CN106835116B - A kind of coated carbides matrix and preparation method thereof - Google Patents
A kind of coated carbides matrix and preparation method thereof Download PDFInfo
- Publication number
- CN106835116B CN106835116B CN201710157652.XA CN201710157652A CN106835116B CN 106835116 B CN106835116 B CN 106835116B CN 201710157652 A CN201710157652 A CN 201710157652A CN 106835116 B CN106835116 B CN 106835116B
- Authority
- CN
- China
- Prior art keywords
- alloy
- base
- phase
- coating
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The present invention is based on the design principles of the alloy material and its preparation process of the regulation of film base interface object phase lattice mismatch and its regulation validity guarantee, provide 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 alloy；By adding Mo simultaneously in the alloy2C and Ru respectively regulates and controls WC base hard phase and Co base Binder Phase lattice constant, promotes metal nitride film forming core, and stable interface object phase crystal structure realizes the Effective Regulation to film base interface object phase lattice mismatch；Mo in WC-Co based alloy2C and Co mass ratio, Ru and Co mass ratio are (10~15): 100, WC 1.5 μm of base Hard Phase Grain Size <, and Co base Binder Phase is close-packed hexagonal structure.Using wet-milling, drying and granulating, compression moulding, the preparation of the technique of pressure sintering containing CO.
Description
Technical field
The present invention relates to a kind of coated carbides matrixes and preparation method thereof, belong to composite powder metallurgy material technology neck
Domain.
Background technique
Coated carbides is made of hard alloy substrate and coating two parts, and coated carbides matrix, which refers to be used as, to be applied
The dedicated 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, between hard alloy substrate and coating film-substrate cohesion 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.Due to spacing of lattice mismatch, asynchronous forming core, alloy bonding phase crystal structure be unstable, boundary
The reasons such as face heterogeneous microstructure uneven, boundary defect, internal stress, at hard alloy substrate and coating interface between atom
In conjunction with the presence usually in the form of non-coherence.
Existing coated carbides matrix mainly has the materials such as WC-Co (YG) and WC-(W, Ti) C-(Ta, Nb) C-Co (YW)
Matter.From the angle of characterization alloying component, YW alloy basis can be indicated with WC-TiC-TaC-NbC-Co.YG and YW hard closes
Gold bonds phase composition by hard phase and Co base, and the grain size of WC hard phase and WC raw material granularity are closely related in alloy.Pass through original
The selection for expecting wc grain size, may be implemented the regulation 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 having high rigidity, high-wearing feature, excellent high-temperature oxidation resistance, high chemical property stability and good
Corrosion resistance is also widely used for the various complexity such as high temperature, humidity, high salinity in addition to the surface for being used as cutting tool is modified
The surfacecti proteon of tool under military service working condition.As typical metal nitride, AlTiN, TiSiN, AlCrN are relatively normal at present
Commercialization coating.Above-mentioned metal nitride usually has crystal structure identical with AlN or TiN, and other alloying elements are logical
It is often solid-solubilized in AlN or TiN lattice, forms solid solution.To AlTiN, when the atomic fraction of wherein Ti is higher than Al, then formed
The crystal structure of TiN；When the atomic fraction of wherein Al is higher than Ti, then the crystal structure of AlN is formed.
On how to improve coating film-substrate cohesion, there are many reports, such as stand and report " a kind of hard alloy and
The method for improving its PVD coating film-substrate cohesion " (application number of invention patent 201410376915.2) proposes one kind and is based on changing
The forming core condition and its forming core homogenieity of kind metal nitride coatings, to enhance film-substrate cohesion and enhancing film-substrate cohesion is steady
Qualitative effective ways.
The present inventor continue research effectively improve the bond strength, i.e. film-substrate cohesion between coating and matrix when, hair
Now currently without the coating substance phase directly contacted based on hard phase in hard alloy substrate and Binder Phase lattice constant with its surface
Between lattice constant match degree regulation and its regulation validity safeguards technique principle report.Inventor sends out in an experiment simultaneously
It is existing: in coating and matrix combination interface position, to form coherence or semicoherent interface, especially formation coherent boundary, can effectively mention
High film-substrate cohesion.Inventor also found simultaneously, add suitable Mo simultaneously in the alloy2C and Ru can significantly reduce hard conjunction
Lattice mismatch between auri body object phase and coating substance phase.It is found based on above-mentioned discovery and a series of experiment, inventor
It effectively improves another approach of coating film-substrate cohesion, and then has obtained the present invention.
Summary of the invention
It is an object of the present invention to provide a kind of coated carbides matrixes.
It is a further object to provide a kind of preparation methods 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 are based on film base interface between coating and matrix
The alloy material design principle of place's object phase lattice mismatch regulation and its regulation validity guarantee designs.The hard alloy
After matrix is in conjunction with its surface covering, the feature with high film-substrate cohesion, film base interface is stabilized lattice mismatch | δ |
=(as–ac)/acThe coherence and/or semicoherent interface of < 5~25%, wherein | δ | it is lattice mismatch, asFor in matrix object phase
The interplanar distance of crystal face A, acFor the interplanar distance of crystal face B in coating substance phase.The crystal face A and crystal face B is in epitaxial growth relationship.
A kind of coated carbides matrix of the present invention, the hard alloy substrate material are WC-Co base cemented carbide；It is described
Contain Mo simultaneously in WC-Co base cemented carbide2C and Ru alloy addition；WC base hard phase in the WC-Co base cemented carbide
1.5 μm of grain size <, the crystal structure of 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 alloy simultaneously2C and Ru is being burnt
Solid solution is formed during knot, WC base hard phase and Co base Binder Phase lattice constant are regulated and controled respectively, promotes coated film
Forming core stablizes film base interface object phase crystal structure, to realize the Effective Regulation to film base interface object phase lattice mismatch.
Preferably, a kind of coated carbides matrix of the present invention, Mo in the WC-Co base cemented carbide2C and Co
Mass ratio is (10~15): 100, Ru and Co mass ratio are (10~15): 100.
Preferably, a kind of coated carbides matrix of the present invention, the WC-Co base cemented carbide includes YG alloy
With YW alloy；In the YG alloy, Mo is removed2Outside C and Ru, the mass ratio < 2 of other alloy addition total amounts and alloy total amount:
100。
Preferably, the YW alloy is the WC-Co base cemented carbide of-NbC of-TaC containing TiC, removes Mo2Outside C and Ru,
The mass ratio > 2:100 of other alloy addition total amounts and alloy total amount.Other alloy additions include TiC, TaC, NbC
Deng.
It is pressed as preferred side, a kind of coated carbides matrix of the present invention, the YG alloy includes that Ultra-fine Grained YG hard closes
Gold.The further preferably Ultra-fine Grained YG hard alloy containing grain growth inhibitors such as Cr, V.
A kind of coated carbides matrix of the present invention, the coating containing metal nitride includes single layer and laminated coating；
Either single layer or laminated coating are metal nitride with the coating material that described matrix is bound directly.
A kind of coated carbides matrix of the present invention, the metal nitride bound directly with matrix have with AlN or
The identical crystal structure of TiN.As optimal technical scheme, the metal nitride include in 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 carbide, WC base hard phase and Co base bonding
There is the Mo element for being capable of forming compound with N element and promoting metal nitride forming core in Xiang Zhongjun, contain in Co base Binder Phase
>=900 DEG C can be increased to by the temperature that face-centered cubic thermal structure is changed into close-packed hexagonal low temperature structure for Co base Binder Phase by having
Ru element.It is added while Mo element and Ru element, guarantor is played to the Effective Regulation of film base interface object phase lattice mismatch
Barrier effect.Using the WC-Co base cemented carbide as coated substrate, it is able to achieve in its surface metallization nitride coatings
Afterwards, the coherence and/or half coherence circle of lattice mismatch < 5~25% at WC base hard phase and coating substance phase interface are stabilized
Face is stabilized the coherence and/or half coherence circle of lattice mismatch < 5~25% at Co base Binder Phase and coating substance phase interface
Face.The expression formula of the lattice mismatch is | δ |=(as–ac)/ac, wherein | δ | it is lattice mismatch, asFor in matrix object phase
The interplanar distance of crystal face A, acFor the interplanar distance of crystal face B in coating substance phase.The crystal face A and crystal face B is in epitaxial growth relationship.
A kind of preparation method of coated carbides matrix of the present invention, embodiment are as follows: match by design component and take each original
Material, by with the raw material that takes, wet-milling successively carries out mixture drying and granulating after mixing in the ball mill, compression moulding, sintering,
Obtain the coated carbides matrix；The last heat preservation sintering stage of the sintering is sintered by vacuum heat-preserving and the pressurization containing CO is protected
Temperature sintering two steps composition；In sintering process, 1360 DEG C of the temperature > in last heat preservation sintering stage.
The sintering process is that the design principle based on the regulation validity guarantee of film base interface object phase lattice mismatch is set
It counts.
Preferably, the last heat preservation sintering stage is sintered by vacuum heat-preserving and pressure heat-preserving containing CO is sintered two step groups
At；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 refer to that vacuum is protected
After the completion of temperature sintering, it is passed through CO and Ar simultaneously in pressure sintering furnace and carries out pressure sintering；Be passed through CO gas gross passes through CO
Volume fraction controlled, be filled with volume and the pressure sintering burner hearth total volume ratio of CO gas are (1~3): 100；It is passed through
The total amount of Ar gas is controlled by gross pressure in pressure sintering furnace, is continued to supplement by subsequent Ar gas, is made 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 are protected
Warm sintering time >=20min, control simultaneously containing gross pressure in CO and Ar gas and furnace reach heat preservation sintering time of > 5MPa >=
40min。
The synergistic effect of sintering temperature, sintering pressure and soaking time can not only promote Mo, Ru alloy addition in alloy
In diffusion-homogenization, and the formation of dissolution and subsequent solid solution of the Mo in WC and Co can be promoted, while can also promoted
The formation of dissolution and subsequent 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 then will lead to products obtained therefrom not by the way of being passed through CO and Ar gas simultaneously and be used to prepare coating
When, the 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
For further preferred embodiment, the physical vaporous deposition includes cathodic vacuum arc deposition method and magnetron sputtering deposition
Method.
Mechanism and advantages of the invention is under:
Electronegativity difference, atomic volume difference, foreign atom spacing, atomic concentration between the lattice constant and constituent element of solid solution
Etc. related, lattice constant decision interplanar distance.In hard alloy liquid sintering process, the appropriate Mo in alloy passes through in liquid
It dissolves, is then precipitated from liquid Co, and then be dissolved in WC in Co.Because forming the WC based solid solution of the atom containing Mo, to make
WC base hard phase lattice constant reduces, to reduce WC base hard phase and AlN or TiN Base Metal nitride object phase lattice constant
Between difference, reduce lattice mismatch.Suitable Ru is formed in cooling procedure by dissolving in liquid Co in alloy
Co based solid solution, to increase the lattice constant of Co based solid solution Binder Phase, reduce Co based solid solution Binder Phase and AlN or
Difference between TiN Base Metal nitride object phase lattice constant, reduces lattice mismatch.
The present invention provides a kind of to be regulated and controled and its be regulated and controled validity guarantee based on film base interface object phase lattice mismatch
The design principle of alloy material and its preparation process.By adding Mo simultaneously in WC-Co based alloy2C and Ru, and pass through burning
The regulation for tying technique promotes the shape of dissolution and subsequent solid solution of the Mo in WC and Co under the double action of high moderate pressure
At the formation of dissolution and subsequent solid solution of the promotion Ru in Co；By the formation of WC base and Co based solid solution, it is hard to adjust WC base
The lattice constant of matter phase and Co base Binder Phase controls Co base Binder Phase crystal structure and its stability, it is made to meet WC base hard
Mutually with the condition of lattice mismatch < 5~25% at coating substance phase interface, it is made to meet Co base Binder Phase and coating substance phase interface
Locate the condition of lattice mismatch < 5~25%, that is, meets the necessary condition for forming coherence and/or semicoherent interface.
The present invention can be dissolved in WC and Co simultaneously using Mo, and the feature and Mo for forming solid solution 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 when growth, to meet the adequate condition for forming coherence and/or semicoherent interface.
The study find that alloying effect can be generated when being dissolved a certain number of Ru in Co, make Co base Binder Phase by face
The temperature that the heart cube thermal structure is changed into close-packed hexagonal low temperature structure is increased to >=900 DEG C, on the one hand may insure either
The temperature (usually≤900 DEG C) that is chemically vapor-deposited is cooled in room temperature process, or from physical vapour deposition (PVD) temperature (usually≤
600 DEG C) it is cooled in room temperature process, the transformation of Co base Binder Phase crystal structure will not all occur, avoid because of crystal structure transition
The formation of caused distortion of lattice and internal stress；On the other hand it may insure that Co base Binder Phase is solid matter in hard alloy substrate
Hexagonal crystallographic texture.Compared with face-centred cubic structure, Patterns for Close-Packed Hexagonal Crystal structure C o base Binder Phase with have and AlN or TiN are brilliant
Lattice mismatch between the metal nitride of body structure significantly reduces, and forms coherence and/or semicoherent interface to meet
Necessary condition.
Simultaneously and rapidly forming core and stable crystal structure are to realize to have the object phase lattice mismatch regulation of film base interface
Effect property provides premise guarantee.
It is easy to cause the surface of Co in liquid sintering process to move the study find that adding alloying element in WC-Co alloy
It moves, forms the RE Containing Ce of random distribution so as to cause alloy sintered compact surface.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
The reduction of base junction resultant force and the unstability of film-substrate cohesion.
The study find that being passed through CO gas too early or excessively in sintering process, it is unfavorable for alloy heterogeneous microstructure and stablizes
Property control；It is passed through appropriate weak carburizing CO gas in liquid-phase sintering later stage, can effectively inhibit sintered body surface RE Containing Ce
Formation, it is ensured that Mo2Strengthening effect of the C and Ru alloy addition to film-substrate cohesion.
In conclusion 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,
Suitable for industrial applications, a kind of reliable solution is provided to further increase the comprehensive performance of coated carbides.This
The alloy material and its system for regulating and controlling and its regulating and controlling validity guarantee based on film base interface object phase lattice mismatch that invention provides
The design principle of standby technique is equally applicable to other kinds of coating composite material.
Detailed description of the invention
Fig. 1 is prepared WC -10Co -1.2Mo in embodiment 12The stereoscan photograph of C -1.5Ru alloy polishing section；
Fig. 2 is prepared WC -10Co -1.2Mo in embodiment 12C -1.5Ru alloy sintered compact 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 substrate and Al0.6Ti0.4N coating interface
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 compact surface X ray diffracting spectrum at room temperature and its
Analyze result；
Fig. 5 is prepared WC -12Co -0.6Cr in embodiment 23C2–0.4VC–1.2Mo2C -1.2Ru alloy polishing section
Stereoscan photograph；
Fig. 6 is prepared WC -6Co -5TiC -6TaC -4NbC -0.9Mo in embodiment 32C -0.78Ru alloy polishing section
Stereoscan photograph.
Alloy structure is WC base hard phase+Co base Binder Phase two phase structure in Fig. 1, the grain size of WC base hard phase in alloy
It is 1.1 μm.
Fig. 2 shows that WC base hard phase has hexagonal structure in alloy, and Co base Binder Phase has 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 relationship is in Fig. 3At the two sides of interfaceLattice mismatch is 3.2%, is formd
Coherent boundary.Interplanar distance is represented in this.
Fig. 4 shows that WC hard phase has hexagonal structure in alloy, and Co base Binder Phase has face-centred cubic structure, and alloy is
Two phase structure；The indices of crystallographic plane of face-centred cubic structure Co are marked in map.
Alloy structure is WC base hard phase+Co base Binder Phase two phase structure in Fig. 5, and grain growth inhibitor Cr, V are present in
In Co base Binder Phase and WC/ bonds phase interface, not formed third phase；The grain size of WC base hard phase is 0.4 μm in alloy.
Alloy structure is WC base 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 base hard phase is 0.9 μm.
In alloy microstructure shown in Fig. 1, Fig. 5 and Fig. 6, Mo is dissolved in WC, and WC base hard phase is solid solution containing Mo；It closes
Ru is dissolved in Co in gold, and Co base Binder Phase is solid solution containing Ru.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
Embodiment 1:
Select business WC, Co, Mo2C, Ru powder is raw material, according to WC -10Co -1.2Mo2(numerical value represents matter to C -1.5Ru
Amount score, %, similarly hereinafter) ingredient progress ingredient.Mixture wet-grinding technology and relative device is as follows: using the ratio of grinding media to material of 4:1, the rolling wet type of 48h
Ball-milling Time.After granulation is dried to wet-milling mixture, uses die forming technique to prepare diameter as 15mm, be highly 4mm
Cylindrical body.Green compact is sintered using the technique of pressure sintering containing CO, the last heat preservation sintering phase temperature of sintering process is
1430℃；After 1430 DEG C of vacuum-sinterings keeps the temperature 30min, it is passed through CO and Ar simultaneously in pressure sintering furnace and carries out pressure sintering,
Wherein the be filled with volume and pressure sintering burner hearth total volume ratio of CO gas are 1:100, continue to supplement by subsequent Ar gas, make to press
Power sintering furnace pressure reaches 5.6MPa, keeps the temperature 60min under 5.6MPa pressure.The stereoscan photograph of alloy polishing section is shown in
Fig. 1, alloy structure are WC base hard phase+Co base Binder Phase two phase structure, and the grain size of WC base hard phase is 1.1 μm in alloy.
X ray diffracting spectrum of the alloy sintered compact surface in vacuum environment, under 920 DEG C of high temperature and its analysis result are shown in Fig. 2, in alloy
WC base hard phase has hexagonal structure, and Co base Binder Phase has close-packed hexagonal structure.Since the Ru alloy being dissolved in Co is turned into
With resulting in the high-temperature stability of close-packed hexagonal structure Co.The crystal structure of object phase can be by consulting the corresponding spy of object in figure
The PDF card for determining number obtains.
CC800/9XL coating apparatus using Cemecon company based on magnetron sputtering technique, according to standard coated pre-treatment
Technique and coating process, the depositing Al on above-mentioned alloy substrate0.6Ti0.4N coating, coating layer thickness are~2 μm.Fig. 3 is WC-
10Co–1.2Mo2C -1.5Ru alloy substrate and Al0.6Ti0.4N coating interface is by inversefouriertransform caudacoria base coherent boundary
High-resolution-ration transmission electric-lens image, film base interface epitaxial growth relationship is in figure Interface two
At sideLattice mismatch is 3.2%, shape
At coherent boundary.Al0.6Ti0.4N coating has crystal structure identical with AlN, is face-centred cubic structure.
Using the film base junction of CSM company, Switzerland big load scratching instrument (Revetest Scratch Tester) measurement coating
With joint efforts, testing conditions are as follows: 120 ° of diamond indenter tip radius of curvature 0.2mm, cone angle, scratch speed 5mm/min, loading speed
100N/min, scratch length 5mm.Test result is that film-substrate cohesion is 90N.
Comparative example 1:
Select the WC -10Co for being~1.1 μm with WC base Hard Phase Grain Size in the alloy of furnace sintering preparation with 1 sample of example
Hard alloy is as matrix, using the identical technique of example 1, the depositing Al on above-mentioned alloy substrate0.6Ti0.4N, coating layer thickness are
~2 μm.Alloy sintered compact surface X ray diffracting spectrum at room temperature and its analysis result are shown in Fig. 4, Co base Binder Phase in alloy
With face-centred cubic structure.Since W, C are dissolved the presence of atom in Co, the cooling rate of pressure sintering furnace is sintered compared with traditional vacuum
Furnace is high, and Co has obtained effective inhibition by the martensitic traoformation that face-centred cubic thermal structure is changed into close-packed hexagonal structure.
Using the film-substrate cohesion of CSM company, Switzerland big load scratching instrument measurement coating, testing conditions are as follows: diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, scratch speed 5mm/min, loading speed 100N/min, scratch length 5mm.Test
It as a result be film-substrate cohesion is 61N.
Embodiment 2:
Select business WC, Co, Mo2C、Ru、Cr3C2, VC powder be raw material, according to WC -12Co -0.6Cr3C2–0.4VC–
1.2Mo2C -1.2Ru ingredient carries out ingredient.Mixture wet-grinding technology and relative device is as follows: using the ratio of grinding media to material of 6:1, the rolling wet type ball of 72h
Time consuming.After granulation is dried to wet-milling mixture, die forming technique is used to prepare diameter for 15mm, highly for 4mm's
Cylindrical body.Green compact is sintered using the technique of pressure sintering containing CO, the last heat preservation sintering phase temperature of sintering process is
1380℃；After 1380 DEG C of vacuum-sinterings keeps the temperature 20min, it is passed through CO and Ar simultaneously in pressure sintering furnace and carries out pressure sintering,
Wherein the be filled with volume and pressure sintering burner hearth total volume ratio of CO gas are 3:100, continue to supplement by subsequent Ar gas, make to press
Power sintering furnace pressure reaches 5.6MPa, keeps the temperature 40min under 5.6MPa pressure.The stereoscan photograph of alloy polishing section is shown in
Fig. 5, the grain size of WC base hard phase is 0.4 μm in alloy.
CC800/9XL coating apparatus using Cemecon company based on magnetron sputtering technique, according to standard coated pre-treatment
Technique and coating process, the depositing Ti on above-mentioned alloy substrate0.89Si0.11N, coating layer thickness are~2 μm.Ti0.89Si0.11N coating
It is face-centred cubic structure with crystal structure identical with TiN.The study found that there are epitaxial growth relationships at film base interface isInterface, lattice mismatch 2.9% forms coherent boundary.
Using the film-substrate cohesion of CSM company, Switzerland big load scratching instrument measurement coating, testing conditions are as follows: diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, scratch speed 5mm/min, loading speed 100N/min, scratch length 5mm.Test
It as a result is film-substrate cohesion > 100N.
Comparative example 2:
Select the WC -12Co-for being~0.4 μm with the WC base Hard Phase Grain Size of furnace sintering preparation with 2 sample of example
0.6Cr3C2- 0.4VC ultra-fine cemented carbide is as coated substrate, using the identical technique of example 2, on above-mentioned alloy substrate
Depositing Ti0.89Si0.11N coating, coating layer thickness are~2 μm.
Using the film-substrate cohesion of CSM company, Switzerland big load scratching instrument measurement coating, testing conditions are as follows: diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, scratch speed 5mm/min, loading speed 100N/min, scratch length 5mm.Test
It as a result be film-substrate cohesion is 85N.
Embodiment 3:
According to using business WC, Co, Mo2C, Ru, WC -25TiC -30TaC -20NbC powder are raw material, according to WC -
6Co–5TiC–6TaC–4NbC–0.9Mo2C -0.78Ru ingredient carries out ingredient.Mixture wet-grinding technology and relative device is as follows: using the ball of 6:1
Expect ratio, the rolling wet ball-milling time of 60h.After granulation is dried to wet-milling mixture, prepared using die forming technique straight
Diameter is 15mm, is highly the cylindrical body of 4mm.Green compact is sintered using the technique of pressure sintering containing CO, sintering process it is last
Heat preservation sintering phase temperature is 1450 DEG C；After 1450 DEG C of vacuum-sinterings keep the temperature 30min, it is passed through CO simultaneously in pressure sintering furnace
Pressure sintering is carried out with Ar, wherein the be filled with volume and pressure sintering burner hearth total volume ratio of CO gas are 2:100, pass through subsequent Ar
Gas continues to supplement, and pressure sintering furnace pressure is made to reach 5.6MPa, keeps the temperature 70min under 5.6MPa pressure.Alloy polishing is cut
The stereoscan photograph in face is shown in Fig. 6, and the grain size of WC base hard phase is 0.9 μm in alloy.
INNOVA coating apparatus using Oerlikon Balzers company based on flash cathodic arc evaporation technology, is 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 coating, coating layer thickness are~2.9 μm.The Al directly contacted with alloy substrate0.66Cr0.34N coating has
Crystal structure identical with AlN is face-centred cubic structure.The study found that there are epitaxial growth relationships at film base interface isInterface, lattice mismatch 9.0% forms semicoherent interface.?
This,Crystal face etc. is all (100) crystal face of three coordinate forms.
Using the film-substrate cohesion of CSM company, Switzerland big load scratching instrument measurement coating, testing conditions are as follows: diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, scratch speed 5mm/min, loading speed 100N/min, scratch length 5mm.Test
It as a result be film-substrate cohesion is 91N.
Comparative example 3:
Select the WC -6Co-for being~0.9 μm with WC base Hard Phase Grain Size in the alloy of furnace sintering preparation with 3 sample of example
5TiC -6TaC -4NbC hard alloy is deposited on above-mentioned alloy substrate as coated substrate using the identical technique of example 3
Al0.65Cr0.30Si0.04W0.01N/Al0.66Cr0.34N laminated coating, coating layer thickness are~2.9 μm.
Using the film-substrate cohesion of CSM company, Switzerland big load scratching instrument measurement coating, testing conditions are as follows: diamond penetrator
120 ° of tip curvature radius 0.2mm, cone angle, scratch speed 5mm/min, loading speed 100N/min, scratch length 5mm.Test
It as a result be film-substrate cohesion is 63N.
From the coated carbides film-substrate cohesion data of embodiment 1,2,3 and the film-substrate cohesion data of corresponding comparative example
Compare it is found that can effectively improve the film-substrate cohesion of coated carbides using hard alloy substrate provided by the invention, in fact
It applies the more corresponding comparative example of 1,3 its film-substrate cohesion of example and improves 44% or more.
Claims (6)
1. a kind of coated carbides matrix, it is characterised in that: the hard alloy substrate is based on film base between coating and matrix
The alloy material design principle of the regulation of interface object phase lattice mismatch and its regulation validity guarantee designs；The hard
After alloy substrate is in conjunction with its surface covering, the feature with high film-substrate cohesion, film base interface is stabilized lattice mismatch
Degree | δ |=(as–ac)/acThe coherence and/or semicoherent interface of < 5 ~ 25%, wherein | δ | it is lattice mismatch, asFor matrix object phase
The interplanar distance of middle crystal face A, acFor the interplanar distance of crystal face B in coating substance phase；The crystal face A and crystal face B is closed in epitaxial growth
System；
The hard alloy substrate material is WC-Co base cemented carbide；Contain Mo simultaneously in the WC-Co base cemented carbide2C and
Ru alloy addition；1.5 μm of the grain size < of WC base hard phase in the WC-Co base cemented carbide, the crystal of Co base Binder Phase
Structure is close-packed hexagonal structure；It is the coating containing metal nitride with the coating that described matrix matches；
Mo in the WC-Co base cemented carbide2C and Co mass ratio are (10 ~ 15): 100, Ru and Co mass ratio are (10 ~ 15):
100；
The coated carbides matrix is prepared by following step: by design component with each raw material is taken, will be existed with the raw material taken
Wet-milling successively carries out mixture drying and granulating, compression moulding after mixing in ball mill, and sintering obtains the coating hard and closes
Auri body；The last heat preservation sintering stage of the sintering is sintered by vacuum heat-preserving and pressure heat-preserving containing CO is sintered two steps and forms；It burns
It ties in process, 1360 DEG C of the temperature > in last heat preservation sintering stage；The sintering of pressure heat-preserving containing CO refers to that vacuum heat-preserving is burnt
After the completion of knot, it is passed through CO and Ar simultaneously in pressure sintering furnace and carries out pressure sintering；The body that be passed through CO gas gross passes through CO
Fraction is controlled, and CO gas is filled with volume and pressure sintering burner hearth total volume ratio as (1 ~ 3): 100；Be passed through Ar gas
Total amount is controlled by gross pressure in pressure sintering furnace, is continued to supplement by subsequent Ar gas, is made stagnation pressure in pressure sintering furnace
5 MPa of power >.
2. a kind of coated carbides matrix according to claim 1, it is characterised in that: the WC-Co base cemented carbide
Including YG alloy and YW alloy；In the YG alloy, Mo is removed2Outside C and Ru, the matter of other alloy addition total amounts and alloy total amount
Amount is than < 2:100；The YW alloy is the WC-Co base cemented carbide of-NbC of-TaC containing TiC, removes Mo2Outside C and Ru, other alloys
The mass ratio > 2:100 of additive total amount and alloy total amount.
3. a kind of coated carbides matrix according to claim 2, it is characterised in that: the YG alloy includes Ultra-fine Grained
YG hard alloy.
4. a kind of coated carbides matrix according to claim 1, it is characterised in that: the painting containing metal nitride
Layer includes single layer and laminated coating；Either single layer or laminated coating, the coating material bound directly with described matrix are gold
Belong to nitride.
5. a kind of coated carbides matrix according to claim 4, it is characterised in that: what described and matrix was bound directly
Metal nitride has crystal structure identical with AlN or TiN.
6. a kind of coated carbides matrix according to claim 1, it is characterised in that: the last heat preservation sintering rank
Section, controls vacuum heat-preserving sintering time >=20 min, and control reaches 5 MPa's of > containing gross pressure in CO and Ar gas and furnace simultaneously
The heat preservation sintering time >=40 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710157652.XA CN106835116B (en) | 2017-03-16 | 2017-03-16 | A kind of coated carbides matrix and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710157652.XA CN106835116B (en) | 2017-03-16 | 2017-03-16 | A kind of coated carbides matrix and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106835116A CN106835116A (en) | 2017-06-13 |
| CN106835116B true CN106835116B (en) | 2019-08-16 |
Family
ID=59144591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710157652.XA Active CN106835116B (en) | 2017-03-16 | 2017-03-16 | A kind of coated carbides matrix and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106835116B (en) |
Families Citing this family (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 |
| EP3784813A1 (en) * | 2018-04-24 | 2021-03-03 | Oerlikon Surface Solutions AG, Pfäffikon | Coating comprising mcral-x coating layer |
| JP6972508B2 (en) * | 2019-12-19 | 2021-11-24 | 株式会社タンガロイ | Carbide and coated cemented carbide, and tools with them |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8512882B2 (en) * | 2007-02-19 | 2013-08-20 | TDY Industries, LLC | Carbide cutting insert |
| CN101429612B (en) * | 2008-12-01 | 2011-01-26 | 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 |
| US10336654B2 (en) * | 2015-08-28 | 2019-07-02 | Kennametal Inc. | Cemented carbide with cobalt-molybdenum alloy binder |
-
2017
- 2017-03-16 CN CN201710157652.XA patent/CN106835116B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106835116A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106835116B (en) | A kind of coated carbides matrix and preparation method thereof | |
| Chen et al. | Effects of nitriding on the microstructure and properties of VAlTiCrMo high-entropy alloy coatings by sputtering technique | |
| Yu et al. | Mechanical, tribological and corrosion performance of WBN composite films deposited by reactive magnetron sputtering | |
| CN104451655B (en) | High temperature resistance material surface alloy coating composite material, coating and preparation method thereof | |
| CN104093881B (en) | Coated cutting tool and preparation method thereof | |
| JP7104626B2 (en) | Cutting tools | |
| JP2013078840A (en) | Cutting tool | |
| CN109402564A (en) | A kind of AlCrSiN and AlCrSiON double-layer nanometer composite coating and preparation method thereof | |
| CN109881148A (en) | A kind of AlCrTiSiN high-entropy alloy nitride coatings of single phase solid solution structure and its preparation method and application | |
| El Garah et al. | Structural and mechanical properties of AlTiTaZr (N) medium entropy films (MEF) obtained by DC magnetron sputtering in dynamic mode | |
| Dyadyura et al. | Influence of roughness of the substrate on the structure and mechanical properties of TiAlN nanocoating condensed by DCMS | |
| JP6064549B2 (en) | Sintered body and method of manufacturing the sintered body | |
| CN110042294A (en) | Carbide chip and preparation method thereof for milling hardened steel | |
| He et al. | Effects of deposition temperature on the microstructure, mechanical properties, high temperature corrosion and oxidation properties of AlCrNbTiZr high entropy alloy coatings | |
| Wendler | Oxidation resistance of nanocrystalline microalloyed γ-TiAl coatings under isothermal conditions and thermal fatigue | |
| JP2009035802A (en) | Cemented carbide | |
| JP2009034811A (en) | Cemented carbide insert for parting, grooving and threading | |
| CN105506580B (en) | Surface modified coat cutting tip and preparation method thereof | |
| CN109252137B (en) | Preparation method of zirconium alloy surface coating | |
| Wang et al. | Effects of nitrogen content on microstructures and mechanical behavior of (TiTaCrMoNb) Nx films | |
| CN110484892B (en) | High-cutting-life Al2O3Base CVD coating alloy and preparation method thereof | |
| Kara et al. | Microstructure, mechanical, and scratch resistance properties of TiAlCrNbN-graded composite coating deposited on AISI H13 steel substrate with pulsed DC closed field unbalanced magnetron sputtering method | |
| JPH02228474A (en) | Coated sintered alloy | |
| Hampshire et al. | Structure and mechanical properties of co-deposited TiAl thin films | |
| Sasaki et al. | Nanocrystalline structure and mechanical properties of vapor quenched Al-Zr-Fe alloy sheets prepared by electron-beam deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191218 Address after: 054800 No.62 Pujiang street, international cashmere Park, Qinghe County, Xingtai City, Hebei Province Patentee after: Hebei Zhuji Cemented Carbide Co., Ltd. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: Central South University |
|
| TR01 | Transfer of patent right |