CN108080647A - Nanometer/superfine WC-Co composite powder end and preparation method thereof - Google Patents
Nanometer/superfine WC-Co composite powder end and preparation method thereof Download PDFInfo
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- CN108080647A CN108080647A CN201711278176.3A CN201711278176A CN108080647A CN 108080647 A CN108080647 A CN 108080647A CN 201711278176 A CN201711278176 A CN 201711278176A CN 108080647 A CN108080647 A CN 108080647A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
Abstract
The invention discloses a kind of nanometer/ultrafine WC Co composite powders and preparation method thereof, and this method includes：(1) by tungstate solution and tungsten precipitant solution hybrid reaction, precipitated to obtain tungsten；(2) by cobalt salt solution and cobalt precipitant solution hybrid reaction, precipitated to obtain cobalt；(3) by tungsten precipitation and cobalt precipitation, carbon black mixing and ball milling and be compacted, to obtain composite powder；(4) composite powder is sent to vacuum drying oven and carries out step reduction and carbonization reaction in situ, to obtain nanometer/ultrafine WC Co composite powders.The characteristics of this method is made full use of in solwution method each element to be evenly distributed with each component the characteristics of atom or molecular distribution and in ball milling mixing and reaction can be promoted to carry out, using solid carbon as reducing agent and carburization agent, low temperature quickly prepares nanometer/ultrafine WC Co composite powders, it effectively prevents using gaseous reducing agent and gaseous carbon sources, technical process is green safe, realizes nanometer/ultrafine WC Co composite powders low cost, quick preparation capable of being industrialized.
Description
Technical field
The invention belongs to nanometer metal ceramic composite powder preparation field, specifically, the present invention relates to nanometers/ultra-fine
WC-Co composite powder end and preparation method thereof.
Background technology
WC-Co hard alloy be the refractory metal hard compounds WC using high rigidity as hard phase, the metal Co of high tenacity
For Binder Phase, there is good intensity and the more composite material of excellent toughness by what powder metallurgical technique was prepared,
The composite material is widely used in oil/gas drilling, geological prospecting, mining, roll, mold materials, cutting element, wear-resisting zero
The fields such as part are one of widest tool materials of current applications, to China's industry manufacture and the national economic development is promoted to play
Very important effect.With scientific and technological progress and the rapid development of economy, higher is proposed to the intensity and hardness of hard alloy
Requirement.But the hardness and strength of ordinary construction hard alloy are a pair of shifting paradox, develop while have
Double high hard alloy of high intensity and high tenacity become research hotspot in the past 20 years.Nanometer/Ultra-fine WC-Co Cemented Carbide is because of it
There is high intensity and high rigidity simultaneously, just widely paid close attention to and studied after developing certainly.And nanometer/ultra-fine
WC-Co composite powder end is the key that prepare high-performance carbide, nearest 20 years, emerges many new preparation methods.
Nanometer/superfine WC-Co composite powder end is prepared at present there are mainly two types of method, from top to bottom method (ball-milling method) and under
And top (solwution method) method.Ball-milling method is generally required using high energy ball mill, and Ball-milling Time is long, less efficient, size distribution
Lack of homogeneity.The shortcomings that overcome traditional ball grinding method, has then developed using metal or metal oxide as raw material, has passed through ball
The new method that in-situ reducing carbonization prepares nanometer/superfine WC-Co composite powder end is carried out after mill activation.Solwution method is that make full use of can
The characteristics of soluble is uniformly distributed in aqueous solution with molecule or atomic level passes through certain processing, such as precipitation, colloidal sol, spray
The methods of mist is dried, is quickly converted to solid precursor powder by each ion in solution, is then obtained by reduction and carbonization step
Obtain nanometer/superfine WC-Co composite powder end.The presoma of solwution method generally carries out reduction and carbonization under gas phase condition so that reduction
The technical process of carbonization is more difficult to control.
Therefore, the existing technology for preparing nanometer/superfine WC-Co composite powder end is further improved.
The content of the invention
It is contemplated that it solves at least some of the technical problems in related technologies.For this purpose, the present invention
One purpose is to propose a kind of nanometer/superfine WC-Co composite powder end and preparation method thereof.This method can effectively avoid using gas
Body reducing agent and gaseous carbon sources, simple for process, cost is relatively low to be suitable for industrialization production, and nanometer/superfine WC-Co of gained is compound
Powder diameter is tiny and even particle size distribution, comprehensive performance are preferable.
In one aspect of the invention, the present invention proposes a kind of method for preparing nanometer/superfine WC-Co composite powder end,
According to an embodiment of the invention, this method includes：
(1) by tungstate solution and tungsten precipitant solution hybrid reaction, precipitated to obtain tungsten；
(2) by cobalt salt solution and cobalt precipitant solution hybrid reaction, precipitated to obtain cobalt；
(3) by tungsten precipitation and cobalt precipitation, carbon black mixing and ball milling and be compacted, to obtain composite powder；
(4) composite powder is sent to vacuum drying oven and carries out step reduction and carbonization reaction in situ, to obtain nanometer/ultra-fine
WC-Co composite powder end.
The method at preparation nanometer/superfine WC-Co composite powder end according to embodiments of the present invention, is prepared respectively by solwution method
Tungsten precipitated product, cobalt precipitated product and carbon black are then carried out ball milling mixing by tungsten precipitated product and cobalt precipitated product, then through original position
Nanometer/superfine WC-Co composite powder end is prepared in the reaction of one step reduction and carbonization.This method make full use of in solwution method each element with
The spy that each component is evenly distributed and reaction can be promoted to carry out to a certain degree in the characteristics of atom or molecular distribution and ball milling mixing
Point, using solid carbon as reducing agent and carburization agent, low temperature quickly prepares nanometer/superfine WC-Co composite powder end, effectively prevents making
With gaseous reducing agent and gaseous carbon sources, technical process is green safe, realizes nanometer/superfine WC-Co composite powder end low cost, can
Industrialized quick preparation.And the nanometer of gained/superfine WC-Co composite powder end grain size is tiny, even particle size distribution, comprehensive performance
Preferably.
In addition, the method according to the above embodiment of the present invention for preparing nanometer/superfine WC-Co composite powder end can also have
Following additional technical characteristic：
In some embodiments of the invention, in step (1), the tungstates is in ammonium tungstate and sodium tungstate
At least one.Be conducive to improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (1), the tungsten precipitating reagent is selected from zinc chloride, zinc acetate, nitre
At least one of sour zinc and zinc sulfate.It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (1), the concentration of the tungstate solution is 0.2-1mol/L.
It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (1), the concentration of the tungsten precipitant solution is 0.2-1mol/
L.It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (1), the temperature of the hybrid reaction is 140-250 degrees Celsius.
It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (2), the cobalt salt is selected from cobalt chloride, cobalt acetate, cobalt nitrate
At least one of with cobaltous sulfate.It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (2), the cobalt precipitating reagent is selected from ammonium oxalate, sodium hydroxide
At least one of with sodium carbonate.It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (2), the concentration of the cobalt salt solution is 0.2-1mol/L.By
This, can further improve the grade at nanometer/superfine WC-Co composite powder end.
In some embodiments of the invention, in step (2), the concentration of the cobalt precipitant solution is 0.2-1mol/
L.It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (3), the tungsten precipitating reagent and the cobalt precipitating reagent, the charcoal
It is black to match somebody with somebody respectively as tungsten source, cobalt source and carbon source, and according to the theoretical value of W, Co, C in final nanometer/superfine WC-Co composite powder end
Than the quality of tungsten precipitating reagent, cobalt precipitating reagent and carbon black, wherein carbon black mass need to be 1.2-2.0 times of theoretical value.It as a result, can be into one
Step improves the grade at nanometer/superfine WC-Co composite powder end.
In some embodiments of the invention, in step (4), the vacuum degree of the vacuum drying oven is less than 0.2Pa, heating speed
Rate is 10-50 degree mins Celsius.It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In some embodiments of the invention, in step (4), the temperature of the step reduction and carbonization reaction is 800-
1000 degrees Celsius.It can further improve the grade at nanometer/superfine WC-Co composite powder end as a result,.
In another aspect of the invention, the present invention proposes a kind of nanometer/superfine WC-Co composite powder end.According to this hair
Bright embodiment, the composite powder are prepared using the method at above-mentioned preparation nanometer/superfine WC-Co composite powder end.By
This, the nanometer/superfine WC-Co composite powder end has many advantages, such as that tiny grain size, even particle size distribution and comprehensive performance are preferable.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
It obtains substantially or is recognized by the practice of the present invention.
Description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become in the description from combination accompanying drawings below to embodiment
Substantially and it is readily appreciated that, wherein：
Fig. 1 is the method flow signal at preparation nanometer/superfine WC-Co composite powder end according to an embodiment of the invention
Figure.
Specific embodiment
The embodiment of the present invention is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or similar label represents same or similar element or has the function of same or like element.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of method for preparing nanometer/superfine WC-Co composite powder end,
According to an embodiment of the invention, with reference to figure 1, this method includes：
S100：By tungstate solution and tungsten precipitant solution hybrid reaction
In the step, tungstate solution and tungsten precipitant solution hybrid reaction precipitate to obtain tungsten.Specifically, first
Tungstates is dissolved in deionized water, is configured to tungstate solution, tungsten precipitating reagent is dissolved in deionized water, it is molten to be configured to tungsten precipitating reagent
Liquid；Then tungstate solution is added in reaction kettle, stirred 5-10 minutes, then add in tungsten precipitant solution, it is molten to adjust reaction
The pH value of liquid is to alkalescence, and closed reactor makes tungstate solution and tungsten precipitant solution anti-under speed of agitator 300-600r/min
Should, 1-6h is kept the temperature, obtains tungsten precipitation.
According to one embodiment of present invention, the concrete type of tungstates is not particularly restricted, those skilled in the art
Member can make choice according to actual needs, a specific embodiment according to the present invention, and tungstates can be selected from ammonium tungstate
At least one of with sodium tungstate.Inventor has found that tungstates is a kind of good tungsten supply solubility salt, by subsequent
Precipitation process and a step reduction and carbonization in situ, can effectively form WC.
According to still a further embodiment, the concrete type of tungsten precipitating reagent is not particularly restricted, the skill of this field
Art personnel can make choice according to actual needs, a specific embodiment according to the present invention, tungsten precipitating reagent can be selected from
At least one of zinc chloride, zinc acetate, zinc nitrate and zinc sulfate.Inventor has found, selects zinc salt that can be carried out with tungstates
Reaction completely, rate of deposition is up to more than 95%, and zinc fusing point is low, can volatilize, will not remain during follow-up step reduction and carbonization
In composite powder, the impurity content for making composite powder is few.
According to still another embodiment of the invention, the concentration of tungstate solution is not particularly restricted, the technology of this field
Personnel can make choice according to actual needs, a specific embodiment according to the present invention, and the concentration of tungstate solution can be with
For 0.2-1mol/L.Inventor has found that tungstates excessive concentration, the grain size of the composite powder of gained is bigger than normal after reaction；And if tungsten
The concentration of hydrochlorate is too low, can cause that the tungstate ion content in reactor is few, and reaction efficiency is relatively low.
According to still another embodiment of the invention, the concentration of tungsten precipitant solution is not particularly restricted, the skill of this field
Art personnel can make choice according to actual needs, a specific embodiment according to the present invention, the concentration of tungsten precipitant solution
Can be 0.2-1mol/L.Inventor has found that the concentration of tungsten precipitant solution will generate shadow to the pattern and grain size of composite powder
It rings, excessive concentration, the presoma reuniting effect generated in precipitation reaction process is apparent, and granularity has the trend of roughening, and concentration
It is too low, then the reaction time will extend, reaction efficiency reduce.
According to still another embodiment of the invention, the temperature of hybrid reaction is not particularly restricted, those skilled in the art
Member can make choice according to actual needs, a specific embodiment according to the present invention, and the temperature of hybrid reaction can be
140-250 degrees Celsius.Inventor has found, if the temperature of hybrid reaction is too low, reacts that carry out speed slow and insufficient, and if mixed
The temperature of conjunction reaction is excessively high, then the granularity roughening of obtained composite powder is apparent.
S200：By cobalt salt solution and cobalt precipitant solution hybrid reaction
In the step, cobalt salt solution and cobalt precipitant solution hybrid reaction precipitate to obtain cobalt.Specifically, first will
Cobalt salt is dissolved in deionized water, is configured to cobalt salt solution, and cobalt precipitating reagent is dissolved in deionized water, is configured to cobalt precipitant solution；So
Cobalt salt solution is added in reaction kettle afterwards, after stirring 5-10 minutes, cobalt precipitant solution is added in, in speed of agitator 300-600r/
Cobalt salt solution is made to be reacted with cobalt precipitant solution under min, keeps the temperature 1-3h, obtains cobalt precipitation.
According to one embodiment of present invention, the concrete type of cobalt salt is not particularly restricted, those skilled in the art
It can make choice according to actual needs, a specific embodiment according to the present invention, cobalt salt can be selected from cobalt chloride, acetic acid
At least one of soluble cobalts such as cobalt, cobalt nitrate and cobaltous sulfate.Inventor's discovery, can be fine using soluble cobalt salt
Be dissolved in deionized water, carry out precipitation reaction abundant.
According to still a further embodiment, the concrete type of cobalt precipitating reagent is not particularly restricted, the skill of this field
Art personnel can make choice according to actual needs, a specific embodiment according to the present invention, cobalt precipitating reagent can be selected from
At least one of ammonium oxalate, sodium hydroxide and sodium carbonate.Inventor find, oxalate denominationby, hydroxide ion, carbonate from
The anion such as son can be very good to form cobalt sediment with cobalt cation, and the yield of gained precipitation is high, and reaction speed is fast, passes through
Reaction process is controlled, can be very good to realize the generation of nanometer cobalt precipitated product.
According to still another embodiment of the invention, the concentration of cobalt salt solution is not particularly restricted, those skilled in the art
Member can make choice according to actual needs, a specific embodiment according to the present invention, and the concentration of cobalt salt solution can be
0.2-1mol/L.Inventor has found that the concentration of cobalt salt solution directly determines the concentration of cobalt ions in solution, concentration of cobalt ions
Height, reaction is fast, but powder diameter has the trend grown up, and concentration of cobalt ions is low, and reaction is slow, and efficiency is low, thus synthesis is needed to examine
Consider cobalt salt solution concentration.Inventor has been surprisingly found that by many experiments, when the concentration of cobalt salt solution is 0.2-1mol/L
The quality at gained nanometer/superfine WC-Co composite powder end can be improved again by significantly improving reaction efficiency.
According to still another embodiment of the invention, the concentration of cobalt precipitant solution is not particularly restricted, the skill of this field
Art personnel can make choice according to actual needs, a specific embodiment according to the present invention, the concentration of cobalt precipitant solution
Can be 0.2-1mol/L.Inventor has found that cobalt precipitant solution excessive concentration will be such that precipitating reagent granularity is moderately roughened, and particle
Between easily reunite, cobalt precipitant solution concentration is too low will to make reaction speed excessively slow, efficiency reduce.
S300：By tungsten precipitation and cobalt precipitation, carbon black mixing and ball milling and it is compacted
In the step, by tungsten precipitation and cobalt precipitation, carbon black mixing and ball milling and it is compacted, to obtain composite powder.Specifically,
By tungsten precipitation and cobalt precipitation, carbon black by certain mass than being sent after mixing to the ball mill ball milling 3- that rotating speed is 200-500r/min
Then 20h is compacted, obtain presoma composite powder.
According to one embodiment of present invention, tungsten precipitating reagent and cobalt precipitating reagent, the mixing quality ratio of carbon black and from special
Limitation, those skilled in the art can make choice according to actual needs, and a specific embodiment according to the present invention, tungsten sinks
Shallow lake agent and cobalt precipitating reagent, carbon black are respectively as tungsten source, cobalt source and carbon source, and according in final nanometer/superfine WC-Co composite powder end
W, the quality of the theoretical value proportioning tungsten precipitating reagent of Co, C, cobalt precipitating reagent and carbon black, wherein carbon black mass need to be the 1.2- of theoretical value
2.0 again.Inventor has found that carbon black necessarily is greater than theoretical carbon value, can mainly be consumed in presoma composite powder decomposable process
Part carbon, and the amount of carbon black can not be too high, too high amounts of carbon black will cause to influence there are substantial amounts of free carbon in composite powder
The grade of composite powder.
S400：Composite powder is sent to vacuum drying oven and carries out step reduction and carbonization reaction in situ
In the step, composite powder is sent to vacuum drying oven and carries out step reduction and carbonization reaction in situ, to obtain nanometer/super
Thin WC-Co composite powder end.Inventor has found that completing two reactions of reduction reaction and carburizing reagent in a step can be effective
Shorten technological process, improve production efficiency, and avoid the oxidation of nano-tungsten powder, improve the grade of composite powder.
According to one embodiment of present invention, the vacuum degree in vacuum drying oven and heating rate are not particularly restricted, ability
The technical staff in domain can make choice according to actual needs, a specific embodiment according to the present invention, the vacuum of vacuum drying oven
Degree can be less than 0.2Pa, and heating rate can be 10-50 degree mins Celsius.Inventor has found that vacuum degree is excessively high, and equipment is wanted
It asks high, and then causes production cost high, be unfavorable for promoting and applying on a large scale, and vacuum degree is to nanometer/superfine WC-Co composite powder
The grade at end is promoted limited.Heating rate is too low, can extend sintering time, and cost increases；And heating rate is excessively high, then pair sets
Standby requirement is high, and maintenance cost is high.
According to still a further embodiment, the temperature of step reduction and carbonization reaction is not particularly restricted, this field
Technical staff can make choice according to actual needs, a specific embodiment according to the present invention, a step reduction and carbonization is anti-
The temperature answered can be 800-1000 degrees Celsius.Inventor has found that, if the temperature of step reduction and carbonization reaction is too low, gained is compound
The dephasigns such as scarce carbon phase in powder content is high, influences the grade of composite powder, and if the temperature of step reduction and carbonization reaction is excessively high
The grain size for making composite powder is quickly increased, it is more difficult to obtain nanometer/superfine WC-Co composite powder end.
The method at preparation nanometer/superfine WC-Co composite powder end according to embodiments of the present invention, is prepared respectively by solwution method
Tungsten precipitated product, cobalt precipitated product and carbon black are then carried out ball milling mixing by tungsten precipitated product and cobalt precipitated product, then through original position
Nanometer/superfine WC-Co composite powder end is prepared in the reaction of one step reduction and carbonization.This method make full use of in solwution method each element with
The spy that each component is evenly distributed and reaction can be promoted to carry out to a certain degree in the characteristics of atom or molecular distribution and ball milling mixing
Point, using solid carbon as reducing agent and carburization agent, low temperature quickly prepares nanometer/superfine WC-Co composite powder end, effectively prevents making
With gaseous reducing agent and gaseous carbon sources, technical process is green safe, realizes nanometer/superfine WC-Co composite powder end low cost, can
Industrialized quick preparation.And the nanometer of gained/superfine WC-Co composite powder end grain size is tiny, even particle size distribution, comprehensive performance
Preferably.
In another aspect of the invention, the present invention proposes a kind of nanometer/superfine WC-Co composite powder end.According to this hair
Bright embodiment, the composite powder are prepared using the method at above-mentioned preparation nanometer/superfine WC-Co composite powder end.By
This, the nanometer/superfine WC-Co composite powder end has many advantages, such as that tiny grain size, even particle size distribution and comprehensive performance are preferable.It needs
Illustrate, be equally applicable to for the described feature and advantage of method at above-mentioned preparation nanometer/superfine WC-Co composite powder end
The nanometer/superfine WC-Co composite powder end, details are not described herein again.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
The sodium tungstate of 329.86g is dissolved in deionized water, is configured to concentration as 1mol/L-1Sodium tungstate solution, 136.3g
Zinc chloride is dissolved in deionized water, is configured to concentration as 1mol/L-1Liquor zinci chloridi, then, by liquor zinci chloridi add in react
In kettle, after stirring 5-10min, sodium tungstate solution is added in after adjusting pH value to alkalescence, subsequent closed reactor makes to occur in kettle anti-
Should, generate ZnWO4Precipitation, process conditions are 140 DEG C, speed of agitator 600r/min, soaking time 1h of temperature.
Then the cobalt chloride of 237.93g is dissolved in deionized water, is configured to concentration as 1mol/L-1Cobalt chloride solution,
124.1g ammonium oxalate is dissolved in deionized water, is configured to concentration as 1mol/L-1Ammonium oxalate solution.Then cobalt chloride solution is added in
In reactor, addition ammonium oxalate is reacted after stirring 5-10min, generates cobalt oxalate precipitation product, and process conditions are room temperature item
Under part, speed of agitator 600r/min, soaking time 1h.
Then by ZnWO4Precipitation, cobalt oxalate precipitation and carbon black carry out ball milling according to WC-6wt.%Co stoichiometric ratios and mix
It closes, rotational speed of ball-mill 200r/min, Ball-milling Time 20h, is compacted gained composite powder after ball milling, be put into vacuum drying oven and carry out
Step reduction and carbonization reaction in situ prepares nanometer/superfine WC-Co composite powder end, and vacuum degree is less than 0.2Pa, heating speed in vacuum drying oven
Rate is 50 DEG C/min, and temperature is 800 DEG C, soaking time 4h, and nanometer WC-6wt.%Co composite powders are made.
Embodiment 2
The ammonium tungstate of 253.55g is dissolved in deionized water, is configured to concentration as 0.2mol/L-1Ammonium tungstate solution,
183.48g zinc acetates are dissolved in deionized water, are configured to concentration as 0.2mol/L-1Zinc acetate solution, then, by zinc acetate solution
It adds in reaction kettle, after stirring 5-10min, adds in ammonium tungstate solution after adjusting pH value to alkalescence, subsequent closed reactor makes kettle
It inside reacts, generates ZnWO4Precipitation, process conditions are 250 DEG C, speed of agitator 300r/min, soaking time 6h of temperature.
Then the cobaltous sulfate of 281.15g is dissolved in deionized water, is configured to concentration as 0.2mol/L-1Cobalt sulfate solution,
105.99g sodium carbonate is dissolved in deionized water, is configured to concentration as 0.2mol/L-1Sodium carbonate liquor.Then by cobalt sulfate solution
It adds in reactor, addition sodium carbonate liquor is reacted after stirring 5-10min, generates cobalt carbonate precipitated product, process conditions
For under room temperature, speed of agitator 300r/min, soaking time 3h.
Then by ZnWO4Precipitation, cobalt carbonate precipitation and carbon black carry out ball milling according to WC-10wt.%Co stoichiometric ratios and mix
It closes, rotational speed of ball-mill 500r/min, Ball-milling Time 3h, is compacted gained composite powder after ball milling, be put into vacuum drying oven and carry out
Step reduction and carbonization reaction in situ prepares nanometer/superfine WC-Co composite powder end, and vacuum degree is less than 0.2Pa, heating speed in vacuum drying oven
Rate is 10 DEG C/min, and temperature is 1000 DEG C, soaking time 1h, and nanometer WC-10wt.%Co composite powders are made.
Embodiment 3
The sodium tungstate of 329.86g is dissolved in deionized water, is configured to concentration as 0.5mol/L-1Sodium tungstate solution,
297.49g zinc nitrates are dissolved in deionized water, are configured to concentration as 0.5mol/L-1Zinc nitrate solution, then, by zinc nitrate solution
It adds in reaction kettle, after stirring 5-10min, adds in sodium tungstate solution after adjusting pH value to alkalescence, subsequent closed reactor makes kettle
It inside reacts, generates ZnWO4Precipitation, process conditions are 180 DEG C, speed of agitator 400r/min, soaking time 3h of temperature.
Then the cobalt nitrate of 291.05g is dissolved in deionized water, is configured to concentration as 0.5mol/L-1Cobalt nitrate solution,
80g sodium hydroxides are dissolved in deionized water, are configured to concentration as 0.5mol/L-1Sodium hydroxide solution.Then by cobalt nitrate solution
It adds in reactor, addition sodium hydroxide solution is reacted after stirring 5-10min, generates cobalt hydroxide precipitated product, technique
Condition is speed of agitator 450r/min, soaking time 2h under room temperature.
Then by ZnWO4Precipitation, cobalt hydroxide precipitation and carbon black carry out ball milling according to WC-15wt.%Co stoichiometric ratios
Gained composite powder is compacted after ball milling by mixing, rotational speed of ball-mill 400r/min, Ball-milling Time 10h, be put into vacuum drying oven into
Row step reduction and carbonization reaction in situ prepares nanometer/superfine WC-Co composite powder end, and vacuum degree is less than 0.2Pa, heating in vacuum drying oven
Rate is 20 DEG C/min, and temperature is 900 DEG C, soaking time 2h, and nanometer WC-15wt.%Co composite powders are made.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment of the present invention or example.In the present specification, schematic expression of the above terms is not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It is combined in an appropriate manner in one or more embodiments or example.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the different embodiments described in this specification or example and different embodiments or exemplary feature
It closes and combines.
Although the embodiment of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
- A kind of 1. method for preparing nanometer/superfine WC-Co composite powder end, which is characterized in that including：(1) by tungstate solution and tungsten precipitant solution hybrid reaction, precipitated to obtain tungsten；(2) by cobalt salt solution and cobalt precipitant solution hybrid reaction, precipitated to obtain cobalt；(3) by tungsten precipitation and cobalt precipitation, carbon black mixing and ball milling and be compacted, to obtain composite powder；(4) composite powder is sent to vacuum drying oven and carries out step reduction and carbonization reaction in situ, so as to obtain nanometer/ultrafine WC- Co composite powders.
- 2. according to the method described in claim 1, it is characterized in that, in step (1), the tungstates be selected from ammonium tungstate and At least one of sodium tungstate；Optional, the tungsten precipitating reagent is selected from least one of zinc chloride, zinc acetate, zinc nitrate and zinc sulfate.
- 3. according to the method described in claim 2, it is characterized in that, in step (1), the concentration of the tungstate solution is 0.2-1mol/L；Optional, the concentration of the tungsten precipitant solution is 0.2-1mol/L.
- 4. according to the method described in claim 3, it is characterized in that, in step (1), the temperature of the hybrid reaction is 140- 250 degrees Celsius.
- 5. according to the method described in claim 1, it is characterized in that, in step (2), the cobalt salt is selected from cobalt chloride, vinegar At least one of sour cobalt, cobalt nitrate and cobaltous sulfate；Optional, the cobalt precipitating reagent is selected from least one of ammonium oxalate, sodium hydroxide and sodium carbonate.
- 6. according to the method described in claim 5, it is characterized in that, in step (2), the concentration of the cobalt salt solution is 0.2- 1mol/L；Optional, the concentration of the cobalt precipitant solution is 0.2-1mol/L.
- 7. according to the method described in claim 1, it is characterized in that, in step (3), the tungsten precipitating reagent is precipitated with the cobalt Agent, the carbon black are respectively as tungsten source, cobalt source and carbon source, and according to W, Co, C in final nanometer/superfine WC-Co composite powder end The quality of theoretical value proportioning tungsten precipitating reagent, cobalt precipitating reagent and carbon black, wherein carbon black mass need to be 1.2-2.0 times of theoretical value.
- 8. according to the method described in claim 1, it is characterized in that, in step (4), the vacuum degree of the vacuum drying oven is less than 0.2Pa, heating rate are 10-50 degree mins Celsius.
- 9. according to the method described in claim 8, it is characterized in that, in step (4), the temperature of the step reduction and carbonization reaction It spends for 800-1000 degrees Celsius.
- 10. a kind of nanometer/superfine WC-Co composite powder end, which is characterized in that the composite powder is appointed using in claim 1-9 What the method at the preparation nanometer/superfine WC-Co composite powder end of one was prepared.
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| CN112760540A (en) * | 2020-12-04 | 2021-05-07 | 崇义章源钨业股份有限公司 | Composite WC-CrC-CoCr thermal spraying powder and preparation method and application thereof |
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