CN104451322B - A kind of tungsten carbide base carbide alloy and preparation method thereof - Google Patents
A kind of tungsten carbide base carbide alloy and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to technical field of alloy material, be specially a kind of tungsten carbide base carbide alloy and preparation method thereof.The present invention is formed accelerant by a certain percentage by least five kinds in molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum, yittrium oxide, tungsten carbide crystal grain can be suppressed too fast and/or irregularly grow, making tungsten carbide base carbide alloy have higher intensity, toughness and plasticity；When especially using with optimal ratio, tungsten carbide base carbide alloy can be made to have more preferable comprehensive mechanical property, effect is more preferable.The granularity of each material is less than or equal to 1.2 μm, and purity is more than 99.9%, each material height is made to mix, and collectively constituted binding agent by cobalt powder and nikel powder, other each material can be made to be fully contacted with it, increase bond area, improve cohesive force, thus the toughness of tungsten carbide base carbide alloy can be improved.The carbon tetrachloride solution adding paraffin in compound material can make paraffin be prone to evenly spread in compound material.
Description
Technical field
The present invention relates to technical field of alloy material, particularly relate to a kind of tungsten carbide base carbide alloy and preparation method thereof.
Background technology
Hard alloy is to be principal phase by the metal carbide powders (WC, TiC, TaC, NbC etc.) of high rigidity infusibility, with transition
Race's metallic cobalt, nickel etc. are as Binder Phase, a kind of alloy material made by powder gold metallurgy technique.Hard alloy has high hard
The premium properties such as degree, high intensity, high tenacity, wear-resistant, the high temperature resistant and coefficient of expansion are little, so be widely used in cutting,
The fields such as boring, mining, instrument shaping and wear part.Compared with high-speed steel, hard alloy has preferable red hardness, works as temperature
When degree is more than 600 DEG C, the high high-speed steel at room temperature of its hardness；When temperature is more than 1000 DEG C, and the hardness of hard alloy is the highest
In room temperature carbon steel.
Cut field at carbide tool, existing sintered carbide tool material be difficult to meet workpiece to be machined precision and
The requirement that surface roughness improves constantly, this just requires on the basis of existing sintered carbide tool material, improves hard further
The combination properties such as the hardness of matter alloy, toughness, intensity, wearability.But, in prior art, produce tungsten carbide base carbide alloy
Time, tungsten carbide crystal grain is during liquid-phase sintering, due to long high temperature sintering, crystal grain would generally grow too quickly and/
Or irregularly grow, cause the hydraulic performance decline of hard alloy.For this problem, the Fast Sintering skill that some are new can be used
Art, such as discharge plasma sintering technique (SPS), high-frequency induction heating sintering technology (HFIHS) or hot isostatic pressing technique (HIP)
Deng, reduce the size of tungsten carbide crystal grain, but this will increase the production cost of hard alloy.
Summary of the invention
The present invention is directed to existing tungsten carbide base carbide alloy because of in preparation process crystals of tungsten carbide too fast and/or irregular
Growth, causes the problem that prepared performance of tungsten carbide base carbide alloy declines, it is provided that a kind of production cost is low, and performance is more excellent
Tungsten carbide base carbide alloy, and the preparation method of this kind of tungsten carbide base carbide alloy.
For achieving the above object, the present invention by the following technical solutions,
A kind of tungsten carbide base carbide alloy, is made up of compound material, and described compound material includes following mass percent
Each component: binding agent 8-20%, accelerant 3-15%, surplus is tungsten carbide；
Described accelerant is made up of at least five kinds in molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide；
In described compound material, the mass percent of molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide is less than respectively
Or equal to 5%；
Described binding agent is made up of cobalt powder, or is made up of cobalt powder and nikel powder, or is made up of cobalt powder and iron powder, or by cobalt powder,
Nikel powder and iron powder composition；In described compound material, the mass percent of cobalt powder is 6-12%, and nikel powder mass percent is 0-6%,
The mass percent of iron powder is 0-2%.
Preferably, in compound material, the mass percent of accelerant is 3-13.2%；It is furthermore preferred that described compound material
In, the mass percent of molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide is respectively less than or equal to 2.2%.
Preferably, in compound material, the mass percent of cobalt powder is 8%.
Preferably, in compound material, the mass percent of nikel powder is 0-4%.
The grain of the above tungsten carbide, cobalt powder, nikel powder, molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide
Degree is respectively less than or equal to 1.2 μm.Preferably, the granularity of the above each material is 0.5-1 μm.
Preferably, described tungsten carbide, cobalt powder, nikel powder, molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide
Purity be all higher than or equal to 99.9% (mass percent).
The preparation method of the above tungsten carbide base carbide alloy, comprises the following steps:
S1, grinding: weigh each component respectively and mix, obtaining compound material；Paraffin, institute is added in compound material
The quality stating paraffin is the 1-3% of compound material quality；Then at 50-70 DEG C, grind compound material 36-72h, then vacuum
It is dried 1-2h.
Preferably, before grinding compound material, in compound material, add carbon tetrachloride, make compound material be immersed in four chlorinations
In carbon；And can be first dissolved in paraffin in carbon tetrachloride mixing again in compound material.The grinding used when grinding compound material
Ball is WC-6Co hard alloy mill ball, and mill ball is 5-10:1 with the mass ratio of compound material.
S2, sieve: compound material is through the sieve more than or equal to 100 mesh, and must sieve mixture.
S3, presintering: the mixture that will sieve makes base substrate, then heating base substrate makes it be gradually heating to 600-800 DEG C, so
Rear insulation 70-90min, is then cooled to room temperature by base substrate.
Preferably, make crude green body by the dry-pressing formed mixture that will sieve, then crude green body is carried out isostatic cool pressing process, shape
Become base substrate.During described isostatic cool pressing, with 5min, pressure is risen to 100-300MPa, then pressurize 5min.
S4, sintering: under nitrogen and/or inert gas shielding or under vacuum condition, heating base substrate makes it be gradually heating to
1350-1430 DEG C, then it is incubated 50-70min, then base substrate is cooled to room temperature.The vacuum of described vacuum condition is
0.1-10Pa。
Compared with prior art, the invention has the beneficial effects as follows: the present invention by molybdenum powder, vanadium carbide, chromium carbide, titanium carbide,
In carborundum, yittrium oxide at least five kinds form accelerant by a certain percentage, and tungsten carbide crystal grain can be suppressed too fast and/or irregular
Growth, makes tungsten carbide base carbide alloy have higher intensity, toughness and plasticity；When especially using with optimal ratio, can
Making tungsten carbide base carbide alloy have more preferable comprehensive mechanical property, effect is more preferable.The granularity of each material is less than or equal to 1.2 μ
M, and purity is more than 99.9%, makes each material height mix, and is collectively constituted binding agent by cobalt powder and nikel powder, can make other
Each material is fully contacted with it, increases bond area, improves cohesive force, thus can improve the tough of tungsten carbide base carbide alloy
Property.During preparing tungsten carbide base carbide alloy, first dissolve paraffin with carbon tetrachloride and pour into again in compound material, stone can be made
Wax is easier to evenly spread in compound material.Carbon tetrachloride the mixing of submergence raw material is added, with tetrachloro in compound material
Changing carbon and carry out wet ball grinding as solvent, compound material is difficult to oxidized, it is simple to be dried, and the dispersion of dried powder body is all
Even, reunite few.The tungsten carbide base carbide alloy prepared by the present invention not only intensity is high, also ensure that simultaneously its have high rigidity and
High tenacity, hardness is 15-25GPa, and fracture toughness is 4-8MPa m1/2.Additionally, by the inventive method, material can be reduced
Milling time, shortens the production cycle, reduces production cost.
Detailed description of the invention
In order to more fully understand the technology contents of the present invention, below in conjunction with specific embodiment, technical scheme is made
It is further described and illustrates.
Embodiment 1-20
The tungsten carbide base carbide alloy that embodiment 1-20 provides is made up of each material shown in table 1 below respectively.
Table 1 embodiment 1-20 forms each component and the mass percent of compound material
In table 1, tungsten carbide, cobalt powder, nikel powder, molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum, the granularity of yittrium oxide
Being 0.8-1.0 μm, purity reaches more than 99.9% (mass percent).
Tungsten carbide base carbide alloy described in above-described embodiment is prepared as follows:
(1) grind: weigh each component respectively and pour in ball grinder, making each component mix, obtain compound material；So
Backward ball grinder adds WC-6Co hard alloy mill ball, and the quality of WC-6Co hard alloy mill ball and compound material it
Ratio is 5-10:1.
Paraffin (the 3% of compound material quality) is first dissolved in carbon tetrachloride (about 10mL), then gained solution is fallen
Enter in the compound material in grinding pot, and continue to add carbon tetrachloride, to carbon tetrachloride completely by compound material submergence, and four
Chlorination carbon liquid level is than high about the 1.5cm of powder body plane of compound material.
At 50-70 DEG C, grind compound material 48h, be then vacuum dried 1-2h.
(2) sieve: will cross the sieve of 100 mesh through grinding dried compound material, must sieve mixture.
(3) molding: make cylinder crude green body by the dry pressuring forming process mixture that will sieve.Then
Crude green body is carried out isostatic cool pressing process, forms base substrate.During isostatic cool pressing, with 5min, pressure is risen to 200MPa, then
Pressurize 5min again.
(4) presintering: heating base substrate makes it be gradually heating to 750 DEG C, is then incubated 80min, is then cooled to by base substrate
Room temperature.The temperature of presintering process controls as shown in table 2 below:
During table 2 presintering, the time dependent situation of temperature
| Time/min | 0→180 | 180→260 | 260→320 | 320→400 | 400→545 |
| Temperature/DEG C | 25→400 | 400 | 400→750 | 750 | 750→25 |
(5) sintering: under nitrogen protection, heating base substrate makes it be gradually heating to 1400 DEG C, is then incubated 60min, then
Base substrate is cooled to room temperature, obtains the cutter of tungsten carbide base carbide alloy material.The temperature of sintering process controls such as table 3 below institute
Show:
During table 3 presintering, the time dependent situation of temperature
| Time/min | 0→25 | 25→100 | 100→300 | 300→360 | 360→550 |
| Temperature/DEG C | 25→400 | 400 | 400→1400 | 1400 | 1400→25 |
Measuring the hardness of tungsten carbide base carbide alloy, fracture toughness etc. prepared by embodiment 1-20 respectively, test result is such as
Shown in table 4 below.
The performance test results of tungsten carbide base carbide alloy prepared by table 4 embodiment 1-20
From the data in table 4, the tungsten carbide base carbide alloy that the present invention provides has higher intensity, hardness and breaks
Split toughness, thus it could be speculated that accelerant used in the present invention can suppress the growth of tungsten carbide crystal grain, anti-blocking during sintering
Change tungsten grain is too fast and/or irregularly grows, and ensures that tungsten carbide base carbide alloy has sufficiently high intensity, plasticity and fracture tough
Property.
In other embodiments, each material composition (tungsten carbide, cobalt powder, nikel powder, molybdenum powder, the carbonization of compound material are formed
Vanadium, chromium carbide, titanium carbide, carborundum, yittrium oxide) can be the granularity powder body that is less than or equal to 1.2 μm, especially granularity is
The powder body of 0.5-1 μm.During preparing tungsten carbide base carbide alloy, the amount of the paraffin added before grinding can also is that compound
The 1-3% of raw materials quality；During grinding, the carbon tetrachloride as solvent also can be replaced with dehydrated alcohol；The milling time of compound material
Can be 36-72h；Grind and dried compound material can cross 100 mesh or above sieve, be more than or equal to obtaining granularity
100 purposes are sieved mixture；Isostatic cool pressing process during molding, pressure can also is that 100-300MPa；Presintering process is
High-temperature can also is that 600-800 DEG C, and temperature retention time can be 70-90min；The maximum temperature of sintering process can also is that
1350-1430 DEG C, temperature retention time can be 50-70min.Additionally, in sintering process, in addition to protecting with nitrogen, it is also possible to make
Use other inert gas shielding, or carry out under the vacuum condition that vacuum is 0.1-10Pa.
The above only further illustrates the technology contents of the present invention with embodiment, in order to reader is easier to understand,
But not representing embodiments of the present invention and be only limitted to this, any technology done according to the present invention extends or recreation, all by this
Bright protection.
Claims (10)
1. a tungsten carbide base carbide alloy, is made up of compound material, it is characterised in that described compound material includes following quality
Each component of percentage ratio: binding agent 8-20%, accelerant 3-15%, surplus is tungsten carbide；
Described accelerant is made up of at least five kinds in molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide；Described
In compound material, the mass percent of molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide respectively less than or etc.
In 5%；
Described binding agent is made up of cobalt powder, or is made up of cobalt powder and nikel powder, or is made up of with iron powder cobalt powder, or by cobalt powder, nikel powder
Form with iron powder；In described compound material, the mass percent of cobalt powder is 6-12%, and nikel powder mass percent is 0-6%, iron powder
Mass percent be 0-2%.
A kind of tungsten carbide base carbide alloy, it is characterised in that in described compound material, accelerant
Mass percent be 3-13.2%.
A kind of tungsten carbide base carbide alloy, it is characterised in that in described compound material, cobalt powder
Mass percent is 8%.
A kind of tungsten carbide base carbide alloy, it is characterised in that in described compound material, nikel powder
Mass percent is 0-4%.
5. according to the arbitrary described a kind of tungsten carbide base carbide alloy of claim 1-4, it is characterised in that described tungsten carbide, cobalt powder,
The granularity of nikel powder, molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide is respectively less than or equal to 1.2 μm.
A kind of tungsten carbide base carbide alloy, it is characterised in that described tungsten carbide, cobalt powder, nikel powder,
The granularity of molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and carbonitride is 0.5-1 μm.
7. according to the arbitrary described a kind of tungsten carbide base carbide alloy of claim 1-4, it is characterised in that described tungsten carbide, cobalt powder,
The purity of nikel powder, molybdenum powder, vanadium carbide, chromium carbide, titanium carbide, carborundum and yittrium oxide is all higher than or equal to 99.9%.
8. the preparation method of a tungsten carbide base carbide alloy as claimed in claim 1, it is characterised in that comprise the following steps:
S1, grinding: weigh each component respectively and mix, obtaining compound material；Paraffin, described stone is added in compound material
The quality of wax is the 1-3% of compound material quality；Then at 50-70 DEG C, grind compound material 36-72h, be then vacuum dried
1-2h；
S2, sieve: compound material is through the sieve more than or equal to 100 mesh, and must sieve mixture；
S3, presintering: the mixture that will sieve makes base substrate, then heating base substrate makes it be gradually heating to 600-800 DEG C, then protects
Temperature 70-90min, is then cooled to room temperature by base substrate；
S4, sintering: under nitrogen and/or inert gas shielding or under vacuum condition, heating base substrate makes it be gradually heating to 1350-
1430 DEG C, then it is incubated 50-70min, then base substrate is cooled to room temperature.
The preparation method of a kind of tungsten carbide base carbide alloy, it is characterised in that in step S1, grinds
Before mill compound material, in compound material, add carbon tetrachloride, make compound material be immersed in carbon tetrachloride.
The preparation method of a kind of tungsten carbide base carbide alloy, it is characterised in that in step S3, logical
Cross the dry-pressing formed mixture that will sieve and make crude green body, then crude green body is carried out isostatic cool pressing process, form base substrate.
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