CN106987752B - 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 PDFInfo
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Abstract
The invention discloses a kind of gradient hard alloy preparation methods of case-carbonizing, it is characterized in that first keeping the temperature the hard alloy green body that 2~4h forms the removing forming agent that porosity is 25%~40% at 550~750 DEG C；Then by SiO2Coat TiH2Core/shell structure powder, thickness is less than 3nm, the number of plies is less than 3 layers and specific surface area and is more than 250m2Graphene, the BaCO of/g3Three kinds of substances in percentage by weight 1:2:1 mixed preparing goes out hydrogeneous carburizing medium；Again by green compact be embedded to it is in hydrogeneous carburizing medium and under 5 ~ 15MPa pressure consolidation；Liquid-phase sintering is finally carried out, the gradient hard alloy of case-carbonizing is prepared.It grows up the present invention overcomes crystal grain existing for prior art the problem serious, carburizing time is long, efficiency is low, the gradient hard alloy of case-carbonizing is prepared in sintering process.
Description
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
For hard alloy as a kind of tool new material, 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 be difficult to meet it is 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
So that 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
It is cooling in hydrogen shield environment, so that 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, is closed 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. it prepares
Carburizer：By weight percentage, by Al2O330~50wt% of fine powder, 10~30wt% of granular graphite and carbonate or/and carbonic acid
It is for use after being uniformly mixed in hydrogen salt 30~50wt% input blenders.B. boat is filled：Prepared carburizer is measured as required
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 being 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；Up to purpose thing 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
Cemented carbide material is susceptible to crystal grain and grows up.Therefore, simple and reliable carburizing tech is found to prepare the ladder of case-carbonizing
It is very necessary to spend hard alloy.
Invention content
When the present invention is for the gradient hard alloy for preparing case-carbonizing at present, crystal grain existing for " sintering+carburizing " technique
It grows up the problem serious, carburizing time is long, efficiency is low, proposes that hard alloy green compact removing forming agent is first formed it into porous life
Base, then by SiO2Coat TiH2Core/shell structure powder, graphene, BaCO3It is uniformly mixed to form when mixing planetary ball mill hydrogeneous
Then porous green compact are put into carburizing medium and carry out consolidation by carburizing medium, finally carry out that table is formed in situ when 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：Various raw material powder dispensings are weighed by weight percentage, and wherein Co is accounted for
3~20wt%, TiC account for 0~30wt%, and TaC accounts for 0~15wt%, and WC is surplus；The powder weighed is mixed and is passed through ball milling, mistake
It filters, is dry, mixing forming agent, compression moulding obtains hard alloy green body；Hard alloy green body is 550~750 in vacuum sintering furnace
DEG C heat preservation 2~4h, vacuum degree be 10~25Pa, is formed porosity be 25%~40% remove forming agent hard alloy green body；
（2）Hydrogeneous carburizing medium is prepared：First weigh the TiH that granularity is 0.5 ~ 1.5 μm2Powder is added to shape in absolute ethyl alcohol
At TiH2The mixed liquor of 35wt% is accounted for, the ultrasonic disperse processing of 20 ~ 40min is then carried out, and is 10 in 80 ~ 100 DEG C and vacuum degree
It is dried in vacuo 1h under the conditions of~20Pa；Solution is prepared as solvent using deionized water and absolute ethyl alcohol mixed liquor again, by a concentration of 0.1
Ethyl orthosilicate is added in~0.8mol/L, by 8 times of TiH being added by ultrasonic disperse of ethyl orthosilicate concentration2Powder, and
Use CH3COOH adjusts pH value to 3~6, the then stirring 8 at 60~80 DEG C~for 24 hours in magnetic stirring apparatus, and at 120 ~ 150 DEG C
1~3h of lower drying, obtains SiO2Coat TiH2Core/shell structure powder；Again by SiO2Coat TiH2Core/shell structure powder, it is thick
Degree is less than 3 layers less than 3nm, the number of plies and specific surface area is more than 250m2Graphene, the BaCO of/g3Three 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 will removing
The hard alloy green body of forming agent is embedded to；The weight ratio of hydrogeneous carburizing medium and de- forming agent hard alloy green body is 5:1, and really
It protects the hydrogeneous carburizing medium thickness taken off around forming agent hard alloy green body and is more than 5mm；Then consolidation contains under 5 ~ 15MPa pressure
Hydrogen carbonizing medium makes its volume-diminished to the 40 ~ 60% of loose state；With threaded lid sealed graphite crucible, carburizing is prevented
Medium escapes；
（4）It is prepared by the gradient hard alloy of case-carbonizing：1350~1500 DEG C of 1~3h of heat preservation, carbon in vacuum sintering furnace
Element is spread from hydrogeneous carburizing medium to carbide surface, is formed the case-carbonizing layer of 250 ~ 600 μ m-thicks, is finally realized surface
It is prepared by the gradient hard alloy of carburizing.
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 mesh screens, it is dry 85~
100 DEG C of progress mix buna forming agent, under 300~400MPa pressure by the 50~120% of cemented carbide powder weight
Compression moulding；When hard alloy green body removes forming agent, heating rate is 1~5 DEG C/min；
（2）When hydrogeneous carburizing medium is prepared, the frequency of ultrasonic wave is 4 × 10 when supersound process4Hz, power 100W, matches
Deionized water and the volume ratio of absolute ethyl alcohol are 1 in the solvent that solution processed uses:10, prepare SiO2Coat TiH2Core/shell structure
When powder, the speed of magnetic agitation is 20~50r/min, core/shell structure powder, graphene, BaCO3When mixing planetary ball mill,
Rotating speed is 300r/min；
（3）The graphite material flexural 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, first it is warming up to 550~750 DEG C with 5~10 DEG C/min and keeps the temperature
1~2h；Then 1100~1250 DEG C are warming up to 5~10 DEG C/min and keep the temperature 1~3h；It is warming up to again with 5~10 DEG C/min
1350~1500 DEG C and 1~3h of heat preservation, sintering vacuum degree is 1~5Pa；Cooling rate after sintering is 1~8 DEG C/min.
The advantage of the invention is that：（1）Using porous green compact as carburizing body, in-situ accomplishes surface is oozed in sintering process
Carbon, this technique compared with traditional first sintering recarburization is more succinct, and there is no crystal grain secondary the problem of growing up；（2）Carburizing
Metal hydride TiH is introduced in agent2, H is decomposited in sintering process2And C+2H occurs with graphene2=CH4, CH4=[C]+H2,
The active atoms of carbon of formation, which enters, realizes carburizing in metal；SiO2It is coated on TiH2Surface can control H2Rate of release avoids quickly
It exhausts；（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）It proposes to ensure between carburizing medium and hard alloy by controlling the degree of packing of carburizing medium
Contact, improve carburizing efficiency；（5）Use graphene for carbon source, the small reactivity bigger of granularity, carburizing is efficient.
Description of the drawings
The process schematic representation of the gradient hard alloy preparation method of the case-carbonizing of Fig. 1 present invention.
Specific implementation mode
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 raw 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 to and is passed through 48h ball millings, 400 mesh screen mistakes
Filter, 90 DEG C of dryings mix buna forming agent, the compression moulding under 320MPa pressure by the 60% of cemented carbide powder weight
Obtain hard alloy green body；Hard alloy green body 620 DEG C of heat preservation 2h in vacuum sintering furnace, heating rate are 2 DEG C/min, vacuum
Degree is 12Pa, forms the hard alloy green body for the removing forming agent that porosity is 28%；
（2）Hydrogeneous carburizing medium is prepared：First weigh the TiH that granularity is 0.5 μm2Powder is added in absolute ethyl alcohol and is formed
TiH2The mixed liquor of 35wt% is accounted for, then carries out the ultrasonic disperse processing of 25min, the frequency of ultrasonic wave is 4 × 104Hz, power are
100W；And it is dried in vacuo 1h under the conditions of 85 DEG C and vacuum degree are 13Pa；Again with volume ratio for 1:10 deionized water and anhydrous
Alcohol mixeding liquid is that solvent prepares solution, and ethyl orthosilicate is added by a concentration of 0.2mol/L, is added by super by 1.6mol/L
The TiH of sound dispersion2CH is used in combination in powder3COOH adjusts pH value to 3, then stirs 10h, magnetic force at 70 DEG C in magnetic stirring apparatus
The speed of stirring is 30r/min, and the dry 1h at 130 DEG C, obtains SiO2Coat TiH2Core/shell structure powder；Again by SiO2
Coat TiH2Core/shell structure powder, thickness is less than 3nm, the number of plies is less than 3 layers and specific surface area and is more than 250m2The graphene of/g,
BaCO3Three 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 300r/min,
Hydrogeneous carburizing medium is made；
（3）Filling of the green compact in hydrogeneous carburizing medium：First hydrogeneous carburizing medium is fitted into graphite crucible, graphite crucible
Graphite material flexural strength be more than 20MPa, then will remove forming agent hard alloy green body embedment；Hydrogeneous carburizing medium with it is de-
The weight ratio of forming agent hard alloy green body is 5:1, and ensure the hydrogeneous carburizing medium around de- forming agent hard alloy green body
Thickness is more than 5mm；Then the hydrogeneous carburizing medium of consolidation under 5MPa pressure, makes its volume-diminished to the 42% of loose state；With band
The lid sealed graphite crucible of screw thread, prevents 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 keeps the temperature 1h；Then with 7
DEG C/min is warming up to 1250 DEG C and keeps the temperature 1h；1420 DEG C being warming up to 8 DEG C/min again and keeping the temperature 1h, sintering vacuum degree is 2Pa；It burns
Cooling rate after knot is 3 DEG C/min, and carbon is spread from hydrogeneous carburizing medium to carbide surface, forms 550 μm
It is prepared by thick case-carbonizing layer, the final gradient hard alloy for realizing case-carbonizing.
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 raw material powder dispensings are weighed by weight percentage, and wherein Co is accounted for
15wt%, WC are surplus；The powder weighed is mixed to and is passed through 72h ball millings, the filtering of 400 mesh screens, 100 DEG C of dryings are closed by hard
Golden powder weight 100% incorporation buna forming agent, under 380MPa pressure compression moulding obtain hard alloy green body；Firmly
Matter alloy green compact 750 DEG C of heat preservation 3h in vacuum sintering furnace, heating rate are 4 DEG C/min, vacuum degree 15Pa, form hole
The hard alloy green body for the removing forming agent that degree is 28%；
（2）Hydrogeneous carburizing medium is prepared：First weigh the TiH that granularity is 0.8 μm2Powder is added in absolute ethyl alcohol and is formed
TiH2The mixed liquor of 35wt% is accounted for, then carries out the ultrasonic disperse processing of 30min, the frequency of ultrasonic wave is 4 × 104Hz, power are
100W；And it is dried in vacuo 1h under the conditions of 90 DEG C and vacuum degree are 15Pa；Again with volume ratio for 1:10 deionized water and anhydrous
Alcohol mixeding liquid is that solvent prepares solution, and ethyl orthosilicate is added by a concentration of 0.6mol/L, is added by super by 4.8mol/L
The TiH of sound dispersion2CH is used in combination in powder3COOH adjusts pH value to 6, then stirs 14h, magnetic force at 70 DEG C in magnetic stirring apparatus
The speed of stirring is 40r/min, and the dry 2h at 140 DEG C, obtains SiO2Coat TiH2Core/shell structure powder；Again by SiO2
Coat TiH2Core/shell structure powder, thickness is less than 3nm, the number of plies is less than 3 layers and specific surface area and is more than 250m2The graphene of/g,
BaCO3Three 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 300r/min,
Hydrogeneous carburizing medium is made；
（3）Filling of the green compact in hydrogeneous carburizing medium：First hydrogeneous carburizing medium is fitted into graphite crucible, graphite crucible
Graphite material flexural strength be more than 20MPa, then will remove forming agent hard alloy green body embedment；Hydrogeneous carburizing medium with it is de-
The weight ratio of forming agent hard alloy green body is 5:1, and ensure the hydrogeneous carburizing medium around de- forming agent hard alloy green body
Thickness is more than 5mm；Then the hydrogeneous carburizing medium of consolidation under 7MPa pressure, makes its volume-diminished to the 50% of loose state；With band
The lid sealed graphite crucible of screw thread, prevents 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 keeps the temperature 2h；Then with 7
DEG C/min is warming up to 1200 DEG C and keeps the temperature 2h；1400 DEG C being warming up to 7 DEG C/min again and keeping the temperature 2h, sintering vacuum degree is 2Pa；It burns
Cooling rate after knot is 4 DEG C/min, and carbon is spread from hydrogeneous carburizing medium to carbide surface, forms 350 μm
It is prepared by thick case-carbonizing layer, the final gradient hard alloy for realizing case-carbonizing.
Claims (2)
1. a kind of gradient hard alloy preparation method 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 raw 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；The powder weighed is mixed and passed through ball milling, filtering, is done
It is dry, mix forming agent, compression moulding obtains hard alloy green body；Hard alloy green body 550~750 DEG C of heat preservations in vacuum sintering furnace
2~4h, vacuum degree are 10~25Pa, form the hard alloy green body for the removing forming agent that porosity is 25%~40%；
（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 is formed
TiH2Account for the mixed liquor of 35wt%, then carry out the ultrasonic disperse processing of 20 ~ 40min, and 80 ~ 100 DEG C and vacuum degree 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 a concentration of 0.1~
Ethyl orthosilicate is added in 0.8mol/L, by 8 times of TiH being added by ultrasonic disperse of ethyl orthosilicate concentration2Powder is used in combination
CH3COOH adjusts pH value to 3~6, the then stirring 8 at 60~80 DEG C~for 24 hours in magnetic stirring apparatus, and at 120 ~ 150 DEG C
Dry 1~3h, obtains SiO2Coat 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 250m2Graphene, the BaCO of/g3Three 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 of agent is embedded to；The weight ratio of hydrogeneous carburizing medium and de- forming agent hard alloy green body is 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 heat preservation, carbon in vacuum sintering furnace
It is spread from hydrogeneous carburizing medium to carbide surface, forms the case-carbonizing layer of 250 ~ 600 μ m-thicks, finally realize case-carbonizing
Gradient hard alloy prepare.
2. the gradient hard alloy preparation method 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 mesh screens, dry at 85~100 DEG C
It carries out, mixes 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, heating rate is 1~5 DEG C/min；
（2）When hydrogeneous carburizing medium is prepared, the frequency of ultrasonic wave is 4 × 10 when supersound process4Hz, power 100W prepare 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 flexural 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 keep the temperature 1~
2h；Then 1100~1250 DEG C are warming up to 5~10 DEG C/min and keep the temperature 1~3h；1350 are warming up to 5~10 DEG C/min again~
1500 DEG C and 1~3h of heat preservation, sintering vacuum degree is 1~5Pa；Cooling rate after sintering is 1~8 DEG C/min.
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| CN110370748B (en) * | 2019-07-31 | 2021-03-16 | 成都工业学院 | Metal-ceramic composite material with high interface 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 |
| CN111996432B (en) * | 2020-09-02 | 2021-02-12 | 四川大学 | Preparation method of ultra-coarse hard alloy material |
| 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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