CN107309434A - A kind of preparation method and application of the spherical molybdenum powder of high-purity compact - Google Patents
A kind of preparation method and application of the spherical molybdenum powder of high-purity compact Download PDFInfo
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract
The invention provides a kind of preparation method and applications of the spherical molybdenum powder of high-purity compact, belong to globular metallic powder technical field of material.The present invention is using conventional reduction molybdenum powder as raw material, the particle size range of molybdenum powder is granulated by adjusting prilling active control, and the molybdenum powder obtained after being sintered to degumming impurities removal is further sieved, effectively control plasma spheroidization before processing granulates the particle diameter of molybdenum powder, is conducive to the Task-size Controlling of final nodularization molybdenum powder.Molybdenum powder particle diameter distribution after granulation and screening process is narrow, coordinate the spheroidizing process parameters such as input power, powder feeding rate and gas flow, the vaporization in molybdenum powder plasma spheroidization processing procedure and scaling loss can effectively be reduced, be conducive to the stabilization of production technology, greatly improve production efficiency and product quality；By introducing hydrogen into degumming impurities removal and the sintering process of molybdenum powder, the impurity content of molybdenum powder before nodularization is effectively reduced；Screening, nodularization, cooling, the collection of molybdenum powder are operated under argon atmosphere simultaneously, effectively reduce the oxygen content of product.
Description
Technical field
Invention is related to a kind of to reduce the side that molybdenum powder prepares the spherical molybdenum powder of size tunable 3D printing high-purity compact as raw material
Method, belongs to globular metallic powder technical field of material.
Background technology
Molybdenum is a kind of important refractory metal, with its superior mechanical property, electric conductivity, elevated temperature strength, anti-corruption
Antioxygenic property is lost, is widely used in Aero-Space, atomic energy, national defence, petrochemical industry, machine-building, electric, metallurgy
The modern industrial technology such as steel field.With the hair at full speed of the modern science and technology particularly high-end technology such as electronic information, Aero-Space
Exhibition, the demand to complex shape, uniform formation high-performance, high-precision molybdenum product is sharply increased.And with 3D printing technique
For the increases material manufacturing technology of representative, due to its fast and flexible, save material, personalized customization advantage, with tungsten, molybdenum, tantalum, niobium
There is obvious advantage in terms of Deng high-melting-point, the high-performance of traditional difficult-to-machine material, the machine-shaping of complex geometric shapes part,
It is the important development direction of advanced manufacturing technology.
Molybdenum powder is the material base of molybdenum part 3D printing technique development, and its composition, pattern, particle size and distribution are direct
Affect the quality and performance of 3D printing molybdenum part.3D printing molybdenum powder not only needs to have good sphericity, consistency height, contained
The low characteristic of oxygen amount, while it is also desirable that its uniform particle sizes, controllable, and volume industrial metaplasia can be carried out with relatively low cost
Production.
The technology of preparing of maturation there is no to be applied to the spherical molybdenum powder of 3D printing size tunable high-purity compact both at home and abroad at present
Production.The molybdenum powder prepared using conventional reduction technique, although technical maturity and cost is relatively low, but obtained shape of molybdenum powder is not advised
Then, consistency is low, and powder agglomeration is serious, poor fluidity；And use the means such as atomization or rotary electrode method to prepare
Molybdenum powder, limited in itself by method, generally existing impurity content is high, particle diameter is big and is distributed unmanageable defect, simultaneously
Production cost is higher, and technology difficulty is big.As can be seen here, the molybdenum powder obtained with existing production technology is difficult to meet 3D printing technique pair
In the demand of high-performance molybdenum powder, therefore particle diameter distribution uniform, controllable is prepared, oxygen content is low, consistency is high, the 3D of good fluidity is beaten
Print high-performance molybdenum powder turns into technology and develops problem urgently to be resolved hurrily.
The content of the invention
The purpose of the present invention is for molybdenum powder poor fluidity, consistency made from existing production technology are low, oxygen content is high, powder
There is provided a kind of preparation method of the spherical molybdenum powder of high-purity compact for the problems such as last particle diameter is difficult to control to.This method is to reduce molybdenum powder as original
Material, prepares the spherical molybdenum powder of high-purity compact of size tunable, and molybdenum powder prepared by this method can meet 3D printing field for high property
The active demand of energy molybdenum powder.
To reach above-mentioned purpose, solution of the invention is as follows：
A kind of preparation method of the spherical molybdenum powder of high-purity compact, comprises the following steps：
Step 1：Reduction molybdenum powder, binding agent and deionized water are mixed, slurry is made；
Step 2：The slurry is subjected to mist projection granulating, molybdenum powder aggregate is obtained after drying；
Step 3：The molybdenum powder aggregate is subjected to degumming, impurities removal and sintering processes, granulation molybdenum powder is obtained；
Step 4：The granulation molybdenum powder is sieved, the granulation molybdenum powder of particle size range needed for obtaining；
Step 5：The granulation molybdenum powder of required particle size range is delivered into plasma torch core area, obtains melting molybdenum powder；
Step 6：By the melting molybdenum powder cooling and solidifying, the spherical molybdenum powder of high-purity compact is obtained.
In an alternative embodiment, the Fisher particle size scope of the reduction molybdenum powder described in step 1 is 0.5 μm -6 μm, purity
It is more than 99.9% in terms of mass fraction；The binding agent is polyvinyl alcohol；The content of the binding agent is the binding agent and institute
State the 1%-10% of deionized water gross mass；Solid phase weight/mass percentage composition is 30%-70% in the slurry.
In an alternative embodiment, mist projection granulating is carried out to the slurry by centrifugal spray dryer in step 2；Institute
The spray drying EAT for stating centrifugal spray dryer is 150 DEG C -250 DEG C, and leaving air temp is 110 DEG C -190 DEG C；Centrifugation
Disk radius is 0.1m-0.3m, and the range of speeds is 10000r/min-15000r/min；Atomizing pressure scope is 0.2MPa-
0.8MPa。
In an alternative embodiment, the degumming of molybdenum powder aggregate is carried out with impurities removal under hydrogen reducing atmosphere in step 3, hydrogen
Gas is not recycled, and degumming is 700 DEG C -1100 DEG C with impurities removal temperature, and degumming is 1h-5h with the impurities removal time；Molybdenum powder group in step 3
The sintering of aggressiveness is carried out in a hydrogen atmosphere, and sintering temperature is 1100 DEG C -1500 DEG C, and sintering time is 1h-3h.
The screening for granulating molybdenum powder is operated in an alternative embodiment, in step 4 and carried out under ar gas environment, screening is obtained
The particle size intervals of granulation molybdenum powder be not more than 10 μm.
In an alternative embodiment, plasma torch power described in step 5 is 30kW-100kW, and working gas is argon
Gas, flow is 10slpm-50slpm, and side gas is argon gas, and flow is 30slpm-150slpm, and what the plasma torch was run is
System pressure is 40kPa-98kPa.
In an alternative embodiment, in step 5 using carrier gas by the granulation molybdenum powder of required particle size range send into the grade from
Daughter torch core area, the carrier gas is argon gas, and flow is 1slpm-10slpm, and the powder feeding rate of granulation molybdenum powder is 40g/min-
200g/min。
Molybdenum powder is melted in an alternative embodiment, in step 6 to cool down in the environment of argon gas atmosphere, temperature are no more than 30 DEG C
Solidification, cooling velocity is not less than 1 × 104K/s。
It is 10 μm -50 μm that the spherical molybdenum powder particle size range of high-purity compact is formed in an alternative embodiment, in step 6, and grain
Footpath interval is less than 10 μm, and Oxygen potential is more than 90%, and molybdenum powder purity is more than 99.99% in terms of mass fraction.
The spherical molybdenum powder of high-purity compact prepared by the above method answering in 3D printing, powder metallurgy and field of thermal spray
With.The advantage of the invention is that：
(1) using conventional reduction molybdenum powder as raw material, material purity is high and with low cost, at the same raw material molybdenum powder size distribution compared with
Width, expands the selection range of raw material；
(2) by adjusting prilling active control molybdenum powder aggregation size scope, and to being obtained after degumming impurities removal sintering
Granulation molybdenum powder further sieve, can effectively control the particle diameter of plasma spheroidization before processing molybdenum powder, be conducive to final nodularization
The Task-size Controlling of molybdenum powder；
(3) the molybdenum powder particle diameter distribution after granulation and screening process is narrow, coordinates adjustable input power, powder feeding rate and gas
The spheroidizing process parameter such as body flow, can effectively reduce the vaporization of molybdenum powder and scaling loss in plasma spheroidization processing procedure, be conducive to
The stabilization of production technology, greatly improves production efficiency and product quality；
(4) degumming impurities removal and the sintering process of molybdenum powder are introduced hydrogen into, the impurity for effectively reducing molybdenum powder before nodularization contains
Amount, at the same the screening of molybdenum powder, nodularization, cooling, collect operated under argon atmosphere, effectively reduce product
Oxygen content.
(5) the spherical molybdenum powder particle diameter that the preparation method is obtained is tiny, is evenly distributed, controllable, and the few oxygen content of impurity is low, fine and close
Degree is high, and good fluidity significantly increases the added value of molybdenum powder, meets demand of the 3D printing industry for high-performance molybdenum powder.
Brief description of the drawings
Fig. 1 is a kind of technique stream for the method for preparing the spherical molybdenum powder of 3D printing high-purity compact provided in an embodiment of the present invention
Cheng Tu；
Fig. 2 is the stereoscan photograph for the spherical molybdenum powder of 3D printing high-purity compact that the embodiment of the present invention 1 is provided；
Fig. 3 is the stereoscan photograph for the spherical molybdenum powder of 3D printing high-purity compact that the embodiment of the present invention 2 is provided；
Fig. 4 is the stereoscan photograph for the spherical molybdenum powder of 3D printing high-purity compact that the embodiment of the present invention 3 is provided.
Embodiment
The present invention is further described with reference to specific embodiment.But it will be understood by a person skilled in the art that, this hair
It is bright to be not limited thereto, any improvement and change made on the basis of the present invention, all within protection scope of the present invention.
The embodiments of the invention provide a kind of preparation method of the spherical molybdenum powder of high-purity compact, comprise the following steps：
Step 1, reduction molybdenum powder, binding agent and deionized water are mixed, slurry is made；
Specifically, it is the molybdenum powder prepared by conventional reduction technique that molybdenum powder is reduced described in the embodiment of the present invention, described to go back
The preferred Fisher particle size scope of former molybdenum powder is 0.5 μm -6 μm, and purity is calculated in mass percent more than 99.9%；The binding agent
Can be polymer matrix and the paraffin based binders, preferably polyvinyl alcohol such as polyvinyl alcohol, polyethylene glycol, stearic acid, paraffin
(PVA)；
In the embodiment of the present invention, first binding agent is well mixed with deionized water, solution A is made, is then added in solution A
Enter to reduce molybdenum powder, by mechanical agitation to well mixed, slurry is made；Wherein, the content of binding agent described in solution A is solution
The 1%-10% of A gross masses；Solid phase weight/mass percentage composition is 30%-70% in slurry.
Step 2, the slurry is subjected to mist projection granulating, molybdenum powder aggregate is obtained after drying；
Specifically, in embodiments of the present invention, mist projection granulating, institute are carried out to the slurry by centrifugal spray dryer
The spray drying EAT for stating centrifugal spray dryer is 150 DEG C -250 DEG C, and leaving air temp is 110 DEG C -190 DEG C；Centrifugation
Disk radius is 0.1m-0.3m, and preferably 0.15m, the range of speeds is 10000r/min-15000r/min；Atomizing pressure scope is
0.2MPa-0.8MPa；Obtained molybdenum powder aggregation size scope is 10 μm -50 μm.
Step 3, the molybdenum powder aggregate is subjected to degumming, impurities removal and sintering processes, obtains granulation molybdenum powder；
Specifically, in the embodiment of the present invention, step 3 includes：
Step 3a：The molybdenum powder aggregate is carried out into degumming in Muffle furnace to handle with impurities removal, atmosphere is hydrogen reducing gas
Atmosphere, hydrogen is not recycled, and is discharged with sharp impurity；Degumming is 700 DEG C -1100 DEG C with impurities removal temperature, and degumming is with the impurities removal time
1h-5h；Degumming is more than 99.99% (mass fraction) with molybdenum powder purity in molybdenum powder aggregate after impurities removal；
Step 3b：Degumming is sintered with the molybdenum powder aggregate after impurities removal in Muffle furnace, sintering atmosphere is hydrogen
Gas；1100 DEG C -1500 DEG C of sintering temperature；Sintering time 1h-3h；The granulation molybdenum powder purity obtained after sintering is more than 99.99% (matter
Measure fraction).
Step 4, the granulation molybdenum powder is sieved, the granulation molybdenum powder of particle size range needed for obtaining；
The screening of granulation molybdenum powder is carried out in the embodiment of the present invention in glove box and under ar gas environment, obtained granulation is sieved
Molybdenum powder particle diameter can be controlled according to demand, required nothing more than particle size intervals and be not more than 10 μm, and the preparation method of the present invention is not influenceed.
Step 5, the granulation molybdenum powder of required particle size range is delivered into plasma torch core area, obtains melting molybdenum powder；
Specifically, in the embodiment of the present invention, step 5 includes：
Step 5a：Set up the high and stable plasma torch of energy density；
Step 5b：Using carrier gas, the granulation molybdenum powder of particle size range needed for filtering out is sent into described etc. by powder feeding probe
Gas ions torch core high-temperature region, obtains melting molybdenum powder；
In the embodiment of the present invention, the preferred power of plasma torch is 30kW-100kW, and working gas is high-purity argon gas,
Flow is 10slpm-50slpm, and side gas is high-purity argon gas, and flow is 30slpm-150slpm, the system of plasma torch operation
Pressure is 40kPa-98kPa；The carrier gas is high-purity argon gas, and flow is 1slpm-10slpm, and the powder feeding rate of molybdenum powder is 40g/
min-200g/min。
Step 6, by the melting molybdenum powder cooling and solidifying, the spherical molybdenum powder of high-purity compact is obtained.
In the embodiment of the present invention, the granulation molybdenum powder filtered out is after plasma torch core absorbs heat rapidly melting, on surface
Nodularization and densification in the presence of tension force, depart from plasma torch, free-falling enters heat-exchanging chamber, in high thermograde
Lower cooling and solidifying, forms the spherical molybdenum powder of high-purity compact；Collector is opened to be collected the spherical molybdenum powder of high-purity compact.
Specifically, in the embodiment of the present invention, atmosphere is environment temperature in high-purity argon gas environment, heat-exchanging chamber in heat-exchanging chamber
No more than 30 DEG C, molybdenum powder cooling velocity is not less than 1 × 104K/s；Temperature after spherical molybdenum powder is cooled down in heat-exchanging chamber is no more than
30 DEG C, collect powder operation and carried out in glove box and under high-purity argon gas environment；Collect obtained molybdenum powder particle size range for 10 μm-
50 μm, and molybdenum powder particle size intervals are less than 10 μm, Oxygen potential is more than 90%, and molybdenum powder purity is calculated in mass percent more than 99.9%.
The preparation method of the spherical molybdenum powder of high-purity compact provided in an embodiment of the present invention, has the advantages that：
(1) using conventional reduction molybdenum powder as raw material, material purity is high and with low cost, at the same raw material molybdenum powder size distribution compared with
Width, expands the selection range of raw material；
(2) by adjusting prilling active control molybdenum powder aggregation size scope, and to being obtained after degumming impurities removal sintering
Granulation molybdenum powder further sieve, can effectively control the particle diameter of plasma spheroidization before processing molybdenum powder, be conducive to final nodularization
The Task-size Controlling of molybdenum powder；
(3) the molybdenum powder particle diameter distribution after granulation and screening process is narrow, coordinates adjustable input power, powder feeding rate and gas
The spheroidizing process parameter such as body flow, can effectively reduce the vaporization of molybdenum powder and scaling loss in plasma spheroidization processing procedure, be conducive to
The stabilization of production technology, greatly improves production efficiency and product quality；
(4) degumming impurities removal and the sintering process of molybdenum powder are introduced hydrogen into, the impurity for effectively reducing molybdenum powder before nodularization contains
Amount, at the same the screening of molybdenum powder, nodularization, cooling, collect operated under argon atmosphere, effectively reduce product
Oxygen content.
(5) the spherical molybdenum powder particle diameter that this method is obtained is tiny, is evenly distributed, controllable, and the few oxygen content of impurity is low, consistency
Height, good fluidity significantly increases the added value of molybdenum powder, meets demand of the 3D printing industry for high-performance molybdenum powder.
The spherical molybdenum powder of high-purity compact prepared by the preparation method of the spherical molybdenum powder of high-purity compact provided in an embodiment of the present invention is removed
Meet demand of the 3D fields for high-performance molybdenum powder, can be applied to outside 3D printing field, can also be applied to powder injection forming,
The field such as the novel powder metallurgy such as micro injection molding, gel casting technology and plasma spray technology.
It is below several specific embodiments of the present invention：
Embodiment 1
The spherical molybdenum powder of 3D printing high-purity compact that particle size range is 10 μm -20 μm is prepared, is comprised the following steps：
Step 1, purity is chosen to be calculated in mass percent more than the routine that 99.9%, Fisher particle size scope is 0.5 μm -1 μm
Reduce material based on molybdenum powder.Use polyvinyl alcohol for binding agent, it is well mixed with deionized water solution A is made, solution A
Middle polyvinyl alcohol content is mass fraction 2%.Reduction molybdenum powder is added in solution A, slurry is made to well mixed in mechanical agitation
B, slurry B solid phases weight/mass percentage composition is 30%.
Step 2, slurry B is subjected to mist projection granulating on centrifugal spray dryer, spray drying EAT is 170
DEG C, leaving air temp is 130 DEG C, and atomizing disk radius is 0.15m, and rotating speed is 15000r/min, and atomizing pressure is 0.75MPa, is obtained
Molybdenum powder aggregation size scope is 5 μm -30 μm.
Step 3, the molybdenum powder aggregate obtained using Muffle furnace to mist projection granulating carries out degumming impurities removal processing, degumming impurities removal gas
Atmosphere is hydrogen atmosphere, and hydrogen is not recycled, in favor of the discharge of impurity；Degumming impurities removal temperature is 750 DEG C, degumming impurities removal time
For 1.5h, obtain purity and be calculated in mass percent more than 99.99% open-textured granulation molybdenum powder.
Step 4, loose granulation molybdenum powder after degumming impurities removal is sintered using Muffle furnace, sintering atmosphere is hydrogen, is burnt
Junction temperature is 1200 DEG C, and sintering time is 1.5h, obtains purity and is calculated in mass percent the granulation comparatively dense more than 99.99%
Molybdenum powder.
Step 5, carry out carrying out vibrosieve to granulating molybdenum powder after sintering in glove box and under ar gas environment, control screen cloth
Aperture interval obtains the finer and close granulation molybdenum powder that particle size range is 10 μm -20 μm.
Step 6, using argon gas as working gas, the high and stable catalytic behavior of materials torch of energy density is set up.Ion
Body torch power is 40kW, and working gas is high-purity argon gas, and flow is 15slpm；Side gas is high-purity argon gas, and flow is 40slpm；From
The system pressure of daughter torch operation is 50kPa.
Step 7, using argon gas as carrier gas, granulation molybdenum powder is sent into plasma torch core high-temperature region by powder feeding probe, carried
Throughput is 2slpm；The powder feeding rate of molybdenum powder is 50g/min；Granulation molybdenum powder is melted in gas ions torch, in surface tension effects
Issue green-ball and densification.
Step 8, melting molybdenum powder departs from plasma torch, and free-falling under gravity enters heat-exchanging chamber；Heat is handed over
It is high-purity argon gas environment to change in room, and environment temperature is 28 DEG C；Molybdenum powder molten drop is 1 × 104K/s-1.5×104K/s thermograde
Lower cooling and solidifying, forms fine and close spherical molybdenum powder.
Step 9, dense spherical molybdenum powder is sufficiently cool in a heat exchanger, is cooled to 28 DEG C, in glove box and high-purity argon
Collector is opened under compression ring border and collects molybdenum powder；Obtained molybdenum powder stereoscan photograph is collected as shown in Fig. 2 molybdenum powder surface is smooth,
Consistency is more than 99%, and molybdenum powder particle diameter is at 10 μm -20 μm, and Oxygen potential is 93%, and molybdenum powder purity, which is calculated in mass percent, to be more than
99.99%.
Embodiment 2
The spherical molybdenum powder of 3D printing high-purity compact that particle diameter is 20 μm -30 μm is prepared, is comprised the following steps：
Step 1, purity is chosen to be calculated in mass percent more than the routine that 99.9%, Fisher particle size scope is 2 μm -4 μm also
Material based on former molybdenum powder.Use polyvinyl alcohol for binding agent, it is well mixed with deionized water solution A is made, in solution A
Polyvinyl alcohol content is mass fraction 5%.Reduction molybdenum powder is added in solution A, slurry B is made to well mixed in mechanical agitation,
Slurry B solid phases weight/mass percentage composition is 40%.
Step 2, slurry B is subjected to mist projection granulating on centrifugal spray dryer, spray drying EAT is 200
DEG C, leaving air temp is 150 DEG C, and atomizing disk radius is 0.15m, and rotating speed is 12000r/min, and atomizing pressure is 0.5MPa, obtains molybdenum
Powder ball aggressiveness particle size range is 15 μm -40 μm.
Step 3, the molybdenum powder aggregate obtained using Muffle furnace to mist projection granulating carries out degumming impurities removal processing, degumming impurities removal gas
Atmosphere is hydrogen atmosphere, and hydrogen is not recycled, in favor of the discharge of impurity；Degumming impurities removal temperature is 900 DEG C, degumming impurities removal time
For 2h, obtain purity and be calculated in mass percent more than 99.99% open-textured granulation molybdenum powder.
Step 4, loose granulation molybdenum powder after degumming impurities removal is sintered using Muffle furnace, sintering atmosphere is hydrogen, is burnt
Junction temperature is 1300 DEG C, and sintering time is 2h, obtains purity and is calculated in mass percent the granulation molybdenum comparatively dense more than 99.99%
Powder.
Step 5, carry out carrying out vibrosieve to granulating molybdenum powder after sintering in glove box and under ar gas environment, control screen cloth
Aperture interval obtains the finer and close granulation molybdenum powder that particle size range is 20 μm -30 μm.
Step 6, using argon gas as working gas, the high and stable catalytic behavior of materials torch of energy density is set up.Ion
Body torch power is 60kW, and working gas is high-purity argon gas, and flow is 25slpm；Side gas is high-purity argon gas, and flow is 70slpm；From
The system pressure of daughter torch operation is 70kPa.
Step 7, using argon gas as carrier gas, granulation molybdenum powder is sent into plasma torch core high-temperature region by powder feeding probe, carried
Throughput is 5slpm；The powder feeding rate of molybdenum powder is 100g/min；Granulation molybdenum powder is melted in gas ions torch, is made in surface tension
With issuing green-ball and densification.
Step 8, melting molybdenum powder departs from plasma torch, and free-falling under gravity enters heat-exchanging chamber；Heat is handed over
It is high-purity argon gas environment to change in room, and environment temperature is 28 DEG C；Molybdenum powder molten drop is 1.2 × 104K/s-1.5×104K/s temperature
Cooled and solidified under gradient, form fine and close spherical molybdenum powder.
Step 9, dense spherical molybdenum powder is sufficiently cool in a heat exchanger, is cooled to 28 DEG C, in glove box and high-purity
Collector is opened under ar gas environment and collects molybdenum powder；Obtained molybdenum powder stereoscan photograph is collected as shown in figure 3, molybdenum powder surface light
Sliding, consistency is more than 99%, and molybdenum powder particle diameter is at 20 μm -30 μm, and Oxygen potential is 89%, and molybdenum powder purity, which is calculated in mass percent, to be more than
99.99%.
Embodiment 3
The spherical molybdenum powder of 3D printing high-purity compact that particle size range is 30 μm -40 μm is prepared, is comprised the following steps：
Step 1, purity is chosen to be calculated in mass percent more than the routine that 99.9%, Fisher particle size scope is 2 μm -5 μm also
Material based on former molybdenum powder.Use polyvinyl alcohol for binding agent, it is well mixed with deionized water solution A is made, in solution A
Polyvinyl alcohol content is mass fraction 8%.Reduction molybdenum powder is added in solution A, slurry B is made to well mixed in mechanical agitation,
Slurry B solid phases weight/mass percentage composition is 60%.
Step 2, slurry B is subjected to mist projection granulating on centrifugal spray dryer, spray drying EAT is 240 DEG C
Leaving air temp is 180 DEG C, and atomizing disk radius is 0.15m, and rotating speed is 11000r/min, and atomizing pressure is 0.3MPa, obtains molybdenum powder
Aggregation size scope is 25 μm -50 μm.
Step 3, the molybdenum powder aggregate obtained using Muffle furnace to mist projection granulating carries out degumming impurities removal processing, degumming impurities removal gas
Atmosphere is hydrogen atmosphere, and hydrogen is not recycled, in favor of the discharge of impurity；Degumming impurities removal temperature is 1000 DEG C, during degumming impurities removal
Between be 2.5h, obtain purity be calculated in mass percent more than 99.99% open-textured granulation molybdenum powder.
Step 4, loose granulation molybdenum powder after degumming impurities removal is sintered using Muffle furnace, sintering atmosphere is hydrogen, is burnt
Junction temperature is 1400 DEG C, and sintering time is 2.5h, obtains purity and is calculated in mass percent the granulation comparatively dense more than 99.99%
Molybdenum powder.
Step 5, carry out carrying out vibrosieve to granulating molybdenum powder after sintering in glove box and under ar gas environment, control screen cloth
Aperture interval obtains the finer and close granulation molybdenum powder that particle size range is 30 μm -40 μm.
Step 6, using argon gas as working gas, the high and stable catalytic behavior of materials torch of energy density is set up.Ion
Body torch power is 90kW, and working gas is high-purity argon gas, and flow is 50slpm；Side gas is high-purity argon gas, and flow is 130slpm；
The system pressure of gas ions torch operation is 90kPa.
Step 7, using argon gas as carrier gas, granulation molybdenum powder is sent into plasma torch core high-temperature region by powder feeding probe, carried
Throughput is 10slpm；The powder feeding rate of molybdenum powder is 150g/min；Granulation molybdenum powder is melted in gas ions torch, is made in surface tension
With issuing green-ball and densification.
Step 8, melting molybdenum powder departs from plasma torch, and free-falling under gravity enters heat-exchanging chamber；Heat is handed over
It is high-purity argon gas environment to change in room, and environment temperature is 28 DEG C；Molybdenum powder molten drop is not less than 1 × 104Cooled down under K/s thermograde
Solidification, forms fine and close spherical molybdenum powder.
Step 9, dense spherical molybdenum powder is sufficiently cool in a heat exchanger, is cooled to 28 DEG C, in glove box and high-purity
Collector is opened under ar gas environment and collects molybdenum powder；Obtained molybdenum powder stereoscan photograph is collected as shown in figure 4, molybdenum powder surface light
Sliding, consistency is more than 99%, and molybdenum powder particle diameter is at 30 μm -40 μm, and Oxygen potential is 85%, and molybdenum powder purity, which is calculated in mass percent, to be more than
99.99%.
Unspecified part of the present invention belongs to general knowledge as well known to those skilled in the art.Described specific embodiment is only pair
Spirit explanation for example of the invention.The personnel of the technical field of the invention can do different repair to described specific embodiment
Change or supplement or replaced using similar mode, but spirit without departing from the present invention or surmount appended claims and defined
Scope.
The undisclosed technology of the present invention belongs to general knowledge as well known to those skilled in the art.
Claims (10)
1. a kind of preparation method of the spherical molybdenum powder of high-purity compact, it is characterised in that comprise the following steps：
Step 1：Reduction molybdenum powder, binding agent and deionized water are mixed, slurry is made；
Step 2：The slurry is subjected to mist projection granulating, molybdenum powder aggregate is obtained after drying；
Step 3：The molybdenum powder aggregate is subjected to degumming, impurities removal and sintering processes, granulation molybdenum powder is obtained；
Step 4：The granulation molybdenum powder is sieved, the granulation molybdenum powder of particle size range needed for obtaining；
Step 5：The granulation molybdenum powder of required particle size range is delivered into plasma torch core area, obtains melting molybdenum powder；
Step 6：By the melting molybdenum powder cooling and solidifying, the spherical molybdenum powder of high-purity compact is obtained.
2. the preparation method of the spherical molybdenum powder of high-purity compact according to claim 1, it is characterised in that：Described in step 1
The Fisher particle size scope for reducing molybdenum powder is 0.5 μm -6 μm, and purity is more than 99.9% in terms of mass fraction；The binding agent is poly- second
Enol；The content of the binding agent is the binding agent and the 1%-10% of the deionized water gross mass；It is solid in the slurry
Phase weight/mass percentage composition is 30%-70%.
3. the preparation method of the spherical molybdenum powder of high-purity compact according to claim 1, it is characterised in that：In step 2 by from
Core type spray dryer carries out mist projection granulating to the slurry；The spray drying EAT of the centrifugal spray dryer is
150 DEG C -250 DEG C, leaving air temp is 110 DEG C -190 DEG C；Centrifugal pan radius is 0.1m-0.3m, and the range of speeds is 10000r/min-
15000r/min；Atomizing pressure scope is 0.2MPa-0.8MPa.
4. the preparation method of the spherical molybdenum powder of high-purity compact according to claim 1, it is characterised in that：Molybdenum powder group in step 3
The degumming of aggressiveness is carried out with impurities removal under hydrogen reducing atmosphere, and hydrogen is not recycled, degumming and impurities removal temperature for 700 DEG C-
1100 DEG C, degumming is 1h-5h with the impurities removal time；The sintering of molybdenum powder aggregate is carried out in a hydrogen atmosphere in step 3, sintering temperature
For 1100 DEG C -1500 DEG C, sintering time is 1h-3h.
5. the preparation method of the spherical molybdenum powder of high-purity compact according to claim 1, it is characterised in that：To granulation in step 4
The screening of molybdenum powder is operated to be carried out under ar gas environment, and the particle size intervals for sieving obtained granulation molybdenum powder are not more than 10 μm.
6. the preparation method of the spherical molybdenum powder of high-purity compact according to claim 1, it is characterised in that：Described in step 5 etc.
Gas ions torch power is 30kW-100kW, and working gas is argon gas, and flow is 10slpm-50slpm, and side gas is argon gas, and flow is
30slpm-150slpm, the system pressure of the plasma torch operation is 40kPa-98kPa.
7. the preparation method of the spherical molybdenum powder of high-purity compact according to claim 1, it is characterised in that：Load is utilized in step 5
The granulation molybdenum powder of required particle size range is sent into the plasma torch core area by gas, and the carrier gas is argon gas, and flow is
1slpm-10slpm, the powder feeding rate of granulation molybdenum powder is 40g/min-200g/min.
8. the preparation method of the spherical molybdenum powder of high-purity compact according to claim 1, it is characterised in that：Molybdenum is melted in step 6
Powder is cooled and solidified in the environment of argon gas atmosphere, temperature are no more than 30 DEG C, and cooling velocity is not less than 1 × 104K/s。
9. the preparation method of the spherical molybdenum powder of high-purity compact according to claim 1, it is characterised in that：Formed in step 6 high
Pure dense spherical molybdenum powder particle size range is 10 μm -50 μm, and particle size intervals are less than 10 μm, and Oxygen potential is more than 90%, molybdenum powder purity
It is more than 99.99% in terms of mass fraction.
10. the spherical molybdenum powder of high-purity compact prepared by the preparation method according to claim any one of 1-9 is in 3D printing, powder
Application in metallurgical and field of thermal spray.
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| CN108115147A (en) * | 2017-12-04 | 2018-06-05 | 中国兵器科学研究院宁波分院 | A kind of complete closely knit, the spherical molybdenum powder of high apparent density the preparation method of cold spraying |
| CN109014198A (en) * | 2018-08-16 | 2018-12-18 | 北京科技大学 | A method of preparing the pure molybdenum part of high-performance |
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