CN108796335A - The preparation method of composite structure hard alloy product - Google Patents
The preparation method of composite structure hard alloy product Download PDFInfo
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- CN108796335A CN108796335A CN201710286486.3A CN201710286486A CN108796335A CN 108796335 A CN108796335 A CN 108796335A CN 201710286486 A CN201710286486 A CN 201710286486A CN 108796335 A CN108796335 A CN 108796335A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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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
-
- 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
- B22F7/06—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 workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—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 workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The method with composite structure hard alloy product is prepared the present invention provides a kind of, is included the following steps：A, internal layer and outer layer carbide alloy mixture are prepared respectively using PM technique, internal layer, outer layer material be respectively and independently selected from WC-Binder or WC-MeC-Binder it is one or two kinds of, wherein, Binder is binder, one or more in Co, Ni, Fe or Cr, MeC is selected from the one or more of transition group refractory carbide；B, internal layer green compact and outer layer green compact are separately formed；C, internal layer and outer layer green compact are set in together, are sintered；D, finished product processing is to get composite structure hard alloy product.Prepared by the present invention has composite structure hard alloy product, and there is proportion and shape to be easy to control, be simple to manufacture, advantage of low cost.
Description
Technical field
The invention belongs to hard alloy technical fields, are related to a kind of preparation skill of the hard metal article with composite construction
Art more particularly to a kind of preparation method of the carbide roll ring product with composite construction, especially a kind of high-speed rod roll
The preparation method of the carbide roll ring of machine steel rolling.
Background technology
Hard alloy be it is a kind of using PM technique prepare, with refractory carbides such as WC, TiC, TaC, NbC
Make hard phase, using the plastic metals such as Co, Ni, Fe and alloy as the composite material of Binder Phase, there is good wearability, heat-resisting
Property, corrosion resistance and higher obdurability, are widely used in the every field of national economy.
Carbide roll ring just has become the standard consumable part of high-speed rod-rolling mill in the 60 to 70's of last century,
By the development of nearly half a century, material, manufacturing process etc. are all quite ripe, and conservative estimation, domestic high line hard closes
Golden collars Year's consumption is at 1200 tons or so.
The working environment of steel rolling collars is complicated, and use condition is harsh, in the operation of rolling roll (ring) directly with high temperature rolled piece
Contact, is subjected to larger roll-force, thermal stress and percussion.In actual use, the collars working lining contacted with rolled piece
(about the 40% of integral thickness) needs high hardness and wearability, and transmits rolling torsion, bears in the collars of erection stress
Layer then needs high intensity and toughness.If collars is designed to internal layer using the good material of obdurability, outer layer is good using wearability
Material composite construction, then can meet actual use simultaneously and the different of collars ectonexine wearability and obdurability are required.So
And in presently disclosed technology, the roll (ring) of this composite construction is mainly used for type, rolling bar field, and high-speed line
Material roll collar of rolling mill, because its rotary speed is fast, centrifugal force is big, the bond strength of composite roll (ring) is insufficient, therefore high speed wire rolling one
As using whole homogeneous carbide roll ring.In fact, high line collars has significant portion of extraordinary failure to be because of assembly tapered sleeve
Axial rift caused by the radial tension of generation.For this purpose, technical staff proposes a large amount of solutions in field.
Patent US5044056 is disclosed prepares hard alloy (outer shroud)+cast iron/steel (inner ring) again using centrifugal casting technique
Close the process of roll (ring).
Patent CN1597161A discloses a kind of cemented carbide/steel composite roller (ring) prepared using metal adhesive
And its process.
Patent CN101386028A, discloses a kind of cemented carbide/steel composite roller and preparation method thereof, this compound to roll
Roller is made of hard alloy outer shroud, steel inner ring and preseting solder, is prepared using vacuum brazing process.
Patent CN 201659142U disclose a kind of line, bar rolling mill mechanical composite roll collar and manufacturing method, this is compound
Collars includes outer layer, inner ring, compression ring and soket head cap screw, and outside inner ring, compression ring is sleeved on inner ring outer layer jacket, compression ring
Be connected and fixed by soket head cap screw between inner ring, the arrangement of soket head cap screw circular array, inner ring and compression ring respectively with
The both sides step of outer layer is in contact.Using being mechanically assembled.
Patent CN 101716656A, disclose a kind of metal ceramic composite roll collar and preparation method thereof, the composite ring by
Collars and matrix are constituted.Its technical solution is：It is first collars green compact through molding or isostatic pressing by alloy powder, 1100
DEG C~1400 DEG C under the conditions of be sintered 10 minutes~180 minutes.Then using the inner wall of collars made from sintering as mold cavity
A part, using casting technique by molten steel or molten iron, it is cast steel/iron to be cast in collars and obtain internal layer, and outer layer is hard alloy
Composite ring.
CN104475455A discloses a kind of composite alloy roller, including five-layer structure, is sequentially followed successively by from the top down：Chromium gold
Belong to layer, adhesive layer, hard alloy carbon tungsten roller ring, nickel metal layer, internal layer spheroidal graphite cast-iron layer sets between the five-layer structure
It is equipped with reinforcement fixture, snubber block is connected with below the internal layer spheroidal graphite cast-iron layer, is set among the snubber block
It is equipped with groove.
Document《Collar and steel bushing adhesion test》(《Hunan is metallurgical》, (2)：It 7-1) reports viscous using metal adhesive
It is hard alloy outer shroud that the method for knot, which prepares outer shroud, and inner ring is the test result of the compound roller ring of steel.
Document《Study of A Composite Hard Metal-Roller Made by HIP Diffusion Bonding》(《Rare Metals Materials and engineering》, 27 (3)：177-
181) it reports and iron base composite material is selected to make composite roll internal layer, it will be with hard alloy outer layer using hot isostatic pressing diffusion connection method
Bond compound test result.
Document《The exploitation of Composite Hard Alloy Manufacture Technology》(《Special Processes of Metal Castings and non-ferrous alloy》Supplementary issue (1)：107-108)
For hard alloy brittleness greatly and production cost height, the examination of hard alloy/cast steel composite roll is prepared using composite casting technology
Test result.
Document《The Application research of cemented carbide composite roll collar》(《Laigang science and technology》, (6) 47-48) report it is quiet using heat etc.
Suppress the application effect that standby internal layer is the composite roll that steel outer layer is hard alloy.
Document《The progress of cemented carbide composite roll collar》(《PM technique》, 26 (1)：60-64)
The technical progress for outlining domestic and international carbide roll ring, cemented carbide composite roll collar, summarize state, inside and outside composite ring system
Standby technique is broadly divided into mechanical connection, gluing knot, casting, hot isostatic pressing, the methods of welding.
Composite roll (ring) described in technical literature disclosed above refers to wear-resisting hard alloy outer shroud and obdurability
Good iron and steel material quality inner ring forms composite roll (ring) by complex methods such as combined type mechanically, cementing formula, metallurgical bond formulas.Its
In, combined type mechanically refers to being connect hard alloy outer shroud with steel (iron) matter inner ring Automatic manual transmission with fastening bolt etc.；Cementing formula
Refer to using metal adhesive by hard alloy outer layer and steel (iron) matter internal layer bonding connection, metallurgical bond formula be by cast,
The method of welding etc. is by ectonexine composite joint.First two combination can not be reliably used for high speed because of low strength
Rod-rolling mill, and it is above-mentioned using casting, welding by hard alloy and the compound technology for preparing composite ring of steel, because of hard
The Physical and mechanical properties of alloy and steel (iron) material, especially hot physical difference is too big, it is caused to obtain abundant metallurgical binding
Technical difficulty is very big, and process costs are very high.
Existing insufficient in view of the above technology, a large amount of technological improvement has also been made in those skilled in that art, such as：
United States Patent (USP) US6511265B1 discloses a kind of Composite rotary tools, including two parts, two parts are by performance
Different hard alloy synthesis.Preparation method is to use a kind of mold of special construction, will form two-part hard alloy
Material powder is packed into the corresponding site of mold simultaneously, common die mould, then densified sintering product.The patent provides a kind of prepare to have
The method of high-strength composite structure hard alloy product, but this method is for the property of the cemented carbide material used in two parts
Can and ingredient limitation it is very big, the mouldability of two kinds of materials and sintering characteristic etc. must match, and otherwise sintering shrinkage will occur not
Unanimously cause two parts that can not bond.For this method to the more demanding of mold, mould structure is complicated simultaneously.Therefore, this method
The deficiencies of it is big that there are technique controlling difficulties, and lumber recovery is not high, and the material used in two parts is limited.
Patent CN1843644A discloses a kind of high line cemented carbide composite roll collar and manufacturing method, the composite ring include
Collars matrix and with the different compound working lining of the material trademark of the collars matrix, collars matrix and compound working lining through sintering
And it is integral.Its preparation process is：Collars matrix and the hard alloy powder for not mixing forming agent are packed into graphite jig simultaneously, passed through
Real latter same be fitted into dedicated intermediate frequency hydraulic vibration sintering machine of vibration dress carries out hot pressed sintering, then carries out secondary positive pressure sintering,
Through grinding, finished product.The patent realizes high line collars working lining high abrasion technology requirement, while can also make to scrap
Collars is reused, but its technique need to first use hot pressed sintering, then carries out secondary positive pressure sintering, and process efficiency is relatively low, at
This is higher.
CN103386417A is disclosed a kind of realized using metallurgical bond technology and is produced based on hard alloy green body
Method without transition zone hard metal article includes successively：A, prepare according to a conventional method Binder Phase weight percent be 8%~
The 30% identical or different hard alloy of two pieces is as green body；B, hard alloy green body is waited for that metallurgical bond face finishes, light
Cleanliness≤Ra0.04mm, rest part carry out conventional machining processing；C, metallurgical bond face, which carries out cleaning treatment simultaneously, is waited for green body
Coat one layer of acetone；D, it assembles；E, the green body assembled is placed in vacuum drying oven, is carried out at a temperature of 1200 DEG C~1450 DEG C true
Empty metallurgical bond is heat-treated 1~1.5 hour, vacuum degree≤0.8Pa, and the hard without transition zone of metallurgical bond is obtained after cooling
Alloy product.The patent overcomes hard alloy in the prior art and is answered with heat present in steel (iron) material bonding or welding process
Power and the coefficient of expansion are different and collars is caused to be suitble to the production of massive article using the defect of failure, but it uses prefabricated conjunction
The processing request of golden base is very high, adhesive surface processing finish to reach≤Ra0.04mm, there is also technological requirement height, cost compared with
High problem.
Patent CN103817150A, discloses a kind of gradient-structure type carbide roll ring and its manufacturing process, outside collars
Forming component gradient between layer and collars core, collars outer layer and collars core have the hard material of different quality content, bonding
Hard material, binding material and/or additive ball mill mixing are become collars ball mill mixing, are dried, mix by material and/or additive
Wax re-dry is cold-pressed into mixing the collars outer layer ball mill mixing of wax and mixing the collars core ball mill mixing place Min layers closed assembly powder of wax
Type becomes collars blank, and collars blank, which is sintered dewaxing, becomes hard alloy, becomes hard alloy roller after Overheating Treatment
Ring, this to have its surface abrasion resistance degree of the carbide roll ring of component gradient to be improved significantly, service life is in same wear strips
15% or so are improved under part, production cost is lower.The art solutions are similar with US6511265B1, also using layering laying
Loading process realizes that the ingredient and/or capability gradient of ectonexine, ectonexine material must satisfy sintering character and match, especially interior
The sintering shrinkage of outer layer must be consistent, and otherwise it is easy to appear the problems that part can not bond.
Patent CN105127432A discloses a kind of Graded-structure Cemented Carbides and preparation method thereof, and technical solution is,
Prepare inner core green compact (or alloy) and outer shroud green compact respectively first, and the sintering shrinkage coefficient for controlling outer shroud green compact is more than inner core,
Inner core green compact is nested in outer shroud green compact, the two is interference fitted to form nest, then nest is put into sintering furnace, in indifferent gas
First sintering, 1200 DEG C~1300 DEG C of sintering temperature are carried out under body atmosphere；Carry out double sintering, sintering temperature are vacuumized again
1380 DEG C~1470 DEG C.The patent, moulding process is simple, easy to control, but sintering process is required high, it is necessary in high vacuum
It is sintered under degree or protective atmosphere, otherwise also will appear the not glued problem in part, simultaneously as the liquid phase diffusion in sintering process
Migration, also results in entire product and homogenizes, i.e., the component gradient of ectonexine and/or capability gradient no longer exist.
Invention content
It is prepared with composite structure hard alloy product in view of the deficiencies of the prior art, the present invention provides a kind of
Method.
Composite structure hard alloy product of the present invention is constituted by inside and outside two layers, and inside and outside layer is respectively ingredient
And/or two kinds of hard alloy materials that performance is different.The composite hard alloy product uses the side of " independent green compact co-sintering "
Method realizes that bonding is compound, by controlling the binder content of internal layer and outer layer hard alloy (individually below with symbol " BIt is interior" and
“BOutside" indicate), internal layer and outer layer hard alloy independently sintered hard phase mean grain size (individually below with symbol " d αIt is interior”
" d αOutside" indicate, press national standard GB3488, ISO4499 or ASTM B390 are evaluated) and internal layer and outer layer hard alloy used in WC
Total carbon content (below with symbol " CtIt is interior" and " CtOutside" indicate) come migration of liquid row when controlling sintering between internal layer and outer layer
For, to solve the problems, such as inside and outside layer sintering when occur deform, bond it is incomplete.
It is well known that the hardness and obdurability of hard alloy are mainly and binder content, WC mean grain sizes are related, generally
For, binder content is high, and WC mean grain sizes are thick, and alloy obdurability is high, and crack resistance is good, and then hardness is high on the contrary, excellent wear resistance.Cause
This will prepare outer abrasion resistant, and the composite structure hard alloy product of internal layer cracking resistance, there are two types of schemes：
Scheme one：Internal layer is made using high binder content hard alloy, low binder content makees outer layer；
Scheme two：Internal layer is made using coarse-grain hard alloy, fine grained cemented carbide makees outer layer.
Present inventor, which tests, to be found, (super when the binder content of inside and outside layer differs greatly according to scheme one
Cross 5wt%), green body is in sintering process, and there are liquid phase long-range migration phenomenons, in general, liquid phase will contain from high-content side to low
Side migration is measured, and concentration gradients are bigger, migration of liquid amount is bigger.This migratory behaviour will cause alloy to homogenize, ingredient and/or
Capability gradient will disappear, and excessively a large amount of migration of liquid also results in the volume change of ectonexine, so as to cause product deformation,
Therefore, it is necessary to control the migration of liquid amount in sintering process.
According to scheme two, when the WC mean grain size differences of inside and outside layer hard alloy are apparent, in blank sintering,
There is also above-mentioned migration of liquid phenomenons, in general, liquid phase is migrated from coarse-grain granularity area to fineness of grain area, and grain size difference is got over
Greatly, migration of liquid amount is bigger.This migratory behaviour will cause coarse grain zone Binder Phase to reduce, and fine grained region Binder Phase increases, and crystal grain is long
Greatly, it disappears so as to cause the hardness gradient of inside and outside layer.It crosses a large amount of migration of liquid and also results in product deformation.
The present inventor further tests discovery, and the total carbon content of inside and outside layer hard alloy is also to influence migration of liquid
Key factor, liquid phase are migrated from high-carbon regions to low-carbon area.But this influence is smaller, and easy artificial adjustment, just can be used for controlling
Make the above-mentioned migration of liquid caused by binder content gradient or grain size difference.Above two scheme can be improved such as a result,
Under：
Scheme one：Internal layer, low binder content (higher carbon are made using high binder content (compared with low carbon content) hard alloy
Content) make outer layer；
Scheme two：Internal layer is made (compared with low carbon content) using coarse-grain hard alloy, fine grained cemented carbide (higher carbon content) is made
Outer layer.
Further improve is, while adjusting matching B, and tri- parameters of d α and Ct control migration of liquid amount, as a result,
Above two scheme is further improved to：
Scheme one：Internal layer, low binder are made using high binder content (compared with low carbon content, compared with little crystal grain degree) hard alloy
Content (higher carbon content) makees outer layer；
Scheme two：Internal layer, fine grained cemented carbide are made (compared with low carbon content, smaller Binder Phase content) using coarse-grain hard alloy
(higher carbon content) makees outer layer.
Specific implementation step is as follows：
A, prepare internal layer and outer layer carbide alloy mixture respectively using PM technique, internal layer, outer layer material point
It is not independently selected from one or two in WC-Binder or WC-MeC-Binder,
Wherein, Binder is binder, one or more in Co, Ni, Fe or Cr, and MeC is selected from transition group infusibility
Metal carbides it is one or more；
B, internal layer green compact and outer layer green compact are separately formed；
C, internal layer and outer layer green compact are set in together, are sintered；
D, finished product processing is to get composite structure hard alloy product.
Preferably, in the step A, Δ B=B is controlledIt is interior-BOutside=2wt%~15wt%,
Wherein, it is the binder content of internal layer hard alloy in B, is the binder content of outer layer hard alloy outside B.
Further preferably, Ct is controlledIt is interior< CtOutside, CtIt is interior=5.85wt%~6.05wt%, CtOutside=5.95wt%~
6.15wt%,
Wherein, it is the WC total carbon contents of internal layer hard alloy in Ct, is the WC total carbon contents of outer layer hard alloy outside Ct.
Still more preferably,：In the step A, Δ d is controlledα=dOutside α-dIn α=0.5 μm~1.0 μm,
Wherein, it is independently sintered obtained hard phase mean grain size for internal layer hard alloy in d α, is outer layer hard outside d α
The hard phase mean grain size that alloy is independently sintered.
Preferably, in the step A, d α are controlledIt is interior=2.0 μm~4.0 μm, d αOutside=1.0 μm~3.0 μm,
Wherein, it is independently sintered obtained hard phase mean grain size for internal layer hard alloy in d α, is outer layer hard outside d α
The hard phase mean grain size that alloy is independently sintered.
Further preferably, in the step A, Ct is controlledIt is interior< CtOutside, CtIt is interior=5.85wt%~6.05wt%, CtOutside=
5.95wt%~6.15wt%,
Wherein, it is the WC total carbon contents of internal layer hard alloy in Ct, is the WC total carbon contents of outer layer hard alloy outside Ct.
Still more preferably, in the step A, Δ B'=B is controlledOutside-BIt is interior=2wt%~5wt%,
Wherein, it is the binder content of internal layer hard alloy in B, is the binder content of outer layer hard alloy outside B.
Still further preferably, in the step C, control
Δ φ=0.2mm~10mm,
Wherein, it is internal layer green compact size in Φ D, in Φ d, in h, is the constriction coefficient being independently sintered in K, Φ D is outer, Φ d
Outside, outside h it is outer layer green compact size, is the constriction coefficient being independently sintered outside K.
The present invention controls Δ B=BIt is interior-BOutside=2wt%~15wt%, Δ B is too small, and migration of liquid driving force is too small when sintering,
It is unfavorable for diffusion bonding, is susceptible to locally unbonded problem；And Δ B is too big, internal layer and outer layer hard alloy can not be same
Densification is completed under one sintering process.
The present invention uses conventional powder metallurgical moulding process, such as just molding system, isostatic cool pressing compacting, is separately formed ring-type
Or cylinder internal layer green compact and annular outer layer green compact.
Wherein：
Internal layer green compact size is Φ DIt is interior×ΦdIt is interior×hIt is interior, the constriction coefficient being independently sintered is KIt is interior；
Outer layer green compact size is Φ DOutside×ΦdOutside×hOutside, the constriction coefficient being independently sintered is KOutside；
Meet：
Δ φ=0.2mm~10mm, Δ φ is not
Preferably too small, because there are dimensional tolerances for powder compact shape, Δ φ is too small, and ectonexine cannot be fully bonded, so as to cause combination
It is insufficient；Bonded area (π DIt is interiorhIt is interior) bigger, Δ φ should be bigger, but no more than 10mm, otherwise outer layer is easy due to overtension
There is axial rift.
Internal layer and outer layer green compact are set in together, are placed on the graphite boat through release treatment, stove co-sintering is entered, it is cold
But it comes out of the stove to get to the good product alloy blank with composite construction of shape.Sintering can be used conventional vacuum-sintering or
Low pressure sintering, sintering temperature generally at 1340 DEG C~1480 DEG C, within outer layer alloys tissue and performance reach subject to requirement.
The hard metal article with composite construction be can be obtained by product alloy blank is machined.Product
Shape is good, and internal layer and outer layer form complete metallurgical binding, and faying face is the diffusion layer that a thickness T is no more than 10mm, this expansion
The ingredient and/or performance of scattered layer are between internal layer and outer layer, and in sintering process, migration of liquid amount is bigger, and thickness of diffusion layer is got over
Width, until entire complex homogenizes.
The present invention overcomes the shortcomings of the prior art and technological difficulties, have simple for process, control simplicity, in conjunction with strong
The advantages such as degree is high, and manufacturing cost is low, the especially more advantage when preparing large scale product.
Description of the drawings
Fig. 1 is the structural schematic diagram of the hard metal article of the present invention with two-layer composite.
Fig. 2 is cut side of the present invention to the detection sample of the composite effect of the two-layer composite hard metal article
Method schematic diagram.
Fig. 3 is that the present invention illustrates the hardness detection method of the two-layer composite hard metal article binding site
Figure.
Fig. 4 is that the present invention illustrates the detection method of the two-layer composite hard metal article faying face bond strength
Figure.
Fig. 5 is Hardness results comparison diagram of the present invention to embodiment 6 and the faying face of comparative example 2.
Fig. 6 is the Hardness results of the faying face of the two-layer compound collars of the invention produced to embodiment 15.
Fig. 7 is the metallographic microstructure figure of the faying face for the two-layer compound collars that the embodiment of the present invention 15 is produced.
Reference numeral：1 is outer layer, and 2 be joint surface, and 3 be outer layer.
Specific implementation mode
Invention is further described in detail with reference to the accompanying drawings and detailed description.But this should not be interpreted as sending out
The range of bright above-mentioned theme is only limitted to following embodiments.
Comparative example 1 and embodiment 1-5, preparation process are as follows：
(1) according to the following table 1, conventional powder metallurgical technology is respectively adopted and prepares internal layer and outer layer by dispensing, ball milling, drying
Required mixture, it is spare.
(2) mixture that step (1) is produced individually is prepared into internal layer green compact and outer layer green compact using compression molding,
In, outer layer green compact size is about(cyclic annular, independent sintering shrinkage COEFFICIENT KOutside=1.26), internal layer green compact ruler
It is very little to be about(cylinder, independent sintering shrinkage COEFFICIENT KIt is interior=1.20).
Note：The outer layer green compact size of comparative example 1 is about(cyclic annular, independent sintering shrinkage COEFFICIENT KOutside
=1.26), internal layer green compact size is about(cylinder, independent sintering shrinkage COEFFICIENT KIt is interior=1.20).
(3) the inside and outside lamination base of step (2) is set in together, dress boat enters stove sintering, and sintering temperature is shown in Table 1, has been sintered
Cheng Hou has a power failure, cooling, coming out of the stove obtains the alloy blank of composite article.
(4) alloy blank for obtaining step (3) is polished end face using grinding, then uses linear cutter, will
Its wire cutting dissection produces the strip sample of 6 × 7 × 20 (mm) specifications in binding site, during sample is with faying face as far as possible
The heart, sample carries out bending strength test again after handling as required (detection bond strength detects bending resistance using three point bending test method
Intensity is loaded as far as possible in faying face) and vickers hardness test (hardness gradient of its faying face is detected, from faying face toward both sides
Vickers hardness is beaten every about 1mm), it the results are shown in Table 1.
Table 1
Table 2
By above-mentioned experimental data as it can be seen that the inside and outside layer bonding state of embodiment 1-5 is better than comparative example 1, embodiment 2,
3 bond strength is significantly better than comparative example 1.
Comparative example 2 and embodiment 6-9, preparation process are as follows：
(1) according to the following table 2, conventional powder metallurgical technology is respectively adopted and prepares internal layer and outer layer by dispensing, ball milling, drying
Required mixture, it is spare.
(2) mixture that step (1) is produced individually is prepared into internal layer green compact and outer layer green compact using compression molding,
In, outer layer green compact size is about(cyclic annular, independent sintering shrinkage COEFFICIENT KOutside=1.28), interior lamination
Base size is about(cyclic annular, independent sintering shrinkage COEFFICIENT KIt is interior=1.24).
(3) the inside and outside lamination base of step (2) is set in together, dress boat enters stove sintering, and sintering temperature is shown in Table 2, has been sintered
Cheng Hou has a power failure, cooling, coming out of the stove obtains the alloy blank of composite article.
(4) alloy blank for obtaining step (3) is polished end face using grinding, then uses linear cutter, will
It dissects the strip sample for producing 6 × 7 × 20 (mm) specifications, and sample carries out bending strength test (detection knot after handling as required
Close intensity) and vickers hardness test (hardness gradient for detecting its faying face), it the results are shown in Table 2.
Table 3
Table 4
By above-mentioned experimental data as it can be seen that the capability gradient of embodiment 6-9 products is significantly better than comparative example 2, bond strength
Also it is better than comparative example 2.
Comparative example 3 and embodiment 10-14, preparation process are as follows：
(1) according to the following table 3, conventional powder metallurgical technology is respectively adopted and prepares internal layer and outer layer by dispensing, ball milling, drying
Required mixture, it is spare.
(2) mixture that step (1) is produced individually is prepared into internal layer green compact and outer layer green compact using compression molding,
In, outer layer green compact size is about(cyclic annular, independent sintering shrinkage COEFFICIENT KOutside=1.28), interior lamination
Base size is about(cyclic annular, independent sintering shrinkage COEFFICIENT KIt is interior=1.22).
(3) the inside and outside lamination base of step (2) is set in together, dress boat enters stove sintering, and sintering temperature is shown in Table 3, has been sintered
Cheng Hou has a power failure, cooling, coming out of the stove obtains the alloy blank of composite article.
(4) alloy blank for obtaining step (3) is polished end face using grinding, then uses linear cutter, will
It dissects the strip sample for producing 6 × 7 × 20 (mm) specifications, and sample carries out bending strength test (detection knot after handling as required
Close intensity) and vickers hardness test (hardness gradient for detecting its faying face), it the results are shown in Table 3.
Table 5
Table 6
By above-mentioned experimental data as it can be seen that the capability gradient of embodiment 10-14 products, bond strength are significantly better than comparison
Example 3.
Embodiment 15, preparation process is as follows：
(1) conventional powder metallurgical technology is respectively adopted by dispensing, ball milling, the dry mixing prepared needed for internal layer and outer layer
Material, it is spare.Wherein internal layer material is WC-15wt.% (Co+Ni+Fe), and outer layer material is：WC-7wt.%TiC-2wt.%TaC-
12wt.% (Co+Ni+Cr).
(2) mixture that step (1) is produced individually is prepared into internal layer green compact and outer layer green compact using compression molding,
China and foreign countries are laminated base size(cyclic annular, independent sintering shrinkage COEFFICIENT KOutside=1.30), internal layer green compact ruler
It is very little to be about(cyclic annular, independent sintering shrinkage COEFFICIENT KIt is interior=1.20).
(3) the inside and outside lamination base of step (2) is set in together, dress boat enters stove sintering, and sintering temperature is 1450 DEG C, is burnt
After the completion of knot, have a power failure, cooling, coming out of the stove obtains having the carbide roll ring product blank of composite construction.
(4) alloy blank for obtaining step (3) is polished end face using grinding, then uses linear cutter, will
It dissects the strip sample for producing 6 × 7 × 20 (mm) specifications, and sample carries out bending strength test (detection again after handling as required
Bond strength is 2797MPa) and vickers hardness test (detect the hardness gradient of its faying face, the thickness of diffusion layer T is about
9mm), the tissue of metallographic microscope detection interface is used in combination.
The data such as bond strength, bonding state, the hardness gradient of 15 product of embodiment are significantly better than the prior art, obtain
Unexpected technique effect.
In the case where not departing from the spirit and essential characteristics of the present invention, the embodiment of the present invention can be embodied as others
Form.Corresponding change is made according to usage.It is high, wear-resisting that internal layer hardness can such as be made, outer layer hardness is low, the high mould of intensity
Has product (such as drawing die, stamping die).For another example, it is contemplated that the present invention may be use with the connection of two hard alloy pieces, the two are hard
Matter alloy components can be same material and/or performance, can also be unlike material and/or performance.Therefore the example of the present invention can
To think it is illustrative and not restricted in all respects, won by the scope of the invention indicated by appended claims
In the range of description above, therefore all changes within its intension and claim equivalent scope are all contained in it and are wanted
Among the range for asking protection.
Claims (8)
1. a kind of preparation method of composite structure hard alloy product, which is characterized in that include the following steps：
A, internal layer and outer layer carbide alloy mixture are prepared respectively using PM technique, internal layer, the material difference of outer layer are only
It is vertical one or two kinds of in WC-Binder or WC-MeC-Binder,
Wherein, Binder is binder, one or more in Co, Ni, Fe or Cr, and MeC is selected from transition group refractory metal
Carbide it is one or more；
B, internal layer green compact and outer layer green compact are separately formed；
C, internal layer and outer layer green compact are set in together, are sintered；
D, finished product processing is to get composite structure hard alloy product.
2. the preparation method of composite structure hard alloy product according to claim 1, it is characterised in that：The step A
In, control Δ B=BIt is interior-BOutside=2wt%~15wt%,
Wherein, BIt is interiorFor the binder content of internal layer hard alloy, BOutsideFor the binder content of outer layer hard alloy.
3. the preparation method of composite structure hard alloy product according to claim 2, it is characterised in that：The step A
In, control CtIt is interior< CtOutside, CtIt is interior=5.85wt%~6.05wt%, CtOutside=5.95wt%~6.15wt%,
Wherein, CtIt is interiorFor the WC total carbon contents of internal layer hard alloy, CtOutsideFor the WC total carbon contents of outer layer hard alloy.
4. the preparation method of composite structure hard alloy product according to claim 3, it is characterised in that：The step A
In, Δ dα=dOutside α-dIn α=0.5 μm~1.0 μm,
Wherein, d αIt is interiorObtained hard phase mean grain size, d α are independently sintered for internal layer hard alloyOutsideIt is only for outer layer hard alloy
The hard phase mean grain size of vertical sintering.
5. the preparation method of composite structure hard alloy product according to claim 1, it is characterised in that：
In the step A, d α are controlledIt is interior=2.0 μm~4.0 μm, d αOutside=1.0 μm~3.0 μm,
Wherein, d αIt is interiorObtained hard phase mean grain size, d α are independently sintered for internal layer hard alloyOutsideIt is only for outer layer hard alloy
The hard phase mean grain size of vertical sintering.
6. the preparation method of composite structure hard alloy product according to claim 5, it is characterised in that：
In the step A, Ct is controlledIt is interior< CtOutside, CtIt is interior=5.85wt%~6.05wt%, CtOutside=5.95wt%~6.15wt%,
Wherein, CtIt is interiorFor the WC total carbon contents of internal layer hard alloy, CtOutsideFor the WC total carbon contents of outer layer hard alloy.
7. the preparation method of composite structure hard alloy product according to claim 6, it is characterised in that：
In the step A, Δ B'=B is controlledOutside-BIt is interior=2wt%~5wt%,
Wherein, BIt is interiorFor the binder content of internal layer hard alloy, BOutsideFor the binder content of outer layer hard alloy.
8. according to the preparation method of any composite structure hard alloy products of claim 1-7, it is characterised in that：
In the step C, controlDIt is interior< dOutside,Δ φ=0.2mm~
10mm,
Wherein, Φ DIt is interior、ΦdIt is interior、hIt is interiorFor internal layer green compact size, KIt is interiorFor the constriction coefficient being independently sintered, Φ DOutside、ΦdOutside、hOutsideFor outer layer
Green compact size, KOutsideFor the constriction coefficient being independently sintered.
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| CN114523109A (en) * | 2022-04-24 | 2022-05-24 | 西部宝德科技股份有限公司 | Preparation method of high-precision gradient pore filter element |
| WO2022268845A1 (en) * | 2021-06-22 | 2022-12-29 | Sandvik Machining Solutions Ab | Method for manufacturing an article comprising cemented carbide and an inserted object |
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Application publication date: 20181113 |