CN106350721A - Preparation method of high-performance WC-Co cemented carbide of plate-like grain structure - Google Patents
Preparation method of high-performance WC-Co cemented carbide of plate-like grain structure Download PDFInfo
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
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Abstract
The invention relates to a preparation method of high-performance WC-Co cemented carbide of a plate-like grain structure and belongs to the field of cemented carbide materials and preparation thereof. The preparation method includes subjecting dispersed and evenly distributed W/Co/C composite powder to carbon regulation, wet grinding, drying, compression molding and carbonizing sintering by one time at 1380-1460 DEG C so as to obtain the high-performance WC-Co cemented carbide of the plate-like grain structure, wherein the W/Co/C composite powder contains W nanopowder and W plate-like grains. The preparation method has the advantages that the novel high-performance WC-Co cemented carbide of the full-density plate-like grain structure, which is almost fully-densified and excellent in overall performance, can be obtained within short sintering time at a low temperature and has a promising industrialized application prospect in the machining fields such as turning, drilling and milling and in the aspects of being used as a coated cemented carbide substrate and the like.
Description
Technical field
The present invention relates to a kind of preparation method of tabular crystal structure high-performance wc-co hard alloy；Belong to hard alloy material
Material and preparation field.
Background technology
Hard phase wc in wc-co hard alloy is belonging to the aeolotropic crystal of hexagonal crystal system, if its hardness is higher
Preferentially grow up in bottom surface (001) face, then the wc crystal grain being in generally triangle or polygonal prism-shaped body shape generates tabular wc crystal grain by changing,
While promoting wc-co hard alloy integral hardness to improve, be conducive to improving the fracture toughness of alloy.The generally biphase wc- of low cobalt
Fracture toughness kic of co hard alloy depends primarily on volume fraction and its mean free path and the composition of γ phase, and it is fine to split
Stricture of vagina forms at more weak wc/wc crystal boundary face, wc/co boundary and extends or pass through Binder Phase fracture, and tabular is brilliant hard
In matter alloy, micro-crack then can by crack deflection, bridge or extract, the various different approach extension such as transgranular fracture.Tabular
Cemented carbide has that hardness is high, wearability and plasticity_resistant deformation ability is strong, high tenacity and thermal shock resistance are good etc. comprehensive
Can, show fabulous effect in manufacture fields such as turning, drilling, millings and as aspects such as coated carbides matrixes, be
The new developing direction in hard alloy field.
At present, by adding other materials (such as tic, y2o3, tabular wc crystal seed etc.) and combine high temperature, high-pressure sinter induction wc
Crystal grain develops to tabular, can prepare the hard alloy of the crystal grain of wc containing tabular, but these preparation method generally existings tabular wc crystalline substance
The quantity of grain and size is difficult to control to, plate-like grain ratio is few or grain orientation is poor, needs special agglomerating plant etc. to lack
Point is so that the combination property such as the hardness of hard alloy, toughness can not effectively improve, and applies limited.Using having tabular
The w powder of pattern and graphite are raw material, and chemosynthesis tabular wc crystal grain is the effective way preparing tabular cemented carbide, but alloy
It is difficult to sintering densification.
Content of the invention
The purpose of the present invention is for the deficiency in existing preparation technology, provides a kind of new full densification tabular crystal structure high
The preparation method of performance wc-co hard alloy.
A kind of preparation method of present invention tabular crystal structure high-performance wc-co hard alloy, comprises the steps:
With each component disperse and the w/co/c composite powder that is evenly distributed is as raw material, by adjusting carbon, wet grinding, drying, compacting
In 1380-1460 DEG C of carburizing sintering after molding, obtain tabular crystal structure high-performance wc-co hard alloy；Described w/co/c
Nanometer w powder and tabular crystalline substance w is contained in composite powder powder.
Preferably；The described each component disperse and w/co/c composite powder being evenly distributed is by following proposal system
Standby:
It is nanometer tungsten source, cobalt salt is contained as cobalt source with water solublity with water solublity tungsten salt, will be molten to nanometer tungsten source, cobalt source, carbon source
After mix homogeneously in the alcohol water blend, obtain mixture a；Then laminar w powder is added in mixing a, after mix homogeneously
It is dried, obtain the mixture b of drying；Mixture b is reduced in 560-820 DEG C under reducing atmosphere, obtains each component disperse
And the w/co/c composite powder being evenly distributed；The radius-thickness ratio of described flake w powder is: 5:1-20:1 and a diameter of 5-30 is micro-
Rice；Described flake w powder is 4:1-9:1 with the mass ratio of nano powder c, and described powder c is the reason that nanometer tungsten source is reduced into tungsten
By value.
As further preferred version,
It is nanometer tungsten source, cobalt salt is contained as cobalt source with water solublity with water solublity tungsten salt, by nanometer tungsten source, cobalt source, carbon source, add
Plus after agent is dissolved in mix homogeneously in alcohol water blend, obtain Mischung；Then laminar w powder is added in Mischung, mix
Close and be uniformly dried afterwards, obtain the mixture d of drying；Mixture d carries out reducing 120- in 560-820 DEG C under reducing atmosphere
300min, obtains each component disperse and the w/co/c composite powder being evenly distributed；The radius-thickness ratio of described flake w powder is: 5:
1-20:1 and a diameter of 5-30 micron；Described flake w powder is 4:1-9:1 with the mass ratio of nano powder c, and described powder c is
Nanometer tungsten source is reduced into the theoretical value of tungsten；Described additive contains vanadic salts for water solublity.It is ammonium metavanadate that described water solublity contains vanadic salts
Or chromic nitrate.In order to lift effect further, in described Mischung, by quality ratio, water solublity tungsten salt: water-soluble carbon source:
Water solublity contains vanadic salts=10-20:15-30:30-60:1-2.5.The mass percentage content of the middle ethanol of described alcohol water blend
For 10-30%.In described Mischung, solute and the mass ratio of solvent are 10:8-10:6.
As further preferred version, described water solublity tungsten salt is metatungstic acid ammonia.
As further preferred version, it is cobalt nitrate that described water solublity contains cobalt salt.
As further preferred version, described carbon source is reducing sugar.Described reducing sugar is more preferably Fructus Vitis viniferae
Sugar or sucrose.
In industrial applications, laminar w powder is added in Mischung or mixture a, after mix homogeneously, adopts vacuum
Heating evaporation or spray drying.
In industrial applications, mixture b or mixing d, after ball milling, are reduced in 560-820 DEG C under reducing atmosphere
120-300min, obtains each component disperse and the w/co/c composite powder being evenly distributed.The condition of described ball milling is: rotating speed(rev/min, d be mill tube diameter/rice) i.e. 0.5-1.1m/s, ball material mass ratio 5:1-10:1.
As further preferred version, mixture b or mixing d put into multicolored vaginal discharge temperature control continuous way four pipe gas after ball milling
Carry out in-situ carbon auxiliary hydrogen reduction, reduction temperature is divided into 5 stages in atmosphere Muffle reduction furnace；The temperature in described 5 stages
Be controlled as 560 DEG C -600 DEG C, 600 DEG C -640 DEG C, 640 DEG C -680 DEG C, 700 DEG C -760 DEG C, 760 DEG C -820 DEG C, described also
The former time is 300min, adopts the noble gases Passivation Treatment such as nitrogen before coming out of the stove.During reduction, hydrogen is excessive.
Preferably；Described the carbon is adjusted to be: toward each component disperse and addition in the w/co/c composite powder that is evenly distributed
Powdery paraffin；The quality of added powdery paraffin is each component disperse and the 2.0- of the w/co/c composite powder quality being evenly distributed
3.0%.
Preferably；During described wet grinding, control rotating speed is:(rev/min, d is mill tube diameter/rice) i.e.
0.5-1.1m/s, control ball material mass ratio are 4:1-6:1, control Ball-milling Time is 24-60 hour；Ball-milling medium used during wet grinding
It is preferably ethanol, the alcohol amount that per kilogram powder adds is 300-400 milliliter.
Preferably；Described compressing pressure is 130-180mpa.
Preferably；It is 90-120min in the time of a 1380-1460 DEG C of carburizing sintering.As excellent further
Select scheme, the temperature of a carburizing sintering is 1410-1440 DEG C.During carburizing sintering, preferably hydrogen molybdenum wire furnace.
A kind of preparation method of present invention tabular crystal structure high-performance wc-co hard alloy, the quality of prepared cobalt
Percentage composition is that the performance of the wc-co hard alloy of 8.5-10.5% is:
Relative density is more than equal to 98.77%, preferably 98.77-99.15%, and coercivity is more than or equal to 18.25ka m-1, be preferably 18.25-19.25ka m-1, fracture toughness kic is more than or equal to 14.17mpa m1/2, be preferably 14.17-
14.34mpa·m1/2, hv30 is more than or equal to 1500kgf mm-2, more preferably 1500-1550kgf mm-2.
Principle and advantage
The nanometer witch culture tabular crystalline substance w/co/c composite powder of each uniform component distribution can be prepared using said method, this is multiple
Close the pressed compact that powder is obtained and lead in hydrogen sintering furnace in molybdenum filament, at a lower temperature the sintering short period can obtain almost completely fine and close
Change, the new full densification tabular crystal structure high-performance wc-co hard alloy of high comprehensive performance, its hardness and sub- fine alloy board
Number hardness quite, and present obvious anisotropy, and fracture toughness be then substantially better than corresponding sub-micro thin trade mark alloy
Performance, in the various manufacture field such as turning, drilling, milling and as the aspect such as coated carbides matrix, there is important work
Industry application prospect.
The sintering shrinkage densification of wc-co hard alloy of the present invention, except under higher temperature, the solid-phase sintering stage passes through bonding
Metal plastic flowing and outside the drastically contraction that produces, the key obtaining full compact texture alloy is wc granule under the liquid-phase sintering stage
Carry out sufficient dense arrangement and the contraction producing because of solution modeling mechanism again.As the main material of wc-co hard alloy,
Usually require that wc Powder Particle Size narrowly distributing, in normal distribution.Particle size distribution can affect the roughening of crystal grain, and distribution is wider, crystal grain
Roughening is more serious.In-situ preparation nanometer w granule of the present invention, its in carbonization, sintering process, due to having higher specific surface
Can, so that alloy system interior energy is significantly increased, the lower temperature solid-phase sintering stage may just take the lead in carbonization generate nanometer wc, and
Earlier liquid phase occurs promoting, while effectively facilitating alloy sintering and shrink densification, because of crystallization of the dissolution and precipitation mechanism, thinner receives
Rice wc crystal grain preferentially dissolves, and preferentially separates out on larger plate-like grain, promotes wc crystal grain that two-dimentional shape further occurs
Core is grown up, and generates more thicker tabular wc crystal grain.
Brief description
The sem photo of the nanometer witch culture tabular crystalline substance w/co/c composite powder that Fig. 1 prepares for embodiment 1.
The sem photo of the novel plate shaped crystalline substance wc-co structure hard alloy that Fig. 2 prepares for embodiment 1.
The sem photo of the novel plate shaped crystalline substance wc-co structure hard alloy that Fig. 3 prepares for comparative example 1.
Specific embodiment
The present invention will be described further by following examples, but protection scope of the present invention not limited to this.
Embodiment 1
Weigh 24 grams of metatungstic acid ammonia, 27 grams of anhydrous glucose, 50 grams of cobalt nitrate and 2.0 grams of chromic nitrate, be dissolved in ethanol, treat
After being sufficiently mixed, add 70 grams of ball milling inductive formation laminar w powder, through ball milling mixing uniform after (Ball-milling Time 2h, ball material
Ratio is for 10:1), the method using ball milling after heating in vacuum evaporation prepares reduction presoma mixed-powder to be used.By presoma
Powder is put into and is carried out in-situ carbon auxiliary hydrogen reduction, reduction temperature 560- in multicolored vaginal discharge temperature control continuous way four pipe atmosphere Muffle reduction furnace
600-640-700-760 DEG C, recovery time 300min, excessive big hydrogen flowing quantity, adopt the passivation of the noble gases such as nitrogen before coming out of the stove
Process.Obtained composite powder, after after testing, again adjusting the mixing of carbon dispensing, adds percentage by weight to be 2.5% powdery paraffin and suitable
Amount ethanol, continues ball milling 48 hours, obtains compound after vacuum drying, then repressed, and in 1410 in logical hydrogen molybdenum wire furnace
DEG C, a carburizing sintering 90min, prepares novel plate shaped crystal structure high-performance wc-co hard alloy.The nanometer tungsten prepared is mixed
Miscellaneous tabular crystalline substance w/co/c composite powder and its a carburizing sintering are obtained novel plate shaped crystalline substance wc-10wt%co structure hard alloy
Stereoscan photograph is shown in accompanying drawing 1 and accompanying drawing 2 respectively, from Fig. 1,2 it can be seen that nanometer tungsten, cobalt and white carbon black be adhered tightly to flat
Flat-shaped tungsten particle surface, is distributed in even dispersion；It is in triangle or polygonal prism different from wc crystal grain in traditional wc-co alloy
Shape, novel plate shaped crystalline substance wc-10wt%co Mathematical Analysis of Al-li Alloy Containing Rare Earth even structure, its wc crystal grain is by substantial amounts of pancake tabular wc crystal grain
Wc crystal grain composition ultra-fine with very small amount.Obtained Cemented Carbide Properties testing result for details see attached table 1.
Embodiment 2
Weigh 20 grams of metatungstic acid ammonia, 27 grams of anhydrous glucose, 50 grams of cobalt nitrate and 2.0 grams of chromic nitrate, be dissolved in ethanol, treat
After being sufficiently mixed, add 73 grams of ball milling inductive formation laminar w powder, through ball milling mixing uniform after (Ball-milling Time 2h, ball material
Ratio is for 10:1), the method using ball milling after heating in vacuum evaporation prepares reduction presoma mixed-powder to be used.By presoma
Powder is put into and is carried out in-situ carbon auxiliary hydrogen reduction, reduction temperature 600- in multicolored vaginal discharge temperature control continuous way four pipe atmosphere Muffle reduction furnace
640-680-760-820 DEG C, recovery time 300min, excessive big hydrogen flowing quantity, adopt the passivation of the noble gases such as nitrogen before coming out of the stove
Process.Obtained composite powder, after after testing, again adjusting the mixing of carbon dispensing, adds percentage by weight to be 2.5% powdery paraffin and suitable
Amount ethanol, continues ball milling 48 hours, obtains compound after vacuum drying, then repressed, and in 1410 in logical hydrogen molybdenum wire furnace
DEG C, a carburizing sintering 90min, prepares novel plate shaped crystal structure high-performance wc-co hard alloy.Obtained Cemented Carbide Properties inspection
Survey the results detailed in subordinate list 1.
Embodiment 3
Weigh 17 grams of metatungstic acid ammonia, 27 grams of anhydrous glucose, 50 grams of cobalt nitrate and 2.0 grams of chromic nitrate, be dissolved in ethanol, treat
After being sufficiently mixed, add 75 grams of ball milling inductive formation laminar w powder, through ball milling mixing uniform after (Ball-milling Time 2h, ball material
Ratio is for 10:1), the method using ball milling after heating in vacuum evaporation prepares reduction presoma mixed-powder to be used.By presoma
Powder is put into and is carried out in-situ carbon auxiliary hydrogen reduction, reduction temperature 560- in multicolored vaginal discharge temperature control continuous way four pipe atmosphere Muffle reduction furnace
600-640-700-760 DEG C, recovery time 300min, excessive big hydrogen flowing quantity, adopt the passivation of the noble gases such as nitrogen before coming out of the stove
Process.Obtained composite powder, after after testing, again adjusting the mixing of carbon dispensing, adds percentage by weight to be 2.5% powdery paraffin and suitable
Amount ethanol, continues ball milling 48 hours, obtains compound after vacuum drying, then repressed, and in 1410 in logical hydrogen molybdenum wire furnace
DEG C, a carburizing sintering 120min, prepares novel plate shaped crystal structure high-performance wc-co hard alloy.Obtained Cemented Carbide Properties
Testing result for details see attached table 1.
Embodiment 4
Weigh 13 grams of metatungstic acid ammonia, 27 grams of anhydrous glucose, 50 grams of cobalt nitrate and 2.0 grams of chromic nitrate, be dissolved in ethanol, treat
After being sufficiently mixed, add 78 grams of ball milling inductive formation laminar w powder, through ball milling mixing uniform after (Ball-milling Time 2h, ball material
Ratio is for 10:1), the method using ball milling after heating in vacuum evaporation prepares reduction presoma mixed-powder to be used.By presoma
Powder is put into and is carried out in-situ carbon auxiliary hydrogen reduction, reduction temperature 560- in multicolored vaginal discharge temperature control continuous way four pipe atmosphere Muffle reduction furnace
600-640-700-760 DEG C, recovery time 300min, excessive big hydrogen flowing quantity, adopt the passivation of the noble gases such as nitrogen before coming out of the stove
Process.Obtained composite powder, after after testing, again adjusting the mixing of carbon dispensing, adds percentage by weight to be 2.5% powdery paraffin and suitable
Amount ethanol, continues ball milling 48 hours, obtains compound after vacuum drying, then repressed, and in 1440 in logical hydrogen molybdenum wire furnace
DEG C, a carburizing sintering 90min, prepares novel plate shaped crystal structure high-performance wc-co hard alloy.Obtained Cemented Carbide Properties inspection
Survey the results detailed in subordinate list 1.
Comparative example 1
Weigh 0 gram of metatungstic acid ammonia, 27 grams of anhydrous glucose, 50 grams of cobalt nitrate and 2.0 grams of chromic nitrate, be dissolved in ethanol, treat
After being sufficiently mixed, add 87.30 grams of ball milling inductive formation laminar w powder, through ball milling mixing uniform after (Ball-milling Time 2h,
Ratio of grinding media to material is 10:1), the method using ball milling after heating in vacuum evaporation prepares reduction presoma mixed-powder to be used.Will be front
Drive body powder and put into and in multicolored vaginal discharge temperature control continuous way four pipe atmosphere Muffle reduction furnace, carry out in-situ carbon auxiliary hydrogen reduction, reduction temperature
560-600-640-700-760 DEG C, recovery time 300min, excessive big hydrogen flowing quantity, adopt the noble gases such as nitrogen before coming out of the stove
Passivation Treatment.Obtained composite powder, after after testing, again adjusting the mixing of carbon dispensing, addition percentage by weight is 2.5% powdery paraffin
And suitable alcohols, continue ball milling 48 hours, after vacuum drying, obtain compound, then repressed, and in logical hydrogen molybdenum wire furnace in
1410 DEG C, a carburizing sintering 90min, prepares novel plate shaped crystal structure high-performance wc-co hard alloy.Obtained hard alloy
Can testing result for details see attached table 1.
The performance test results of the wc-10wt%co sintered body that the different embodiment of table 1 is produced
P: pressure surface；V: vertical pressure surface.
Claims (10)
1. a kind of preparation method of tabular crystal structure high-performance wc-co hard alloy is it is characterised in that comprise the steps:
With each component disperse and the w/co/c composite powder that is evenly distributed is as raw material, by adjusting carbon, wet grinding, drying, compressing
Afterwards in 1380-1460 DEG C of carburizing sintering, obtain tabular crystal structure high-performance wc-co hard alloy；Described w/co/c is combined
Nanometer w powder and tabular crystalline substance w is contained in powder.
2. the preparation method of a kind of tabular crystal structure high-performance wc-co hard alloy according to claim 1, its feature exists
In；The described each component disperse and w/co/c composite powder being evenly distributed is prepared by following proposal:
It is nanometer tungsten source, cobalt salt is contained as cobalt source with water solublity with water solublity tungsten salt, nanometer tungsten source, cobalt source, carbon source are dissolved in wine
After mix homogeneously in smart aqueous solution, obtain mixture a；Then laminar w powder is added in mixing a, is dried after mix homogeneously,
Obtain the mixture b of drying；Mixture b is reduced in 560-820 DEG C under reducing atmosphere, obtains each component disperse and distribution
Uniform w/co/c composite powder；The radius-thickness ratio of described flake w powder is: 5:1-20:1 and a diameter of 5-30 micron；Described
Laminar w powder is 4:1-9:1 with the mass ratio of nano powder c, and described powder c is the theoretical value that nanometer tungsten source is reduced into tungsten.
3. the preparation method of a kind of tabular crystal structure high-performance wc-co hard alloy according to claim 2, its feature exists
In:
It is nanometer tungsten source, cobalt salt contained as cobalt source with water solublity, by nanometer tungsten source, cobalt source, carbon source, additive with water solublity tungsten salt
After being dissolved in mix homogeneously in alcohol water blend, obtain Mischung；Then laminar w powder is added in Mischung, mixing is all
It is dried after even, obtain the mixture d of drying；Mixture d carries out reducing 120-300min in 560-820 DEG C under reducing atmosphere,
Obtain each component disperse and the w/co/c composite powder being evenly distributed；Described flake w powder radius-thickness ratio be: 5:1-20:1 and
A diameter of 5-30 micron；Described flake w powder is 4:1-9:1 with the mass ratio of nano powder c, and described powder c is nanometer tungsten source
It is reduced into the theoretical value of tungsten；Described additive contains chromic salts for water solublity.
4. the preparation method of a kind of tabular crystal structure high-performance wc-co hard alloy according to claim 3, its feature exists
In；
In described Mischung, by quality ratio, water solublity tungsten salt: water-soluble carbon source: water solublity contains chromic salts=10-20:15-
30:30-60:1-2.5.
Described water solublity tungsten salt is metatungstic acid ammonia；
It is cobalt nitrate that described water solublity contains cobalt salt；
Described carbon source is reducing sugar；Described reducing sugar is more preferably glucose or sucrose.
5. the preparation method of a kind of tabular crystal structure high-performance wc-co hard alloy according to Claims 2 or 3, it is special
Levy and be；
Mixture b or mixture d, after ball milling, carries out reducing 120-300min in 560-820 DEG C under reducing atmosphere, obtains each
Component disperse and the w/co/c composite powder being evenly distributed；The condition of described ball milling is: rotating speed 0.5-1.1m/s, ball material mass ratio
5:1-10:1, control Ball-milling Time is 32-60 hour.
6. the preparation method of a kind of tabular crystal structure high-performance wc-co hard alloy according to Claims 2 or 3, it is special
Levy and be；
Mixture b or mixing d puts into after ball milling that to carry out in-situ carbon in multicolored vaginal discharge temperature control continuous way four pipe atmosphere Muffle reduction furnace auxiliary
Help hydrogen reduction, reduction temperature is divided into 5 stages；The temperature in described 5 stages be controlled as 560 DEG C -600 DEG C, 600
DEG C -640 DEG C, 640 DEG C -680 DEG C, 700 DEG C -760 DEG C, 760 DEG C -820 DEG C, the time of described reduction is 300min, adopts before coming out of the stove
With the noble gases Passivation Treatment such as nitrogen.
7. the preparation method of a kind of tabular crystal structure high-performance wc-co hard alloy according to claim 1, its feature exists
The carbon is adjusted to be in described: addition powdery paraffin toward each component disperse and in the w/co/c composite powder that is evenly distributed；Added powdery
The quality of paraffin is each component disperse and the 2.0-3.0% of the w/co/c composite powder quality being evenly distributed.
8. the preparation method of a kind of tabular crystal structure high-performance wc-co hard alloy according to claim 1, its feature exists
In:
During wet grinding, control rotating speed is 0.5-1.1m/s, control ball material mass ratio is 4:1-6:1, control Ball-milling Time to be that 24-60 is little
When；
When compressing, control pressure is 130-180mpa.
9. the preparation method of a kind of tabular crystal structure high-performance wc-co hard alloy according to claim 1, its feature exists
In: a 1380-1460 DEG C of carburizing sintering time be 90-120min；During carburizing sintering, sintering furnace used is hydrogen molybdenum
Silk stove.
10. a kind of tabular crystal structure high-performance wc-co hard according to claim 1,2,3,4,7,8,9 any one closes
Gold preparation method it is characterised in that: the weight/mass percentage composition of prepared cobalt be 8.5-10.5% wc-co hard alloy
Performance be:
Relative density is more than equal to 98.77%；
Coercivity is more than or equal to 18.25ka m-1；
Fracture toughness kicMore than or equal to 14.17mpa m1/2；
Hv30 is more than or equal to 1500kgf mm-2.
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| CN108237221A (en) * | 2018-03-14 | 2018-07-03 | 北京工业大学 | A kind of preparation method of the WC-Co hot spray powders with liquid-phase sintering tissue signature |
| CN108237221B (en) * | 2018-03-14 | 2019-09-27 | 北京工业大学 | A kind of preparation method of the WC-Co hot spray powder with liquid-phase sintering tissue signature |
| CN110142414A (en) * | 2019-06-25 | 2019-08-20 | 赵立夫 | A kind of preparation method of nanocrystalline NC cutting tool hard alloy compound powder |
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