CN107986793A - A kind of preparation method of boronation zirconium powder - Google Patents
A kind of preparation method of boronation zirconium powder Download PDFInfo
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- CN107986793A CN107986793A CN201711500206.0A CN201711500206A CN107986793A CN 107986793 A CN107986793 A CN 107986793A CN 201711500206 A CN201711500206 A CN 201711500206A CN 107986793 A CN107986793 A CN 107986793A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
- C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a kind of preparation method of boronation zirconium powder, comprise the following steps：A, B powder is placed in the graphite crucible that inner wall scribbles BN powder, is together placed in hydrogen reducing furnace reduction；B, Zr powder is placed in inner wall scribbles in the graphite crucible of BN powder and reduced in hydrogen；C, by B powder made from step a and step b and Zr powder in molar ratio for 1: 1 either 2: 1 or 12: 1 ratio ball milling；D, by the dry materials after ball milling；E, under conditions of pressure is 10~30GPa, 800~2400 DEG C, when sintering 0.5~8 is small are warming up to the heating rate of 0.5~30 DEG C/min；F, 40~60 mesh sieve nets are crossed after chromium boride block is crushed；G, by obtained chromium boride particle ball milling, screening.Method using the present invention can prepare the high-quality boronation zirconium powder that grain crystalline is complete, thing is mutually single.
Description
Technical field
The present invention relates to a kind of preparation method of boronation zirconium powder.
Background technology
As the outstanding person in superhigh temperature ceramic material, zirconium boride ceramic material has excellent physical and chemical performance, such as
High-melting-point, high rigidity, high stability and corrosion resistance, good electrical and thermal conductivity performance and neutron control ability, therefore in superelevation
Adiabator, high temperature resistant structure ceramics, composite material, refractory material, abrasion-proof corrosion-proof erosion resisting coating, high temperature resistance, electrode material, cut
Material, neutron-absorbing material, lapping etc. is cut to have broad application prospects.In this regard, many research works both domestic and external
Person has carried out extensive research to this material.
The Zhang Tianmei of Harbin Institute of Technology is in its Master's thesis of 2006《Self- propagating magnesium reduction process prepares high-purity
Zirconium diboride micro mist》In, using self- propagating magnesiothermic reduction high―temperature nuclei technology utilization ZrO2-B2O3- Mg systems exothermic reaction success
It is prepared for ZrB2Micro mist, but can cause Mg and B in this method preparation process2O3A large amount of volatilizations, and also after synthetic powder
Through overpickling, environment can thus be polluted, and the ZrB synthesized2The purity of micro mist is not high, is only 96.31%.
Ma Chengliang of Zhengzhou University et al. was at its 2008 years《Journal of Inorganic Materials》The scientific paper delivered《Zirconium diboride powder
The commercial synthesis of body》In, with ZrO2、B4C, C is completed in vaccum sensitive stove and electric arc furnaces respectively for raw material using carbothermic method
The commercial synthesis of zirconium diboride powder, but to finding in the material phase analysis of synthetic sample to contain 1.6% graphite impurities.
The Li Rui of Wuhan University of Technology is in its Master's thesis of 2011《The Fast back-projection algorithm and machine of superfine zirconium boride powder
Reason research》In, ultra-fine two boron of Fast back-projection algorithm is heat-treated by boron using the boron amorphous powder after nano zircite and refinement as raw material
Change zirconium powder body, but this method there are it is more the shortcomings that：
(1) during boron thermal reduction, B element does not generate zirconium boride with Zr element compounds completely, and part B is with gaseous state
The form volatilization of oxide, it is expensive since B element has the status being equal with rare earth element in commercial Application, therefore
The zirconium boride cost of this method synthesis is very high.
(2) thinning preprocess boron powder has been carried out using agitating ball mill before powder synthesis, has been carried out again after powder synthesis
Chemical purification and heat treatment, process is long, pollutes environment, is of high cost.
(3) oxygen containing 1.07wt% in the finished powder of synthesis, shows that such a synthetic method cannot get single thing phase, this
Application of this material in production technology will be limited.
Zhao Dan of the National University of Defense technology et al. was at its 2011 years《Journal of Inorganic Materials》The scientific paper delivered《React legal system
Standby zirconium boride superhigh temperature resistant coating》In, using zirconium powder, boron powder and phenolic resin as raw material, pass through high temperature sintering after mud brushing
Method is prepared for ZrB on C/SiC surfaces2Coating, but study in the coating for finding to prepare and contain a small amount of ZrC and ZrO2。
Cao Yingnan of Wuhan University Of Technology et al. was at its 2014 years《Silicate journal》The scientific paper delivered《Colloidal sol-solidifying
Glue carbothermic method prepares Zirconium boride ultrafine powder》In, use sol-gel, carbo-thermal process with zirconium oxychloride, boric acid,
Glucose has synthesized ZrB for raw material under the chelation of citric acid and ethylene glycol2Superfine powder, but study and find this method
The ZrB of synthesis2ZrO can more or less be contained2, and this method is of high cost, chemical solution is dealt with improperly can also cause environment
Pollution, and it is unfavorable for large-scale production.
Cao of Jilin University can be in its Master's thesis of 2015《The high temperature and pressure of zirconium diboride prepares transitivity and pattern
Research》In, using metal Zr powder and amorphous B powder as raw material, using cubic hinge press use the method for high temperature and pressure pressure for
Under conditions of 5.0GPa, temperature are 1700 DEG C -2000 DEG C, insulation 30min has synthesized pure phase ZrB2Block materials, realize ZrB2
The synthesizing of block materials, sintering integratedization.Then with the ZrO of high-purity2Powder and B powder are heat-treated as raw material using high pressure boron
Method has synthesized ZrB under conditions of 5.0GPa, 1300 DEG C -2050 DEG C2Cylinder.The ZrB that last author is purchased with the market again2
Powder and B2O3Powder is that raw material is prepared for ZrB under conditions of pressure is 5.0GPa, temperature is 1900 DEG C2Single crystal grain, carefully analyzes
The synthetic method of author can still find many shortcomings：
(1) for the chemical purity of the amorphous B powder used for 99.99%, the market price of this high-purity B powder is common B powder valency
10 times of lattice, therefore synthesis is carried out using this raw material and causes cost very high.
(2) it is cold-pressed in a mold before powder synthesis, the ZrB of synthesis2The consistency of cylinder reached 93% with
On, which adds the difficulty for being broken into powder, this is applied this material is limited as the market of powder.
(3) during the thermal reduction of high pressure boron, ZrO2The molar ratio of powder and B powder is 3: 10, is much higher than ZrB2In 1: 2
Molar ratio, and due to using high-purity B powder, necessarily causing the powder cost of synthesis very high.
(4) in ZrB2In the preparation process of monocrystalline, high-purity B make use of2O3Powder, and be cold-pressed again, with use
Zr powder and B powder directly synthesize ZrB2Monocrystalline is compared to process is long, efficiency is low, of high cost.
According to the binary phase diagraml of boron-zirconium system, zirconium boride ceramic has ZrB, ZrB2And ZrB12Three kinds of compounds, at present document
Or the problem of preparation method in relation to ZrB2 is constantly present this or that in patent, and in relation to ZrB and ZrB12The report of preparation method
Road is even more almost without thus preparing using a kind of technique is simple, energy consumption is low new method that grain crystalline is complete, finished product is in single
The high-quality boronation zirconium powder of one thing phase is actually necessary to improve the application value of boronation zirconia material industrially.
The content of the invention
The high-quality boronation zirconium powder that grain crystalline is complete, thing is mutually single can be prepared the object of the present invention is to provide a kind of
Method.
In order to achieve the above object, technical scheme comprises the following steps：
A, B powder is placed in the graphite crucible that inner wall scribbles BN powder, be together placed in hydrogen reducing furnace, 1000~
Purification and impurity removal under the conditions of 1500 DEG C, when the recovery time is 2~3 small, obtains high-purity B powder that purity is more than 99.8%；
B, Zr powder is placed in inner wall to scribble in the graphite crucible of BN powder in hydrogen reducing furnace, in 1000~1500 DEG C of bars
Reduction deoxygenation is carried out under part, when the recovery time is 2~3 small, obtains reduction Zr powder；
C, by B powder made from step a and step b and Zr powder in molar ratio for 1: 1 either 2: 1 or 12: 1 ratio add
Into ball grinder, when ball milling 4~96 is small；
D, the material after ball milling is placed in vacuum drying chamber and is dried in 60~100 DEG C, drying time is 16~48
Hour；
E, by dried material transposition in the graphite crucible that inner wall scribbles BN powder, then in pressure it is 5~20GPa
Under the conditions of, 1400~2400 DEG C are warming up to the heating rate of 0.5~30 DEG C/min, when sintering 0.5~8 is small, obtains zirconium boride
Block；
F, 60~100 mesh sieve nets are crossed after zirconium boride block is crushed, obtain zirconium boride particle；
G, obtained zirconium boride particle ball milling, screening, wherein ball milling are used into the sintered carbide ball of WC bases, ball material mass ratio
For (3~4): 1, Ball-milling Time for 24~60 it is small when；Screening uses ultrasonic wave sieving machine, and sieve mesh number is 325~650 mesh.
The quality percent purity of raw material B powder is not less than 95.0% in the step a.
The quality percent purity of raw material Zr powder is not less than 99.5% in the step b.
Ball-milling medium used is the ethanol that water content is 0.01~0.5% in the step c, ball milling used
The material of tank and ball milling ball is polytetrafluoroethylene (PTFE).
Beneficial effects of the present invention：
(1) present invention is preceding first with the processing for carrying out heating reduction to material in hydrogen reducing furnace in high temperature and pressure synthesis
Mode, can effectively reduce the impurity contents such as oxygen in water in B powder, hydrogen peroxide insoluble matter, oxygen and Zr powder, greatly improve
Synthesis raw materials used purity, reduces the purchase cost of high pure raw material；
(2) ball milling step in preparation method selects polytetrafluoroethylene (PTFE) as ball using edible alcohol as ball-milling medium
The material of grinding jar and ball milling ball, effectively prevent the addition of impurity element in mechanical milling process；Vacuum drying chamber pair is used after ball milling
Mixed material is dried, and avoids the secondary oxidation of B powder and Zr powder；
(3) synthesis technique of high temperature and pressure can overcome kinetic barrier high in zirconium boride crystal growth, accelerate B powder and Zr
The reaction rate of powder, realizes the effective controllable of synthetic crystal structure, improves the integrality of zirconium boride powder grain crystallization,
And it ensure that the zirconium boride product synthesized after release cooling can keep the crystalline substance under its high-temperature high-pressure state under normal pressure and temperature
Body structure and material performance；
(4) present invention use high temperature and pressure synthesis mode, can according to B/Zr molar ratios n before synthesis (n=1 either 2 or
12) setting, prepares the boronation zirconium powder for complying fully with design of material thing phase composition, this powder can be ZrB,
ZrB2、ZrB12Or the mixture of this three；
(5) method technical process itself is controllable, and process route is short, and Objective is strong, easy to operate, energy-efficient, and safety
Good reliability.Finished product zirconium boride powder diameter is evenly distributed, grain crystalline is complete, chemical purity >=99.8%, and product quality is steady
Qualitative good, performance, which has, compared with the boronation zirconia material of conventional method synthesis is obviously improved, and the boronation zirconia material for making to produce exists
Excellent physicochemical property is shown in commercial Application, available for alloy material, coating material, high-temperature structural material, corrosion-resistant material
The fields such as material, wear-resistant material, neutron absorber material, cutting material.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the ZrB powder prepared using the method for the present invention.
Fig. 2 is the ZrB prepared using the method for the present invention2The X ray diffracting spectrum of powder.
Fig. 3 is the ZrB prepared using the method for the present invention2The SEM sem images (× 4500) of powder.
Fig. 4 is the ZrB prepared using the method for the present invention2The SEM sem images (× 8000) of powder.
Fig. 5 is the SEM sem images (× 4500) of the ZrB powder prepared using the method for the present invention.
Fig. 6 is the ZrB prepared using the method for the present invention12The SEM sem images (× 8000) of powder.
Embodiment
The invention will be further described with reference to the accompanying drawings and detailed description.
Embodiment 1：
(1) B powder and Zr powder are placed on inner wall respectively first to scribble in the graphite crucible of BN powder, utilize hydrogen reducing furnace
High temperature reduction removal of impurities is carried out, the wherein reduction temperature of boron powder is 1000 DEG C, and the reduction temperature of zirconium powder is 800 DEG C；
(2) the B powder after cleaning and Zr powder will be reduced according to the ratio that molar ratio is 1: 1, be added separately to ball mill mixing tank
Middle ball milling mixing 4h, ball-milling medium are edible alcohol, and ball grinder and ball milling ball use the material of polytetrafluoroethylene (PTFE)；
(3) mixture after ball milling is poured into stainless steel pallet, is then placed into being dried in vacuum drying chamber, done
Dry temperature is 60 DEG C, drying time 48h；
(4) then dried material transposition, graphite crucible is placed in the graphite crucible that inner wall scribbles BN powder
In high temperature and high pressure containers, under conditions of pressure is 5GPa in control container, 1400 are warming up to the heating rate of 0.5 DEG C/min
DEG C, 0.5h is sintered, obtains block ZrB；
(5) block ZrB is put into mechanical crushing appliance and is crushed, crossed 100 mesh sieve nets afterwards, obtain ZrB particles；
(6) obtained ZrB particles are put into ball milling 48h in ball mill, then select 650 mesh sieve nets to be sieved, to obtain the final product
To -650 mesh boronation zirconium powders of chemical formula ZrB.
Embodiment 2：
(1) B powder and Zr powder are placed on inner wall respectively first to scribble in the graphite crucible of BN powder, utilize hydrogen reducing furnace
High temperature reduction removal of impurities is carried out, the wherein reduction temperature of boron powder is 1500 DEG C, and the reduction temperature of zirconium powder is 1100 DEG C；
(2) the B powder after cleaning and Zr powder will be reduced according to the ratio that molar ratio is 1: 1, be added separately to ball mill mixing tank
Middle ball milling mixing 96h, ball-milling medium are edible alcohol, and ball grinder and ball milling ball use the material of polytetrafluoroethylene (PTFE)；
(3) mixture after ball milling is poured into stainless steel pallet, is then placed into being dried in vacuum drying chamber, done
Dry temperature is 100 DEG C, drying time 36h；
(4) then dried material transposition, graphite crucible is placed in the graphite crucible that inner wall scribbles BN powder
In high temperature and high pressure containers, under conditions of pressure is 20GPa in control container, 2400 are warming up to the heating rate of 30 DEG C/min
DEG C, 8h is sintered, obtains block ZrB；
(5) block ZrB is put into mechanical crushing appliance and is crushed, crossed 100 mesh sieve nets afterwards, obtain ZrB particles；
(6) obtained ZrB particles are put into ball milling 48h in ball mill, then select 650 mesh sieve nets to be sieved, to obtain the final product
To -650 mesh boronation zirconium powders of chemical formula ZrB.
Embodiment 3：
(1) B powder and Zr powder are placed on inner wall respectively first to scribble in the graphite crucible of BN powder, utilize hydrogen reducing furnace
High temperature reduction removal of impurities is carried out, the wherein reduction temperature of boron powder is 1250 DEG C, and the reduction temperature of zirconium powder is 950 DEG C；
(2) the B powder after cleaning and Zr powder will be reduced according to the ratio that molar ratio is 1: 1, be added separately to ball mill mixing tank
Middle ball milling mixing 48h, ball-milling medium are edible alcohol, and ball grinder and ball milling ball use the material of polytetrafluoroethylene (PTFE)；
(3) mixture after ball milling is poured into stainless steel pallet, is then placed into being dried in vacuum drying chamber, done
Dry temperature is 80 DEG C, drying time 42h；
(4) then dried material transposition, graphite crucible is placed in the graphite crucible that inner wall scribbles BN powder
In high temperature and high pressure containers, under conditions of pressure is 13GPa in control container, 1900 are warming up to the heating rate of 15 DEG C/min
DEG C, 4h is sintered, obtains block ZrB；
(5) block ZrB is put into mechanical crushing appliance and is crushed, crossed 100 mesh sieve nets afterwards, obtain ZrB particles；
(6) obtained ZrB particles are put into ball milling 48h in ball mill, then select 650 mesh sieve nets to be sieved, to obtain the final product
To -650 mesh boronation zirconium powders of chemical formula ZrB.
Embodiment 4：
(1) B powder and Zr powder are placed on inner wall respectively first to scribble in the graphite crucible of BN powder, utilize hydrogen reducing furnace
High temperature reduction removal of impurities is carried out, the wherein reduction temperature of boron powder is 1300 DEG C, and the reduction temperature of zirconium powder is 1000 DEG C；
(2) the B powder after cleaning and Zr powder will be reduced according to the ratio that molar ratio is 2: 1, be added separately to ball mill mixing tank
Middle ball milling mixing 48h, ball-milling medium are edible alcohol, and ball grinder and ball milling ball use the material of polytetrafluoroethylene (PTFE)；
(3) mixture after ball milling is poured into stainless steel pallet, is then placed into being dried in vacuum drying chamber, done
Dry temperature is 85 DEG C, drying time 42h；
(4) then dried material transposition, graphite crucible is placed in the graphite crucible that inner wall scribbles BN powder
In high temperature and high pressure containers, under conditions of pressure is 14GPa in control container, 1800 are warming up to the heating rate of 10 DEG C/min
DEG C, 3h is sintered, obtains block ZrB2；
(5) by block ZrB2It is put into mechanical crushing appliance and is crushed, crosses 100 mesh sieve nets afterwards, obtain ZrB2 particles；
(6) by obtained ZrB2Particle is put into ball milling 60h in ball mill, then selects 650 mesh sieve nets to be sieved, to obtain the final product
To chemical formula ZrB2- 650 mesh boronation zirconium powders.
Embodiment 5：
(1) B powder and Zr powder are placed on inner wall respectively first to scribble in the graphite crucible of BN powder, utilize hydrogen reducing furnace
High temperature reduction removal of impurities is carried out, the wherein reduction temperature of boron powder is 1000 DEG C, and the reduction temperature of zirconium powder is 800 DEG C；
(2) the B powder after cleaning and Zr powder will be reduced according to the ratio that molar ratio is 2: 1, be added separately to ball mill mixing tank
Middle ball milling mixing 4h, ball-milling medium are edible alcohol, and ball grinder and ball milling ball use the material of polytetrafluoroethylene (PTFE)；
(3) mixture after ball milling is poured into stainless steel pallet, is then placed into being dried in vacuum drying chamber, done
Dry temperature is 60 DEG C, drying time 48h；
(4) then dried material transposition, graphite crucible is placed in the graphite crucible that inner wall scribbles BN powder
In high temperature and high pressure containers, under conditions of pressure is 5GPa in control container, 1400 are warming up to the heating rate of 0.5 DEG C/min
DEG C, 0.5h is sintered, obtains block ZrB2；
(5) by block ZrB2It is put into mechanical crushing appliance and is crushed, crosses 100 mesh sieve nets afterwards, obtain ZrB2Particle；
(6) by obtained ZrB2Particle is put into ball milling 60h in ball mill, then selects 650 mesh sieve nets to be sieved, to obtain the final product
To chemical formula ZrB2- 650 mesh boronation zirconium powders.
Embodiment 6：
(1) B powder and Zr powder are placed on inner wall respectively first to scribble in the graphite crucible of BN powder, utilize hydrogen reducing furnace
High temperature reduction removal of impurities is carried out, the wherein reduction temperature of boron powder is 1450 DEG C, and the reduction temperature of zirconium powder is 1100 DEG C；
(2) the B powder after cleaning and Zr powder will be reduced according to the ratio that molar ratio is 2: 1, be added separately to ball mill mixing tank
Middle ball milling mixing 72h, ball-milling medium are edible alcohol, and ball grinder and ball milling ball use the material of polytetrafluoroethylene (PTFE)；
(3) mixture after ball milling is poured into stainless steel pallet, is then placed into being dried in vacuum drying chamber, done
Dry temperature is 100 DEG C, drying time 36h；
(4) then dried material transposition, graphite crucible is placed in the graphite crucible that inner wall scribbles BN powder
In high temperature and high pressure containers, under conditions of pressure is 20GPa in control container, 2400 are warming up to the heating rate of 25 DEG C/min
DEG C, 8h is sintered, obtains block ZrB2；
(5) by block ZrB2It is put into mechanical crushing appliance and is crushed, crosses 100 mesh sieve nets afterwards, obtain ZrB2Particle；
(6) by obtained ZrB2Particle is put into ball milling 60h in ball mill, then selects 650 mesh sieve nets to be sieved, to obtain the final product
To chemical formula ZrB2- 650 mesh boronation zirconium powders.
Embodiment 7：
(1) B powder and Zr powder are placed on inner wall respectively first to scribble in the graphite crucible of BN powder, utilize hydrogen reducing furnace
High temperature reduction removal of impurities is carried out, the wherein reduction temperature of boron powder is 1500 DEG C, and the reduction temperature of zirconium powder is 1100 DEG C；
(2) the B powder after cleaning and Zr powder will be reduced according to the ratio that molar ratio is 12: 1, be added separately to ball mill mixing tank
Middle ball milling mixing 96h, ball-milling medium are edible alcohol, and ball grinder and ball milling ball use the material of polytetrafluoroethylene (PTFE)；
(3) mixture after ball milling is poured into stainless steel pallet, is then placed into being dried in vacuum drying chamber, done
Dry temperature is 100 DEG C, drying time 36h；
(4) then dried material transposition, graphite crucible is placed in the graphite crucible that inner wall scribbles BN powder
In high temperature and high pressure containers, under conditions of pressure is 20GPa in control container, 2400 are warming up to the heating rate of 28 DEG C/min
DEG C, 8h is sintered, obtains block ZrB12；
(5) by block ZrB12It is put into mechanical crushing appliance and is crushed, crosses 100 mesh sieve nets afterwards, obtain ZrB12
Grain；
(6) by obtained ZrB12Particle is put into ball milling 50h in ball mill, then selects 650 mesh sieve nets to be sieved, to obtain the final product
To chemical formula ZrB12- 650 mesh boronation zirconium powders.
Claims (4)
1. a kind of preparation method of boronation zirconium powder, it is characterized in that, comprise the following steps：
A, B powder is placed in the graphite crucible that inner wall scribbles BN powder, be together placed in hydrogen reducing furnace, 1000~1500
Purification and impurity removal under the conditions of DEG C, when the recovery time is 2~3 small, obtains high-purity B powder that purity is more than 99.8%；
B, Zr powder is placed in inner wall to scribble in the graphite crucible of BN powder in hydrogen reducing furnace, under the conditions of 1000~1500 DEG C
Reduction deoxygenation is carried out, when the recovery time is 2~3 small, obtains reduction Zr powder；
C, by B powder made from step a and step b and Zr powder in molar ratio for 1: 1 either 2: 1 or 12: 1 ratio be added to ball
In grinding jar, when ball milling 4~96 is small；
D, the material after ball milling is placed in vacuum drying chamber and is dried in 60~100 DEG C, when drying time is 16~48 small；
E, by dried material transposition in the graphite crucible that inner wall scribbles BN powder, then in the condition that pressure is 5~20GPa
Under, 1400~2400 DEG C are warming up to the heating rate of 0.5~30 DEG C/min, when sintering 0.5~8 is small, obtains zirconium boride block；
F, 60~100 mesh sieve nets are crossed after zirconium boride block is crushed, obtain zirconium boride particle；
G, obtained zirconium boride particle ball milling, screening, wherein ball milling are used into the sintered carbide ball of WC bases, ball material mass ratio is (3
~4): 1, when Ball-milling Time is 24~60 small；Screening uses ultrasonic wave sieving machine, and sieve mesh number is 325~650 mesh.
2. a kind of preparation method of boronation zirconium powder according to claim 1, it is characterized in that, raw material B powder in the step a
Quality percent purity be not less than 95.0%.
3. a kind of preparation method of boronation zirconium powder according to claim 1, it is characterized in that, Cr material in the step b
The quality percent purity of powder is not less than 99.5%.
4. a kind of preparation method of boronation zirconium powder according to claim 1, it is characterized in that, used in the step c
Ball-milling medium is the ethanol that water content is 0.01~0.5%, and the material of ball grinder used and ball milling ball is poly- four
Vinyl fluoride.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111302805A (en) * | 2020-03-13 | 2020-06-19 | 中国科学院兰州化学物理研究所 | Ternary boride-zirconium boride composite material and preparation method thereof |
| CN114538457A (en) * | 2020-11-27 | 2022-05-27 | 有研工程技术研究院有限公司 | High-purity silicon tetraboride powder and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041079A (en) * | 2019-05-13 | 2019-07-23 | 山东理工大学 | The preparation method of zirconium dodeca-boride ceramic material |
| CN110041079B (en) * | 2019-05-13 | 2022-12-02 | 山东理工大学 | Preparation method of zirconium dodecaboride ceramic material |
| CN111302805A (en) * | 2020-03-13 | 2020-06-19 | 中国科学院兰州化学物理研究所 | Ternary boride-zirconium boride composite material and preparation method thereof |
| CN114538457A (en) * | 2020-11-27 | 2022-05-27 | 有研工程技术研究院有限公司 | High-purity silicon tetraboride powder and preparation method thereof |
| CN114538457B (en) * | 2020-11-27 | 2023-08-15 | 有研工程技术研究院有限公司 | High-purity silicon tetraboride powder and preparation method thereof |
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