CN113716565B - Superfine tungsten carbide powder and preparation method thereof and hard alloy - Google Patents
Superfine tungsten carbide powder and preparation method thereof and hard alloy Download PDFInfo
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Abstract
The invention discloses superfine tungsten carbide powder, a preparation method thereof and hard alloy, wherein the method comprises the following steps: (1) Reducing the purple tungsten in a hydrogen atmosphere to obtain superfine tungsten powder; (2) passivating the superfine tungsten powder; (3) Mixing the passivated superfine tungsten powder obtained in the step (2) with carbon black and an inhibitor for carbonization so as to obtain tungsten carbide blocks; (4) Crushing the tungsten carbide blocks to obtain superfine tungsten carbide powder, wherein the specific surface area of the tungsten carbide is 3.0-3.8 m 2 And/g. Thus, the method can prepare BET of more than or equal to 3.0m 2 Per gram of ultrafine tungsten carbide powder.
Description
Technical Field
The invention belongs to the field of powder metallurgy, and particularly relates to superfine tungsten carbide powder, a preparation method thereof and hard alloy.
Background
The nano/superfine grain hard alloy has superior performance which is incomparable with common hard alloy, and the capability of meeting the requirements of modern processing industry and special application fields on new material processing is greatly improved. The nano/superfine structure hard alloy has the characteristics of high wear resistance and high toughness, and is widely applied to manufacturing tools and dies which are suitable for high load, high stress wear, sharpness and good rigidity, such as a Printed Circuit Board (PCB) micro drill, a V-CUT cutter, a milling cutter and the like.
The main raw material of the nanometer/superfine grain hard alloy is superfine tungsten carbide powder, and the quality of the tungsten carbide powder is mainly influenced by the quality of the superfine tungsten powder and tungsten oxide. The research shows that the purple tungsten consists of a large number of irregular needle-shaped or rod-shaped whiskers, the whiskers are mutually staggered to form an arch bridge shape to cause a plurality of communicated pores, and the excellent air permeability of the purple tungsten determines that the purple tungsten is the most suitable raw material for producing superfine tungsten carbide at present. Mainly, mainlyThe process flow is as follows: tungsten trioxide is used as a raw material, purple tungsten and superfine tungsten powder are prepared in a reducing atmosphere, a proper amount of carbon black is added, the mixture is uniformly mixed, carbonization is carried out in a molybdenum wire furnace, and the obtained tungsten carbide block is crushed by air flow to prepare the superfine tungsten carbide powder. The conventional tungsten trioxide has smaller specific surface area, low porosity and poor air permeability, is unfavorable for the reduction reaction, and is difficult to control the morphology of the purple tungsten stably, so that more abnormal large particles exist in the superfine tungsten carbide prepared subsequently, and the BET is difficult to reach 3.0m 2 And/g.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide an ultrafine tungsten carbide powder, a method for preparing the same, and cemented carbide, which can prepare a powder having BET of 3.0m or more 2 Per gram of ultrafine tungsten carbide powder.
In one aspect of the invention, a method of preparing ultrafine tungsten carbide powder is provided. According to an embodiment of the invention, the method comprises:
(1) Reducing the purple tungsten in a hydrogen atmosphere to obtain superfine tungsten powder;
(2) Passivating the superfine tungsten powder;
(3) Mixing the passivated superfine tungsten powder obtained in the step (2) with carbon black and an inhibitor for carbonization so as to obtain tungsten carbide blocks;
(4) Crushing the tungsten carbide blocks so as to obtain superfine tungsten carbide powder;
wherein the specific surface area of the purple tungsten is 3.0-3.8 m 2 /g。
According to the method for preparing the superfine tungsten carbide powder, the specific surface area is firstly 3.0-3.8 m 2 And (3) carrying out reduction on per gram of purple tungsten in a hydrogen atmosphere to obtain superfine tungsten powder. Because the superfine tungsten powder has high activity and is easy to self-ignite, the superfine tungsten powder needs to be subjected to passivation treatment so as to obtain passivated superfine tungsten powder, thereby improving the safety of subsequent carbonization reaction; then mixing the passivated ultra-fine tungsten powder with carbon black and inhibitor, wherein the passivated ultra-fine tungsten powder and the carbon black occurThe carbonization reaction, the inhibitor can further reduce the activity of the superfine tungsten powder, thereby achieving the purpose of inhibiting the growth of tungsten carbide; and sintering at high temperature to obtain tungsten carbide blocks, and finally crushing the tungsten carbide blocks to obtain the superfine tungsten carbide powder. Thus, by using the process of the present application, BET.gtoreq.3.0 m can be prepared 2 Per gram of ultrafine tungsten carbide powder.
In addition, the method for preparing ultrafine tungsten carbide powder according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, the purple tungsten is prepared by the following method: calcining the tungsten oxide furnace end powder at a low temperature in an oxygen-enriched atmosphere so as to obtain tungsten trioxide; and carrying out high-temperature reduction calcination on the tungsten trioxide in a reducing atmosphere so as to obtain the purple tungsten, wherein the tungsten oxide furnace end powder comprises tungsten trioxide, ammonium paratungstate and intermediate tungsten oxide.
In some embodiments of the invention, in step (1), the hydrogen flow rate during the reduction is 40-60 m 3 And/h, wherein the time is 4-6 h.
In some embodiments of the invention, in step (1), the feed rate of the purple tungsten is 25 to 40kg/h and the reduction temperature is 630 to 940 ℃.
In some embodiments of the present invention, the passivation treatment is performed by rapidly cooling the ultra-fine tungsten powder in an inert atmosphere in step (2), wherein the flow rate of the inert atmosphere is 5-20L/min.
In some embodiments of the invention, in step (3), the carbon black and the inhibitor are used in an amount of 100% by mass of the passivated ultra-fine tungsten powder, the carbon black and the inhibitor: (6.5-6.84): (0.2-0.8) and mixing.
In some embodiments of the invention, in step (3), the inhibitor comprises at least one of vanadium carbide, chromium carbide, and tantalum carbide.
In some embodiments of the invention, in step (3), the carbonization is performed at a temperature of 1100-1200 ℃ for a time of 2-4 hours.
In some embodiments of the invention, in step (4), the crushing is performed using a gas crushing apparatus having a grinding gas pressure of 7 to 10mbar and a classifier wheel speed of 3800 to 4500r/min.
In a second aspect of the present invention, the present invention provides an ultrafine tungsten carbide powder. According to the embodiment of the invention, the superfine tungsten carbide powder is prepared by adopting the method. Thus, BET of 3.0m or more can be produced by the above method 2 The superfine tungsten carbide powder of/g can be used for preparing hard alloy with high hardness and high toughness, and further can be applied to manufacturing tools and dies which are suitable for high load, high stress abrasion, sharpness and good rigidity.
In a third aspect of the invention, the invention provides a cemented carbide. According to the embodiment of the invention, the hard alloy is prepared from the superfine tungsten carbide powder. Therefore, the hard alloy has higher hardness and toughness, and can be applied to manufacturing tools and dies which are suitable for high load, high stress abrasion, sharpness and good rigidity.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow chart of a method for preparing ultrafine tungsten carbide powder according to one embodiment of the invention;
FIG. 2 is a schematic process flow diagram of a method for preparing ultrafine tungsten carbide powder according to one embodiment of the invention;
FIG. 3 is a flow chart of a method of treating tungsten oxide burner powder according to one embodiment of the present invention;
FIG. 4 is an SEM image of ultra-fine tungsten carbide powder prepared according to example 1;
FIG. 5 is an SEM image of ultra-fine tungsten carbide powder prepared according to example 2;
FIG. 6 is an SEM image of ultra-fine tungsten carbide powder prepared according to example 3;
FIG. 7 is an SEM image of ultra-fine tungsten carbide powder prepared according to example 4;
FIG. 8 is an SEM image of ultrafine tungsten carbide powder prepared according to comparative example 1;
fig. 9 is an SEM image of the ultrafine tungsten carbide powder prepared according to comparative example 2.
Detailed Description
The following detailed description of embodiments of the invention, examples of which are illustrated in the accompanying drawings and, by way of example, are intended to be illustrative, and not to be construed as limiting, of the invention.
In one aspect of the invention, a method of preparing ultrafine tungsten carbide powder is provided. Referring to fig. 1-2, the method according to an embodiment of the present invention includes:
s100: reduction of purple tungsten in hydrogen atmosphere
In this step, the specific surface area is 3.0 to 3.8m 2 And (3) reducing the per gram purple tungsten in a hydrogen atmosphere to obtain the superfine tungsten powder.
Further, the feeding speed of the purple tungsten is 25-40 kg/h, and the hydrogen flow is 40-60 m 3 And/h. The inventor finds that the faster the feeding speed of the purple tungsten is, the thicker the purple tungsten layer is, the thicker tungsten powder prepared by reduction is, and if the feeding speed of the purple tungsten is too fast, the hydrogen in the furnace is insufficient to thoroughly reduce the purple tungsten, so that the product quality is affected; if the feeding speed of the purple tungsten is too slow, the reduction speed is too fast, and the generated tungsten powder is subjected to solid phase sintering and grows up, so that the preparation of superfine tungsten powder is not facilitated. Meanwhile, the larger the hydrogen flow is, the finer the tungsten powder is, if the hydrogen flow is too large, the refining effect on the tungsten powder is not large, the hydrogen waste is caused, and the large-flow hydrogen is easy to take away more fine powder, so that the burner powder is too much; if the hydrogen flow is too small, the reduction reaction is incomplete, thereby affecting the product quality. Therefore, the feeding speed and the hydrogen flow of the purple tungsten can be adopted, the product quality can be improved, and the hydrogen waste and the generation of excessive furnace end powder are avoided.
Further, in the reduction process, the reduction temperature is 630-940 ℃ and the time is 4-6 h. The inventor finds that if the reduction temperature is too low, the required reduction time is longer, and meanwhile, incomplete powder reduction is easy to cause; if the reduction temperature is too high, the reduction reaction speed is increased, and the particle size of the tungsten powder is thicker, so that the preparation of superfine tungsten powder is not facilitated. Meanwhile, if the reduction time is too long, the tungsten powder grows up by sintering, which is not beneficial to the preparation of superfine powder; if the reduction time is too short, the reduction is easy and incomplete, and the oxygen content of tungsten powder is high. Therefore, the reduction temperature and time are adopted, so that the preparation of the superfine tungsten powder is facilitated.
According to one embodiment of the present invention, the above-mentioned reduction process includes a first reduction, a second reduction and a third reduction, and the temperatures of the first reduction, the second reduction and the third reduction are gradually increased in a gradient, wherein the temperature of the first reduction is 630 to 720 ℃, the temperature of the second reduction is 750 to 830 ℃, and the temperature of the third reduction is 840 to 940 ℃.
Further, referring to fig. 3, the purple tungsten is prepared by the following method:
sa: calcining tungsten oxide furnace end powder at low temperature in oxygen-enriched atmosphere
In the step, the tungsten oxide furnace end powder is subjected to low-temperature calcination in an oxygen-enriched atmosphere so as to obtain tungsten trioxide. The inventor finds that because the tungsten oxide furnace end powder has complex phase components, the purple tungsten directly prepared by taking the tungsten oxide furnace end powder as a raw material has the defects of poor appearance, low specific surface area, uneven particles and the like, the low-temperature calcination pretreatment is needed, and thus the tungsten trioxide with single phase, large specific surface area and good air permeability is prepared.
According to one embodiment of the present invention, the tungsten oxide burner powder includes tungsten trioxide, ammonium paratungstate, and intermediate tungsten oxide. Specifically, the sources of tungsten oxide burner powder are as follows: ammonium paratungstate can produce a large amount of steam and ammonia in the calcination process, and ammonia can be decomposed into inert gas nitrogen and strong reducing gas hydrogen at high temperature, and in order to obtain tungsten trioxide with single phase, an air draft measure opposite to the feeding direction is generally adopted so as to achieve the effect of timely discharging steam, ammonia and hydrogen. During the process of air draft, a large amount of fine tungsten oxide and unreacted ammonium paratungstate powder are drawn out of the furnace tube along with the air, thereby generating tungsten oxide furnace end powder comprising tungsten trioxide, ammonium paratungstate and intermediate tungsten oxide, and the intermediate tungsten oxide generally refers to intermediate products in the process of preparing tungsten oxide from ammonium paratungstate.
Further, the feeding speed of the tungsten oxide furnace end powder is 200-300 kg/h. The inventors found that if the feeding rate of the tungsten oxide burner powder is too slow, the yield is insufficient, and if the feeding rate of the tungsten oxide burner powder is too fast, incomplete reaction is easily caused. Thus, with the feed rate of the present application, the reaction can be ensured to be complete and the yield can be improved.
Further, the low-temperature calcination is performed in a rotary furnace, the rotating speed of the rotary furnace is 20-30 r/min, and the low-temperature calcination temperature is 420-500 ℃. The inventor finds that if the rotating speed of the rotary furnace is too low, the material calcination time is longer, so that particle cracks are easy to be closed, the porosity is reduced, and the air permeability of particles is poor; if the rotating speed of the rotary furnace is too high, the material calcination time is insufficient, incomplete calcination is easily caused, and the tungsten trioxide phase is not single. Meanwhile, if the low-temperature calcination temperature is too low, incomplete calcination is easily caused, while if the low-temperature calcination temperature is too high, particle sintering growth and crack closure are easily caused, and air permeability is reduced. Therefore, the tungsten trioxide with single phase, large specific surface area and good air permeability can be obtained by adopting the rotating speed of the rotary furnace and the low-temperature calcination temperature.
Further, the low-temperature calcination process is accompanied by air draft, preferably by air draft measures in the opposite direction to the feeding direction, and the frequency of air draft is 1-4 Hz. The inventor finds that because the content of ammonium paratungstate in the tungsten oxide furnace end powder is small, the amount of water vapor and ammonia generated by calcination is small, the air draft frequency can be relatively low, and too high air draft frequency easily causes that materials in the furnace are carried out along with wind in the calcination process, a large amount of tungsten oxide furnace end powder is generated again, and the recycling of the materials is not facilitated. Therefore, by adopting the air draft frequency, the tungsten oxide furnace end powder can be prevented from being generated again, and the recovery of materials is facilitated.
Preferably, before the tungsten oxide furnace end powder is subjected to low-temperature calcination in an oxygen-enriched atmosphere, the tungsten oxide furnace end powder is subjected to ultrasonic sieving pretreatment, so that large-particle impurities and mechanical impurities are removed, and the purity of the materials is ensured.
Sb: calcining tungsten trioxide in reducing atmosphere at high temperature
In this step, the above tungsten trioxide is subjected to high-temperature reduction calcination in a reducing atmosphere to obtain rod-shaped purple tungsten. Compared with the tungsten violet obtained by only carrying out high-temperature reduction calcination on the tungsten oxide furnace end powder, the tungsten violet rod obtained by carrying out low-temperature calcination on the tungsten oxide furnace end powder under the oxygen-enriched atmosphere and then carrying out high-temperature reduction calcination on the tungsten oxide furnace end powder under the reducing atmosphere has higher specific surface area and more excellent performance, and is more suitable for the production of superfine tungsten powder and superfine tungsten carbide powder; compared with the prior art that the rod-shaped purple tungsten with excellent performance is prepared by using the tungsten trioxide with high specific surface area and good air permeability, the invention carries out recovery treatment on the tungsten oxide furnace end powder, thereby greatly reducing the cost.
Further, the feeding rate of the tungsten trioxide is 80-120 kg/h. The inventor finds that if the feeding speed of tungsten trioxide is too high, the material layer in the furnace is too thick, the reduction is easy to be carried out in place, the single-phase purple tungsten cannot be prepared, meanwhile, the feeding speed is too high, the partial pressure of water vapor in the furnace is large, and the rod-shaped purple tungsten with short length and thick diameter is easy to generate; if the feeding speed of tungsten trioxide is too slow, the production efficiency is low, the material layer in the furnace is thin, the reduced materials are few, the concentration of the reducing gas is relatively high, tungsten trioxide is excessively reduced to generate tungsten dioxide instead of purple tungsten, and meanwhile, excessive sintering is easy to occur, so that the product quality is influenced. Thus, with the feed rate of tungsten trioxide according to the present application, single phase violet tungsten can be obtained, and over-reduction, over-sintering, and formation of rod-like violet tungsten of short length and large diameter are avoided.
Further, the high-temperature calcination temperature is 700 to 800 ℃. The inventor finds that if the high-temperature calcination temperature is too low, the reaction rate is slow, the reduction degree is insufficient, and thus the phase composition of the purple tungsten is complex; if the high-temperature calcination temperature is too high, the sintering growth is easy to produce columnar purple tungsten. Thus, by adopting the high-temperature calcination temperature of the present application, a suitable reduction degree can be ensured, and rod-shaped purple tungsten with single phase component can be obtained.
Further, the flow rate of the reducing atmosphere is 0.5-1.2 m 3 And/h, wherein the reducing atmosphere is ammonia, a mixed gas containing nitrogen and hydrogen or a mixed gas containing ammonia and nitrogen. The inventor finds that if the flow rate of the reducing atmosphere is too low, water vapor generated in the reducing process cannot be discharged in time, so that crystal grains grow up and materials are agglomerated; if the flow rate of the reducing atmosphere is too high, excessive reduction is liable to occur, and tungsten dioxide and even tungsten powder are produced. Therefore, by adopting the reducing atmosphere flow, tungsten trioxide can be prevented from being excessively reduced, grains grow up and materials are prevented from agglomerating.
Preferably, the high temperature calcination is performed in a rotary kiln at a rotation speed of 10 to 25r/min. The inventor finds that if the rotating speed of the rotary furnace is too slow, the production efficiency is affected, so that the production cost is increased; if the rotating speed of the rotary furnace is too high, the materials are easy to be reduced in place, so that the phase components are complex, and the single-phase purple tungsten cannot be prepared. Therefore, the rotating speed of the rotary furnace can be adopted, so that the production cost can be reduced, and single-phase purple tungsten can be obtained.
The inventor finds that firstly, the tungsten oxide furnace end powder is subjected to low-temperature calcination in an oxygen-enriched atmosphere, and because the tungsten oxide furnace end powder has complex phase components, the purple tungsten directly prepared by taking the tungsten oxide furnace end powder as a raw material has the defects of poor appearance, low specific surface area, uneven particles and the like, the tungsten oxide furnace end powder needs to be subjected to low-temperature calcination pretreatment, so that the tungsten trioxide with single phase, large specific surface area and good air permeability is prepared; then the tungsten trioxide obtained by low-temperature calcination is subjected to high-temperature reduction calcination in a reducing atmosphere, and the BET is more than or equal to 3.0m can be stably prepared 2 And/g and is elongated rod-shaped purple tungsten. Compared with the tungsten violet obtained by only carrying out high-temperature reduction calcination on the tungsten oxide furnace end powder, the tungsten violet rod obtained by carrying out low-temperature calcination on the tungsten oxide furnace end powder under the oxygen-enriched atmosphere and then carrying out high-temperature reduction calcination on the tungsten oxide furnace end powder under the reducing atmosphere has higher specific surface area and better performance, and is more suitable for the production of superfine tungsten powder and superfine tungsten carbide powder; and simultaneously compared with the prior art, the method utilizes the high-ratio meterThe tungsten trioxide rod-shaped purple tungsten with good area and air permeability and excellent preparation performance realizes the recovery treatment of the tungsten oxide furnace end powder, thereby greatly reducing the cost. In addition, compared with the treatment of the tungsten oxide furnace end powder by an ammonia dissolving-impurity removing-recrystallization recovery process, the method has the advantage that the treatment cost is remarkably reduced. Therefore, by adopting the method for treating the tungsten oxide furnace end powder, not only can the BET (BET) not less than 3.0m be stably prepared 2 And/g of the purple tungsten in a slender rod shape, the recovery cost of the existing tungsten oxide furnace end powder is reduced, the production efficiency is improved, and the productivity of the purple tungsten is greatly improved.
S200: passivating the superfine tungsten powder
In the step, the superfine tungsten powder obtained in the step S100 is subjected to passivation treatment. Because the superfine tungsten powder has high activity and is easy to self-ignite, the superfine tungsten powder needs to be passivated, thereby improving the safety of the subsequent carbonization reaction. Specifically, the passivation treatment is realized by rapidly cooling ultrafine tungsten powder in an inert atmosphere.
Further, the flow rate of the inert atmosphere is 5-20L/min. The inventor finds that if the flow of the inert atmosphere is too large, the thinner tungsten powder is taken away by the easy belt, so that the material waste is caused; if the flow of the inert atmosphere is too small, the cooling speed is low, the passivation treatment time is long, and the efficiency is low. Therefore, the passivation efficiency can be improved and the material waste can be avoided by adopting the flow of the inert atmosphere.
S300: mixing the passivated superfine tungsten powder obtained in the step S200 with carbon black and an inhibitor for carbonization
In the step, the passivated superfine tungsten powder obtained in the step S200 is mixed with carbon black and an inhibitor for carbonization, wherein the passivated superfine tungsten powder and the carbon black undergo carbonization reaction, and the inhibitor can further reduce the activity of the superfine tungsten powder, so that the aim of inhibiting the growth of tungsten carbide is achieved, and a tungsten carbide block is obtained after high-temperature sintering.
Further, the mass ratio of the carbon black to the inhibitor is 100: (6.5-6.84): (0.2-0.8) and mixing. The inventors found that when the content of carbon black is too high, it is liable to cause excessive free carbon, resulting inAffecting powder properties; if the content of carbon black is too low, tungsten powder is incompletely carbonized and has brittle phase W 2 C formation also affects powder properties. In addition, the inhibitor has a certain inhibition effect on grain growth, and if the content of the inhibitor is too high, the content of the inhibitor is continuously increased, so that a better refining effect cannot be achieved; if the content of the inhibitor is too low, the inhibition effect is poor, and the product requirement cannot be met. Therefore, the performance of the superfine tungsten carbide powder can be improved by adopting the proportion of the powder.
Further, the carbonization temperature is 1100-1200 ℃ and the time is 2-4 h. The inventor finds that if the carbonization temperature is too high and the carbonization time is too long, the particles are easier to sinter and grow up, which is not beneficial to the preparation of superfine tungsten carbide; if the carbonization temperature is too low and the carbonization time is too short, incomplete carbonization is easy to occur, thereby affecting the product quality. Therefore, the carbonization temperature and the carbonization time are adopted, so that the preparation of the superfine tungsten carbide powder is facilitated.
It should be noted that the type of the inhibitor is not particularly limited, and those skilled in the art may select at least one of vanadium carbide, chromium carbide and tantalum carbide according to actual needs.
S400: crushing the tungsten carbide block
In the step, the tungsten carbide block obtained in the step S300 is crushed so as to obtain superfine tungsten carbide powder.
Preferably, the crushing is carried out using a gas crushing apparatus having a grinding gas pressure of 7 to 10mbar and a classifier wheel rotation speed of 3800 to 4500r/min. The inventor finds that the larger the rotating speed of the classifying wheel and the grinding air pressure are, the finer the granularity of the prepared tungsten carbide powder is, if the rotating speed of the classifying wheel and the grinding air pressure are too large, the loss of the classifying wheel and the equipment is increased, the service life of the equipment is reduced, and the production cost is increased. If the rotating speed of the classifying wheel and the grinding air pressure are too small, the crushing degree of the tungsten carbide is insufficient, the granularity is thicker, and the preparation of superfine tungsten carbide powder is not facilitated. Therefore, the adoption of the rotating speed of the classifying wheel and the grinding air pressure is beneficial to preparing the superfine tungsten carbide powder, and the production cost is reduced.
The inventors found that the ratio table is first to be usedThe area is 3.0-3.8 m 2 And (3) carrying out reduction on per gram of purple tungsten in a hydrogen atmosphere to obtain superfine tungsten powder. Because the superfine tungsten powder has high activity and is easy to self-ignite, the superfine tungsten powder needs to be subjected to passivation treatment so as to obtain passivated superfine tungsten powder, thereby improving the safety of subsequent carbonization reaction; then mixing the passivated superfine tungsten powder with carbon black and an inhibitor, wherein the passivated superfine tungsten powder and the carbon black carry out carbonization reaction, and the inhibitor can further reduce the activity of the superfine tungsten powder, thereby achieving the purpose of inhibiting the growth of tungsten carbide; and sintering at high temperature to obtain tungsten carbide blocks, and finally crushing the tungsten carbide blocks to obtain the superfine tungsten carbide powder. Thus, by using the process of the present application, BET.gtoreq.3.0 m can be prepared 2 Per gram of ultrafine tungsten carbide powder. Further, the tungsten oxide furnace end powder is subjected to low-temperature calcination and high-temperature reduction calcination to obtain the rod-shaped purple tungsten with the specific surface area of 3.0m 2 The specific surface area of the prepared superfine tungsten carbide powder is higher and reaches 3.0m compared with the tungsten violet obtained by reducing the conventional tungsten trioxide 2 The method can be used for preparing hard alloy with high hardness and high toughness, and further can be applied to manufacturing tools and dies which are suitable for high load, high stress abrasion, sharpness and good rigidity, and the method is used for recycling the tungsten oxide furnace end powder, so that the production cost is greatly reduced.
In a second aspect of the present invention, the present invention provides an ultrafine tungsten carbide powder. According to the embodiment of the invention, the superfine tungsten carbide powder is prepared by adopting the method. Thus, BET of 3.0m or more can be produced by the above method 2 The superfine tungsten carbide powder of/g can be used for preparing hard alloy with high hardness and high toughness, and further can be applied to manufacturing tools and dies which are suitable for high load, high stress abrasion, sharpness and good rigidity. It should be noted that the features and advantages described above for the method for preparing ultrafine tungsten carbide powder are equally applicable to the ultrafine tungsten carbide powder, and will not be described here again.
In a third aspect of the invention, the invention provides a cemented carbide. According to the embodiment of the invention, the hard alloy is prepared from the superfine tungsten carbide powder. Therefore, the hard alloy has higher hardness and toughness, and can be applied to manufacturing tools and dies which are suitable for high load, high stress abrasion, sharpness and good rigidity. It should be noted that the features and advantages described above for the ultrafine tungsten carbide powder and the preparation method thereof are also applicable to the cemented carbide, and are not described herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
1. The tungsten oxide furnace end powder is subjected to ultrasonic sieving pretreatment for removing large particle impurities and mechanical impurities, so that the purity of the materials is ensured.
2. Feeding the sieved tungsten oxide furnace end powder into a rotary furnace through a screw feeder to perform low-temperature oxygen-enriched calcination, wherein the calcination process comprises the following steps: the rotation speed of the furnace tube is 20r/min, the temperature is 420 ℃, the air draft frequency is 1Hz, the feeding speed is 200kg/h, and the specific surface area of the obtained tungsten trioxide is 2.8m 2 The/g is increased to 3.2m 2 /g。
3. And conveying the tungsten trioxide calcined at the low temperature and rich in oxygen to another rotary furnace through an automatic feeding and discharging device, and preparing the rod-shaped purple tungsten by adopting a high-temperature reduction calcination process. The specific process comprises the following steps: the rotation speed of the furnace tube is 10r/min, the temperature is 730 ℃, and the NH is 3 Flow rate of 0.7m 3 And/h, the feeding speed is 80kg/h. The specific surface area of the prepared purple tungsten is 3.08m 2 And/g, the microcosmic appearance is in a slender rod shape, most rods are mutually bonded together, and a small part exists in a single rod shape.
4. Taking the purple tungsten as a raw material, and reducing the raw material in a hydrogen atmosphere to obtain hydrogen with the flow of 44m 3 And/h, the reduction time is 4h, the feeding amount is 30kg/h, and the reduction temperature is 650/780/940 ℃.
5. Passivating the superfine tungsten powder in inert atmosphere to obtain passivated superfine tungsten powder, wherein the preparation process comprises the following steps: the flow rate of the inert atmosphere was 8L/min.
6. Taking passivated ultrafine tungsten powder as a main raw material, and adding the passivated ultrafine tungsten powder, carbon black and TaC according to the mass ratio of 100:6.72:0.3, after uniformly mixing, carbonizing to obtain tungsten carbide blocks, and crushing by air flow to obtain superfine tungsten carbide powder, wherein the carbonization and crushing process comprises the following steps: carbonizing at 1200 deg.C for 2.5h under hydrogen atmosphere, and the gas flow crushing condition of the obtained tungsten carbide block is grinding pressure 7mbar and classifying wheel rotation speed 4200r/min.
7. The BET of the prepared superfine tungsten carbide powder is 3.05m 2 And/g, the particles are uniform, the dispersibility is good, coarse particles and nano agglomerates are avoided, and an SEM (scanning electron microscope) diagram is shown in figure 4.
Example 2
1. The tungsten oxide furnace end powder is subjected to ultrasonic sieving pretreatment for removing large particle impurities and mechanical impurities, so that the purity of the materials is ensured.
2. Feeding the sieved tungsten oxide furnace end powder into a rotary furnace through a screw feeder to perform low-temperature oxygen-enriched rapid calcination, wherein the calcination process comprises the following steps: the rotation speed of the furnace tube is 30r/min, the temperature is 500 ℃, the air draft frequency is 4Hz, the feeding speed is 280kg/h, and the specific surface area of the obtained tungsten trioxide is 2.8m 2 The/g is increased to 3.5m 2 /g。
3. And conveying the tungsten trioxide calcined at the low temperature and rich in oxygen to another rotary furnace through an automatic feeding and discharging device, and preparing the rod-shaped purple tungsten by adopting a high-temperature reduction calcination process. The specific process comprises the following steps: the rotation speed of the furnace tube is 20r/min, the temperature is 800 ℃, and the NH is 3 Flow rate of 0.6m 3 /h，N 2 The flow rate is 0.3m 3 And/h, the feed rate was 110kg/h. The specific surface area of the prepared purple tungsten is 3.02m 2 And/g, the surface layers of the particles are in a slender rod shape and are mutually bonded, and the inner layer is in a thick rod shape with larger diameter.
4. The ultra-fine tungsten powder is prepared by taking the purple tungsten as a raw material and reducing the raw material in a hydrogen atmosphere, and the preparation process comprises the following steps: the hydrogen flow rate is 50m 3 And/h, the reduction time is 5h, the feeding amount is 30kg/h, and the reduction temperature is 650/820/920 ℃.
5. Passivating the superfine tungsten powder in inert atmosphere to obtain passivated superfine tungsten powder, wherein the preparation process comprises the following steps: the flow rate of the inert atmosphere was 10L/min.
6. Taking passivated ultrafine tungsten powder as a main raw material, and adding the passivated ultrafine tungsten powder, carbon black and VC in a mass ratio of 100:6.72:0.4, after uniformly mixing, carbonizing to obtain tungsten carbide blocks, and crushing by air flow to obtain superfine tungsten carbide powder, wherein the carbonization and crushing process comprises the following steps: carbonizing at 1100 deg.c in hydrogen atmosphere for 3.5 hr to obtain tungsten carbide block with gas flow crushing condition of grinding pressure 7mbar and classifying wheel rotation speed 4200r/min.
7. The BET of the prepared superfine tungsten carbide powder is 3.25m 2 And/g, the particles are uniform, the dispersibility is good, coarse particles are avoided, and small amount of nano agglomerates exist due to large BET, and the SEM image is shown in figure 5.
Example 3
1. The tungsten oxide furnace end powder is subjected to ultrasonic sieving pretreatment for removing large particle impurities and mechanical impurities, so that the purity of the materials is ensured.
2. Feeding the sieved tungsten oxide furnace end powder into a rotary furnace through a screw feeder to perform low-temperature oxygen-enriched rapid calcination, wherein the calcination process comprises the following steps: the rotation speed of the furnace tube is 27r/min, the temperature is 460 ℃, the air draft frequency is 2Hz, the feeding speed is 260kg/h, and the specific surface area of the obtained tungsten trioxide is 2.8m 2 The/g is increased to 3.8m 2 /g。
3. And conveying the tungsten trioxide calcined at the low temperature and rich in oxygen to another rotary furnace through an automatic feeding and discharging device, and preparing the rod-shaped purple tungsten by adopting a high-temperature reduction calcination process. The specific process comprises the following steps: the rotation speed of the furnace tube is 15r/min, the temperature is 760 ℃, and N is the same 2 The flow rate is 0.3m 3 /h，H 2 The flow is of an amount of 0.3m 3 And/h, the feeding speed is 100kg/h. The specific surface area of the prepared purple tungsten is 3.27m 2 And/g, the microcosmic appearance is in a shape of a long and thin rod, a small part of microcosmic appearance is in a shape of a short rod, a large part of rods are bonded together, and a small part of microcosmic appearance exists in a shape of a single rod.
4. The ultra-fine tungsten powder is prepared by taking the purple tungsten as a raw material and reducing the raw material in a hydrogen atmosphere, and the preparation process comprises the following steps: the hydrogen flow is 56m 3 And/h, the reduction time is 5.5h, the feeding amount is 35kg/h, and the reduction temperature is 650/820/920 ℃.
5. Passivating the superfine tungsten powder in inert atmosphere to obtain passivated superfine tungsten powder, wherein the preparation process comprises the following steps: the flow rate of the inert atmosphere was 15L/min.
6. Taking the passivated ultrafine tungsten powder as a main raw material, and adding the passivated ultrafine tungsten powder, carbon black and Cr 3 C 2 The mass ratio of (2) is 100:6.72:0.4, after uniformly mixing, carbonizing to obtain tungsten carbide blocks, and crushing by air flow to obtain superfine tungsten carbide powder, wherein the carbonization and crushing process comprises the following steps: carbonizing at 1150 deg.c for 3.0 hr in hydrogen atmosphere to obtain tungsten carbide block with gas flow crushing condition of grinding pressure 9mbar and classifying wheel rotation speed 4100r/min.
7. The BET of the prepared superfine tungsten carbide powder is 3.34m 2 The particles were uniform and no coarse particles, and the SEM image was shown in FIG. 6 because of the large BET presence of more nano-agglomerates.
Example 4
1. The tungsten oxide furnace end powder is subjected to ultrasonic sieving pretreatment for removing large particle impurities and mechanical impurities, so that the purity of the materials is ensured.
2. Feeding the sieved tungsten oxide furnace end powder into a rotary furnace through a screw feeder to perform low-temperature oxygen-enriched rapid calcination, wherein the calcination process comprises the following steps: the rotation speed of the furnace tube is 27r/min, the temperature is 480 ℃, the air draft frequency is 2Hz, the feeding speed is 260kg/h, and the specific surface area of the obtained tungsten trioxide is 2.8m 2 The/g is increased to 4.0m 2 /g。
3. And conveying the tungsten trioxide calcined at the low temperature and rich in oxygen to another rotary furnace through an automatic feeding and discharging device, and preparing the rod-shaped purple tungsten by adopting a high-temperature reduction calcination process. The specific process comprises the following steps: the rotation speed of the furnace tube is 15r/min, the temperature is 780 ℃, and N is the same as that of the furnace tube 2 Flow rate of 0.6m 3 /h，H 2 The flow rate is 0.3m 3 Per hour, the feeding speed is 100 kg/hour, and the specific surface area of the prepared purple tungsten is 3.58m 2 And/g, the microcosmic appearance is in a slender rod shape, the dispersibility is good, and only a small amount of bonding phenomenon exists.
4. The ultra-fine tungsten powder is prepared by taking the purple tungsten as a raw material and reducing the raw material in a hydrogen atmosphere, and the preparation process comprises the following steps: the hydrogen flow is 56m 3 And/h, the reduction time is 5.5h, the feeding amount is 35kg/h, and the reduction temperature is 650/820/920 ℃.
5. Passivating the superfine tungsten powder in inert atmosphere to obtain passivated superfine tungsten powder, wherein the preparation process comprises the following steps: the flow rate of the inert atmosphere was 18L/min.
6. Taking the passivated ultrafine tungsten powder as a main raw material, and adding the passivated ultrafine tungsten powder, carbon black and Cr 3 C 2 And the mass ratio of VC is 100:6.72:0.4:0.35, uniformly mixing, carbonizing to obtain tungsten carbide blocks, and crushing by air flow to obtain superfine tungsten carbide powder, wherein the carbonization and crushing process comprises the following steps: carbonizing at 1120 deg.c for 3.5 hr in hydrogen atmosphere to obtain tungsten carbide block with grinding pressure of 9mbar and classifying wheel rotation speed of 4100r/min.
7. The BET of the prepared superfine tungsten carbide powder is 3.48m 2 The particles were uniform and no coarse particles were present, and the SEM image was shown in FIG. 7 because of the large number of nano-agglomerates present in BET.
Comparative example 1
1. The tungsten oxide furnace end powder is subjected to ultrasonic sieving pretreatment for removing large particle impurities and mechanical impurities, so that the purity of the materials is ensured.
2. The sieved tungsten oxide furnace end powder enters a rotary furnace through a screw feeder to be subjected to high-temperature reduction calcination, and the specific process comprises the following steps of: the rotation speed of the furnace tube is 14r/min, the temperature is 740 ℃, and the NH is high 3 Flow rate of 0.6m 3 Per hour, the feeding speed is 60 kg/hour, and the specific surface area of the prepared purple tungsten is 2.86m 2 The majority of the particles are thick rods with larger diameters, the adhesion phenomenon is serious, a large number of small short rods exist, and only a small number of slender rods exist.
3. The ultra-fine tungsten powder is prepared by taking the purple tungsten as a raw material and reducing the raw material in a hydrogen atmosphere, and the preparation process comprises the following steps: the hydrogen flow is 56m 3 And/h, the reduction time is 5.5h, the feeding amount is 35kg/h, and the reduction temperature is 650/820/920 ℃.
4. Passivating the superfine tungsten powder in inert atmosphere to obtain passivated superfine tungsten powder, wherein the preparation process comprises the following steps: the flow rate of the inert atmosphere was 12L/min.
5. Taking the passivated ultrafine tungsten powder as a main raw material, and adding the passivated ultrafine tungsten powder, carbon black and Cr 3 C 2 The mass ratio of (2) is 100:6.72:0.4, evenly mixing, carbonizing to obtain tungsten carbide blocks, crushing by air flow to obtain superfine tungsten carbide powder and carbonThe chemical and crushing process comprises the following steps: carbonizing at 1150 deg.c for 3.0 hr in hydrogen atmosphere to obtain tungsten carbide block with gas flow crushing condition of grinding pressure 9mbar and classifying wheel rotation speed 4100r/min.
6. Ultrafine tungsten carbide powder BET of 2.9m 2 In g, a small amount of coarse particles was present, and the SEM image thereof was shown in FIG. 8.
Comparative example 2
1. Taking conventional tungsten trioxide as a raw material, and feeding the tungsten trioxide into a rotary furnace through a screw feeder to perform high-temperature reduction calcination, wherein the specific process comprises the following steps of: the rotation speed of the furnace tube is 14r/min, the temperature is 740 ℃, and the NH is high 3 Flow rate of 0.6m 3 Per hour, the feeding speed is 60 kg/hour, and the specific surface area of the prepared purple tungsten is 2.8m 2 /g。
2. The ultra-fine tungsten powder is prepared by taking the purple tungsten as a raw material and reducing the raw material in a hydrogen atmosphere, and the preparation process comprises the following steps: the hydrogen flow is 56m 3 And/h, the reduction time is 5.5h, the feeding amount is 35kg/h, and the reduction temperature is 650/820/920 ℃.
3. Passivating the superfine tungsten powder in inert atmosphere to obtain passivated superfine tungsten powder, wherein the preparation process comprises the following steps: the flow rate of the inert atmosphere was 12L/min.
4. Taking the passivated ultrafine tungsten powder as a main raw material, and adding the passivated ultrafine tungsten powder, carbon black and Cr 3 C 2 The mass ratio of (2) is 100:6.72:0.4, after uniformly mixing, carbonizing to obtain tungsten carbide blocks, and crushing by air flow to obtain superfine tungsten carbide powder, wherein the carbonization and crushing process comprises the following steps: carbonizing at 1150 deg.c for 3.0 hr in hydrogen atmosphere to obtain tungsten carbide block with gas flow crushing condition of grinding pressure 9mbar and classifying wheel rotation speed 4100r/min.
5. Ultrafine tungsten carbide powder BET of 2.78m 2 In g, a small amount of coarse particles was present, and the SEM image thereof was shown in FIG. 9.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (9)
1. A method for preparing ultrafine tungsten carbide powder, comprising:
(1) Reducing the purple tungsten in a hydrogen atmosphere to obtain superfine tungsten powder;
(2) Passivating the superfine tungsten powder;
(3) Mixing the passivated superfine tungsten powder obtained in the step (2) with carbon black and an inhibitor for carbonization so as to obtain tungsten carbide blocks;
(4) Crushing the tungsten carbide blocks to obtain superfine tungsten carbide powder,
wherein the specific surface area of the purple tungsten is 3.0-3.8 m 2 /g，
In the step (1), the reduction temperature is 630-940 ℃,
in the step (2), the passivation treatment is realized by rapidly cooling the superfine tungsten powder in an inert atmosphere,
in step (3), the inhibitor comprises at least one of vanadium carbide, chromium carbide and tantalum carbide,
in the step (3), the carbonization temperature is 1100-1200 ℃,
the purple tungsten is prepared by the following method:
calcining the tungsten oxide furnace end powder at a low temperature in an oxygen-enriched atmosphere so as to obtain tungsten trioxide;
the tungsten trioxide is subjected to high-temperature reduction calcination in a reducing atmosphere so as to obtain purple tungsten,
wherein the tungsten oxide furnace end powder comprises tungsten trioxide, ammonium paratungstate and intermediate tungsten oxide,
the low-temperature calcination temperature is 420-500 ℃, and the high-temperature reduction calcination temperature is 700-800 ℃.
2. The method of claim 1, wherein in the reducing step (1), the hydrogen flow is 40-60 m 3 And/h, wherein the time is 4-6 h.
3. The method according to claim 2, wherein in the step (1), the feeding speed of the purple tungsten is 25-40 kg/h.
4. The method according to claim 1, wherein in the step (2), the flow rate of the inert atmosphere is 5-20 l/min.
5. The method according to claim 1, wherein in the step (3), the carbon black and the inhibitor are used in an amount such that the mass ratio of the passivated ultra-fine tungsten powder, the carbon black and the inhibitor is 100: (6.5 to 6.84): (0.2 to 0.8) and mixing.
6. The method of claim 1, wherein in step (3), the carbonization time is 2 to 4 hours.
7. The method according to claim 1, wherein in the step (4), the crushing is performed by using a gas crushing device, the grinding gas pressure of the gas crushing device is 7-10 mbar, and the rotation speed of the classifying wheel is 3800-4500 r/min.
8. An ultrafine tungsten carbide powder, characterized in that the ultrafine tungsten carbide powder is prepared by the method of any one of claims 1-7.
9. A cemented carbide, characterized in that it is prepared from the ultrafine tungsten carbide powder according to claim 8.
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