CN112357896A - Preparation method and device of superfine titanium carbonitride - Google Patents
Preparation method and device of superfine titanium carbonitride Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
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- B02C17/183—Feeding or discharging devices
- B02C17/1835—Discharging devices combined with sorting or separating of material
- B02C17/1855—Discharging devices combined with sorting or separating of material with separator defining termination of crushing zone, e.g. screen denying egress of oversize material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
- B02C23/16—Separating or sorting of material, associated with crushing or disintegrating with separator defining termination of crushing or disintegrating zone, e.g. screen denying egress of oversize material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
- B02C23/16—Separating or sorting of material, associated with crushing or disintegrating with separator defining termination of crushing or disintegrating zone, e.g. screen denying egress of oversize material
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Abstract
The invention belongs to the technical field of metal ceramic powder, and discloses a preparation method and a device of superfine titanium carbonitride, wherein in the preparation of ingredients, titanium dioxide and carbon black are selected as raw materials to be subjected to ball milling to obtain uniformly mixed powder; putting the obtained powder into a vacuum carbon tube furnace, and carbonizing at 1800-1868 ℃ for 8 hours in a nitrogen atmosphere to obtain a high-temperature carbonized material; breaking and sieving, namely breaking and sieving the high-temperature carbonized material; carbonizing by low-temperature nitrogen, putting the sieved high-temperature carbonized material into a vacuum carbon tube furnace, vacuumizing, introducing nitrogen, and preserving heat at 1456-1553 ℃ for 12 hours to obtain the titanium carbonitride, so that the contents of carbon and nitrogen in the produced titanium carbonitride are nearly equal, the influence of nitrogen deficiency or carbon deficiency on the performance of the titanium carbonitride is reduced, titanium dioxide and carbon generated by reverse reaction and residual free carbon in the high-temperature carbonized material can be reduced, the titanium carbonitride can be generated secondarily, the contents of free carbon and oxygen in the finally produced titanium carbonitride are reduced, and the finally produced titanium carbonitride is a single-phase solid solution.
Description
Technical Field
The invention belongs to the technical field of metal ceramic powder, and particularly relates to a preparation method and a device of superfine titanium carbonitride.
Background
Titanium-containing ceramic coatings such as TiN, TiC and the like become coating materials with great application prospect due to high hardness, high wear resistance and good chemical stability. Currently TiN coatings and TiC coatings are widely used in industry. However, the TiC coating is too brittle and easily collapses during use; and the TiN coating has insufficient oxidation resistance, abrasion resistance and the like under high temperature conditions, so that the further development of the TiN coating is limited. Titanium carbonitride (TiCN) is a non-oxide material with excellent performance and wide application, is a coating material with excellent performance, is a solid solution of TiN and TiC, and has the characteristics and advantages of the TiN and the TiC. Compared with TiC, TiCN has more excellent plasticity and wear resistance; compared with TiN, TiCN has better performances of resisting adhesion abrasion and wear resistance of abrasive particles and lower friction factor, can further improve the performances of heat resistance, corrosion resistance and the like of the workpiece, and has important practical significance for prolonging the service life of the workpiece.
In recent years, with the intensive research on methods for preparing TiCN powder, such as self-propagating combustion, sol-gel, gas phase, and plasma methods have attracted considerable attention, but these methods have disadvantages of expensive equipment, complicated process, high raw material cost, low yield, impure synthesis, and the like, thus limiting the industrial scale production thereof. The method has the advantages of simple equipment, short process flow and low raw material price. So that the TiCN powder is prepared at present by mainly reducing TiO by carbothermic2Mainly adopts the method.
The prior domestic titanium carbonitride production process generally adopts the following steps:
1. the titanium dioxide, titanium carbide and carbon black mixture are carbonized at high temperature in the nitrogen atmosphere, the method has incomplete solid solution, and the phase composition detection shows that the mixture is non-single-phase solid solution;
2. the titanium carbide and titanium nitride mixture is subjected to intermediate-frequency high-temperature solid solution in an argon atmosphere, and the product produced by the method has large average particle size, coarse particles and low purity, and is difficult to meet the production requirement of hard alloy products.
China's inventionThe patent application No. 201010534952.3 discloses a method for preparing titanium carbonitride hard alloy material, which selects raw material TiO2And C, mixing, placing the mixture into a sintering container, compacting, filling nitrogen, sintering for 40-60 minutes at 1220-1240 ℃, and then sintering for 60-80 minutes at 1630-1670 ℃. To TiO 22The heating reaction is carried out by stages to reduce TiO under the condition that the oxygen potential is continuously weakened and the nitrogen potential is kept unchanged2The oxygen in (1) is sufficiently removed. The oxygen content of TiCN is reduced.
Disclosure of Invention
In view of the above, the present invention provides a method and an apparatus for preparing ultrafine titanium carbonitride, which can obtain titanium carbonitride particles having a single-phase solid solution and a small particle size.
The invention solves the technical problems by the following technical means: a preparation method of superfine titanium carbonitride comprises the following steps:
s100: preparing ingredients, namely ball-milling titanium dioxide and carbon black serving as raw materials to obtain uniformly mixed powder;
s200: high-temperature carbonization, namely filling the powder obtained in the S100 into a vacuum carbon tube furnace, and carbonizing for 8 hours at 1800-1868 ℃ in a nitrogen atmosphere to obtain a high-temperature carbonized material;
s300: breaking and sieving, namely breaking and sieving the high-temperature carbonized material obtained in the S200;
s400: and (3) carbonizing at low temperature, placing the sieved high-temperature carbonized material into a vacuum carbon tube furnace, vacuumizing, introducing nitrogen, and preserving heat at 1456-1553 ℃ for 12 hours to obtain the titanium carbonitride.
The beneficial effect of this scheme:
firstly, a process of firstly carrying out high-temperature nitrogen carbonization and then carrying out low-temperature nitrogen carbonization is adopted, the preparation temperature of the first high-temperature nitrogen carbonization is 1800-1868 ℃, so that the contents of carbon and nitrogen in the produced titanium carbonitride are approximately equal, the influence of nitrogen deficiency or carbon deficiency on the performance of the titanium carbonitride is reduced, and the Vickers hardness performance of the finally generated titanium carbonitride is improved.
And after the first high-temperature nitrogen carbonization, crushing the generated high-temperature carbonized material containing the titanium carbonitride, and performing second low-temperature nitrogen carbonization to ensure that the residual carbon monoxide and the titanium carbide in the high-temperature carbonized material can react reversely to generate titanium dioxide and carbon, the titanium dioxide and the carbon generated by reverse reaction and the residual free carbon in the high-temperature carbonized material can generate the titanium carbonitride for the second time, so that the content of the free carbon and the oxygen in the finally produced titanium carbonitride is reduced, and the finally produced titanium carbonitride is a single-phase solid solution and has good hardness performance.
And thirdly, the low-temperature nitrogen carbonization is a high-temperature carbonized material generated at 1456-1553 ℃, the reaction temperature is low, and the agglomeration of the titanium carbonitride powder particles of the product can be avoided, so that the titanium nitride powder particles with small particle size can be obtained.
The invention also provides a preparation device of the superfine titanium carbonitride, which comprises a first ball mill, a high-temperature vacuum carbon tube furnace, a second ball mill, a filter sieve, a low-temperature vacuum carbon tube furnace, an air inlet system and air exhaust equipment, wherein the feed end of the high-temperature vacuum carbon tube furnace is butted with the discharge end of the first ball mill, the feed end of the second ball mill is butted with the discharge end of the high-temperature carbon tube furnace, the filter sieve is arranged at the discharge end of the second ball mill, the feed end of the low-temperature vacuum carbon tube furnace is butted with the discharge end of the second ball mill, the air inlet system is communicated with the high-temperature vacuum carbon tube furnace and the low-temperature vacuum carbon tube furnace, and the air exhaust equipment is communicated with the high-temperature vacuum carbon tube furnace and the.
The beneficial effect of this scheme: and (3) carrying out ball milling and sieving on titanium carbonitride generated by reaction in a high-temperature vacuum carbon tube furnace in an inert gas environment by using a ball mill, and carrying out low-temperature nitrogen carbonization in a low-temperature vacuum carbon tube furnace to finally obtain the high-purity titanium carbonitride superfine powder. The device for preparing the titanium carbonitride has the advantages of simple process, high yield, low cost and high product purity.
Drawings
FIG. 1 is a schematic flow diagram of a process for preparing titanium carbonitride in accordance with the present invention;
FIG. 2 is a graph of Gibbs free energy versus reaction temperature for a process for the preparation of titanium carbonitride in accordance with the present invention;
FIG. 3 is a schematic structural view of an apparatus for preparing ultrafine titanium carbonitride in accordance with the present invention;
FIG. 4 is a schematic structural view of a first ball mill in example 4 of the present invention;
FIG. 5 is a schematic structural view of a transmission structure in embodiment 4 of the invention;
FIG. 6 is a schematic structural view of a filter sieve in example 4 of the present invention;
FIG. 7 is a schematic structural view of a transmission structure in embodiment 5 of the invention;
in the figure: 100-superfine titanium carbonitride preparation device, 10-first ball mill, 11-ball mill body, 111-ball valve switch, 12-heat preservation cover, 13-spring, 14-transmission structure, 141-first helical gear, 142-second helical gear, 143-first transmission rod, 144-first transmission gear, 145-second transmission gear, 146-third transmission gear, 147-second transmission gear, 148-cam, 149-connecting plate, 15-shaft lever, 16-limiting disc, 20-high temperature vacuum carbon tube furnace, 30-second ball mill, 40-filter sieve, 41-bulge, 50-low temperature vacuum carbon tube furnace, 60-air inlet system, 70-air extraction equipment, 80-angle sensor and 90-electric cylinder.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and those skilled in the art will appreciate the advantages and utilities of the present invention from the disclosure herein.
Example 1
A process for preparing superfine titanium carbonitride includes such steps as proportionally mixing titanium dioxide and carbon black in the mole ratio of 1:2, ball grinding while covering the carbon black on the surface of titanium dioxide particles, and preparing titanium carbonitride from the tungsten and titanium alloy balls. Then the obtained titanium dioxide and carbon black powder is put into a vacuum carbon tube furnace and carbonized for 8 hours at the high temperature of 1800 ℃ in the nitrogen atmosphere to obtain the high-temperature carbonized material containing titanium carbonitride, residual free carbon, carbon monoxide and other substances. And (3) crushing and sieving the obtained high-temperature carbonized material by adopting a ball mill, wherein the sieve mesh size is 200 meshes, and crushing and sieving are carried out to ensure that all substances in the high-temperature carbonized material form powder, so that the secondary reaction is facilitated. And finally, putting the sieved high-temperature carbonized material powder into a vacuum carbon tube furnace, vacuumizing, introducing nitrogen, and preserving the heat at 1456 ℃ for 12 hours to obtain a titanium carbonitride product.
Example 2
A process for preparing superfine titanium carbonitride includes such steps as proportionally mixing titanium dioxide and carbon black in the mole ratio of 1:2, ball grinding while covering the carbon black on the surface of titanium dioxide particles, and preparing titanium carbonitride from the tungsten and titanium alloy balls. Then the obtained titanium dioxide and carbon black powder is put into a vacuum carbon tube furnace and carbonized for 8 hours at 1868 ℃ in nitrogen atmosphere to obtain the high-temperature carbonized material containing titanium carbonitride, residual free carbon, carbon monoxide and other substances. And (3) crushing and sieving the obtained high-temperature carbonized material by adopting a ball mill, wherein the sieve mesh size is 200 meshes, and crushing and sieving are carried out to ensure that all substances in the high-temperature carbonized material form powder, so that the secondary reaction is facilitated. And finally, putting the sieved high-temperature carbonized material powder into a vacuum carbon tube furnace, vacuumizing, introducing nitrogen, and preserving heat at 1553 ℃ for 12 hours to obtain a titanium carbonitride product.
Example 3
A process for preparing superfine titanium carbonitride includes such steps as proportionally mixing titanium dioxide and carbon black in the mole ratio of 1:2, ball grinding while covering the carbon black on the surface of titanium dioxide particles, and preparing titanium carbonitride from the tungsten and titanium alloy balls. Then the obtained titanium dioxide and carbon black powder is put into a vacuum carbon tube furnace and carbonized for 8 hours at 1840 ℃ in nitrogen atmosphere to obtain the high-temperature carbonized material containing titanium carbonitride, residual free carbon, carbon monoxide and other substances. And (3) crushing and sieving the obtained high-temperature carbonized material by adopting a ball mill, wherein the sieve mesh size is 200 meshes, and crushing and sieving are carried out to ensure that all substances in the high-temperature carbonized material form powder, so that the secondary reaction is facilitated. And finally, putting the sieved high-temperature carbonized material powder into a vacuum carbon tube furnace, vacuumizing, introducing nitrogen, and preserving heat at 1500 ℃ for 12 hours to obtain a titanium carbonitride product.
The above-mentioned method for preparing ultrafine titanium carbonitride at three different temperatures is shown in FIG. 1 and FIG. 2. The specific effects and principles are as follows;
in the invention, titanium dioxide and carbon black are selected as raw materials to prepare titanium carbonitride, and the main chemical formula is shown as follows;
TiO2+2C+1/2N2—TiN+2CO (1)；
TiO2+3C—TiC+2CO (2)；
TiC+1/2N2—TiC+C (3)；
the overall reaction formula is: 2TiO 22+4C+2N2→2TiN+4CO；
Solid solution of titanium nitride and titanium carbide in any proportion: (1-x) TiC + xTiN → Ti (C)1-xNx)；
Firstly, a process of firstly carrying out high-temperature nitrogen carbonization and then carrying out low-temperature nitrogen carbonization is adopted, the preparation temperature of the first high-temperature nitrogen carbonization is 1800-1868 ℃, and the Gibbs free energy of the reaction (1) and the reaction (2) approaches to the same value, so that the contents of carbon and nitrogen in the titanium carbonitride produced by the reaction (1) and the reaction (2) approach to the same value, the influence of nitrogen deficiency or carbon deficiency on the performance of the titanium carbonitride is reduced, and the Vickers hardness performance of the finally produced titanium carbonitride is improved.
And secondly, after the first high-temperature nitrogen carbonization, crushing the generated high-temperature carbonized material containing the titanium carbonitride, performing second low-temperature nitrogen carbonization, and performing reverse reaction of reaction (2) at 1456-1553 ℃ to enable the carbon monoxide and the titanium carbide remained in the high-temperature carbonized material to reversely react to generate titanium dioxide and carbon, wherein the titanium dioxide and the carbon generated by the reverse reaction and the free carbon remained in the high-temperature carbonized material can secondarily generate the titanium carbonitride in the reactions (1) and (3) and reduce the content of the free carbon and the oxygen in the finally produced titanium carbonitride, so that the finally produced titanium carbonitride is a single-phase solid solution and has good hardness performance.
And thirdly, the low-temperature nitrogen carbonization is a high-temperature carbonized material generated at 1456-1553 ℃, the reaction temperature is low, and the agglomeration phenomenon of titanium carbonitride powder particles of a product can be avoided, so that titanium nitride powder particles with small particle size are obtained, and the Vickers hardness performance of the finally generated titanium carbonitride is improved.
Example 4
Referring to fig. 3 to 6, a device 100 for preparing ultrafine titanium carbonitride comprises a first ball mill 10, a high temperature carbon nanotube furnace 20, a second ball mill 30, a filter sieve 40, a low temperature carbon nanotube furnace 50, an air intake system 60 and an air pumping device 70, wherein a feed end of the high temperature carbon nanotube furnace 20 is in butt joint with a discharge end of the first ball mill 10, a feed end of the second ball mill 30 is in butt joint with a discharge end of the high temperature carbon nanotube furnace, the filter sieve 40 is installed at a discharge end of the second ball mill 30, a feed end of the low temperature carbon nanotube furnace 50 is in butt joint with a discharge end of the second ball mill 30, the air intake system 60 is communicated with the high temperature carbon nanotube furnace 20 and the low temperature carbon nanotube furnace 50, and the air pumping device 70 is communicated with the high temperature carbon nanotube furnace 20 and the low temperature carbon nanotube furnace 50.
Thus, titanium dioxide and carbon black raw materials are placed into the first ball mill 10 for grinding and crushing, then placed into the high-temperature vacuum carbon tube furnace 20, the air inlet system 60 is started to be filled with nitrogen gas for reaction to generate a titanium carbonitride high-temperature carbonized material, and then the titanium carbonitride high-temperature carbonized material is placed into the second ball mill 30 for ball milling. After sieving, placing the mixture into a low-temperature vacuum carbon tube furnace 50, starting an air extraction device 70 for vacuumizing, and then filling nitrogen into an air inlet system 60 again for low-temperature nitrogen carbonization to finally obtain high-purity titanium carbonitride ultrafine powder. The device for preparing the titanium carbonitride has the advantages of simple process, high yield, low cost and high product purity.
Wherein, first ball mill 10 includes ball mill body 11, heat preservation lid 12, spring 13 and drive structure 14, be equipped with ball valve switch 111 on the ball mill body 11, the quantity of heat preservation lid 12 is two, two heat preservation lid 12 lids close on the lateral wall of ball mill body 11, adopt 15 sliding connection of axostylus axostyle between two heat preservation lids 12, 15 outsides of axostylus axostyle enclose and have closed spring 13, spring 13's both ends are fixed with a spacing dish 16 respectively, keep away from spacing dish 16 and the spring 13 fixed connection of heat preservation lid 12, another fast spacing dish 16 and 15 sliding connection of axostylus axostyle, and support with heat preservation lid 12 and hold, ball valve switch 111 closes through the lid of two heat preservation lid 12 ball mill bodies 11 of drive structure 14 control.
So, when titanium dioxide and carbon black raw materials ball-mill in ball mill body 11, heat preservation lid 12 laminating ball mill body 11 plays the effect that the heat that will avoid the friction to produce distributes away, and the frictional heat that titanium dioxide and carbon black raw materials powder produced when the ball-mill can play and preheat, increases the active effect of titanium dioxide.
When the ball valve switch 111 is rotated to discharge materials and the materials enter the high-temperature vacuum carbon tube furnace 20 for reaction, the transmission structure 14 is also pushed by the ball valve switch 111, so that the heat-insulating cover 12 is opened from the ball mill body 11, heat is rapidly dissipated, and the service life of the ball mill is prolonged.
Wherein, the transmission structure 14 comprises a first bevel gear 141 which rotates coaxially with the ball valve switch 111, a second bevel gear 142 which is externally engaged with the first bevel gear 141, a first transmission rod 143 which is fixedly connected with the second bevel gear 142, a first transmission gear 144 which is fixed at one end of the first transmission rod 143 far away from the second bevel gear 142, and a second transmission gear 145 which is externally engaged with the first transmission gear 144, the second transmission gear 145 is connected with the discharge end of the ball mill body 11 by adopting a bearing, and three transmission gears 146 which are externally engaged with the second transmission gear 145, the number of the third transmission gears 146 is two, the two third transmission gears 146 are respectively positioned at two sides of the second transmission gear 145, a second transmission rod 147 whose one end is fixedly connected with the third transmission gear 146, and a cam 148 which is fixed at one end of the second transmission rod 147 far away from the third transmission gear 146, the cam 148 is abutted against the heat preservation cover 12, the first transmission rod 143 and the second transmission rod 147 are in transition fit with a connecting plate 149, and the connecting plate 149 is fixed on the discharge end of the ball mill body 11.
Thus, when the ball valve switch 111 is switched from the closed state to the open state, the ball valve switch 111 is rotated to drive the first bevel gear 141 to rotate, the first bevel gear 141 drives the second bevel gear 142 to rotate, the second bevel gear 142 drives the first transmission rod 143 to rotate, the first transmission rod 143 drives the first transmission gear 144 to rotate, the first transmission gear 144 drives the second transmission gear 145 to rotate relative to the discharge end of the ball mill body 11, the second transmission gear 145 drives the third transmission gears 146 on both sides to rotate, the third transmission gears 146 drive the second transmission rods 147 to rotate, the second transmission rods 147 drive the cams 148 to rotate, the cams 148 are switched from the contact between one end of the short half shaft and the thermal insulation cover 12 to the contact between one end of the long half shaft and the thermal insulation cover 12, so that the thermal insulation cover 12 is pushed away from the ball mill body 11 when the ball valve switch 111 is opened, and the first ball mill 10 dissipates heat rapidly when discharging, the service life of the first ball mill 10 is prolonged.
When the rotary ball valve switch 111 is switched from the open state to the closed state, the cam 148 rotates, one end of the short half shaft of the cam is abutted to the heat preservation cover 12, under the action of the gravity of the heat preservation cover 12 and the elastic force of the spring 13, the limiting plate pushes the heat preservation cover 12, so that the two heat preservation covers 12 slide relative to the shaft rod 15 to be attached to the ball mill body 11, the effect of dissipating heat generated by friction is achieved, the friction heat generated by the titanium dioxide and carbon black raw material powder during ball milling can be preheated, and the effect of titanium dioxide activity is increased.
Referring to fig. 6, the number of the filter screens 40 is two, the two filter screens 40 are overlapped, the two filter screens 40 are connected in a sliding manner, one filter screen 40 is fixedly connected with the discharge end of the second ball mill 30, the other filter screen 40 is integrally formed with a protrusion 41, and the protrusion 41 extends out of the discharge end of the second ball mill 30 and is rotatably connected with the discharge end of the second ball mill 30.
Thus, when the filtering holes of the two filtering screens 40 are completely overlapped, the filtering hole diameter is maximum. When the protrusion 41 is rotated, the filtering holes of the two filtering screens 40 can be staggered, and the effect of reducing the filtering hole diameter is obtained.
Referring to fig. 6, the cross section of the filter screen 40 is U-shaped. The effects of increasing the filtering area and improving the filtering speed are achieved. In other embodiments of this embodiment, the filter screen 40 may also be provided in the shape of a disk. The size of the filter apertures can now be adjusted by the desired relative rotation of the two filter screens 40.
Referring to fig. 6, a labyrinth seal is used between the two filter screens 40, and a labyrinth seal is also used between the protrusion 41 and the discharge end of the second ball mill 30. A groove is arranged on the port wall of the discharge end of the second ball mill 30, and the filter screen 40 is matched with the groove. The two filter screens 40 are matched with each other, so that a zigzag labyrinth gap is formed, and the purpose of leakage resistance is achieved.
Example 5
Referring to fig. 3 and 7, the apparatus 100 for preparing ultrafine titanium carbonitride in the present embodiment is substantially the same as that in embodiment 4, except that the transmission structure 14 is different.
Specifically, the transmission structure 14 includes an angle sensor 80 disposed on a ball switch 111, and two electric cylinders 90 electrically connected to the angle sensor 80, and each electric cylinder 90 is fixedly connected to one of the heat-insulating covers 12.
So, when ball valve switch 111 rotates, detect the turned angle of two numerical values by angle sensor 80, preset on angle sensor 80 by two numerical values, the angle when opening and closing that corresponds ball valve switch 111 respectively, electric cylinder 90's extension corresponds these two numerical values respectively with the shrink, when ball valve switch 111 converts the state of closing into the state of opening, reach one of them preset numerical value of angle sensor 80, then the electric cylinder drive, the push rod of electric cylinder begins the shrink, drive two heat preservation covers 12 and move toward the direction of keeping away from ball mill body 11, make first ball mill 10 dispel the heat fast when the blowing, prolong first ball mill 10's life. When the rotary ball valve switch 111 is switched from the open state to the closed state and reaches another preset value of the angle sensor 80, the electric cylinder is started again, the push rod of the electric cylinder starts to extend, so that the two heat preservation covers 12 slide to the state of being attached to the ball mill body 11 relative to the shaft rod 15, the effect of avoiding heat generated by friction is achieved, the friction heat generated by the titanium dioxide and carbon black raw material powder during ball milling can be preheated, and the effect of increasing the activity of the titanium dioxide is achieved.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The technology, the shape and the construction part which are not described in detail in the invention are all in the scope of the claims of the invention of the known technology. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (10)
1. The preparation method of the superfine titanium carbonitride is characterized by comprising the following steps:
s100: preparing ingredients, namely ball-milling titanium dioxide and carbon black serving as raw materials to obtain uniformly mixed powder;
s200: high-temperature carbonization, namely filling the powder obtained in the S100 into a vacuum carbon tube furnace, and carbonizing for 8 hours at 1800-1868 ℃ in a nitrogen atmosphere to obtain a high-temperature carbonized material;
s300: breaking and sieving, namely breaking and sieving the high-temperature carbonized material obtained in the S200;
s400: and (3) carbonizing at low temperature, placing the sieved high-temperature carbonized material into a vacuum carbon tube furnace, vacuumizing, introducing nitrogen, and preserving heat at 1456-1553 ℃ for 12 hours to obtain the titanium carbonitride.
2. The method for preparing ultrafine titanium carbonitride according to claim 1, characterized in that: and tungsten-titanium alloy balls are used as media for ball milling in S100 and S300.
3. The utility model provides a preparation facilities of superfine titanium carbonitride, its characterized in that, including first ball mill, high temperature vacuum carbon tube stove, second ball mill, filter sieve, low temperature vacuum carbon tube stove, air intake system and air exhaust equipment, the feed end of high temperature vacuum carbon tube stove with the discharge end butt joint of first ball mill, second ball mill feed end with the discharge end butt joint of high temperature carbon tube stove, the filter sieve is installed the discharge end department of second ball mill, the feed end of low temperature vacuum carbon tube stove with the discharge end butt joint of second ball mill, air intake system with high temperature vacuum carbon tube stove with low temperature vacuum carbon tube stove intercommunication, air exhaust equipment with high temperature vacuum carbon tube stove with low temperature vacuum carbon tube stove intercommunication.
4. The apparatus for preparing ultrafine titanium carbonitride according to claim 3, characterized in that: the first ball mill comprises a ball mill body, two heat-insulation covers, a spring and a transmission structure, wherein the ball mill body is provided with ball valve switches, the number of the heat-insulation covers is two, the heat-insulation covers are covered on the outer side wall of the ball mill body, two shaft lever sliding connections are adopted between the heat-insulation covers, the spring is enclosed on the outer side of the shaft lever, two ends of the spring are respectively fixed with a limiting disc, the limiting disc far away from the heat-insulation covers is fixedly connected with the spring, the other quick limiting disc is connected with the shaft lever sliding connections and is abutted to the heat-insulation covers, and the ball valve switches control the covering of the two heat-insulation covers on the ball mill body through the transmission structure.
5. The apparatus for preparing ultrafine titanium carbonitride according to claim 4, characterized in that: the transmission structure comprises a first helical gear which coaxially rotates with the ball valve switch, a second helical gear which is externally meshed with the first helical gear, a first transmission rod which is fixedly connected with the second helical gear, a first transmission gear which is fixed at one end of the first transmission rod away from the second helical gear, and a second transmission gear which is externally meshed with the first transmission gear, wherein the second transmission gear is connected with the discharge end of the ball mill body by adopting a bearing, and third transmission gears which are externally meshed with the second transmission gear, the number of the third transmission gears is two, the two third transmission gears are respectively positioned at two sides of the second transmission gear, one end of the second transmission gear is fixedly connected with the second transmission rod, and a cam which is fixed at one end of the second transmission rod away from the third transmission gear is abutted against the heat-insulating cover, the first transmission rod and the second transmission rod are in transition fit with a connecting plate, and the connecting plate is fixed at the discharging end of the ball mill body.
6. The apparatus for preparing ultrafine titanium carbonitride according to claim 5, characterized in that: the quantity of filter sieve is two, two filter sieve coincide, two filter sieve sliding connection each other, one of them filter sieve with the discharge end fixed connection of second ball mill, another integrated into one piece has the arch on the filter sieve, the arch stretches out the discharge end of second ball mill, and with the discharge end of second ball mill rotates to be connected.
7. The apparatus for preparing ultrafine titanium carbonitride according to claim 6, characterized in that: the cross-sectional area of the filter screen is U-shaped.
8. The apparatus for preparing ultrafine titanium carbonitride according to claim 7, characterized in that: labyrinth sealing is adopted between the two filter sieves, and labyrinth sealing is also adopted between the bulge and the discharge end of the second ball mill.
9. The apparatus for preparing ultrafine titanium carbonitride according to claim 6, characterized in that: the filter sieve is disc-shaped.
10. The apparatus for preparing ultra-fine titanium carbonitride of claim 4, characterized in that: the transmission structure comprises an angle sensor arranged on a ball valve switch and two electric cylinders electrically connected with the angle sensor, wherein each electric cylinder is fixedly connected with a heat-insulating cover.
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