CN109128209A - A kind of preparation method of chromium-doped cobalt powder - Google Patents
A kind of preparation method of chromium-doped cobalt powder Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of chromium-doped cobalt powder, this method is achieved by the steps of: 1) preparing cobalt chloride solution and ammonium bicarbonate soln；2) Hexaaquachromium chloride is added into cobalt chloride solution；3) oil removing is carried out respectively to ammonium bicarbonate soln and doping cobalt chloride solution；4) solution is mixed and is reacted；5) product is filtered and washed；6) the doping cobalt carbonate after washing is dried and is crushed under certain condition；7) the doping cobaltous carbonate powder being crushed is restored under conditions of being passed through hydrogen；8) doped products after reduction are passivated and are crushed, object is made.Chromium using doping way doped chemical of the present invention enters cobalt carbonate lattice, to make that good dispersion is finally made, the chromium-doped cobalt powder of uniform particle sizes；By selecting the cobalt powder of incorporation chromium to manufacture hard alloy, the physical property of the toughness of hard alloy, corrosivity and wearability can be significantly improved, so as to improve the service performance of alloy.
Description
Technical field
The invention belongs to metal cobalt powder preparation technical fields, are related to a kind of preparation method of chromium-doped cobalt powder.
Background technique
Cobalt powder is the irregular powder of grey, is dissolved in acid, is magnetic, oxidizable in humid air, and usually hard closes
The good adhesion agent of gold is one of the important source material for producing hard alloy, and pattern and granularity determine superhard alloy material
Adhesive property, intensity and toughness are most important to the service performance of superhard alloy material.
With the development of science and technology, cobalt powder has obtained widely in the special industry of diamond tool and hard alloy at present
It is purity is high, epigranular, good dispersion, grain shape close to spherical to the basic demand of cobalt powder using, hard alloy, reunites
Degree is low etc..At this moment, researcher often can start with from carbonic acid cobalt precursor used when preparing cobalt powder, to change cobalt powder
Performance, by retrieval find, prepare cobalt powder currently with the cobalt carbonate of some doped metallic elements, be to grind at this stage
The direction studied carefully, however, the partial size that prior art preparation goes out doped metallic elements cobalt carbonate is uneven, bad dispersibility causes to prepare
The partial size of cobalt powder is uneven out, bad dispersibility etc., therefore studies new with special crystal phase, uniform particle sizes and good dispersion
The cobalt powder of doped metallic elements is urgent problem in diamond tool and hard carbide industry at this stage.
Summary of the invention
In view of this, being solved existing the main purpose of the present invention is to provide a kind of preparation method of chromium-doped cobalt powder
There is in technology the problem of uneven cation doping powder diameter, poor dispersion.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows: a kind of preparation side of chromium-doped cobalt powder
Method, this method are achieved by the steps of:
Step 1: the carbon that cobalt chloride solution and ammonia density that the concentration for preparing cobalt is 80~140g/L are 160~230g/L
Sour hydrogen ammonium salt solution, it is spare；
Step 2: Hexaaquachromium chloride is added into the cobalt chloride solution, stir evenly, it is molten to obtain doping cobalt chloride
Liquid；
Step 3: carrying out oil removing respectively to the ammonium bicarbonate soln and the doping cobalt chloride solution；
Step 4: the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing are reacted, pH is controlled
Value is 7.0~7.3, and reaction generates doping cobalt carbonate；
Step 5: the doping cobalt carbonate is filtered, and three times with 30~50 DEG C of water washing, wash 20 every time~
30min；
Step 6: negative pressure is dried the doping cobalt carbonate after washing, is crushed at 80~120 DEG C, it is made chromium-doped
Cobaltous carbonate powder.
Step 7: the chromium-doped cobaltous carbonate powder at 300~400 DEG C and is passed through the mixing gas bar of hydrogen, nitrogen
5~10h, cooling 4~6h are restored under part；
Step 8: the chromium-doped cobaltous carbonate powder after reduction saves to 12 in nitrogen or carbon dioxide atmosphere~
For 24 hours, it then is passivated and is crushed, the chromium-doped cobalt powder of object-is made.
Preferably, in the step 1, the preparation method of cobalt chloride solution are as follows: take a certain amount of cobalt chloride, thereto plus
Enter 50~70 DEG C of water, and stirring and dissolving, the concentration for being configured to cobalt is the cobalt chloride solution of 80~140g/L.
Preferably, in the step 1, the preparation method of ammonium bicarbonate soln are as follows: take a certain amount of ammonium hydrogen carbonate, be added
50~60 DEG C of water, and stirring and dissolving, the concentration for preparing ammonification is the ammonium bicarbonate soln of 160~230g/L.
Preferably, in the step 2, the concentration for adulterating chromium in cobalt chloride solution is 0.1~0.5g/L.
Preferably, in the step 4, pH value is specially 7.25 ± 5.
Preferably, it is 20~40s that the time is crushed in the step 8.
Another technical solution of the invention is achieved in that a kind of preparation method of chromium-doped cobalt powder, this method
It is achieved by the steps of:
The concentration that step 1) prepares cobalt chloride solution and ammonia that the concentration of cobalt is 90~120g/L respectively in NaOH solution tank NaOH is
The ammonium bicarbonate soln of 180~210g/L；
Hexaaquachromium chloride is added into NaOH solution tank NaOH for step 2) in cobalt chloride solution, stir evenly, and obtains doping cobalt chloride
Solution；
Step 3) carries out oil removing to the ammonium bicarbonate soln and the doping cobalt chloride solution respectively；
The pure water of 1~2L is added into reaction kettle as bottom liquid for step 4), heats to reacting kettle jacketing hot water；
Step 5) is fed with peristaltic pump, and doping cobalt chloride solution and ammonium bicarbonate soln are added in reaction kettle simultaneously, into
Keep the flow of doping cobalt chloride solution constant during material, the flow control pH value by adjusting ammonium bicarbonate soln is 7.0
~7.3,2~4h of reaction generates doping cobalt carbonate；
The doping cobalt carbonate is filtered by step 6), and three times with 30~50 DEG C of water washing, every time wash 20~
30min；
Step 7) is dried 10 to the doping cobalt carbonate after washing under conditions of 80~120 DEG C, -0.1~0MPa~
It is crushed 20~40s after 20h, obtains chromium-doped cobaltous carbonate powder；
The chromium-doped cobaltous carbonate powder at 300~400 DEG C and is passed through the gaseous mixture condition of hydrogen, nitrogen by step 8)
5~10h of lower reduction, cooling 4~6h；
Chromium-doped cobaltous carbonate powder after the reduction is saved 12 in nitrogen or carbon dioxide atmosphere by step 9)
~for 24 hours, then be passivated and be crushed, the chromium-doped cobalt powder of object-is made.
Preferably, in the step 5), when being fed with peristaltic pump, the flow for adulterating cobalt chloride is 1~2L/h.
Preferably, in the step 4), using pure water as bottom liquid, by after oil removing doping cobalt chloride solution and oil removing after
Ammonium bicarbonate soln is reacted.
Preferably, pure water is heated, bottom liquid temperature is made to reach 30~50 DEG C, the doping cobalt chloride after oil removing is molten
Ammonium bicarbonate soln after liquid and oil removing, which is added in the reaction kettle for having bottom liquid, to be reacted.
Compared with prior art, when preparing doping cobalt powder presoma cobalt carbonate using doping way of the present invention, doped chemical
Chromium almost all enters in cobalt carbonate lattice, so that degree of adhesion is low, good fluidity, dispersibility between making finally to be made doping cobalt powder
It is good, the chromium-doped cobalt powder of uniform particle sizes；The pattern of the cobalt carbonate of precursor doped chromium decides the pattern of cation doping powder particles,
The latter has very big a dependence and inheritance to the former, and the former spherical in shape or spherical, the latter that by SEM detects its crystal form
It is same spherical in shape or spherical by XRD, SEM detection, and the α-Co powder spherical in shape or spherical of face-centred cubic structure；Pass through
It selects the cobalt powder of incorporation chromium to manufacture hard alloy, the toughness of hard alloy, wearability and corrosive can be significantly improved
Physical property, so as to improve the service performance of alloy.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the preparation method of chromium-doped cobalt powder of the present invention；
Fig. 2 is the electron-microscope scanning figure of prior art routine cobalt powder；
Fig. 3 is the electron-microscope scanning figure of chromium-doped cobalt powder produced by the present invention；
Fig. 4 is the energy spectrum diagram of cobalt powder chromium-doped made from the embodiment of the present invention 1；
Fig. 5 is the XRD spectra of cobalt powder chromium-doped made from the embodiment of the present invention 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The present invention provides a kind of preparation method of chromium-doped cobalt powder, this method is achieved by the steps of:
Step 1: taking a certain amount of cobalt chloride, 50~70 DEG C of water, and stirring and dissolving are added thereto, is configured to cobalt
Concentration is the cobalt chloride solution of 80~140g/L；A certain amount of ammonium hydrogen carbonate is taken, 50~60 DEG C of water, and stirring and dissolving is added,
The concentration for preparing ammonification is the ammonium bicarbonate soln of 160~230g/L, spare；It is prepared respectively by using the water of certain temperature
Cobalt chloride and ammonium bicarbonate soln make cobalt chloride and ammonium hydrogen carbonate obtain sufficient dissolution, while it is molten to also improve cobalt chloride
The dispersibility of cobalt ions in liquid, the dispersibility of carbanion in ammonium bicarbonate soln；
Step 2: Hexaaquachromium chloride (CrCl is added into cobalt chloride solution3·6H2O), stir evenly, obtain doping chlorine
Change cobalt liquor；By first by Hexaaquachromium chloride (CrCl3·6H2O) be added cobalt chloride aqueous solution in, realize chromium and
Cobalt element is sufficiently exchanged and is sufficiently mixed ion level, so that dispersibility of the chromium ion in cobalt chloride solution is improved,
So that the uniform particle sizes of the cobalt carbonate of chromium-doped (Cr) for preparing, good dispersion；
Step 3: oil removing is carried out respectively to ammonium bicarbonate soln and the doping cobalt chloride solution, by ammonium hydrogen carbonate
Solution and doping cobalt chloride solution carry out oil removing process, to play the role of removal of impurities, while also improving in two kinds of solution
The dispersibility of cobalt ions, chromium ion and carbanion；
Step 4: the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing are reacted, pH is controlled
Value is 7.0~7.3, and reaction generates doping cobalt carbonate, by being reacted at above-mentioned pH, the carbonic acid of chromium-doped (Cr) obtained
Cobalt button diameter is small；
Step 5: doping cobalt carbonate is filtered, and three times with 30~50 DEG C of water washing, every time washing 20~
30min；
Step 6: under conditions of 80~90 DEG C, -0.1~0MPa to the doping cobalt carbonate after washing carry out drying 10~
It is crushed 20~40s after 20h, obtains the cobaltous carbonate powder of chromium-doped (Cr)；It is done by the way that the doping cobalt carbonate after washing is carried out negative pressure
Dry, the doping cobalt carbonate after can effectively preventing washing is reunited, so that the cobalt carbonate dispersibility of chromium-doped (Cr) dramatically increases；
It is crushed by carrying out air-flow to the doping cobalt carbonate after negative pressure drying, so that the aggregate in the doping cobalt carbonate after negative pressure drying
It is broken, realizes substantially reducing for the cobalt carbonate precipitation density of chromium-doped (Cr)；
Step 7: by the doping cobaltous carbonate powder being crushed reduction 5 at 300~400 DEG C and under conditions of being passed through hydrogen~
10h；
Step 8: the doping cobaltous carbonate powder after reduction saves to 12 in nitrogen or carbon dioxide atmosphere~for 24 hours,
20~40s is passivated and be crushed again, and the cobalt powder of object-chromium-doped (Cr) is made；Pass through the cobaltous carbonate powder after restoring
In nitrogen or carbon dioxide atmosphere save 12~be passivated for 24 hours, so that the cobalt powder surface of chromium-doped (Cr) is discharged completely,
Improve its oxidation resistance.
The present invention provides the preparation method of another chromium-doped cobalt powder, this method is achieved by the steps of:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 50~70 DEG C of water, and stirring and dissolving are added thereto,
The concentration for being configured to cobalt (Co) is the cobalt chloride solution of 90~120g/L；A certain amount of ammonium hydrogen carbonate is taken to be put into another again molten
In flow container, 50~60 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the bicarbonate of 180~210g/L
Ammonium salt solution, it is spare；
Hexaaquachromium chloride (CrCl is added into NaOH solution tank NaOH for step 2) in prepared cobalt chloride solution2·6H2O), stir
It mixes uniformly, obtains doping cobalt chloride solution, wherein the concentration of chromium (Cr) is 0.1~0.5g/L；
Step 3) carries out oil removing to ammonium bicarbonate soln and the doping cobalt chloride solution respectively；
The pure water that 1~2L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
The reaction kettle for having bottom liquid is added to 30~50 DEG C, then by the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing
In reacted；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is that 1~2L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, by adjusting ammonium hydrogen carbonate
The flow of solution come control pH value be 7.25 ± 5, reaction 2~4h generate doping cobalt carbonate, pass through keep doping cobalt chloride solution
Flow it is constant and change the flow of ammonium bicarbonate soln to control pH value in reaction, keep its reaction process easy to operate, and upper
It states and is reacted under pH, the cobalt carbonate partial size of chromium-doped (Cr) obtained is small；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 30~50 DEG C of hot water, and every time washing 20~
30min；
Step 7) under conditions of 80~120 DEG C, -0.1~0MPa to washing after doping cobalt carbonate carry out drying 10~
It is crushed 20~40s after 20h, obtains the cobaltous carbonate powder of chromium-doped (Cr)；
Step 8) by the cobaltous carbonate powder of chromium-doped (Cr) reduction 5 at 300~400 DEG C and under conditions of being passed through hydrogen~
10h；
The cobaltous carbonate powder of chromium-doped (Cr) after reduction is saved 12 in nitrogen or carbon dioxide atmosphere by step 9)
~for 24 hours, then it is passivated and is crushed 20~40s, the cobalt powder of object-chromium-doped (Cr) is made.
Embodiment 1
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 50 DEG C of water, and stirring and dissolving are added thereto, prepares
The cobalt chloride solution that concentration at cobalt (Co) is 90g/L；A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again, to
50 DEG C of water, and stirring and dissolving is wherein added, the concentration for preparing ammonification is the ammonium bicarbonate soln of 180g/L, spare；
Step 2) takes the prepared cobalt chloride solution of 3L, and 7.69gCrCl is added3·6H2O is stirred evenly, and obtains chromium
(Cr) concentration is that 0.5g/L (500ppm) doping cobalt chloride is molten；
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively；
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
To 30 DEG C, then by the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing be added in the reaction kettle for having bottom liquid into
Row reaction；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is that 1L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, molten by adjusting ammonium hydrogen carbonate
The flow of liquid come control pH value be 7.25 ± 5, reaction 2h generate doping cobalt carbonate；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 30 DEG C of hot water, every all over washing 20min；
Step 7) under conditions of 80 DEG C, -0.1MPa to washing after doping cobalt carbonate be dried after 10h and be crushed 20s, obtain
The cobaltous carbonate powder of chromium-doped (Cr)；
Step 8) is gone back by the cobaltous carbonate powder of chromium-doped (Cr) at 300 DEG C and under the conditions of being passed through the gaseous mixture of hydrogen, nitrogen
Former 5h, cooling 4h；
Step 9) saves the cobaltous carbonate powder of chromium-doped (Cr) after reduction in nitrogen or carbon dioxide atmosphere
12h, then it is passivated and is crushed 20s, the cobalt powder-I of object-chromium-doped (Cr) is made.
Embodiment 2
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 60 DEG C of water, and stirring and dissolving are added thereto, prepares
The cobalt chloride solution that concentration at cobalt (Co) is 100g/L；A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again,
55 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 190g/L, spare；
Step 2) takes the prepared resulting cobalt chloride solution of 3L, and 4.61gCrCl is added3·6H2O is stirred evenly, and is obtained
Concentration to chromium (Cr) is the doping cobalt chloride solution of 0.3g/L (300ppm)；
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively；
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
To 40 DEG C, then by the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing be added in the reaction kettle for having bottom liquid into
Row reaction；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is that 1.5L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, by adjusting ammonium hydrogen carbonate
The flow of solution come control pH value be 7.25 ± 5, reaction 3h generate doping cobalt carbonate；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 40 DEG C of hot water, every all over washing 30min；
Step 7) is crushed under conditions of 100 DEG C, -0.05MPa to being adulterated after 15h is dried in cobalt carbonate after washing
30s obtains the cobaltous carbonate powder of chromium-doped (Cr)；
Step 8) is gone back by the cobaltous carbonate powder of chromium-doped (Cr) at 350 DEG C and under the conditions of being passed through the gaseous mixture of hydrogen, nitrogen
Former 8h, cooling 5h；
Step 9) saves the cobaltous carbonate powder of chromium-doped (Cr) after reduction in nitrogen or carbon dioxide atmosphere
15h, then it is passivated and is crushed 30s, the cobalt powder-II of object-chromium-doped (Cr) is made.
Embodiment 3
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 70 DEG C of water, and stirring and dissolving are added thereto, prepares
The cobalt chloride solution that concentration at cobalt (Co) is 110g/L；A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again,
60 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 200g/L, spare；
The cobalt chloride solution that step 2) takes 3L prepared, and 1.54gCrCl is added3·6H2O is stirred evenly, and obtains chromium
(Cr) concentration is the doping cobalt chloride solution of 0.1g/L (100ppm)；
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively；
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
To 50 DEG C, then by the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing be added in the reaction kettle for having bottom liquid into
Row reaction；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is that 2L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, molten by adjusting ammonium hydrogen carbonate
The flow of liquid come control pH value be 7.25 ± 5, reaction 4h generate doping cobalt carbonate；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 50 DEG C of hot water, every all over washing 40min；
Step 7) under conditions of 120 DEG C, 0MPa to washing after doping cobalt carbonate be dried after 20h and be crushed 40s, must mix
The cobaltous carbonate powder of miscellaneous chromium (Cr)；
Step 8) is gone back by the cobaltous carbonate powder of chromium-doped (Cr) at 400 DEG C and under the conditions of being passed through the gaseous mixture of hydrogen, nitrogen
Former 10h, cooling 6h；
Step 9) saves the cobaltous carbonate powder of chromium-doped (Cr) after reduction in nitrogen or carbon dioxide atmosphere
20h, then it is passivated and is crushed 40s, the cobalt powder-III of object-chromium-doped (Cr) is made.
Experiment and result
The cobalt powder-I, the cobalt powder-II for adulterating Cr, the cobalt powder-III for adulterating Cr of Cr will be adulterated obtained by embodiment 1 to embodiment 5
And existing conventional doping cobalt powder carries out Fei Shi partial size, apparent density, tap density, oxygen content, phosphorus content and laser particle size
Physical property is measured and is compared, as a result as described in Table 1:
Table 1 adulterates the cobalt powder and conventional doping cobalt powder physical property comparing result of Cr
As can be seen from Table 1 with chromium-doped (Cr) content increase, the Fei Shi partial size of the cobalt powder of chromium-doped (Cr), pine
Dress density (AD) and laser particle size increased, while also than the Fei Shi partial size of conventional cobalt powder, apparent density (AD) with
And laser particle size is big.
It is illustrated in figure 2 the electron-microscope scanning figure of existing conventional doping cobalt powder, as shown in figure 3, mixing for the embodiment of the present invention 1
The electron-microscope scanning figure of the cobaltous carbonate powder of miscellaneous chromium, comparison can be seen that the particle diameter distribution of the cobalt dust of chromium-doped (Cr) from figure
More uniform, good dispersion, particle diameter distribution is uniform.
It is illustrated in figure 4 the energy spectrum diagram of cobalt powder chromium-doped made from the embodiment of the present invention 1, it is seen that Cr
(chromium) element is distributed relatively uniform in whole system.
It is illustrated in figure 5 the XRD spectra of cobalt powder chromium-doped made from embodiment 1, it can be seen that produced by the present invention
Chromium-doped cobalt powder is the α-Co powder spherical in shape or spherical of face-centred cubic structure, is produced using the cobalt powder of this crystalline structure hard
Matter alloy can increase its toughness.
Compared with the existing technology, when preparing doping cobalt powder presoma cobalt carbonate using doping way of the present invention, doped chemical
Chromium almost all enters in cobalt carbonate lattice, so that chromium in chromium-doped cobalt carbonate obtained be made to divide in cobalt carbonate particle
Cloth is uniform, and particle is made to become loose and coarse, it is however generally that, the pattern of the cobalt carbonate of precursor doped chromium decides doping
The pattern of cobalt powder particle, the latter have very big dependence and inheritance to the former, therefore, make to glue between finally obtained doping cobalt powder
Lian Du is low, good fluidity, good dispersion, the chromium-doped cobalt powder of uniform particle sizes；By SEM to the cobalt carbonate of chromium-doped (Cr)
Pattern detect that its crystal form is spherical in shape or spherical, is detected by the cobalt powder of XRD, SEM to chromium-doped (Cr) and is equally in
It is spherical or spherical, and be in the α-Co powder spherical in shape or spherical of face-centred cubic structure, this also illustrates doped chemical simultaneously
Chromium (Cr) inhibits α-Co to the conversion of ε-Co；Spherical or spherical α-Co powder has minimum porosity and opposite sliding friction
Factor, superior expansion and ductility show good miscibilty, this is to hard alloy when with other material mixings
Compression moulding plays positive effect；Meanwhile hard alloy is manufactured by selecting the cobalt powder of incorporation chromium (Cr), it can significant effective
Raising hard alloy toughness, wearability and corrosive physical property, so as to improve the service performance of alloy.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (10)
1. a kind of preparation method of chromium-doped cobalt powder, which is characterized in that this method is achieved by the steps of:
Step 1: the bicarbonate that cobalt chloride solution and ammonia density that the concentration for preparing cobalt is 80~140g/L are 160~230g/L
Ammonium salt solution, it is spare；
Step 2: Hexaaquachromium chloride is added into the cobalt chloride solution, stir evenly, obtains doping cobalt chloride solution；
Step 3: carrying out oil removing respectively to the ammonium bicarbonate soln and the doping cobalt chloride solution；
Step 4: the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing are reacted, control pH value is
7.0~7.3, reaction generates doping cobalt carbonate；
Step 5: the doping cobalt carbonate is filtered, and three times with 30~50 DEG C of water washing, wash 20 every time~
30min；
Step 6: negative pressure is dried the doping cobalt carbonate after washing, is crushed at 80~120 DEG C, chromium-doped carbon is made
Sour cobalt dust.
Step 7: by the chromium-doped cobaltous carbonate powder at 300~400 DEG C and under the conditions of being passed through the gaseous mixture of hydrogen, nitrogen
Restore 5~10h, cooling 4~6h；
Step 8: the chromium-doped cobaltous carbonate powder after reduction saves to 12 in nitrogen or carbon dioxide atmosphere~for 24 hours, then
It is passivated and is crushed, the chromium-doped cobalt powder of object-is made.
2. the preparation method of the chromium-doped cobalt powder of one kind according to claim 1, which is characterized in that in the step 1,
The preparation method of cobalt chloride solution are as follows: take a certain amount of cobalt chloride, 50~70 DEG C of water, and stirring and dissolving are added thereto, matches
The concentration that cobalt is made is the cobalt chloride solution of 80~140g/L.
3. the preparation method of the chromium-doped cobalt powder of one kind according to claim 1, which is characterized in that in the step 1,
The preparation method of ammonium bicarbonate soln are as follows: take a certain amount of ammonium hydrogen carbonate, 50~60 DEG C of water, and stirring and dissolving is added, prepares
The concentration of ammonification is the ammonium bicarbonate soln of 160~230g/L.
4. the preparation method of the chromium-doped cobalt powder of one kind according to claim 1, which is characterized in that in the step 2,
The concentration for adulterating chromium in cobalt chloride solution is 0.1~0.5g/L.
5. the preparation method of the chromium-doped cobalt powder of one kind according to claim 1, which is characterized in that in the step 4,
PH value is specially 7.25 ± 5.
6. the preparation method of the chromium-doped cobalt powder of one kind according to claim 1, which is characterized in that broken in the step 8
The broken time is 20~40s.
7. a kind of preparation method of chromium-doped cobalt powder, which is characterized in that this method is achieved by the steps of:
Step 1) prepared respectively in NaOH solution tank NaOH the concentration of cobalt chloride solution and ammonia that the concentration of cobalt is 90~120g/L be 180~
The ammonium bicarbonate soln of 210g/L；
Hexaaquachromium chloride is added into NaOH solution tank NaOH for step 2) in cobalt chloride solution, stir evenly, and obtains doping cobalt chloride solution；
Step 3) carries out oil removing to the ammonium bicarbonate soln and the doping cobalt chloride solution respectively；
The pure water of 1~2L is added into reaction kettle as bottom liquid for step 4), heats to reacting kettle jacketing hot water；
Step 5) is fed with peristaltic pump, and doping cobalt chloride solution and ammonium bicarbonate soln are added in reaction kettle simultaneously, fed
In journey keep doping cobalt chloride solution flow it is constant, by adjust ammonium bicarbonate soln flow control pH value be 7.0~
7.3,2~4h of reaction generates doping cobalt carbonate；
The doping cobalt carbonate is filtered by step 6), and three times with 30~50 DEG C of water washing, every time wash 20~
30min；
After 10~20h is dried to the doping cobalt carbonate after washing under conditions of 80~120 DEG C, -0.1~0MPa in step 7)
Broken 20~40s, obtains chromium-doped cobaltous carbonate powder；
Step 8) is gone back by the chromium-doped cobaltous carbonate powder at 300~400 DEG C and under the conditions of being passed through the gaseous mixture of hydrogen, nitrogen
5~10h of original, cooling 4~6h；
Chromium-doped cobaltous carbonate powder after the reduction saves 12 by step 9) in nitrogen or carbon dioxide atmosphere~
For 24 hours, it then is passivated and is crushed, the chromium-doped cobalt powder of object-is made.
8. the preparation method of the chromium-doped cobalt powder of one kind according to claim 7, which is characterized in that in the step 5),
When being fed with peristaltic pump, the flow for adulterating cobalt chloride is 1~2L/h.
9. the preparation method of the chromium-doped cobalt powder of one kind according to claim 7, which is characterized in that in the step 4),
Using pure water as bottom liquid, the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing are reacted.
10. the preparation method of the chromium-doped cobalt powder of one kind according to claim 9, which is characterized in that add to pure water
Heat makes bottom liquid temperature reach 30~50 DEG C, adds by the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing
Enter to have and be reacted in the reaction kettle of bottom liquid.
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