CN109680196A - A kind of surface layer richness cobalt is without cubic phase gradient hard alloy - Google Patents

A kind of surface layer richness cobalt is without cubic phase gradient hard alloy Download PDF

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CN109680196A
CN109680196A CN201710973297.3A CN201710973297A CN109680196A CN 109680196 A CN109680196 A CN 109680196A CN 201710973297 A CN201710973297 A CN 201710973297A CN 109680196 A CN109680196 A CN 109680196A
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hard alloy
powder
surface layer
tin
alloy
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王东玉
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

In order to improve hardness, the wearability of hard alloy, a kind of surface layer richness cobalt is prepared for without cubic phase gradient hard alloy.Using WC powder, Co powder, TiN powder, TiC powder, VC powder and Cr3C2Powder is raw material, and surface layer richness cobalt generates important influence to the performance of hard alloy without cubic phase gradient hard alloy, the content of TiN.The additive amount of TiN excessively can then form blocked up Nitride Phase unevenly distributed in carbide surface, and the mechanical property of hard alloy is caused to reduce.The additive amount of TiN is excessively few then cannot to form Nitride Phase in carbide surface, lead to the failure promoted to Cemented Carbide Properties.Without cubic phase gradient hard alloy, hardness, densification degree, bending strength are all increased dramatically obtained surface layer richness cobalt.The present invention can provide a kind of new production technology to prepare high performance gradient hard alloy.

Description

A kind of surface layer richness cobalt is without cubic phase gradient hard alloy
Technical field
The present invention relates to a kind of cemented carbide materials more particularly to a kind of surface layer richness cobalt without cubic phase gradient hard alloy.
Background technique
Hard alloy is a kind of by hard phase (WC, TiC, TaC, VC and Cr, C: etc.) and Binder Phase (Co, Ni and Fe) use Powder metallurgical technique production have high rigidity and high-wearing feature material, be widely used in cutting tool, mining tool, mold, The industrial circles such as measurer, wear part and mechanical seal.Hard alloy by brittle hard phase and toughness bonding phase composition, Its key property determines cemented carbide material, and there are the contradictions between wearability and toughness, and this contradiction is in traditional uniform knot It is difficult to solve in structure hard alloy.
With the rapid development of various precision instruments, mold, cutter and electronic communication, to WC-Co hard alloy Performance requirement is higher and higher.The failure mode of cemented carbide parts is mainly surface abrasion under practical fretting wear operating condition.Using Process for treating surface can improve hard alloy on the basis of not reducing hard alloy substrate toughness with enhancing hard alloy surface Surface hardness and wearability, to extend cemented carbide parts service life.
Summary of the invention
The purpose of the invention is to improve the hardness of hard alloy, wearability, devise a kind of surface layer richness cobalt without cube Phase gradient hard alloy.
The technical solution adopted by the present invention to solve the technical problems is:
Surface layer richness cobalt without cubic phase gradient hard alloy prepare raw material include: average grain diameter be 0.8 μm, purity is greater than 99.99wt%WC powder, average grain diameter is 0.8 μm, purity is greater than 99.9wt%Co powder, and average grain diameter is 1 μm, purity is greater than 99.95wt%TiN powder, average grain diameter is 1 μm, purity is greater than 99.95wt%TiC powder, and average grain diameter is 0.8 μm, purity is big It is 1 μm in 99.95wt%VC powder and average grain diameter, purity is greater than 99.95wt%Cr3C2Powder.
Preparation step of the surface layer richness cobalt without cubic phase gradient hard alloy are as follows: claim starting powder by experimental design Weight, ingredient, pour into after preparing and carry out wet-milling in planetary ball mill, ball-milling medium is carbon tetrachloride, drum's speed of rotation 60r/ Min, ratio of grinding media to material 7:1, Ball-milling Time 38h.After ball milling, pellet obtained is dried in vacuo, drying time is 50min, drying temperature are 40 DEG C, and paraffin is then added and pelletizes as binder.The powder made is added into mo(u)ldenpress Middle carry out compression moulding, then carries out isostatic cool pressing, pressing pressure 180MPa.The green compact made is put into vacuum sintering furnace It is sintered, sintering temperature is 1460 DEG C, soaking time 90min.
Detecting step of the surface layer richness cobalt without cubic phase gradient hard alloy are as follows: quality F210 type electronic balance, density are adopted With Archimedes's drainage, material phase analysis D8Advance type X-ray diffractometer, microstructure uses NanoSEM430 superelevation Resolution ratio field emission scanning electron microscope, hardness and fracture toughness are measured by Vickers indentation method.
For the surface layer richness cobalt without cubic phase gradient hard alloy, the addition of TiN is able to ascend the mechanical property of hard alloy Energy.The effect of TiN mainly can generate Nitride Phase in carbide surface, propose the toughness of hard alloy, hardness It is high.TiN can also inhibit hard alloy crystal grain during sintering to grow up, and make have object phase group more evenly inside hard alloy At and Cemented Carbide Properties promoted key.
The surface layer richness cobalt generates the performance of hard alloy important without cubic phase gradient hard alloy, the content of TiN Influence.The additive amount of TiN excessively can then form blocked up Nitride Phase unevenly distributed in carbide surface, cause hard The mechanical property of matter alloy reduces.The additive amount of TiN is excessively few then cannot to form Nitride Phase in carbide surface, cause to hard The failure that matter alloy property is promoted.
The surface layer richness cobalt without cubic phase gradient hard alloy, this technique of vacuum-sintering be beneficial to TiN activation and The synthesis of nitride enables carbide surface to generate uniform Nitride Phase, has hard alloy obtained excellent Mechanical property.
The beneficial effects of the present invention are:
Using WC powder, Co powder, TiN powder, TiC powder, VC powder and Cr3C2Powder is raw material, by ingredient, ball milling, Dry, granulation, forming, sintering process are successfully prepared the surface layer richness cobalt with excellent mechanical performance and close without cubic phase gradient hard Gold.Wherein, the addition of TiN is able to suppress growing up for crystal grain in sintering process, and carbide surface formed one layer it is uniform Nitride Phase is the key that Cemented Carbide Properties are promoted.Obtained surface layer richness cobalt is hard without cubic phase gradient hard alloy Degree, densification degree, bending strength are all increased dramatically.The present invention can provide to prepare high performance gradient hard alloy A kind of new production technology.
Specific embodiment
Case study on implementation 1:
Surface layer richness cobalt without cubic phase gradient hard alloy prepare raw material include: average grain diameter be 0.7 μm, purity is greater than 96.44wt%WC powder, average grain diameter is 0.75 μm, purity is greater than 98.9wt%Co powder, and average grain diameter is 1.5 μm, purity is big In 97.95wt%TiN powder, average grain diameter is 0.8 μm, purity is greater than 98.95wt%TiC powder, and average grain diameter is 0.75 μm, pure Degree is greater than 99.84wt%VC powder and average grain diameter is 0.9 μm, and purity is greater than 99.65wt%Cr3C2Powder.Surface layer richness cobalt without cube The research specific steps of phase gradient hard alloy are as follows: by starting powder by experimental design weighing, ingredient, pour into row after preparing Wet-milling is carried out in celestial body grinding machine, ball-milling medium is carbon tetrachloride, drum's speed of rotation 62r/min, ratio of grinding media to material 7.1:1, ball milling Time is 37.5h.After ball milling, pellet obtained is dried in vacuo, drying time 54min, drying temperature 39 DEG C, paraffin is then added and pelletizes as binder.The powder made is added to and carries out compression moulding in mo(u)ldenpress, then Carry out isostatic cool pressing, pressing pressure 179MPa.The green compact made is put into vacuum sintering furnace and is sintered, sintering temperature is 1399 DEG C, soaking time 89min.Detecting step of the surface layer richness cobalt without cubic phase gradient hard alloy are as follows: quality F210 type Electronic balance, density use Archimedes's drainage, material phase analysis D8Advance type X-ray diffractometer, and microstructure uses NanoSEM430 ultrahigh resolution field emission scanning electron microscope, hardness and fracture toughness are measured by Vickers indentation method.
Case study on implementation 2:
Alloy A is divided into surface layer, transition zone and interior layer group to inner by table in the section of 1398 DEG C of vacuum heat-preserving 69min samples At.Surface layer is about 19 μm of 1 thickness of region；Followed by 1 about 29 μm of thickness of transition zone；And the microstructure of alloy interior layer It is influenced almost without by denitrogenation atmosphere, there is the presence such as more (Ti, W) (C, N) solid solution.Pure TiN thermal stability is very high, Even if will not still decompose under 1630 DEG C of vacuum environments, but in the presence of having WC, the thermodynamic property that can reduce TiN is stablized Property, it can react, release under 1398 DEG C of vacuum environments.TiN is decomposed under high temperature, and the N on surface layer is escaped at first, It is dischargingDuring, due to coupling effect strong between Ti atom and N atom, the Ti atom of alloy surface passes through liquid phase Co during Ti atom is to alloy internal migration, will lead to alloy surface and form atom vacancy to alloy internal migration.Cause This, liquid phase Co flows to alloy surface, finally forms toughness region of the rich cobalt without cubic phase on gradient hard alloy surface layer.WC is average Crystal grain is no more than 498nm, and crystal grain is tiny, and distribution is relatively uniform, meets requirement of the ultra-fine cemented carbide to WC grain.
Case study on implementation 3:
The section of alloy B is not divided into 3 layers significantly then, but can find out the cubic carbides in its interior layer containing Ti or nitrogen carbon Compound is more densely distributed than surface region.Although there is gradient to be formed, gradient layer is not obvious enough.It may be due to being added in alloy B TiN content it is not high enough, only 4.9wt% is unfavorable for decomposition of the hard alloy surface layer TiN under denitrogenation environment.Inside alloy B Region WC grain is equally relatively fine.
Case study on implementation 4:
Within the scope of certain thickness, Co content inwards, shows the trend successively decreased by table；And Ti content then shows and incremental becomes Gesture.The Co content of alloy section surface region is up to 20.27%, hence it is evident that the Co content higher than in experimental formula 16%；Ti and N content Disappear substantially；The content of W and C is increased slightly, but is changed unobvious.During vacuum liquid-phase sintering, Ti element is by table Vacancy is left towards internal migration, this vacancy needs other members usually to fill, and otherwise can generate many gaps, and then form volume Defect.Due to the liquid-phase sintering that is sintered to of WC-Co hard alloy, Co phase is liquid phase at 1419 DEG C, has good mobility, So Co element fills atom vacancy caused by Ti elements diffusion to alloy surface directional migration, and then forms surface layer and be rich in Ductile layers of the cobalt without cubic phase.The gradient distribution of alloy B has much room for improvement, so not carrying out element variation analysis.
Case study on implementation 5:
The surface alloy A is mainly two-phase: WC and Co phase does not detect TiN phase；Alloy B surface be mainly WC, WC1-x phase and Co phase also detects that TiN phase, it may be possible to decompose completely since the TiN content of alloy B surface is seldom, or even.
Case study on implementation 6:
The surface fracture toughness of alloy (A and B) is substantially better than the fracture toughness of its core, and alloy A is especially pronounced.At 1419 DEG C After vacuum liquid-phase sintering 69min, alloy A surface fracture toughness is up to 20.9MPam1/2, and the fracture toughness of alloy B surface is only There is 15.6MPam1/2, it may be possible to since in alloy B, the TiN content of addition is insufficient, and causes to be unfavorable for the abundant of liquid phase Co Migration, and then do not form ideal toughness surface layer.But the fracture toughness of alloy A and B core is not much different, and is maintained at 14~ 15MPa·m1/2.The surface hardness of alloy A and B are not much different, but the core hardness of alloy A is higher than alloy B, it may be possible to alloy A The TiN content of core is higher than alloy B, because the micro-vickers hardness of WC is 2079HV30, and cubic phase TiN, TiC and Ti (C, N hardness) is then generally higher than 2996HV30。
Case study on implementation 7:
The preparation process can realize WC-Co hard alloy surface layer for rich ductile layers of the cobalt without cubic phase.With surface obdurability height Gradient hard alloy, can be conducive to prevent high temperature deposition coating in cooling procedure the generation in face crack source and effectively resistance Only the crackle inside alloy is to extended surface.

Claims (4)

1. a kind of surface layer richness cobalt without cubic phase gradient hard alloy prepare raw material include: average grain diameter be 0.8 μm, purity is greater than 99.99wt%WC powder, average grain diameter is 0.8 μm, purity is greater than 99.9wt%Co powder, and average grain diameter is 1 μm, purity is greater than 99.95wt%TiN powder, average grain diameter is 1 μm, purity is greater than 99.95wt%TiC powder, and average grain diameter is 0.8 μm, purity is big It is 1 μm in 99.95wt%VC powder and average grain diameter, purity is greater than 99.95wt%Cr3C2Powder.
2. richness cobalt in surface layer according to claim 1 is without cubic phase gradient hard alloy, it is characterized in that surface layer richness cobalt without cube The preparation step of phase gradient hard alloy are as follows: by starting powder by experimental design weighing, ingredient, planet ball is poured into after preparing Carry out wet-milling in grinding machine, ball-milling medium is carbon tetrachloride, drum's speed of rotation 60r/min, ratio of grinding media to material 7:1, and Ball-milling Time is 38h after ball milling, pellet obtained is dried in vacuo, drying time 50min, and drying temperature is 40 DEG C, then plus Enter paraffin to pelletize as binder, the powder made is added to and carries out compression moulding in mo(u)ldenpress, then carries out cold etc. The green compact made is put into vacuum sintering furnace and is sintered by static pressure, pressing pressure 180MPa, and sintering temperature is 1460 DEG C, Soaking time is 90min.
3. richness cobalt in surface layer according to claim 1 is without cubic phase gradient hard alloy, it is characterized in that surface layer richness cobalt without cube The detecting step of phase gradient hard alloy are as follows: quality F210 type electronic balance, density use Archimedes's drainage, object phase point Analysis D8Advance type X-ray diffractometer, microstructure use NanoSEM430 ultrahigh resolution field emission scanning electron microscope, firmly Degree and fracture toughness are measured by Vickers indentation method.
4. richness cobalt in surface layer according to claim 1 is without cubic phase gradient hard alloy, it is characterized in that the surface layer richness cobalt Without cubic phase gradient hard alloy, the addition of TiN is able to ascend the mechanical property of hard alloy, and the effect of TiN mainly can Nitride Phase is generated in carbide surface, is improved the toughness of hard alloy, hardness, TiN can also inhibit sintered Hard alloy crystal grain is grown up in journey, makes that there is object phase composition and Cemented Carbide Properties more evenly to mention inside hard alloy The key risen, the surface layer richness cobalt generate the performance of hard alloy important without cubic phase gradient hard alloy, the content of TiN Influence, the additive amount of TiN excessively can then form blocked up Nitride Phase unevenly distributed in carbide surface, cause hard The mechanical property of matter alloy reduces, and the additive amount of TiN is excessively few then cannot to form Nitride Phase in carbide surface, causes to hard The failure that matter alloy property is promoted, for the surface layer richness cobalt without cubic phase gradient hard alloy, this technique of vacuum-sintering is beneficial In the activation of TiN and the synthesis of nitride, carbide surface is enable to generate uniform Nitride Phase, closes hard obtained Fitting has excellent mechanical property.
CN201710973297.3A 2017-10-18 2017-10-18 A kind of surface layer richness cobalt is without cubic phase gradient hard alloy Pending CN109680196A (en)

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Application publication date: 20190426