CN103540781A - Method for producing ultra-coarse grain cemented carbide through utilizing high energy stirring and ball-milling technology - Google Patents
Method for producing ultra-coarse grain cemented carbide through utilizing high energy stirring and ball-milling technology Download PDFInfo
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Abstract
The invention relates to a method for producing ultra-coarse grain cemented carbide through utilizing a high energy stirring and ball-milling technology. Preparation raw materials comprise WC, Co and a small amount of NbC or/and TaC which is served as an additive, wherein the particle granularity of the WC is not less than 15 micrometers, and the WC accounts for 82.0-95.5wt%, the Co accounts for 4.5-18wt%, and the additive accounts for 0.0-0.5wt%. The preparation method comprises the following steps: (1) a high energy stirring and ball milling process, namely, filling all the preparation raw materials, i.e. the WC, cobalt powder and the additive into a high energy stirring ball mill, and adding a plasticizer and a ball-milling addition agent for ball milling; (2) a vacuum drying and granulating process; and (3) conventionally pressing a mixture for forming, and carrying out vacuum sintering or pressure sintering within a scope of 1400 DEG C-1480 DEG C. By utilizing the technology, the milling effect of the powder can be greatly improved, the ball milling time is obviously shortened, the production efficiency is improved, the energy consumption is reduced, and alloy crystal grains are uniformly distributed.
Description
Technical field:
The invention belongs to metallic substance technical field, relate to a kind of novel technique, by adopting high-energy stirring ball mill technique to prepare the method for extra-coarse grained carbide alloy.
Background technology:
Extra-coarse grained carbide alloy refers to the Wimet that mean grain size is greater than 4 microns, due to it characteristic that possesses high thermal conductivity, high tenacity, be widely used in the industries such as coal mining, engineering construction, metal chipless working, iron and steel rolling, there is the work-ing life that is much better than conventional Wimet.
United States Patent (USP) 5505902 and the 5529804 disclosed methods of preparing extra-coarse grained carbide alloy, be that coarse grained WC is disperseed and gradation sizing by jet grinding, removes the part WC that thin WC particle is only selected coarsness, then coarse particles carried out to cobalt coating.The cobalt coating method that patent 5505902 adopts is melten gel-gel method, and WC, methyl alcohol and triethylamine are mixed in reactor, and when heating, methyl alcohol can evaporate, and cobalt precipitates and forms melten gel gel in WC grain.The method that patent 5529804 adopts is polyvalent alcohol liquid phase reduction, and by carrying out after the acetate+water of cobalt+WC mixing, spray dried is dry, and mixed processes is improved, to avoid the fragmentation of coarse particles WC.The compound of producing by above patented method, then adopt conventional compression moulding and sintering method, can prepare cobalt contents is 6%, mean grain size is the extra-coarse grained carbide alloy of 6 microns.
That Chinese patent CN200910042940.6 be take is that WC is main body composition, through WC powder and cobalt/nickel ammine solution of mechanical pretreatment, be raw material, by choose reasonable WC raw material granularity and powder pre-treating technique, adopt hydro-thermal High Pressure Hydrogen reducing process to prepare the Wimet that WC-Co/Ni composite powder is prepared grain fineness number >=4.5 micron.These preparation methods need powder to carry out comparatively complicated pre-treatment, and complex process and long flow path, and production cost is high, is difficult to form the batch production of economization.
It is raw material that Chinese patent CN101824574A adopts super thick wolfram varbide and cobalt powder, carries out pre-mixing, then adds forming agent and is pressed into agglomerate, puts into debinding furnace and carries out degreasing and pre-burning.To after the agglomerate fragmentation after pre-burning, add again cobalt powder wet-milling again, then adopt conventional compression moulding and sintering method, obtain extra-coarse grained Wimet.The technical process of this patent is longer, needs to add twice degreasing of forming agent twice, and production energy consumption is higher, and easily brings impurity in the shattering process of agglomerate, is unfavorable for producing highly purified product.
It is raw material that Chinese patent CN101985717A adopts super thick wolfram varbide and cobalt powder, carries out pre-mixing, then adds forming agent and is pressed into agglomerate, puts into debinding furnace and carries out degreasing and pre-burning.To after the agglomerate fragmentation after pre-burning, add again cobalt powder and nano Co
2w
4c prepares burden and wet-milling again, then adopts conventional compression moulding and sintering method, obtains extra-coarse grained Wimet.This patent is similar with patent CN101824574A, still exists technical process longer, and production energy consumption is higher, easily brings the shortcoming of impurity into.
The method that Chinese patent CN102634684A announces is first cobalt powder and super coarse particles WC to be carried out to pre-mixing at mixing tank, then the material after pre-mixing is packed into and in ball mill, carries out slow-revving slight ball milling.To the slip obtaining routinely the mode of production be dried, compacting, sintering, can obtain extra-coarse grained degree alloy.The flow process of this patent is relatively short, and production cost is lower, is relatively applicable to suitability for industrialized production.But still there is defect in this patent: after pre-mixing, in the slight ball milling of material in ball mill, because the rotating speed of ball mill is low, the kinetic energy of mill ball is lower, and WC particle is existed to obvious surface abrasion, thereby produces more fine powder.The uniform crystal particles degree of the alloy that final production goes out is like this not high.
In sum, although although prepare now the patent of extra-coarse grained carbide alloy and increase gradually, all there is defect more or less.
Summary of the invention:
The invention provides a kind of preparation method of new extra-coarse grained carbide alloy, technical process is short, production efficiency is high, energy consumption is lower, and the size-grade distribution of final extra-coarse grained alloy is more even.
For reaching above object, solution of the present invention is
High-energy stirring ball mill is prepared the method for extra-coarse grained carbide alloy, raw materials comprises that WC, Co and a small amount of NbC as additive are or/and TaC, WC particle granularity >=15 μ m wherein, content is 82.0～95.5wt%, the content of Co is 4.5～18wt%, and the content of additive is 0.0～0.5wt%; Preparation method is as follows:
(1) high-energy stirring ball mill operation: be that WC, cobalt powder, additive pack high-energy stirring ball mill machine into by whole raw materials, and add binder and ball-milling additive to carry out ball milling, it is grinding medium that volumetric concentration is greater than 90% alcohol; Ball milling parameter is: rotational speed of ball-mill 100-110rpm, stacking factor are 0.3～0.4, solid-liquid mass ratio is that 5: 1, mill ball diameter are 10.0mm ± 0.2mm, ratio of grinding media to material 2～4: 1, Ball-milling Time 100～180 minutes;
(2) vacuum-drying granulation process: after operation (1) is finished, the slip of gained is packed in vacuum stirring moisture eliminator, be dried and granulate, obtain the solid mixture with certain fluidity.
(3) compound is carried out to conventional compression moulding, vacuum sintering or pressure sintering within the scope of 1400 ℃～1480 ℃, the alloy grain degree of producing is 5.0～14.0 microns, porosity is less than A04B00.
The ball-milling additive amount of adding in operation (1) is 1: 2000 with the mass ratio of whole raw materials gross weights.
The ball-milling additive adding in operation (1) is oleic acid, and oleic acid is 1: 2000 with the mass ratio of whole raw materials gross weights.
The amount of the forming agent adding in operation (1) accounts for 2% of whole raw materials gross weights.
The forming agent adding in operation (1) is paraffin, and paraffin accounts for 2% of whole raw materials gross weights.
The present invention compared with prior art has following characteristics:
High-energy stirring ball mill machine is owing to being to continue the application of force initiatively, at a high speed, and larger to the reactive force of material compared with rotary mill, grinding effect exceeds more than 5～10 times.And stirring ball-milling is to take volumetric fracture as main to the fragmentation of WC particle, surface fracture is auxiliary, with respect to rolling ball milling (the surface fracture situation to WC particle is more), can obtain the more uniform compound of size-grade distribution like this.Mechanical milling process is a dynamical system, and the surface of the WC particle being broken can be very high, and secondary agglomeration very easily occurs, and reduces grinding efficiency, affects mixture quality.In order to guarantee mixture quality, employing adds appropriate oleic acid as suspending agent in slip, can make particle surface with identical electric charge, repels each other, reach the effect of dispersion, thereby make powder particle can be evenly distributed in the mobile solid-state system of stable liquid of energy that forms thickness in medium.Paraffin directly adds in mechanical milling process as the binding agent of carbide alloy mixture, is conducive to improve compound viscosity, and very even, prevents that binding agent from producing segregation.Finally obtain weave construction evenly, the Wimet of excellent property.
Compared with prior art, this technique has following outstanding advantages:
1: adopt high-energy stirring ball mill machine, greatly improve the grinding effect to powder, Ball-milling Time significantly shortens, improving productivity, Energy Intensity Reduction;
2: alloy grain is more evenly distributed;
3: after ball milling, mixture particle is even, viscosity is good, is easy to compression moulding.
Accompanying drawing explanation
Fig. 1 is the metallographic structure of WC-6%Co alloy, and mean grain size is 10 microns.
Embodiment:
Embodiment 1:
According to 94wt%WC+6wt%Co preparation raw material, (the average Fisher particle size of wolfram varbide is 15 μ m, the Fei Shi mean particle size of cobalt powder is 1.3 μ m.) add the volumetric concentration of 250ml/Kg to be greater than 90% alcohol as grinding medium, and in compound slip, adding the oleic acid of 0.5g/Kg as suspending agent, 2wt% paraffin is as binding agent.Above-mentioned material carries out ball milling in agitating ball mill, and the speed setting of the agitating arm of ball mill is 100 revs/min, and stacking factor is 0.4, ratio of grinding media to material 2: 1; After ball milling 120 minutes, unload slip and carry out vacuum-drying.By vacuum sintering at 1450 ℃ after compound moulding, detection mean grain size is: 10 μ m, and porosity A02B00, metallographic structure figure as shown in fig. 1, can be clearly seen that the alloy grain of the hart metal product obtaining is evenly distributed.
Embodiment 2:
According to 87wt%WC+13wt%Co preparation raw material, (wolfram varbide Fei Shi mean particle size is 15 μ m, the Fei Shi mean particle size of cobalt powder is 1.3 μ m.) add the alcohol of 260ml/Kg as grinding medium, and in compound slip, adding the oleic acid acid of 0.5g/Kg as suspending agent, 2wt% paraffin is as binding agent.Above-mentioned material carries out ball milling in agitating ball mill, and the speed setting of the agitating arm of ball mill is 100 revs/min, and stacking factor is 0.4, mill ball diameter is 10.0mm ± 0.2mm, ratio of grinding media to material 4: 1; After ball milling 150 minutes, unload slip and carry out vacuum-drying.By vacuum sintering at 1430 ℃ after compound moulding, detection mean grain size is: 5 μ m, porosity A02B00.
Claims (5)
1. high-energy stirring ball mill is prepared the method for extra-coarse grained carbide alloy, raw materials comprises that WC, Co and a small amount of NbC as additive are or/and TaC, WC particle granularity >=15 μ m wherein, content is 82.0～95.5wt%, the content of Co is 4.5～18wt%, and the content of additive is 0.0～0.5wt%; Preparation method is as follows:
(1) high-energy stirring ball mill operation: be that WC, cobalt powder, additive pack high-energy stirring ball mill machine into by whole raw materials, and add binder and ball-milling additive to carry out ball milling, it is grinding medium that volumetric concentration is greater than 90% alcohol; Ball milling parameter is: rotational speed of ball-mill 100-110rpm, stacking factor are 0.3～0.4, solid-liquid mass ratio is that 5: 1, mill ball diameter are 10.0mm ± 0.2mm, ratio of grinding media to material 2～4: 1, Ball-milling Time 100～180 minutes;
(2) vacuum-drying granulation process: after operation (1) is finished, the slip of gained is packed in vacuum stirring moisture eliminator, be dried and granulate, obtain the solid mixture with certain fluidity.
(3) compound is carried out to conventional compression moulding, vacuum sintering or pressure sintering within the scope of 1400 ℃～1480 ℃, the alloy grain degree of producing is 5.0～14.0 microns, porosity is less than A04B00.
2. high-energy stirring ball mill is prepared the method for extra-coarse grained carbide alloy as described in claim 1, it is characterized in that: the ball-milling additive amount of adding in operation (1) is 1: 2000 with whole mass ratioes of raw materials gross weights.
3. described in claim 2, high-energy stirring ball mill is prepared the method for extra-coarse grained carbide alloy, it is characterized in that: the ball-milling additive adding in operation (1) is oleic acid, and oleic acid is 1: 2000 with whole mass ratioes of raw materials gross weights.
4. high-energy stirring ball mill is prepared the method for extra-coarse grained carbide alloy as described in claim 1, it is characterized in that: the amount of the forming agent adding in operation (1) accounts for 2% of whole raw materials gross weights.
5. high-energy stirring ball mill is prepared the method for extra-coarse grained carbide alloy as described in claim 4, it is characterized in that: the forming agent adding in operation (1) is paraffin, and paraffin accounts for 2% of whole raw materials gross weights.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103862038A (en) * | 2014-03-14 | 2014-06-18 | 中南大学 | Extra-coarse hard alloy parcel powder and preparation method thereof |
| CN103938049A (en) * | 2014-03-18 | 2014-07-23 | 界首市创力生产力促进中心有限公司 | High strength and high wear resistant ring used for stirrer |
| CN105170986A (en) * | 2015-10-29 | 2015-12-23 | 株洲西迪硬质合金科技股份有限公司 | Gradient hard alloy, preparation method and cutting tooth head |
| CN106222465A (en) * | 2016-08-30 | 2016-12-14 | 河南省大地合金股份有限公司 | A kind of preparation method of hard alloy |
| CN106636836A (en) * | 2017-01-22 | 2017-05-10 | 四川理工学院 | Preparation method of ultra-coarse hard alloy |
| CN106756392A (en) * | 2016-12-14 | 2017-05-31 | 单麒铭 | A kind of oil field preparation method of WC Co carboloy nozzles |
| CN106834778A (en) * | 2017-01-03 | 2017-06-13 | 崇义恒毅陶瓷复合材料有限公司 | Hard alloy and preparation method |
| CN107052348A (en) * | 2017-04-11 | 2017-08-18 | 济南市冶金科学研究所有限责任公司 | A kind of manufacture method of inner-cooled hard alloy knife bar of the two ends with counterbore |
| CN108611540A (en) * | 2018-07-13 | 2018-10-02 | 昆山长野超硬合金有限公司 | A kind of hard alloy and preparation method thereof for diamond coatings |
| CN113774264A (en) * | 2021-09-16 | 2021-12-10 | 中交隧道工程局有限公司 | Preparation method of coarse-grain WC-Co-X hard alloy based on addition of ultrafine powder |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103862038A (en) * | 2014-03-14 | 2014-06-18 | 中南大学 | Extra-coarse hard alloy parcel powder and preparation method thereof |
| CN103938049A (en) * | 2014-03-18 | 2014-07-23 | 界首市创力生产力促进中心有限公司 | High strength and high wear resistant ring used for stirrer |
| CN105170986A (en) * | 2015-10-29 | 2015-12-23 | 株洲西迪硬质合金科技股份有限公司 | Gradient hard alloy, preparation method and cutting tooth head |
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| CN106222465A (en) * | 2016-08-30 | 2016-12-14 | 河南省大地合金股份有限公司 | A kind of preparation method of hard alloy |
| CN106756392A (en) * | 2016-12-14 | 2017-05-31 | 单麒铭 | A kind of oil field preparation method of WC Co carboloy nozzles |
| CN106834778A (en) * | 2017-01-03 | 2017-06-13 | 崇义恒毅陶瓷复合材料有限公司 | Hard alloy and preparation method |
| CN106834778B (en) * | 2017-01-03 | 2018-09-28 | 崇义恒毅陶瓷复合材料有限公司 | Hard alloy and preparation method |
| CN106636836A (en) * | 2017-01-22 | 2017-05-10 | 四川理工学院 | Preparation method of ultra-coarse hard alloy |
| CN107052348A (en) * | 2017-04-11 | 2017-08-18 | 济南市冶金科学研究所有限责任公司 | A kind of manufacture method of inner-cooled hard alloy knife bar of the two ends with counterbore |
| CN108611540A (en) * | 2018-07-13 | 2018-10-02 | 昆山长野超硬合金有限公司 | A kind of hard alloy and preparation method thereof for diamond coatings |
| CN113774264A (en) * | 2021-09-16 | 2021-12-10 | 中交隧道工程局有限公司 | Preparation method of coarse-grain WC-Co-X hard alloy based on addition of ultrafine powder |
| CN113774264B (en) * | 2021-09-16 | 2022-08-26 | 中交隧道工程局有限公司 | Preparation method of coarse-grain WC-Co-X hard alloy based on adding superfine powder |
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Application publication date: 20140129 |