CN106835116A - A kind of coated carbides matrix and preparation method thereof - Google Patents
A kind of coated carbides matrix and preparation method thereof Download PDFInfo
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- CN106835116A CN106835116A CN201710157652.XA CN201710157652A CN106835116A CN 106835116 A CN106835116 A CN 106835116A CN 201710157652 A CN201710157652 A CN 201710157652A CN 106835116 A CN106835116 A CN 106835116A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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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
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
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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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
Alloy material and its design principle of preparation technology that the present invention is ensured based on the thing phase lattice mismatch regulation and control of film base interface and its regulation and control validity, there is provided a kind of coated carbides matrix that high film-substrate cohesion can be formed with metal nitride.Hard alloy substrate material of the present invention is WC-Co based alloys；By adding Mo simultaneously in the alloy2C and Ru, regulates and controls to WC bases hard phase and Co base Binder Phase lattice parameters respectively, promotes metal nitride film forming core, stable interface thing phase crystal structure to realize the Effective Regulation to film base interface thing phase lattice mismatch；Mo in WC-Co based alloys2C is (10~15) with Co mass ratioes, Ru and Co mass ratioes:100, WC 1.5 μm of base Hard Phase Grain Size ＜, Co bases Binder Phase is close-packed hexagonal structure.Prepared using wet-milling, drying and granulating, the compressing, technique of pressure sintering containing CO.
Description
Technical field
The present invention relates to a kind of coated carbides matrix and preparation method thereof, belong to composite powder metallurgy material technology neck
Domain.
Background technology
Coated carbides is made up of hard alloy substrate and coating two parts, and coated carbides matrix refers to be used as to apply
The special matrix of layer hard alloy, abbreviation hard alloy substrate.Combination at hard alloy substrate and coating interface between atom
State (i.e. coherence, half coherence and non-coherence) and its stability, to the film-substrate cohesion between hard alloy substrate and coating and
Its stability tool has a significant impact.Improve film-substrate cohesion and its stability be improve cutting tool coated with hard alloy product quality and
The important means of service life.Because spacing of lattice mismatch, asynchronous forming core, alloy bonding phase crystal structure are unstable, boundary
The reasons such as face heterogeneous microstructure is uneven, boundary defect, internal stress, at hard alloy substrate and coating interface between atom
With reference to typically with the presence of non-co- case form.
Existing coated carbides matrix, mainly there is the materials such as WC-Co (YG) and WC-(W, Ti) C-(Ta, Nb) C-Co (YW)
Matter.From the angle for characterizing alloying component, YW alloys basis can be represented with WC-TiC-TaC-NbC-Co.YG and YW hard is closed
Gold bonds phase composition by hard phase and Co bases, and the grain size of WC hard phases is closely related with WC raw material granularities in alloy.By original
Expect the selection of wc grain size, it is possible to achieve the regulation and control to WC grain degree in alloy.
Metal nitride is the most common material in coated carbides floating coat part.Metal nitride is usually cubic crystal
Body structure, because with high rigidity, high-wearing feature, excellent high-temperature oxidation resistance, stable chemical nature high and good
Decay resistance, in addition to the surface as cutting tool is modified, is also widely used for the various complexity such as high temperature, humidity, salinity high
The surfacecti proteon of instrument under military service working condition.Used as typical metal nitride, AlTiN, TiSiN, AlCrN are more normal at present
Commercialization coating.Above-mentioned metal nitride generally have with AlN or TiN identical crystal structures, other alloying elements lead to
Often it is solid-solubilized in AlN or TiN lattices, forms solid solution.To AlTiN, when wherein the atomic fraction of Ti is higher than Al, then formed
The crystal structure of TiN；When wherein the atomic fraction of Al is higher than Ti, then the crystal structure of AlN is formed.
On how to improve the existing many reports of coating film-substrate cohesion, such as open and stand and report " a kind of hard alloy and
The method for improving its PVD coating film-substrate cohesion " (application for a patent for invention number 201410376915.2), it is proposed that one kind is based on changing
The forming core condition and its forming core homogenieity of kind metal nitride coatings, so that it is steady with enhancing film-substrate cohesion to strengthen film-substrate cohesion
Qualitatively effective ways.
The present inventor sends out when continuation is studied and effectively improves the bond strength, i.e. film-substrate cohesion between coating and matrix
Now currently without the coating substance phase based on hard phase in hard alloy substrate and Binder Phase lattice parameter with its surface directly contact
Between lattice constant match degree regulation and control and its regulation and control validity safeguards technique principle report.Inventor sends out in an experiment simultaneously
It is existing：In coating and matrix combination interface position, coherence or semicoherent interface are formed, especially form coherent boundary, can effectively carried
High film-substrate cohesion.While inventor also found, appropriate Mo is added simultaneously in the alloy2C and Ru, can significantly reduce hard conjunction
Lattice mismatch between auri body thing phase and coating substance phase.Based on above-mentioned discovery and a series of experiment, inventor finds
Effectively improve another approach of coating film-substrate cohesion, and then draw the present invention.
The content of the invention
It is an object of the present invention to provide a kind of coated carbides matrix.
It is a further object to provide a kind of preparation method of coated carbides matrix, to effectively improve coating
The film-substrate cohesion and its stability of hard alloy, extend the service life of coated carbides.
A kind of coated carbides matrix of the present invention, the hard alloy substrate is to be based on film base interface between coating and matrix
The alloy material design principle of place's thing phase lattice mismatch regulation and control and its regulation and control validity guarantee is designed.The hard alloy
After matrix is combined with its face coat, the feature with high film-substrate cohesion, film base interface stable existence lattice mismatch | δ |
=(as–ac)/acThe coherence and/or semicoherent interface of ＜ 5~25%, wherein | δ | is lattice mismatch, asFor in matrix thing phase
The interplanar distance of crystal face A, acIt is the interplanar distance of crystal face B in coating substance phase.The crystal face A and crystal face B is in epitaxial growth relation.
A kind of coated carbides matrix of the present invention, the hard alloy substrate material is WC-Co base cemented carbides；It is described
Contain Mo simultaneously in WC-Co base cemented carbides2C and Ru alloy additions；WC base hard phases in the WC-Co base cemented carbides
The crystal structure of 1.5 μm of grain size ＜, Co base Binder Phase is close-packed hexagonal structure；It is containing gold with the coating that described matrix matches
Belong to the coating of nitride.
A kind of coated carbides matrix of the present invention, by making an addition to the Mo in WC-Co based alloys simultaneously2C and Ru is burning
Solid solution is formed during knot, WC bases hard phase and Co base Binder Phase lattice parameters are regulated and controled respectively, promote coated film
Forming core, stabilization film base interface thing phase crystal structure, so as to realize the Effective Regulation to film base interface thing phase lattice mismatch.
Preferably, a kind of coated carbides matrix of the invention, Mo in the WC-Co base cemented carbides2C and Co
Mass ratio is (10~15):100, Ru is (10~15) with Co mass ratioes:100.
Preferably, a kind of coated carbides matrix of the invention, the WC-Co base cemented carbides include YG alloys
With YW alloys；In the YG alloys, except Mo2Outside C and Ru, the mass ratio ＜ 2 of other alloy addition total amounts and alloy total amount:
100。
Preferably, the YW alloys are the WC-Co base cemented carbides of-NbC of-TaC containing TiC, except Mo2Outside C and Ru,
The mass ratio ＞ 2 of other alloy addition total amounts and alloy total amount:100.Described other alloy additions include TiC, TaC, NbC
Deng.
Pressed as preferred side, a kind of coated carbides matrix of the invention, the YG alloys are closed including Ultra-fine Grained YG hard
Gold.More preferably containing the Ultra-fine Grained YG hard alloy of the grain growth inhibitors such as Cr, V.
A kind of coated carbides matrix of the present invention, the coating containing metal nitride includes individual layer and laminated coating；
Either individual layer or laminated coating, with described matrix directly in conjunction with coating material be metal nitride.
A kind of coated carbides matrix of the present invention, it is described with matrix directly in conjunction with metal nitride have with AlN or
TiN identical crystal structures.As optimal technical scheme, the metal nitride include AlTiN, TiSiN, AlCrN at least
It is a kind of.
A kind of coated carbides matrix of the present invention, the WC-Co base cemented carbides, its WC bases hard phase and Co bases are bonded
Xiang Zhongjun exists and can form compound with N element and promote the Mo elements of metal nitride forming core, contains in its Co base Binder Phase
Having, Co bases Binder Phase can be brought up to by the temperature that face-centered cubic thermal structure is changed into close-packed hexagonal low temperature structure >=900 DEG C
Ru elements.Added while Mo elements and Ru elements, the Effective Regulation to film base interface thing phase lattice mismatch serves guarantor
Barrier is acted on.Using the WC-Co base cemented carbides as coated substrate, can realize in its surface metallization nitride coatings
Afterwards, at stable existence WC bases hard phase and coating substance boundary lattice mismatch ＜ 5~25% coherence and/or half coherence circle
The coherence and/or half coherence circle of lattice mismatch ＜ 5~25% at face, stable existence Co bases Binder Phase and coating substance boundary
Face.The expression formula of the lattice mismatch is | δ |=(as–ac)/ac, wherein | δ | is lattice mismatch, asFor in matrix thing phase
The interplanar distance of crystal face A, acIt is the interplanar distance of crystal face B in coating substance phase.The crystal face A and crystal face B is in epitaxial growth relation.
A kind of preparation method of coated carbides matrix of the present invention, its embodiment is：Match somebody with somebody by design component and take each original
Material, will match somebody with somebody the wet-milling in the ball mill of the raw material that takes it is well mixed after carry out compound drying and granulating successively, compressing, sintering,
Obtain the coated carbides matrix；The last heat preservation sintering stage of the sintering is sintered by vacuum heat-preserving and is pressurizeed containing CO and protects
Temperature sintering two steps composition；In sintering circuit, 1360 DEG C of the temperature ＞ in last heat preservation sintering stage.
The sintering process is that the design principle based on the thing phase lattice mismatch regulation and control validity guarantee of film base interface sets
Meter is formed.
Preferably, the last heat preservation sintering stage is sintered by vacuum heat-preserving and pressure heat-preserving containing CO sinters two step groups
Into；The last heat preservation sintering stage refers to the maximum temperature stage of sintering；The temperature ＞ in the sintering maximum temperature stage
1360℃。
A kind of preparation method of coated carbides matrix of the present invention, the sintering of pressure heat-preserving containing CO refers to that vacuum is protected
After the completion of temperature sintering, being passed through CO and Ar carries out pressure sintering simultaneously in pressure sintering furnace；Be passed through CO gas grosses pass through CO
Volume fraction be controlled, be filled with volume and the pressure sintering burner hearth cumulative volume ratio of CO gases are (1~3):100；It is passed through
The total amount of Ar gas is controlled by gross pressure in pressure sintering furnace, is supplemented by the continuation of follow-up Ar gas, makes pressure sintering furnace
Interior gross pressure ＞ 5MPa.
A kind of preparation method of coated carbides matrix of the present invention, the last heat preservation sintering stage, control vacuum is protected
Warm sintering time >=20min, control simultaneously containing gross pressure in CO and Ar gas and stove reach heat preservation sintering time of ＞ 5MPa >=
40min。
The synergy of sintering temperature, sintering pressure and soaking time, can not only promote Mo, Ru alloy addition in alloy
In diffusion-homogenization, and can promote Mo in WC and Co dissolving and follow-up solid solution formation, while can also promote
The formation of dissolvings and follow-up solid solution of the Ru in Co；The presence of appropriate CO, can prevent Co in the richness on alloy sintered compact surface
Collection.In the present invention, once not by the way of CO and Ar gas is passed through simultaneously, then products obtained therefrom can be caused for prepares coating
When, the hydraulic performance decline of coating.
The matrix that the present invention is developed, in prepares coating, the preparation method of coating is preferably physical vaporous deposition.Make
It is further preferred scheme, the physical vaporous deposition includes cathodic vacuum arc deposition method and magnetron sputtering deposition
Method.
Mechanism of the invention and advantages are under：
Electronegativity difference, atomic volume difference, foreign atom spacing, atomic concentration between the lattice parameter and constituent element of solid solution
Etc. relevant, lattice parameter decision interplanar distance.In hard alloy liquid sintering process, the appropriate Mo in alloy is by liquid
Dissolved in Co, then separated out from liquid Co, and then the solid solution in WC.Because forming the WC based solid solutions containing Mo atoms, so that
WC base hard phases lattice parameter reduction, so as to reduce WC bases hard phase with AlN or TiN Base Metal nitride thing phase lattice parameters
Between difference, reduce lattice mismatch.Appropriate Ru dissolves by liquid Co in alloy, is formed in cooling procedure
Co based solid solutions, so as to increased the lattice parameter of Co based solid solution Binder Phases, reduce Co based solid solutions Binder Phase and AlN or
Difference between TiN Base Metal nitride thing phase lattice parameters, reduces lattice mismatch.
Regulate and control and its regulate and control validity guarantee based on film base interface thing phase lattice mismatch the invention provides a kind of
The design principle of alloy material and its preparation technology.By adding Mo simultaneously in WC-Co based alloys2C and Ru, and by burning
The regulation and control of technique are tied, under the double action of moderate pressure high, promotes the shape of dissolvings and follow-up solid solution of the Mo in WC and Co
Into the formation of dissolvings and follow-up solid solution of the promotion Ru in Co；By the formation of WC bases and Co based solid solutions, adjustment WC bases are hard
The lattice parameter of matter phase and Co base Binder Phases, controls Co base Binder Phase crystal structures and its stability, it is met WC base hard
With the condition of lattice mismatch ＜ 5~25% at coating substance boundary, it is set to meet Co bases Binder Phase and coating substance boundary
Locate the condition of lattice mismatch ＜ 5~25%, that is, meet the necessary condition for forming coherence and/or semicoherent interface.
The present invention can be while the solid solution in WC and Co, forms the feature of solid solution using Mo, and Mo can be formed with N
Compound, can promote metal nitride in the characteristic of the quick forming core of alloy substrate surface synchronization, reduce metal nitride extension
Caused distortion of lattice during growth, so as to meet the adequate condition to form coherence and/or semicoherent interface.
The study find that, as a number of Ru of solid solution in Co, alloying effect can be produced, make Co base Binder Phases by face
The temperature that the heart cube thermal structure is changed into close-packed hexagonal low temperature structure brings up to >=900 DEG C, on the one hand may insure either
Chemically vapour deposition temperature (generally≤900 DEG C) is cooled in room temperature process, or from physical vapour deposition (PVD) temperature (generally≤
600 DEG C) it is cooled in room temperature process, all without the transformation that Co base Binder Phase crystal structures occur, it is to avoid because of crystal structure transition
Caused distortion of lattice and the formation of internal stress；On the other hand Co bases Binder Phase is solid matter in may insure hard alloy substrate
Hexagonal crystallographic texture.Compared with face-centred cubic structure, Patterns for Close-Packed Hexagonal Crystal structure C o bases Binder Phase with have and AlN or TiN are brilliant
Lattice mismatch between the metal nitride of body structure is significantly reduced, so as to meet to form coherence and/or semicoherent interface
Necessary condition.
Simultaneously and rapidly the crystal structure of forming core and stabilization is to realize having to the thing phase lattice mismatch regulation and control of film base interface
Effect property is there is provided premise guarantee.
The study find that, the surface that Co during alloying element is easily caused liquid sintering process is added in WC-Co alloys is moved
Move, so as to cause alloy sintered compact surface to form the RE Containing Ce of random distribution.Various surface treatments before coating are difficult to dispel completely
Except RE Containing Ce, there is the inhomogeneity of combination interface institutional framework so as to cause alloy substrate and coating interface, so as to cause film
Reduction and the unstability of film-substrate cohesion that base junction is made a concerted effort.
The study find that, CO gases are passed through too early or excessively in sintering process, it is unfavorable for alloy heterogeneous microstructure stabilization
Property control；Appropriate weak carburizing CO gases are passed through in liquid-phase sintering later stage, can effectively suppress sintered body surface RE Containing Ce
Formation, it is ensured that Mo2Reinforcing effect of the C and Ru alloy additions to film-substrate cohesion.
In sum, a kind of coated carbides matrix provided by the present invention and preparation method thereof, can effectively improve
Film-substrate cohesion between metal nitride coatings and hard alloy substrate, can extend the service life of coated carbides,
It is suitable to industrial applications, for the combination property for further improving coated carbides provides a kind of reliable solution.This
The alloy material and its system that are ensured based on the thing phase lattice mismatch regulation and control of film base interface and its regulation and control validity that invention is provided
The design principle of standby technique is equally applicable to other kinds of coating composite material.
Brief description of the drawings
Fig. 1 is prepared WC -10Co -1.2Mo in embodiment 12The stereoscan photograph of C -1.5Ru alloy polishing sections；
Fig. 2 is prepared WC -10Co -1.2Mo in embodiment 12C -1.5Ru alloy sintered compacts surface in vacuum environment,
X ray diffracting spectrum and its analysis result under 920 DEG C of high temperature；
Fig. 3 is prepared WC -10Co -1.2Mo in embodiment 12C -1.5Ru alloy substrates and Al0.6Ti0.4N coating interfaces
By the high-resolution-ration transmission electric-lens image of inversefouriertransform caudacoria base coherent boundary；
Fig. 4 be in comparative example 1 prepared WC -10Co alloy sintered compacts surface X ray diffracting spectrum at room temperature and its
Analysis result；
Fig. 5 is prepared WC -12Co -0.6Cr in embodiment 23C2–0.4VC–1.2Mo2C -1.2Ru alloy polishing sections
Stereoscan photograph；
Fig. 6 is prepared WC -6Co -5TiC -6TaC -4NbC -0.9Mo in embodiment 32C -0.78Ru alloy polishing sections
Stereoscan photograph.
Alloy structure is WC base hard phase+Co base Binder Phase two phase structures, the grain size of WC bases hard phase in alloy in Fig. 1
It is 1.1 μm.
Fig. 2 shows that WC bases hard phase has hexagonal structure in alloy, and Co base Binder Phases have close-packed hexagonal structure；In figure
The indices of crystallographic plane of close-packed hexagonal structure Co are labeled using three coordinate forms；Three-coordinate (hkl) and 4-coordinate system (hkil)
Transforming relationship formula be i=-(h+k).
Film base interface epitaxial growth relation is in Fig. 3At the both sides of interfaceLattice mismatch is 3.2%, is formd
Coherent boundary.Interplanar distance is represented in this.
Fig. 4 shows that WC hard phases have hexagonal structure in alloy, and Co base Binder Phases have face-centred cubic structure, and alloy is
Two phase structure；The indices of crystallographic plane of face-centred cubic structure Co are marked in collection of illustrative plates.
Alloy structure is WC base hard phase+Co base Binder Phase two phase structures in Fig. 5, and grain growth inhibitor Cr, V are present in
Boundary is bonded with WC/ in Co base Binder Phases, third phase is not formed；The grain size of WC bases hard phase is 0.4 μm in alloy.
Alloy structure is WC bases hard phase+(W, Ti, Ta, Nb) C hard phase+Co base Binder Phase three-phase structure, alloy in Fig. 6
The grain size of middle WC bases hard phase is 0.9 μm.
In alloy microstructure shown in Fig. 1, Fig. 5 and Fig. 6, Mo solid solutions in WC, WC base hard phases are solid solution containing Mo；Close
Ru solid solutions in Co in gold, Co base Binder Phases are solid solution containing Ru.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1：
From business WC, Co, Mo2C, Ru powder are raw material, according to WC -10Co -1.2Mo2(numerical value represents matter to C -1.5Ru
Amount fraction, %, similarly hereinafter) composition carries out dispensing.Compound wet-grinding technology and relative device is as follows：Using 4:1 ratio of grinding media to material, the rolling wet type of 48h
Ball-milling Time.After granulation is dried to wet-milling compound, a diameter of 15mm is prepared using die forming technique, be highly 4mm
Cylinder.Pressed compact is sintered using the technique of pressure sintering containing CO, the last heat preservation sintering phase temperature of sintering circuit is
1430℃；After 1430 DEG C of vacuum-sintering insulation 30min, being passed through CO and Ar carries out pressure sintering simultaneously in pressure sintering furnace,
The volume that is filled with of wherein CO gases is 1 with pressure sintering burner hearth cumulative volume ratio:100, supplemented by the continuation of follow-up Ar gas, make pressure
Power sintering furnace pressure reaches 5.6MPa, and 60min is incubated under 5.6MPa pressure.The stereoscan photograph of alloy polishing section is shown in
Fig. 1, alloy structure is WC base hard phase+Co base Binder Phase two phase structures, and the grain size of WC bases hard phase is 1.1 μm in alloy.
Alloy sintered compact surface is in vacuum environment, the X ray diffracting spectrum under 920 DEG C of high temperature and its analysis result are shown in Fig. 2, in alloy
WC base hard phases have hexagonal structure, and Co base Binder Phases have close-packed hexagonal structure.Due to Ru, the alloy of solid solution is turned into Co
With result in the high-temperature stability of close-packed hexagonal structure Co.The crystal structure of thing phase can be corresponding by consulting thing in figure spy
The PDF cards for determining number are obtained.
The CC800/9XL coating apparatus of magnetron sputtering technique are based on using Cemecon companies, according to standard coated pre-treatment
Technique and coating process, the depositing Al on above-mentioned alloy substrate0.6Ti0.4N coatings, coating layer thickness is~2 μm.Fig. 3 be WC-
10Co–1.2Mo2C -1.5Ru alloy substrates and Al0.6Ti0.4N coating interfaces are by inversefouriertransform caudacoria base coherent boundary
High-resolution-ration transmission electric-lens image, film base interface epitaxial growth relation is in figure Interface two
At sideLattice mismatch is 3.2%, shape
Into coherent boundary.Al0.6Ti0.4N coatings have with AlN identical crystal structures, be face-centred cubic structure.
The film base junction of coating is measured using CSM companies of Switzerland big load scratching instrument (Revetest Scratch Tester)
With joint efforts, testing conditions are：120 ° of diamond indenter tip radius of curvature 0.2mm, cone angle, cut speed 5mm/min, loading speed
100N/min, cut length 5mm.Test result is that film-substrate cohesion is 90N.
Comparative example 1：
It is~1.1 μm of WC -10Co from WC base Hard Phase Grain Sizes in the alloy prepared with stove sintering with the sample of example 1
Hard alloy as matrix, using the identical technique of example 1, the depositing Al on above-mentioned alloy substrate0.6Ti0.4N, coating layer thickness is
~2 μm.Alloy sintered compact surface X ray diffracting spectrum at room temperature and its analysis result are shown in Fig. 4, Co bases Binder Phase in alloy
With face-centred cubic structure.Due to the presence of W, C solid solution atom in Co, the cooldown rate of pressure sintering furnace is sintered compared with traditional vacuum
Stove is high, and Co has obtained effective suppression by the martensitic traoformation that face-centred cubic thermal structure is changed into close-packed hexagonal structure.
The film-substrate cohesion of coating is measured using CSM companies of Switzerland big load scratching instrument, testing conditions are：Diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, cut speed 5mm/min, loading speed 100N/min, cut length 5mm.Test
Result is that film-substrate cohesion is 61N.
Embodiment 2：
From business WC, Co, Mo2C、Ru、Cr3C2, VC powder be raw material, according to WC -12Co -0.6Cr3C2–0.4VC–
1.2Mo2C -1.2Ru compositions carry out dispensing.Compound wet-grinding technology and relative device is as follows：Using 6:1 ratio of grinding media to material, the rolling wet type ball of 72h
Time consuming.After granulation is dried to wet-milling compound, a diameter of 15mm is prepared using die forming technique, be highly 4mm's
Cylinder.Pressed compact is sintered using the technique of pressure sintering containing CO, the last heat preservation sintering phase temperature of sintering circuit is
1380℃；After 1380 DEG C of vacuum-sintering insulation 20min, being passed through CO and Ar carries out pressure sintering simultaneously in pressure sintering furnace,
The volume that is filled with of wherein CO gases is 3 with pressure sintering burner hearth cumulative volume ratio:100, supplemented by the continuation of follow-up Ar gas, make pressure
Power sintering furnace pressure reaches 5.6MPa, and 40min is incubated under 5.6MPa pressure.The stereoscan photograph of alloy polishing section is shown in
Fig. 5, the grain size of WC bases hard phase is 0.4 μm in alloy.
The CC800/9XL coating apparatus of magnetron sputtering technique are based on using Cemecon companies, according to standard coated pre-treatment
Technique and coating process, the depositing Ti on above-mentioned alloy substrate0.89Si0.11N, coating layer thickness is~2 μm.Ti0.89Si0.11N coatings
With with TiN identical crystal structures, be face-centred cubic structure.Research finds that film base interface has epitaxial growth relation and isInterface, lattice mismatch is 2.9%, forms coherent boundary.
The film-substrate cohesion of coating is measured using CSM companies of Switzerland big load scratching instrument, testing conditions are：Diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, cut speed 5mm/min, loading speed 100N/min, cut length 5mm.Test
Result is film-substrate cohesion ＞ 100N.
Comparative example 2：
From being with WC base Hard Phase Grain Sizes prepared by stove sintering with the sample of example 2~0.4 μm of WC -12Co -
0.6Cr3C2- 0.4VC ultra-fine cemented carbides as coated substrate, using the identical technique of example 2, on above-mentioned alloy substrate
Depositing Ti0.89Si0.11N coatings, coating layer thickness is~2 μm.
The film-substrate cohesion of coating is measured using CSM companies of Switzerland big load scratching instrument, testing conditions are：Diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, cut speed 5mm/min, loading speed 100N/min, cut length 5mm.Test
Result is that film-substrate cohesion is 85N.
Embodiment 3：
According to using business WC, Co, Mo2C, Ru, WC -25TiC -30TaC -20NbC powder be raw material, according to WC -
6Co–5TiC–6TaC–4NbC–0.9Mo2C -0.78Ru compositions carry out dispensing.Compound wet-grinding technology and relative device is as follows：Using 6:1 ball
Material ratio, the rolling wet ball-milling time of 60h.After granulation is dried to wet-milling compound, prepared using die forming technique straight
Footpath is 15mm, is highly the cylinder of 4mm.Pressed compact is sintered using the technique of pressure sintering containing CO, sintering circuit it is last
Heat preservation sintering phase temperature is 1450 DEG C；After 1450 DEG C of vacuum-sintering insulation 30min, CO is passed through simultaneously in pressure sintering furnace
Pressure sintering is carried out with Ar, the volume that is filled with of wherein CO gases is 2 with pressure sintering burner hearth cumulative volume ratio:100, by follow-up Ar
The continuation supplement of gas, makes pressure sintering furnace pressure reach 5.6MPa, and 70min is incubated under 5.6MPa pressure.Alloy polishing cuts
The stereoscan photograph in face is shown in Fig. 6, and the grain size of WC bases hard phase is 0.9 μm in alloy.
The INNOVA coating apparatus of flash cathodic arc evaporation technology are based on using Oerlikon Balzers companies, are pressed
According to standard coated pre-treating technology and coating process, the depositing Al on above-mentioned alloy substrate0.65Cr0.30Si0.04W0.01N/
Al0.66Cr0.34N laminated coatings, coating layer thickness is~2.9 μm.With the Al of alloy substrate directly contact0.66Cr0.34N coatings have
It is face-centred cubic structure with AlN identical crystal structures.Research finds that film base interface has epitaxial growth relation and isInterface, lattice mismatch is 9.0%, forms semicoherent interface.
This,Crystal face etc. is all (100) crystal face of three coordinate forms.
The film-substrate cohesion of coating is measured using CSM companies of Switzerland big load scratching instrument, testing conditions are：Diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, cut speed 5mm/min, loading speed 100N/min, cut length 5mm.Test
Result is that film-substrate cohesion is 91N.
Comparative example 3：
Be from WC base Hard Phase Grain Sizes in the alloy prepared with stove sintering with the sample of example 3~0.9 μm of WC -6Co -
5TiC -6TaC -4NbC hard alloy, using the identical technique of example 3, is deposited as coated substrate on above-mentioned alloy substrate
Al0.65Cr0.30Si0.04W0.01N/Al0.66Cr0.34N laminated coatings, coating layer thickness is~2.9 μm.
The film-substrate cohesion of coating is measured using CSM companies of Switzerland big load scratching instrument, testing conditions are：Diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, cut speed 5mm/min, loading speed 100N/min, cut length 5mm.Test
Result is that film-substrate cohesion is 63N.
From the film-substrate cohesion data of the coated carbides film-substrate cohesion data of embodiment 1,2,3 and corresponding comparative example
Compare and understand, the hard alloy substrate provided using the present invention can effectively improve the film-substrate cohesion of coated carbides, real
Apply the more corresponding comparative example of example 1,3 its film-substrate cohesion and improve more than 44%.
Claims (10)
1. a kind of coated carbides matrix, it is characterised in that：The hard alloy substrate is to be based on film base between coating and matrix
The alloy material design principle of interface thing phase lattice mismatch regulation and control and its regulation and control validity guarantee is designed；The hard
After alloy substrate is combined with its face coat, the feature with high film-substrate cohesion, film base interface stable existence lattice mismatch
Degree | δ |=(as–ac)/acThe coherence and/or semicoherent interface of ＜ 5~25%, wherein | δ | is lattice mismatch, asIt is matrix thing
The interplanar distance of crystal face A, a in phasecIt is the interplanar distance of crystal face B in coating substance phase；The crystal face A and crystal face B is in epitaxial growth
Relation.
2. a kind of coated carbides matrix according to claim 1, it is characterised in that：The hard alloy substrate material
It is WC-Co base cemented carbides；Contain Mo simultaneously in the WC-Co base cemented carbides2C and Ru alloy additions；WC-Co the bases
1.5 μm of the grain size ＜ of WC bases hard phase in hard alloy, the crystal structure of Co base Binder Phases is close-packed hexagonal structure；With it is described
The coating that matrix matches is the coating containing metal nitride.
3. a kind of coated carbides matrix according to claim 2, it is characterised in that：WC-Co the base cemented carbides
Middle Mo2C is (10~15) with Co mass ratioes:100, Ru is (10~15) with Co mass ratioes:100.
4. a kind of coated carbides matrix according to claim 2, it is characterised in that：WC-Co the base cemented carbides
Including YG alloys and YW alloys；In the YG alloys, except Mo2Outside C and Ru, the matter of other alloy addition total amounts and alloy total amount
Amount is than ＜ 2:100；The YW alloys are the WC-Co base cemented carbides of-NbC of-TaC containing TiC, except Mo2Outside C and Ru, other alloys
The mass ratio ＞ 2 of additive total amount and alloy total amount:100.
5. a kind of coated carbides matrix according to claim 4, it is characterised in that：The YG alloys include Ultra-fine Grained
YG hard alloy.
6. a kind of coated carbides matrix according to claim 2, it is characterised in that：The painting containing metal nitride
Layer includes individual layer and laminated coating；Either individual layer or laminated coating, with described matrix directly in conjunction with coating material be gold
Category nitride.
7. a kind of coated carbides matrix according to claim 6, it is characterised in that：It is described with matrix directly in conjunction with
Metal nitride has and AlN or TiN identical crystal structures.
8. a kind of method for preparing the coated carbides matrix as described in any one in claim 1~7, it is characterised in that：
By design component with taking each raw material, will match somebody with somebody the wet-milling in the ball mill of the raw material that takes it is well mixed after carry out compound successively and dry system
Grain, compressing, sintering, obtains the coated carbides matrix；The last heat preservation sintering stage of the sintering is protected by vacuum
Temperature sintering and pressure heat-preserving containing CO sinter two steps composition；In sintering circuit, 1360 DEG C of the temperature ＞ in last heat preservation sintering stage.
9. the preparation method of a kind of coated carbides matrix according to claim 8, it is characterised in that：It is described to add containing CO
Pressure heat preservation sintering refers to that after the completion of vacuum heat-preserving sintering, being passed through CO and Ar carries out pressure sintering simultaneously in pressure sintering furnace；Institute
It is passed through CO gas grosses to be controlled by the volume fraction of CO, CO gases are filled with volume and pressure sintering burner hearth cumulative volume ratio
It is (1~3):100；The total amount of be passed through Ar gas is controlled by gross pressure in pressure sintering furnace, by follow-up Ar gas after
Continuous supplement, makes gross pressure ＞ 5MPa in pressure sintering furnace.
10. a kind of preparation method of the coated carbides matrix according to any one in claim 8~9, its feature
It is：The last heat preservation sintering stage, control vacuum heat-preserving sintering time >=20min, control contains CO and Ar gas and stove simultaneously
Interior gross pressure reaches the heat preservation sintering time >=40min of ＞ 5MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107354383A (en) * | 2017-07-07 | 2017-11-17 | 安徽同盛环件股份有限公司 | A kind of high abrasion composite alloy ring and its preparation technology |
| US20210123141A1 (en) * | 2018-04-24 | 2021-04-29 | Oerlikon Surface Solutions Ag, Pfäffikon | COATING COMPRISING MCrAl-X COATING LAYER |
| JP2021095623A (en) * | 2019-12-19 | 2021-06-24 | 株式会社タンガロイ | Cemented carbide and coated cemented carbide, and tool including the same |
| CN113136518A (en) * | 2021-04-25 | 2021-07-20 | 四川德克普数控机床有限公司 | Manufacturing method of round nose milling cutter and numerically controlled grinder thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008103605A2 (en) * | 2007-02-19 | 2008-08-28 | Tdy Industries, Inc. | Carbide cutting insert |
| CN101429612A (en) * | 2008-12-01 | 2009-05-13 | 株洲钻石切削刀具股份有限公司 | WC-Co hard alloy with low Co content on surface and its sintering process |
| CN106480350A (en) * | 2015-08-28 | 2017-03-08 | 肯纳金属公司 | There is the hard carbide of cobalt molybdenum alloy binding agent |
-
2017
- 2017-03-16 CN CN201710157652.XA patent/CN106835116B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008103605A2 (en) * | 2007-02-19 | 2008-08-28 | Tdy Industries, Inc. | Carbide cutting insert |
| CN101429612A (en) * | 2008-12-01 | 2009-05-13 | 株洲钻石切削刀具股份有限公司 | WC-Co hard alloy with low Co content on surface and its sintering process |
| CN106480350A (en) * | 2015-08-28 | 2017-03-08 | 肯纳金属公司 | There is the hard carbide of cobalt molybdenum alloy binding agent |
Non-Patent Citations (4)
| Title |
|---|
| 中国材料研究学会超硬材料及制品专业委员会: "《中国超硬材料与制品 50周年精选文集》", 30 September 2014, 浙江大学出版社 * |
| 何菊生等: ""半导体外延层晶格失配度的计算"", 《南昌大学学报（理科版）》 * |
| 傅又红: ""钨钛钴类硬质合金表面亮花的形成及其对产品性能的影响"", 《硬质合金》 * |
| 赵时璐: "《多弧离子镀Ti-Al-Zr-Cr-N系复合硬质膜》", 28 February 2013, 冶金工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107354383A (en) * | 2017-07-07 | 2017-11-17 | 安徽同盛环件股份有限公司 | A kind of high abrasion composite alloy ring and its preparation technology |
| US20210123141A1 (en) * | 2018-04-24 | 2021-04-29 | Oerlikon Surface Solutions Ag, Pfäffikon | COATING COMPRISING MCrAl-X COATING LAYER |
| US11661657B2 (en) * | 2018-04-24 | 2023-05-30 | Oerlikon Surface Solutions Ag, Pfäffikon | Coating comprising MCrAl-X coating layer |
| JP2021095623A (en) * | 2019-12-19 | 2021-06-24 | 株式会社タンガロイ | Cemented carbide and coated cemented carbide, and tool including the same |
| CN113136518A (en) * | 2021-04-25 | 2021-07-20 | 四川德克普数控机床有限公司 | Manufacturing method of round nose milling cutter and numerically controlled grinder thereof |
| CN113136518B (en) * | 2021-04-25 | 2022-03-01 | 四川德克普数控机床有限公司 | Manufacturing method of round nose milling cutter and numerically controlled grinder thereof |
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