CN107619980B - A kind of ultra-fine grain cobalt-free hard alloy and preparation method thereof - Google Patents
A kind of ultra-fine grain cobalt-free hard alloy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to powder metallurgical technologies more particularly to a kind of ultra-fine grain cobalt-free hard alloy and preparation method thereof.Ultra-fine grain cobalt-free hard alloy provided by the invention, including the following raw material and its mass fraction: 75-90 parts of tungsten carbide, 0.5-1.0 parts of metal carbonyl powder, 0.1-1.0 parts of vanadium carbide, 10-20 parts of tantalum carbide, 0.6-1.0 parts of niobium carbide, 2.0-4.0 parts of titanium carbide, 0.02-0.04 parts of rare earth oxide.In ultra-fine grain cobalt-free hard alloy provided by the invention, tungsten carbide partial size is smaller and is evenly distributed, and mean grain size reaches 0.1-0.2 μm, and hardness reaches 2425-2528N/mm up to HRA88.6-90.8, bending strength2, compression strength is nonmagnetic, wearability is good, intensity is high, hardness is high up to 3988-4126MPa, has good mechanical performance.
Description
Technical field
The invention belongs to powder metallurgical technology more particularly to a kind of ultra-fine grain cobalt-free hard alloy and its preparation sides
Method.
Background technique
Hard alloy has that hardness is high, wearability is good, thermal expansion coefficient is small and good chemical stability etc. is a series of
Excellent performance is widely used in the manufacture of the various molds such as cold-forging die of stretching die, fastener, sizing die etc..With manufacture
With the raising of application technology level, hard alloy is by expanded application in punching press, forming, punching, punching and machine press mould.One
As hard alloy-either W-Co kind, W-Co-Ti kind, although having the good characteristics such as very high intensity, hardness and wearability,
But because containing metallic cobalt, thus be all it is ferromagnetic, mold is made when carrying out Magnaglo forming with it, is easy to make mould
Have viscous powder, generate plucking, seriously affect the dimensional accuracy and surface quality of magnetic blank, thus should not as Magnaglo at
Shape mold.If replacing cobalt that hard alloy is made with iron powder, also there is a problem of because of the ferromagnetism of iron itself same.It is especially close
Over a little years, with the rapid development of China's magnetic material especially hard magnetic material, the demand to no magnetic mold is even more growing day by day.
Chinese patent application CN101760685A disclose a kind of superfine WC-Co cemented carbide containing rare earth element and
Preparation method, the weight of WC hard phase accounts for the 85-94% of hard alloy in the hard alloy, and the weight of Co bonding phase accounts for firmly
The 5-14% of matter alloy, the weight of grain growth inhibitor account for the 0.3-2% of hard alloy, rare earth metal member in rare earth addition
The weight of element accounts for the 0.2-1.2% of Co bonding phase；Preparation method includes: to weigh various powder raw materials, ball milling, drying, granulation
Mixture compression moulding, sintering, cooling are obtained into hard alloy as mixture.The Cemented Carbide Properties stabilization of the invention mentions
Height is easy implementation and production application.
Chinese patent application CN101967593A disclose a kind of ultrafine crystal grain hard alloy material containing rare earth and its
Preparation method, the ultrafine crystal grain hard alloy material containing rare earth are mixed by weight percentage by the ultra-fine grain of following components
Conjunction is sintered: WC: Co: (VC+Cr2C3)∶(TaC+TiC+NbC)∶Y2O3Equal to 88-94: 6-10: 0.5-1: 0.2-1.5:
0.1-0.5；Preparation method includes: after the ultra-fine grain of the composition to be mixed to oscillation in ultrasonator, through high energy ball
Grinding machine ball milling is carbide mixing fine powders end, then through drying, forms green compact；Again by green compact in vacuum dewaxing-sintering furnace,
Or heat and keep the temperature in low pressure furnace, in the case where keeping the temperature atmosphere, cooling is come out of the stove.The hard alloy of the invention have high hardness and
Wearability, hardness is up to HRA94.
Contain Co in the hard alloy of above two scheme preparation, there is magnetism, be not able to satisfy as Magnaglo
The requirement of shaping dies.Magnetic material factory will consume a large amount of mold, past or even present, many magnetic materials production factories every year
Family using nonmagnetic steel (such as 1Cr18Ni9Ti, 70Mn, 9Mn9 etc.) production Magnaglo molding die, this mold performance compared with
Difference, hardness is low, and service life is short, and the serious plucking of die wall after a period of use, and die cavity deformation, bread seriously affect magnetic
The dimensional accuracy and surface quality of property blanks.Therefore, develop a kind of good wearability, long service life, intensity it is high,
Hardness is high, production technology simplicity non-magnetic hard alloy material is significantly.
Summary of the invention
In order to solve the technical problems existing in the prior art, the purpose of the present invention is to provide a kind of ultra-fine grains without cobalt
Hard alloy and preparation method thereof.Ultra-fine grain cobalt-free hard alloy provided by the invention is free of cobalt, wide using common and source
General, by carbonyl nickel powder and carbonyl iron dust by certain mass than the metal carbonyl powder that forms as tungsten carbide bonding phase, by thin
Change hardness, bending strength and compression strength that crystal grain improves hard alloy, makes the hardness of hard alloy up to HRA88.6-90.8, resist
Curved intensity reaches 2425-2528N/mm2, compression strength is nonmagnetic, wearability is good, intensity is high, hardness up to 3988-4126MPa
Height has good mechanical performance.In addition, ultra-fine grain cobalt-free hard alloy long service life provided by the invention, produces work
Skill is easy, at low cost.
Technical scheme is as follows:
A kind of ultra-fine grain cobalt-free hard alloy, including the following raw material and its mass fraction: 75-90 parts of tungsten carbide, carbonyl
0.5-1.0 parts of metal powder, 0.1-1.0 parts of vanadium carbide, 10-20 parts of tantalum carbide, 0.6-1.0 parts of niobium carbide, titanium carbide 2.0-4.0
Part, 0.02-0.04 parts of rare earth oxide.
Preferably, the ultra-fine grain cobalt-free hard alloy, including the following raw material and its mass fraction: 82 parts of tungsten carbide,
0.6 part of metal carbonyl powder, 0.5 part of vanadium carbide, 14 parts of tantalum carbide, 0.8 part of niobium carbide, 3 parts of titanium carbide, rare earth oxide 0.03
Part.
Preferably, the metal carbonyl powder is made of carbonyl nickel powder and carbonyl iron dust in mass ratio 4: 1.
Preferably, the rare earth oxide is made of yttrium oxide and scandium oxide in mass ratio 3: 1.
Preferably, the tungsten carbide partial size is 0.25-0.3 μm, the metal carbonyl powder, vanadium carbide, tantalum carbide, carbonization
Niobium, titanium carbide partial size are 0.1-1 μm, and the rare earth oxide granularity is 80-100nm, purity 99.99%.
In addition, including the following steps: the present invention also provides a kind of preparation method of ultra-fine grain cobalt-free hard alloy
S1: taking tungsten carbide and rare earth oxide by definite quality number, and the nitric acid copper water that mass concentration is 15-20% is added
Solution 100-120mL, is sufficiently stirred, and mixed liquor is made, and above-mentioned mixed liquor is transported to atomizer and is atomized, after atomization
Fine droplet, which sprays into closed high temperature reaction stove, to be reacted, and reactant A is made, is provided in reacting furnace by carbon and restores atmosphere,
Reacting furnace temperature is 900-1100 DEG C；
S2: reactant A made from step S1 is collected from the smoke outlet of reacting furnace, after passing through elution and drying respectively, is received
Collection obtains modified material B；
S3: metal carbonyl powder, the vanadium carbide, carbonization of modification material B and definite quality number that step S2 is collected
Tantalum, titanium carbide are uniformly mixed, and dehydrated alcohol is added as ball-milling medium, is placed in ball mill and carries out ball milling, liquid-solid ratio is
400-500mL/kg, ratio of grinding media to material 5-8: 1, drum's speed of rotation control are obtained in 100-135r/min, Ball-milling Time 80-100h
Wet mixture C；
S4: being placed in vacuum desiccator dry 1-3h for wet mixture C made from step S3, mixes wax, granulation, mixing is made
Expect D；
S5: by mixture D isostatic pressing made from step S4, pressure is controlled in 150-280MPa, obtains green compact E, right
The green compact E is modified and geometric dimension, surface quality testing；
S6: hard alloy is made using the positive carbon high-temp sintering process of low pressure in green compact E made from step S5.
Preferably, the copper nitrate aqueous solution 110mL that mass concentration is 18% is added in the step S1, reacting furnace temperature is
1000℃；
Preferably, liquid-solid ratio is 480mL/kg in the step S3, and ratio of grinding media to material 6: 1, drum's speed of rotation control is in 115r/
Min, Ball-milling Time 95h；
Preferably, dry 2h in the step S4；
Preferably, pressure is controlled in 220MPa in the step S5.
Preferably, the positive carbon high-temp sintering process of the step S6 mesolow includes the following steps:
1) it charges, vacuumizes；
2) it is warming up to 300-500 DEG C of dewaxing, keeps the temperature 2-3h；
3) it is warming up to 1200-1400 DEG C, keeps the temperature 1-3h；
4) 1500-1600 DEG C of low temperature carburization 1-2h；
5) it is warming up to 1650 DEG C of final sintering temperature, keeps the temperature 1h；
6) Ar pressurization is filled, pressure is controlled in 8-12MPa, heat-insulating pressurizing 1-2h；
7) decompression cooling, discharging.
It is furthermore preferred that the positive carbon high-temp sintering process of step S6 mesolow includes the following steps:
1) it charges, vacuumizes；
2) 450 DEG C of dewaxings are warming up to, 2.5h is kept the temperature；
3) 1350 DEG C are warming up to, 2h is kept the temperature；
4) 1550 DEG C of low temperature carburization 1.5h；
5) it is warming up to 1650 DEG C of final sintering temperature, keeps the temperature 1h；
6) Ar pressurization is filled, pressure is controlled in 10MPa, heat-insulating pressurizing 1.5h；
7) decompression cooling, discharging.
For the tungsten carbide that the present invention is 0.25-0.3 μm using partial size as raw material, adding vanadium carbide reduces alloy property to burning
The sensibility of junction temperature and time increases the sintering temperature of hard alloy magnetic force and hardness qualification and the range of time；Addition
The tantalum carbide of certain content improves the inoxidizability and wearability of hard alloy；Add certain content niobium carbide, titanium carbide composition
Composite grain grow up inhibitor, inhibit tungsten carbide crystal grain to grow up, enhance the hardness of hard alloy；Carbonyl nickel powder can make raw material
Powder is uniform in sintering process diafiltration, increases hard alloy toughness, and carbonyl iron dust can be improved the wearability of alloy, hair of the invention
Bright people adds the carbonyl nickel powder of mass ratio 4: 1 and the metal carbonyl powder of carbonyl iron dust composition, research hair in hard alloy material
Existing, the metal carbonyl powder formed using the proportion can replace cobalt powder as bonding phase, make the present invention in the case where not adding cobalt
It remains to obtain the hard alloy for having many advantages, such as that hardness is high, bending strength is high, compression strength is high, and the carbonyl formed with the proportion
Metal powder is able to suppress the growth of composite grain.
Containing the rare earth oxide being made of on a small quantity yttrium oxide and scandium oxide in mass ratio 3: 1 in raw material of the present invention, by with
The rare earth oxide of proportion composition improves the heat resistance of hard alloy to the modification of tungsten carbide.Rare earth oxide is to tungsten carbide
Modified method is powder by atomization method: taking tungsten carbide and rare earth oxide by definite quality number, addition mass concentration is 15-
20% copper nitrate aqueous solution 100-120mL, is sufficiently stirred, mixed liquor is made, by above-mentioned mixed liquor be transported to atomizer into
Row atomization, the fine droplet after atomization, which sprays into closed high temperature reaction stove, to be reacted, and reactant A is made, in reacting furnace by
Carbon provides reduction atmosphere, and reacting furnace temperature is 900-1100 DEG C, and the material after reaction is collected from the smoke outlet of reacting furnace, leads to respectively
After crossing elution and drying, modified material is collected.By above-mentioned powder by atomization method, make rare earth oxide and tungsten carbide in pyroreaction
It comes into full contact with, react in furnace, tungsten carbide is modified, and then make rare earth oxide to the humidification of hard alloy heat resistance
It is more significant.
Compared with prior art, ultra-fine grain cobalt-free hard alloy provided by the invention has the advantage that
(1) ultra-fine grain cobalt-free hard alloy provided by the invention, mean grain size reach 0.1-0.2 μm, and hardness is reachable
HRA88.6-90.8, bending strength reach 2425-2528N/mm2, compression strength up to 3988-4126MPa, intensity is high, hardness is high,
Wearability is good, has good mechanical performance；
(2) ultra-fine grain cobalt-free hard alloy provided by the invention, long service life, production technology are easy；
(3) ultra-fine grain cobalt-free hard alloy provided by the invention is free of cobalt, using common and from a wealth of sources, uses simultaneously
Bonding phase by carbonyl nickel powder and carbonyl iron dust by certain mass than the metal carbonyl powder that forms as tungsten carbide, can reduce enterprise
Industry cost saves rare metal resources for country.
Specific embodiment
The present invention is further described below by way of specific embodiment, but the present invention is not limited only to following embodiment.
Embodiment 1, a kind of ultra-fine grain cobalt-free hard alloy
The ultra-fine grain cobalt-free hard alloy is made of following component and its mass fraction: the carbonization that partial size is 0.28 μm
75 parts of tungsten, partial size are 0.5 part of 0.45 μm of metal carbonyl powder, partial size is 0.15 μm 0.1 part of vanadium carbide, the carbon that partial size is 0.4 μm
Change the rare earth oxygen that 10 parts of tantalum, 0.6 part of the niobium carbide that partial size is 0.4 μm, 2.0 parts of the titanium carbide that partial size is 0.2 μm, granularity are 90nm
0.02 part of compound.
The metal carbonyl powder is made of carbonyl nickel powder and carbonyl iron dust in mass ratio 4: 1.
The rare earth oxide is made of yttrium oxide and scandium oxide in mass ratio 3: 1.
Preparation method:
S1: taking tungsten carbide and rare earth oxide by definite quality number, and it is water-soluble that the copper nitrate that mass concentration is 18% is added
Liquid 110mL, is sufficiently stirred, and mixed liquor is made, and above-mentioned mixed liquor is transported to atomizer and is atomized, the small liquid after atomization
Drop, which sprays into closed high temperature reaction stove, is reacted, and reactant A is made, is provided in reacting furnace by carbon and restores atmosphere, reacting furnace
Temperature is 1000 DEG C；
S2: reactant A made from step S1 is collected from the smoke outlet of reacting furnace, after passing through elution and drying respectively, is received
Collection obtains modified material B；
S3: metal carbonyl powder, the vanadium carbide, carbonization of modification material B and definite quality number that step S2 is collected
Tantalum, titanium carbide are uniformly mixed, and dehydrated alcohol is added as ball-milling medium, is placed in ball mill and carries out ball milling, liquid-solid ratio is
480mL/kg, ratio of grinding media to material 6: 1, drum's speed of rotation are controlled in 118r/min, Ball-milling Time 95h, obtain wet mixture C；
S4: being placed in vacuum desiccator dry 2h for wet mixture C made from step S3, mixes wax, granulation, mixture is made
D；
S5: by mixture D isostatic pressing made from step S4, pressure is controlled in 220MPa, green compact E is obtained, to described
Green compact E is modified and geometric dimension, surface quality testing；
S6: green compact E made from step S5 being sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) being charged,
It vacuumizes；300 DEG C of dewaxings are warming up to, 2h is kept the temperature；3) 1200 DEG C are warming up to, 1h is kept the temperature；4) 1500 DEG C of low temperature carburization 1h；5) it heats up
To 1650 DEG C of final sintering temperature, 1h is kept the temperature；6) Ar pressurization is filled, pressure is controlled in 8MPa, heat-insulating pressurizing 1h；7) decompression cooling,
Discharging.
Embodiment 2, a kind of ultra-fine grain cobalt-free hard alloy
The ultra-fine grain cobalt-free hard alloy is made of following component and its mass fraction: the carbonization that partial size is 0.28 μm
90 parts of tungsten, 1 part of the metal carbonyl powder that partial size is 0.45 μm, 1 part of the vanadium carbide that partial size is 0.15 μm, the carbonization that partial size is 0.4 μm
The rare earth oxide that 20 parts of tantalum, 1 part of the niobium carbide that partial size is 0.4 μm, 4 parts of the titanium carbide that partial size is 0.2 μm, granularity are 90nm
0.04 part.
The metal carbonyl powder is made of carbonyl nickel powder and carbonyl iron dust in mass ratio 4: 1.
The rare earth oxide is made of yttrium oxide and scandium oxide in mass ratio 3: 1.
Preparation method:
S1: taking tungsten carbide and rare earth oxide by definite quality number, and it is water-soluble that the copper nitrate that mass concentration is 18% is added
Liquid 110mL, is sufficiently stirred, and mixed liquor is made, and above-mentioned mixed liquor is transported to atomizer and is atomized, small after atomization
Drop, which sprays into closed high temperature reaction stove, to be reacted, and reactant A is made, is provided in reacting furnace by carbon and restores atmosphere, reaction
Furnace temperature is 1000 DEG C；
S2: reactant A made from step S1 is collected from the smoke outlet of reacting furnace, after passing through elution and drying respectively, is received
Collection obtains modified material B；
S3: metal carbonyl powder, the vanadium carbide, carbonization of modification material B and definite quality number that step S2 is collected
Tantalum, titanium carbide are uniformly mixed, and dehydrated alcohol is added as ball-milling medium, is placed in ball mill and carries out ball milling, liquid-solid ratio is
480mL/kg, ratio of grinding media to material 6: 1, drum's speed of rotation are controlled in 118r/min, Ball-milling Time 95h, obtain wet mixture C；
S4: being placed in vacuum desiccator dry 2h for wet mixture C made from step S3, mixes wax, granulation, mixture is made
D；
S5: by mixture D isostatic pressing made from step S4, pressure is controlled in 220MPa, green compact E is obtained, to described
Green compact E is modified and geometric dimension, surface quality testing；
S6: green compact E made from step S5 being sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) being charged,
It vacuumizes；500 DEG C of dewaxings are warming up to, 3h is kept the temperature；3) 1400 DEG C are warming up to, 3h is kept the temperature；4) 1600 DEG C of low temperature carburization 2h；5) it heats up
To 1650 DEG C of final sintering temperature, 1h is kept the temperature；6) Ar pressurization is filled, pressure is controlled in 12MPa, heat-insulating pressurizing 2h；7) decompression cooling,
Discharging.
Embodiment 3, a kind of ultra-fine grain cobalt-free hard alloy
The ultra-fine grain cobalt-free hard alloy is made of following component and its mass fraction: the carbonization that partial size is 0.28 μm
82 parts of tungsten, 0.6 part of the metal carbonyl powder that the partial size that partial size is 0.2 μm is 0.45 μm, 0.5 part of the vanadium carbide that partial size is 0.15 μm,
14 parts of the tantalum carbide that partial size is 0.4 μm, 0.8 part of the niobium carbide that partial size is 0.4 μm, 3 parts of the titanium carbide that partial size is 0.2 μm, granularity
It is 0.06 part of rare earth oxide of 90nm.
The metal carbonyl powder is made of carbonyl nickel powder and carbonyl iron dust in mass ratio 4: 1.
The rare earth oxide is made of yttrium oxide and scandium oxide in mass ratio 3: 1.
Preparation method:
S1: taking tungsten carbide and rare earth oxide by definite quality number, and it is water-soluble that the copper nitrate that mass concentration is 18% is added
Liquid 110mL, is sufficiently stirred, and mixed liquor is made, and above-mentioned mixed liquor is transported to atomizer and is atomized, small after atomization
Drop, which sprays into closed high temperature reaction stove, to be reacted, and reactant A is made, is provided in reacting furnace by carbon and restores atmosphere, reaction
Furnace temperature is 1000 DEG C；
S2: reactant A made from step S1 is collected from the smoke outlet of reacting furnace, after passing through elution and drying respectively, is received
Collection obtains modified material B；
S3: metal carbonyl powder, the vanadium carbide, carbonization of modification material B and definite quality number that step S2 is collected
Tantalum, titanium carbide are uniformly mixed, and dehydrated alcohol is added as ball-milling medium, is placed in ball mill and carries out ball milling, liquid-solid ratio is
480mL/kg, ratio of grinding media to material 6: 1, drum's speed of rotation are controlled in 118r/min, Ball-milling Time 95h, obtain wet mixture C；
S4: being placed in vacuum desiccator dry 2h for wet mixture C made from step S3, mixes wax, granulation, mixture is made
D；
S5: by mixture D isostatic pressing made from step S4, pressure is controlled in 220MPa, green compact E is obtained, to described
Green compact E is modified and geometric dimension, surface quality testing；
S6: green compact E made from step S5 being sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) being charged,
It vacuumizes；450 DEG C of dewaxings are warming up to, 2.5h is kept the temperature；3) 1350 DEG C are warming up to, 2h is kept the temperature；4) 1550 DEG C of low temperature carburization 1.5h；5)
It is warming up to 1650 DEG C of final sintering temperature, keeps the temperature 1h；6) Ar pressurization is filled, pressure is controlled in 10MPa, heat-insulating pressurizing 1.5h；7) it drops
Pressure cooling, discharging.
Comparative example 1, a kind of ultra-fine grain cobalt-free hard alloy
The ultra-fine grain cobalt-free hard alloy is made of following component and its mass fraction: the carbonization that partial size is 0.28 μm
82 parts of tungsten, 0.6 part of the metal carbonyl powder that the partial size that partial size is 0.2 μm is 0.45 μm, 0.5 part of the vanadium carbide that partial size is 0.15 μm,
14 parts of the tantalum carbide that partial size is 0.4 μm, 0.8 part of the niobium carbide that partial size is 0.4 μm, 3 parts of the titanium carbide that partial size is 0.2 μm, granularity
It is 0.06 part of rare earth oxide of 90nm.
The metal carbonyl powder is made of carbonyl nickel powder and carbonyl iron dust in mass ratio 1: 1.
The rare earth oxide is made of yttrium oxide and scandium oxide in mass ratio 3: 1.
Preparation method is similar to Example 3.
Difference with embodiment 3 is that the metal carbonyl powder is by carbonyl nickel powder and 1: 1 group in mass ratio of carbonyl iron dust
At.
Comparative example 2, a kind of ultra-fine grain cobalt-free hard alloy
The ultra-fine grain cobalt-free hard alloy is made of following component and its mass fraction: the carbonization that partial size is 0.28 μm
82 parts of tungsten, 0.6 part of the metal carbonyl powder that the partial size that partial size is 0.2 μm is 0.45 μm, 0.5 part of the vanadium carbide that partial size is 0.15 μm,
14 parts of the tantalum carbide that partial size is 0.4 μm, 0.8 part of the niobium carbide that partial size is 0.4 μm, 3 parts of the titanium carbide that partial size is 0.2 μm, granularity
It is 0.06 part of rare earth oxide of 90nm.
The metal carbonyl powder is made of carbonyl nickel powder and carbonyl iron dust in mass ratio 4: 1.
The rare earth oxide is made of yttrium oxide and scandium oxide in mass ratio 1: 1.
Preparation method is similar to Example 3.
Difference with embodiment 3 is that rare earth oxide is made of yttrium oxide and scandium oxide in mass ratio 1: 1.
Comparative example 3, a kind of ultra-fine grain cobalt-free hard alloy
The ultra-fine grain cobalt-free hard alloy is made of following component and its mass fraction: the carbonization that partial size is 0.28 μm
82 parts of tungsten, 0.6 part of the metal carbonyl powder that the partial size that partial size is 0.2 μm is 0.45 μm, 0.5 part of the vanadium carbide that partial size is 0.15 μm,
14 parts of the tantalum carbide that partial size is 0.4 μm, 0.8 part of the niobium carbide that partial size is 0.4 μm, 3 parts of the titanium carbide that partial size is 0.2 μm, granularity
It is 0.06 part of rare earth oxide of 90nm.
The metal carbonyl powder is made of carbonyl nickel powder and carbonyl iron dust in mass ratio 4: 1.
The rare earth oxide is made of yttrium oxide and scandium oxide in mass ratio 3: 1.
Preparation method:
S1: taking all raw materials by definite quality number, and dehydrated alcohol is added after mixing as ball-milling medium, is placed in
Ball milling is carried out in ball mill, liquid-solid ratio 480mL/kg, ratio of grinding media to material 6: 1, drum's speed of rotation control is in 118r/min, ball milling
Between be 95h, obtain wet mixture；
S2: being placed in vacuum desiccator dry 2h for wet mixture obtained in step S1, mixes wax, granulation, mixing is made
Material；
S3: by mixture isostatic pressing obtained by step S2, pressure control is modified green compact after 220MPa, taking-up
With geometric dimension, surface quality testing；
S4: green compact obtained in S3 is sintered in low-pressure sintering furnace with the positive carbon high-temp sintering process of low pressure: 1) charging, takes out true
It is empty；450 DEG C of dewaxings are warming up to, 2.5h is kept the temperature；3) 1350 DEG C are warming up to, 2h is kept the temperature；4) 1550 DEG C of low temperature carburization 1.5h；5) it heats up
To 1650 DEG C of final sintering temperature, 1h is kept the temperature；6) Ar pressurization is filled, pressure is controlled in 10MPa, heat-insulating pressurizing 1.5h；7) it is depressured cold
But, discharging.
Difference with embodiment 3 is that the atomization system of the first two rare-earth oxide modified tungsten carbide is omitted in preparation method
Powder step.
The performance test of test example 1, ultra-fine grain cobalt-free hard alloy
1, test material: ultra-fine grain cobalt-free hard alloy made from embodiment 1-3, comparative example 1-3.
2, test method:
Hardness is carried out to ultra-fine grain cobalt-free hard alloy made from embodiment 1-3, comparative example 1-3 using Rockwell apparatus
Detection.
Ultra-fine grain cobalt-free hard alloy made from embodiment 1-3, comparative example 1-3 is carried out using universal testing machine
Bending strength detection.
Pressure resistance is carried out to high pressure resistant high-temperature rigid alloy made from embodiment 1-3, comparative example 1-3 using pressure testing machine
Degree detection.
It is averaged using metallographic microscope to ultra-fine grain cobalt-free hard alloy made from embodiment 1-3, comparative example 1-3
Grain size detection.
3, test result:
Every testing result is as shown in table 1:
Table 1: the performance test results of each ultra-fine grain cobalt-free hard alloy in embodiment, comparative example
As shown in Table 1, it is small to have both tungsten carbide mean grain size simultaneously for ultra-fine grain cobalt-free hard alloy produced by the present invention,
The advantages that hardness is high, bending strength is high, compression strength is high, and performance indexes is significantly better than the conjunction of hard made from comparative example
Gold, especially best with the performance of embodiment 3, for hardness HRA up to 90.8, bending strength reaches 2528N/mm2, compression strength reaches
4126MPa, 0.12 μm of tungsten carbide mean grain size, plasticity_resistant deformation ability is good, has good mechanical performance.
Test example 2, the application in mold for molding magnetic material powder
Ultra-fine grain cobalt-free hard alloy made from 1-3 of the embodiment of the present invention, comparative example 1-3 is made for magnetic material
The molding mold in feed powder end, and measure its specific wear rate with ball mill damage testing machine, with ball milling determination of wear testing machine its with it is straight
Coefficient of friction when the WC-6%Co ball opposite grinding of diameter 5mm, the results are shown in Table 2.
Table 2: embodiment, the specific wear rate of comparative example and coefficient of friction compare
As shown in Table 2, by ultra-fine grain cobalt-free hard alloy produced by the present invention, it is manufactured for magnetic material powder at
The mold of type has good resistance abrasive wear behavior, and coefficient of friction is small, long service life.
Basic principles and main features and advantages of the present invention of the invention, the technology of the industry has been shown and described above
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these variation and
Improvement is both fallen within the scope of claimed invention, and the claimed scope of the invention is by appended claims and its equivalent
It defines.
Claims (5)
1. a kind of ultra-fine grain cobalt-free hard alloy, which is characterized in that including the following raw material and its mass fraction: tungsten carbide 75-
90 parts, 0.5-1.0 parts of metal carbonyl powder, 0.1-1.0 parts of vanadium carbide, 10-20 parts of tantalum carbide, 0.6-1.0 parts of niobium carbide, titanium carbide
2.0-4.0 0.02-0.04 parts of part, rare earth oxide；The metal carbonyl powder is by carbonyl nickel powder and carbonyl iron dust 4:1 in mass ratio
Composition, the rare earth oxide are made of yttrium oxide and scandium oxide 3:1 in mass ratio.
2. ultra-fine grain cobalt-free hard alloy as described in claim 1, which is characterized in that including the following raw material and its mass parts
Number: 82 parts of tungsten carbide, 0.6 part of metal carbonyl powder, 0.5 part of vanadium carbide, 14 parts of tantalum carbide, 0.8 part of niobium carbide, 3 parts of titanium carbide, dilute
0.03 part of native oxide.
3. ultra-fine grain cobalt-free hard alloy as claimed in claim 1 or 2, which is characterized in that the tungsten carbide partial size is
0.25-0.3 μm, the metal carbonyl powder, vanadium carbide, tantalum carbide, niobium carbide, titanium carbide partial size are 0.1-1 μm, the rare earth
Oxide particle size is 80-100nm, purity 99.99%.
4. a kind of preparation method of ultra-fine grain cobalt-free hard alloy as described in any one of claims 1-3, which is characterized in that
The following steps are included:
S1: taking tungsten carbide and rare earth oxide by definite quality number, and the copper nitrate aqueous solution that mass concentration is 15-20% is added
100-120mL is sufficiently stirred, and mixed liquor is made, and above-mentioned mixed liquor is transported to atomizer and is atomized, small after atomization
Drop, which sprays into closed high temperature reaction stove, to be reacted, and reactant A is made, is provided in reacting furnace by carbon and restores atmosphere, reaction
Furnace temperature is 900-1100 DEG C；
S2: reactant A made from step S1 is collected from the smoke outlet of reacting furnace, after passing through elution and drying respectively, is collected
To modified material B；
S3: metal carbonyl powder, vanadium carbide, tantalum carbide, the carbon of modification material B and definite quality number that step S2 is collected
It is uniformly mixed to change niobium, titanium carbide, dehydrated alcohol is added as ball-milling medium, is placed in ball mill and carries out ball milling, liquid-solid ratio is
400-500mL/kg, ratio of grinding media to material 5-8:1, drum's speed of rotation control are obtained in 100-135r/min, Ball-milling Time 80-100h
Wet mixture C；
S4: being placed in vacuum desiccator dry 1-3h for wet mixture C made from step S3, mixes wax, granulation, mixture D is made；
S5: by mixture D isostatic pressing made from step S4, pressure is controlled in 150-280MPa, green compact E is obtained, to described
Green compact E is modified and geometric dimension, surface quality testing；
S6: ultra-fine grain cobalt-free hard alloy is made using the positive carbon high-temp sintering process of low pressure in green compact E made from step S5.
5. the preparation method of ultra-fine grain cobalt-free hard alloy as claimed in claim 4, which is characterized in that in the step S6
The positive carbon high-temp sintering process of low pressure includes the following steps:
1) it charges, vacuumizes；
2) it is warming up to 300-500 DEG C of dewaxing, keeps the temperature 2-3h；
3) it is warming up to 1200-1400 DEG C, keeps the temperature 1-3h；
4) 1500-1600 DEG C of low temperature carburization 1-2h；
5) it is warming up to 1650 DEG C of final sintering temperature, keeps the temperature 1h；
6) Ar pressurization is filled, pressure is controlled in 8-12MPa, heat-insulating pressurizing 1-2h；
7) decompression cooling, discharging.
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| CN111500914A (en) * | 2020-04-26 | 2020-08-07 | 山东沂水机床厂有限公司 | Hard alloy for numerical control machine tool and preparation method thereof |
| CN111621685B (en) * | 2020-07-21 | 2021-08-31 | 广东正信硬质材料技术研发有限公司 | Corrosion-resistant hard alloy with double-crystal structure and preparation method thereof |
| CN115074592A (en) * | 2022-06-28 | 2022-09-20 | 河源正信硬质合金有限公司 | High-temperature-resistant high-toughness hard alloy material for die and preparation method thereof |
| CN117845086A (en) * | 2024-03-06 | 2024-04-09 | 崇义章源钨业股份有限公司 | Binding phase-free superfine hard alloy and preparation method thereof |
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