CN104046878A - Preparation method of hard alloy with cobalt gradient structure - Google Patents
Preparation method of hard alloy with cobalt gradient structure Download PDFInfo
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- CN104046878A CN104046878A CN201410200088.1A CN201410200088A CN104046878A CN 104046878 A CN104046878 A CN 104046878A CN 201410200088 A CN201410200088 A CN 201410200088A CN 104046878 A CN104046878 A CN 104046878A
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Abstract
The invention discloses a preparation method of hard alloy with a cobalt gradient structure, and the preparation method comprises the steps of preparing a low carbon hard alloy green body and sintering the hard alloy with the cobalt gradient structure; the step of sintering the hard alloy with the cobalt gradient structure is as follows: first sintering the low carbon hard alloy green body in vacuum environment by using conventional dewaxing and deoxidation processes, then turning to carburizing atmosphere sintering when a liquid phase sintering temperature reached, and after thermal insulation is end, cooling in a furnace to obtain the hard alloy with the cobalt gradient structure. According to the preparation method, the hard alloy with the cobalt gradient structure can be obtained by only sintering one time, compared with a method for preparing the hard alloy with the cobalt gradient structure by sintering two times, the preparation method has the advantages of simple process, easy process control, reduced production procedures, production cost reduction, and production efficiency improvement, and is beneficial to industrial production, the obtained hard alloy with the cobalt gradient structure is not sintered two times, so that alloy surface crystalline grains may not grow excessively, and the hard alloy has excellent mechanical properties.
Description
Technical field
The present invention relates to the preparing technical field of Wimet, particularly relate to a kind of preparation method of the Wimet with cobalt gradient-structure.
Background technology
Because Wimet has high strength, high rigidity, high elastic coefficient, wear-resistant, corrosion-resistant, thermal expansivity is little and the series of advantages such as high chemical stability, therefore have a wide range of applications at industrial circles such as digging, metal processing and moulds.But conventional Wimet is the two-phase uniform formation of WC phase and Binder Phase, and its external and internal compositions and mechanical property are consistent, its wear resistance and fracture toughness property exist this those long relations that disappear between the two.Under many service conditions, traditional uniform texture Wimet shows obvious inferior position.For example, it is wear-resisting and overall shock-resistant that this generic request of rock drilling carbamide tool is bored tooth surface, tradition uniform texture Wimet can not meet this kind of working conditions conventionally, prepares the important method that Graded-structure Cemented Carbides is considered to solve Wear Resistance and toughness contradiction.
In the patent documentation " being best suited for the cemented carbide body of rock-boring and ore cutting " that Sandvik AB of Sweden is 85108173 at application number, disclose one and prepared gradient function Wimet method,, prepare to coordinate by the green compact of pre-burning low carbon content and be divided into WC+ γ phase+η phase (W or C are dissolved in the sosoloid in Co, are referred to as γ phase; Co
3w
3c or Co
6w
6c, is referred to as η phase) body material of three-phase contexture, then adopt the method for solid phase carburizing to obtain the cobalt Wimet of structure in gradient mutually.The Z.Z.Fang of Univ Utah USA professor discloses a kind of functionally gradient carboloy method in the patent documentation " having functionally gradient carboloy of the rigid surface of design and preparation method thereof " of application number 201010003392,, prepare to coordinate by pre-burning green compact and be divided into the body material of WC+ γ phase two-phase structure or WC+ γ+η phase three-phase contexture, then adopt method of gas carburizing to prepare the cobalt Wimet of structure in gradient mutually.As can be seen here, aforesaid method all must, through twice sintering, increase production process, has improved production cost, and twice sintering easily causes alloy grain excessively to grow up simultaneously, and alloy mechanical property is declined.Open source literature " single-sinter process is prepared the research of two-phase graded alloy " is thought, can prepare cobalt gradient hard alloy in the carburizing of solid state sintering stage by once sintered.But Wimet is in the solid state sintering stage, the vacuum tightness of environment is too low is unfavorable for removing of oxygen element in Wimet green compact, causes having hole and cobalt pond defect in final sintered alloy, affects the mechanical property of product; And in the solid state sintering stage, Wimet green compact mesoporosity is still communicated with, carburizing atmosphere is easy to be deep into along open pore green compact inside, make the inside and outside while carburizing of Wimet green compact, cause in the inside and outside Co of liquid phase sintering stage Wimet green compact, do not exist carbon and tungsten concentration difference and and osmotic pressure, be finally difficult to be prepared into the Wimet with cobalt gradient-structure.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art, a kind of preparation method of the Wimet with cobalt gradient-structure is provided, by making from top layer to the Wimet of core direction cobalt contents distribution gradient once sintered low-carbon (LC) Wimet green compact, there is technique simple, process is easy, production process is simplified, and production cost reduces, the feature that production efficiency improves.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of the Wimet with cobalt gradient-structure, comprises the steps:
Prepare the step of low-carbon (LC) Wimet green compact;
The sintering step of cobalt Graded-structure Cemented Carbides, this step is that first described low-carbon (LC) Wimet green compact are adopted to conventional dewaxing, deoxidization technique sintering in vacuum environment, while arriving liquid phase sintering temperature, transfer carburizing atmosphere sintering to, after insulation finishes, furnace cooling can make the Wimet with cobalt gradient-structure.
The described step of preparing low-carbon (LC) Wimet green compact is to obtain the low-carbon (LC) Wimet green compact of carbon content in W-Co-C phasor WC+ γ+η triple-phase region by batching, pressing mode.
Its vacuum tightness≤500pa of described vacuum environment.
The carbon activity scope of described carburizing atmosphere is: 0.4≤carbon activity≤1.
Described carbon atmosphere is by containing CO, CH
4and C
2h
2in the mixed gas of at least one gas provide.
Described liquid phase sintering temperature is 1300～1500 DEG C.
The preparation method of a kind of Wimet with cobalt gradient-structure of the present invention, to obtain the low-carbon (LC) Wimet green compact in W-Co-C phasor WC+ γ+η triple-phase region by batching, compacting, first gained low-carbon (LC) Wimet green compact are adopted to conventional dewaxing, deoxidization technique sintering in vacuum environment, while arriving liquid phase sintering temperature, transfer carburizing atmosphere sintering to, owing to adopting carburizing atmosphere sintering, the carbon activity in sintering environment to be greater than the carbon activity of WC+ γ+η Wimet inside when the liquid phase sintering.In the time that C element spreads from carbide surface to core direction in liquid phase Co, along with the increase of carbon concentration in the Co of top layer, in top layer, η phase and C react and generate WC and Co, and the liquid phase Co amount on top layer is increased, and see formula (1):
η phase+C → WC+Co (1)
Meanwhile, W and C all may be dissolved in the liquid phase Co of WC-Co Wimet, have the relation in formula (2):
[W]·[C]＝k (2)
In formula, [W] is the concentration of W in liquid phase Co, and [C] is the concentration of C in liquid phase Co, and k is constant, and, in the liquid phase Co of Wimet, the concentration of C raises, and the concentration of W reduces.Therefore,, along with C element in sintering environment is constantly spread to core direction by carbide surface by liquid phase Co, in liquid phase Co, C concentration and W concentration can change to core direction surfacewise in gradient.Owing to there is concentration difference to core direction surfacewise in C element in liquid phase Co and W element, there is osmotic pressure to core direction surfacewise in liquid phase Co, liquid phase Co can be under the effect of osmotic pressure, to internal migration, form Wimet top layer Co content low and WC+ γ+η triple-phase region and the high structure of WC+ γ two-phase region handover region Co content by Wimet top layer.And in inside, WC+ γ+η triple-phase region, the concentration of W and the concentration of C are relatively-stationary, only relevant with liquid phase sintering temperature, there is not gradient difference, can not form the liquid phase Co migration that osmotic pressure causes yet, therefore, do not change at the content of Wimet core WC+ γ+η triple-phase region Co, maintain the average cobalt contents of Wimet.After Wimet liquid phase sintering finishes, is cooling, prepare and there is cobalt Graded-structure Cemented Carbides.Co content that this alloy has WC+ γ two-phase region, top layer is low, hardness is high, the middle layer Co content of WC+ γ+η triple-phase region and WC+ γ two-phase region handing-over is high, good toughness, and core WC+ γ+η triple-phase region Co content is structure and the performance that average cobalt contents, rigidity are high.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention is owing to only can preparing the Wimet with cobalt gradient-structure by once sintered, compare the method by twice sintering preparation with cobalt Graded-structure Cemented Carbides, its technique is simple, process control is easy, production process reduces, production cost reduces, production efficiency improves, be conducive to suitability for industrialized production, the Wimet that gained has a cobalt gradient-structure is not due to through twice sintering, alloy surface crystal grain is not excessively grown up, outermost layer cobalt phase content is lower than the average cobalt contents of alloy, there is high rigidity and good abrasion resistance properties, and middle layer cobalt phase content is higher than the average cobalt contents of alloy, there is good toughness, therefore there is excellent comprehensive mechanical property.
Below in conjunction with drawings and Examples, the present invention is described in further detail; But the preparation method of a kind of Wimet with cobalt gradient-structure of the present invention is not limited to embodiment.
Brief description of the drawings
Fig. 1 is the super depth-of-field microscope picture after the carburizing of Wimet green compact in the embodiment of the present invention one;
Fig. 2 is the metallograph after the carburizing of Wimet green compact in the embodiment of the present invention one;
Fig. 3 is the super depth-of-field microscope picture after the carburizing of Wimet green compact in the embodiment of the present invention two;
Fig. 4 is the metallograph after the carburizing of Wimet green compact in the embodiment of the present invention two;
Fig. 5 is the super depth-of-field microscope picture after the carburizing of Wimet green compact in the embodiment of the present invention three;
Fig. 6 is the metallograph after the carburizing of Wimet green compact in the embodiment of the present invention three.
Embodiment
Embodiment mono-
Get low-carbon (LC) WC-Co Wimet green compact (Co content be 6wt%, C content be the Fsss granularity of 5.5wt%, WC be 3.0 μ m).First be under 100pa, to adopt conventional dewaxing, deoxidization technique sintering in vacuum tightness, while arriving 1420 DEG C of liquid phase sintering temperature, transfer carburizing atmosphere sintering to, 30min is processed in carburizing insulation, and carburizing source is CH
4+ H
2, total dividing potential drop is 500Pa, and in carburizing atmosphere, carbon activity is 0.48, and after carburizing atmosphere sintering, furnace cooling can make the Wimet with cobalt gradient-structure.Accompanying drawing 1 is the super depth of field photo of prepared Wimet metallographic face; Utilize reagent in village (10% sodium hydroxide and 10% Tripotassium iron hexacyanide equal-volume mixed aqueous solution) that prepared Wimet metallographic face is gently corroded to 8-12 second, the metallographic of observing is shown in accompanying drawing 2, and the WC+ γ two-phase region thickness that carburizing produces is about 1.25mm.Micro-hardness testing is 1632HV1 apart from the hardness mean value in carbide surface 0.2mm region, the hardness mean value 1431HV1 in 0.2mm region, interface, distance W C+ γ+η triple-phase region in WC+ γ two-phase region, middle layer, core WC+ γ+η triple-phase region hardness mean value 1565HV1, shows the hardness distribution gradient of Wimet; Corresponding EDAX results shows, the cobalt contents in above-mentioned 3 regions is respectively 4.8wt%, 10.5wt%, 6.1wt%, proves that thus alloy forms Co gradient-structure, has obtained the Wimet of cobalt gradient-structure.
Embodiment bis-
Getting the low-carbon (LC) WC-Co Wimet green compact identical with embodiment mono-, is first under 20pa, to adopt conventional dewaxing, deoxidization technique sintering in vacuum tightness, transfers carburizing atmosphere sintering to after arriving 1440 DEG C of liquid phase sintering temperature, carburizing treatment 60min, and carburizing source is CO+H
2, total dividing potential drop is 1000Pa, and in carburizing atmosphere, carbon activity is 0.6, and furnace cooling can make the Wimet with cobalt gradient-structure, and accompanying drawing 3 is super depth of field photos of prepared Wimet metallographic face; Utilize reagent in village (10wt% sodium hydroxide and 10wt% Tripotassium iron hexacyanide equal-volume mixed aqueous solution) that prepared Wimet metallographic face is gently corroded to 8-12 second, the metallographic of observing is shown in accompanying drawing 4, and the WC+ γ two-phase region thickness that carburizing produces is about 2mm.Micro-hardness testing is 1684HV1 apart from the hardness mean value in carbide surface 0.2mm region, 0.2mm region, interface, distance W C+ γ+η triple-phase region hardness mean value 1350HV1 in WC+ γ two-phase region, middle layer, core WC+ γ+η triple-phase region hardness mean value 1573HV1, shows the hardness distribution gradient of Wimet; Corresponding EDAX results shows, the cobalt contents in above-mentioned 3 regions is respectively 4.3wt%, 11.1wt%, 6.0wt%, proves that thus alloy forms Co gradient-structure, has obtained the Wimet of cobalt gradient-structure.
Embodiment tri-
Getting the low-carbon (LC) Wimet green compact identical with embodiment mono-, is first under 50pa, to adopt conventional dewaxing, deoxidization technique sintering in vacuum tightness, transfers carburizing atmosphere sintering to after arriving 1460 DEG C of liquid phase sintering temperature, carburizing treatment 90min, and carburizing source is CH
4+ H
2, total dividing potential drop is 2000Pa, and in carburizing atmosphere, carbon activity is 0.75, and furnace cooling can make the Wimet with cobalt gradient-structure, and accompanying drawing 5 is super depth of field photos of prepared Wimet metallographic face; Utilize reagent in village (10wt% sodium hydroxide and 10wt% Tripotassium iron hexacyanide equal-volume mixed aqueous solution) that prepared Wimet metallographic face is gently corroded to 8-12 second, the metallographic of observing is shown in accompanying drawing 6, and the WC+ γ two-phase region thickness that carburizing produces is about 2.5mm.Micro-hardness testing is 1705HV1 apart from the hardness mean value in carbide surface 0.2mm region, interface, distance W C+ γ+η triple-phase region 0.2mm zone leveling value 1292HV1 in WC+ γ two-phase region, middle layer, core WC+ γ+η triple-phase region hardness mean value 1598HV1, shows the hardness distribution gradient of Wimet; Corresponding EDAX results shows, the cobalt contents in above-mentioned 3 regions is respectively 3.9wt%, 11.8wt%, 6.2wt%, proves that thus alloy forms Co gradient-structure, has obtained the Wimet of cobalt gradient-structure.
The preparation method of a kind of Wimet with cobalt gradient-structure of the present invention, to obtain the low-carbon (LC) Wimet green compact in W-Co-C phasor WC+ γ+η triple-phase region by batching, compacting, first gained low-carbon (LC) Wimet green compact are adopted to conventional dewaxing, deoxidization technique sintering in vacuum environment, while arriving liquid phase sintering temperature, transfer carburizing atmosphere sintering to, owing to adopting carburizing atmosphere sintering, the carbon activity in sintering environment to be greater than the carbon activity of WC+ γ+η Wimet inside when the liquid phase sintering.In the time that C element spreads from carbide surface to core direction in liquid phase Co, along with the increase of carbon concentration in the Co of top layer, in top layer, η phase and C react and generate WC and Co, and the liquid phase Co amount on top layer is increased, and see formula (1):
η phase+C → WC+Co (1)
Meanwhile, W and C all may be dissolved in the liquid phase Co of WC-Co Wimet, have the relation in formula (2):
[W]·[C]＝k (2)
In formula, [W] is the concentration of W in liquid phase Co, and [C] is the concentration of C in liquid phase Co, and k is constant, and, in the liquid phase Co of Wimet, the concentration of C raises, and the concentration of W reduces.Therefore,, along with C element in sintering environment is constantly spread to core direction by carbide surface by liquid phase Co, in liquid phase Co, C concentration and W concentration can change to core direction surfacewise in gradient.Owing to there is concentration difference to core direction surfacewise in C element in liquid phase Co and W element, there is osmotic pressure to core direction surfacewise in liquid phase Co, liquid phase Co can be under the effect of osmotic pressure, to internal migration, form Wimet top layer Co content low and WC+ γ+η triple-phase region and the high structure of WC+ γ two-phase region handover region Co content by Wimet top layer.And in inside, WC+ γ+η triple-phase region, the concentration of W and the concentration of C are relatively-stationary, only relevant with liquid phase sintering temperature, there is not gradient difference, can not form the liquid phase Co migration that osmotic pressure causes yet, therefore, do not change at the content of Wimet core WC+ γ+η triple-phase region Co, maintain the average cobalt contents of Wimet.After Wimet liquid phase sintering finishes, is cooling, prepare and there is cobalt Graded-structure Cemented Carbides.Co content that this alloy has WC+ γ two-phase region, top layer is low, hardness is high, the middle layer Co content of WC+ γ+η triple-phase region and WC+ γ two-phase region handing-over is high, good toughness, and core WC+ γ+η triple-phase region Co content is structure and the performance that average cobalt contents, rigidity are high.
The present invention is owing to only can preparing the Wimet with cobalt gradient-structure by once sintered, compare the method by twice sintering preparation with cobalt Graded-structure Cemented Carbides, its technique is simple, process control is easy, production process reduces, production cost reduces, production efficiency improves, be conducive to suitability for industrialized production, the Wimet that gained has a cobalt gradient-structure is not due to through twice sintering, alloy surface crystal grain is not excessively grown up, outermost layer cobalt phase content is lower than the average cobalt contents of alloy, there is high rigidity and good abrasion resistance properties, and middle layer cobalt phase content is higher than the average cobalt contents of alloy, there is good toughness, therefore there is excellent comprehensive mechanical property.
Above-mentioned is preferred embodiment of the present invention, not the present invention is done to any pro forma restriction.Although the present invention discloses as above with preferred embodiment, but not in order to limit the present invention.Any those of ordinary skill in the art, in the situation that not departing from technical solution of the present invention scope, can utilize the technology contents of above-mentioned announcement to make many possible variations and modification to technical solution of the present invention, or the equivalent embodiment of assimilation such as are revised as.Therefore, every content that does not depart from technical solution of the present invention,, all should drop in the scope of technical solution of the present invention protection any simple modification made for any of the above embodiments, equivalent variations and modification according to the technology of the present invention essence.
Claims (10)
1. a preparation method with the Wimet of cobalt gradient-structure, is characterized in that: comprise the steps:
Prepare the step of low-carbon (LC) Wimet green compact;
The sintering step of cobalt Graded-structure Cemented Carbides, this step is that first described low-carbon (LC) Wimet green compact are adopted to conventional dewaxing, deoxidization technique sintering in vacuum environment, while arriving liquid phase sintering temperature, transfer carburizing atmosphere sintering to, after insulation finishes, furnace cooling can make the Wimet with cobalt gradient-structure.
2. the preparation method of the Wimet with cobalt gradient-structure according to claim 1, is characterized in that: the described step of preparing low-carbon (LC) Wimet green compact is to obtain the low-carbon (LC) Wimet green compact of carbon content in W-Co-C phasor WC+ γ+η triple-phase region by batching, pressing mode.
3. the preparation method of the Wimet with cobalt gradient-structure according to claim 1 and 2, is characterized in that: its vacuum tightness≤500pa of described vacuum environment.
4. the preparation method of the Wimet with cobalt gradient-structure according to claim 1 and 2, is characterized in that: the carbon activity scope of described carburizing atmosphere is: 0.4≤carbon activity≤1.
5. the preparation method of the Wimet with cobalt gradient-structure according to claim 3, is characterized in that: the carbon activity scope of described carburizing atmosphere is: 0.4≤carbon activity≤1.
6. according to the preparation method of the Wimet with cobalt gradient-structure described in claim 1 or 2 or 5, it is characterized in that: described carbon atmosphere is by containing CO, CH
4and C
2h
2in the mixed gas of at least one gas provide.
7. the preparation method of the Wimet with cobalt gradient-structure according to claim 3, is characterized in that: described carbon atmosphere is by containing CO, CH
4and C
2h
2in the mixed gas of at least one gas provide.
8. the preparation method of the Wimet with cobalt gradient-structure according to claim 4, is characterized in that: described carbon atmosphere is by containing CO, CH
4and C
2h
2in the mixed gas of at least one gas provide.
9. the preparation method of the Wimet with cobalt gradient-structure according to claim 1 and 2, is characterized in that: described liquid phase sintering temperature is 1300～1500 DEG C.
10. the preparation method of the Wimet with cobalt gradient-structure according to claim 6, is characterized in that: described liquid phase sintering temperature is 1300～1500 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104630530A (en) * | 2015-01-29 | 2015-05-20 | 南京航空航天大学 | Preparation method of Ti(C, N)-based metal ceramic of gradient structure |
| CN105177336A (en) * | 2015-09-07 | 2015-12-23 | 中南大学 | Method for rapidly preparing extra-coarse crystalline grain gradient hard alloy |
| CN108149183A (en) * | 2017-12-26 | 2018-06-12 | 中石化石油机械股份有限公司 | A kind of hard alloy of surface hardness gradient distribution and preparation method thereof |
| CN108637248A (en) * | 2018-04-25 | 2018-10-12 | 厦门金鹭特种合金有限公司 | Method capable of improving magnetic saturation of hard alloy pre-sintered blank |
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| CN102031400A (en) * | 2010-10-25 | 2011-04-27 | 北京科技大学 | Process for preparing beta layer removing gradient hard alloy |
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| CN102031400A (en) * | 2010-10-25 | 2011-04-27 | 北京科技大学 | Process for preparing beta layer removing gradient hard alloy |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630530A (en) * | 2015-01-29 | 2015-05-20 | 南京航空航天大学 | Preparation method of Ti(C, N)-based metal ceramic of gradient structure |
| CN105177336A (en) * | 2015-09-07 | 2015-12-23 | 中南大学 | Method for rapidly preparing extra-coarse crystalline grain gradient hard alloy |
| CN108149183A (en) * | 2017-12-26 | 2018-06-12 | 中石化石油机械股份有限公司 | A kind of hard alloy of surface hardness gradient distribution and preparation method thereof |
| CN108149183B (en) * | 2017-12-26 | 2021-02-26 | 中石化江钻石油机械有限公司 | Hard alloy with surface hardness in gradient distribution and preparation method thereof |
| CN108637248A (en) * | 2018-04-25 | 2018-10-12 | 厦门金鹭特种合金有限公司 | Method capable of improving magnetic saturation of hard alloy pre-sintered blank |
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Application publication date: 20140917 |