CN108705086A - A kind of method that the printing of 3D gels prepares steel bonded carbide - Google Patents
A kind of method that the printing of 3D gels prepares steel bonded carbide Download PDFInfo
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- CN108705086A CN108705086A CN201810509081.6A CN201810509081A CN108705086A CN 108705086 A CN108705086 A CN 108705086A CN 201810509081 A CN201810509081 A CN 201810509081A CN 108705086 A CN108705086 A CN 108705086A
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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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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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
- B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
- B22F12/50—Means for feeding of material, e.g. heads
- B22F12/53—Nozzles
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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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
- B22F10/18—Formation of a green body by mixing binder with metal in filament form, e.g. fused filament fabrication [FFF]
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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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
- B33Y10/00—Processes of additive manufacturing
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
A kind of method that the printing of 3D gels prepares steel bonded carbide, belongs to material increasing field.By hard phase powders such as titanium carbides and as the iron(-)base powder uniform simultaneously drying and screening of alcohol ball milling mixing of Binder Phase.Mixed-powder is mixed into coupling agent to improve slurry stability again.Powder is uniformly mixed again to obtain printing slurry with premixed liquid made of organic monomer and solvent and dispersant.The printing slurry of preparation have the characteristics that stably dispersing, not free settling, be not easy to reunite, solid volume content it is higher.By adjusting the print parameters such as nozzle diameter, printing floor height, extruded velocity, print speed, realize that successively printing solidification obtains printing green body using 3D gel printers.Printing green body is obtained into steel bonded carbide product by drying, degreasing, high temperature sintering.The method of the present invention can prepare the steel bonded carbide product that complex-shaped, dimensional accuracy is high, even tissue, mechanical property are good.Raw material powder is easy to get, and adaptation material ranges are wide, and production efficiency is high, and manufacturing cost is low.
Description
Technical field
The present invention relates to a kind of methods that the printing of 3D gels prepares steel bonded carbide, belong to material increasing field.
Background technology
Three-dimensional fast shaping prints (three dimensional print) abbreviation 3D printing, also referred to as increasing material manufacturing.
3D printing technique is entirely different with traditional processing method, is based on threedimensional model technology, and by adding up layer by layer, processing is final to be obtained
To the technology of product.3D printing technique is related to multiple subjects such as CAD modelings, machinery, laser and material, by means of threedimensional model number
According to any complicated component can be manufactured by being molded using successively accumulation mode from bottom to top.3D gel printing shaping technologies
Comprehensive 3D direct writes printing and gel injection-moulding method under the control of the computer with the slurry configured carry out successively printing solidification and come
Formation of parts green body.Its printing " ink " is by having the characteristics that the slurry of shear shinning, high solid volume fraction is formed, printer
Slurry is ejected on print platform, while causing organic monomer in slurry in some way and occurring in very short time freely
Particle is carried out in-stiu coating by base polymerisation, the tridimensional network macromolecule organic of formation, the rapid solidified forming of slurry,
Slurry forms part blanks after printing solidified forming from level to level, and green compact finally obtain fine and close part after degreasing and sintering.
Steel bonded carbide is a kind of engineering material occurred in five sixties of eighties of last century, and steel bonded carbide is with steel
For Binder Phase, using refractory carbide, nitride and carbonitride etc. as the composite material of hard phase.Steel bonded carbide
In contain a large amount of steel matrix, therefore have heat-treatability and machinability.Simultaneously this kind of material with it is industrial in use it is various
Wear-resistant material, which is compared, has minimum friction coefficient.Therefore, the blank between high-speed steel and hard alloy has been filled up in its appearance.
Steel bonded carbide has extensive operational characteristic, good physical mechanical overall characteristic, excellent chemical stabilization
Property.These excellent performance characteristics make the application range of steel bonded carbide also increasingly increase, the gate applied such as plastics industry
Bushing, control plastics flow nozzle, lower blade, punch and mold；Making ide, scoring knife, volute mould, the punch of packing industry
With blank-holding tool etc., steel bonded carbide, which is particularly suitable for making, requires specular light, the high warm extrusion of surface no marking and drawing
Stretch mold.
Steel bonded carbide generally use powder metallurgy process prepare, PM technique by powder processed, forming, be sintered
To the metal product haveing excellent performance, make which obviate the defect generated in casting process and component segregations, and it may be implemented
Near-net-shape reduces later stage mach needs, to reduce the consumption of the energy and manpower by improving raw material availability.But
No matter it is using other manufacturing process such as compression moulding or injection mouldings, for preparing big part, shaped piece and other complexity are made
Product, conventional powder metallurgical method are all difficult to be competent at.Gel injection-moulding method developed in recent years, is similarly subjected to the limit of mold
New technology is urgently researched and developed in system, the preparation of steel bonded carbide.Therefore it is hard steel knot to may be implemented using such 3D gels printing technique
The 3D printing of matter alloy shapes, and improves its mechanical property, cost-effective.
Invention content
Manufacture that complex-shaped, dimensional accuracy is high the purpose of the present invention is to provide a kind of no mould low cost, near-net-shape
The method of steel bonded carbide product, to obtain the complicated shape steel bonded carbide product of excellent in mechanical performance.
The principle of the present invention is as follows：Steel bonded carbide raw material powder mixing process be the titanium carbide that will centainly match,
The hard phase powders such as tungsten carbide and as Binder Phase iron(-)base powder carry out rolling ball milling, ball-milling medium select alcohol, it
The raw material powder after ball milling is passed through into drying and screening afterwards, obtains uniform steel bonded carbide mixed-powder.Using wet-milling side
Method mixes steel bonded carbide raw material powder, obtains uniform raw material powder, improves slurry, printing green body and sintering
The uniformity of product afterwards.Before being mixed with organic matter printing system, it is added in above-mentioned steel bonded carbide mixed-powder even
Join agent titanate esters, to improve powder and print the affinity between organic-compound system, hence it is evident that improve the outstanding of final printing slurry
Buoyancy and stability.Prepare the organic matter premixed liquid of printing later, then by processed raw material powder and premixed liquid according to
Certain volume ratio is mixed, prepare stablize, not free settling, be not easy the high solid volume content reunited, have shearing become
The steel bonded carbide slurry of dilute feature.Then printed using 3D gel printers, in print procedure add initiator and
Catalyst or curing agent are cured with realizing in printing, by adjusting nozzle diameter, printing floor height, extruded velocity, print speed
Equal print parameters, to obtain the printing green body of high intensity.It will printing body drying, degreasing, high temperature sintering acquisition dense structure
Uniform steel bonded carbide product.
Based on principles above and purpose, the process of the method for the present invention includes：The preparation of steel bonded carbide raw material powder is beaten
The preparation of print material slurry, the setting of print parameters, printing, the high temperature sintering etc. for printing green body.Its concrete technology is as follows：
(1) by hard phase powder and iron(-)base powder ball milling, ball-milling medium uses alcohol, ball milling to use steel ball, ball material matter
Amount is than (3~8)：1, Ball-milling Time for 24 hours~48h, be dried in vacuo after ball milling and be sieved to obtain mixed-powder；
(2) in organic solvent by the dissolving of coupling agent titanate esters, the mixed-powder high speed shearing that step (1) is added is mixed
It closes, wherein titanate esters account for 0.3~0.8wt.% of mixed-powder, and organic solvent accounts for 5~8wt.% of mixed-powder；
(3) by organic monomer and organic solvent according to volume ratio 1：4~4：1 mixing, and point of 0.4~1.2wt.% is added
Powder is configured to the premixed liquid with organic monomer concentration 20vol.%~80vol.%；
(4) premixed liquid for obtaining the steel bonded carbide raw material powder that step (2) obtains with step (3) is according to volume ratio
(3~4)：1 mixing, stirs evenly the slurry that 50~65vol.% of solid volume content can be obtained；
(5) slurry that step (4) obtains is fitted into the barrel of 3D gel printers, by the article shape of required printing
Computer control system is imported to be printed, it is 0.1~1.0mm to print selected nozzle diameter, printable layer a height of 0.08~
0.8mm, rate of extrusion are 50.0~500.0mm3/ min, print speed are 5~20mm/s, often complete one layer of printing, spraying dress
One layer of misty initiator benzoyl peroxide (BPO) and catalyst n, N, N&apos will be sprayed to print surface by setting;,N'Tetramethyl second
Diamines (TEMED) is realized to be cured in printing；
(6) will print obtained green body be dried in vacuo 8 at 30~50 DEG C~for 24 hours, will protected by dry green body
Protect atmosphere in 100~400 DEG C of 5~10h of degreasing, then in a vacuum 1200~1500 DEG C progress high temperature sintering, sintering time 1
~2h obtains the steel bonded carbide product that dimensional accuracy is high, consistency is high, surface quality is good, comprehensive mechanical property is excellent.
Further, the hard phase powder is one kind in TiC, WC, Ti (C, N), and the hard phase Powder Particle Size is 1~20
Micron, accounts for 5~60wt.% in the alloy.
Further, the fe-based alloy powder is in iron powder, stainless steel powder, high temperature alloy powder, high speed comminuted steel shot, tool comminuted steel shot
It is a kind of；The mixed powder that ferrochrome powder, ferromanganese powder, ferrosilicon powder, nickel powder are formed either is added in iron powder；The fe-based alloy powder
Granularity is 100~500 mesh.
Further, the organic monomer is acrylamide, Methacrylamide, hydroxyethyl methacrylate (HEMA)
One kind, the organic solvent are one kind of toluene, ethyl alcohol, ortho-xylene, isopropanol.
Further, the dispersant is one kind in calgon, neopelex, sodium pyrophosphate.
Compared with prior art, the method have the advantages that：On the one hand, compared with existing 3D gels printing technique,
Prepared by the mixed powder of 1~step 4 of combining step, pretreatment, premixed liquid and slurry, make the hard phase powder of ceramic property with
The iron-based powder of metallicity can form suspension slurry uniform, stablize, dispersion, can make slurry that dispersion be kept to suspend
State 8 hours or more, ingredient and performance for follow-up 3D printing process and product uniformly establish good basis.On the other hand,
Compared with the 3D printings method such as laser 3D printing, the powder that the method for the present invention uses all is used in the conventional methods such as powder metallurgy
Powder passes through for example, TiC, WC, Ti (C, N) powder is all the powder for preparing hart metal product with conventional powder metallurgical method
Reduction, carbonization, ball mill crushing obtain, and shape is irregular；Without being for the methods of laser 3D printing specific customization
Spherical powder.Iron(-)base powder is also in this way, for example the method for the present invention can be using most common spongy in powder metallurgy
Reduced iron powder, cerioid are crushed iron alloy powder, can also use potato shape water-atomized iron powder, spherical aerosolization stainless steel, high temperature
The powder such as alloyed powder, high speed comminuted steel shot.Method for realizing 3D printing in a manner of powdering in the prior art, to the granularity model of powder
It encloses, apparent density, mobility also have strict demand；And the method for the present invention is also more loose to these parameter requests.Therefore, this hair
Bright method, without specifically limited, high without sphericity metal powder, is easy to obtain by conventional powder preparation method to raw material powder
, the advantages such as equipment cost is low, production efficiency is high are added, the cost of 3D printing steel bonded carbide can be greatly lowered.
And the high, mechanics by the Steel-bonded Cemented Carbide product consistency obtained by the printing of slurry and the sintering of printing green body
Performance is good, to make the method for the present invention have good mass industrial application value.
Specific implementation mode
The printing of 3D gels has material wide adaptation range (gold relative to other 3D printing techniques such as SLS/SLM, FDM, DIP
Belong to, ceramics and composite material), equipment cost low (no laser system and ultraviolet system), the advantages such as printing effect height.Using
3D gel printing techniques need to prepare stable slurry, successfully and are equably printed to be realized in print procedure, and protect
Demonstrate,prove the uniformity of product.Steel bonded carbide be in terms of ingredient by the bonding phase composition of the hard phase and ferrous metal of ceramic-like,
Raw material powder adheres to different materials type separately, and property is totally different.Therefore how to prepare stable slurry is one of important link.
The method of the present invention prepares the slurry that can be used for the printing of 3D gels by following 4 steps：
(1) by hard phase powder and iron(-)base powder ball milling, ball-milling medium uses alcohol, ball milling to use steel ball, ball material matter
Amount is than (3~8)：1, Ball-milling Time for 24 hours~48h, be dried in vacuo after ball milling and be sieved to obtain mixed-powder；
(2) in organic solvent by the dissolving of coupling agent titanate esters, the mixed-powder high speed shearing that step (1) is added is mixed
It closes, wherein titanate esters account for 0.3~0.8wt.% of mixed-powder, and organic solvent accounts for 5~8wt.% of mixed-powder；
(3) by organic monomer and organic solvent according to volume ratio 1：4~4：1 mixing, and point of 0.4~1.2wt.% is added
Powder is configured to the premixed liquid with organic monomer concentration 20vol.%~80vol.%；
(4) premixed liquid for obtaining the steel bonded carbide raw material powder that step (2) obtains with step (3) is according to volume ratio
(3~4)：1 mixing, stirs evenly the slurry that 50~65vol.% of solid volume content can be obtained.
Wherein step (1) is first that used various raw material powder ball milling mixings are uniform.Involved by the process
Hard phase powder is one kind in TiC, WC, Ti (C, N), and the hard phase Powder Particle Size is 1~20 micron, account for 5 in the alloy~
60wt.%；The fe-based alloy powder is one kind in iron powder, stainless steel powder, high temperature alloy powder, high speed comminuted steel shot, tool comminuted steel shot；Or
Person is the mixed powder for adding ferrochrome powder, ferromanganese powder, ferrosilicon powder, nickel powder in iron powder and being formed；The granularity of the fe-based alloy powder is
100~500 mesh.Due to differences such as the difference of powder properties and granularities, by the long period in the organic solvents such as ethyl alcohol ball
Mill, these raw material powder particle sizes is reduced, especially fe-based alloy powder, especially by the heterogeneity ball milling of these powder to
Even distribution just can guarantee final material tissue and the uniformity of performance in this way.Here powder cannot be printed with subsequent
Ball milling mixing is uniform together for machine objects system because powder be uniformly mixed need the time for 24 hours~48h, and organic object ties up to so
Cause character to change under long-time ball milling, is thickened and uneven；The uniformly mixed purpose of different powder is not achieved in short time ball milling.
Wherein step (2) is the addition coupling agent titanate esters in the powder mixed, can be first dissolved in titanate esters few
It measures in organic solvent, then is uniformly mixed by high speed shear.Here it is to preferably make to increase the effect of coupling agent titanate esters
Hard phase scatter in 3D printing organic-compound system.The prior art is only added in step (4) in no step (2)
Certain dispersant, since hard phase belongs to ceramic property, and granularity in the feed is thinner, can in tissue after the sintering
The segregation that can find hard phase, makes structural homogenity be deteriorated, and the data of mechanical property have larger discrete, and bending strength discreteness can
Up to 100MPa or more.Before mixed slurry is made, coupling agent titanate esters are added in the good powder of ball milling mixing, are had to hard phase
Strong adsorptivity improves the surface state of hard phase, behind be mixed again with organic-compound system slurry printing sintering after, group
There is no the segregation of hard phase, the discreteness of mechanical performance data to be clearly better in knitting, bending strength discreteness is obviously reduced
Within 20MPa.In addition, mixed a small amount of organic solvent for having dissolved titanate esters in the powder by high speed shear, it can high efficiency
It realizes mixing, reduces drying process, preparation printing slurry, process simplification can be directly used in.In particular, coupling is added herein
After agent titanate esters, the dispersibility of powder and suspension are obviously improved when step (4) being made to prepare slurry, and slurry stability is also by original
It being less than 4 hours when not adding, improves significantly to 8 hours or more, industrialization 3D printing slurry can be used as to use.And expect
The solid content of slurry is also increased to 65vol.% by original 55vol.%, this can reduce sintering shrinkage, and it is follow-up to be conducive to control
Sintering warpage obtains the more accurate product of size and shape.
When wherein step (3) prepares premixed liquid, the organic monomer described in the method for the present invention is acrylamide, methacryl
One kind of amine, hydroxyethyl methacrylate (HEMA), the organic solvent be toluene, ethyl alcohol, ortho-xylene, isopropanol one
Kind.Dispersant is also dissolved wherein, is conducive to dispersant and comes into full contact with powder particle surface, preferably play the work of dispersant
With.The dispersant is one kind in calgon, neopelex, sodium pyrophosphate.Organic list in premixed liquid
The ratio of body and solvent is adjusted according to combined factors such as required solids in pulp amount, viscosity and powder sizes.Then in step
(4) it will be uniformly mixed and be added to the powder of coupling agent and be uniformly mixed with premixed liquid, become printing slurry.
The process that above-mentioned steps 1~4 prepare 3D printing slurry is complementary, and only independent link adjusting all can not
It achieves the desired results.For example, the Ball-milling Time of step (1), ratio of grinding media to material will influence powder size, it will also influence coupling agent and divide
Powder dosage can influence solid content, influence viscosity, influence slurry stability.Therefore each ring to following processes is just needed
Section will be adjusted.Coupling agent used in amounts will be adjusted according to hard phase content, powder size, organic monomer and solvent ratios etc.
Section.The variation of its dosage can influence dispersant dosage, solid content, viscosity below, influence slurry stability.Organic monomer and solvent
Ratio needs are adjusted according to solid content, viscosity, powder size, coupling agent and dispersant dosage etc..
The present invention realizes that the 3D printing of product shapes by following steps (5)：
(5) slurry that step (4) obtains is fitted into the barrel of 3D gel printers, by the article shape of required printing
Computer control system is imported to be printed, it is 0.1~1.0mm to print selected nozzle diameter, printable layer a height of 0.08~
0.8mm, rate of extrusion are 50.0~500.0mm3/ min, print speed are 5~20mm/s, often complete one layer of printing, spraying dress
One layer of misty initiator benzoyl peroxide (BPO) and catalyst n, N, N&apos will be sprayed to print surface by setting;,N'Tetramethyl second
Diamines (TEMED) is realized to be cured in printing.
Slurry is printed as required product by the present invention in this step, first imports the drawing of product by processing
The computer control system of 3D gel printers, according to the viscosity of slurry and the setting printing of article shape and dimension precision requirement
Parameter, including nozzle diameter, printing floor height, rate of extrusion, print speed.Start print procedure after print parameters setting, beats
Print successively carries out, and often completes one layer of printing, and spraying device will spray one layer of misty initiator peroxidating to print surface
Benzoyl (BPO) and catalyst n, N, N',N'Tetramethylethylenediamine (TEMED), causes and accelerates the curing process, and will print shape
Shape is fixed, and is realized and is cured in printing, is successively stacked and is obtained end article.
Then, the method for the present invention is will to print body drying and sintering, technique such as step (6)：
(6) will print obtained green body be dried in vacuo 8 at 30~50 DEG C~for 24 hours, will protected by dry green body
Protect atmosphere in 100~400 DEG C of 5~10h of degreasing, then in a vacuum 1200~1500 DEG C progress high temperature sintering, sintering time 1
~2h obtains the steel bonded carbide product that dimensional accuracy is high, consistency is high, surface quality is good, comprehensive mechanical property is excellent.
Printing green body is taken off partial solvent and is further cured by drying, is carried out convenient for follow-up sintering process.Dry temperature
Degree is unsuitable excessively high, otherwise will cause to crack；Drying time wants long enough, otherwise can cause sintering crack.Sintering process is low early period
The organic-compound system of printing is first decomposed and is removed by thermophase, and the temperature and time in this removing stage will control proper, temperature
High de-agglomeration can cause to crack soon, and the low decomposition of temperature not exclusively heats up again also will appear same problem.It is also same road to remove the time
Reason.It is then warming up to high temperature sintering densification, obtains end article.Sintering temperature depends on hard phase content, hard phase content
High then sintering temperature is high.
Hard phase powder described in the method for the present invention is one kind in TiC, WC, Ti (C, N), and the hard phase Powder Particle Size is 1
~20 microns, 5~60wt.% is accounted in the alloy.These three hard phase powder are common in hard alloy, are also normal in the industry
See.Its granule size and content are determined according to application field.Fe-based alloy powder described in the method for the present invention is iron powder, stainless steel
One kind in powder, high temperature alloy powder, high speed comminuted steel shot, tool comminuted steel shot, selecting any as binder phase material is led according to application
Domain, such as corrosion-resistant field select stainless steel, heatproof field to select high temperature alloy, wear-resisting field selection high-speed steel or tool steel.
These powder are the types that field of powder metallurgy is related to, and iron powder is reduction method or water atomization production, and other alloyed powders are atomizations
Method produces.The alloying element of addition can also by adding the acquisitions such as ferrochrome powder, ferromanganese powder, ferrosilicon powder, nickel powder in iron powder, by
This alloying component designed.The granularity of the fe-based alloy powder is 100~500 mesh, and this range is common, thus may be used
To control the cost of raw material.
Compared with prior art, the method have the advantages that：On the one hand, compared with existing 3D gels printing technique,
Prepared by the mixed powder of 1~step 4 of combining step, pretreatment, premixed liquid and slurry, make the hard phase powder of ceramic property with
The iron-based powder of metallicity can form suspension slurry uniform, stablize, dispersion, can make slurry that dispersion be kept to suspend
State 8 hours or more, ingredient and performance for follow-up 3D printing process and product uniformly establish good basis.On the other hand,
Compared with the 3D printings method such as laser 3D printing, the powder that the method for the present invention uses all is used in the conventional methods such as powder metallurgy
Powder passes through for example, TiC, WC, Ti (C, N) powder is all the powder for preparing hart metal product with conventional powder metallurgical method
Reduction, carbonization, ball mill crushing obtain, and shape is irregular；Without being for the methods of laser 3D printing specific customization
Spherical powder.Iron(-)base powder is also in this way, for example the method for the present invention can be using most common spongy in powder metallurgy
Reduced iron powder, cerioid are crushed iron alloy powder, can also use potato shape water-atomized iron powder, spherical aerosolization stainless steel, high temperature
The powder such as alloyed powder, high speed comminuted steel shot.Method for realizing 3D printing in a manner of powdering in the prior art, to the granularity model of powder
It encloses, apparent density, mobility also have strict demand；And the method for the present invention is also more loose to these parameter requests.Therefore, this hair
Bright method, without specifically limited, high without sphericity metal powder, is easy to obtain by conventional powder preparation method to raw material powder
, the advantages such as equipment cost is low, production efficiency is high are added, the cost of 3D printing steel bonded carbide can be greatly lowered.
And the high, mechanics by the Steel-bonded Cemented Carbide product consistency obtained by the printing of slurry and the sintering of printing green body
Performance is good, to make the method for the present invention have good mass industrial application value.
Embodiment 1
(1) by the iron powder ball milling of 1~2 micron of TiC powder and 400 mesh, hard phase accounts for 5wt.%, ball milling in entire alloy
Medium uses alcohol, ball milling to use steel ball, ball material mass ratio 3：1, Ball-milling Time 48h are dried in vacuo after ball milling and are sieved to obtain
Mixed-powder；
(2) in organic solvent by the dissolving of coupling agent titanate esters, the mixed-powder high speed shearing that step (1) is added is mixed
It closes, wherein titanate esters account for mixed-powder 0.3wt.%, and organic solvent accounts for mixed-powder 5wt.%；
(3) by organic monomer and organic solvent according to volume ratio 1：4 mixing, and the dispersant of 0.4wt.% is added, it prepares
At the premixed liquid with organic monomer concentration 20vol.%；The organic monomer is acrylamide, and the organic solvent is
Toluene, the dispersant are calgon；
(4) premixed liquid for obtaining the steel bonded carbide raw material powder that step (2) obtains with step (3) is according to volume ratio
3：1 mixing, stirs evenly the slurry that solid volume content 50vol.% can be obtained；
(5) slurry that step (4) obtains is fitted into the barrel of 3D gel printers, by the article shape of required printing
It imports computer control system to be printed, it is 0.1mm, a height of 0.08mm of printable layer to print selected nozzle diameter, is squeezed out
Rate is 50.0mm3/ min, print speed 5mm/s, often complete one layer of printing, and spraying device will spray one layer to print surface
Misty initiator benzoyl peroxide (BPO) and catalyst n, N, N',N'Tetramethylethylenediamine (TEMED) realizes side printing
Side cures；
(6) obtained green body will be printed and is dried in vacuo 8h at 30 DEG C, by the green body by drying in protective atmosphere
100~400 DEG C of degreasing 5h, then 1200 DEG C of progress high temperature sinterings, sintering time 1h in a vacuum, obtain dimensional accuracy it is high,
The steel bonded carbide product that consistency is high, surface quality is good, comprehensive mechanical property is excellent.
Embodiment 2
(1) by 15~20 microns of Ti (C, N) powder and the stainless steel powder ball milling of 100 mesh, hard phase accounts in entire alloy
15wt.%, ball-milling medium use alcohol, ball milling to use steel ball, ball material mass ratio 8：1, for 24 hours, vacuum is dry after ball milling for Ball-milling Time
Dry and sieving obtains mixed-powder；
(2) in organic solvent by the dissolving of coupling agent titanate esters, the mixed-powder high speed shearing that step (1) is added is mixed
It closes, wherein titanate esters account for mixed-powder 0.5wt.%, and organic solvent accounts for mixed-powder 6wt.%；
(3) by organic monomer and organic solvent according to volume ratio 4：1 mixing, and the dispersant of 1.2wt.% is added, it prepares
At the premixed liquid with organic monomer concentration 80vol.%；The organic monomer is Methacrylamide, and described is organic molten
Agent is ethyl alcohol, and the dispersant is neopelex；
(4) premixed liquid for obtaining the steel bonded carbide raw material powder that step (2) obtains with step (3) is according to volume ratio
4：1 mixing, stirs evenly the slurry that solid volume content 65vol.% can be obtained；
(5) slurry that step (4) obtains is fitted into the barrel of 3D gel printers, by the article shape of required printing
It imports computer control system to be printed, it is 1.0mm, a height of 0.8mm of printable layer to print selected nozzle diameter, squeezes out speed
Rate is 500.0mm3/ min, print speed 20mm/s, often complete one layer of printing, and spraying device will spray one layer to print surface
Misty initiator benzoyl peroxide (BPO) and catalyst n, N, N',N'Tetramethylethylenediamine (TEMED) realizes side printing
Side cures；
(6) obtained green body will be printed to be dried in vacuo at 50 DEG C for 24 hours, by the green body by drying in protective atmosphere
100~400 DEG C of degreasing 10h, then 1350 DEG C of progress high temperature sinterings, sintering time 2h in a vacuum, obtain dimensional accuracy it is high,
The steel bonded carbide product that consistency is high, surface quality is good, comprehensive mechanical property is excellent.
Embodiment 3
(1) the high-speed steel sphere of powder of 2~3 microns of WC powder and 300 mesh being ground, hard phase accounts for 35wt.% in entire alloy,
Ball-milling medium uses alcohol, ball milling to use steel ball, ball material mass ratio 6：1, Ball-milling Time 36h are dried in vacuo and are sieved after ball milling
Obtain mixed-powder；The mixed powder that ferrochrome powder, ferromanganese powder, ferrosilicon powder, nickel powder are formed either is added in iron powder；
(2) in organic solvent by the dissolving of coupling agent titanate esters, the mixed-powder high speed shearing that step (1) is added is mixed
It closes, wherein titanate esters account for mixed-powder 0.4wt.%, and organic solvent accounts for mixed-powder 6wt.%；
(3) by organic monomer and organic solvent according to volume ratio 1：1 mixing, and the dispersant of 0.8wt.% is added, it prepares
At the premixed liquid with organic monomer concentration 50vol.%；The organic monomer is hydroxyethyl methacrylate (HEMA), institute
The organic solvent stated is ortho-xylene, and the dispersant is sodium pyrophosphate；
(4) premixed liquid for obtaining the steel bonded carbide raw material powder that step (2) obtains with step (3) is according to volume ratio
3：1 mixing, stirs evenly the slurry that solid volume content 50vol.% can be obtained；
(5) slurry that step (4) obtains is fitted into the barrel of 3D gel printers, by the article shape of required printing
It imports computer control system to be printed, it is 0.5mm, a height of 0.48mm of printable layer to print selected nozzle diameter, is squeezed out
Rate is 250mm3/ min, print speed 10mm/s, often complete one layer of printing, and spraying device will spray one layer to print surface
Misty initiator benzoyl peroxide (BPO) and catalyst n, N, N',N'Tetramethylethylenediamine (TEMED) realizes side printing
Side cures；
(6) obtained green body will be printed and is dried in vacuo 12h at 40 DEG C, by the green body by drying in protective atmosphere
100~400 DEG C of degreasing 8h, then 1400 DEG C of progress high temperature sinterings, sintering time 1.5h obtain dimensional accuracy in a vacuum
Steel bonded carbide product high, consistency is high, surface quality is good, comprehensive mechanical property is excellent.
Embodiment 4
(1) the tool steel sphere of powder of 5~6 microns of TiC powder and 400 mesh is ground, hard phase accounts in entire alloy
40wt.%, ball-milling medium use alcohol, ball milling to use steel ball, ball material mass ratio 5：1, Ball-milling Time 40h, vacuum is dry after ball milling
Dry and sieving obtains mixed-powder；The mixed powder that ferrochrome powder, ferromanganese powder, ferrosilicon powder, nickel powder are formed either is added in iron powder；
(2) in organic solvent by the dissolving of coupling agent titanate esters, the mixed-powder high speed shearing that step (1) is added is mixed
It closes, wherein titanate esters account for mixed-powder 0.7wt.%, and organic solvent accounts for mixed-powder 7wt.%；
(3) by organic monomer and organic solvent according to volume ratio 3：1 mixing, and the dispersant of 1.0wt.% is added, it prepares
At the premixed liquid with organic monomer concentration 75vol.%；The organic monomer is Methacrylamide, and described is organic molten
Agent is isopropanol, and the dispersant is neopelex；
(4) premixed liquid for obtaining the steel bonded carbide raw material powder that step (2) obtains with step (3) is according to volume ratio
4：1 mixing, stirs evenly the slurry that solid volume content 65vol.% can be obtained；
(5) slurry that step (4) obtains is fitted into the barrel of 3D gel printers, by the article shape of required printing
It imports computer control system to be printed, it is 0.4mm, a height of 0.38mm of printable layer to print selected nozzle diameter, is squeezed out
Rate is 300.0mm3/ min, print speed 15mm/s, often complete one layer of printing, and spraying device will spray one to print surface
Layer misty initiator benzoyl peroxide (BPO) and catalyst n, N, N',N'Tetramethylethylenediamine (TEMED) realizes that side is beaten
Print side solidification；
(6) obtained green body will be printed and is dried in vacuo 20h at 50 DEG C, by the green body by drying in protective atmosphere
100~400 DEG C of degreasing 8h, then 1480 DEG C of progress high temperature sinterings, sintering time 2h in a vacuum, obtain dimensional accuracy it is high,
The steel bonded carbide product that consistency is high, surface quality is good, comprehensive mechanical property is excellent.
Embodiment 5
(1) by the iron powder ball milling of 2~3 microns of TiC powder and 400 mesh, hard phase accounts for 60wt.%, ball in entire alloy
Grinding media uses alcohol, ball milling to use steel ball, ball material mass ratio 6：1, Ball-milling Time 48h are dried in vacuo and are sieved after ball milling
To mixed-powder；Ferrochrome powder 6wt%, ferromanganese powder 2wt%, ferrosilicon powder 0.5wt%, nickel powder 1.5wt% are added wherein in iron powder；
(2) in organic solvent by the dissolving of coupling agent titanate esters, the mixed-powder high speed shearing that step (1) is added is mixed
It closes, wherein titanate esters account for mixed-powder 0.8wt.%, and organic solvent accounts for mixed-powder 8wt.%；
(3) by organic monomer and organic solvent according to volume ratio 1：4 mixing, and the dispersant of 1.2wt.% is added, it prepares
At the premixed liquid with organic monomer concentration 20vol.%；The organic monomer is acrylamide, and the organic solvent is
Ortho-xylene, the dispersant are sodium pyrophosphate；
(4) premixed liquid for obtaining the steel bonded carbide raw material powder that step (2) obtains with step (3) is according to volume ratio
4：1 mixing, stirs evenly the slurry that solid volume content 65vol.% can be obtained；
(5) slurry that step (4) obtains is fitted into the barrel of 3D gel printers, by the article shape of required printing
It imports computer control system to be printed, it is 0.2mm, a height of 0.18mm of printable layer to print selected nozzle diameter, is squeezed out
Rate is 150mm3/ min, print speed 8mm/s, often complete one layer of printing, and spraying device will spray one layer to print surface
Misty initiator benzoyl peroxide (BPO) and catalyst n, N, N',N'Tetramethylethylenediamine (TEMED) realizes side printing
Side cures；
(6) obtained green body will be printed and is dried in vacuo 16h at 40 DEG C, by the green body by drying in protective atmosphere
100~400 DEG C of degreasing 6h, then 1500 DEG C of progress high temperature sinterings, sintering time 2h in a vacuum, obtain dimensional accuracy it is high,
The steel bonded carbide product that consistency is high, surface quality is good, comprehensive mechanical property is excellent.
Claims (5)
1. a kind of method that the printing of 3D gels prepares steel bonded carbide, it is characterised in that including steps are as follows：
(1) by hard phase powder and fe-based alloy powder ball milling, ball-milling medium uses alcohol, ball milling to use steel ball, ball material mass ratio (3
~8)：1, Ball-milling Time for 24 hours~48h, be dried in vacuo after ball milling and be sieved to obtain mixed-powder；
(2) in organic solvent by the dissolving of coupling agent titanate esters, the mixed-powder high speed shear-mixed of step (1) is added,
Middle titanate esters account for 0.3~0.8wt.% of mixed-powder, and organic solvent accounts for 5~8wt.% of mixed-powder；
(3) by organic monomer and organic solvent according to volume ratio 1：4~4：1 mixing, and the dispersion of 0.4~1.2wt.% is added
Agent is configured to the premixed liquid with organic monomer concentration 20vol.%~80vol.%；
(4) premixed liquid for obtaining steel bonded carbide raw material powder that step (2) obtains with step (3) according to volume ratio (3~
4)：1 mixing, stirs evenly the slurry that 50~65vol.% of solid volume content can be obtained；
(5) slurry that step (4) obtains is fitted into the barrel of 3D gel printers, the article shape of required printing is imported
Computer control system is printed, and it is 0.1~1.0mm to print selected nozzle diameter, and printable layer a height of 0.08~
0.8mm, rate of extrusion are 50.0~500.0mm3/ min, print speed are 5~20mm/s, often complete one layer of printing, spraying dress
One layer of misty initiator benzoyl peroxide (BPO) and catalyst n, N, N&apos will be sprayed to print surface by setting;,N'Tetramethyl second
Diamines (TEMED) is realized to be cured in printing；
(6) will print obtained green body be dried in vacuo 8 at 30~50 DEG C~for 24 hours, by by dry green body in protection gas
100~400 DEG C of 5~10h of degreasing in atmosphere, then in a vacuum 1200~1500 DEG C progress high temperature sintering, sintering time be 1~
2h obtains the steel bonded carbide product that dimensional accuracy is high, consistency is high, surface quality is good, comprehensive mechanical property is excellent.
2. the method that 3D gels printing as described in claim 1 prepares steel bonded carbide, it is characterised in that：The hard
Phase powder is one kind in TiC, WC, Ti (C, N), and the hard phase Powder Particle Size is 1~20 micron, account for 5 in the alloy~
60wt.%.
3. the method that 3D gels printing as described in claim 1 prepares steel bonded carbide, it is characterised in that：The iron-based closes
Bronze is one kind in iron powder, stainless steel powder, high temperature alloy powder, high speed comminuted steel shot, tool comminuted steel shot；Chromium is either added in iron powder
The mixed powder that iron powder, ferromanganese powder, ferrosilicon powder, nickel powder are formed；The granularity of the fe-based alloy powder is 100~500 mesh.
4. the method that 3D gels printing as described in claim 1 prepares steel bonded carbide, it is characterised in that：Described is organic
Monomer is one kind of acrylamide, Methacrylamide, hydroxyethyl methacrylate (HEMA), and the organic solvent is first
One kind of benzene, ethyl alcohol, ortho-xylene, isopropanol.
5. the method that 3D gels printing as described in claim 1 prepares steel bonded carbide, it is characterised in that：The dispersion
Agent is one kind in calgon, neopelex, sodium pyrophosphate.
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| CN113118455A (en) * | 2021-04-23 | 2021-07-16 | 吉林大学重庆研究院 | 3D printing method for preparing metal artificial bone based on slurry direct writing |
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| CN113600830B (en) * | 2021-08-30 | 2022-06-21 | 北京工业大学 | Method for hard alloy photoprinting using responsive polymer matrix |
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