CN104087790B - For the adding method of grain growth inhibitor prepared by ultra-fine cemented carbide - Google Patents
For the adding method of grain growth inhibitor prepared by ultra-fine cemented carbide Download PDFInfo
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Abstract
The present invention relates to the adding methods of the grain growth inhibitor prepared for ultra-fine cemented carbide.Specifically, a kind of adding method of the grain growth inhibitor prepared for ultra-fine cemented carbide is disclosed, including：Design the ingredient of Co based alloy powder；Co based alloy powder containing grain growth inhibitor element is prepared using coprecipitation；And corresponding tungsten carbide powder and Co based alloy powder are weighed according to formula rate, wet grinding media is added in after mixing and carries out wet-milling so that the particle surface of the equably cladded wolfram carbide powder of the Co based alloys containing grain growth inhibitor element.It to be in addition, the invention also discloses a kind of crystallite dimensions below sub-micron（Comprising but be not limited only to nano-scale range）Ultra-fine cemented carbide.The carburizing temperature of the ultra-fine cemented carbide is from the limitation of Co, and WC carbonizations are completely so that crystal grain is more complete, and defect is few.
Description
Technical field
The present invention relates to the production technical field of hard alloy, and more particularly to being prepared for ultra-fine cemented carbide
The adding method of grain growth inhibitor.
Background technology
Hard alloy is that a kind of hard compounds by refractory metal and binding metal are prepared by powder metallurgical technique
Alloy material, outstanding feature is that hardness is high, intensity is high, wearability is good and has certain toughness, is widely used as cutter material,
Mold materials, wear-resistant material, mine tool materials etc..However, the mechanical property of conventional rigid alloy is difficult to synchronous raising, especially
It is hardness and toughness, it is difficult to meet increasing production requirement.
The study found that when the crystallite dimension of hard alloy enters ultra-fine scope, the hardness and toughness of hard alloy are presented
Double high trend namely adjoint hardness improve, and toughness also has a degree of increase.Therefore, ultra-fine or nanoscale hard alloy
Research have become the emphasis direction of following development high-performance carbide material.
Super-fine cobalt powder is the important source material for preparing ultra-fine cemented carbide, and quality has for the quality of ultra-fine cemented carbide
Significant impact.For preparing ultra-fine cemented carbide, have to the purity of cobalt powder, pattern, granularity and its distribution etc. extremely tight
The requirement of lattice.Purity is high, oxygen content is low, impurity is few, granularity is small and the cobalt powder of narrowly distributing is just suitable for producing ultra-fine cemented carbide.
For preparing ultra-fine cemented carbide, in addition to cobalt powder and tungsten carbide powder, as inhibiting the grain growth grown up of crystal grain
Inhibitor is also essential.Common grain growth inhibitor has：Chromium（Cr）, vanadium（V）, tantalum（Ta）, niobium（Nb）Wait crystal grain
The carbide of growth inhibitor element.Research shows that the mechanism of action of these grain growth inhibitor element carbides is mainly
It is solid-solubilized in binding metal Co, limits tungsten carbide when in the liquid-phase sintering stage（WC）Crystallization of the dissolution and precipitation mechanism in Co, so as to
The crystal grain of WC is prevented to grow up.
At present, there are mainly three types of the methods that grain growth inhibitor is added during ultra-fine cemented carbide is prepared：
（1）Using superfine WC power, ultra-fine binding metal powder（Co powder, Ni powder, Fe powder etc.）And grain growth inhibitor etc.
Raw material carries out ball milling mixing, drying and granulating or spraying granulation, is then pressed into type, and finally sintering obtains ultra-fine cemented carbide.
This is the method that generally uses at present, but distinct issues are this small amount of grain growth inhibitors in the side that the ball milling stage adds
Formula, the dispersion effect of powder is unsatisfactory, the heterogeneous structures structures such as thick, the cobalt pond of folder is easy to cause, so as to product
It can be unfavorable.
（2）Ball milling mixing, drying and granulating or spraying system are carried out using superfine WC-Co composite powder and grain growth inhibitor
Grain, is then pressed into type, and finally sintering obtains ultra-fine cemented carbide.This method is that the preparation to grow up in recent ten years surpasses
The novel method of thin hard alloy, the advantage is that and employ WC-Co composite powder, but the addition manner of grain growth inhibitor
Do not change, so as to fail fundamentally to solve the problems, such as that it is scattered that composite powder is difficult to.
（3）Ball milling, drying and granulating or spraying system are carried out using the composite powder of the superfine WC-Co containing grain growth inhibitor
Grain, is then pressed into type, and finally sintering obtains ultra-fine cemented carbide.When the advantages of this method, is to prepare WC-Co composite powder
With regard to introducing the soluble-salt of grain growth inhibitor, the composite powder of the WC-Co containing grain growth inhibitor is obtained.However, due to
The presence of cobalt limits subsequent carburizing temperature.On the one hand, if carburizing temperature is excessively high, composite powder particle becomes very hard, then ball
It is difficult to crush during mill, it is high so as to cause the porosity of product；And on the other hand, if carburizing temperature is low, carbonization is incomplete, from
And it is imperfect that tungsten carbide is caused to crystallize, defect is more.
In short, ultra-fine cemented carbide, grain growth suppression are produced using above-mentioned three kinds of grain growth inhibitor adding methods
The dispersion effect of preparation is unsatisfactory, it is difficult to it is uniformly dispersed, and then the grain size for being easy to cause hard alloy is uneven, so as to
It is unfavorable for preparing nano level superfine hard alloy.
Therefore, it is necessary to a kind of methods of improved addition hard alloy grain growth inhibitor.
The content of the invention
Aspects and advantages of the present invention will be illustrated partly or can be clear according to the explanation or can in the following description
Understood by implementing the present invention.
According to the present invention, it will just inhibit the grain growths such as WC grain grows up Cr, V at the preparatory phase of cobalt powder and inhibit
Agent element solid solution into cobalt powder to obtain Co-based alloy powder.By this method, inhibit instead of individual Co powder and grain growth
Both raw materials of agent powder are difficult to point so as to avoid grain growth inhibitor in the ball milling stage addition of CEMENTED CARBIDE PRODUCTION
Dissipate uniform deficiency.
Roughly, the present invention provides a kind of adding method of the grain growth inhibitor for ultra-fine cemented carbide,
Suitable for will be containing grain growth inhibitor element Co based alloys powder be applied to the preparation of hard alloy, particularly ultra-fine hard closes
The preparation of gold.This method comprises the following steps：Design the ingredient of Co based alloy powder；Preparation contains grain growth inhibitor element
Co based alloy powder；And wet-milling carbide alloy mixture.
In one embodiment, the method according to the invention is included according to the performance requirement of hard alloy, design it is different into
The Co based alloy powder divided, such as：It is 2%~20% containing Cr, containing the Co based alloy powder that V is 2%~10%.
In one embodiment, the method according to the invention is further included is pressed down using coprecipitation to prepare containing grain growth
The Co based alloy powder of preparation element.According to the present invention, the Co containing grain growth inhibitor element is prepared using coprecipitation
The process of based alloy powder, specifically comprises the following steps：
（1）By soluble cobalt and one or more grain growth inhibitor members that can inhibit hard alloy crystal grain and grow up
Plain soluble salt, which is dissolved in distilled water, is configured to 0.5-2.0mol/L mixing salt solutions；
（2）Precipitating reagent is added in distilled water and is configured to 0.8-2.5mol/L precipitant solutions；
（3）Mixing salt solution and precipitant solution are added in reaction vessel and react to generate cobalt-based complex salt simultaneously
Them is made to precipitate；
（4）Separation of solid and liquid is carried out to the sediment comprising cobalt-based complex salt and is cleaned to cobalt-based complex salt；And
（5）Cobalt-based complex salt is calcined, the micron order containing grain growth inhibitor element is obtained after decomposition（Contain
Nanoscale）Cobalt-based alloy powder.
In one embodiment, it is added drop-wise in mixing salt solution and precipitant solution in reaction vessel and carries out reaction 0.5-2
Hour after, carry out ageing 1-5 it is small when.
In one embodiment, separation of solid and liquid is carried out by the way of separation or centrifugation is filtered.
In one embodiment, put it into before being calcined to cobalt-based complex salt in drying box and place is dried
Reason.
In one embodiment, in cleaning process, first the sediment comprising cobalt-based complex salt is carried out using distilled water
It is cleaned multiple times and is then cleaned using absolute ethyl alcohol, to remove the impurity in sediment.
In one embodiment, when mixed solution is added in reaction vessel, at the uniform velocity stirred, and reaction temperature
25 DEG C -80 DEG C of scope is heated to using the electric heating tube of such as copper material.Meanwhile control the pH value of solution in 2-8, such as
By way of adding ammonium hydroxide.
In an alternative embodiment, mixing salt solution and precipitant solution reacted in reaction vessel 0.5-2 it is small when it
Afterwards, obtain including the sediment of cobalt-based complex salt when aged 1-5 is small.Then, it is therein to remove first to sediment undergoes washing
Impurity afterwards by the modes solid-liquid separation such as suction filtration sediment, finally obtains cobalt-based complex salt.Similarly, cleaning process
It is middle that first sediment is cleaned multiple times using distilled water and is then cleaned using absolute ethyl alcohol.
In one embodiment, cobalt-based complex salt is calcined in high temperature furnace under anti-oxidation atmosphere, temperature range is
350-500 DEG C, when soaking time is 2-5 small, the cobalt-base alloys containing grain growth inhibitor element is obtained through decomposing postcooling
Powder.
According to one embodiment of present invention, soluble cobalt includes but are not limited to cobalt chloride, cobalt nitrate, cobalt acetate.
According to one embodiment of present invention, the grain growth inhibitor element bag that hard alloy crystal grain is grown up can be inhibited
It includes but is not limited only to chromium, vanadium, tantalum, niobium.
According to one embodiment of present invention, precipitating reagent includes but are not limited to oxalic acid, oxalates, carbonate.
According to one embodiment of present invention, anti-oxidation atmosphere includes but are not limited to vacuum, hydrogen atmosphere, argon gas gas
Atmosphere.
In one embodiment, the method according to the invention, which is further included, weighs corresponding WC powder according to formula rate, contains
The Co based alloy powder of grain growth inhibitor element（Pure Co powder is also needed if necessary）, the raw material powder prepared is then poured into ball mill
In, ratio of grinding media to material is 3~6：1, wet grinding media is added in by 300~500ml/kg, when ball milling 40~100 is small.Wherein, wet grinding media bag
It includes but is not limited only to water, alcohol or hexane.
According to another embodiment of the present invention, a kind of ultra-fine cemented carbide is additionally provided, uses side according to the present invention
Method is made.Wherein, scope of the crystallite dimension of the ultra-fine cemented carbide between 1 nanometer to 1000 nanometers.
For the above method embodiment variations and modifications within the scope and spirit of this invention, and can herein into
One step describes.
Description of the drawings
The present invention is specifically described below with reference to attached drawing and with reference to example, advantages of the present invention and realization method will
More obvious, wherein content is only used for explanation of the present invention shown in attached drawing, without forming to the present invention in all senses
On limitation, attached drawing is only illustrative, not strictly drawn to scale.In the accompanying drawings：
Fig. 1 shows the adding method of the grain growth inhibitor according to the present invention prepared for ultra-fine cemented carbide；
Fig. 2 is the flow chart according to the Co based alloy powder being used to prepare containing grain growth inhibitor element of the present invention；
And
Fig. 3 is the XRD spectrum according to the Co-Cr-V alloyed powders prepared by the example 1 of the present invention.
Specific embodiment
Now will be in detail with reference to the embodiment of the present invention, one or more of examples are shown in the drawings.Each example
It is to be provided in a manner of illustrating the present invention, and is not intended to limit the present invention.In fact, it will be apparent to those skilled in the art that
It without departing from the scope or spirit of the invention, can various modification can be adapted in the present invention and modification.For example, be shown as or
The feature for being described as the part of one embodiment can be used with another embodiment, to generate another embodiment.Therefore,
It is desirable that, the present invention includes these modifications and variations being included into the range of appended claims and its equivalent program.
As those skilled in the art, it should be apparent that, grain growth inhibitor element（Such as Cr, V）It is mainly logical
The crystallization of the dissolution and precipitation mechanism for being solid-solubilized in and inhibiting WC grain in binding metal Co is crossed, so as to which WC grain be prevented to grow up.The present invention is by adopting
Be raw material with the Co based alloy powder containing the grain growth inhibitors element such as Cr, V, substitute grain growth inhibitor and part or
Whole Co powder are come for producing ultra-fine cemented carbide.The grain growth inhibitors elements such as Cr, V in this Co based alloys powder are
It is fully solid-solubilized in Co matrixes, as a kind of single-phase binding metal alloyed powder, can be good at solving grain growth suppression
Preparation disperses non-uniform problem in mechanical milling process, so as to obtain the uniform ultra-fine cemented carbide of ingredient.Moreover, according to this hair
The ultra-fine cemented carbide of bright preparation, due to not using WC-Co composite powder, therefore carburizing temperature is from the limitation of Co, so as to WC carbon
Change completely, crystal grain is more complete, and defect is few.
Specifically, the present invention provides a kind of adding methods for ultra-fine cemented carbide grain growth inhibitor.Such as Fig. 1
Shown in, the method comprising the steps of 10：The composition design of Co based alloy powder；Step 20：Contain grain growth inhibitor element
The preparation of Co based alloy powder；And step 30：The wet-milling of carbide alloy mixture so that contain grain growth inhibitor element
Co based alloys are uniformly coated on WC particle surface.
In step 10, according to the performance requirement of hard alloy, the Co based alloy powder of heterogeneity is designed, such as：Containing Cr
For the Co based alloy powder that 2%~20%, V is 2%~10%.In one embodiment, YG8 trades mark hard alloy is prepared namely containing Co
Amount is about 8%（Mass fraction）, remaining is WC.Through design, containing Cr about 20% in Co based alloy meal components, containing V about 10%,
That is Co0.7-Cr0.2-V0.1 alloyed powders.In another embodiment, it is about to prepare YG6 trades mark hard alloy namely amount containing Co
6%（Mass fraction）, remaining is WC.Through design, contain Cr about 10% in Co based alloy meal components, containing V about 15%, i.e. Co0.75-
Cr0.1-V0.15 alloyed powders.
Then, in step 20, the Co based alloy powder containing grain growth inhibitor element is prepared.Specifically, using bag
It includes but is not limited to coprecipitation to prepare Co based alloy powder.Hereinafter, will be described in preparing containing crystalline substance using coprecipitation
The process of the Co based alloy powder of grain growth inhibitor element.
Finally, in step 30, corresponding WC powder, the Co containing grain growth inhibitor element are weighed according to formula rate
Based alloy powder also needs pure Co powder if necessary.Then, the raw material powder prepared is poured into ball mill, ratio of grinding media to material is 3~6：1, it presses
300~500ml/kg adds in wet grinding media, when ball milling 40~100 is small.Pass through wet-milling so that contain grain growth inhibitor element
Co based alloys be uniformly coated on WC particle surface.Here, ratio of grinding media to material refers to the matter of abrasive body and raw material powder in ball mill
The ratio between amount and wet grinding media include but not limited to water, alcohol, hexane.For example, in one embodiment, ratio of grinding media to material 4：1,
Hexane is added in by 400ml/kg, when ball milling 90 is small.In another embodiment, ratio of grinding media to material 3：1, alcohol is added in by 300ml/kg,
When ball milling 98 is small.
The Co based alloy powder containing grain growth inhibitor element is prepared using coprecipitation next, will be described in detail
Process.By and large, under ionic condition, the grain growth inhibitors element such as precipitating reagent ion and Co ions and Cr, V is utilized
Ionic reaction generates the sediment of complex salt.Then, complex salt is decomposed by calcining, finally obtains the grain growths such as Cr, V suppression
The Co based alloy powder of preparation element solid solution wherein.
Fig. 2 shows the process according to an embodiment of the invention for being used to prepare cobalt-based alloy powder.First, by soluble cobalt
Salt（For example, cobalt chloride, cobalt nitrate or cobalt acetate etc.）It is dissolved in distilled water and being configured to grain growth inhibitor element soluble salt
0.5-2.0mol/L, the preferably mixing salt solution 100 of 0.65-1.5mol/L and more preferably 1.0mol/L.Here, crystal grain
Growth inhibitor element includes but are not limited to chromium, vanadium, tantalum, niobium etc., and wherein grain growth inhibitor element soluble salt includes example
Such as chromium chloride, chromic nitrate, ammonium metavanadate or combination thereof, growing up for hard alloy crystal grain can be inhibited.Then, Huo Zhe
While step 100, precipitating reagent is added in distilled water to the precipitant solution 200 for being configured to 0.8-2.5mol/L.For example, by grass
Acid or oxalates, which are added in distilled water, is made precipitant solution.In the process, precipitating reagent and cobalt ions and the life of other crystal grain
Long inhibitor element ion reacts to generate cobalt-based complex salt and them is made to precipitate.Wherein, precipitating reagent includes but not limited to
Oxalic acid, oxalates, carbonate or combination thereof.
The obtained mixing salt solution of step 100 and the obtained precipitant solution of step 200 are added to reaction vessel
（For example, 100L single-glass reaction kettles, model BK-100, use temperature range -80~280 DEG C）In reacted to generate Co
Base complex salt 300.In the process, at the uniform velocity stirred in reaction vessel, range of reaction temperature is for example with copper material
Electric heating tube is heated to 25 DEG C -80 DEG C.Meanwhile control pH value in 2-8 for example, by adding the modes such as ammonium hydroxide, keep the temperature 0.5-2
Hour（h）.
Preferably, ageing is performed after reaction 300（For example, when 1-5 is small）400 is heavy comprising cobalt-based complex salt to obtain
Starch namely precipitation completely after, by the precipitation just generated placed together with mother liquor a period of time.Then, sediment is carried out
Separation 500 is filtered, such as the pressure in bottle,suction is reduced using aspiration pump, achievees the purpose that separation of solid and liquid.Certainly, can also adopt
With other separate modes, for example, centrifuging.Then cleaning 600 is carried out to sediment, to remove impurity wherein included simultaneously
Obtain cobalt-based complex salt.For example, sediment is cleaned multiple times first with distilled water, then carried out repeatedly with absolute ethyl alcohol again
Cleaning.It is noted that in another alternative embodiment, use is then that separation of solid and liquid is first carried out to sediment, then right again
Sediment is cleaned.
Preferably, 700 are dried to Co base complex salts.Specifically, by Co base complex salts insert in drying box in 50 DEG C-
When heat preservation 8-12 is small at a temperature of 110 DEG C and preferably 80 DEG C and when preferably 10 is small.It is after dry 700, Co bases is compound
Salt is placed in high temperature furnace under the anti-oxidation atmosphere of vacuum or hydrogen or argon gas etc. calcining 800 so that the compound salinity of cobalt-based
Solution.In the process, temperature remains 350 DEG C -500 DEG C, and the time continues 2-5h.Finally, obtained through cooling containing grain growth
The Co based alloys powder 900 of inhibitor element.
As used herein, term " sediment " includes Co bases complex salt obtained by the reaction and indwelling in impurity therein.
Next, micron order according to the present invention is described by specific example（Containing nanoscale）The preparation of cobalt-based alloy powder.
Example 1
It is calculated according to designed composition proportion and weighs corresponding cobalt chloride, chromium chloride, vanadium chloride, then dissolved in simultaneously
The mixing salt solution of 0.65 mol/L is configured in distilled water.It weighs suitable ammonium oxalate addition distilled water and is configured to 0.8 mol/
The precipitating reagent salting liquid of L.Then, above-mentioned mixing salt solution and precipitant solution are added drop-wise in reaction kettle simultaneously, evenly stirred
It mixes, and is warming up to 50 DEG C of heat preservations, ammonium hydroxide, which is added dropwise, makes solution be in faintly acid（PH is 6 or so）, react 0.5h and obtain Co base complex salts.
It first staticly settles after reaction, then will filter and separate comprising the sediment of Co base complex salts.Afterwards, to sediment first with steaming
Distilled water is cleaned multiple times, then is cleaned multiple times with absolute ethyl alcohol to obtain Co base complex salts.Then, Co base complex salts are put into drying box
In in 50 DEG C of drying process, soaking time 12h.After drying, Co base complex salts are calcined under vacuo in high temperature furnace, temperature
For 350 DEG C, 4 h are kept the temperature, finally obtain the Co based alloys that containing grain growth inhibitor element, crystallite dimension is about 60nm
Powder.
Example 2
It is calculated according to designed composition proportion and weighs corresponding cobalt nitrate, chromic nitrate, ammonium metavanadate, it is then molten simultaneously
Enter the mixing salt solution that 1.0 mol/L are configured in distilled water.It weighs suitable 1.25 mol/L oxalic acid and adds in distilled water preparation
Into solution.Then, above two mixed liquor is added drop-wise in reaction kettle simultaneously, is evenly stirred evenly with blender in 25 DEG C,
Ammonium hydroxide, which is added dropwise, makes solution be in faintly acid（PH is 6 or so）, react 1h and obtain Co base complex salts.It first staticly settles after reaction,
Then it will filter and separate comprising the sediment of Co base complex salts.Afterwards, sediment is first cleaned multiple times with distilled water, then with anhydrous
Ethyl alcohol is cleaned multiple times to obtain Co base complex salts.Then, Co base complex salts are put into drying box in 80 DEG C of drying process, heat preservation
Time is 10h.After drying, Co base complex salts to be calcined in a hydrogen atmosphere in high temperature furnace, temperature is 450 DEG C, keeps the temperature 3 h,
Finally obtain the Co based alloy powder that containing grain growth inhibitor element, crystallite dimension is about 40nm.
Example 3
It is calculated according to designed composition proportion and weighs corresponding cobalt chloride, chromium chloride, ammonium metavanadate, it is then molten simultaneously
Enter the mixing salt solution that 1.5 mol/L are configured in distilled water.Suitable 2.5 mol/L oxalic acid addition distilled water is weighed to be configured to
Solution.Then, above two mixed liquor is added drop-wise in reaction kettle simultaneously, is evenly stirred evenly, and be warming up to blender
80 DEG C of heat preservations, ammonium hydroxide, which is added dropwise, makes solution be in alkalescent（PH is 8 or so）, react 2h and obtain Co base complex salts.After reaction first
It staticly settles, then will filter and separate comprising the sediment of Co base complex salts.Afterwards, it is first repeatedly clear with distilled water to sediment
It washes, then is cleaned multiple times with absolute ethyl alcohol to obtain Co base complex salts.Then, Co base complex salts are put into drying box in 110 DEG C
Drying process, soaking time 8h.After drying, Co base complex salts are calcined under an argon atmosphere in high temperature furnace, temperature 500
DEG C, 2 h are kept the temperature, finally obtain the Co based alloy powder that containing grain growth inhibitor element, crystallite dimension is about 85nm.
As shown in Figure 3, the XRD spectrum of the Co-Cr-V alloyed powders prepared by embodiment according to the present invention 1 is shown,
Middle abscissa is angle of diffraction, and ordinate is intensity.As shown in the figure, the powder prepared only includes Co phases and cobalt oxide phase, and
There is no individual grain growth inhibitor element V and Cr phase.It can be seen that V and Cr, which have been dissolved into Co phases, forms displacement admittedly
Solution.
Compared with existing cobalt powder technology of preparing, using the cobalt-based of the element containing grain growth inhibitor obtained by the present invention
Alloyed powder at least has the following advantages that：
1st, tests prove that, prepared Co bases complex salt can decompose completely at a lower temperature, so as to solve Co
Base complex salt uses the problem that could be only decomposed at high temperature during conventional method, significantly reduces energy consumption, has saved the energy.
2nd, prepared Co based alloy powder according to the present invention, will inhibit the grain growth suppression that hard alloy crystal grain is grown up
Preparation element is solid-solubilized in Co completely, so as to avoid scattered lack is not easy when adding grain growth inhibitor in the ball milling stage
Point is conducive to prepare ultra-fine cemented carbide.
In general, the adding method of the grain growth inhibitor according to the present invention prepared for ultra-fine cemented carbide,
It uses the Co based alloys powder containing grain growth inhibitor element to be substituted traditionally for raw material, and individually addition grain growth inhibits
Agent and the mode of Co powder can well solve grain growth inhibitor and disperse non-uniform problem in mechanical milling process, obtain
The uniform ultra-fine cemented carbide of ingredient.Simultaneously as not using WC-Co composite powder, ultra-fine hard prepared in accordance with the present invention
The carburizing temperature of alloy is from the limitation of Co, and WC carbonizations are completely so that the WC lattices for the ultra-fine cemented carbide prepared are complete, brilliant
The tiny, epigranular of grain, hence it is evident that improve every mechanical property of hard alloy.
This written explanation has used the example including optimal mode to disclose the present invention, and also makes those skilled in the art
It can implement the present invention, including making and using any device or system and any method being combined of execution.The present invention can
Obtain patent scope be defined by the claims, and may include those skilled in the art it is contemplated go out other examples.If
These other examples have has no different structural details or if these other examples from the written language of claim
Including the written language with claim the equivalent constructions element without essence difference, then it is assumed that these examples are in claim
Within the scope of.
Claims (9)
1. a kind of adding method of the grain growth inhibitor prepared for ultra-fine cemented carbide, comprises the following steps：
a）Design the ingredient of the cobalt-based alloy powder containing grain growth inhibitor element；
b）The cobalt-based alloy powder is prepared using coprecipitation；And
c）Corresponding tungsten carbide powder and the cobalt-based alloy powder are weighed according to formula rate, wet grinding media is added in after mixing and carries out
Wet-milling so that the cobalt-based alloy powder containing grain growth inhibitor element equably coats the particle table of the tungsten carbide powder
Face；
Wherein, the cobalt-based alloy powder is prepared using coprecipitation to comprise the following steps：
By soluble cobalt and the grain growth inhibitor element soluble salt that hard alloy crystal grain grows up can be inhibited it is dissolved in distillation
The mixing salt solution of 0.5-2.0mol/L is configured in water；
Precipitating reagent is added in distilled water to the precipitant solution for being configured to 0.8-2.5mol/L；And
The mixing salt solution and the precipitant solution, which are added in reaction vessel, makes the control of mixed solution pH value in 6-8
It is reacted to generate cobalt-based complex salt and them is made to precipitate；And
Wherein, the precipitating reagent includes oxalic acid, oxalates.
2. according to the method described in claim 1, it is characterized in that, it is 2% that the ingredient of the cobalt-based alloy powder contains Cr by mass
~20%, it is 2%~10% containing V.
3. according to the method described in claim 1, it is characterized in that, the method further includes：By the tungsten carbide powder and described
Cobalt-based alloy powder is poured into ball mill after mixing, and ratio of grinding media to material is 3~6：1, add in wet grinding media, ball by 300~500ml/kg
When mill 40~100 is small.
4. according to the method described in claim 3, it is characterized in that, the wet grinding media includes water, alcohol or hexane.
5. it according to the method described in claim 1, is further included it is characterized in that, preparing the cobalt-based alloy powder using coprecipitation
Following steps：
Separation of solid and liquid is carried out to the sediment comprising the cobalt-based complex salt and is cleaned to the cobalt-based complex salt；And
The cobalt-based complex salt is calcined, the cobalt-based alloy powder containing grain growth inhibitor element is obtained after decomposition.
6. according to the method described in claim 5, it is characterized in that, the separation of solid and liquid include filter separation or centrifuge,
And the cleaning includes cleaning the sediment using distilled water and then using absolute ethyl alcohol to the precipitation
Object is cleaned.
7. according to the method described in claim 5, it is characterized in that, the soluble cobalt includes cobalt chloride, cobalt nitrate, acetic acid
Cobalt or combination thereof and the grain growth inhibitor element soluble salt include chromium chloride, chromic nitrate, ammonium metavanadate or
Combination thereof.
8. according to the method described in claim 5, it is characterized in that, the cobalt-based alloy powder include cobalt phase and cobalt oxide phase, and
There is no individual grain growth inhibitor element phase.
9. a kind of ultra-fine cemented carbide is used and is made according to the method any one of claim 1-8, the hard
Scope of the crystallite dimension of alloy between 1 nanometer to 1000 nanometers.
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| CN105755305B (en) * | 2015-12-28 | 2019-11-05 | 国家纳米科学中心 | It is a kind of for calibrating the preparation method of the high hardness value nano hardness standard substance of nano-hardness tester |
| SE541073C2 (en) * | 2016-11-18 | 2019-03-26 | Epiroc Drilling Tools Ab | Drill bit insert for percussive rock drilling |
| CN106825599B (en) * | 2017-01-19 | 2019-03-05 | 北京科技大学 | A kind of preparation method for the WC-Co nanometer powder adding grain growth inhibitor |
| CN110616344B (en) * | 2018-06-19 | 2020-07-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing superfine hard alloy by adopting nano-scale crystal grain inhibitor vanadium carbide |
| CN113857474A (en) * | 2021-09-01 | 2021-12-31 | 河海大学 | Preparation method of WC surface-coated Co powder added with Ce element |
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| SE512754C2 (en) * | 1997-09-05 | 2000-05-08 | Sandvik Ab | Ways to manufacture ultra-fine WC-Co alloys |
| KR100374705B1 (en) * | 2000-06-19 | 2003-03-04 | 한국기계연구원 | A Process for Manufacturing WC/Co based Cemented Carbide |
| CN102049525B (en) * | 2009-10-29 | 2012-08-29 | 北京有色金属研究总院 | Preparation method of spherical nanometer cobalt alloy powder containing transition metal elements |
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