CN102078965A - Method for preparing WC-Co (tungsten carbide-cobalt) nano-powder - Google Patents
Method for preparing WC-Co (tungsten carbide-cobalt) nano-powder Download PDFInfo
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- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 37
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910009043 WC-Co Inorganic materials 0.000 title abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 64
- OQEBWHLKWJNDCX-UHFFFAOYSA-N oxocobalt oxotungsten Chemical compound [Co]=O.[W]=O OQEBWHLKWJNDCX-UHFFFAOYSA-N 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 20
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- 238000010438 heat treatment Methods 0.000 claims abstract description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 12
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims 4
- 238000010668 complexation reaction Methods 0.000 claims 3
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- 150000004767 nitrides Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
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- SFJBWZNTPHYOEH-UHFFFAOYSA-N cobalt Chemical compound [Co].[Co].[Co] SFJBWZNTPHYOEH-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
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- HHIQWSQEUZDONT-UHFFFAOYSA-N tungsten Chemical compound [W].[W].[W] HHIQWSQEUZDONT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing WC-Co (tungsten carbide-cobalt) nano-powder, which comprises the following steps of: firstly, preparing tungsten oxide-cobalt oxide powder by adopting a citrate or package method; secondly, introducing ammonia gas into the obtained tungsten oxide-cobalt oxide powder for nitridation to obtain tungsten nitride-cobalt nitride powder; and thirdly, mixing the obtained tungsten nitride-cobalt nitride powder with carbon black, performing ball milling, and performing heat treatment under a vacuum or inert atmosphere with the air pressure of less than 200Pa to obtain the WC-Co nano-powder; or directly charging the obtained tungsten nitride-cobalt nitride powder into a tube furnace, and introducing mixed gas of methane and hydrogen gas into the tube furnace for carbonization to obtain the WC-Co nano-powder. The preparation process disclosed by the invention has the advantages of simplicity and practicality, strong maneuverability, and easiness of large-scale production. Moreover, the prepared powder has the advantages of small particle diameter, uniform particle size distribution and good sintering activity.
Description
Technical field
The present invention relates to a kind of preparation method of tungsten-cobalt carbide nano-powder, specifically, relate to a kind ofly prepare the method for tungsten-cobalt carbide nano-powder, belong to the nano powder preparation technical field based on the nitride conversion method.
Background technology
Carbide alloy is since coming out the thirties in 20th century, because of its high rigidity and high strength in industrial production always in occupation of critical positions, be described as " tooth of industry ", the extensive of its purposes almost relates to each department of national economy and the every field of modern technologies, at aspects such as metal cutting, oil drilling, drilling tool, grinding tool materials purposes widely arranged.
The WC-Co carbide alloy belongs to fragile material, and its hardness and intensity are a pair of paradox, improves alloy rigidity and will cause intensity to reduce, and causes hardness to descend otherwise improve alloy strength.Recent study shows: for the WC-Co carbide alloy of given composition, when the average grain size of WC phase in the alloy is reduced to 1 μ m when following, the hardness of carbide alloy and intensity can not only improve simultaneously, and the amplitude that improves will increase along with further reducing of WC grain size.Therefore, be the performance that improves alloy by the crystallite dimension that reduces WC from one of main direction of the carbide alloy research sixties in 20th century.The preparation carbide alloy normally adopts the method for ball milling that the WC powder is mixed with the Co powder earlier, then its moulding is carried out again the method for sintering.But traditional ball grinding method is difficult to guarantee that the ultrafine WC powder mixes with the even of Co powder, so be the feedstock production ultra-fine cemented carbide with the WC-Co nano composite powder mostly at present.For example: the superfine WC-Co cemented carbide of human WC-Co nano composite powders such as B.K.Kim preparation, its intensity level is 4400MPa, hardness reaches Hv=2050, and the intensity of the ordinary rigid alloy of identical component has only 2300MPa, hardness Hv=1650; The Nanodyne company of the U.S. produces the microbit that printed circuit board drilling is used with the WC-Co nano composite powder, and its wearability significantly improves, and wear rate reduces by 30～40% than common drill bit, and the life-span is about 2.9 times of common drill bit.Research also shows, is raw material with the WC-Co composite nano-powder, and the employing plasma spray technology of fusing, rapid condensation fast prepares wear-resistant coating, and coating still keeps the nanostructured characteristic, has significantly improved the abrasion property energy.
At present, the preparation method of WC-Co nano composite powder can be divided into two big classes, i.e. mechanical alloying method gentle one solid reaction method.Mechanical alloying method is lower owing to production efficiency, cost is high, easily bring reason such as other impurity into is difficult to carry out suitability for industrialized production, and therefore gas one solid reaction methods that adopt prepare the WC-Co nano composite powder more.So-called gas one solid reaction method is about to tungsten, cobalt/cobalt oxide powder (as CoWO
4, WO
3-CoO or CoWO
4-WO
3Deng), under the effect of gas (as feeding H
2, CO, CH
4-H
2, CO-CO
2Deng gas), form the WC-Co nano composite powder by gas one solid reaction.The advantage of the solid reaction method of gas one is: can fully contact between gas and the solid particle, reduction, the carbonisation of oxidate powder are carried out rapidly, therefore reaction only needs at a lower temperature, can finish in the short period, helps the formation and the maintenance of nanostructured.
Utilize gas one solid reaction principle, the Nanodyne company of the U.S. has successfully realized industrialization with " the spraying thermal transition method " of people such as B.H.Kear invention.This method is at first made mixed solution with the salt of tungsten and cobalt, prepares tungsten-cobalt composite oxide powder through technologies such as atomization dryings, adopts fluidization that oxide powder is reduced with hydrogen then, uses CO/H again
2Carry out carbonization, use CO/CO at last
2Carry out carbon elimination processing three step process and obtain the WC-Co composite nano-powder.The shortcoming of the method is the difficult control of employed fluid unit costliness and technology; Adopt high-purity gas and reaction time long, the production cost height.It is reported that WC-Co composite nano-powder that this Nanodyne company produced because price is too high, was forced to stop production in 2002.
Summary of the invention
The present invention is directed to above-mentioned existing in prior technology defective and problem, a kind of method for preparing the tungsten-cobalt carbide nano-powder based on the nitride conversion method is provided.
The preparation method of tungsten-cobalt carbide nano-powder provided by the invention comprises following concrete steps:
A) adopt citrate method or pack to prepare tungsten oxide-cobalt oxide powder, the process that described citrate legal system is equipped with tungsten oxide-cobalt oxide powder is: at first ammonium metatungstate, cobalt nitrate and citric acid are dissolved in respectively in the deionized water by the certain molar ratio example, are mixed with the settled solution of ammonium metatungstate, cobalt nitrate and citric acid; In 60～90 ℃ water-bath, carry out complex reaction then; Drying obtains tungsten oxide-cobalt oxide presoma, and tungsten oxide-cobalt oxide presoma is calcined under air atmosphere, promptly gets tungsten oxide-cobalt oxide powder; The process that described pack prepares tungsten oxide-cobalt oxide powder is: at first ammonium metatungstate and citric acid are dissolved in respectively in the deionized water by the certain molar ratio example, are mixed with the settled solution of ammonium metatungstate and citric acid; In 60～90 ℃ water-bath, carry out complex reaction then; Drying obtains the presoma of tungsten oxide; The presoma of tungsten oxide is calcined under air atmosphere, obtained the tungsten oxide powder; The tungsten oxide powder is mixed with cobalt nitrate ball milling in ethanol, and drying promptly gets tungsten oxide-cobalt oxide powder;
B) tungsten oxide-cobalt oxide powder that obtains is placed tube furnace, logical ammonia nitrogenize obtains tungsten nitride-cobalt nitride powder;
C) tungsten nitride that step b) is obtained-cobalt nitride powder mixes with carbon black, is that solvent, tungsten-carbide ball are ball-milling medium with ethanol, mixes on the roll-type ball mill, and the rotary evaporation drying obtains W
2The N/CoN/C mixed powder is with W
2The N/CoN/C mixed powder places in the graphite crucible, in carbon shirt-circuiting furnace, is lower than under the vacuum of 200Pa at air pressure or heat-treats under the inert atmosphere, promptly gets the tungsten-cobalt carbide nano-powder; Perhaps, tungsten nitride-cobalt nitride powder that step b) is obtained directly places tube furnace, and the mist of ventilating methane and hydrogen carries out carbonization then, promptly gets the tungsten-cobalt carbide nano-powder.
Ammonium metatungstate in the step a), cobalt nitrate and citric acid three's mol ratio is 1: (0.075～0.6): 1.
The time of the complex reaction in the step a) is preferably 0.5～10 hour.
Drying condition in the step a) was preferably: 100～250 ℃ of dryings 1～24 hour.
Calcination condition in the step a) was preferably: 500～800 ℃ of calcinings 1～12 hour.
Logical ammonia nitridation conditions in the step b) is preferably: ammonia flow is 1～5L/min, and temperature is 500～900 ℃, and heating rate is 0.5～8 ℃/min, and temperature retention time is 1～5 hour.
The mol ratio of the tungsten nitride in the step c)-cobalt nitride powder and carbon black is preferably 1: 1～and 1: 3.
The incorporation time on the roll-type ball mill in the step c) is preferably 5～48 hours.
Heat-treat condition in the step c) was preferably: 800～1300 ℃ of heat treatments 2～4 hours.
Carbonization condition in the step c) is preferably: the volume ratio of methane and hydrogen is 1: 5～1: 10, and the flow of mist is 20ml～200ml/min, and carburizing temperature is 700～1000 ℃, and carbonization time is 1～4 hour.
Compared with prior art, the present invention has following beneficial effect:
1) preparation technology is simple, practical, can be handling strong, accomplish scale production easily.
2) adopt the nitride conversion method, not only raw material is cheap and easy to get, and greatly reduces synthesis temperature, has reduced cost of material and energy consumption.
3) little (average grain diameter of the powder that carbonization obtains for solid phase is 90～150nm to Zhi Bei diameter of particle; The average grain diameter of the powder that obtains for gas carburization is 30～90nm), and even particle size distribution, and degree of aggregation is low; And have good sintering activity, can realize densified at 1200～1400 ℃ of hot pressed sinterings.
Description of drawings
Fig. 1 is the TEM figure of the WC-Co nano-powder that makes of embodiment 2.
Specific implementation method
The present invention is described in further detail and completely below in conjunction with embodiment, but do not limit content of the present invention.
Embodiment 1
Take by weighing 0.1mol ammonium metatungstate, 20mmol cobalt nitrate and 0.1mol citric acid, be dissolved in the 100ml deionized water, be mixed with the mixed solution of clarification; In 70 ℃ water-bath, carry out complex reaction 5 hours; Filter,, obtain tungsten oxide-cobalt oxide presoma 120 ℃ of dryings 12 hours; Tungsten oxide-cobalt oxide presoma was calcined 1 hour under 700 ℃ of air atmospheres, obtained tungsten oxide-cobalt oxide powder.
Tungsten oxide-cobalt oxide the powder that obtains is placed tube furnace, logical ammonia nitrogenize, ammonia flow is controlled at 3L/min, and temperature is 750 ℃, and heating rate is 2 ℃/min, is incubated 3 hours, obtains tungsten nitride-cobalt nitride powder.
12 gram tungsten nitride-cobalt nitride powders are mixed with the 0.62g carbon black, are that solvent, tungsten-cobalt carbide ball are that mill is situated between with ethanol, mix 24 hours on the roll-type ball mill, and the rotary evaporation drying obtains W
2The N/CoN/C mixed powder is with W
2The N/CoN/C mixed powder places in the graphite crucible, and in carbon shirt-circuiting furnace, air pressure is lower than under the vacuum of 200Pa, and reactant is heated to 1000 ℃ and be incubated 3 hours, promptly gets the WC-Co nano-powder, and average grain diameter is 120nm.
The prepared WC-Co nano-powder of present embodiment is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, illustrates that prepared WC-Co nano-powder has good sintering activity.
Embodiment 2
The difference of present embodiment and embodiment 1 only is: the tungsten nitride-cobalt nitride powder that obtains is directly placed tube furnace, the mist of ventilating methane and hydrogen carries out carbonization, the volume ratio of methane and hydrogen is 1: 8, the flow of mist is 200ml/min, carburizing temperature is 750 ℃, carbonization time is 2 hours, promptly gets the WC-Co nano-powder, and average grain diameter is 45nm.
All the other contents are all with identical described in the embodiment 1.
Fig. 1 is the TEM photo of prepared WC-Co nano-powder, and as seen from Figure 1: powder granule is tiny, and average grain diameter is 45nm.
The prepared WC-Co nano-powder of present embodiment is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, illustrates that prepared WC-Co nano-powder has good sintering activity.
Embodiment 3
The difference of present embodiment and embodiment 1 only is: the 12g tungsten nitride-cobalt nitride powder and the 0.62g carbon black that obtain are prepared burden, being loaded in the mixing tank, is that solvent, tungsten-carbide ball are that mill is situated between with ethanol, mixes 24 hours on the roll-type ball mill, the rotary evaporation drying obtains W again
2The N/CoN/C mixed powder is with W
2The N/CoN/C mixed powder places in the graphite crucible, in sintering furnace, feeds argon gas, and reactant is heated to 900 ℃ and be incubated 2 hours, promptly gets the WC-Co nano-powder, and average grain diameter is 120nm.
All the other contents are all with identical described in the embodiment 1.
The prepared WC-Co nano-powder of present embodiment is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, illustrates that prepared WC-Co nano-powder has good sintering activity.
Embodiment 4
The difference of present embodiment and embodiment 1 only is the preparation process of tungsten oxide-cobalt oxide powder: at first take by weighing 0.1mol ammonium metatungstate and 0.1mol citric acid, be dissolved in the 100ml deionized water, be mixed with the mixed solution of clarification; In 70 ℃ water-bath, carry out complex reaction 5 hours; Filter,, obtain the tungsten oxide presoma 120 ℃ of dryings 12 hours; The tungsten oxide presoma was calcined 1 hour under 700 ℃ of air atmospheres, obtained the tungsten oxide powder; The tungsten oxide powder that obtains was mixed 16 hours with 20mmol cobalt nitrate ball milling in ethanol, and drying obtains tungsten oxide-cobalt oxide powder.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 90nm; This WC-Co nano-powder is through 1100～1300 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 5
The difference of present embodiment and embodiment 1 only is: take by weighing 0.1mol ammonium metatungstate, 7.5mmol cobalt nitrate and 0.1mol citric acid, be dissolved in the 100ml deionized water.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 100nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 6
The difference of present embodiment and embodiment 1 only is: take by weighing 0.1mol ammonium metatungstate, 60mmol cobalt nitrate and 0.1mol citric acid, be dissolved in the 100ml deionized water.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 110nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 7
The difference of present embodiment and embodiment 1 only is: the time of carrying out complex reaction in 60 ℃ water-bath is 10 hours.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 100nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 8
The difference of present embodiment and embodiment 1 only is: the time of carrying out complex reaction in 90 ℃ water-bath is 0.5 hour.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 120nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 9
The difference of present embodiment and embodiment 1 only is: the condition that tungsten oxide-the cobalt oxide presoma is calcined under air atmosphere is: 500 ℃ of calcinings 12 hours, obtain tungsten oxide-cobalt oxide powder.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 90nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 10
The difference of present embodiment and embodiment 1 only is: the condition that tungsten oxide-the cobalt oxide presoma is calcined under air atmosphere is: 800 ℃ of calcinings 1 hour, obtain tungsten oxide-cobalt oxide powder.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 150nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 11
The difference of present embodiment and embodiment 1 only is: tungsten oxide-cobalt oxide powder carries out the ammonia nitrogenize in tube furnace condition is: ammonia flow is controlled at 1L/min, temperature is 500 ℃, heating rate is 0.5 ℃/min, is incubated 5 hours, obtains tungsten nitride-cobalt nitride powder.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 90nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 12
The difference of present embodiment and embodiment 1 only is: tungsten oxide-cobalt oxide powder carries out the ammonia nitrogenize in tube furnace condition is: ammonia flow is controlled at 5L/min, temperature is 900 ℃, heating rate is 8 ℃/min, is incubated 1 hour, obtains tungsten nitride-cobalt nitride powder.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 150nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 13
Present embodiment only is with the difference of embodiment 1: getting 12 gram tungsten nitride-cobalt nitride powders and mix with the 0.31g carbon black, is that solvent, tungsten-carbide ball are that mill is situated between with ethanol, mixes 48 hours on the roll-type ball mill, and the rotary evaporation drying obtains W
2The N/CoN/C mixed powder is with W
2The N/CoN/C mixed powder places in the graphite crucible, and in carbon shirt-circuiting furnace, air pressure is lower than under the condition of 200Pa, is heated to 1300 ℃ and be incubated 2 hours, obtains the WC-Co nano-powder.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 150nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
Embodiment 14
Present embodiment only is with the difference of embodiment 1: getting 10 gram tungsten nitride-cobalt nitride powders and mix with the 0.94g carbon black, is that solvent, tungsten-carbide ball are that mill is situated between with ethanol, mixes 5 hours on the roll-type ball mill, and the rotary evaporation drying obtains W
2The N/CoN/C mixed powder is with W
2The N/CoN/C mixed powder places in the graphite crucible, and in carbon shirt-circuiting furnace, air pressure is lower than under the condition of 200Pa, is heated to 800 ℃ and be incubated 4 hours, obtains the WC-Co nano-powder.
All the other contents are all with identical described in the embodiment 1.
Analyze after testing and learn: the average grain diameter of the WC-Co nano-powder that present embodiment makes is 90nm; This WC-Co nano-powder is through 1200～1400 ℃/1h, 25MPa hot pressed sintering, and relative density is higher than 97%, has good sintering activity.
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| CN105328202A (en) * | 2014-08-13 | 2016-02-17 | 南京理工大学 | Preparation method of cobalt nano material |
| CN105458291A (en) * | 2015-12-09 | 2016-04-06 | 株洲硬质合金集团有限公司 | Preparing method of composite tungsten cobalt oxide powder |
| CN105537606A (en) * | 2015-12-30 | 2016-05-04 | 钢铁研究总院 | Preparation method of ultra-fine tungsten carbide powder |
| CN107311175A (en) * | 2017-06-28 | 2017-11-03 | 中国航发北京航空材料研究院 | A kind of graphene is modified the preparation method of tungsten carbide self-lubricating abrasion-resistant additive |
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| CN105458291A (en) * | 2015-12-09 | 2016-04-06 | 株洲硬质合金集团有限公司 | Preparing method of composite tungsten cobalt oxide powder |
| CN105537606A (en) * | 2015-12-30 | 2016-05-04 | 钢铁研究总院 | Preparation method of ultra-fine tungsten carbide powder |
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| CN111617791A (en) * | 2019-02-27 | 2020-09-04 | 天津大学 | A Z-type heterostructure tungsten nitride-tungsten trioxide composite material and its preparation method and application |
| CN111617791B (en) * | 2019-02-27 | 2022-10-11 | 天津大学 | Z-type heterostructure tungsten nitride-tungsten trioxide composite material and preparation method and application thereof |
| CN109972018A (en) * | 2019-05-10 | 2019-07-05 | 赣州有色冶金研究所 | A kind of WC-Co-RE composite powder and the preparation method and application thereof |
| WO2021136059A1 (en) * | 2020-01-03 | 2021-07-08 | 广东工业大学 | Preparation system and method capable of controlling size of nano-conductor/semiconductor material |
| CN112758902A (en) * | 2021-01-06 | 2021-05-07 | 西南科技大学 | Optimized electronic configuration Co for efficient oxygen evolution reaction4Preparation method of N nanosheet |
| CN112758902B (en) * | 2021-01-06 | 2022-01-28 | 西南科技大学 | Optimized electronic configuration Co for efficient oxygen evolution reaction4Preparation method of N nanosheet |
| CN114535592A (en) * | 2022-02-25 | 2022-05-27 | 宇辰新能源材料科技无锡有限公司 | Large-apparent-density superfine cobalt powder and preparation method thereof |
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