CN105154742B - A kind of method for preparing hard alloy with stability regulation and control - Google Patents
A kind of method for preparing hard alloy with stability regulation and control Download PDFInfo
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- CN105154742B CN105154742B CN201510492599.XA CN201510492599A CN105154742B CN 105154742 B CN105154742 B CN 105154742B CN 201510492599 A CN201510492599 A CN 201510492599A CN 105154742 B CN105154742 B CN 105154742B
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- 239000000956 alloy Substances 0.000 title claims abstract description 99
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000033228 biological regulation Effects 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007670 refining Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000007667 floating Methods 0.000 claims abstract description 5
- 230000001360 synchronised effect Effects 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 229910009043 WC-Co Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000007423 decrease Effects 0.000 claims description 4
- 230000005496 eutectics Effects 0.000 claims description 4
- 238000003913 materials processing Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000000843 powder Substances 0.000 abstract description 7
- 238000005255 carburizing Methods 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- 241001354491 Lasthenia californica Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
A kind of method for preparing hard alloy with stability regulation and control, belongs to Hardmetal materials and powder metallurgical technology.Hard alloy pole is prepared first, take two hard alloy poles, vertically end is adjacent up and down, it is sequentially placed into the vertical floating region of zone refining stove, vacuumize, operation power is set as the 60 95% of general power, power is increased to setting power in 20 30 minutes, after hard alloy pole contact jaw forms the stable molten state of pencil, fall the hard alloy pole in face, the synchronous hard alloy pole for also dropping above, until hard alloy pole above takes out, becomes area and melts the hard alloy bar after processing；After Qu Rong is processed, hard alloy bar is placed in vacuum heat treatment furnace or carbide furnace, is passed through the carburizing atmospheres such as methane or carbon monoxide, is incubated 13 hours at 900 1100 DEG C, is cooled to room temperature with the furnace, obtain super coarse-grain hard alloy bar.The present invention can the superior super coarse-grain hard alloy of processability.
Description
Technical field
The present invention relates to a kind of method for preparing hard alloy with stability regulation and control, belongs to Hardmetal materials and powder smelting
Technology for gold field.
Background technology
The hard material that performance is best, application benefit is maximum in WC-Co series hard alloy always hard alloy field, one
Degree causes the change of world's tool die material.Different according to WC average grain size, if generally WC-Co series hard alloy is divided into
Dry grade.The general alloy by WC average grain size more than 6 microns is referred to as super coarse-grain hard alloy.With WC average grain size
Compare for the conventional rigid alloy of 1-2 micron, super coarse-grain hard alloy has following performance advantage：With high impact flexibility,
With the increase of WC grain size in hard alloy, impact flexibility and fracture toughness are significantly improved；With excellent red hardness,
Under more than 1000 DEG C of hot conditions, apparently higher than conventional rigid alloy, its deformation of creep is little for the hardness of super coarse-grain hard alloy；
With high thermal conductivity, thermal fatigue resistance and thermal shock resistance are good, under the conditions of Co content identical, in super coarse-grain hard alloy
Crystal boundary ratio is significantly reduced, and high thermal conductivity effectively reduces the generation probability of fire check；Applied widely, especially big load,
Under the bad working environments such as high-frequency circulation impact, with excellent performance.
Super coarse-grain hard alloy has the toughness for significantly improving while excellent hardness and wearability is kept,
It is the preferred material of the heavy-duty machinery critical component needed for engineer operation such as coal excavation, rock mining, constructing road, with very
Wide application prospect, is focus R＆D direction that current hard alloy field receives much concern in the world.China realizes producing at present
The coarse-grain hard alloy of industry, WC average grain size are generally less than 5 microns, and super coarse-grain hard alloy forms far away hard alloy
, also there is larger gap with international most advanced level in heavy industrialization product on market.Such as the coarse-grain such as button, pick hard is closed
Gold, home products is commonly present that WC grain abnormal growth, crystal grain corner angle are sharp, there is certain density crystal defect, Co phase in crystal grain
The problems such as skewness, have a strong impact on performance and the service life of product.
It is generally believed that, excess of export coarse-grain hard alloy to be prepared it may first have to the WC powder of big particle is prepared, then
By sintering densification, the hard alloy block material of texture of coarse crystal is obtained.According to domestic and foreign literature, existing multiple sides
Method can prepare coarse-grained WC powder, such as aluminothermic process, cast tungsten carbide method, high temperature cabonization method, tungsten carbide, powder classification method
Deng.Although these methods can prepare coarse-grained WC powder, but the before sintering mistake mixed with Co powder by coarse-grained WC
Cheng Zhong, is very easy to cause coarse granule and its internal WC grain to occur to produce part abnormal grain growth during broken, sintering, and
Co phase is difficult to the problems such as being uniformly distributed in sintering process.Therefore, the key for preparing super coarse-grain hard alloy is how to realize
In heating process, WC grain continues, equably grows up, and abnormal grain! growth and Co phase segregation do not occur.
Content of the invention
The present invention i.e. for the present Research that at present prepared by super coarse-grain hard alloy and technical bottleneck problem, provide one kind with
The method that heat endurance regulation and control prepare super coarse-grain hard alloy.Its core technology principle is：In polycrystal alloy, grain structure is steady
Qualitatively controlling element is system free energy.In micron order coarse-grain alloy, the driving force that crystal grain is grown up is system free energy
Reduce.If in polycrystal alloy, system free energy keeps the trend of monotonic decreasing, then grain structure will be lasting, uniform, steady
Surely grow up, e.g., the regular grain growth that pure homogeneous structure occurs in intensification heat treatment process.However, if there are other
Factor causes system free energy to reduce, and such as solute atoms is separated out from parent phase in Grain Boundary Segregation, second etc., the drive that crystal grain is grown up
Power will be obviously reduced, so that cause crystal grain to be grown up stagnation.Therefore, the present invention causes the possibility of system free energy reduction from elimination
Factor is started with, and promotes alloy system free energy to continue monotonic decreasing as far as possible, and so as to promote crystal grain constantly uniformly to grow up, this is
Inner principle with the super coarse-grain hard alloy of heat endurance adjusting seed size tissue preparation.
A kind of method for preparing hard alloy with stability regulation and control that the present invention is provided, it is characterised in that including following step
Suddenly：
(1) the WC-Co hard alloy sintered material that Co phase is evenly distributed in WC matrix is prepared so as to which Co content is
5.0-10.0wt%, oxygen content<0.10wt%, free carbon content<0.10wt%；The cemented carbide sintered body materials processing is become
Cylindrical bar, diameter 10-20mm, length 20-80mm；
Above-mentioned WC-Co hard alloy sintered material can be using the technical method of the patent for having authorized, the patent No.
ZL200910091185.0.
(2) two hard alloy poles prepared by step (1) are taken, and vertically end is adjacent up and down, is sequentially placed into zone refining
The vertical floating region of stove, is evacuated to furnace pressure<10-4Pa, sets operation power as the 60-95% of general power, in 20-30 minute
The interior operation power that power is increased to setting, after two hard alloy pole contact jaws form the stable molten state of pencil, with
The speed of 10-30mm/h declines following hard alloy pole, and the synchronous hard alloy pole for also declining above, until above
Hard alloy pole is taken out from stove, makes hard alloy pole above become the hard alloy bar after process is melted in area；
(3) hard alloy bar after molten for step (2) gained area process is placed in vacuum heat treatment furnace or carbide furnace, is passed through
The carburizing atmosphere such as methane or carbon monoxide, is incubated 1-3 hour at 900-1100 DEG C, cools to room temperature with the furnace, obtain super coarse-grain hard
Matter alloy bar.
General power is preferably such that hard alloy pole during decline, two hard alloy pole contact jaws
WC-Co heterogeneous structure reaches eutectic state or the power being completely melt needed for state.
Compared with the preparation method of existing super coarse-grain hard alloy, the present invention has essential feature as follows and technology is excellent
Gesture：
(1) hard conjunction is prepared preferably by existing patented technology (granted patent number 200910091185.0) in step (1)
Used as original material, this technology can ensure that Co phase is evenly distributed in WC matrix to golden sintered body, and can control oxygen content exactly
And free carbon content, this is to keep pure substance phase, uniform initial grain tissue in subsequent preparation process, avoided abnormal grain
The primary premise that grows up；
(2) step (2) carries out the key effect of zone refining process and is：Make WC-Co heterogeneous structure reach eutectic state or
State is completely melt, crystal defect is eliminated in liquid phase state；The purification effect of Qu Rong can remove solute atoms that may be present
Or impurity element is in the segregation of crystal boundary, suppress to cause system free energy downward trend because interface energy reduces, it is to avoid crystal boundary migration
By pinning effect；
(3) important function of step (3) is to mend carbon, due in zone refining processing procedure, in high temperature, liquid phase state
Under, a small amount of carbon can be dissolved in liquid phase Co and cause WC matrix to lack carbon, and the hard alloy bar after processing to zone refining is in carbon gas
Carbon is mended in atmosphere, it is ensured that intact carbon phase in the final super coarse-grain hard alloy for preparing, embrittlement will not occur and resist with high
Impact flexibility.
Description of the drawings
The displaing micro tissue topography of the super coarse-grain hard alloy of WC-7Co that Fig. 1 embodiment of the present invention 1 is prepared.
The displaing micro tissue topography of the super coarse-grain hard alloy of WC-9Co that Fig. 2 embodiment of the present invention 2 is prepared.
Specific embodiment
Following examples further illustrate the present invention, but the present invention is not limited to following examples.
Embodiment 1
Prepare the WC-Co hard alloy sintered material that Co phase is evenly distributed in WC matrix so as to which Co content is
7.0wt%, oxygen content<0.10wt%, free carbon content<0.10wt%；The cemented carbide sintered body materials processing is become cylinder
Shape bar, diameter 10mm, length 20mm；Above-mentioned WC-Co hard alloy sintered material can be using the technology of the patent for having authorized
Method, patent No. ZL200910091185.0.Two hard alloy poles of preparation are taken, vertically end is adjacent up and down, puts successively
In the vertical floating region of zone refining stove, furnace pressure is evacuated to<10-4Pa, sets operation power as the 60% of general power, total work
For causing hard alloy pole during decline, the WC-Co heterogeneous structure of two hard alloy pole contact jaws reaches rate
Power was increased to setting power in 20 minutes by the power needed for eutectic state, treated that two hard alloy pole contact jaws are formed
After the stable molten state of pencil, following hard alloy pole is declined with the speed of 30mm/h, the synchronous hard for also declining above is closed
Golden pole, until hard alloy pole above takes out from stove, the hard alloy pole that makes above becomes after area melts and process
Hard alloy bar；Hard alloy bar after molten for area process is placed in vacuum heat treatment furnace, CO gas are passed through,
900 DEG C are incubated 3 hours, cool to room temperature with the furnace, obtain super coarse-grain hard alloy bar, and its microscopic structure is shown in Fig. 1, performance number
According to being shown in table 1.
Embodiment 2
Prepare the WC-Co hard alloy sintered material that Co phase is evenly distributed in WC matrix so as to which Co content is
9.0wt%, oxygen content<0.10wt%, free carbon content<0.10wt%；The cemented carbide sintered body materials processing is become cylinder
Shape bar, diameter 20mm, length 80mm；Above-mentioned WC-Co hard alloy sintered material can be using the technology of the patent for having authorized
Method, patent No. ZL200910091185.0.Two hard alloy poles of preparation are taken, vertically end is adjacent up and down, puts successively
In the vertical floating region of zone refining stove, furnace pressure is evacuated to<10-4Pa, sets operation power as the 95% of general power, total work
For causing hard alloy pole during decline, the WC-Co heterogeneous structure of two hard alloy pole contact jaws reaches rate
Power was increased to setting power in 30 minutes by the power being completely melt needed for state, treated two hard alloy pole contacts
After end forms the stable molten state of pencil, following hard alloy pole is declined with the speed of 10mm/h, is synchronously also declined above
Hard alloy pole, until hard alloy pole above is taken out from stove, makes hard alloy pole above become molten place of area
Hard alloy bar after reason；Hard alloy bar after molten for area process is placed in carbide furnace, methane gas is passed through, at 1100 DEG C
Insulation 1 hour, cools to room temperature with the furnace, obtains super coarse-grain hard alloy bar, and its microscopic structure is shown in Fig. 2, and performance data is shown
In table 1.
The average grain size of WC-Co hard alloy prepared by 1 embodiment of the present invention of table and mechanical performance data
| Co content | Average grain size | Hardness | Fracture toughness | |
| Embodiment 1 | 7.0wt% | 15.1μm | HV 820kgf/mm2 | 22MPa·m1/2 |
| Embodiment 2 | 9.0wt% | 18.6μm | HV 860kgf/mm2 | 25MPa·m1/2 |
Claims (2)
1. a kind of method for preparing hard alloy with stability regulation and control, it is characterised in that comprise the following steps：
(1) the WC-Co hard alloy sintered material that Co phase is evenly distributed in WC matrix is prepared so as to which Co content is 5.0-
10.0wt%, oxygen content<0.10wt%, free carbon content<0.10wt%；The cemented carbide sintered body materials processing is become cylinder
Shape bar, diameter 10-20mm, length 20-80mm；
(2) two hard alloy poles prepared by step (1) are taken, and vertically end is adjacent up and down, is sequentially placed into zone refining stove
Vertical floating region, is evacuated to furnace pressure<10-4Pa, sets operation power as the 60-95% of general power, will within 20-30 minute
Power increases to setting operation power, after two hard alloy pole contact jaws form the stable molten state of pencil, with 10-
The speed of 30mm/h declines following hard alloy pole, and the synchronous hard alloy pole for also declining above, until above is hard
Matter alloy pole is taken out from stove, makes hard alloy pole above become the hard alloy bar after process is melted in area；
(3) hard alloy bar after molten for step (2) gained area process is placed in vacuum heat treatment furnace or carbide furnace, is passed through methane
Or carbon monoxide, 1-3 hour is incubated at 900-1100 DEG C, cool to room temperature with the furnace, obtain super coarse-grain hard alloy bar.
2. according to a kind of method for preparing hard alloy with stability regulation and control of claim 1, it is characterised in that general power is for making
Hard alloy pole is obtained during decline, the WC-Co heterogeneous structure of two hard alloy pole contact jaws reaches eutectic state
Or the power being completely melt needed for state.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019078975A1 (en) * | 2017-10-19 | 2019-04-25 | Enneti Ravi K | High strength and erosion resistant powder blends |
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| US10584404B2 (en) | 2016-09-30 | 2020-03-10 | Global Tungsten & Powders Corp. | High strength and abrasion resistant body powder blend |
| CN106636836A (en) * | 2017-01-22 | 2017-05-10 | 四川理工学院 | Preparation method of ultra-coarse hard alloy |
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| JP2003155538A (en) * | 2001-11-19 | 2003-05-30 | Kyoritsu Gokin Co Ltd | Hard metal alloy |
| US20120177453A1 (en) * | 2009-02-27 | 2012-07-12 | Igor Yuri Konyashin | Hard-metal body |
| CN102703745A (en) * | 2012-06-04 | 2012-10-03 | 厦门钨业股份有限公司 | Preparation method of extra coarse grain hard alloy |
| CN102732766B (en) * | 2012-07-06 | 2014-08-06 | 四川大学 | Coarse grain hard alloy material and preparation method thereof |
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| WO2019078975A1 (en) * | 2017-10-19 | 2019-04-25 | Enneti Ravi K | High strength and erosion resistant powder blends |
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