CN100575515C - A kind of method for preparing ultra-fine crystal WC-Co hard alloy - Google Patents
A kind of method for preparing ultra-fine crystal WC-Co hard alloy Download PDFInfo
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- CN100575515C CN100575515C CN200710120263A CN200710120263A CN100575515C CN 100575515 C CN100575515 C CN 100575515C CN 200710120263 A CN200710120263 A CN 200710120263A CN 200710120263 A CN200710120263 A CN 200710120263A CN 100575515 C CN100575515 C CN 100575515C
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Abstract
A kind of method for preparing ultra-fine crystal WC-Co hard alloy belongs to performance function material field.Mixed powder consists of: Co:8-11wt%, VC:0.001-0.7wt%, Cr
3C
2: 0.001-0.8wt%, surplus is that grain-size is 0.2-0.5 μ m WC; Handle carrying out mechanical alloying after the mixed powder weighing by weight percentage, ball milling time 15-60min, drum's speed of rotation are 800-1400rmin
-1Ratio of grinding media to material is 5: 1-10: 1, and the add-on of ball-milling medium is the 5-10mm that exceeds the ball powder surface of packing into; Mixed powder is pre-formed as the preform that density is 50-70%, adopts the cubic apparatus ultra-high pressure sintering to prepare the superfine WC-Co Wimet then, sintering voltage is 1.25V-1.40V, and sintering pressure is 10-12GPa, and sintering time is 60-120s.Advantage is, applies very high pressure and make the powder quick densifying in heating, and the product that makes reaches full densification, and hardness can reach 93.1HRA, and the WC grain size is not almost grown up.
Description
Technical field
The invention belongs to performance function material field, a kind of method for preparing ultra-fine crystal WC-Co hard alloy particularly is provided, can suppress WC grain and grow up, improve WC-Co Wimet performance.
Background technology
The WC-Co Wimet has special resistance to abrasion, high rigidity, good fracture toughness property and ultimate compression strength, be applied to plunger, fluid cylinder, the finishing roller of erosion resistant part and structure unit, high pressure vessel, the top hammer of diamond synthesis, the roll of steel wire rolling mill etc., occupy extremely important status in fields such as machinery, metallurgy, cutting tool, precision instrument, military projects.Along with the developing rapidly of industries such as electronics, precision sizing, medical science, space flight, the performance of common WC-Co Wimet can not meet the demands in recent years, and the raising of its performance mainly is reducing of grain fineness number.
Confirm that now along with reducing of WC grain size, the hardness of Wimet, toughness, wear resistance, heat-shock resistance, thermal conductivity and oxidation-resistance all can be significantly improved, and sintering temperature reduces.Therefore, become a megatrend of current cemented carbide industry to the development of superfine nano Wimet by traditional Wimet.WC grain is that the following ultra-fine cemented carbide of 0.5 μ m has excellent comprehensive performances because of it, in the difficult-to-machine material field, fields such as microelectronics industry precision die processing industry, wood working, medical science are used widely.The nano hard alloy of WC grain below 100nm should have better performance.Therefore, it becomes one of focus that the various countries scientist competitively studies in " refractory metal and mechanically resistant material " field.
At present, the major company of states such as Sweden, Germany, Japan has released the ultra-fine cemented carbide near nanostructure separately respectively, and wherein the thinnest with the T002 granularity of Sandvik company especially, its alloy granularity has reached 200nm.The Zhuzhou of China, Zi Gong two factories also release the ultra-fine cemented carbide near nanostructure of oneself respectively, and grain-size is less than 500nm, and it is above with more than the 4000MPa that hardness and intensity index reach HRA93 respectively.Wuhan University of Technology is by the spraying conversion-reduction and carbonization prepares the method for nano composite powder continuously, adopts the low pressure sintering technology, and the alloy granularity of preparing of success is 350nm, and hardness reaches 93.4HRA, and intensity reaches the ultra-fine cemented carbide of 3800MPa.But also there is not a company can produce hard metal article about 100nm so far in the world.This mainly is the restriction that is subjected to sintering technology, and current sintering technology can't very be controlled growing up of nanocrystal in the sintering process effectively.Because the densification of nano powder agglomerating and WC grain size are determining its performance, therefore just at present people focus mostly on the greatly densification of sintered compact and WC grain of the research of nano hard alloy grown up in the control.
Traditional sintering cemented carbide is to be heated under the temperature that liquid phase occurs to carry out in special atmosphere oven or vacuum oven, and its sintering temperature height, time are long, cause serious the growing up of hard phase crystal grain generation.Although taked a lot of measures, as adding grain growth inhibitor, microwave sintering, discharge plasma sintering etc., sintering time is all more than 30min, so still unavoidably growing up of hard phase crystal grain can be taken place.According to the research of liquid phase sintering mechanism, suppress the growth of crystal grain to greatest extent, must shorten sintering time.
The cubic apparatus ultra-high pressure sintering is to apply the novel sintered technology that very high pressure makes the powder quick densifying in heating.This kind technology can increase nano material densification motivating force, and sintering rate is accelerated, and reduction temperature, shortening time reach the purpose that suppresses grain growth.Both at home and abroad for adopting cubic apparatus ultra-high pressure sintering prepared superfine WC-Co Wimet not appear in the newspapers.
Summary of the invention
Content of the present invention is to provide a kind of method for preparing ultra-fine crystal WC-Co hard alloy, has shortened sintering time, has improved production efficiency.
A kind of preparation method of superfine WC-Co Wimet among the present invention, its mixed powder consists of: Co:8-11wt%, VC:0.001-0.7wt%, Cr
3C
2: 0.001-0.8wt%, surplus is that grain-size is 0.2-0.5 μ mWC; Handle carrying out mechanical alloying after the mixed powder weighing by weight percentage, ball milling time 15-60min, drum's speed of rotation are 800-1400rmin
-1Ratio of grinding media to material is 5: 1-10: 1, and the add-on of ball-milling medium is the 5-10mm that exceeds the ball powder surface of packing into; Mixed powder is pre-formed as the preform that density is 50-70%, adopts the cubic apparatus ultra-high pressure sintering to prepare the superfine WC-Co Wimet then, sintering voltage is 1.25V-1.40V, and sintering pressure is 10-12GPa, and sintering time is 60-120s.Can prepare the ultra-fine cemented carbide that the WC grain size is grown up hardly by aforesaid method.
Before described powder forming several powder particles are carried out mechanical alloying (high-energy ball milling) operation, the equipment of described mechanical alloying (high-energy ball milling) can be planetary ball mill, stirring ball mill and oscillatory type ball mill.Described mechanical alloying (high-energy ball milling) can be a dry type, also can be wet type, and described dry type ball milling is to carry out under protective atmosphere, and described wet ball-milling is to adopt the organism liquid mixing, and described machine thing liquid comprises ethanol, acetone, sherwood oil etc.Handle by described mechanical alloying (high-energy ball milling), can make the raw material powder particle deform, rupture and combine again, increase the specific surface area and inner defective of powder particle, thereby increase raw material powder particulate activation evergy, thus can acceleration of sintering, improve the performance of sintered compact.Particularly, can make the abundant mixing of powder of adding, reduce bigger coacervate in the ultrafine WC powder.The equipment of mechanical alloyings such as planetary ball mill, stirring ball mill and oscillatory type ball mill can satisfy above-mentioned requirements.Protective atmosphere in the described dry type ball milling and the organism liquid in the described wet ball-milling can prevent oxidation and the untoward reaction of raw material powder particle in mechanical milling process.
That described preliminary shaping comprises is normal pressure-sintered, in decompression or vacuum sintering, pressure sintering, hot pressing, hot isostatic pressing, discharge plasma sintering, electric spark sintering, the microwave sintering 1～3 kind.Can prepare the preform that density is 50-70% by aforesaid method.
Described preliminary shaping is to carry out under protective atmosphere, and described protective atmosphere is vacuum, argon gas, hydrogen, nitrogen, cracked ammonium etc.Adopt protective atmosphere can prevent oxidation and the untoward reaction of described powder in sintering process.
Described ultra-high pressure sintering is to apply the novel sintered technology that very high pressure makes the powder quick densifying in heating.This kind technology has increased super-fine material densification motivating force, and sintering rate is accelerated, and reduction temperature, shortening time reach the purpose that suppresses grain growth.Be characterized in to make material to reach high-density rapidly, and crystalline structure even atom, electronic state are changed, thereby give the performance that material does not reach under sintering usually.Ultra-high pressure sintering has been compared series of advantages with other sintering methods: at first, contact very closely between powder particle under the high pressure with local extruding and be particularly conducive to upward bonding of atom of their surfaces, densification process when secondly the high compression state of system can promote the material sintering greatly, and shortening sintering time, make particle have little time to grow up or fully do not grow up and just finished densification, thereby suppress grain growth effectively.
The invention has the advantages that make the powder quick densifying owing to apply very high pressure in heating, the product that makes reaches full densification, hardness can reach 93.1HRA, and the WC grain size is not almost grown up.The superfine WC-Co Wimet of preparation has the density height, grain-size is tiny and hardness is high, can reach the performance requriements of Wimet.Compare with other sintering methods, can shorten sintering time greatly, each sample only several minutes just can be finished, and can enhance productivity the having a extensive future of industrialization greatly.
Concrete form of implementation
The following describes form of implementation of the present invention.These forms of implementation only are the examples of enumerating in order to deepen the understanding of the present invention, should not be construed as limiting the invention certainly.Scope of the present invention should be the content in the claim.Under the prerequisite that does not surmount main idea of the present invention, form of implementation can be done diversified change.This point should be understood that for the industry.
Embodiment 1:
Raw material: particle diameter is that the WC powder of 0.2 μ m, pure Co powder and particle diameter are that the VC powder quality ratio of 2.94 μ m is 88.7: 11: 0.3.
The raw material powder of getting said ratio adopts high-energy ball milling 30min to mix, after drying, pack in the graphite jig, carrying out hot pressed sintering is shaped, sintering process is: the temperature rise rate with 50 ℃/min heats up, apply the pressure of 40MPa, when temperature is elevated to 750 ℃, be incubated 5 minutes, hot compacting finishes.To be cooled to below 100 ℃ the time, take out the demoulding.Then hot pressing pressed compact, graphite grazing sheet, carbon steel supercharging sheet and integrate insulation, agalmatolite jacket heat insulation and the pressure transmission purpose makes up, the sample that combines is put into six-plane piercer and is carried out energising sintering under the hyperpressure, sintering voltage is 1.25V, sintering pressure is 10GPa, and sintering time is 75s.Promptly make sample and reach full densification, hardness is 91.8HRA, the ultra-fine cemented carbide of WC grain size 0.23 μ m.
Embodiment 2:
Raw material: particle diameter is that the WC powder of 0.2 μ m, pure Co powder and particle diameter are the Cr of 3.6 μ m
3C
2The powder quality ratio is 88.6: 11: 0.4.
The raw material powder of getting said ratio adopts high-energy ball milling 30min to mix, after drying, pack in the graphite jig, carrying out hot pressed sintering is shaped, sintering process is: the temperature rise rate with 50 ℃/min heats up, apply the pressure of 40MPa, when temperature is elevated to 750 ℃, be incubated 5 minutes, hot compacting finishes.To be cooled to below 100 ℃ the time, take out the demoulding.Then hot pressing pressed compact, graphite grazing sheet, carbon steel supercharging sheet and integrate insulation, agalmatolite jacket heat insulation and the pressure transmission purpose makes up, the sample that combines is put into six-plane piercer and is carried out energising sintering under the hyperpressure, sintering voltage is 1.25V, sintering pressure is 10GPa, and sintering time is 75s.Promptly make sample and reach full densification, hardness is 93.1HRA, the ultra-fine cemented carbide that WC grain is not grown up.
Embodiment 3:
Raw material: particle diameter is that the WC powder of 0.5 μ m, pure Co powder and particle diameter are the Cr of 3.6 μ m
3C
2The powder quality ratio is 91.6: 8: 0.6.
The raw material powder of getting said ratio adopts high-energy ball milling 30min to mix, after drying, pack in the graphite jig, carrying out hot pressed sintering is shaped, sintering process is: the temperature rise rate with 50 ℃/min heats up, apply the pressure of 40MPa, when temperature is elevated to 750 ℃, be incubated 5 minutes, hot compacting finishes.To be cooled to below 100 ℃ the time, take out the demoulding.Then hot pressing pressed compact, graphite grazing sheet, carbon steel supercharging sheet and integrate insulation, agalmatolite jacket heat insulation and the pressure transmission purpose makes up, the sample that combines is put into six-plane piercer and is carried out energising sintering under the hyperpressure, sintering voltage is 1.4V, sintering pressure is 12GPa, and sintering time is 120s.Promptly make sample and reach full densification, hardness is 92.7HRA, the ultra-fine cemented carbide that WC grain is not grown up.
Above-mentioned form of implementation only is the example of enumerating in order to deepen the understanding of the present invention, can also do diversified change certainly.For example employed in the above-described embodiments inhibitor VC and Cr
3C
2, can replace with TiC, TaC etc., can obtain same or similar effects with the foregoing description.
Claims (1)
1, a kind of method for preparing ultra-fine crystal WC-Co hard alloy, it is characterized in that: mixed powder consists of: Co:8-11wt%, VC:0.001-0.7wt%, Cr
3C
2: 0.001-0.8wt%, surplus is that grain-size is 0.2-0.5 μ m WC; Handle carrying out mechanical alloying after the mixed powder weighing by weight percentage, ball milling time 15-60min, drum's speed of rotation are 800-1400rmin
-1Ratio of grinding media to material is 5: 1-10: 1, and the add-on of ball-milling medium is the 5-10mm that exceeds the ball powder surface of packing into; Mixed powder is pre-formed as the preform that density is 50-70%, adopts the cubic apparatus ultra-high pressure sintering to prepare the superfine WC-Co Wimet then, sintering voltage is 1.25V-1.40V, and sintering pressure is 10-12GPa, and sintering time is 60-120s;
The mixed powder particle is carried out the equipment that mechanical alloying handles is planetary ball mill, stirring ball mill or oscillatory type ball mill described; Described ball milling is dry type ball milling or wet ball-milling, and the dry type ball milling is to carry out under protective atmosphere; Wet ball-milling adopts the organism liquid mixing, and organism liquid comprises ethanol, acetone, sherwood oil or hexane;
That described premolding comprises is normal pressure-sintered, in decompression or vacuum sintering, pressure sintering, hot pressing, hot isostatic pressing, discharge plasma sintering, electric spark sintering, the microwave sintering 1～3 kind.
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| CN200710120263A CN100575515C (en) | 2007-08-14 | 2007-08-14 | A kind of method for preparing ultra-fine crystal WC-Co hard alloy |
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| CN200710120263A CN100575515C (en) | 2007-08-14 | 2007-08-14 | A kind of method for preparing ultra-fine crystal WC-Co hard alloy |
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| US9518308B2 (en) | 2013-12-23 | 2016-12-13 | King Fahd University Of Petroleum And Minerals | High-density and high-strength WC-based cemented carbide |
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| US9518308B2 (en) | 2013-12-23 | 2016-12-13 | King Fahd University Of Petroleum And Minerals | High-density and high-strength WC-based cemented carbide |
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