CN106987752A - A kind of gradient hard alloy preparation method of case-carbonizing - Google Patents

A kind of gradient hard alloy preparation method of case-carbonizing Download PDF

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CN106987752A
CN106987752A CN201710300224.8A CN201710300224A CN106987752A CN 106987752 A CN106987752 A CN 106987752A CN 201710300224 A CN201710300224 A CN 201710300224A CN 106987752 A CN106987752 A CN 106987752A
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hard alloy
carbonizing
prepared
case
green body
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CN106987752B (en
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郭智兴
熊计
陈诚
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Sichuan University
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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
    • 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
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • 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
    • B22F3/10—Sintering only
    • B22F3/1035—Liquid phase sintering
    • 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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
    • C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
    • C23C8/64—Carburising
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Abstract

The invention discloses a kind of gradient hard alloy preparation method of case-carbonizing, it is characterized in that being first incubated hard alloy green body of 2~4h formation porositys for 25%~40% removing forming agent at 550~750 DEG C；Then by SiO2Coat TiH2Core/shell structure powder, thickness, which is less than 3nm, the number of plies and is less than 3 layers and specific surface area, is more than 250m2/ g graphene, BaCO3Three kinds of substances in percentage by weight 1:2:1 mixed preparing goes out hydrogeneous carburizing medium；Green compact are embedded in the hydrogeneous carburizing medium and consolidation under 5 ~ 15MPa pressure again；Liquid-phase sintering is finally carried out, the gradient hard alloy of case-carbonizing is prepared.Instant invention overcomes existing process exist crystal grain grow up seriously, carburizing time length, efficiency is low the problem of, the gradient hard alloy of case-carbonizing is prepared in sintering process.

Description

A kind of gradient hard alloy preparation method of case-carbonizing
Technical field
The present invention relates to a kind of preparation method of hard alloy, more particularly to a kind of gradient hard alloy system of case-carbonizing Preparation Method, belongs to Hard Materials On Wed.
Background technology
Hard alloy is as a kind of instrument new material, and it is (to typically refer to period of element with refractory metal hard compounds The carbide of transition elements in table, nitride, boride and silicide etc.) it is base, with iron group metal (such as cobalt, nickel, iron) Binding metal is done, the high rigidity that is manufactured with powder metallurgy process, high-wearing feature material.But, homogeneous material is difficult to meet more next More complicated operating mode, with the proposition of gradient hard alloy concept, by way of in case-carbonizing improving material property obtains The attention of people.
CN102002664A discloses a kind of preparation method of Graded-structure Cemented Carbides, the method for first passing through surface oxidation Decarburization in carbide surface certain depth is obtained graded alloy presoma, i.e., standard rigid alloy is embedded in a certain proportion of Mg(OH)2And Al2O3Mixed fillers in be heated to 1420-1450 DEG C of high-temperature heat treatment certain time in hydrogen atmosphere, and Cooled down in hydrogen shield environment, partial decarburization is generated η phases, then the sample of decarburization in graphite Pack carburizing processing is carried out, treatment temperature is 1420-1450 DEG C, closed so as to obtain the gradient-structure hard of Binder Phase in gradient Gold.CN1526847A discloses a kind of Carburization Treatment method of hard metal article, it is characterised in that this method includes：A. prepare Carburizer：By weight percentage, by Al2O330~50wt% of fine powder, 10~30wt% of granular graphite and carbonate or/and carbonic acid In 30~50wt% of hydrogen salt input agitators, it is uniformly mixed rear stand-by.B. boat is filled：The carburizer prepared is measured on request It is fitted into graphite boat, while the hard alloy that the metallographic structure produced according to a conventional method is uniform and mechanical performance is consistent is burnt Knot body is embedded in carburizer.C. Carburization Treatment：The above-mentioned graphite boat installed is sent into heat-treatment furnace, 1390~1450 50~120min of Carburization Treatment in DEG C temperature range；Purpose thing is produced after cooling.But the method for carburizing of the present invention needs cold etc. quiet This special installation of press, and each product is put into independent jacket, production efficiency is not high；And using 95% graphite powder and 5% aluminium oxide powder is not high as carburizer activity, and the green compact hole for passing through isostatic pressed is few, activated carbon in carburizing process Absorption position is few.These can all influence carburizing efficiency.
But, the above method is to carry out Carburization Treatment after the completion of sintering cemented carbide again, carburizing time length it is inefficient and Easily there is crystal grain and grown up in Hardmetal materials.Therefore, simple and reliable carburizing tech is found to prepare the ladder of case-carbonizing Spend hard alloy very necessary.
The content of the invention
When the present invention is directed to the gradient hard alloy for preparing case-carbonizing at present, the crystal grain that " sintering+carburizing " technique is present Grow up serious, carburizing time length, the problem of efficiency is low, propose that hard alloy pressed compact removing forming agent first is formed it into porous life Base, then by SiO2Coat TiH2Core/shell structure powder, graphene, BaCO3It is uniformly mixed to form during mixing planetary ball mill hydrogeneous Porous green compact, are then put into carburizing medium and carry out consolidation by carburizing medium, finally carry out being formed in situ table during liquid-phase sintering The gradient hard alloy of face carburizing.
The gradient hard alloy preparation method of the case-carbonizing of the present invention, it is characterised in that comprise the steps of successively：
（1）It is prepared by de- forming agent hard alloy green body：Weighing various material powder dispensings by weight percentage, wherein Co accounts for 3~ 20wt%, TiC account for 0~30wt%, and TaC accounts for 0~15wt%, and WC is surplus；By the powder weighed mix and pass through ball milling, it is filtering, dry It is dry, mix forming agent, compressing obtain hard alloy green body；Hard alloy green body 550~750 DEG C of insulations in vacuum sintering furnace 2~4h, vacuum is 10~25Pa, forms hard alloy green body of the porosity for 25%~40% removing forming agent；
（2）Hydrogeneous carburizing medium is prepared：First weigh the TiH that granularity is 0.5 ~ 1.5 μm2Powder is added in absolute ethyl alcohol and formed TiH2Account for 35wt% mixed liquor, then carry out 20 ~ 40min ultrasonic disperse processing, and 80 ~ 100 DEG C and vacuum be 10~ 1h is dried in vacuo under the conditions of 20Pa；Solution is prepared by solvent of deionized water and absolute ethyl alcohol mixed liquor again, by concentration be 0.1~ 0.8mol/L adds tetraethyl orthosilicate, by 8 times of the tetraethyl orthosilicate concentration TiH added by ultrasonic disperse2Powder, is used in combination CH3COOH adjusts pH value to 3~6, then stirs 8~24h at 60~80 DEG C in magnetic stirring apparatus, and at 120 ~ 150 DEG C 1~3h is dried, SiO is obtained2Coat TiH2Core/shell structure powder；Again by SiO2Coat TiH2Core/shell structure powder, thickness It is less than 3 layers less than 3nm, the number of plies and specific surface area is more than 250m2/ g graphene, BaCO3Three kinds of substances in percentage by weight 1:2: 1 mixing, and 1 ~ 2h of ball milling in planetary ball mill, are made hydrogeneous carburizing medium；
（3）Filling of the green compact in hydrogeneous carburizing medium：First hydrogeneous carburizing medium is fitted into graphite crucible, then removing is molded The hard alloy green body embedment of agent；Hydrogeneous carburizing medium and the weight ratio of de- forming agent hard alloy green body are 5:1, and ensure to take off Hydrogeneous carburizing medium thickness around forming agent hard alloy green body is more than 5mm；Then consolidation is hydrogeneous under 5 ~ 15MPa pressure oozes Carbon medium, makes its volume-diminished to the 40 ~ 60% of loose state；With threaded lid sealed graphite crucible, carburizing medium is prevented Effusion；
（4）It is prepared by the gradient hard alloy of case-carbonizing：1350~1500 DEG C of 1~3h of insulation, carbon in vacuum sintering furnace Spread from hydrogeneous carburizing medium to carbide surface, form the case-carbonizing layer of 250 ~ 600 μ m-thicks, finally realize case-carbonizing Gradient hard alloy prepare.
It is prepared by the gradient hard alloy of the case-carbonizing of the present invention, further characterized in that：
（1）Ball-milling Time is 24~72h when prepared by hard alloy green body, and filtering uses 400 eye mesh screens, dries at 85~100 DEG C Carry out, mix buna forming agent by the 50~120% of cemented carbide powder weight, be pressed under 300~400MPa pressure Type；When hard alloy green body removes forming agent, programming rate is 1~5 DEG C/min；
（2）When hydrogeneous carburizing medium is prepared, the frequency of ultrasonic wave is 4 × 10 when ultrasonically treated4Hz, power is 100W, is prepared molten Deionized water and the volume ratio of absolute ethyl alcohol are 1 in the solvent that liquid is used:10, prepare SiO2Coat TiH2Core/shell structure powder When, the speed of magnetic agitation is 20~50r/min, core/shell structure powder, graphene, BaCO3When mixing planetary ball mill, rotating speed For 300r/min；
（3）The graphite material rupture strength of green compact graphite crucible used when being loaded in carburizing medium is more than 20MPa；
（4）When prepared by the gradient hard alloy of case-carbonizing, be first warming up to 5~10 DEG C/min and 550~750 DEG C and be incubated 1~ 2h；Then 1100~1250 DEG C are warming up to 5~10 DEG C/min and are incubated 1~3h；1350 are warming up to 5~10 DEG C/min again~ 1500 DEG C and 1~3h of insulation, sintering vacuum is 1~5Pa；Cooling rate after terminating is 1~8 DEG C/min.
The advantage of the invention is that：（1）Using porous green compact as carburizing body, realize that surface is oozed in sintering process situ The problem of carbon, this technique compared with traditional first sintering recarburization is more succinct, and to be not in that crystal grain is secondary grow up；（2）Carburizing Metal hydride TiH is introduced in agent2, H is decomposited in sintering process2And occur C+2H with graphene2=CH4, CH4=[C]+H2, The active atoms of carbon of formation, which enters in metal, realizes carburizing；SiO2It is coated on TiH2Surface can control H2Rate of release, it is to avoid quick Exhaust；（3）The porous green compact formed after green compact removing forming agent have huge surface area, are conducive to the absorption of active atoms of carbon With the raising of carburizing efficiency；（4）Propose by controlling the degree of packing of carburizing medium to ensure between carburizing medium and hard alloy Contact, improve carburizing efficiency；（5）Use graphene for carbon source, the small reactivity of its granularity is bigger, carburizing efficiency high.
Brief description of the drawings
The process schematic representation of the gradient hard alloy preparation method of the case-carbonizing of Fig. 1 present invention.
Embodiment
Example 1：The gradient hard alloy of case-carbonizing is prepared according to the following steps：
（1）It is prepared by de- forming agent hard alloy green body：Various material powder dispensings are weighed by weight percentage, and wherein Co is accounted for 8wt%, TiC account for 5wt%, and TaC accounts for 1wt%, and WC is surplus；The powder weighed is mixed and passes through 48h ball millings, 400 eye mesh screen mistakes Filter, 90 DEG C of dryings mix buna forming agent by the 60% of cemented carbide powder weight, compressing under 320MPa pressure Obtain hard alloy green body；Hard alloy green body 620 DEG C of insulation 2h in vacuum sintering furnace, programming rate is 2 DEG C/min, vacuum Spend for 12Pa, form hard alloy green body of the porosity for 28% removing forming agent；
（2）Hydrogeneous carburizing medium is prepared：First weigh the TiH that granularity is 0.5 μm2Powder, which is added in absolute ethyl alcohol, forms TiH2Account for 35wt% mixed liquor, then carries out 25min ultrasonic disperse processing, the frequency of ultrasonic wave is 4 × 104Hz, power is 100W； And it is dried in vacuo 1h under the conditions of 85 DEG C and vacuum are 13Pa；Again using volume ratio as 1:10 deionized water and absolute ethyl alcohol is mixed It is that solvent prepares solution to close liquid, is that 0.2mol/L adds tetraethyl orthosilicate by concentration, is added by 1.6mol/L and pass through ultrasonic disperse TiH2Powder, and use CH3COOH adjusts pH value to 3, then stirs 10h at 70 DEG C in magnetic stirring apparatus, magnetic agitation Speed is 30r/min, and dries 1h at 130 DEG C, obtains SiO2Coat TiH2Core/shell structure powder；Again by SiO2Cladding TiH2Core/shell structure powder, thickness, which is less than 3nm, the number of plies and is less than 3 layers and specific surface area, is more than 250m2/ g graphene, BaCO3 Three kinds of substances in percentage by weight 1:2:1 mixing, and the ball milling 1h in planetary ball mill, rotational speed of ball-mill is 300r/min, is made Hydrogeneous carburizing medium；
（3）Filling of the green compact in hydrogeneous carburizing medium：First hydrogeneous carburizing medium is fitted into graphite crucible, the stone of graphite crucible Black material rupture strength is more than 20MPa, then the hard alloy green body for removing forming agent is embedded to；Hydrogeneous carburizing medium and de- shaping The weight ratio of agent hard alloy green body is 5:1, and ensure the hydrogeneous carburizing medium thickness around de- forming agent hard alloy green body More than 5mm；Then the hydrogeneous carburizing medium of consolidation under 5MPa pressure, makes its volume-diminished to the 42% of loose state；With threaded Lid sealed graphite crucible, prevent carburizing medium from escaping；
（4）It is prepared by the gradient hard alloy of case-carbonizing：First it is warming up to 650 DEG C with 6 DEG C/min and is incubated 1h；Then with 7 DEG C/ Min is warming up to 1250 DEG C and is incubated 1h；1420 DEG C being warming up to 8 DEG C/min again and being incubated 1h, sintering vacuum is 2Pa；Sintering Cooling rate after end is 3 DEG C/min, and carbon is spread from hydrogeneous carburizing medium to carbide surface, forms 550 μ m-thicks Case-carbonizing layer, finally realize case-carbonizing gradient hard alloy prepare.
Example 2：The gradient hard alloy of case-carbonizing is prepared according to the following steps：
（1）It is prepared by de- forming agent hard alloy green body：Various material powder dispensings are weighed by weight percentage, and wherein Co is accounted for 15wt%, WC are surplus；The powder weighed is mixed and passes through 72h ball millings, 400 mesh sieve net filtrations, 100 DEG C of dryings are closed by hard 100% incorporation buna forming agent of golden powder weight, it is compressing under 380MPa pressure to obtain hard alloy green body；Firmly Matter alloy green compact 750 DEG C of insulation 3h in vacuum sintering furnace, programming rate is 4 DEG C/min, and vacuum is 15Pa, forms hole Spend the hard alloy green body of the removing forming agent for 28%；
（2）Hydrogeneous carburizing medium is prepared：First weigh the TiH that granularity is 0.8 μm2Powder, which is added in absolute ethyl alcohol, forms TiH2Account for 35wt% mixed liquor, then carries out 30min ultrasonic disperse processing, the frequency of ultrasonic wave is 4 × 104Hz, power is 100W； And it is dried in vacuo 1h under the conditions of 90 DEG C and vacuum are 15Pa；Again using volume ratio as 1:10 deionized water and absolute ethyl alcohol is mixed It is that solvent prepares solution to close liquid, is that 0.6mol/L adds tetraethyl orthosilicate by concentration, is added by 4.8mol/L and pass through ultrasonic disperse TiH2Powder, and use CH3COOH adjusts pH value to 6, then stirs 14h at 70 DEG C in magnetic stirring apparatus, magnetic agitation Speed is 40r/min, and dries 2h at 140 DEG C, obtains SiO2Coat TiH2Core/shell structure powder；Again by SiO2Cladding TiH2Core/shell structure powder, thickness, which is less than 3nm, the number of plies and is less than 3 layers and specific surface area, is more than 250m2/ g graphene, BaCO3 Three kinds of substances in percentage by weight 1:2:1 mixing, and the ball milling 1h in planetary ball mill, rotational speed of ball-mill is 300r/min, is made Hydrogeneous carburizing medium；
（3）Filling of the green compact in hydrogeneous carburizing medium：First hydrogeneous carburizing medium is fitted into graphite crucible, the stone of graphite crucible Black material rupture strength is more than 20MPa, then the hard alloy green body for removing forming agent is embedded to；Hydrogeneous carburizing medium and de- shaping The weight ratio of agent hard alloy green body is 5:1, and ensure the hydrogeneous carburizing medium thickness around de- forming agent hard alloy green body More than 5mm；Then the hydrogeneous carburizing medium of consolidation under 7MPa pressure, makes its volume-diminished to the 50% of loose state；With threaded Lid sealed graphite crucible, prevent carburizing medium from escaping；
（4）It is prepared by the gradient hard alloy of case-carbonizing：First it is warming up to 640 DEG C with 8 DEG C/min and is incubated 2h；Then with 7 DEG C/ Min is warming up to 1200 DEG C and is incubated 2h；1400 DEG C being warming up to 7 DEG C/min again and being incubated 2h, sintering vacuum is 2Pa；Sintering Cooling rate after end is 4 DEG C/min, and carbon is spread from hydrogeneous carburizing medium to carbide surface, forms 350 μ m-thicks Case-carbonizing layer, finally realize case-carbonizing gradient hard alloy prepare.

Claims (2)

1. the gradient hard alloy preparation method of a kind of case-carbonizing, it is characterised in that comprise the steps of successively：
（1）It is prepared by de- forming agent hard alloy green body：Weighing various material powder dispensings by weight percentage, wherein Co accounts for 3~ 20wt%, TiC account for 0~30wt%, and TaC accounts for 0~15wt%, and WC is surplus；By the powder weighed mix and pass through ball milling, it is filtering, dry It is dry, mix forming agent, compressing obtain hard alloy green body；Hard alloy green body 550~750 DEG C of insulations in vacuum sintering furnace 2~4h, vacuum is 10~25Pa, forms hard alloy green body of the porosity for 25%~40% removing forming agent；
（2）Hydrogeneous carburizing medium is prepared：First weigh the TiH that granularity is 0.5 ~ 1.5 μm2Powder is added in absolute ethyl alcohol and formed TiH2Account for 35wt% mixed liquor, then carry out 20 ~ 40min ultrasonic disperse processing, and 80 ~ 100 DEG C and vacuum be 10~ 1h is dried in vacuo under the conditions of 20Pa；Solution is prepared by solvent of deionized water and absolute ethyl alcohol mixed liquor again, by concentration be 0.1~ 0.8mol/L adds tetraethyl orthosilicate, by 8 times of the tetraethyl orthosilicate concentration TiH added by ultrasonic disperse2Powder, is used in combination CH3COOH adjusts pH value to 3~6, then stirs 8~24h at 60~80 DEG C in magnetic stirring apparatus, and at 120 ~ 150 DEG C 1~3h is dried, SiO is obtained2Coat TiH2Core/shell structure powder；Again by SiO2Coat TiH2Core/shell structure powder, thickness It is less than 3 layers less than 3nm, the number of plies and specific surface area is more than 250m2/ g graphene, BaCO3Three kinds of substances in percentage by weight 1:2: 1 mixing, and 1 ~ 2h of ball milling in planetary ball mill, are made hydrogeneous carburizing medium；
（3）Filling of the green compact in hydrogeneous carburizing medium：First hydrogeneous carburizing medium is fitted into graphite crucible, then removing is molded The hard alloy green body embedment of agent；Hydrogeneous carburizing medium and the weight ratio of de- forming agent hard alloy green body are 5:1, and ensure to take off Hydrogeneous carburizing medium thickness around forming agent hard alloy green body is more than 5mm；Then consolidation is hydrogeneous under 5 ~ 15MPa pressure oozes Carbon medium, makes its volume-diminished to the 40 ~ 60% of loose state；With threaded lid sealed graphite crucible, carburizing medium is prevented Effusion；
（4）It is prepared by the gradient hard alloy of case-carbonizing：1350~1500 DEG C of 1~3h of insulation, carbon in vacuum sintering furnace Spread from hydrogeneous carburizing medium to carbide surface, form the case-carbonizing layer of 250 ~ 600 μ m-thicks, finally realize case-carbonizing Gradient hard alloy prepare.
2. it is prepared by the gradient hard alloy of case-carbonizing according to claim 1, further characterized in that：
（1）Ball-milling Time is 24~72h when prepared by hard alloy green body, and filtering uses 400 eye mesh screens, dries at 85~100 DEG C Carry out, mix buna forming agent by the 50~120% of cemented carbide powder weight, be pressed under 300~400MPa pressure Type；When hard alloy green body removes forming agent, programming rate is 1~5 DEG C/min；
（2）When hydrogeneous carburizing medium is prepared, the frequency of ultrasonic wave is 4 × 10 when ultrasonically treated4Hz, power is 100W, prepares solution Deionized water and the volume ratio of absolute ethyl alcohol are 1 in the solvent used:10, prepare SiO2Coat TiH2Core/shell structure powder When, the speed of magnetic agitation is 20~50r/min, core/shell structure powder, graphene, BaCO3When mixing planetary ball mill, rotating speed For 300r/min;
（3）The graphite material rupture strength of green compact graphite crucible used when being loaded in carburizing medium is more than 20MPa；
（4）When prepared by the gradient hard alloy of case-carbonizing, be first warming up to 5~10 DEG C/min and 550~750 DEG C and be incubated 1~ 2h；Then 1100~1250 DEG C are warming up to 5~10 DEG C/min and are incubated 1~3h；1350 are warming up to 5~10 DEG C/min again~ 1500 DEG C and 1~3h of insulation, sintering vacuum is 1~5Pa；Cooling rate after terminating is 1~8 DEG C/min.
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CN107460391A (en) * 2017-09-11 2017-12-12 山东大学 A kind of gradient hard alloy cutter material and its fast preparation method for adding graphene
CN110372410A (en) * 2019-07-31 2019-10-25 成都工业学院 A kind of metal-ceramic composite material and preparation method thereof
CN110370748A (en) * 2019-07-31 2019-10-25 成都工业学院 A kind of metal-ceramic composite material of high interfacial bonding strength and preparation method thereof
CN111996432A (en) * 2020-09-02 2020-11-27 四川大学 Preparation method of ultra-coarse hard alloy material
CN114921703A (en) * 2022-06-02 2022-08-19 自贡硬质合金有限责任公司 Surface hardened WC-Co-based hard alloy and preparation method thereof

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CN107460391A (en) * 2017-09-11 2017-12-12 山东大学 A kind of gradient hard alloy cutter material and its fast preparation method for adding graphene
CN107460391B (en) * 2017-09-11 2018-12-07 山东大学 A kind of gradient hard alloy cutter material and its fast preparation method adding graphene
CN110372410A (en) * 2019-07-31 2019-10-25 成都工业学院 A kind of metal-ceramic composite material and preparation method thereof
CN110370748A (en) * 2019-07-31 2019-10-25 成都工业学院 A kind of metal-ceramic composite material of high interfacial bonding strength and preparation method thereof
CN110372410B (en) * 2019-07-31 2021-08-24 成都工业学院 Metal-ceramic composite material and preparation method thereof
CN111996432A (en) * 2020-09-02 2020-11-27 四川大学 Preparation method of ultra-coarse hard alloy material
CN111996432B (en) * 2020-09-02 2021-02-12 四川大学 Preparation method of ultra-coarse hard alloy material
CN114921703A (en) * 2022-06-02 2022-08-19 自贡硬质合金有限责任公司 Surface hardened WC-Co-based hard alloy and preparation method thereof
CN114921703B (en) * 2022-06-02 2023-09-05 自贡硬质合金有限责任公司 WC-Co-based hard alloy with hardened surface layer and preparation method thereof

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