CN106903319A - A kind of Multi-layer spherical material and preparation method thereof - Google Patents
A kind of Multi-layer spherical material and preparation method thereof Download PDFInfo
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- CN106903319A CN106903319A CN201710089886.5A CN201710089886A CN106903319A CN 106903319 A CN106903319 A CN 106903319A CN 201710089886 A CN201710089886 A CN 201710089886A CN 106903319 A CN106903319 A CN 106903319A
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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
- B22F9/02—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
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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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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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
- B22F1/16—Metallic particles coated with a non-metal
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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
- B22F1/17—Metallic particles coated with metal
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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
- B22F3/225—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 by injection molding
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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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/026—Spray drying of solutions or suspensions
Abstract
The invention discloses a kind of Multi-layer spherical material and preparation method thereof, the method is comprised the following steps：First material powder is once granulated to form the first spheroidal particle；First spheroidal particle is carried out into pre-sintering, to form spherical particle；Spherical particle is mixed with the second material powder carries out secondary granulation；Second spheroidal particle is carried out into secondary pre-sintering, sphere material is formed；The sphere material that will be obtained carries out subsequent forming technique.The preparation method of the Multi-layer spherical material that the present invention is provided, dusty material is carried out nodularization by the preparation method, the useful load and mobility of dusty material can be improved, abrasion of the high rigidity powder to equipment is reduced, the dimensional contraction amount of product can be reduced, reduce consumption of binder, greatly shorten degreasing time, improve production efficiency and size Control precision, the Multi-layer spherical material excellent combination property that the present invention is provided, have widened the range of application of material.
Description
Technical field
The present invention relates to powder metallurgical technology, more particularly, to a kind of Multi-layer spherical material and preparation method thereof.
Background technology
Powder metallurgy is used to producing metal dust or (or metal dust and inorganic non-metallic powder is mixed with metal dust
Compound) as raw material, the technical process such as by compacting or injection moulding and follow-up degreasing, sintering, manufacture metal material,
The technology of ceramic material and composite and all kinds product.
At present, powder metallurgy there is a problem in that：
For inorganic non-metallic ceramics material, because its fusion temperature is very high, it is impossible to carry out the atomization granulation of molten condition, no
Hard spheric granules can be formed；
Using injection molding technique, for high rigidity dusty material, because powder is aspherical, high rigidity dusty material with
Banbury, comminutor and injector wall friction, it is especially very big with the equipment surface scuffing amount that dusty material is contacted, easily cause
Dusty material pollutes, and surface color changes after causing dusty material to sinter, and influences material property；Simultaneously for fine powder material
Material can ensure there is preferable mobility, it is necessary to many binding agents coats and carry out banburying granulation, binder amount increase
Follow-up degreasing time can be caused to extend, product amount of contraction increases, product size is difficult to control to.
Using automatic dry pressuring forming process, aspherical powder does not have steady flow, and packed density is unstable, product
Quality control is difficult to stabilization；Simultaneously, it is necessary to many binding agents can just have shape-retaining ability, but many binding agents cause product again
Amount of contraction increases, and degreasing time is relative to be extended, and product size is difficult to control to.
In addition, some dusty material combination properties are poor, such as ceramic material or cermet material, although hardness is high,
But its sintering temperature is high, toughness is low, it is easy to brittle fracture, such as oxygen occur under conditions of with breach or shock loading
Change aluminium ceramics, zirconia ceramics and silicon nitride ceramics fracture toughness it is very low, it is impossible to enough prepare heat shock resistance and stress impact
Structural member.
Therefore, existing powder metallurgical technique technology can't resolve that product size precision controlling is difficult, yielding problem of Cracking with
And the problem of combination property difference, limit the application of powder material.
The content of the invention
It is an object of the present invention to provide a kind of new solution of Multi-layer spherical material.
It is a further object to provide a kind of new solution of the preparation method of Multi-layer spherical material.
According to the first aspect of the invention, there is provided a kind of preparation method of Multi-layer spherical material, comprise the following steps：
S101, the first material powder is once granulated, formed the first spheroidal particle；
S102, first spheroidal particle is carried out into pre-sintering, to form spherical particle；
S103, the spherical particle is mixed with the second material powder carry out secondary granulation, so that the second material powder bag
Spherical particle surface is overlayed on, the second spheroidal particle is obtained；
S104, the second spheroidal particle is carried out secondary pre-sintering, form sphere material；
S105, the sphere material for obtaining step S104 carry out subsequent forming technique.
Preferably, toughness of the toughness of first material powder less than second material powder.
Preferably, first material powder is selected from nonmetallic ceramics powder and/or metal ceramic powder, second material
Feed powder end is selected from any one or more mixture in nonmetallic ceramics powder, metal ceramic powder or metal dust.
Preferably, described nonmetallic ceramics powder is selected from oxide ceramics, nitride ceramics, boride ceramics or silication
In thing ceramics any one, described metal ceramic powder is selected from oxide base cermet, carbide-base ceramics, nitride
In based ceramic metal, boride-base cerment or silicide based ceramic metal any one, described metal dust is selected from transition
Metal.
Preferably, the first spheroidal particle in the step S101 is prepared via a method which：
S201, the first material powder, solvent and abrading-ball are placed in ball mill；
Binding agent is added in S202, mechanical milling process, and continues to be milled to well mixed；
After the completion of S203, ball milling, abrading-ball is filtered out, the suspension that ball milling mixing is completed is carried out into mist projection granulating, form institute
Need the first spheroidal particle.
Preferably, between step S104, S105, the step of third time is granulated at least also is included, to be formed at least
Three layers of Multi-layer spherical material, the Multi-layer spherical material constantly increases from inside to outside per layer of material toughness.
Preferably, the S102 steps, including：
First spheroidal particle is carried out into pre-sintering, to form interconnection spherical particle, the cause of the spherical particle
Density is 50% -90%；
Spherical particle to being connected with each other carries out swing crushing, forms the spherical particle of independent dispersion, and to scattered ball
Shape particle carries out gradation sizing, forms the different particle of size distribution.
Preferably, the S105 steps include：
Sphere material is screened, is noted after being granulated to the spherical bilayer material banburying that particle mean size is 15-20 μm
Penetrate shaping.
Preferably, the S105 steps include：
Sphere material is screened, the spherical bilayer material that particle mean size is 100-200 μm is carried out dry-pressing formed.
According to another aspect of the present invention, there is provided a kind of Multi-layer spherical material, the Multi-layer spherical material is according to above-mentioned
Preparation method be made.
The preparation method of the Multi-layer spherical material that the present invention is provided, dusty material carries out nodularization by the preparation method, can be with
The useful load and mobility of dusty material are improved, the abrasion to equipment is reduced, consumption of binder can be reduced, greatly shortened de-
The fat time, productivity ratio is improved, product constriction coefficient can be reduced, reduce deflection, improve product size control stability.Separately
Outward, the Multi-layer spherical material excellent combination property that the present invention is provided, has widened range of application.
It was found by the inventors of the present invention that existing powder metallurgical technique can't resolve the problem of material combination property difference.Therefore,
The technical assignment to be realized of the present invention or technical problem to be solved be it is that those skilled in the art never expect or
It is not expected that, therefore the present invention is a kind of Multi-layer spherical material and preparation method thereof new technical scheme.
By referring to the drawings to the detailed description of exemplary embodiment of the invention, further feature of the invention and its
Advantage will be made apparent from.
Brief description of the drawings
The accompanying drawing for being combined in the description and constituting a part for specification shows embodiments of the invention, and even
It is used to explain principle of the invention together with its explanation.
Fig. 1 is the process chart of the preparation method of the Multi-layer spherical material of the embodiment of the present invention；
Fig. 2 is the structural representation of the first material powder of the embodiment of the present invention；
Fig. 3 is the structural representation of the spherical particle of the embodiment of the present invention；
Fig. 4 is the structural representation of the second spheroidal particle of the embodiment of the present invention.
Specific embodiment
Describe various exemplary embodiments of the invention in detail now with reference to accompanying drawing.It should be noted that：Unless had in addition
Body illustrates that the part and the positioned opposite of step, numerical expression and numerical value for otherwise illustrating in these embodiments do not limit this
The scope of invention.
The description only actually at least one exemplary embodiment is illustrative below, never as to the present invention
And its any limitation applied or use.
May be not discussed in detail for technology, method and apparatus known to person of ordinary skill in the relevant, but suitable
In the case of, the technology, method and apparatus should be considered as a part for specification.
In all examples shown here and discussion, any occurrence should be construed as merely exemplary, without
It is as limitation.Therefore, other examples of exemplary embodiment can have different values.
It should be noted that：Similar label and letter represents similar terms in following accompanying drawing, therefore, once a certain Xiang Yi
It is defined in individual accompanying drawing, then it need not be further discussed in subsequent accompanying drawing.
The implication of the several keywords to being related in the present invention and the claim advocated is explained as follows below：
As used herein：
Degreasing：It refer to the technical process for removing binding agent in process of injection molding.
Sintering：Refer to the heat treatment by powder or the base substrate of preparation at a temperature of less than key component fusing point, and keep
The sufficiently long time is realized being densified completely or being almost densified completely, it is therefore intended that by intergranular metallurgy；
It is pre-sintered：Refer to the heating to pressed compact at a temperature of less than final sintering temperature, realize part densification
Process.
Toughness：It refer to the ability of material energy absorption in plastic deformation and fracture process.Toughness is better, then fragility occurs
The possibility of fracture is smaller.
Consistency：The complete fully dense percentage of the densification levels of sintering, i.e. actual density relative theory.
Useful load：Refer to that under the conditions of injection moulding is met, powder volume accounts for feeding (the i.e. mixing of powder and binding agent
Thing) volume percentage.
Wherein, useful load is low can cause Material shrinkage coefficient big, and size is unstable after material sintering, will also result in product each
Individual position distortions are inconsistent, cause internal stress to produce, and deposit deformation, problems of crack after sintering.
Particle mean size：The cumulative particle sizes percentile of one sample reaches particle diameter corresponding when 50%, its physics
Meaning is that particle diameter accounts for 50% more than its particle, and the particle less than it also accounts for 50%.
A kind of preparation method of Multi-layer spherical material is the embodiment of the invention provides, as shown in figure 1, comprising the following steps：
S101, the first material powder is once granulated, formed the first spheroidal particle.
Specifically, above-mentioned first spheroidal particle can be prepared via a method which：
S201, the first material powder of offer, add solvent and abrading-ball, are placed in ball mill together；
Binding agent is added in S202, mechanical milling process, and continues to be milled to well mixed；
After the completion of S203, ball milling, abrading-ball is filtered out, the suspension that ball milling mixing is completed is placed in sponging granulator, it is right
Above-mentioned suspension carries out a mist projection granulating, the first spheroidal particle needed for being formed.
Preferably, above-mentioned first material powder is selected from nonmetallic ceramics powder and/or metal ceramic powder, you can with right and wrong
The mixing of metal ceramic powder or metal ceramic powder any one, or two kinds.Wherein, nonmetallic ceramics powder is selected from oxygen
Compound ceramics (such as zirconium oxide, aluminum oxide, magnesia, calcium oxide or chromium oxide), nitride ceramics (such as titanium nitride, nitridation
Boron, silicon nitride and tantalum nitride, Talide, titanium carbide or titanium nitride), carbide ceramics (titanium carbonitride, carborundum,
Titanium carbide, titanium carbonitride or tungsten carbide), boride ceramics (titanium boride, tantalum boride, vanadium boride, chromium boride, zirconium boride, boronation
Tungsten, molybdenum boride, niobium (Nb) boride or hafnium boride) or silicide ceramics (such as silication manganese, iron suicide, cobalt silicide, nickle silicide, silication
Titanium, zirconium silicide, niobium silicide, vanadium silicide or niobium silicide) in any one；Described metal ceramic powder is selected from oxide base
Appoint in ceramics, carbide-base ceramics, nitride based ceramic metal, boride-base cerment or silicide based ceramic metal
It is a kind of.
Preferably, above-mentioned solvent can select water, or organic solvent, such as absolute ethyl alcohol, acetone, benzene or four chlorinations
Carbon etc..And above-mentioned ball milling can use various ball milling methods, for example planetary ball mill, rolling ball milling, stirring ball-milling, vibratory milling or
Sand mill etc., Ball-milling Time can be 10min -300h.
Preferably, above-mentioned binding agent can select polyvinyl alcohol, polyvinyl butyral resin, paraffin or rubber etc..
It should be noted that because the fusing point of various ceramic powders is very high, if it is desired to which it is atomized
Granulation, it is necessary to and its temperature high, more than 3500 DEG C, existing equipment cannot meet this temperature requirement to typical temperature, because
This above-mentioned first spheroidal particle is produced by mist projection granulating.
Further, have for the use for improving useful load, reducing follow-up binding agent, in step S101 certain particle size and
First spheroidal particle of size distribution is the screening that spheric granules is formed to step S203, and described size distribution can be 1 μ
The combination of the powder of m -300 μm particle size range, above-mentioned first spheroidal particle size distribution can be used for it is follow-up dry-pressing formed, and
If late stage process selects injection moulding, size distribution can be further defined to 15 μm -18 μm.It is obvious also possible to according to tool
Body, by changing the time that later-stage secondary is granulated, the first spheroidal particle granularity is defined as in the range of needs using needing.
First material powder structure of the embodiment of the present invention as shown in Fig. 2 spheroidizing of powder can avoid the damage to machine,
Apparent density of powder can be improved, the specific surface area of nodular powder particle is reduced, so that useful load is improved, and the first spherical grain
Sharp friction will not be produced between son, good fluidity, the first spheroidal particle force transmission effect be good in later stage moulding process, each portion
Divide density and stress distribution relatively uniform, therefore it is more preferable to be made the conformality of product.
S102, first spheroidal particle is carried out into pre-sintering, to form spherical particle, spherical particle configuration such as Fig. 3 institutes
Show, specifically include：
First spheroidal particle is carried out into pre-sintering, to form interconnection spherical particle, the cause of the spherical particle
Density is 50% -90%；
Spherical particle to being connected with each other carries out swing crushing, forms the spherical particle of independent dispersion, and to scattered ball
Shape particle carries out gradation sizing, forms the different particle of size distribution.
It refers to spherical when it is 50% -90% that spherical particle is by pre-sintered consistency that above-mentioned spherical particle is connected with each other
Grain is coupled together each other, but not exclusively bonds together into bulk, is easy to be broken into scattered spherical particle.Broken mesh
Mark is to break the adhesion part between the spherical particle during pre-sintering, and crumbling method is selected according to actual needs, can be with
Selection vibration screen is crushed, and vibration force size makes spheroidal particle not be broken in itself, only breaks the junction between particle.
The pre-sintering of the first spheroidal particle is carried out in sintering atmosphere in the embodiment of the present invention, before pre-sintering, first should
Spheric granules is put into debinding furnace, and degreasing is carried out under conventional degreasing condition, and the height of pre-sintering temperature is according to pre-sintered specific
The species setting of the first material powder, scope can be 300 DEG C -2000 DEG C.The pre-burning junction temperature of such as hard alloy particle particle
It is 1000 DEG C -1200 DEG C to spend, and the pre-sintering temperature of aluminum oxide is 1200 DEG C -1400 DEG C, so that spherical particle consistency is
50% -90%, spherical particle has certain intensity after pre-sintering, makes spherical particle during post-production, such as close
Be broken failure during refining, granulation or injection moulding.Also, spherical particle has some strength and densification after pre-sintering
Degree, can improve the useful load of powder, and spheroidal particle has excellent mobility relative to powder, and material is reduced after injection moulding
Material internal stress and skewness phenomenon, it is to avoid fragile material cracking after sintering.Wherein, sintering atmosphere is according to specific first material
The species of powder is selected, and can be air atmosphere, hydrogen atmosphere, inert gas atmosphere, methane gas atmosphere, nitrogen atmosphere
With one or more combinations of ammonia atmosphere.
S103, the spherical particle is mixed with the second material powder carry out secondary granulation, so that the second material powder bag
Spherical particle surface is overlayed on, the second spheroidal particle is obtained.Second material powder of the present embodiment is selected from nonmetallic ceramics powder, gold
Any one or more mixture in category ceramic powders or metal dust, wherein, nonmetallic ceramics powder is selected from can be selected from such as
Oxide ceramics (such as zirconium oxide, aluminum oxide, magnesia, calcium oxide or chromium oxide), nitride ceramics (such as titanium nitride, nitrogen
Change boron, silicon nitride and tantalum nitride, Talide, titanium carbide or titanium nitride), carbide ceramics (titanium carbonitride, carbonization
Silicon, titanium carbide, titanium carbonitride or tungsten carbide), boride ceramics (titanium boride, tantalum boride, vanadium boride, chromium boride, zirconium boride, boron
Change tungsten, molybdenum boride, niobium (Nb) boride or hafnium boride) or silicide ceramics (such as silication manganese, iron suicide, cobalt silicide, nickle silicide, silicon
Change titanium, zirconium silicide, niobium silicide, vanadium silicide or niobium silicide) in any one, described metal ceramic powder is selected from oxide fund
In category ceramics, carbide-base ceramics, nitride based ceramic metal, boride-base cerment or silicide based ceramic metal
Any one, described metal dust is selected from transition element, i.e. transition metal, it is to be understood that can also select as needed
The alloy of transition metal.
Preferably, toughness of the toughness of first material powder less than second material powder.First material powder
It is 3 with the mass ratio of the second material powder:1-1:3.It is understood that the hardness of the first material powder is high, toughness is low, second
The toughness of material powder is high, hardness is low, and double-decker connecting inner the first material powder high rigidity characteristic and outside second material
Feed powder end high tenacity characteristic, the double-decker of forming properties optimization.For example, the first material powder is less nonmetallic using toughness
Ceramic powders or metal ceramic powder any one, or its mixed-powder is obtained spherical particle, the second material powder using toughness compared with
Big ceramics, cermet or metal dust any one, or its mixed-powder carries out secondary granulation to spherical particle, makes original
Particle surface wraps up one layer of bigger ceramics of toughness, cermet or metal dust.
Wherein, the second material powder will mix with solvent and binding agent, and solvent is removed after mixing, then just with spherical particle
Carry out secondary granulation.
Preferably, the method for the secondary granulation is using rolling granulation or disc granulation.
S104, the second spheroidal particle is carried out secondary pre-sintering, form sphere material, as shown in Figure 4.Made by secondary
Particle after grain is sintered again, makes the second material powder for being wrapped in spherical particle surface Nian Jie with spherical particle firmly,
Form two-layer heterogeneity compound particle.Such as the first material powder is hardness nonmetallic ceramics powder high, the second material powder
End is toughness metal dust higher, and metal dust wraps up nonmetallic ceramics powder after secondary granulation, and it is metal to form outer layer
Material, liner is the double layer particle of ceramic material, and being then put into particle in the sintering furnace of reducing atmosphere carries out second pre-burning
Knot, in the presence of driving force is sintered, the fusing of metal dust part and infiltration to inside ceramic particle, formed have it is comprehensive very well
Close the spherical bilayer material of performance (such as high tenacity high rigidity).
Wherein, according to the species of the second material powder, sintering temperature is the 50%- of the melting temperature of the second material powder
90%, it is ensured that the second material powder part is melted and spherical particle is combined.Sintering atmosphere may be selected air gas according to powder weight
Atmosphere, hydrogen atmosphere, inert gas atmosphere, methane gas atmosphere, nitrogen atmosphere, one or more groups of decomposition ammonia atmosphere
Close.
More preferable intensity and consistency are made it have by carrying out pre-sintering to the second spheroidal particle, is further improved and is loaded
Amount, reduces material internal stress after injection moulding, it is to avoid fragile material ftractures；Meanwhile, with more preferable intensity, can avoid
Be broken failure during banburying, granulation or injection moulding.
Preferably, before the S104 steps, methods described also includes：
Spherical particle is screened according to size, obtains the spherical particle of different-grain diameter, choose different-grain diameter scope
Particle is mixed, and degreasing is carried out under degreasing condition.Wherein, the spherical particle of different-grain diameter is mixed, and can be improved
Useful load, so as to reduce the usage amount of binding agent, reduces degreasing time.
In an alternative embodiment of the invention, the step of third time is granulated at least also is being included after secondary granulation, to be formed extremely
Few three layers Multi-layer spherical material, the Multi-layer spherical material constantly increases from inside to outside per layer of material toughness.This area skill
Art personnel should be understood that Multi-layer spherical material is comprehensive according to the Multi-layer spherical material that the property difference of each layer of selection is obtained
Difference specifically can be adjusted the number of plies and each layer of material by matter according to use demand difference.
S105, the sphere material for obtaining step S104 carry out subsequent forming technique.Specifically include：
Sphere material is screened according to size, to particle mean size for 15-20 μm of spherical bilayer material carry out banburying,
Injection moulding is carried out after prilling；The spherical bilayer material that particle mean size is 100-200 μm is carried out dry-pressing formed, it is also possible to
In 3D printing technique.Certainly, particle mean size can be controlled by process conditions such as the times of secondary granulation, can be according to bilayer
The purposes of sphere material carries out the control of particle mean size.
The spherical bilayer material or Multi-layer spherical material of the embodiment of the present invention can use dry-pressing or injection molding.Example
The above-mentioned spherical bilayer material for preparing the preparation of Multi-layer spherical material preparation method is such as chosen, two kinds of materials are combined into a spherical material
Material, in injection moulding or dry-pressing formed and after carrying out degreasing, sintering process, layer materials be combined with each other, formed in it is hard outer
Tough composite structure, material possesses excellent combination property.
Specifically, dry process is to be mixed the sphere material of preparation with a small amount of binding agent, then suppressed,
Can be manual dry pressuring forming process, or automatic dry pressuring forming process, degreasing then be carried out to the blank after shaping, is burnt
Knot, forms final products blank.Binding agent is polyvinyl alcohol, polyvinyl butyral resin or paraffin, the mass fraction of binding agent
It is sphere material and the 0.1%-2% of binding agent gross mass.And degreasing can use thermal debinding process, can also be taken off using solvent
Fat technique, it would however also be possible to employ catalysis degreasing technique.
Injection molding technique is to be kneaded the sphere material of preparation and binding agent, and the material after mixing is cut
The particle of preparation is carried out injection moulding by granulation, preferably a diameter of 2-5mm, the cylindrical particle of length 3-10mm, is formed and produced
Product embryo material shape.Above-mentioned binding agent can be that wax-based binder, modeling based binder or water based adhesive, or two kinds are viscous
Tie the combination of agent；Above-mentioned degreasing can using thermal debinding process, solvent degreasing technique and catalysis degreasing technique, or this
The combination of several techniques；Above-mentioned sintering can be the combination of vacuum-sintering, atmosphere sintering, or several sintering process.
It should be noted that the degreasing time of the injection molding technique of existing some materials is up to tens hours, example
Such as cured base aluminum oxide or tungsten-carbide cermet, this causes greatly obstruction to production efficiency.In Multi-layer spherical material system
During standby, the present invention is processed by the way that degreasing is divided into several sections, carries out degreasing before pre-sintered and secondary pre-sintering, i.e.,
Spherical particle, the second spheroidal particle are carried out into degreasing and pre-sintering respectively, the spherical bilayer material for being formed below does not have binding agent.
Because spherical bilayer material is small relative to Specific Surface Area Measurement, therefore, spherical bilayer material in follow-up mixing, addition
The amount of binding agent is just relatively few, and the interstitial channels between void ratio original powder during degreasing between spheric granules are big, contract significantly
Short degreasing time, improves productivity ratio.
Embodiment 1
A kind of Multi-layer spherical material is the embodiment of the invention provides, the Multi-layer spherical material is according to embodiments of the present invention
Multi-layer spherical material preparation method is made；The preparation method, comprises the following steps：
The hard alloy tungsten carbide that particle mean size is 0.6 μm and particle mean size is 3 μm is chosen, and purity is 99.9%
Cobalt powder is used as raw material；It should be noted that the hard alloy tungsten carbide that particle mean size is 3 μm is 0.6 μm than particle mean size
The toughness of hard alloy tungsten carbide is big.
Configuration quality fraction is respectively two kinds of material mixed-powders of 3% cobalt, 97% tungsten carbide, wherein, mass fraction is
The particle mean size of 97% tungsten carbide is 0.6 μm；
Configuration quality fraction is respectively two kinds of material mixed-powders of 15% cobalt, 85% tungsten carbide, wherein, mass fraction is
The particle mean size of 85% tungsten carbide is 3 μm；
The mixed-powder of 3% cobalt of 4kg, 97% tungsten carbide is added in ball mill, absolute ethyl alcohol 4L works are continuously added
It is solvent, adds sintered carbide ball 6kg to carry out ball milling, ball milling adds the paraffin of 40g to continue ball milling afterwards for a period of time.Wherein, ball
Mill volume is 8L, and drum's speed of rotation is 350rpm, ball milling 5h, is discharged after ball milling, filters out sintered carbide ball, obtains above-mentioned mixed
Close the mixed liquor of powder；
Above-mentioned mixed liquor is added to carries out mist projection granulating in spray dryer, spray dryer rotating speed is 12000rpm,
Obtain spheric granules of the size distribution at 5 μm -35 μm.Spheric granules is put into debinding furnace again carry out degreasing, and skimming temp is
600 DEG C, the time is 3h, and is continuously heating to 1200 DEG C and carries out pre-sintering, obtains the spherical particle with some strength；
The spherical particle immersion such as polysaccharide solution of starch, and taking-up are dried, the ball of Surface coating polysaccharide is obtained
Shape particle；
Another 15% cobalt, the mixed-powder of 85% tungsten carbide for taking 3kg, adds absolute ethyl alcohol 4L as solvent, is put into planet
Mixed in ball mill, ball milling adds the paraffin of 40g to continue ball milling afterwards for a period of time, dry using vacuum drying mode after mixing
Dry removing solvent, then will the complete mixed-powder of drying and above-mentioned Surface coating polysaccharide spherical particle granulate in roller or
Rolling granulation is carried out in granulating disc, to obtain double-decker.The double-decker is one layer 15% of spherical particle Surface coating
The mixed-powder of cobalt, 85% tungsten carbide, carries out gradation sizing, obtains second spheroidal particle of the size distribution between 5-20 μm；
Degreasing and pre-sintering are carried out to the second spheroidal particle, degreasing time is 2h, and skimming temp is 600 DEG C, pre-burning junction temperature
It is 1200 DEG C to spend, and obtains spherical bilayer material.Spherical bilayer material is added into wax-based binder, dry-pressing formed, Huo Zheji is carried out
It is continuous to carry out mixing granulator, obtain the hard alloy feeding for injecting.
Embodiment 2
The present embodiment provides a kind of preparation method of Multi-layer spherical material, and the preparation method comprises the following steps：
By particle mean size for the zirconia material powder of 500nm adds planetary ball mill or sand mill, anhydrous second is added
The ratio of the mixed solvent of alcohol and acetone, wherein absolute ethyl alcohol and acetone respectively accounts for 50%, and solvent and zirconia material powder
Mass ratio is 6:1；Add a diameter of 3mm, 6mm, 10mm zirconium oxide balls, the zirconium oxide balls weight ratio of above-mentioned different-diameter
It is 5:3:2；And to the polyvinyl butyral resin of zirconium oxide weight 1.5% is added in mixed solvent, ball milling mixing 1 hour is filtered
Fall zirconium oxide balls, form zirconium oxide suspension.
The suspension of above-mentioned preparation is added to carries out mist projection granulating in sponging granulator, adjustable spraying drying machine rotating speed is extremely
8000rpm, drying machine inlet temperature is 80 DEG C, and outlet temperature is 100 DEG C, and regulation wriggling flow rate pump is 20ml/min, forms grain
Footpath is distributed as 5 μm -15 μm of zirconium oxide spheric granules；
Degreasing is carried out during zirconium oxide spheric granules is added into debinding furnace, degreasing maximum temperature is 600 DEG C, and degreasing time is
5h, after the completion of degreasing, carries out pre-sintered to zirconium oxide spheric granules or carries out pre-sintering, pre-burning in relaying air sintering furnace
Knot maximum temperature is 1200 DEG C, and being formed has some strength, the zirconium oxide spheroidal particle of mutual residual adhesion；
Zirconium oxide spheroidal particle to above-mentioned mutual residual adhesion is put into vibratory sieve, and adds hard alloy ball particle to shake
It is dynamic broken, gradation sizing is carried out, obtain the zirconium oxide spheroidal particle with different-grain diameter distribution；
Cobalt metal powder is taken, is added in ball mill, and be added thereto to the paraffin of organic solvent and 40g, and carry out ball
Mill mixing, incorporation time is 20min, filters out abrading-ball after being well mixed and is vacuum dried, and obtains being mixed with the cobalt dust of paraffin；
Screening particle diameter is 5-15 μm of zirconium oxide spheroidal particles of section, is put into starch solution, drying is then taken out, to surface
Have the cobalt dust for adding in sticking zirconium oxide spheroidal particle and being mixed with paraffin, zirconium oxide spheroidal particle and cobalt after cladding starch
The mass ratio of metal dust is 5:1, it is pre-mixed using V-type batch mixer, it is then placed in roller pelletizer or disc granulation
Secondary granulation is carried out in machine, the spherical bilayer particle of Surface coating cobalt metal powder is obtained, its particle mean size is 20 μm；
Then spherical bilayer particle is put into carries out degreasing and secondary pre-sintering in hydrogen furnace, pre-sintering temperature is 1100
DEG C, obtain the spherical bilayer material with some strength.
Above-mentioned spherical bilayer material, in order to increase mobility, adds in a concrete application in the spherical bilayer material
Enter the binding agents such as polyformaldehyde, high density polyethylene (HDPE), then carry out banburying granulation, obtain for injection molding technique feeding；
Injection moulding is carried out to feeding, required product shape is obtained, product is placed under reducing atmosphere and is sintered, sinter highest
Temperature is 1450 DEG C, is incubated two hours, obtains required sized products.
The secondary granulation of above-described embodiment can also be realized by following steps：
Cobalt metal powder is taken, is added in ball mill, and be added thereto to the paraffin of organic solvent and 40g, and carry out ball
Mill mixing, incorporation time is 20min, filters out abrading-ball after being well mixed and is vacuum dried, and obtains being mixed with the cobalt dust of paraffin；
During 15 μm -200 μm of zirconium oxide spheroidal particle is added into roller pelletizer or granulating disc, and add mixed
There is the cobalt powder of paraffin, secondary cladding granulation is carried out in comminutor, obtaining Surface coating has metallic cobalt powder, particle size distribution
It is 20-250 μm of spherical bilayer particle, the spherical bilayer particle can be used for dry-pressing formed.
In an alternative embodiment of the invention, there is provided a kind of Multi-layer spherical material, the Multi-layer spherical material is according to this hair
The preparation method of bright embodiment is made.
Although being described in detail to some specific embodiments of the invention by example, the skill of this area
Art personnel it should be understood that example above is merely to illustrate, rather than in order to limit the scope of the present invention.The skill of this area
Art personnel to above example it should be understood that can modify without departing from the scope and spirit of the present invention.This hair
Bright scope is defined by the following claims.
Claims (10)
1. a kind of preparation method of Multi-layer spherical material, it is characterised in that comprise the following steps：
S101, the first material powder is once granulated, formed the first spheroidal particle；
S102, first spheroidal particle is carried out into pre-sintering, to form spherical particle；
S103, the spherical particle is mixed with the second material powder carry out secondary granulation, so that the second material powder is coated on
Spherical particle surface, obtains the second spheroidal particle；
S104, the second spheroidal particle is carried out secondary pre-sintering, form sphere material；
S105, the sphere material for obtaining step S104 carry out subsequent forming technique.
2. method according to claim 1, it is characterised in that the toughness of first material powder is less than second material
The toughness at feed powder end.
3. method according to claim 2, it is characterised in that first material powder is selected from nonmetallic ceramics powder
And/or metal ceramic powder, second material powder is selected from nonmetallic ceramics powder, metal ceramic powder or metal dust
In any one or more mixture.
4. method according to claim 3, it is characterised in that described nonmetallic ceramics powder be selected from oxide ceramics,
In nitride ceramics, boride ceramics or silicide ceramics any one, described metal ceramic powder is selected from oxide base
Appoint in ceramics, carbide-base ceramics, nitride based ceramic metal, boride-base cerment or silicide based ceramic metal
One kind, described metal dust is selected from transition metal.
5. method according to claim 1, it is characterised in that the first spheroidal particle in the step S101 is by such as
It is prepared by lower section method：
S201, the first material powder, solvent and abrading-ball are placed in ball mill；
Binding agent is added in S202, mechanical milling process, and continues to be milled to well mixed；
After the completion of S203, ball milling, abrading-ball is filtered out, the suspension that ball milling mixing is completed is carried out into mist projection granulating, the needed for being formed
One spheroidal particle.
6. method according to claim 1, it is characterised in that between step S104, S105, at least also includes the
The step of three granulations, to form at least three layers of Multi-layer spherical material, the Multi-layer spherical material per layer of material toughness by
Constantly increase from inside to outside.
7. method according to claim 1, it is characterised in that the S102 steps, first spheroidal particle is carried out
When pre-sintered, to form interconnection spherical particle, the consistency of the spherical particle is 50% -90%；
Spherical particle to being connected with each other carries out swing crushing, forms the spherical particle of independent dispersion, and to scattered spherical
Grain carries out gradation sizing, forms the different particle of size distribution.
8. method according to claim 1, it is characterised in that the S105 steps include：
Sphere material is screened, is injected into after being granulated to the spherical bilayer material banburying that particle mean size is 15-20 μm
Type.
9. method according to claim 1, it is characterised in that the S105 steps include：
Sphere material is screened, the spherical bilayer material that particle mean size is 100-200 μm is carried out dry-pressing formed.
10. a kind of Multi-layer spherical material, it is characterised in that the Multi-layer spherical material is according to claim any one of 1-9
Preparation method be made.
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