A kind of preparation method of nanometer of toughening superfine WC-Co cemented carbide
Technical field
The present invention relates to a kind of hard alloy preparation technical fields, specifically directly add the alloy of various metals composition
Nanometer additive generates the obdurability WC-Co hard alloy preparation method of Grain-Boundary Phase, especially prepares obdurability Ultra-fine Grained hard
The method of alloy.
Background technique
Hard alloy has the advantages that high rigidity, high intensity, high-wearing feature, strong corrosion resistance and thermal expansion coefficient are low etc., mesh
It is preceding to be widely used in cutting tool, bored tooth and ore crushing machine etc., it is intermetallic composite coating, oil drilling, mining etc. are no
The important materials that can lack.However, hard alloy belongs to fragile material, the bad bottleneck of performance be between hardness and strength i.e.
There is contradictions between wearability and toughness: ordinary rigid alloy rigidity height then low strength, and intensity height then lower hardness.
The study found that in the case where cobalt phase content is constant, when WC grain drops to 1 μm or less, the hardness of hard alloy
It is then improved simultaneously with intensity, and the amplitude of this raising further decreases and more obvious with grain size.However, due to system
Powder is easy to grow up in standby sintering process of ultrafine hard alloy, causes the complex process for obtaining the hard alloy of small grains, note
Item of anticipating is various, technological parameter require it is high so that producer will significantly more new equipment, it is general right so that cost be made to be increased sharply
It has little significance in actual production.
It is one of the effective way for improving alloy property that metallic addition is added in hard alloy, and metallic addition is to hard
The influence of matter alloy property at many aspects disclosed in numerous scientific workers, as the resistance to of alloy can be improved in metallic addition
Mill property, impact resistance, high-temperature behavior, cutting ability etc..Common metallic addition have W, Mo, Cr, V, Nb, Ta, Al, Cu, Ru,
Zr, Re and rare earth metal etc.: addition W improves the use temperature of hard alloy, enhances the high-temperature behavior of alloy;Mo's is main
Wetability of the liquid metal to TiC hard phase when effect is to improve sintering;The available physics of Cr, machine are added in hard alloy
Tool and the good alloy of service performance;V, Nb and Ta are added in hardmetall binder, they can make carbon during the sintering process
Compound generates gradient distribution, enhances the stability of alloy;A1 differs larger with the atomic radius of Co, Al to Co matrix compared with
Good invigoration effect;Cu is added in TiC base cemented carbide can be improved the wearability of hard alloy;To WC-Co hard alloy
The ability of the thermal fatigue resistance of alloy can be enhanced in middle addition Ru;A small amount of Re is added in hard alloy can increase hard alloy
Hardness and wearability;Rare earth element is added in hard alloy, alloy high-temp intensity and inoxidizability can be made to greatly improve, not
It, can the larger toughness for improving alloy in the case where reducing hardness.
Experiments have shown that nanoparticle is suitably added in hard alloy substrate, hardness, wearability, the toughness of composite material
It is significantly improved.The use of nanometer additive is low compared with the usage amount of common additives, and small with the gap of WC grain (great circle),
Arrangement is finer and close, and the size of common additives easily forms formation of crack almost with WC same order.Therefore, simply with it
It pursues and hard alloy particle is completely formed nanoscale, change not as good as the addition nano-element progress nanosizing in hard alloy is attempted
Property, achieve the purpose that service performance can be improved again by neither improving very big cost with this.The present invention develops cashier according to the above thinking
Meter Zeng Ren WC-Co hard alloy preparation new process, the process to improve China's hard carbide industry production technology level,
High quality down-stream processing with high added-value hart metal product is developed, competitiveness is improved, torsion is realized in the unfavorable situation in international market
The benign cycle of raw material finished product, has a very important significance.
Summary of the invention
The purpose of the present invention is prepare the current situation of high-performance carbide technology for metal nano doping to provide one
The preparation for having both high tenacity Yu high-wearing feature hard alloy of kind simple process, additive utilization rate height, energy conservation and environmental protection, low cost
Method.
The technical scheme is that directly adding various metals into the WC-Co hard alloy of common submicron order
Composite nanometer additive prepares a kind of method of high-performance carbide, and specific steps include:
(1) the WC coarse powder material by partial size less than 5mm is worked in 0.7~0.8MPa by JZDB-100 type airflow milling press respectively
The fine powder material that average particle size is 0.1~0.5 μm is milled under power, the protection of grinding chamber oxygen content≤10ppm high-purity argon gas;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 50~80MPa, prepares the spherical fine powder material that average particle size is 0.1~0.5 μm;
(3) mixed using vacuum arc melting ingot casting+quickly-packaging plasma arc method preparation R-M nano metal in situ
Close powder;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WCxCoyRatio carries out equal with R-M nano metal additive package made from (3) step
Even mixing 5~10 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 4~6:1, and using ethane as abrasive media, paraffin is added, and carries out 2~3 agitation grindings, and the agitation grinding time is 1~6
Hour, form slurry, then filtering, under conditions of 50~220 DEG C it is dry through atomization drying or vacuum desiccator, cross 100 mesh
Sieve, is made carbide alloy mixture grain;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 350~450 DEG C × 1~2h,
After continue to vacuumize heating;Gas disposal is carried out at negative pressure of vacuum, 1000~1100 DEG C × 0.3~0.6h, and continues to heat up;
Solid-phase sintering, rear applying argon gas to -0.06MPa are carried out at 1150~1250 DEG C × 0.3~0.7h, and continue to heat up;Work as temperature
Argon gas is filled with when reaching setting sintering temperature into furnace body, and is 3~10MPa, 1280~1420 DEG C × 1~2h in furnace pressure
Under the conditions of be sintered after naturally cool to 900 DEG C, it is rear open outer circulation it is cooling improve cooling rate make furnace temperature be down to 100 DEG C with
Under;It is finally heat-treated twice: being for the first time quenching treatment: 950~1050 DEG C × 0.1~0.5h;Second is at tempering
Reason: 300~500 DEG C × 3~5h, as superfine WC-Co cemented carbide finished product.
WC as described abovexCoyMiddle x, y are mass percent, and x=70~99%, y=1~30%.
Above-mentioned nano metal additive package R-M average grain diameter is 30~80nm, and each element purity is all larger than 99.9wt%,
Wherein R-M(R represents rare earth element La and Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sc, Er, Lu, Sm, Tm, Yb, Eu one kind or more
Kind;M:Fe, Ni, Co, Al, Cu, Cr, Ta, Nb, V, Ti, Ru, Re, Zr, Zn, Mg are one or more) nano metal mixed powder R(R
Represent rare earth element), the additive amount of Fe, Ni, Co, Al, Cu, Cr, Ta, Nb, V, Ti, Ru, Re, Zr, Zn, Mg element account for Co bonding
The percentage range of phase fine powder material quality is respectively a=0.1~2%, b=0~30%, c=0~30%, d=0~30%, e=0~20%, f
=0~20%, g=0~5%, h=0~5%, i=0~5%, j=0~5%, k=0~5%, l=0~20%, m=0~20%, n=0~10%, o=
0~10%, p=0~10%.
The invention has the following advantages over the prior art:
1, compared with superfine WC-Co cemented carbide technology of preparing compare, the method for the present invention can not only produce average grain
Degree is 0.5 μm of superfine WC power below, and productivity can more traditional ball-milling method improve 4~5 times, and output capacity be up to 99.5% with
On, production cost can reduce by 50% or so;The powder fineness of preparation is uniform, and granularity normal distribution is relatively narrow, grain shape rule,
Purity is high, active big, good dispersion.Simultaneously as air-flow crusher is the autogenous grinding principle according to material and carries out powder to material
Broken, powder is contaminated few.Thus the present invention has that high production efficiency, with short production cycle, production cost is low, product quality and pure
The features such as high is spent, and saves a large amount of working hour and energy consumption.
2, compared with conventional superfine WC-Co cemented carbide, hardness improves nanometer toughening WC-Co hard alloy of the present invention
1.0 HRA or more, bending strength and fracture toughness improve about 20~30% or so, and wearability improves 150% or more, and service life mentions
It is high by 80%.
3, since the nano particle pinning of nano metal compound additive is in the grain boundary WC, make during the sintering process
Its aggregation growth is hindered, and WC grain nucleation rate is far longer than growth rate, so that hard alloy crystal grain has been refined,
Make the microstructure of alloy become more evenly, it is fine and close, the wellability of material is effectively improved, and reduces voidage, metallurgy melts
The defects of conjunction property is good, no apparent cavity, to improve the hardness of material, wearability and comprehensive performance.
4, since the local grain-boundary strength of nanoparticle is especially high, after nano metal compound additive is added, hard alloy
Fracture mode by based on grain boundary fracture turn to based on transgranular fracture, meanwhile, bifurcated turn to the micro-crack to be formed due to increase
Break surface is added, has absorbed more energy, therefore formd the dissipation mechanism of impact energy, to play toughening effect.
5, the new method that the multiple metallic element mixed nanometer prepares high-performance superfine cemented carbide solves single nanometer
Metallic element doping, which improves alloy property, has the problem of limitation, and for multiple metallic element mixed nanometer, it solves mostly golden
The doping process belonged between element nano-powder, between nano-powder and sub-micron alloyed powder is comparatively laborious, repeatedly adulterates process
Middle metal nano powder is easy to oxidation and is mixed into impurity, and conventional sintering process crystal grain is easy the problems such as growing up, and makes powder after mixing
Body ingredient is uniform, sintered alloy performance with higher and preferable consistency.
6, compared with conventional cemented carbide preparation method, the multiple metallic element mixed nanometer toughening ultra-fine crystal WC-Co hard
The novel preparation method of alloy can use the same oligomict alloy of letter by adjusting the ingredient of mixing nanometer metal additive alloy
More trade mark hart metal products are prepared, the production technology and management intensity of ingredient Yu powder process processed is enormously simplified, can be applied to
The preparation of other performance trade mark hard alloy.
Specific embodiment
Invention will be described in further detail by example below, but following examples is only present invention example therein
Son, does not represent rights protection scope defined by the present invention, the scope of the present invention is with claims
It is quasi-.
Embodiment 1:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the Ce-V nano metal mixed powder of 50nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC94Co6.0(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
6.5% Ce-V nano metal additive package carries out uniformly mixing 5 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 3 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1100 DEG C × 0.5h, and continues to heat up;At 1250 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 5MPa, 1400 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1050℃×0.3h;Second is tempering: 500 DEG C × 5h.
Comparative example 1:
Identical raw material are pressed into WC94Co6.0(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 1
It makes comparisons, comparison result is as shown in table 1:
1. embodiment 1 of table is with 1 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 1 |
0.45 |
94.5 |
3700 |
11.0 |
Comparative example 1 |
0.50 |
93.0 |
3000 |
9.0 |
Embodiment 2:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the Y-Ce-Co-V nano metal mixed powder of 50nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC94Co6.0(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
27% Y-Ce-Al-Co-V nano metal additive package carries out uniformly mixing 8 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 5 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1080 DEG C × 0.5h, and continues to heat up;At 1230 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 5MPa, 1380 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1050℃×0.3h;Second is tempering: 500 DEG C × 5h.
Comparative example 2:
Identical raw material are pressed into WC94Co6.0(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 2
It makes comparisons, comparison result is as shown in table 2:
2. embodiment 2 of table is with 2 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 2 |
0.40 |
94.3 |
3800 |
11.3 |
Comparative example 2 |
0. 50 |
93.0 |
3000 |
9.0 |
Embodiment 3:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the Sm-Cr nano metal mixed powder of 50nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC92Co8.0(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
6% Sm-Cr nano metal additive package carries out uniformly mixing 8 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 5 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1080 DEG C × 0.5h, and continues to heat up;At 1230 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 5MPa, 1380 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1050℃×0.3h;Second is tempering: 500 DEG C × 5h.
Comparative example 3:
Identical raw material are pressed into WC92Co8.0(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 3
It makes comparisons, comparison result is as shown in table 3:
3. embodiment 3 of table is with 3 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 3 |
0.40 |
94.0 |
3900 |
11.4 |
Comparative example 3 |
0.40 |
92.5 |
3200 |
9.3 |
Embodiment 4:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the Sm-Nd-Ni-Cr nano metal mixed powder of 50nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC92Co8.0(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
21.5% Sm-Nd-Ni-Cr nano metal additive package carries out uniformly mixing 8 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 5 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1070 DEG C × 0.5h, and continues to heat up;At 1220 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 5MPa, 1370 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1050℃×0.3h;Second is tempering: 500 DEG C × 5h.
Comparative example 4:
Identical raw material are pressed into WC92Co8.0(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 4
It makes comparisons, comparison result is as shown in table 4:
4. embodiment 4 of table is with 4 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 4 |
0.42 |
93.8 |
4000 |
11.7 |
Comparative example 4 |
0.4 |
92.5 |
3200 |
9.3 |
Embodiment 5:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the La-Nb nano metal mixed powder of 60nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC90Co10(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
6.2% La-Nb nano metal additive package carries out uniformly mixing 8 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 5 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1070 DEG C × 0.5h, and continues to heat up;At 1220 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 5MPa, 1370 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1030℃×0.3h;Second is tempering: 450 DEG C × 5h.
Comparative example 5:
Identical raw material are pressed into WC90Co10(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 5
It makes comparisons, comparison result is as shown in table 5:
5. embodiment 5 of table is with 5 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 5 |
0.35 |
93.5 |
4100 |
11.7 |
Comparative example 5 |
0.45 |
92.0 |
3300 |
9.5 |
Embodiment 6:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the La-Dy-Fe-Nb nano metal mixed powder of 60nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC90Co10(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
20.5% La-Dy-Fe-Nb nano metal additive package carries out uniformly mixing 8 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 5 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1060 DEG C × 0.5h, and continues to heat up;At 1200 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 5MPa, 1350 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1030℃×0.3h;Second is tempering: 450 DEG C × 5h.
Comparative example 6:
Identical raw material are pressed into WC90Co10(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 6
It makes comparisons, comparison result is as shown in table 6:
6. embodiment 6 of table is with 6 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 6 |
0.32 |
93.1 |
4300 |
12.0 |
Comparative example 6 |
0.45 |
92.0 |
3300 |
9.5 |
Embodiment 7:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the La-Ce-Pr-Al-Co-V nano metal mixed powder of 60nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC88Co12(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
27% La-Ce-Pr-Al-Co-V nano metal additive package carries out uniformly mixing 10 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 6 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1060 DEG C × 0.5h, and continues to heat up;At 1200 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 5MPa, 1350 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1000℃×0.3h;Second is tempering: 400 DEG C × 5h.
Comparative example 7:
Identical raw material are pressed into WC88Co12(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 7
It makes comparisons, comparison result is as shown in table 7:
7. embodiment 7 of table is with 7 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 7 |
0.30 |
93.0 |
4400 |
12.3 |
Comparative example 7 |
0.50 |
91.5 |
3500 |
9.8 |
Embodiment 8:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the La-Ce-Pr-Nd-Al-Co-Zr-V nano metal mixed powder of 60nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC88Co12(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
30% La-Ce-Pr-Nd-Al-Co-Zr-V nano metal additive package carries out uniformly mixing 10 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 6 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1050 DEG C × 0.5h, and continues to heat up;At 1180 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 8MPa, 1330 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1000℃×0.3h;Second is tempering: 400 DEG C × 5h.
Comparative example 8:
Identical raw material are pressed into WC88Co12(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 8
It makes comparisons, comparison result is as shown in table 8:
8. embodiment 8 of table is with 8 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 8 |
0.32 |
92.8 |
4500 |
12.5 |
Comparative example 8 |
0.50 |
91.5 |
3500 |
9.8 |
Embodiment 9:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the Y-Ce-Sm-Nd-Cu-Co-Ta-V nano metal mixed powder of 60nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC85Co15(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
33% Y-Ce-Sm-Nd-Cu-Co-Ta-V nano metal additive package carries out uniformly mixing 10 minutes, rear 200 mesh of mistake;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 6 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1050 DEG C × 0.5h, and continues to heat up;At 1180 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 8MPa, 1330 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1000℃×0.3h;Second is tempering: 300 DEG C × 5h.
Comparative example 9:
Identical raw material are pressed into WC85Co15(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the performance of itself and embodiment 9
It makes comparisons, comparison result is as shown in table 9:
9. embodiment 9 of table is with 9 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 9 |
0.25 |
92.0 |
4700 |
12.9 |
Comparative example 9 |
0.40 |
90.0 |
3800 |
10.5 |
Embodiment 10:
(1) by partial size less than 5mm WC coarse powder material respectively by JZDB-100 type airflow milling in 0.75MPa operating pressure, grind
The fine powder material that average particle size is 0.2 μm is milled under mill room oxygen content≤10ppm high-purity argon gas protection;
(2) Binder Phase Co powder is prepared using the hydraulic atomized production line of JTSWH-50 type, under protection of argon gas high water pressure
Power is 80MPa, prepares the spherical fine powder material that average particle size is 0.2 μm;
(3) average grain size is prepared using vacuum arc melting ingot casting+quickly-original position packaging plasma arc method
For the Y-Ce-Sm-Nd-La-Cu-Co-Re-Ti-V nano metal mixed powder of 60nm;
(4) in argon gas protection atmosphere, (1) and (2) step are made using HDQH-1 type impulse type rapid airflow mixer
WC hard phase and Co Binder Phase fine powder material press WC85Co15(wt%) ratio accounts for Co Binder Phase fine powder material quality with made from (3) step
40% Y-Ce-Sm-Nd-La-Cu-Co-Re-Ti-V nano metal additive package carries out uniformly mixing 10 minutes, rear mistake 200
Mesh;
(5) mixed-powder in step (4) is added in agitating ball mill, abrasive media is WC-Co hard alloy ball, ball
Material is than being 5:1, and using ethane as abrasive media, paraffin is added, and carries out 3 agitation grindings, and the agitation grinding time is 6 hours, is formed
Slurry, then filtering, under conditions of 200 DEG C through atomization drying, sieve with 100 mesh sieve, carbide alloy mixture grain is made;
(6) mixture made from (5) step is suppressed using XY40 Full-automatic hydraulic powder former, pressure 25MPa,
Green compact are made by 300MPa isostatic cool pressing;
(7) green compact are fitted into pressure sintering furnace, carry out dewaxing treatment at negative pressure of vacuum, 400 DEG C × 2h, after continue to take out
Vacuum heating;Gas disposal is carried out at negative pressure of vacuum, 1030 DEG C × 0.5h, and continues to heat up;At 1150 DEG C × 0.5h into
Row solid-phase sintering, rear applying argon gas to -0.06MPa, and continue to heat up;It is filled with when temperature reaches setting sintering temperature into furnace body
Argon gas, and 900 DEG C are naturally cooled to after being sintered under the conditions of furnace pressure is 8MPa, 1300 DEG C × 2h, it is rear to open outer follow
The cooling cooling rate that improves of ring makes to ask temperature drop to 100 DEG C or less;It is finally heat-treated twice: being for the first time quenching treatment:
1000℃×0.3h;Second is tempering: 300 DEG C × 5h.
Comparative example 10:
Identical raw material are pressed into WC85Co15(wt%) ratio carries out ingredient, rear using traditional wet-milling, forming, vacuum-sintering
The methods of prepare the superfine WC-Co cemented carbide for being not added with nano metal additive package, by the property of itself and embodiment 10
It can make comparisons, comparison result is as shown in table 10:
10. embodiment 10 of table is with 10 grain size of comparative example compared with mechanical property
Title |
Grain size (μm) |
Hardness (HRA) |
Bending strength (MPa) |
Fracture toughness (MPa/m2) |
Embodiment 10 |
0.2 |
91.5 |
4800 |
13.2 |
Comparative example 10 |
0.40 |
90.0 |
3800 |
10.5 |
Above embodiments result explanation: nano metal additive package toughening ultra-fine crystal WC-Co hard of the present invention
The WC-Co hard alloy mechanical property of the more conventional Ultra-fine Grained alloying technology preparation of the preparation method of alloy increased, especially
Toughness, this method can also be applied to the preparation of other trade mark hard alloy.