CN103924144B - A kind of soap-free emulsion polymeization phase ultrafine WC hard alloy preparation method - Google Patents
A kind of soap-free emulsion polymeization phase ultrafine WC hard alloy preparation method Download PDFInfo
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Abstract
A kind of preparation method of soap-free emulsion polymeization phase ultrafine WC hard alloy.Co content is lower than 0.5wt% in soap-free emulsion polymeization phase ultrafine WC hard alloy of the present invention, and grain growth inhibitor accounts for 0.3-1.0wt%, remaining is WC.Design use the ultrafine WC composite powder containing micro grain growth inhibitor prepared in spraying thermal reduction method and superfine WC-Co composite powder end as raw material, by high-energy ball milling 36-72h after the hydrocarbon black powder of certain ingredients proportions and addition lower than 0.4wt%, by hot pressing or hot isostatic pressing or air pressure reinforced sintering method in 1550-1750 DEG C of sintering 1-3h.Prepared soap-free emulsion polymeization phase ultra-fine cemented carbide has excellent comprehensive performance, and Vickers hardness reaches 3000-3500HV0.05, fracture toughness reaches 7.1-8.0MPam1/2, cross-breaking strength reaches 900-1200MPa, and crystallite dimension is 0.2-0.5 μm.The novel hard alloy available extensive use in the field for requiring high-wearing feature and highly corrosion resistant.
Description
Technical field：
The present invention relates to a kind of preparation methods of soap-free emulsion polymeization phase ultrafine WC hard alloy.
Background technique：
Conventional cemented carbide is the tool materials critically important by one kind of WC hard phase and γ-Co bonding phase composition, it has
There is the features such as high intensity, high rigidity, high elastic modulus, wear-resistant, corrosion-resistant, low thermal coefficient of expansion and high chemical stability,
It is widely used as cutter, drilling tool, wear-resisting spare part etc..The intensity and toughness of WC-Co hard alloy with the increase of Co content and
It improves, but the increase of Co content also reduces hard alloy wearability and corrosion resistance simultaneously.Therefore in certain special occasions,
For example require under the working environment of high rigidity, high-wearing feature and high corrosion resistance, traditional WC-Co hard alloy can no longer meet
It is required that therefore the novel non-bond cemented carbide of research become inevitable development trend.
Non-bond cemented carbide refers to a kind of high-wearing feature WC hard alloy for being lower than 0.5 % of mass fraction containing Co, with
Traditional WC-Co hard alloy, which is compared, has higher hardness, wearability, corrosion resistance and more superior polishing characteristic, while its
The cost of raw material substantially reduces, and reduces due to Co60Influence of the radioactivity to human body and environment.Due to the WC of normal granulometry
Powder can not prepare the higher block of consistency when Co content is extremely low by conventional sintering mode, and use ultra-fine WC powder not
But the nearly full alloy of compact texture can be obtained and hardness, intensity and the toughness of material can also increase substantially, therefore without viscous
Tying phase ultra-fine cemented carbide becomes an important research direction of hard alloy.
Currently, correlative study both domestic and external is mainly used adds micro Co and Coarse Grain in ultra-fine WC powder
Agent after high-energy ball milling, passes through high frequency induction current sintering, hot pressed sintering or electric discharge using this element mixed-powder as raw material
The methods of plasma sintering technique prepares soap-free emulsion polymeization phase ultra-fine cemented carbide.But during ball milling mixing, micro Co and crystal grain
Inhibitor of growing up is difficult to be evenly distributed in raw material powder system, this easily causes the ingredient of micro Co and grain growth inhibitor
Segregation, leads in sintering process that WC grain is extremely non-homogeneous to grow up, and material is made to show unstable mechanical property, final serious
The service performance of soap-free emulsion polymeization phase ultra-fine cemented carbide is influenced, therefore soap-free emulsion polymeization phase ultra-fine cemented carbide is unable to get always reality
It is widely applied.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to propose a kind of soap-free emulsion polymeization phase ultrafine WC hard alloy preparation
Method.
The purpose of the present invention can be achieved by the following measures：
（1）Ultrafine WC composite powder and spraying thermal reduction side containing grain growth inhibitor are prepared in spraying thermal reduction method
The superfine WC-Co composite powder end of method preparation, wherein the wt% of 0.3-1.0 containing grain growth inhibitor in ultrafine WC composite powder, brilliant
The big inhibitor of grain length is two or more in vanadium carbide, chromium carbide, titanium carbide, hafnium carbide, tantalum carbide and niobium carbide, is surpassed
Co content is 1-15 wt% in thin WC-Co composite powder end, ultrafine WC composite powder and superfine WC-Co composite powder end 11- in proportion
99:1 prepares the ultra-fine mixed-powder of soap-free emulsion polymeization phase ultra-fine cemented carbide ingredient；
（2）Add the hydrocarbon black powder that content is less than 0.4 wt% of mixed raw material powder systems；
（3）Using planetary type ball-milling or vibratory milling by ultra-fine WC powder and superfine WC-Co containing grain growth inhibitor
Composite powder carries out high-energy ball milling processing, and rotational speed of ball-mill is 200-500 rpm, and Ball-milling Time is 36-72 h；
（4）Soap-free emulsion polymeization phase ultra-fine cemented carbide is prepared using different sintering processings：
Powder is sintered by densification using hot pressed sintering, hot pressed sintering carries out 60 under 1750 DEG C and 20 MPa
min；
Or heating isostatic pressing is pre-sintered using vacuum.1 h first is pre-sintered in 1700 DEG C of progress vacuum to powder.It
Hip treatment is used to vacuum pre-sintered body afterwards, hip treatment carries out 1 h under 1550 DEG C and 1000 MPa；
Or powder is sintered by densification using gas pressure sintering technology, gas pressure sintering is filled in 1650 DEG C of 90 min of heat preservation
N2Air pressure is set to reach 10-30 MPa, 40 min of pressure maintaining later.
The present invention prepare gained non-bond cemented carbide have excellent comprehensive performance, Vickers hardness, fracture toughness and
Cross-breaking strength respectively reaches 3000-3500 HV0.05、7.1-8.0 MPa·m1/2With 900-1200 MPa, crystallite dimension
It 0.2-0.5 μm, can be in the application field for requiring high-wearing feature and highly corrosion resistant（As high-pressure medium nozzle, sealing ring, valve,
And bearing parts etc.）In available extensive use.
Compared with prior art, the present invention having the following advantages that：
（1）Easily occur micro Co during the sintering process for soap-free emulsion polymeization phase ultrafine WC hard alloy and is difficult to Dispersed precipitate
With WC grain non-homogeneous the problem of growing up, in terms of design of material, design is used with the preparation of spraying thermal reduction method the present invention
Ultrafine WC containing micro grain growth inhibitor（Wherein grain growth inhibitor be vanadium carbide, chromium carbide, titanium carbide, hafnium carbide,
Tantalum carbide and niobium carbide, ingredient are 0.3-1.0 wt%）With superfine WC-Co composite powder end（Co in superfine WC-Co composite powder end
Content is 1-15 wt%）For raw material, pass through high-energy ball-milling process 11-99 in proportion:1 is configured to soap-free emulsion polymeization phase ultra-fine cemented carbide
The WC composite powder of ingredient is uniformly distributed grain growth inhibitor and micro Co disperse, effectively prevents WC in sintering process
Unevenly growing up for crystal grain, obtains soap-free emulsion polymeization phase Ultra-fine Grained WC cemented carbide material；
（2）Soap-free emulsion polymeization phase ultrafine WC cemented carbide material good combination property obtained is prepared through the invention, in crystal grain
Degree, hardness, bending strength etc. are reached advanced world standards, and wherein crystallite dimension is 0.2-0.5 μm, Vickers hardness, fracture
Toughness and cross-breaking strength respectively reach 3000-3500 HV0.05、7.1-8.0 MPa·m1/2With 900-1200 MPa.
Specific embodiment
Embodiment 1：
（1）By percent mass proportioning（By taking total powder quality 100g as an example）Weigh each powder constituent element quality：
| Powder title | WC-0.1VC-0.3Cr3C2 | WC-6Co | Carbon black |
| Quality（g） | 91.7 | 8 | 0.3 |
（2）Mixed-powder is subjected to high-energy ball milling using hard alloy abrading-ball in high energy ball mill.Revolving speed is when ball milling
360 r•min-1, 48 h of Ball-milling Time is dry by powder under vacuum after milling, is ground up, sieved.
（3）The hot pressed sintering of powder.Hot pressing temperature：1750 DEG C, soaking time：60 min, hot pressing pressure：20 MPa.
（4）Crystallite dimension measurement and mechanics properties testing are carried out to sintered sample.Prepared soap-free emulsion polymeization is mutually ultra-fine
WC Cemented Carbides Fracture Toughness is 7.15 MPam1/2, Vickers hardness is 3150 HV0.05, 910 MPa of cross-breaking strength, crystalline substance
Granularity is 390 nm.
Embodiment 2：
（1）By percent mass proportioning（By taking total powder quality 100g as an example）Weigh each powder constituent element quality：
| Powder title | WC-0.1VC-0.2Cr3C2-0.2TiC | WC-8Co | Carbon black |
| Quality（g） | 95.9 | 4 | 0.1 |
（2）Mixed-powder is subjected to high-energy ball milling using hard alloy abrading-ball in high energy ball mill, revolving speed is when ball milling
300 r•min-1, 36 h of Ball-milling Time is dry by powder under vacuum after milling, is ground up, sieved.
（3）The hot pressed sintering of powder.Hot pressing temperature：1750 DEG C, soaking time：60 min, hot pressing pressure：20 MPa.
（4）Crystallite dimension measurement and mechanics properties testing are carried out to sintered sample.Prepared soap-free emulsion polymeization is mutually ultra-fine
WC Cemented Carbides Fracture Toughness is 7.15 MPam1/2, cross-breaking strength is 964 MPa, and Vickers hardness is 3450 HV0.05,
Mean grain size is 420 nm.
Embodiment 3：
（1）By percent mass proportioning（By taking total powder quality 100g as an example）Weigh each powder constituent element quality：
| Powder title | WC-0.5TiC-0.5HfC | WC-8Co | Carbon black |
| Quality（g） | 96.8 | 3 | 0.2 |
（2）Mixed-powder is subjected to high-energy ball milling using hard alloy abrading-ball in high energy ball mill, revolving speed is when ball milling
250 r•min-1, 72 h of Ball-milling Time is dry by powder under vacuum after milling, is ground up, sieved.
（3）Produce powder compact.Pressing pressure：100 MPa.
（4）The vacuum of powder compact is pre-sintered.Sintering temperature：1700 DEG C, sintering time：1 h.
（5）The hip treatment of vacuum pre-sintered body.Hip temperature：1550 DEG C, hot isostatic pressing power 1000
MPa, time：1 h.
（6）Crystallite dimension measurement and mechanics properties testing are carried out to sintered sample.Prepared soap-free emulsion polymeization is mutually ultra-fine
WC Cemented Carbides Fracture Toughness is 7.85 MPam1/2, cross-breaking strength is 1178 MPa, Vickers hardness 3050
HV0.05, grain size is 480 nm.
Embodiment 4：
（1）By percent mass proportioning（By taking total powder quality 100g as an example）Weigh each powder constituent element quality：
| Powder title | WC-0.2TiC-0.2HfC-0.3NbC | WC-6Co | Carbon black |
| Quality（g） | 92.7 | 7 | 0.3 |
（2）Mixed-powder is subjected to high-energy ball milling using hard alloy abrading-ball in high energy ball mill, revolving speed is when ball milling
200 r•min-1, 40 h of Ball-milling Time is dry by powder under vacuum after milling, is ground up, sieved.
（3）Produce powder compact.Pressing pressure：100 MPa.
（4）The vacuum of powder compact is pre-sintered.Sintering temperature：1700 DEG C, sintering time：1 h.
（5）The hip treatment of vacuum pre-sintered body.Hip temperature：1550 DEG C, hot isostatic pressing power 1000
MPa, time：1 h.
（6）Crystallite dimension measurement and mechanics properties testing are carried out to sintered sample.Prepared soap-free emulsion polymeization is mutually ultra-fine
WC Cemented Carbides Fracture Toughness is 7.62 MPam1/2, cross-breaking strength is 1034 MPa, Vickers hardness 3110
HV0.05, grain size is 230 nm.
Embodiment 5：
（1）By percent mass proportioning（By taking total powder quality 100g as an example）Weigh each powder constituent element quality：
（2）Mixed-powder is subjected to high-energy ball milling using hard alloy abrading-ball in high energy ball mill, revolving speed is when ball milling
500 r•min-1, 70 h of Ball-milling Time is dry by powder under vacuum after milling, is ground up, sieved.
（3）Produce powder compact.Pressing pressure：260 MPa.
（4）The pressure sintering of powder compact.5 DEG C/min to 400 DEG C of heating rate, 40 min are kept the temperature, then heating speed
10 DEG C/min of rate is then heated to 1650 DEG C, keeps the temperature 90 min, fills N2Gas makes air pressure reach 20 MPa, later pressure maintaining 40
Min, sintering are completed, and furnace is cold.
（5）Crystallite dimension measurement and mechanics properties testing are carried out to sintered sample.Prepared soap-free emulsion polymeization is mutually ultra-fine
WC Cemented Carbides Fracture Toughness is 7.32 MPam1/2, cross-breaking strength is 936 MPa, Vickers hardness 3280
HV0.05, grain size is 350 nm.
Claims (4)
1. a kind of preparation method of soap-free emulsion polymeization phase ultrafine WC hard alloy, it is characterised in that include the following steps：
（1）Ultrafine WC composite powder containing grain growth inhibitor and by spraying thermal reduction method system are prepared in spraying thermal reduction method
Standby superfine WC-Co composite powder end is raw material, wherein the wt% of 0.3-1.0 containing grain growth inhibitor in ultrafine WC composite powder,
Grain growth inhibitor is two or more in vanadium carbide, chromium carbide, titanium carbide, hafnium carbide, tantalum carbide and niobium carbide,
Co content is 1-15 wt% in superfine WC-Co composite powder end, and ultrafine WC composite powder and superfine WC-Co composite powder end are in proportion
11-99:1 prepares the ultra-fine mixed-powder of soap-free emulsion polymeization phase ultra-fine cemented carbide ingredient；
（2）Add the hydrocarbon black powder that content is less than 0.4 wt% of mixed raw material powder systems；
（3）Using planetary type ball-milling or vibratory milling by containing grain growth inhibitor ultra-fine WC powder and superfine WC-Co it is compound
Powder carries out high-energy ball milling processing, and rotational speed of ball-mill is 200-500 rpm, and Ball-milling Time is 36-72 h；
（4）Soap-free emulsion polymeization phase ultra-fine cemented carbide is prepared using different sintering processings, the Vickers hardness of non-bond cemented carbide is broken
It splits toughness and cross-breaking strength respectively reaches 3000-3500 HV0.05、7.1-8.0 MPa·m1/2It is brilliant with 900-1200 MPa
0.2-0.5 μm of particle size.
2. the preparation method of soap-free emulsion polymeization phase ultrafine WC hard alloy as described in claim 1, it is characterised in that：Step（4）In
The sintering processing is that powder is sintered densification using hot pressed sintering, and hot pressed sintering is under 1750 DEG C and 20 MPa
Carry out 60 min.
3. the preparation method of soap-free emulsion polymeization phase ultrafine WC hard alloy as described in claim 1, it is characterised in that：Step（4）In
The sintering processing is that heating isostatic pressing is pre-sintered using vacuum：1 first is pre-sintered in 1700 DEG C of progress vacuum to powder
H, uses hip treatment to vacuum pre-sintered body later, and hip treatment carries out 1 under 1550 DEG C and 1000 MPa
h。
4. the preparation method of soap-free emulsion polymeization phase ultrafine WC hard alloy as described in claim 1, it is characterised in that：Step（4）In
The sintering processing is that powder is sintered densification using gas pressure sintering technology, and gas pressure sintering keeps the temperature 90 at 1650 DEG C
Min fills N2Air pressure is set to reach 10-30 MPa, 40 min of pressure maintaining later.
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