CN110014163A - Tungsten alloy powder and its preparation method and application - Google Patents
Tungsten alloy powder and its preparation method and application Download PDFInfo
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- CN110014163A CN110014163A CN201910322886.4A CN201910322886A CN110014163A CN 110014163 A CN110014163 A CN 110014163A CN 201910322886 A CN201910322886 A CN 201910322886A CN 110014163 A CN110014163 A CN 110014163A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
Abstract
This application involves a kind of tungsten alloy powders and its preparation method and application, belong to composite metal powder technical field.A kind of preparation method of tungsten alloy powder, comprising: thermal reduction and plasma spheroidization are carried out to tungsten base precursor powder, tungsten base precursor powder uses tungsten powder and metal salt to obtain for raw material granulation.The application uses the raw material of tungsten powder and metal salt as slurry, makes metal salt uniform deposition on tungsten powder particles surface by the method for granulation, particle does not have hollow structure, improves the compactness of particle.Compound deoxygenation is carried out by thermal reduction and plasma spheroidization again, the oxygen content of spherical tungsten based composite powder is reduced, further decreases the porosity of powder, improve the compactness of powder.Prepared tungsten alloy powder has the characteristics that sphericity is high, each distributions of metallic elements is uniform in fine and close, particle, oxygen content is low.
Description
Technical field
This application involves composite metal powder technical fields, and in particular to a kind of tungsten alloy powder and preparation method thereof and
Using.
Background technique
The used tungsten alloy powder of present laser 3D printing generally uses powder mixing method, i.e., passes through W and Cu powder in proportion mixed
Material machine or the preparation of ball mill mixing, for powder mixing method since W and Cu density difference is larger, there are powder mixing unevenly to ask
Topic, subsequent precinct laser thawing prepare tungsten alloy nonuniform organization, be also easily introduced if using ball mill impurity cause, can not
Meet requirement of the precinct laser thawing technology to starting powder well.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the embodiment of the present application includes providing a kind of tungsten alloy powder and its preparation side
Method and application obtain the powder that sphericity is high, uniformity is good, fine and close and low oxygen content.
In a first aspect, the embodiment of the present application proposes a kind of preparation method of tungsten alloy powder, comprising: to tungsten base presoma
The step of the step of powder is heat-treated and plasma spheroidization, it is main that tungsten base precursor powder, which uses tungsten powder and metal salt,
Raw material is granulated and obtains.
The application uses the raw material of tungsten powder and metal salt as slurry, can be with uniform deposition by the method metal salt of granulation
On tungsten powder particles surface, particle does not have hollow structure, improves the compactness of particle.Again by thermal reduction and plasma spheroidization into
The compound deoxygenation of row, can reduce the oxygen content of spherical tungsten based composite powder, further decrease the porosity of powder, improve powder
Compactness.
In the section Example of the application, the mass ratio of tungsten powder and metal salt is 70-97:3-30.
In the quality than in range, metal salt can uniformly, adequately be deposited on tungsten powder particles surface.
In the section Example of the application, raw material further includes bonding agent and water, tungsten powder and the mixture of metal salt, Nian Jie
The mass ratio of agent and water is 1:0.01-0.1:0.1-3.
In the range of the mass ratio, the slurry that mixture, bonding agent and the water of tungsten powder and metal salt are formed passes through spraying
It is granulated obtained powder, tungsten powder and metal salt are distributed more uniform in powder granule, and the more uniform precipitation of metal salt is heavy
Product is on tungsten powder particles surface.
In the section Example of the application, the step of thermal reduction include: by tungsten base precursor powder 500-800 DEG C,
0.1-2h is calcined under the conditions of protective atmosphere, then the cooling under reducing atmosphere condition.
By thermal reduction under this condition, the metal salt in tungsten base precursor powder is decomposed, reduction is converted into metal, tungsten base
Precursor powder can be changed into subsphaeroidal POROUS TUNGSTEN/metal salt powder, can more reduce the oxygen content of powder.
In the section Example of the application, the step of plasma spheroidization includes: that the tungsten base by thermal reduction is compound
For powder under the protection of carrier gas, then the hydrogen plasma zone melting for being 8000-12000 DEG C in temperature is cooled into spherical shape
Tungsten based composite powder.
Porous tungsten based composite powder can form the higher powder of sphericity by plasma spheroidization under this condition
Body, while the densification of powder is improved, porosity is reduced, oxygen content is further reduced.
In the section Example of the application, during plasma spheroidization, carrier gas is argon gas, any one in helium
Or two kinds, the flow of carrier gas is 1-5L/min, and central gas is 15~25L/min of argon gas, and plasma side gas is hydrogen and argon gas
Mixed gas, hydrogen and argon gas molar ratio are 0.05-0.5:1, and the flow of plasma side gas is 45-75L/min.
On the one hand powder evaporates powder superficies oxide using high temperature in the plasma spheroidization of the condition
It is separated with powder, on the other hand utilizes hydrogen stronger oxygen combining power under superhigh temperature, so that the oxygen in powder further diverges from,
Reduce oxygen content.
In the section Example of the application, the chamber pressure in hydrogen plasma region is 0.01-0.15Mpa, tungsten base
The feed rate of precursor powder is 0.1-100g/min.
The condition facilitates the deoxygenation of powder and the formation of spheric granules.
It further include the spherical tungsten based composite powder progress that plasma nodularization obtains in the section Example of the application
Cleaning, and dry step under 50-150 DEG C of inert atmosphere.
The step can remove spherical tungsten based composite powder adhering on surface nanometer powder, further decrease spherical tungsten base
The oxygen content of composite granule.
Second aspect, the embodiment of the present application propose a kind of tungsten alloy powder, by the preparation method of above-mentioned tungsten alloy powder
It is prepared.
The tungsten alloy powder good fluidity as made from the above method, consistency are high, Oxygen potential is high, oxygen content is low, particle
Interior each distributions of metallic elements is uniform.
The third aspect, the embodiment of the present application propose above-mentioned tungsten alloy powder in the application of 3D printing and spraying field.
Tungsten alloy powder provided by the present application is conducive to improve the consistency of laser 3D printing molding and spraying process, can be with
Applied in 3D printing and spraying technology field.
Detailed description of the invention
Technical solution in ord to more clearly illustrate embodiments of the present application, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only some embodiments of the application, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the process flow diagram of the preparation method of tungsten alloy powder provided by the present application；
Fig. 2 is the surface topography map for the precursor powder that the embodiment of the present application 1 provides；
Fig. 3 is the powder sectional view for the precursor powder that the embodiment of the present application 1 provides；
Fig. 4 is the powder sectional view for the precursor powder that the embodiment of the present application 1 provides；
Fig. 5 is the XRD detection figure for spherical porous tungsten/copper composite powder that the embodiment of the present application 1 provides；
Fig. 6 is the XRD detection figure for the spherical compacted W-Cu composite powder that the embodiment of the present application 1 provides；
Fig. 7 is the surface topography SEM figure for the spherical compacted W-Cu composite powder that the embodiment of the present application 1 provides；
Fig. 8 is the section SEM figure for the spherical compacted W-Cu composite powder that the embodiment of the present application 1 provides.
Specific embodiment
It, below will be in the embodiment of the present application to keep the purposes, technical schemes and advantages of the embodiment of the present application clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
A kind of tungsten alloy powder of the embodiment of the present application and its preparation method and application is specifically described below.
Fig. 1 is please referred to, Fig. 1 is the process flow diagram of the preparation method for the tungsten alloy powder that application provides.The application
Embodiment proposes a kind of preparation method of tungsten alloy powder, comprising: carries out thermal reduction and plasma to tungsten base precursor powder
Body nodularization, tungsten base precursor powder use tungsten powder and metal salt to obtain for raw material granulation.
In the prior art, the problem of that there are tungsten is uneven with Metal Distribution for tungsten alloy powder, and powder is hollow structure, causes
The performance of tungsten alloy powder is unable to satisfy the requirement of 3D printing.In the section Example of the application, the original of tungsten base precursor powder
Material includes mixture, bonding agent and the water of tungsten powder and metal salt, obtains slurry after mixing, obtains tungsten base precursor by being granulated
End.It should be noted that metal salt can be soluble metallic salt, during granulation, metal salt is deposited on tungsten powder particles
Surface, realization tungsten powder are uniformly distributed with the presoma of alloy phase.Meanwhile due to the presence of tungsten powder particles in slurry, preparation
Hollow structure is not present in powder, and compactness is good.
Uniformly, be adequately deposited on tungsten powder particles surface for metal salt, in the section Example of the application, tungsten powder and
The mass ratio of metal salt is 70-97:3-30, and optionally, the mass ratio of tungsten powder and metal salt is 80-90:10-20, optionally, tungsten
The mass ratio of powder and metal salt can be 7:2,8:3,80:15,95:20,75:10.Wherein, the average grain diameter of tungsten powder is 500nm-
5μm.The pattern of tungsten powder can be sheet, spherical shape, needle-shaped, irregular etc..Metal salt can be the elements such as Fe, Cu, Ni, Co
One or more of nitrate, chloride.
Further, in the section Example of the application, the quality of the mixture of tungsten powder and metal salt, bonding agent and water
Than for 1:0.01-0.1:0.1-3, optionally, mass ratio can be 1:0.03:1,1:0.05:2,1:0.08:3,1:0.01:2.
Wherein, bonding agent is one or more of polyethylene glycol, starch, chitosan and PVA mixing.
Under the conditions of room temperature (5-30 DEG C), bonding agent is uniformly mixed to obtain viscous liquid with water.Optionally, it was mixing
The mixture of above-mentioned raw materials is heated in journey to 60-80 DEG C, constant temperature 0.5-1h obtains viscous liquid.By tungsten powder, metal salt and viscosity
Liquid is mixed to get slurry.Slurry is granulated to obtain tungsten base precursor powder.
In the section Example of the application, slurry is granulated using spray dryer, charging rate 0.1-
0.5L/h, nozzle temperature are 280-350 DEG C, revolving speed 10-30r/min.Spray granulation method compares the other methods such as mixing method,
Powder obtained is free from foreign meter, and uniformity is good, and grain diameter is small.The Product size that mist projection granulating obtains is 10-300 μm.
Thermal reduction.Tungsten base precursor powder is calcined into 0.1-2h under 500-800 DEG C, reducing atmosphere condition, then is being restored
It is cooling under atmospheric condition.During thermal reduction, the metal salt in tungsten base precursor powder is decomposed, reduction is converted into metal, tungsten
Base precursor powder is changed into subsphaeroidal POROUS TUNGSTEN/metal salt powder.Tungsten/metal salt powder is the powder that tungsten and metal salt form
End.And heat-treating step reduces the oxygen content of powder, and the oxygen content of obtained tungsten based composite powder is generally 3000-
10000ppm.Reducing atmosphere is the general technology of the art, and in the section Example of the application, reducing atmosphere is nitrogen
With the mixture of hydrogen.
Plasma spheroidization.Porous tungsten based composite powder is fitted into the feeder of plasma spheroidization device.Tungsten base
Composite granule is conveyed through high temperature hydrogen heating region under the protection of carrier gas, and the temperature in the region is 8000-12000 DEG C.
At such a temperature, tungsten based composite powder oxide on surface is gasificated into steam and is detached from powder, meanwhile, using hydrogen under superhigh temperature
Stronger oxygen combining power, so that the oxygen in powder further diverges from.Due to high temperature, tungsten based composite powder is in a very short period of time
(0.005-0.1s) melts, and spherical droplets are formed under the action of surface tension, and drop is heated at high temperature with flow shedding
Qu Hou forms fine and close spherical tungsten based composite powder during cooling chamber decline, and collects in collection device.
Wherein, the power of plasma device is 15-100kw, and carrier gas is one or both of argon gas, helium, carrier gas
Flow be 1~5L/min.Central gas is 15~25L/min of argon gas, and plasma side gas is the mixed gas of hydrogen and argon gas,
Hydrogen and argon gas molar ratio are 0.05-0.5:1, and the flow of gas ions side gas is 45~75L/min.Chamber pressure be 0.01~
0.15Mpa.The feed rate of presoma is 0.1~100g/min.
The application using plasma spheronization process densifies tungsten based composite powder, reduces porosity, may be used also
So that powder nodularization, Oxygen potential is greater than 99%.The application is by thermal reduction and plasma spheroidization to tungsten base precursor powder
Compound deoxygenation is carried out, so that the oxygen content of spherical tungsten based composite powder is lower than 100ppm.
During plasma spheroidization, the oxygen element in spherical tungsten based composite powder is transferred to spherical tungsten based composite powder
Adhering on surface nanometer powder in.In order to further decrease the oxygen content of spherical tungsten based composite powder, by this part nano powder
Body is separated with spherical composite powder.In the section Example of the application, spherical tungsten based composite powder is placed in solution ultrasonic
Cleaning 2-3 times, is drying to obtain target product tungsten alloy powder under 50-150 DEG C of inert atmosphere.Inert atmosphere is this technology neck
The general technology in domain, in the section Example of the application, inert atmosphere is nitrogen.
The application uses the raw material of tungsten powder and metal salt as slurry, makes metal salt uniform by the method for mist projection granulating
It is deposited on tungsten powder particles surface, particle does not have hollow structure, improves the compactness of particle.Pass through thermal reduction and plasma ball again
Change and carry out compound deoxygenation, reduces the oxygen content of spherical tungsten based composite powder.Plasma spheroidization further decreases the hole of powder
Rate improves the compactness of powder.After plasma spheroidization, powder is cleaned, washes away the nanometer powder of powder surface, into one
Step reduces the oxygen content of spherical tungsten based composite powder.
Second aspect, the embodiment of the present application propose a kind of tungsten alloy powder, by the preparation method of above-mentioned tungsten alloy powder
It is prepared.Powder fluidity obtained is good, consistency is high, Oxygen potential is high, oxygen content is low, interior each distributions of metallic elements in particle
Uniformly, be conducive to improve the consistency of laser 3D printing forming process.
The third aspect, the tungsten alloy powder as made from the above method have preferable performance, can be applied to 3D
Printing field.
The feature of the application and performance are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of tungsten alloy powders, are mainly made by following steps:
Tungsten powder (0.1-5 microns) is mixed with nitric acid copper hydrate by the mass ratio of W:Cu=77:23.In room temperature condition
Under, a certain amount of starch is added to the water, stirs and is to slowly warm up to 80 DEG C, constant temperature obtained viscous liquid after 1 hour.
Above-mentioned uniform mixed powder is added in prepared viscous liquid, suspension slurry, powder in slurry are stirred to get
Last mixture, water, binder mass ratio be 1:1:0.03.Above-mentioned slurry is granulated using spray dryer, wherein into
Material speed is 0.3L/h, and nozzle temperature is 300 DEG C, rotating speed of shower nozzle 30r/min.
Precursor powder is warming up to 500 DEG C under a nitrogen, then in nitrogen, hydrogen volume than the mixed atmosphere for 1:1
Lower calcining 1h, then sample is cooled to room temperature in the case where nitrogen, hydrogen volume are than for the mixed atmosphere of 1:1, is obtained subsphaeroidal porous
Tungsten/copper composite powder.
POROUS TUNGSTEN/copper composite powders after reduction are subjected to nodularization in 40KW plasma spheroidization device, are obtained spherical
Fine and close W-Cu composite powder.Wherein, feed rate 30g/min, carrier gas are the Ar of 1L/min, and central gas is the argon of 20L/min
Gas, plasma side gas are hydrogen/argon gas mixed gas, and molar ratio is hydrogen: argon gas=0.1:1, plasma side gas
Flow is 60L/min.Chamber pressure is 0.1Mpa.Spherical compacted W-Cu composite powder is placed in water ultrasonic cleaning 2-3 times,
Then in N2Under protective atmosphere, 80 DEG C drying, obtain W-20%Cu composite granule.
Embodiment 2
The present embodiment provides a kind of tungsten alloy powders, are mainly made by following steps:
Tungsten powder (0.05-2 microns) is mixed with nitric acid copper hydrate by the mass ratio of W:Cu=65:35.In room temperature condition
Under, a certain amount of starch is added to the water, stirs and is to slowly warm up to 90 DEG C, constant temperature obtained viscous liquid after 1 hour.
Above-mentioned uniform mixed powder is added in prepared viscous liquid, suspension slurry, powder in slurry are stirred to get
Last mixture, water, binder mass ratio be 1:1:0.02.Above-mentioned slurry is granulated using spray dryer, wherein into
Material speed is 0.25L/h, and nozzle temperature is 350 DEG C, rotating speed of shower nozzle 25r/min.
Precursor powder is warming up to 600 DEG C under a nitrogen, then in nitrogen, hydrogen volume than the mixed atmosphere for 1:1
Lower calcining 0.5h, then sample is cooled to room temperature in the case where nitrogen, hydrogen volume are than for the mixed atmosphere of 1:1, is obtained subsphaeroidal more
Hole tungsten/copper composite powder.
POROUS TUNGSTEN/copper composite powders after reduction are subjected to nodularization in 60KW plasma spheroidization device, are obtained spherical
Fine and close W-Cu composite powder.Wherein, feed rate 80g/min, carrier gas are the argon gas of 2L/min, and central gas is 30L/min's
Argon gas, plasma side gas are hydrogen/argon gas mixed gas, and molar ratio is hydrogen: argon gas=0.15:1, plasma side gas
Flow be 90L/min.Chamber pressure is 0.08Mpa.Spherical compacted W-Cu composite powder is placed in water ultrasonic cleaning 2-3
It is secondary, then in N2Under protective atmosphere, 70 DEG C drying, obtain W-30%Cu composite granule.
Embodiment 3
The present embodiment provides a kind of preparation methods of tungsten alloy powder, are mainly made by following steps:
Tungsten powder (0.05-2 microns) is mixed with nickel nitrate hydrate by the mass ratio of W:Ni=85:15.In room temperature condition
Under, a certain amount of starch is added to the water, stirs and is to slowly warm up to 70 DEG C, constant temperature obtained viscous liquid after 1 hour.
Above-mentioned uniform mixed powder is added in prepared viscous liquid, suspension slurry, powder in slurry are stirred to get
Last mixture, water, binder mass ratio be 1:1:0.015.Above-mentioned slurry is granulated using spray dryer, wherein into
Material speed is 0.25L/h, and nozzle temperature is 325 DEG C, rotating speed of shower nozzle 20r/min.
Precursor powder is warming up to 550 DEG C under a nitrogen, then in nitrogen, hydrogen volume than the mixed atmosphere for 1:1
Lower calcining 0.5h, then sample is cooled to room temperature in the case where nitrogen, hydrogen volume are than for the mixed atmosphere of 1:1, is obtained subsphaeroidal more
Hole tungsten/nickel composite powder.
POROUS TUNGSTEN/nickle composite powder after reduction is subjected to nodularization in 60KW plasma spheroidization device, is obtained spherical
Fine and close tungsten nickel composite powder.Wherein, feed rate 60g/min, carrier gas are the argon gas of 2L/min, and central gas is 30L/min's
Argon gas, plasma side gas are hydrogen/argon gas mixed gas, and molar ratio is hydrogen: argon gas=0.1:1, plasma side gas
Flow be 90L/min.Chamber pressure is 0.1Mpa.Spherical compacted tungsten nickel composite powder is placed in water ultrasonic cleaning 2-3
It is secondary, then in N2Under protective atmosphere, 70 DEG C drying, obtain W-10%Ni composite granule.
Embodiment 4
The present embodiment provides a kind of preparation methods of tungsten alloy powder, are mainly made by following steps:
Tungsten powder (1-5 microns) is mixed with nickel nitrate hydrate by the mass ratio of W:Ni=65:35.At room temperature,
A certain amount of starch is added to the water, stir and is to slowly warm up to 85 DEG C, constant temperature obtained viscous liquid after 2 hours.
Above-mentioned uniform mixed powder is added in prepared viscous liquid, suspension slurry, powder in slurry are stirred to get
Last mixture, water, binder mass ratio be 1:1:0.03.Above-mentioned slurry is granulated using spray dryer, wherein into
Material speed is 0.5L/h, and nozzle temperature is 350 DEG C, rotating speed of shower nozzle 20r/min.
Precursor powder is warming up to 600 DEG C under a nitrogen, then in nitrogen, hydrogen volume than the mixed atmosphere for 1:1
Lower calcining 2h, then sample is cooled to room temperature in the case where nitrogen, hydrogen volume are than for the mixed atmosphere of 1:1, is obtained subsphaeroidal porous
Tungsten/nickel composite powder.
POROUS TUNGSTEN/nickle composite powder after reduction is subjected to nodularization in 80KW plasma spheroidization device, is obtained spherical
Fine and close tungsten nickel composite powder.Wherein, feed rate 100g/min, carrier gas are the argon gas of 2L/min, and central gas is 40L/min's
Argon gas, plasma side gas are hydrogen/argon gas mixed gas, and molar ratio is hydrogen: argon gas=0.15:1, plasma side gas
Flow be 100L/min.Chamber pressure is 0.05Mpa.Spherical compacted tungsten nickel composite powder is placed in water ultrasonic cleaning 2-
3 times, then in N2Under protective atmosphere, 70 DEG C drying, obtain W-30%Ni composite granule.
Embodiment 5
The present embodiment provides a kind of preparation methods of tungsten alloy powder, are mainly made by following steps:
Tungsten powder (1-5 microns) and nickel nitrate hydrate, ferric nitrate are mixed by the mass ratio of W:Ni:Fe=75:12.5:12.5
It closes.At room temperature, a certain amount of PVA is added to the water, stirs and is to slowly warm up to 85 DEG C, constant temperature obtains after 2 hours
Viscous liquid.
Above-mentioned uniform mixed powder is added in prepared viscous liquid, suspension slurry, powder in slurry are stirred to get
Last mixture, water, binder mass ratio be 1:1:0.02.Above-mentioned slurry is granulated using spray dryer, wherein into
Material speed is 0.4L/h, and nozzle temperature is 250 DEG C, rotating speed of shower nozzle 30r/min.
Precursor powder is warming up to 600 DEG C under a nitrogen, then in nitrogen, hydrogen volume than the mixed atmosphere for 1:1
Lower calcining 1.5h, then sample is cooled to room temperature in the case where nitrogen, hydrogen volume are than for the mixed atmosphere of 1:1, is obtained subsphaeroidal more
Hole tungsten/nickel iron composite powder.
POROUS TUNGSTEN after reduction/nickel iron composite granule is subjected to nodularization in 80KW plasma spheroidization device, obtains ball
Shape densification tungsten/nickel iron composite powder.Wherein, feed rate 50g/min, carrier gas are the argon gas of 2L/min, central gas 40L/
The argon gas of min, plasma side gas are hydrogen/argon gas mixed gas, and molar ratio is hydrogen: argon gas=0.15:1, plasma
The flow of body side gas is 100L/min.Chamber pressure is 0.1Mpa.Spherical compacted tungsten/nickel iron composite powder is placed in water
Ultrasonic cleaning 2-3 times, then in N2Under protective atmosphere, 70 DEG C drying, obtain W-10%Ni-10%Fe composite granule.
Embodiment 6
The present embodiment provides a kind of preparation methods of tungsten alloy powder, are mainly made by following steps: by tungsten powder (0.5-
3 microns) it is mixed with nickel nitrate hydrate, cobalt nitrate by the mass ratio of W:Ni:Co=75:12.5:12.5.At room temperature,
A certain amount of polyethylene glycol is added to the water, stir and is to slowly warm up to 60 DEG C, constant temperature obtained viscous liquid after 1 hour.
Above-mentioned uniform mixed powder is added in prepared viscous liquid, suspension slurry, powder in slurry are stirred to get
Last mixture, water, binder mass ratio be 1:1:0.01.Above-mentioned slurry is granulated using spray dryer, wherein into
Material speed is 0.1L/h, and nozzle temperature is 300 DEG C, rotating speed of shower nozzle 20r/min.
Precursor powder is warming up to 700 DEG C under a nitrogen, then in nitrogen, hydrogen volume than the mixed atmosphere for 1:1
Lower calcining 2h, then sample is cooled to room temperature in the case where nitrogen, hydrogen volume are than for the mixed atmosphere of 1:1, is obtained subsphaeroidal porous
Tungsten/nickel cobalt composite powder.
POROUS TUNGSTEN after reduction/nickel cobalt composite granule is subjected to nodularization in 15KW plasma spheroidization device, obtains ball
Shape densification tungsten/nickel cobalt composite powder.Wherein, feed rate 5g/min, carrier gas are the argon gas of 0.5L/min, and central gas is
The argon gas of 10L/min, plasma side gas are hydrogen/argon gas mixed gas, and molar ratio is hydrogen: argon gas=0.05:1, etc.
The flow of gas ions side gas is 20L/min.Chamber pressure is 0.1Mpa.Spherical compacted tungsten/nickel cobalt composite powder is placed in water
Middle ultrasonic cleaning 2-3 times, then in N2Under protective atmosphere, 70 DEG C drying, obtain W-10%Ni-10%Co composite granule.
Embodiment 7
The present embodiment provides a kind of preparation methods of tungsten alloy powder, are mainly made by following steps:
Tungsten powder (2-5 microns) and nickel nitrate hydrate, copper nitrate are mixed by the mass ratio of W:Ni:Cu=75:12.5:12.5
It closes.At room temperature, a certain amount of chitosan is added to the water, after stirring and being to slowly warm up to 90 DEG C, constant temperature 1 hour
To viscous liquid.
Above-mentioned uniform mixed powder is added in prepared viscous liquid, suspension slurry, powder in slurry are stirred to get
Last mixture, water, binder mass ratio be 1:1:0.01.Above-mentioned slurry is granulated using spray dryer, wherein into
Material speed is 0.25L/h, and nozzle temperature is 320 DEG C, rotating speed of shower nozzle 25r/min.
Precursor powder is warming up to 650 DEG C under a nitrogen, then in nitrogen, hydrogen volume than the mixed atmosphere for 1:1
Lower calcining 1h, then sample is cooled to room temperature in the case where nitrogen, hydrogen volume are than for the mixed atmosphere of 1:1, is obtained subsphaeroidal porous
Tungsten/nickel copper composite powder.
POROUS TUNGSTEN after reduction/nickel copper composite granule is subjected to nodularization in 40KW plasma spheroidization device, obtains ball
Shape densification tungsten/nickel copper composite powder.Wherein, feed rate 35g/min, carrier gas are the argon gas of 1L/min, central gas 20L/
The argon gas of min, plasma side gas are hydrogen/argon gas mixed gas, and molar ratio is hydrogen: argon gas=0.05:1, plasma
The flow of body side gas is 60L/min.Chamber pressure is 0.08Mpa.Spherical compacted tungsten/nickel copper composite powder is placed in water
Ultrasonic cleaning 2-3 times, then in N2Under protective atmosphere, 70 DEG C drying, obtain W-10%Ni-10%Cu composite granule.
Comparative example 1
This comparative example provides a kind of tungsten alloy powder, is mainly made by following steps:
The preparation method of this comparative example and the preparation method of embodiment 1 the difference is that: this comparative example is with tungsten powder, cobalt
Powder, titanium valve, chromium powder, chromium carbide are raw material, are mixed to get slurry with water and bonding agent.The wherein matter of mixed-powder, water, bonding agent
Amount is than being 1:1:0.03.Composite powder is obtained using thermal reduction, plasma spheroidization and cleaning.
Comparative example 2
This comparative example provides a kind of tungsten alloy powder, is mainly made by following steps:
The preparation method of this comparative example and the preparation method of embodiment 1 the difference is that: mist projection granulating obtains forerunner
After body powder, without thermal reduction, directly progress plasma spheroidization processing, cleaning obtains composite powder.
Comparative example 3
This comparative example provides a kind of tungsten alloy powder, is mainly made by following steps:
The preparation method of this comparative example and the preparation method of embodiment 1 the difference is that: after plasma spheroidization, no
It is cleaned, directly obtains composite granule.
Test example 1
Composite granule made from embodiment 1-7, comparative example 1-3 is chosen, is detected respectively, testing result is as follows:
1 testing result of table
As shown in Table 1, the sphericity of powder is checked made from the embodiment 1-7 using preparation method provided by the present application
Height, consistency is high, and oxygen content is lower than 100ppm, and Elemental redistribution is uneven.Compared with comparative example 1, embodiment 1 uses tungsten powder and metal
Salt is that raw material prepares slurry, and the uniformity of powder is good, and tungsten copper is evenly distributed in particle.Compared with comparative example 2, embodiment 1 is adopted
With thermal reduction with the compound deoxygenation of plasma spheroidization so that the oxygen content of composite granule reduces.Compared with comparative example 3, embodiment 1
It is also cleaned after plasma spheroidization, removes the nanometer powder of powder surface, reduce the oxygen content of composite granule.
Test example 2
The precursor powder that the mist projection granulating in embodiment 1 obtains is chosen, performance detection is carried out to the powder.The presoma
For the granularity of powder at 10-50 μm, powder is in subsphaeroidal, internal porous.Fig. 2, Fig. 3 and Fig. 4 are the back scattering of the precursor powder
Electron microscope, Fig. 2 are the surface topography map of precursor powder, and Fig. 3 and Fig. 4 are the powder sectional view of precursor powder.It can by Fig. 2
Know, the precursor powder surface that mist projection granulating obtains has hole.Fig. 3 and Fig. 4 it is found that precursor powder be solid construction, tungsten,
Copper is evenly distributed in particle, and mantoquita precipitation is deposited on tungsten powder surface, part tungsten powder is coated (grizzled particle) completely, no
It crosses since mantoquita content is low, part tungsten powder is not wrapped by (light-colored particles).
Spherical porous tungsten/copper composite powder in embodiment 1 by thermal reduction is chosen to be detected.Fig. 5 is spherical porous
Tungsten/copper composite powder XRD testing result, by the XRD analysis result of Fig. 5 it is found that powder is by tungsten, metallic copper group after reduction
At.Analysis by titration is used to measure the mass ratio of tungsten, copper as 76.5:23.5.Nitrogen oxygen analyzer measurement result shows: oxygen content is
2890ppm。
The spherical compacted W-Cu composite powder obtained in embodiment 1 by plasma spheroidization is chosen, it is detected.
Fig. 6 is that the XRD of spherical compacted W-Cu composite powder detects figure, and Fig. 7 is the surface topography SEM of spherical compacted W-Cu composite powder
Figure, Fig. 8 are that the section SEM of spherical compacted W-Cu composite powder schemes.It will be appreciated from fig. 6 that powder is still by tungsten, metallic copper after nodularization
Composition.But due to W, Cu physicochemical property difference, Cu evaporates just seriously during nodularization, so that Cu content reduces in XRD,
The diffraction maximum peak height of Cu reduces in XRD.Analysis by titration is used to measure the mass ratio of tungsten, copper as=80.3:20.7.By Fig. 7 and
Fig. 8 it is found that powder sphericity is obviously improved after nodularization, also eliminate by internal void, close to densification completely.Internal W phase (light tone striped),
Cu (dark-coloured striped) is uniformly distributed.
Test example 3
W-Cu composite powder made from embodiment 1 and commercially available spherical tungsten copper powder are chosen, wherein commercially available spherical shape tungsten copper powder
For tungsten powder (D50=35 μm) and pure copper powder (D50=5 μm) it is mixed by W:Cu=80:20 mass ratio.
Print conditions: 3D laser printing apparatus is used, respectively with W-Cu composite powder made from embodiment 1 and commercially available spherical shape
Tungsten copper powder is that raw material carries out 3D laser printing.Laser power is 200W, prints linear velocity 300mm/s.
Print result: the printed sample relative density of W-Cu composite powder made from embodiment 1 is 93.8%, oxygen content
For 189ppm.The printed sample relative density of commercially available spherical shape tungsten copper powder is 85.3%, oxygen content 3297ppm.
Embodiments described above is some embodiments of the present application, instead of all the embodiments.The reality of the application
The detailed description for applying example is not intended to limit claimed scope of the present application, but is merely representative of the selected implementation of the application
Example.Based on the embodiment in the application, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall in the protection scope of this application.
Claims (10)
1. a kind of preparation method of tungsten alloy powder characterized by comprising the step heat-treated to tungsten base precursor powder
The step of rapid and plasma spheroidization, the tungsten base precursor powder use tungsten powder and metal salt to obtain for primary raw material granulation.
2. the preparation method of tungsten alloy powder according to claim 1, which is characterized in that the tungsten powder and the metal salt
Mass ratio be 70-97:3-30.
3. the preparation method of tungsten alloy powder according to claim 1 or 2, which is characterized in that the raw material further includes gluing
Connect agent and water, the mass ratio of the mixture of the tungsten powder and the metal salt, the bonding agent and the water is 1:0.01-
0.1:0.1-3。
4. the preparation method of tungsten alloy powder according to claim 1, which is characterized in that the step of thermal reduction wraps
It includes: the tungsten base precursor powder being calcined into 0.1-2h under 500-800 DEG C, reducing atmosphere condition, then in reducing atmosphere condition
Lower cooling.
5. the preparation method of tungsten alloy powder according to claim 1, which is characterized in that the step of the plasma spheroidization
It suddenly include: the tungsten based composite powder that obtains the tungsten base precursor powder by thermal reduction under the protection of carrier gas, in temperature
For 8000-12000 DEG C of hydrogen plasma zone melting, it is then cooled into spherical tungsten based composite powder.
6. the preparation method of tungsten alloy powder according to claim 5, which is characterized in that the step of the plasma spheroidization
In rapid, the carrier gas is argon gas, any one or two kinds in helium, and the flow of the carrier gas is 1~5L/min, and central gas is
15~25L/min of argon gas, plasma side gas are the mixed gas of hydrogen and argon gas, and hydrogen and argon gas molar ratio are 0.05-
0.5:1, the flow of plasma side gas are 45-75L/min.
7. the preparation method of tungsten alloy powder according to claim 5, which is characterized in that the hydrogen plasma region
Chamber pressure is 0.01-0.15Mpa, and the feed rate of the tungsten base precursor powder is 0.1-100g/min.
8. the preparation method of tungsten alloy powder according to claim 1, which is characterized in that further include plasma nodularization
Obtained spherical tungsten based composite powder is cleaned, and dry step under 50-150 DEG C of inert atmosphere.
9. a kind of tungsten alloy powder, which is characterized in that by the preparation of tungsten alloy powder as claimed in any one of claims 1 to 8
Method is prepared.
10. tungsten alloy powder as claimed in claim 9 is in the application of 3D printing and spraying field.
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Application publication date: 20190716 |