CN108315628A - Coating spraying and 3D printing cermet material based on (Ti, Me) CN-Co and preparation method thereof - Google Patents

Coating spraying and 3D printing cermet material based on (Ti, Me) CN-Co and preparation method thereof Download PDF

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Publication number
CN108315628A
CN108315628A CN201810162467.4A CN201810162467A CN108315628A CN 108315628 A CN108315628 A CN 108315628A CN 201810162467 A CN201810162467 A CN 201810162467A CN 108315628 A CN108315628 A CN 108315628A
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powder
cermet
spheroidization
ball milling
preparation
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CN108315628B (en
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赵明建
陈可
陈一可
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Chengdu Jintai Jinggong Technology Co Ltd
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Chengdu Jintai Jinggong Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • 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
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/10—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying using centrifugal force
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Abstract

The invention discloses one kind being based on (Ti, Me) coating spraying of CN Co and 3D printing cermet material and preparation method thereof, the cermet material is (Ti, Me) CN Co and at least one of selected from Ni, Mo and Fe, (Ti, Me) content of CN is 60~95%, Co and the content selected from least one of Ni, Mo and Fe is 5~40%；Metal Me in (Ti, the Me) CN is at least one of W, Mo, Ta, V, Cr, Nb and Zr, is produced by batch mixing drying, spheroidization powder, sintering processes.The methods of roller nodularization, radio frequency plasma nodularization or mist projection granulating nodularization progress may be used in powder spheroidization.Cermet material provided by the invention improves the binding force between coating and matrix as coating material, is used as 3D printing material, the quality of 3D printing product can be improved.

Description

Coating spraying and 3D printing cermet material based on (Ti, Me) CN-Co and its system Preparation Method
Technical field
The invention belongs to heat spray coating layer materials and 3D printing Material Field, are beaten more particularly to a kind of coating spraying and 3D Cermet composite alloy material of print and preparation method thereof.
Background technology
Caused by the failure mode of metal works is mainly worn.Although taking heat treatment, Metamorphism treatment, the means such as doping Its wearability can be improved, but extremely limited to the raising of case hardness, limit the performance of its potentiality.In turn, workpiece surface Coating technology come into being, and cermet is also taken as common coating material and uses.Usually cermet material is hard Degree it is higher, the ability of surface resistance to deformation is stronger, and wearability is better, when its as coating in use, be more conducive to raising workpiece The wearability on surface；And its obdurability (intensity and toughness) is higher, impact resistance is better.Therefore, hardness and obdurability have become To evaluate the important indicator of cermet performance.And traditional metal ceramic coating material, due to its main stock size and shape The raw material powder of shape, directly uses after being simply mixed.Its advantage is that cost is relatively low, but the disadvantage is that since powder size is distributed Range is big, and pattern is uneven, and the associativity of sprayed on material and matrix will be caused to be deteriorated, and the complexity in thermal spray process is anti- It answers, the uniformity of ingredient is also a big problem.These problems will lead to the degradation of coating, be used so as to cause workpiece Journey coating material cracks, and the generation for phenomena such as falling off influences the use of product.
It is essentially a kind of rapid shaping technique for the 3D printing of cermet material.Some are complicated The cermet workpiece of shape prepares molding, and used traditional powder using traditional PM technique one difficult to realize Last metallurgical raw material, and it is relatively inaccessible to requirement of the 3D printing technique to its raw material.In 3D printing Rapid Prototyping Process, conventional powder Metallurgical raw material is extremely difficult to the high compactness and strong mechanical performance of prior powder metallurgy product.So the metal as 3D printing Ceramic raw material generally requires uniform spherical powder, and the method (such as air-flow spheroidization) of existing frequently-used powder spheroidization powder Cost is higher, and commercial applications are limited by larger.
Invention content
It is an object of the invention to the present situations and deficiency for the prior art, provide a kind of painting being based on (Ti, Me) CN-Co Layer spraying and 3D printing cermet material and preparation method thereof, to improve the combination between the performance of coating and coating and matrix Power meets requirement of the 3D printing to cermet raw material, improves the quality of 3D printing product, reduces cost of material.
Coating spraying and 3D printing cermet material provided by the invention based on (Ti, Me) CN-Co are spherical powder End, group, which is grouped as, includes by percentage to the quality：(Ti, Me) CN-Co and at least one of selected from Ni, Mo and Fe, (Ti, Me) The content of CN is 60~95%, Co and the content selected from least one of Ni, Mo and Fe is 5~40%；In (Ti, the Me) CN Metal Me be at least one of W, Mo, Ta, V, Cr, Nb and Zr.
In the technical solution of above-mentioned cermet material, the Me in (Ti, the Me) CN, content priority acccess control is in Ti With the range of Me gross masses 5~40%.
The preparation method of above-mentioned cermet material, comprises the following steps that：
(1) batch mixing is dried, and each raw material powder and ball milling agent of formula ratio are added to abundant ball milling in ball milling mixing equipment It is mixed to get mixture, obtained mixture, which is placed in drying equipment, fully dries, and obtains drying mixture；
(2) the drying mixture that step (1) obtains was crushed 300~600 mesh sieve, by the powder that is sieved by spheroidization powder Material is sent into roller spheroidization equipment by powder spheroidization, and then sieving removes grain size more than 30 mesh and the spherical powder less than 120 mesh End is to get to the spherical powder of even particle size distribution；
And forming agent is added before pelletizing；
(3) spherical powder made from step (2) is put into vacuum sintering furnace, is evacuated to 1 × 10-1Pa by sintering processes Below or be continually fed into Ar gas keep vacuum sintering furnace in air pressure be 500~1200Pa, be warming up to 350~600 DEG C heat preservation 2~ 8 hours forming agents with removal addition, then in 1 × 10-1Pa of vacuum hereinafter, be warming up to 800~1300 DEG C fire it is 0.5~4 small When, then furnace cooling is to get to the spherical powder of cermet composite alloy；
Or it comprises the following steps that：
(1) batch mixing is dried, and each raw material powder and ball milling agent of formula ratio are added to abundant ball milling in ball milling mixing equipment It is mixed to get mixture, obtained mixture, which is placed in drying equipment, fully dries, and obtains drying mixture；
(2) green compact is molded, and the sieve of 30~80 mesh of mixture made from step (1) is sieved and is granulated, then will sieving Pellet green compact is molded；
And forming agent is added before pelletizing；
(3) fire broken, step (2) obtained in shaping blank merging vacuum sintering furnace, be evacuated to 1 × 10-1Pa with It is 500~1200Pa to descend or be continually fed into Ar gas and keep air pressure in vacuum sintering furnace, is warming up to 350~600 DEG C of heat preservations 2~8 Hour to remove forming agent, then in 1 × 10-1Pa of vacuum hereinafter, being warming up to 800~1300 DEG C fires 0.5~4 hour, then Sintered shaping blank is broken into 30-100 microns of particulate material by furnace cooling；
(4) radio frequency plasma nodularization, by the particulate material that grain size that step (3) obtains is 30-100 microns be placed in radio frequency etc. from Lower progress nodularization is protected in argon gas in sub- spheroidization device, obtains the spherical powder of cermet composite alloy；
Or it comprises the following steps that：
(1) batch mixing is dried, and each raw material powder, ball milling agent and the forming agent of formula ratio are added in ball milling mixing equipment and filled Bulb separation mill is mixed to get mixed slurry；
(2) mist projection granulating, the slurry that step (1) is obtained are sent into centrifugal spray granulation drying machine and carry out mist projection granulating, obtain To spherical powder；
(3) sintering heat treatment, the spherical powder that step (2) obtains is placed in vacuum sintering furnace, with 3~10 DEG C/min's Heating rate is warming up to 800~1300 DEG C of 0.5~5h of sintering, then cools to room temperature with the furnace to get to the compound conjunction of cermet The spherical powder of gold.
In above-mentioned cermet composite alloy spherical powder preparation method technical solution, ball milling mixing produces mixture mistake The ball milling agent that journey is added preferentially selects alcohol or acetone；The forming agent being added in mixing process or forming process, preferentially One kind in polyethylene glycol, paraffin, buna and SD glue is selected, the addition priority acccess control of forming agent is in the total matter of raw material powder The range of amount 0.5~5%.
In the preparation method of above-mentioned cermet composite alloy spherical powder, the spheroidization that powder spheroidization uses rolls Cylinder, preferentially uses cylinder wall for jacket structured drum apparatus, and during spheroidization, it is 50~80 DEG C that temperature is passed through in chuck Circulating water flow, drum rotation speed are 15~45r/min, and the spheroidization time is 10~20min.
In the preparation method of above-mentioned cermet composite alloy spherical powder, the operation of radio frequency plasma spheroidization device is excellent It first controls and is：30~100KW of power, argon gas 15~40slpm of working flow, argon gas protect 100~200slpm of flow, system negative Press 0.1~0.5atm, powder feeding 2~8slpm of throughput, 20~60g/min of powder feed rate；The electric discharge of radio frequency plasma spheroidization device The temperature of plasma, which preferably controls, is not less than 3200 DEG C.
In the preparation method of above-mentioned cermet composite alloy spherical powder, the centrifugal spray granulation drying machine operation Priority acccess control is：100~350 DEG C of inlet temperature, outlet temperature set 80~250 DEG C, 10~25kr/min of rotating speed, and slurry is sent into speed Spend 5~22ml/min.
Compared with prior art, the invention has the advantages that：
1, the cermet composite alloy spherical powder prepared using the method for the invention, spherical powder ingredient can basis It needs to adjust, simultaneously as the sintering after spheroidization belongs to solid-state diffusion sintering, component segregation is small, and high uniformity makes spraying Or the microstructure of the product after 3D printing is evenly, properties of product consistency higher.
2, cermet composite alloy spherical powder provided by the invention solves carbon nitrogen for 3D printing material Compound material porosity height and the shortcomings that poor mechanical property under conditions of 3D printing rapid shaping.
3, cermet composite alloy spherical powder provided by the invention can improve coating since it is solid-solution powder With the binding property of matrix, effectively reduces the stress between coating and matrix and improve the performance of coating.It can also adjust simultaneously The mechanical properties such as the toughness of coating
4, cermet composite alloy spherical powder preparation method provided by the invention, it is simple for process, it is low for equipment requirements, The manufacturing cost of spherical powder substantially reduces, and is particularly suitable for industrialized production.
Description of the drawings
Fig. 1 is the spherical powder that embodiment 2 prepares gained
Specific implementation mode
Cermet composite alloy spherical powder of the present invention and preparation method thereof is made into one by the following examples Walk explanation.
In following embodiment, the percentage in the chemical formula of the composite alloy containing cermet before each component represents the group Divide the mass percent in nitrogenous master alloy, that does not write percentage before component exactly represents it as surplus.
Embodiment 1
1. dispensing batch mixing is dried
Weigh 4kg Co powder and 6kg Ti (C0.7,N0.3) powder, polyethylene glycol 500g is added, each raw material is passed through into ball mill mixing Method is uniformly mixed, and ball milling agent alcohol, then vacuum drying obtain mixture；
2. spheroidization
By step, 1. the broken sieving powdered of mixture obtained, the sieving sieve mesh number are 300 mesh；Then using rolling Powder spheroidization is used in combination the sieve of 30 mesh to be sieved, takes the powder by sieve by the method for cylinder spheroidization；Again with the sieve of 50 mesh Net sieving, take not the powder by sieve to get to the spherical powder of even particle size distribution；
3. sloughing forming agent and heat treatment
By step 2. in spherical powder obtained be put into vacuum sintering furnace, be evacuated to 1 × 10-1Pa hereinafter, being warming up to 600 DEG C of heat preservations, 2 hours forming agents added with removal；Then 1 × 10-1Pa is down in air pressure hereinafter, be warming up to again 800 DEG C into Row is fired 4 hours；Then furnace cooling is to get to the spherical powder of cermet composite alloy；
The spheroidization process, using roller spheroidization, equipment cylinder wall is jacket structured, the flowing water being passed through in chuck, At 50 DEG C, drum rotation speed 15r/min, the spheroidization time is 10min for water temperature control.
Embodiment 2
1. dispensing batch mixing is dried
Weigh TiC0.5N0.5 powder：9.5kg；Co powder:0.4kg；Fe powder：Polyethylene glycol 50g is added, by each raw material in 0.1kg It is uniformly mixed by ball mill mixing method, ball milling agent is alcohol, then vacuum drying obtains mixture；
2. being molded
It is sieved and is granulated with the sieve of 30 mesh, be then molded the pellet green compact after granulation；
3. pre-burned and broken
By step 2. in green compact obtained be put into vacuum sintering furnace, be evacuated to 1 × 10-1Pa hereinafter, being warming up to 350 8 hours forming agents added with removal of heat preservation；Then 1 × 10-1Pa is down in air pressure hereinafter, being warming up to 800 again is fired 4 Hour；Then furnace cooling will be broken into 30 microns of particle with sintered green compact.
4. plasma discharging nodularization
By step 3. in composite cermet particle obtained be placed in ball in the radio frequency plasma spheroidization device of stable operation Change and obtains composite cermet spherical powder.Plasma discharging spheroidizing process parameter is：Power is 30KW, argon gas working flow For 15slpm, it is 100slpm that argon gas, which protects flow, and system negative pressure is 0.1atm, and powder feeding throughput is 2slpm, and powder feed rate is 20g/min.The temperature of the wherein described plasma discharging nodularization plasma is 3400 DEG C.
Embodiment 3
1. dispensing batch mixing is dried
Weigh (Ti, 20W, 15Mo, 5Ta) C0.7N0.3 powder：6kg；Co powder：2.5kg；Ni powder:1kg；Mo powder 0.5kg, stone Each raw material is uniformly mixed by wax 200g by ball mill mixing method, and ball milling agent is acetone, then vacuum drying obtains mixture；
2. being molded
It is sieved and is granulated with the sieve of 80 mesh, be then molded the pellet green compact after granulation；
3. pre-burned and broken
By step 2. in green compact obtained be put into vacuum sintering furnace, be then continually fed into and keep the air pressure in vacuum drying oven to be The flowing Ar gas of 500pa is warming up to 600 DEG C of heat preservations, 2 hours forming agents added with removal；Then 1 × 10- is down in air pressure 1Pa is fired 0.5 hour hereinafter, being warming up to 1350 DEG C again；It is micro- to be broken into 100 by then furnace cooling for sintered green compact The particle of rice.
4. plasma discharging nodularization
By step 3. in composite cermet particle obtained be placed in ball in the radio frequency plasma spheroidization device of stable operation Change and obtains composite cermet spherical powder.Plasma discharging spheroidizing process parameter is：Operation power is 100KW, argon gas work Flow is 40slpm, and it is 200slpm that argon gas, which protects flow, and system negative pressure is 0.5atm, and powder feeding throughput is 8slpm, powder feeding speed Degree is 60g/min.The temperature of the wherein described plasma discharging nodularization plasma is 3600 DEG C.
Embodiment 4
1. dispensing batch mixing is dried
Weigh TiC0.7N0.3 powder：2kg；WC：3kg；Mo2C：1kg；Co powder:2.7kg；Ni powder：1.3kg is added fourth and receives rubber Each raw material is uniformly mixed by glue 100g by ball mill mixing method, and ball milling agent is acetone, then vacuum drying obtains mixture；
2. being molded
It is sieved and is granulated with the sieve of 60 mesh, be then molded the pellet green compact after granulation；
3. pre-burned and broken
By step 2. in green compact obtained be put into vacuum sintering furnace, be then continually fed into keep vacuum drying oven in air pressure be, The flowing Ar gas of 1200Pa is warming up to 400 DEG C of heat preservations, 6 hours forming agents added with removal；Then 1 × 10- is down in air pressure 1Pa is fired 3 hours hereinafter, being warming up to 1200 DEG C again；Then furnace cooling will be broken into 60 microns with sintered green compact Particle.
4. plasma discharging nodularization
By step 3. in composite cermet particle obtained be placed in ball in the radio frequency plasma spheroidization device of stable operation Change and obtains composite cermet spherical powder.Operation power is 60KW, and argon gas working flow is 30slpm, and argon gas protection flow is 120slpm, system negative pressure are 0.3atm, and powder feeding throughput is 6slpm, powder feed rate 30g/min.Wherein it is described electric discharge etc. from The temperature of bulbec plasma is 3900 DEG C.
Embodiment 5
1. dispensing batch mixing is dried
Weigh TiC0.7N0.3 powder：9.4kg；MoC：0.1kg；Co powder:0.5kg is added SD glue 300g, each raw material is passed through Ball mill mixing method is uniformly mixed, and ball milling agent is acetone, then vacuum drying obtains mixture；
2. spheroidization
By step, 1. the broken sieving powdered of mixture obtained, the sieving sieve mesh number are 300 mesh；Then using rolling Powder spheroidization is used in combination the sieve of 30 mesh to be sieved, takes the powder by sieve by the method for cylinder spheroidization；Again with the sieve of 50 mesh Net sieving, take not the powder by sieve to get to the spherical powder of even particle size distribution；
3. sloughing forming agent and heat treatment
By step 2. in spherical powder obtained be put into vacuum sintering furnace, be evacuated to 1 × 10-1Pa hereinafter, being warming up to 350 DEG C of heat preservations, 8 hours forming agents added with removal；Then 1 × 10-1Pa is down in air pressure hereinafter, be warming up to again 800 DEG C into Row is fired 4 hours；Then furnace cooling is to get to the spherical powder of cermet composite alloy；
The spheroidization process is that it is double-layer structure, hollow to use roller spheroidization, cylinder wall, and hollow space can It is passed through circulation water, at 50 DEG C, drum rotation speed 15r/min, the spheroidization time is 10min for water temperature control.
Embodiment 6
1. dispensing batch mixing is dried
Weigh (Ti, 5W) C0.7N0.3 powder：9.5kg；Ni powder:0.5kg is added paraffin 400g, each raw material is passed through ball milling Batch mixing method is uniformly mixed, and ball milling agent is alcohol, then vacuum drying obtains mixture；
2. spheroidization
By step, 1. the broken sieving powdered of mixture obtained, the sieving sieve mesh number are 600 mesh；Then using rolling Powder spheroidization is used in combination the sieve of 100 mesh to be sieved, takes the powder by sieve by the method for cylinder spheroidization；Again with 120 purposes Sieve is sieved, take not the powder by sieve to get to the spherical powder of even particle size distribution；
3. sloughing forming agent and heat treatment
By step 2. in spherical powder obtained be put into vacuum sintering furnace, be then continually fed into keep vacuum drying oven in air pressure be The flowing Ar gas of 500Pa is warming up to 600 DEG C of heat preservations, 2 hours forming agents added with removal；Then 1 × 10- is down in air pressure 1Pa is fired 0.5 hour hereinafter, being warming up to 1300 DEG C again；Then furnace cooling is to get to the ball of cermet composite alloy Shape powder；
The spheroidization process is that it is double-layer structure, hollow to use roller spheroidization, cylinder wall, and hollow space can It is passed through circulation water, at 80 DEG C, drum rotation speed 45r/min, the spheroidization time is 20min for water temperature control.
Embodiment 7
1. dispensing batch mixing is dried
Weigh (Ti, 20W, 15Mo, 5Ta) C0.5N0.5 powder：4.65kg；TiCN:0.25kg；WC:2kg；MoC：1kg； TaC:1kg；NbC:0.1kg；Mo powder:1kg；Polyethylene glycol 350g is added, each raw material is uniformly mixed by ball mill mixing method, ball Grinding agent is alcohol, then vacuum drying obtains mixture；
2. spheroidization
By step, 1. the broken sieving powdered of mixture obtained, the sieving sieve mesh number are 600 mesh；Then using rolling Powder spheroidization is used in combination the sieve of 100 mesh to be sieved, takes the powder by sieve by the method for cylinder spheroidization；Again with 120 purposes Sieve is sieved, take not the powder by sieve to get to the spherical powder of even particle size distribution；
3. sloughing forming agent and heat treatment
By step 2. in spherical powder obtained be put into vacuum sintering furnace, be then continually fed into keep vacuum drying oven in air pressure be The flowing Ar gas of 1200Pa is warming up to 600 DEG C of heat preservations, 2 hours forming agents added with removal；Then 1 × 10- is down in air pressure 1Pa is fired 0.5 hour hereinafter, being warming up to 1300 DEG C again；Then furnace cooling is to get to the ball of cermet composite alloy Shape powder；
The spheroidization process is that it is double-layer structure, hollow to use roller spheroidization, cylinder wall, and hollow space can It is passed through circulation water, at 80 DEG C, drum rotation speed 45r/min, the spheroidization time is 20min for water temperature control.
Embodiment 8
1. dispensing batch mixing is dried
Weigh (Ti, 5Cr, 2V, 0.2Nb) C0.3N0.7 powder:2kg；WC powder:1.5kg；Cr3C2:0.5kg；VC:0.5kg； TaC powder:1kg；NbC:0.5kg；Co powder:1.8kg；Ni powder:1.8kg；Fe powder:0.4kg is added paraffin 200g, each raw material is led to It crosses ball mill mixing method to be uniformly mixed, taking-up obtains mixed slurry；
2. mist projection granulating
Mist projection granulating processing is carried out to 1. slurry that step obtains using high speed centrifugation Spray Grain-make Drier, to obtain Spherical powder；The mist was granulated technique:Inlet temperature is set as 100 DEG C, and outlet temperature is set as 80 DEG C, and atomizer rotating speed is set For 10kr/min, slurry input speed is 5ml/min；
3. being heat-treated
By step 2. in obtained spherical powder be placed in vacuum sintering furnace and be heat-treated, heating rate is 3 DEG C/min, at heat It is 800 DEG C to manage temperature, heat treatment time 5h；Then room temperature is cooled to the furnace to get to the spherical shape of cermet composite alloy Powder.
Embodiment 9
1. dispensing batch mixing is dried
Weigh (Ti, 10W, 5Mo, 1Zr) C0.7N0.3 powder:9.4kg；ZrC:0.1kg；Co powder:SD glue is added in 0.5kg Each raw material is uniformly mixed by 90g by ball mill mixing method, and taking-up obtains mixed slurry；
2. mist projection granulating
Mist projection granulating processing is carried out to 1. slurry that step obtains using high speed centrifugation Spray Grain-make Drier, to obtain Spherical powder；The mist was granulated technique:Inlet temperature is set as 350 DEG C, and outlet temperature is set as 250 DEG C, atomizer rotating speed It is set as 25kr/min, slurry input speed is 22ml/min；
3. being heat-treated
By step 2. in obtained spherical powder be placed in vacuum sintering furnace and be heat-treated, heating rate is 10 DEG C/min, heat Treatment temperature is 1300 DEG C, heat treatment time 0.5h；Then room temperature is cooled to the furnace to get to cermet composite alloy Spherical powder.
Embodiment 10
1. dispensing batch mixing is dried
Weigh TiC0.7N0.3 powder:0.095kg；(Ti,10W,5Ta)C0.3N0.7:0.005kg；WC:3kg；Mo2C powder: 1.5kg；TaC powder:1kg；Cr3C2 powder:1kg；VC powder:0.5kg；Fe powder:2kg；Ni powder:0.9kg；SD glue 400g are added, it will be each Raw material is uniformly mixed by ball mill mixing method, and ball milling agent is acetone, then vacuum drying obtains mixture；
2. spheroidization
By step, 1. the broken sieving powdered of mixture obtained, the sieving sieve mesh number are 300 mesh；Then using rolling Powder spheroidization is used in combination the sieve of 60 mesh to be sieved, takes the powder by sieve by the method for cylinder spheroidization；Again with the sieve of 80 mesh Net sieving, take not the powder by sieve to get to the spherical powder of even particle size distribution；
3. sloughing forming agent and heat treatment
By step 2. in spherical powder obtained be put into vacuum sintering furnace, be evacuated to 1 × 10-1Pa hereinafter, being warming up to 450 DEG C of heat preservations, 5 hours forming agents added with removal；Then 1 × 10-1Pa is down in air pressure hereinafter, be warming up to again 1000 DEG C into Row is fired 3 hours；Then furnace cooling is to get to the spherical powder of cermet composite alloy；
The spheroidization process is that it is double-layer structure, hollow to use roller spheroidization, cylinder wall, and hollow space can It is passed through circulation water, at 50 DEG C, drum rotation speed 15r/min, the spheroidization time is 10min for water temperature control.
Embodiment 11
1. dispensing batch mixing is dried
Weigh TiC0.7N0.3 powder:3kg；(Ti,10W,8Mo)C0.5N0.5:1kg；WC：3kg；Mo2C：2kg；Fe powder: 1kg；Buna 450g is added, each raw material is uniformly mixed by ball mill mixing method, ball milling agent is acetone, then vacuum drying obtains Mixture；
2. being molded
It is used in combination the sieve of 60 mesh to be sieved to be granulated, is then molded the pellet green compact after granulation；
3. pre-burned and broken
By step 2. in green compact obtained be put into vacuum sintering furnace, be then continually fed into keep vacuum drying oven in air pressure be, The flowing Ar gas of 1200Pa is warming up to 400 DEG C of heat preservations, 6 hours forming agents added with removal；Then 1 × 10- is down in air pressure 1Pa is fired 3 hours hereinafter, being warming up to 1200 DEG C again；Then furnace cooling will be broken into 60 microns with sintered green compact Particle.
4. plasma discharging nodularization
By step 3. in composite cermet particle obtained be placed in ball in the radio frequency plasma spheroidization device of stable operation Change and obtains composite cermet spherical powder.Operation power is 60KW, and argon gas working flow is 30slpm, and argon gas protection flow is 120slpm, system negative pressure are 0.3atm, and powder feeding throughput is 6slpm, powder feed rate 30g/min.Wherein it is described electric discharge etc. from The temperature of bulbec plasma is 3200 DEG C.
Embodiment 12
1. dispensing batch mixing is dried
Weigh (Ti, 5W) C0.7N0.3 powder:8kg；Fe powder:2kg is added paraffin 500g, each raw material is passed through ball mill mixing Method is uniformly mixed, and ball milling agent is alcohol, then vacuum drying obtains mixture；
2. spheroidization
By step, 1. the broken sieving powdered of mixture obtained, the sieving sieve mesh number are 600 mesh；Then using rolling Powder spheroidization is used in combination the sieve of 90 mesh to be sieved, takes the powder by sieve by the method for cylinder spheroidization；Again with 100 purposes Sieve is sieved, take not the powder by sieve to get to the spherical powder of even particle size distribution；
3. sloughing forming agent and heat treatment
By step 2. in spherical powder obtained be put into vacuum sintering furnace, be then continually fed into keep vacuum drying oven in air pressure be The flowing Ar gas of 500Pa is warming up to 600 DEG C of heat preservations, 2 hours forming agents added with removal；Then 1 × 10- is down in air pressure 1Pa is fired 0.5 hour hereinafter, being warming up to 1300 DEG C again；Then furnace cooling is to get to the ball of cermet composite alloy Shape powder；
The spheroidization process is that it is double-layer structure, hollow to use roller spheroidization, cylinder wall, and hollow space can It is passed through circulation water, at 80 DEG C, drum rotation speed 35r/min, the spheroidization time is 20min for water temperature control.

Claims (9)

1. one kind being based on the coating spraying and 3D printing cermet material of (Ti, Me) CN-Co, it is characterised in that cermet material Material is spherical powder, and group, which is grouped as, includes by percentage to the quality：(Ti, Me) CN-Co and in Ni, Mo and Fe at least one Kind, the content of (Ti, Me) CN is 60~95%, Co and the content selected from least one of Ni, Mo and Fe is 5~40%；It is described Metal Me in (Ti, Me) CN is at least one of W, Mo, Ta, V, Cr, Nb and Zr.
2. cermet material according to claim 1, it is characterised in that it is total that the Me in (Ti, the Me) CN accounts for Ti and Me The 5~40% of quality.
3. the preparation method of cermet material described in claims 1 or 2, it is characterised in that comprise the following steps that：
(1) batch mixing is dried, and each raw material powder and ball milling agent of formula ratio are added to abundant ball milling mixing in ball milling mixing equipment Mixture is obtained, obtained mixture, which is placed in drying equipment, fully dries, and obtains drying mixture；
(2) the drying mixture that step (1) obtains was crushed 300~600 mesh sieve, sieving powder materials was sent by spheroidization powder Enter roller spheroidization equipment by powder spheroidization, more than 30 mesh and the spherical powder less than 120 mesh, i.e., then sieving removes grain size Obtain the spherical powder of even particle size distribution；
And forming agent is added before pelletizing；
(3) spherical powder made from step (2) is put into vacuum sintering furnace, is evacuated to 1 × 10-1Pa or less by sintering processes Or it is 500~1200Pa to be continually fed into Ar gas to keep air pressure in vacuum sintering furnace, and it is small to be warming up to 350~600 DEG C of heat preservations 2~8 When to remove the forming agent of addition, then in 1 × 10-1Pa of vacuum hereinafter, be warming up to 800~1300 DEG C fire 0.5~4 hour, Then furnace cooling is to get to the spherical powder of cermet composite alloy；
Or it comprises the following steps that：
(1) batch mixing is dried, and each raw material powder and ball milling agent of formula ratio are added to abundant ball milling mixing in ball milling mixing equipment Mixture is obtained, obtained mixture, which is placed in drying equipment, fully dries, and obtains drying mixture；
(2) green compact is molded, and the sieve sieving of 30~80 mesh of mixture made from step (1) is granulated, and then will be sieved pellet Green compact is molded；
And forming agent is added before pelletizing；
(3) fire broken, step (2) obtained in shaping blank merging vacuum sintering furnace, be evacuated to 1 × 10-1Pa or less or It is 500~1200Pa that person, which is continually fed into Ar gas and keeps air pressure in vacuum sintering furnace, is warming up to 350~600 DEG C and keeps the temperature 2~8 hours To remove forming agent, then fired 0.5~4 hour in 1 × 10-1Pa of vacuum hereinafter, being warming up to 800~1300 DEG C, then with stove It is cooling, sintered shaping blank is broken into 30-100 microns of particulate material；
(4) particulate material that the grain size that step (3) obtains is 30-100 microns is placed in radio frequency plasma ball by radio frequency plasma nodularization Makeup carries out nodularization in setting under argon gas is protected, and obtains the spherical powder of cermet composite alloy；
Or it comprises the following steps that：
(1) batch mixing is dried, and each raw material powder, ball milling agent and the forming agent of formula ratio are added to abundant ball in ball milling mixing equipment Mill is mixed to get mixed slurry；
(2) mist projection granulating, the slurry that step (1) is obtained are sent into centrifugal spray granulation drying machine and carry out mist projection granulating, obtain ball Shape powder；
(3) sintering heat treatment, the spherical powder that step (2) obtains is placed in vacuum sintering furnace, with the heating of 3~10 DEG C/min Rate is warming up to 800~1300 DEG C of 0.5~5h of sintering, then cools to room temperature with the furnace to get to cermet composite alloy Spherical powder.
4. the preparation method of cermet material according to claim 3, it is characterised in that ball milling mixing produces mixed slurry The ball milling agent that process is added is alcohol or acetone.
5. the preparation method of cermet material according to claim 3, it is characterised in that the forming agent be polyethylene glycol, One kind in paraffin, buna and SD glue, the addition of forming agent are the 0.5~5% of raw material powder gross mass.
6. according to claim 3 or the preparation method of 4 or 5 cermet materials, it is characterised in that powder spheroidization uses Spheroidization roller, cylinder wall be it is jacket structured, be passed through in chuck temperature be 50~80 DEG C of circulating water flows, drum rotation speed be 15~ 45r/min, spheroidization time are 10~20min.
7. according to claim 3 or the preparation method of 4 or 5 cermet materials, it is characterised in that radio frequency plasma nodularization It is 30~100KW that device, which runs power, and argon gas working flow is 15~40slpm, and it is 100~200slpm that argon gas, which protects flow, System negative pressure is 0.1~0.5atm, and powder feeding throughput is 2~8slpm, and powder feed rate is 20~60g/min.
8. the preparation method of cermet material according to claim 7, it is characterised in that the radio frequency plasma nodularization dress The temperature for the discharge plasma set is not less than 3200 DEG C.
9. according to claim 3 or the preparation method of 4 or 5 cermet materials, it is characterised in that the centrifugal spray is made Grain drying machine operation inlet temperature is 100~350 DEG C, and outlet temperature is set as 80~250 DEG C, and rotating speed is 10~25kr/min, slurry It is 5~22ml/min that material, which is sent into speed,.
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