, control furnace pressure are continuously heating to 1350 DEG C in 1~1.01 atmospheric pressure, keep the temperature 45min, close nitrogen, are taken out in stove
Vacuum degree≤30Pa, fast cooling to room temperature.It is 0.22 to measure carbon/nitrogen ratio using carbon oxygen, nitrogen oxygen analyzer after product is taken out:
0.78, determine that production powder is Ti (C0.22,N0.78).Impurities analysis, gained Ti (C are carried out using XRF0.22,N0.78) purity
More than 98.9%, O content is less than 1%, and impurity and content are as shown in table 5.
Table 5.Ti (C0.22,N0.78) powder impurity and content
| Impurity element | Mass fraction (%) |
| O | 0.901 |
| Na | 0.029 |
| Al | 0.008 |
| K | 0.010 |
| Ca | 0.012 |
| Fe | 0.026 |
| Zr | 0.015 |
| Ba | 0.030 |
| W | 0.027 |
In embodiment six, by 26.3Kg titanium dioxide powders, 10.5Kg carbon powders with high-energy ball milling by solid solution ratio 3:7 ratio
Example is individually ground into the slurry within the scope of 50nm~100nm, and the dispersant of mass ratio 1% is added in process of lapping, has ground
Two kinds of slurries are uniformly mixed by Cheng Houzai, and slurry is dried using mist projection granulating, and control rate of drying makes diameter of particle exist
20 μm~50 μ ms be distributed, pattern be spherical shape, dried powder is filled into the reaction of Rapid Nitriding device, then
Rapid Nitriding device is put into carbothermic reduction furnace, and nitrogen pipeline is connected, and vacuum degree≤30Pa will be evacuated in stove, with 20 DEG C/min's
Rate is warming up to 1000 DEG C, opens the pressure control device of Rapid Nitriding device fluid distributor, keeps nitrogen air inlet to divide and is
5kPa, control furnace pressure are continuously heating to 1350 DEG C in 1~1.01 atmospheric pressure, keep the temperature 15min, close nitrogen, are taken out in stove
Vacuum degree≤30Pa, fast cooling to room temperature.It is 0.60 to measure carbon/nitrogen ratio using carbon oxygen, nitrogen oxygen analyzer after product is taken out:
0.40, determine that production powder is Ti (C0.60,N0.40).Impurities analysis, gained Ti (C are carried out using XRF0.60,N0.40) purity
More than 99.5%, O content is less than 0.4%, and impurity and content are as shown in table 6.
Table 6.Ti (C0.60,N0.40) powder impurity and content
| Impurity element | Mass fraction (%) |
| O | 0.334 |
| Na | 0.021 |
| Al | 0.008 |
| K | 0.007 |
| Ca | 0.010 |
| Fe | 0.022 |
| Zr | 0.014 |
| Ba | 0.024 |
| W | 0.028 |
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (10)
1. a kind of method of Rapid Nitriding production titanium carbonitride, nitridation titanium valve, which is characterized in that including：
Step 1：It is according to mass ratio：Titanium dioxide powder:Carbon black=2.0~3.2:1 weighs raw material；
Step 2：By the raw material by solid solution ratio 3:7 ratio is individually ground into after particle size is 45nm~90nm and mixes
Even slurry；
Step 3：By the slurry spray granulating and drying, make powder material particle diameter distribution in 9 μm~53 μ ms；
Step 4：The dried material is filled into the reactor in reacting furnace, is proceeded as follows and parameter setting：
S1：It adjusts vacuum degree in reacting furnace and is not more than 30Pa, be warming up to 900 DEG C~1000 DEG C；
S2：It is passed through nitrogen, it is 4kPa~6kPa to keep nitrogen air inlet partial pressure, and control furnace pressure is in 1~1.01 atmospheric pressure；
S3：1300 DEG C~1500 DEG C are warming up to, control soaking time is 10~60min；
S4：Nitrogen is closed, is vacuumized, vacuum degree in reacting furnace is made to be not more than 30Pa, fast cooling to room temperature.
2. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
It is uniformly mixed after being individually ground to raw material using the method for high-energy ball milling in the step 2.
3. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
Reactor is using Rapid Nitriding device in the step 4；
The Rapid Nitriding device includes the reactor for loading powder and the fluid distributor for being passed through nitrogen, the fluid distributor
Mounted on reactor bottom.
4. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
Heating control is at 1000 DEG C in the S1.
5. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
Heating rate is 20 DEG C/min in the S1.
6. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
Reacting furnace in the step 4 is atmosphere sintering furnace.
7. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
Reacting furnace in the step 4 is carbothermic reduction furnace.
8. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
Dispersing depolymerization auxiliary agent is added in process of lapping in the step 2.
9. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
Carbon/nitrogen the ratio for regulating and controlling product titanium carbonitride by controlling the soaking time in the S3, nitrogenizing titanium valve.
10. the method for Rapid Nitriding production titanium carbonitride according to claim 1, nitridation titanium valve, which is characterized in that
The purity of the raw material titanium dioxide powder and carbon black is more than or equal to 98%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336612A (en) * | 2018-09-20 | 2019-02-15 | 成都美奢锐新材料有限公司 | A kind of preparation method of super fine titanium carbonitride powder |
| CN109399585A (en) * | 2018-11-24 | 2019-03-01 | 冯良荣 | A method of preparing titanium carbonitride |
| CN110819934A (en) * | 2019-10-28 | 2020-02-21 | 西安特种设备检验检测院 | Preparation method of microbial corrosion resistant TiN/Ti ceramic metal composite coating |
| CN115821140A (en) * | 2022-11-24 | 2023-03-21 | 河南融发新材料科技有限公司 | Titanium-containing alloy for metallurgy and low-cost production method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974403A (en) * | 2006-12-12 | 2007-06-06 | 四川大学 | Mechanical activation-reaction heat treating preparation process of nanometer titanium carbonitride |
| CN102671581A (en) * | 2011-05-11 | 2012-09-19 | 储晞 | Method and reactor for producing particle materials |
| CN103130506A (en) * | 2013-03-15 | 2013-06-05 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing superfine titanium carbonitride |
-
2018
- 2018-05-31 CN CN201810547772.5A patent/CN108424147A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974403A (en) * | 2006-12-12 | 2007-06-06 | 四川大学 | Mechanical activation-reaction heat treating preparation process of nanometer titanium carbonitride |
| CN102671581A (en) * | 2011-05-11 | 2012-09-19 | 储晞 | Method and reactor for producing particle materials |
| CN103130506A (en) * | 2013-03-15 | 2013-06-05 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing superfine titanium carbonitride |
Non-Patent Citations (1)
| Title |
|---|
| 向道平等: "纳米晶Ti (C0.45,N0.55)固溶体粉末的合成与表征", 《稀有金属材料与工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336612A (en) * | 2018-09-20 | 2019-02-15 | 成都美奢锐新材料有限公司 | A kind of preparation method of super fine titanium carbonitride powder |
| CN109399585A (en) * | 2018-11-24 | 2019-03-01 | 冯良荣 | A method of preparing titanium carbonitride |
| CN110819934A (en) * | 2019-10-28 | 2020-02-21 | 西安特种设备检验检测院 | Preparation method of microbial corrosion resistant TiN/Ti ceramic metal composite coating |
| CN115821140A (en) * | 2022-11-24 | 2023-03-21 | 河南融发新材料科技有限公司 | Titanium-containing alloy for metallurgy and low-cost production method thereof |
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