CN104313380B - A kind of step sintering prepares the method for high-compactness Nanograin Cemented Carbide - Google Patents
A kind of step sintering prepares the method for high-compactness Nanograin Cemented Carbide Download PDFInfo
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Abstract
A kind of step sintering prepares the method for high-compactness Nanograin Cemented Carbide, belongs to new material and Novel powder metallurgy technical field.Mixed-powder first with nanoscale purple tungsten, cobalt oxide and white carbon black and vanadium oxide and chromium oxide is raw material, the amount ratio of above-mentioned raw materials is determined according to the requirement of Co content in final hard alloy, after raw material mixing and ball milling being processed, briquet is also sent into and is carried out reaction in-situ in vacuum drying oven and prepare the nano composite powder of distributed components, favorable dispersibility;Nano composite powder is loaded high-strength sintered-carbide die, carries out discharge plasma sintering, the technique use segmentation pressurization, heating up and being incubated, obtain crystal grain and grow up controllable presintering block;Finally the block after presintering is put into and high-strength graphite mould carries out high temperature, short time plasma discharging Fast Sintering densification, finally give the Nanograin Cemented Carbide block materials of densification.The inventive method can be effectively improved consistency and the mechanical property of hard alloy block material.
Description
Technical field
The present invention relates to the preparation method of a kind of high-compactness nanocrystalline WC-Co hard alloy,
The porosity of Nanograin Cemented Carbide is reduced, it is thus achieved that high consistency and mechanics by step sintering
Performance, belongs to new material and Novel powder metallurgy technical field.
Background technology
In hard alloy, WC-Co series hard metal is because having high hardness, toughness and bending resistance
Intensity and the indispensable tool materials of the high-tech area that becomes, the most nanocrystalline hard closes
Gold, shows hardness and the toughness combination property of excellence.But, existing WC-Co system receives
The preparation of rice cemented carbide block materials still rests on the laboratory research stage, prepares at present
The Nanograin Cemented Carbide block go out full densification, having hard high-strength concurrently yet suffers from being stranded the most greatly
Difficult, it is impossible to meet the industrial pressing needs to high-performance nano cemented carbide.
In the past research worker generally used increases grain growth inhibitor addition and Fast Sintering
Method prepares Nanograin Cemented Carbide, although hard phase WC grain in reducing hard alloy
Size aspect has reached Expected Results, but the relatively low problem of the consistency of sintering block is the most always
It is difficult to break through.
No matter the preparation of hard alloy block material uses solid-phase sintering or liquid-phase sintering, sintering temperature
Degree is all more than 1000 DEG C, and it is inevitable phenomenon that WC grain is grown up in sintering process,
Controlling WC grain Size growth, reducing sintering temperature is inevitable approach, but relatively low sintering temperature
Degree cannot be got rid of again between powder particle and the gas of particle surface absorption, causes the hole of sintering block
Porosity is higher, and consistency is low, it is impossible to obtain having receiving of the mechanical property such as high tenacity, high intensity
Rice cemented carbide.For the preparation research present situation of domestic and international Nanograin Cemented Carbide, Wo Menyan
Study carefully have developed a kind of use high pressure presintering after carry out two steps of fast low temperature densification again
The preparation of method sintering technology has the Nanograin Cemented Carbide block materials of high-compactness, the most all
Have no relevant report.
Summary of the invention
It is an object of the invention to provide and a kind of obtain high-compactness, nanocrystalline by step sintering
The method of grain tissue WC-Co hard alloy block materials.First with nanoscale purple tungsten
(WO2.72)、Co3O4With white carbon black (C) and vanadium oxide (V2O3) and chromium oxide (Cr2O3)
Mixed-powder be raw material, according to the requirement meter of Co content in final hard alloy block material
Calculating the amount ratio of above-mentioned raw materials, after raw material mixing and ball milling being processed, briquet is also sent into true
Empty stove is carried out reaction in-situ prepare distributed components, favorable dispersibility mean diameter about
The WC-Co-VC/Cr of 70nm3C2Composite powder;Secondly by nano WC-Co-VC/Cr3C2
Composite powder loads high-strength sintered-carbide die, carries out discharge plasma sintering, uses segmentation to add
The technology path pressed, heat up and be incubated and processing step, obtain having high-compactness and crystal grain be long
Big controllable presintering block;Finally the block after presintering is put in high-strength graphite mould
Carry out high temperature, short time plasma discharging Fast Sintering densification, finally give consistency and exceed
The nearly full-compact nanometer cemented carbide block materials of 99.0%.Nanocrystalline prepared by the present invention
The technology path energy consumption of WC-Co hard alloy block materials is low and environmental protection, prepared block
Material has high consistency and mechanical property, for nanometer while ensureing nanocrystalline grain size
The batch preparation of cemented carbide and commercial Application provide important technical foundation.
The step sintering that the present invention provides prepares high-compactness Nanograin Cemented Carbide block materials
Method, it is characterised in that comprise the following steps:
(1) the raw material V first grain growth inhibitor synthesized2O3And Cr2O3With nanometer purple tungsten
WO2.72, cobalt oxide Co3O4Mix and uniformly refine ball-milling treatment, ball milling work with white carbon black
Skill parameter is: ratio of grinding media to material is 25:1-30:1, and Ball-milling Time is 100-150h, mixing after ball milling
Close powder put into vacuum response stove prepare comprise grain growth inhibitor VC/Cr3C2's
WC-Co-VC/Cr3C2Nano composite powder;
(2) WC-Co-VC/Cr that step (1) is prepared3C2Nano composite powder loads hard
Matter alloy mold precompressed, is then placed in discharging plasma sintering equipment carrying out cryogenic high pressure pre-burning
Knot, uses following technological parameter: under sintering pressure 100-300MPa, and temperature is from room temperature liter
To 100 DEG C, heating rate is 10-50 DEG C/min, is incubated 10-30min at 100 DEG C;Insulation knot
Shu Hou, temperature is risen to 300 DEG C by 100 DEG C, and heating rate is 10-50 DEG C/min, at 300 DEG C
Lower insulation 10-30min;After insulation terminates, increase sintering pressure is to 300-500MPa, at this
Under pressure, temperature is risen to 500-700 DEG C by 300 DEG C, and heating rate is 10-100 DEG C/min,
30-60min it is incubated at a temperature of 500-700 DEG C;
(3) in sintered-carbide die step (2) obtained, block after presintering loads high-strength stone
In ink mould, put into and discharging plasma sintering equipment carries out second step densification sintering, use
Technological parameter be: sintering pressure is 70-240MPa, and heating rate is 50-100 DEG C/min,
Sintering temperature is 980-1040 DEG C, is incubated 1-3min, insulation knot at a temperature of 980-1040 DEG C
It is cooled to 300 DEG C with the cooldown rate of 10-100 DEG C/min after bundle, then cools to room temperature with the furnace,
Finally obtain the Nanograin Cemented Carbide block materials with high-compactness.
In the present invention, the consumption of white carbon black guarantees to form WC-Co and grain growth inhibitor
VC/Cr3C2There is not free carbon simultaneously.
The mass fraction of grain growth inhibitor in the Nanograin Cemented Carbide block materials of preparation
For 1.0%-2.0%, determine V in raw material according to concrete numerical value2O3And Cr2O3Consumption.
Compared with the preparation method of existing Nanograin Cemented Carbide sintering block materials, this
Bright internal feature and creativeness are embodied in:
(1) existing method is all straight in WC-Co composite powder end or WC, Co mixed-powder
Connecing interpolation grain growth inhibitor to obtain sintering dusty material, and the present invention is to first pass through
Single step reaction prepares that mass fraction is controlled, particle diameter be nanoscale containing grain growth inhibitor
Nano WC-Co-VC/Cr3C2Composite powder, by a step in-situ reaction preparation containing crystalline substance
The WC-Co composite powder end of the big inhibitor of grain length, can generate the starting stage of WC in reaction
Just make part C, Cr atom dissolve in Co phase or be present in WC grain surface, thus ensure crystalline substance
The distributing homogeneity of the big inhibitor of grain length and effectively suppress WC grain to grow up at subsequent process;Logical
Cross the composite powder of fabricated in situ multiphase coexistence, it is achieved chromium, the compound interpolation of vanadium carbide, permissible
Play Cr3C2Effect effectively promote the fracture toughness of hard alloy block material, the work of VC
With effectively promoting the hardness of hard alloy block material, thus realize material comprehensive mechanical property
Optimization so that the hardness of hard alloy block prepared by the present invention reaches 2000kg/mm2With
On, fracture toughness reaches 11.0MPa.m simultaneously1/2Above, hence it is evident that surmounted in having been reported and put
The performance data of Nanograin Cemented Carbide prepared by electricity plasma agglomeration.Therefore, with existing method
Comparing, the present invention is preparing the process of sintered powder material, powder characteristics and manufacturing cycle
Etc. aspect have breakthrough.
(2) to nano WC-Co-VC/Cr in the present invention3C2It is pre-that composite powder carries out high pressure low temperature
Sintering, on the one hand carries out heat treatment in advance to powder, miscellaneous except having removal powder surface adsorption
Outside the effect of matter, the most effectively release granular boundary and the internal local stress existed, pre-increasing
Reduce what WC grain in subsequent high temperature sintering process was grown up while sintering block consistency
Driving force;On the other hand, use sintered-carbide die to solve graphite jig to be unable to reach
A difficult problem for more than 250MPa comprcssive strength, thus realize at cold stage, powder being applied enough
Big pressure so that in nanometer powder between granule and particle surface absorption gas maximum
The discharge of degree, effectively reduces in later stage high-temperature sintering process interstitial at bulk inner
Probability, thus increase substantially the consistency of sintering block.
(3) presintering processes and gas in powder is excluded substantially, carries out presintering block
In plasma discharging Fast Sintering densification process, venting exhaust air technique step can be no longer set
Suddenly, and directly implement quickly heating, isothermal treatment for short time to presintering block, it is achieved the most in short-term
The interior final sintering densification to presintering block, so, is ensureing that sintering block is filled
The crystal grain caused in temperature-rise period is effectively suppressed to grow up while dividing densification.By we's legal system
The consistency of the standby nanocrystalline WC-Co hard alloy block materials obtained is above 99.0%,
Nanograin Cemented Carbide block materials consistency significantly more than current report is difficult to reach
The result of more than 97.0%, and Nanograin Cemented Carbide block materials prepared by this method is simultaneously
Possess hardness and the fracture toughness combination property of excellence.
Accompanying drawing explanation
Nanometer WC-12Co-1.0 (the VC/Cr used in Fig. 1 embodiment3C2) the micro-shape of composite powder
Looks figure;
Sweeping of nanocrystalline WC-12Co hard alloy block material microstructure prepared by Fig. 2 present invention
Retouch Electronic Speculum figure;
Nanocrystalline WC-12Co hard alloy block material prepared by Fig. 3 present invention is microstructural
Radio mirror figure.
Detailed description of the invention
Following instance further illustrates the present invention, but the present invention is not limited to following example.
Embodiment 1
According to preparing WC-Co-VC/Cr3C2Grain growth inhibitor in composite powder
VC/Cr3C2Mass fraction is 1.0wt.%, VC and Cr3C2Mass ratio close to 1:1, by crystalline substance
The raw material V of grain length big inhibitor synthesis2O3And Cr2O3With nanometer purple tungsten WO2.72, oxidation
Cobalt Co3O4Mixing with white carbon black and uniformly refine ball-milling treatment, milling parameters is: ball
Material ratio is 25:1, and Ball-milling Time is 100h, and the mixed-powder after ball milling puts into vacuum response stove
Prepare and comprise grain growth inhibitor VC/Cr3C2WC-Co-VC/Cr3C2Nano composite powder
End (see Fig. 1);
The WC-Co-VC/Cr that will prepare3C2It is pre-that composite powder loads sintered-carbide die
Pressure, is then placed in discharging plasma sintering equipment carrying out cryogenic high pressure presintering, uses as follows
Technological parameter: under sintering pressure 100MPa, temperature rises to 100 DEG C from room temperature, and heat up speed
Rate is 10 DEG C/min, is incubated 30min at 100 DEG C;After insulation terminates, temperature is risen by 100 DEG C
To 300 DEG C, heating rate is 10 DEG C/min, is incubated 30min at 300 DEG C;Insulation terminates
After, increase sintering pressure is to 300MPa, and temperature is risen to 700 DEG C by 300 DEG C at this pressure,
Heating rate is 10 DEG C/min, is incubated 60min at a temperature of 700 DEG C;
Block after above-mentioned first step presintering is loaded in high-strength graphite mould, puts into electric discharge etc.
Carrying out second step densification sintering in ion agglomerating plant, the technological parameter of employing is: sintering pressure
Power is 70MPa, and heating rate is 50 DEG C/min, and sintering temperature is 1040 DEG C, at 1040 DEG C
At a temperature of be incubated 3min, insulation terminate after be cooled to 300 DEG C with the cooldown rate of 10 DEG C/min,
Then cool to room temperature with the furnace, finally obtain the Nanograin Cemented Carbide block with high-compactness
Material (see Fig. 2), its performance parameter is shown in Table 1.
Embodiment 2
According to preparing WC-Co-VC/Cr3C2Grain growth inhibitor in composite powder
VC/Cr3C2Mass fraction is 1.5wt.%, VC and Cr3C2Mass ratio close to 1:1, by crystalline substance
The raw material V of grain length big inhibitor synthesis2O3And Cr2O3With nanometer purple tungsten WO2.72, oxidation
Cobalt Co3O4Mixing with white carbon black and uniformly refine ball-milling treatment, milling parameters is: ball
Material ratio is 28:1, and Ball-milling Time is 130h, and the mixed-powder after ball milling puts into vacuum response stove
Prepare and comprise grain growth inhibitor VC/Cr3C2WC-Co-VC/Cr3C2Nano composite powder
End;
The WC-Co-VC/Cr that will prepare3C2It is pre-that composite powder loads sintered-carbide die
Pressure, is then placed in discharging plasma sintering equipment carrying out cryogenic high pressure presintering, uses as follows
Technological parameter: under sintering pressure 200MPa, temperature rises to 100 DEG C from room temperature, and heat up speed
Rate is 30 DEG C/min, is incubated 20min at 100 DEG C;After insulation terminates, temperature is risen by 100 DEG C
To 300 DEG C, heating rate is 30 DEG C/min, is incubated 20min at 300 DEG C;Insulation terminates
After, increase sintering pressure is to 400MPa, and temperature is risen to 600 DEG C by 300 DEG C at this pressure,
Heating rate is 50 DEG C/min, is incubated 45min at a temperature of 600 DEG C;
Block after above-mentioned first step presintering is loaded in high-strength graphite mould, puts into electric discharge etc.
Carrying out second step densification sintering in ion agglomerating plant, the technological parameter of employing is: sintering pressure
Power is 150MPa, and heating rate is 75 DEG C/min, and sintering temperature is 1010 DEG C, at 1010 DEG C
At a temperature of be incubated 2min, insulation terminate after be cooled to 300 DEG C with the cooldown rate of 50 DEG C/min,
Then cool to room temperature with the furnace, finally obtain the Nanograin Cemented Carbide block with high-compactness
Material (see Fig. 3), its performance parameter is shown in Table 1.
Embodiment 3
According to preparing WC-Co-VC/Cr3C2Grain growth inhibitor in composite powder
VC/Cr3C2Mass fraction is 2.0wt.%, VC and Cr3C2Mass ratio close to 1:1, by crystalline substance
The raw material V of grain length big inhibitor synthesis2O3And Cr2O3With nanometer purple tungsten WO2.72, oxidation
Cobalt Co3O4Mixing with white carbon black and uniformly refine ball-milling treatment, milling parameters is: ball
Material ratio is 30:1, and Ball-milling Time is 150h, and the mixed-powder after ball milling puts into vacuum response stove
Prepare and comprise grain growth inhibitor VC/Cr3C2WC-Co-VC/Cr3C2Nano composite powder
End;
The WC-Co-VC/Cr that will prepare3C2It is pre-that composite powder loads sintered-carbide die
Pressure, is then placed in discharging plasma sintering equipment carrying out cryogenic high pressure presintering, uses as follows
Technological parameter: under sintering pressure 300MPa, temperature rises to 100 DEG C from room temperature, and heat up speed
Rate is 50 DEG C/min, is incubated 10min at 100 DEG C;After insulation terminates, temperature is risen by 100 DEG C
To 300 DEG C, heating rate is 50 DEG C/min, is incubated 10min at 300 DEG C;Insulation terminates
After, increase sintering pressure is to 500MPa, and temperature is risen to 500 DEG C by 300 DEG C at this pressure,
Heating rate is 100 DEG C/min, is incubated 30min at a temperature of 700 DEG C;
Block after above-mentioned first step presintering is loaded in high-strength graphite mould, puts into electric discharge etc.
Carrying out second step densification sintering in ion agglomerating plant, the technological parameter of employing is: sintering pressure
Power is 240MPa, and heating rate is 100 DEG C/min, and sintering temperature is 980 DEG C, at 980 DEG C
At a temperature of be incubated 1min, insulation terminate after be cooled to 300 DEG C with the cooldown rate of 100 DEG C/min,
Then cool to room temperature with the furnace, finally obtain the Nanograin Cemented Carbide block with high-compactness
Material, its performance parameter is shown in Table 1.
The performance parameter of nanocrystalline WC-Co hard alloy block materials prepared by the different embodiment of table 1
Claims (3)
1. the method preparing high-compactness Nanograin Cemented Carbide block materials by step sintering, it is special
Levy and be, comprise the following steps:
(1) the raw material V first grain growth inhibitor synthesized2O3And Cr2O3With nanometer purple tungsten WO2.72, oxygen
Change cobalt Co3O4Mixing with white carbon black and uniformly refine ball-milling treatment, milling parameters is: ratio of grinding media to material is
25:1-30:1, Ball-milling Time is 100-150h, the mixed-powder after ball milling put into vacuum response stove prepare comprise
Grain growth inhibitor VC/Cr3C2WC-Co-VC/Cr3C2Nano composite powder;
(2) WC-Co-VC/Cr that step (1) is prepared3C2Nano composite powder loads sintered-carbide die
Precompressed, is then placed in discharging plasma sintering equipment carrying out cryogenic high pressure presintering, uses following technique to join
Number: under sintering pressure 100-300MPa, temperature rises to 100 DEG C from room temperature, and heating rate is 10-50 DEG C/min,
It is incubated 10-30min at 100 DEG C;After insulation terminates, temperature is risen to 300 DEG C by 100 DEG C, and heating rate is
10-50 DEG C/min, at 300 DEG C, it is incubated 10-30min;After insulation terminates, increase sintering pressure extremely
300-500MPa, temperature is risen to 500-700 DEG C by 300 DEG C at this pressure, and heating rate is 10-100 DEG C
/ min, is incubated 30-60min at a temperature of 500-700 DEG C;
(3) during in sintered-carbide die step (2) obtained, block after presintering loads high-strength graphite mould,
Putting into and carry out second step densification sintering in discharging plasma sintering equipment, the technological parameter of employing is: sintering
Pressure is 70-240MPa, and heating rate is 50-100 DEG C/min, and sintering temperature is 980-1040 DEG C,
Being incubated 1-3min at a temperature of 980-1040 DEG C, insulation is cooled to the cooldown rate of 10-100 DEG C/min after terminating
300 DEG C, then cool to room temperature with the furnace, finally obtain the Nanograin Cemented Carbide block material with high-compactness
Material.
2. according to the method for claim 1, it is characterised in that brilliant in the Nanograin Cemented Carbide block materials of preparation
The mass fraction of the big inhibitor of grain length is 1.0%-2.0%, determines V in raw material according to concrete numerical value2O3And Cr2O3
Consumption.
3. the high-compactness Nanograin Cemented Carbide block materials prepared according to the method for claim 1 or 2.
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