CN105219997B - Hard alloy nitrogenous foundry alloy Binder Phase powder and preparation method thereof - Google Patents
Hard alloy nitrogenous foundry alloy Binder Phase powder and preparation method thereof Download PDFInfo
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Abstract
The first hard alloy of the present invention is made up of with nitrogenous foundry alloy Binder Phase powder the multiple elements design grain growth inhibitor that mass fraction is 5%~50% and the Binder Phase metal that mass fraction is 50%~95%.Second hard alloy is made up of with nitrogenous foundry alloy Binder Phase powder the additive of multiple elements design grain growth inhibitor, the Binder Phase metal that mass fraction is 50%~90% and mass fraction 0.1%~5% that mass fraction is 5%~49.9%.Present invention also offers above two hard alloy with nitrogenous foundry alloy Binder Phase raw powder's production technology, step is：(1) dispensing；(2) batch mixing and drying；(3) sinter, (4) crush.The present invention provides new bonding phase raw material for the preparation of hard alloy, new way is provided to introduce nitrogen in hard alloy, so as to be conducive to preparing the more preferable hard alloy of the comprehensive mechanical performances such as hardness, intensity and toughness.
Description
Technical field
The invention belongs to hard alloy field, more particularly to hard alloy Binder Phase powder and preparation method thereof.
Background technology
Hard alloy because with a series of excellent properties such as hardness high, wearability, red hardness and preferable toughness, extensively
It is applied to prepare cutting tool, mining and wear parts.Usual alloy rigidity is higher, and its wearability is better, the obdurability of alloy
(intensity and toughness) is higher, and its impact resistance is better.Therefore, hardness and obdurability have turned into the important of evaluation Cemented Carbide Properties
Index.Regulate and control the hardness and obdurability of alloy, the main content for including control Binder Phase, hard-phase particles size, hard phase with
Bond the means such as the uniformity of distributed mutually.The particle size for reducing Binder Phase content or reducing hard phase WC is conducive to improving alloy
Hardness, but the reduction of alloy obdurability can be caused；Conversely, the particle size of raising Binder Phase content or increase hard phase WC is then
Be conducive to the raising of obdurability, but can cause the alloy rigidity to reduce.Therefore, the hardness of hard alloy, intensity and toughness are difficult together
When be improved, this contradiction limits further applying for hard alloy.
In the liquid-phase sintering step of conventional rigid alloy preparation process, it is that influence hard alloy is hard that hard phase crystal grain is grown up
The key factor of degree, intensity and toughness.Because Ostwald cures mechanism, liquid-phase sintering necessarily causes average of WC in sintered body
Particle size is more than the average original dimension of its raw material, i.e., sintering result in hard phase crystal grain and grow up.Particularly to prepare Ultra-fine Grained hard
In matter alloy process, it is easy to cause grain discontinuity to grow up.In order to control growing up for crystal grain, often addition is few in industrial production
Amount grain growth inhibitor (grain refiner) (such as VC, Cr3C2, TaC etc.) to obtain, granularity is tiny and uniform hard alloy.
However, existing commercially available conventional inhibitor granularity is larger (mostly more than micron level), the granularity with raw material WC is mismatched, and is caused
When preparing hard alloy, particularly preparing ultra-fine cemented carbide, inhibitor is difficult to uniform point in carbide alloy mixture
Cloth, influences it to suppress the effect that crystal grain is grown up.Although being applied in combination two kinds and above inhibitor effect being more preferable, this is further carried
The mixed uniformly difficulty of compound high, so as to increase cost.Chinese patent CN102828061A, CN103343257A,
CN104046828A discloses multiple elements design grain refiner and preparation method thereof, although solve needs group to improve thinning effect
Close using the problem of two kinds and above inhibitor, but addition due to inhibitor in hard alloy is very low, general control
In 1% (weight percentage) below, under existing working condition, by common mechanical mixture, still it is difficult to ensure that so
The uniformity that the inhibitor of few additive is distributed in compound, is finally difficult to ensure that the suppression effect grown up to hard phase crystal grain
Really.Additionally, sintering temperature is very high in existing preparation method, and then accelerates growing up for hard phase crystal grain, and there is liquid in Binder Phase
It is to cause the first cause of this problem that the temperature of phase is too high.
Generally, there are two kinds of approach to introducing nitrogen in hard alloy：1) sintered by nitrogen atmosphere, closed to hard
Gold introduces nitrogen, N.G.Hashe et al. (Int.J.Refract.Met.＆Hard Mater.27 (2009) 20-25) and have studied
Sintered hard alloy, as a result shows that N can effectively control crystal grain to grow up in a nitrogen atmosphere, and the hard-phase particles size point that narrows
Cloth scope, C.Buchegger et al. (Int.J.Refract.Met.＆Hard Mater.49 (2015) 67-74) research show nitrogen
Sintered hard alloy under the conditions of gas, can influence the diffusion coefficient of inhibitor；2) in the way of to add nitride/carbonitride,
Nitrogen is introduced to hard alloy, Chinese patent CN102534340B is with multi-element composite titanium carbonitride solid solution in hard alloy
Nitrogen is introduced, interface wet ability, reinforcing Binder Phase, crystal grain thinning can be effectively improved, improve alloy property.As can be seen here, suitably
Introducing nitrogen can produce obvious beneficial effect to hard alloy, but the mode of existing two kinds of introducings nitrogen has limitation
Property：The former is only capable of introducing nitrogen in alloy surface certain depth, and there is gradient, it is impossible to obtains the homogeneous hard of performance and closes
Gold；Though the latter solves the gradient problem of nitrogen distribution to a certain extent, nitrogen is prohibited by nitride/carbonitride particle
Plug with molten metal, its distributing homogeneity is affected.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided hard alloy is with nitrogenous foundry alloy Binder Phase powder
And preparation method thereof, it is to introduce nitrogen in hard alloy to carry so that the preparation for hard alloy provides new bonding phase raw material
For new way, so as to prepare the more preferable hard alloy of the comprehensive mechanical performances such as hardness, intensity and toughness.
The nitrogenous foundry alloy Binder Phase powder of hard alloy of the present invention is in conventional adhesive phase metallic cobalt, nickel and iron
Introduce multi-element composite carbon nitride thing to be formed, according to whether addition additive can be divided into two kinds.
The first hard alloy of the present invention, with nitrogenous foundry alloy Binder Phase powder, is 5%~50% by mass fraction
Multi-element composite carbon nitride thing and Binder Phase metal that mass fraction is 50%~95% composition, the multi-element composite carbon nitride thing
It is carbon chromium nitride based solid solution (Cry,M11-y)2(Cx,N1-x), vanadium carbide nitride based solid solution (Vy,M21-y)(Cx,N1-x), carbon nitridation
Titanium-based solid solution (Tiy,M31-y)(Cx,N1-x) at least one, the Binder Phase metal be cobalt, nickel, iron at least one；
(the Cry,M11-y)2(Cx,N1-x) in, constituent element M1 be vanadium, titanium, molybdenum, tantalum, niobium, zirconium at least one, 0.1≤x≤0.9,
0.5 ＜ y≤0.95；(the Vy,M21-y)(Cx,N1-x) in, constituent element M2 is at least one in chromium, titanium, molybdenum, tantalum, niobium, zirconium, 0.1
≤ x≤0.9,0.5 ＜ y≤0.95；(the Tiy,M31-y)(Cx,N1-x) in, M3 is at least in vanadium, chromium, molybdenum, tantalum, niobium, zirconium
Kind, 0.1≤x≤0.9,0.5 ＜ y≤0.95.
Above-mentioned the first hard alloy with nitrogenous foundry alloy Binder Phase powder, structure be with Binder Phase metal as solvent, with
Multi-element composite carbon nitride thing is the solid solution phase of solute, or structure is with Binder Phase metal as solvent, with multi-element composite carbon nitride thing
For the compound phase that the solid solution phase of solute is constituted with multi-element composite carbon nitride thing.
Second hard alloy of the present invention with nitrogenous foundry alloy Binder Phase powder, by mass fraction be 5%~
49.9% multi-element composite carbon nitride thing, the Binder Phase metal that mass fraction is 50%~90% and mass fraction 0.1%~5%
Additive composition, the multi-element composite carbon nitride thing be carbon chromium nitride based solid solution (Cry,M11-y)2(Cx,N1-x), carbon nitridation
Vanadium base solid solution (Vy,M21-y)(Cx,N1-x), titanium carbonitride based solid solution (Tiy,M31-y)(Cx,N1-x) at least one, institute
It is at least one in cobalt, nickel, iron to state Binder Phase metal, and the additive is at least one in WC, TiC, TaC, NbC；Institute
State (Cry,M11-y)2(Cx,N1-x) in, constituent element M1 is at least one in vanadium, titanium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5
＜ y≤0.95；(the Vy,M21-y)(Cx,N1-x) in, constituent element M2 is at least one in chromium, titanium, molybdenum, tantalum, niobium, zirconium, 0.1≤x
≤ 0.9,0.5 ＜ y≤0.95；(the Tiy,M31-y)(Cx,N1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium,
0.1≤x≤0.9,0.5 ＜ y≤0.95.
State the nitrogenous foundry alloy Binder Phase powder of hard alloy for above-mentioned second, structure be with Binder Phase metal as solvent,
Solid solution phase with multi-element composite carbon nitride thing and additive as solute, or structure is with Binder Phase metal as solvent, with polynary multiple
It is the solid solution phase and multi-element composite carbon nitride thing, the compound phase of additive of solute to close carbonitride and additive.
Above-mentioned the first hard alloy that the present invention is provided nitrogenous foundry alloy Binder Phase raw powder's production technology, technique step
It is rapid as follows：
(1) dispensing
Raw material is at least one in cobalt powder, nickel powder, iron powder, the oxide of cobalt, the oxide of nickel, the oxide of iron,
(Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,N1-x) powder, (Tiy,M31-y)(Cx,N1-x) powder, (Cry,M11-y)2(Cx,
N1-x) in metal constituent element oxide and carbon source, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,
M31-y)(Cx,N1-x) in metal constituent element oxide and carbon source at least one；
(the Cry,M11-y)2(Cx,N1-x) in, constituent element M1 is at least one in vanadium, titanium, molybdenum, tantalum, niobium, zirconium, 0.1≤x
≤ 0.9,0.5 ＜ y≤0.95；(the Vy,M21-y)(Cx,N1-x) in, constituent element M2 is at least in chromium, titanium, molybdenum, tantalum, niobium, zirconium
Kind, 0.1≤x≤0.9,0.5 ＜ y≤0.95；(the Tiy,M31-y)(Cx,N1-x) in, M3 is in vanadium, chromium, molybdenum, tantalum, niobium, zirconium
At least one, 0.1≤x≤0.9,0.5 ＜ y≤0.95；
According to above-mentioned the first hard alloy component of nitrogenous foundry alloy Binder Phase powder and the mass fraction of each component
Measure various raw materials；
(2) batch mixing and drying
Each raw material is uniform by ball milling mixing, then dry to obtain compound；
(3) sinter
Sintered in confined reaction stove：
At least one in raw material is cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,
N1-x) powder, (Tiy,M31-y)(Cx,N1-x) at least one in powder when, use first method：Compound prepared by step (2)
It is placed in reacting furnace, reacting furnace is evacuated to 1~1 × 10-2Begin to warm up and continue to vacuumize after Pa, when reaction in-furnace temperature
When rising to 600~1350 DEG C, the heat preservation sintering 0.5~6 hour at this temperature and continuation vacuumized conditions, after heat preservation sintering terminates
Temperature is cooled to the furnace under vacuumized conditions to be come out of the stove less than 100 DEG C；
When raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,
N1-x) in metal constituent element oxide and carbon source, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,
M31-y)(Cx,N1-x) in metal constituent element oxide and carbon source in it is at least one when, use second method：By step (2)
The compound of preparation is placed in reacting furnace, and reacting furnace is evacuated into 1~1 × 10-2Begin to warm up and continue to vacuumize after Pa, when
Stop vacuumizing when temperature rises to 800~1600 DEG C, be 0.01~0.1MPa to nitrogen to nitrogen pressure is passed through in reacting furnace, herein
Heat preservation sintering 1~6 hour at nitrogen pressure and 800~1600 DEG C, heat preservation sintering cools to temperature with the furnace and goes out less than 100 DEG C after terminating
Stove；
Or sintered in open reactive stove：
Reacting furnace gas outlet open in the state of heating reaction furnace and to reacting furnace in be passed through flowing protective gas or
Reacting gas, when the temperature that region is sintered in reacting furnace rises to 600~1600 DEG C, step (2) gained compound is continuously sent
Enter the sintering region of the reacting furnace heat preservation sintering under mobile status, compound moves out burning in 0.5~6 hour in sintering zone sintering
Tie region is cooled below 100 DEG C and comes out of the stove into the cooled region of reacting furnace；
At least one in raw material is cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,
N1-x) powder, (Tiy,M31-y)(Cx,N1-x) at least one in powder when, to the protective gas that flowing is passed through in reacting furnace；
When raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,
N1-x) in metal constituent element oxide and carbon source, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,
M31-y)(Cx,N1-x) in metal constituent element oxide and carbon source in it is at least one when, to the reaction that flowing is passed through in reacting furnace
Gas；
(4) crush
By the product after coming out of the stove is by ball mill crushing and sieves, that is, the nitrogenous foundry alloy Binder Phase powder of hard alloy is obtained
Body.
Hard alloy nitrogenous foundry alloy Binder Phase raw powder's production technology, technique are stated in above-mentioned second of present invention offer
Step is as follows：
(1) dispensing
Raw material is at least one in cobalt powder, nickel powder, iron powder, the oxide of cobalt, the oxide of nickel, the oxide of iron,
(Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,N1-x) powder, (Tiy,M31-y)(Cx,N1-x) powder, (Cry,M11-y)2(Cx,
N1-x) in metal constituent element oxide and carbon source, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,
M31-y)(Cx,N1-x) in metal constituent element oxide and carbon source at least one, in WC powder, TiC powder, TaC powder, NbC powder
It is at least one；
(the Cry,M11-y)2(Cx,N1-x) in, constituent element M1 is at least one in vanadium, titanium, molybdenum, tantalum, niobium, zirconium, 0.1≤x
≤ 0.9,0.5 ＜ y≤0.95；(the Vy,M21-y)(Cx,N1-x) in, constituent element M2 is at least in chromium, titanium, molybdenum, tantalum, niobium, zirconium
Kind, 0.1≤x≤0.9,0.5 ＜ y≤0.95；(the Tiy,M31-y)(Cx,N1-x) in, M3 is in vanadium, chromium, molybdenum, tantalum, niobium, zirconium
At least one, 0.1≤x≤0.9,0.5 ＜ y≤0.95；
According to above-mentioned second hard alloy component of nitrogenous foundry alloy Binder Phase powder and the mass fraction of each component
Measure various raw materials；
(2) batch mixing and drying
Each raw material is uniform by ball milling mixing, then dry to obtain compound；
(3) sinter
Sintered in confined reaction stove：
At least one in raw material is cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,
N1-x) powder, (Tiy,M31-y)(Cx,N1-x) at least one in powder, during at least one in WC powder, TiC powder, TaC powder, NbC powder,
Use first method：Compound prepared by step (2) is placed in reacting furnace, reacting furnace is evacuated to 1~1 × 10-2Pa
After begin to warm up and continue to vacuumize, when reacting in-furnace temperature and rising to 600~1350 DEG C, in this temperature and continue to vacuumize bar
Heat preservation sintering 0.5~6 hour under part, heat preservation sintering cools to temperature with the furnace under vacuumized conditions and goes out less than 100 DEG C after terminating
Stove, obtains final product hard alloy with nitrogenous foundry alloy Binder Phase；
When raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,
N1-x) in metal constituent element oxide and carbon source, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,
M31-y)(Cx,N1-x) in metal constituent element oxide and carbon source at least one, in WC powder, TiC powder, TaC powder, NbC powder
When at least one, second method is used：Compound prepared by step (2) is placed in reacting furnace, reacting furnace is evacuated to 1
~1 × 10-2Begin to warm up and continue to vacuumize after Pa, stop vacuumizing when temperature rises to 800~1600 DEG C, in reacting furnace
It is 0.01~0.1MPa, the heat preservation sintering 1~6 hour at this nitrogen pressure and 800~1600 DEG C, insulation to be passed through nitrogen to nitrogen pressure
Cool to temperature after terminating with the furnace to be come out of the stove less than 100 DEG C, obtain final product hard alloy with nitrogenous foundry alloy Binder Phase；
Or sintered in open reactive stove：
Reacting furnace gas outlet open in the state of heating reaction furnace and to reacting furnace in be passed through flowing protective gas or
Reacting gas, when the temperature that region is sintered in reacting furnace rises to 600~1600 DEG C, step (2) gained compound is continuously sent
Enter the sintering region of the reacting furnace heat preservation sintering under mobile status, compound moves out burning in 0.5~6 hour in sintering zone sintering
Tie region is cooled below 100 DEG C and comes out of the stove into the cooled region of reacting furnace, that is, the nitrogenous foundry alloy of hard alloy is obtained
Binder Phase；
At least one in raw material is cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,
N1-x) powder, (Tiy,M31-y)(Cx,N1-x) at least one in powder, during at least one in WC powder, TiC powder, TaC powder, NbC powder,
To the protective gas that flowing is passed through in reacting furnace；
When raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,
N1-x) in metal constituent element oxide and carbon source, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,
M31-y)(Cx,N1-x) in metal constituent element oxide and carbon source at least one, in WC powder, TiC powder, TaC powder, NbC powder
When at least one, to the reacting gas that flowing is passed through in reacting furnace.
(4) crush
By the product after coming out of the stove is by ball mill crushing and sieves, that is, the nitrogenous foundry alloy Binder Phase powder of hard alloy is obtained
Body.
With nitrogenous foundry alloy Binder Phase raw powder's production technology, the oxide of the cobalt is an oxygen to above two hard alloy
Change at least one in cobalt, cobalt sesquioxide, cobaltosic oxide；The oxide of nickel be nickel monoxide, nickel sesquioxide in extremely
Few one kind；The oxide of iron is at least one in di-iron trioxide, ferroso-ferric oxide；
(the Cry,M11-y)2(Cx,N1-x) in metal constituent element oxide and carbon source, (Vy,M21-y)(Cx,N1-x) in metal
The oxide and carbon source of constituent element, (Tiy,M31-y)(Cx,N1-x) in metal constituent element oxide and carbon source in, the oxidation of metal constituent element
Thing is as follows：The oxide of vanadium is at least one in vanadic anhydride, vanadium trioxide；The oxide of chromium is chrome green；
Titanyl compound is titanium dioxide；The oxide of molybdenum is molybdenum trioxide；The oxide of tantalum is tantalum pentoxide；The oxide of niobium is
Niobium pentaoxide；The oxide of zirconium is zirconium dioxide；Carbon source is at least one in carbon black, activated carbon, graphite.
With nitrogenous foundry alloy Binder Phase raw powder's production technology, step (3) is in open reactive for above two hard alloy
When being sintered in stove, the protective gas is at least one in argon gas, hydrogen, nitrogen；The reacting gas is in nitrogen, ammonia
At least one.
Above two hard alloy nitrogenous foundry alloy Binder Phase the raw powder's production technology, (Cry,M11-y)2(Cx,
N1-x) powder, (Vy,M21-y)(Cx,N1-x) powder can be by " receiving containing high-energy-milling disclosed in patent application CN104046828A
Rice multiple elements design grain growth inhibitor preparation method " is obtained, (the Tiy,M31-y)(Cx,N1-x) powder can be " open by paper
CRN method prepares the research of (Ti, W, Mo, V) CN solid-solution powders under system " (Zhu Yunfeng etc., functional material, 2012
Year the 17th phase volume 43) disclosed in method be obtained.
Compared with prior art, the invention has the advantages that：
1st, it is of the invention for the preparation of hard alloy provides new bonding phase raw material and first to nitrogen is introduced in Binder Phase first
Element, to provide a kind of new way to introducing nitrogen in hard alloy.
2nd, the method for the invention is uniformly divided by by multi-element composite carbon nitride thing (grain growth inhibitor) with vast scale
It is scattered to prepare nitrogenous foundry alloy Binder Phase powder in Binder Phase, realization adds polynary in the form of foundry alloy in hard alloy
Compound carbonitride, due to when content of the multi-element composite carbon nitride thing in Binder Phase is significantly larger than directly adds in hard phase
Content, compared to directly addition in hard phase, its addition be easier to be sufficiently mixed in Binder Phase it is uniform, then by multiple elements design
When the Binder Phase that carbonitride has been mixed is mixed with hard, multi-element composite carbon nitride thing can be significantly improved and divided in hard alloy
The uniformity of cloth.Furthermore, hard alloy of the present invention nitrogenous foundry alloy Binder Phase and Binder Phase metallic cobalt, nickel and iron phase
Than fusing point is lower, and the temperature that liquid phase occurs in sintering when hard alloy is prepared is significantly reduced, and above two factor is all conducive to system
It is standby go out crystal grain is tiny, microstructure hard alloy evenly.
3rd, nitrogen is introduced by hard alloy by nitrogenous foundry alloy Binder Phase of the present invention, nitrogen can be made in hard
It is more evenly distributed in alloy, is conducive to the homogeneity of hard alloy crystal grain and performance.
4th, experiment shows, prepares hard alloy using nitrogenous foundry alloy Binder Phase of the present invention and use multiple elements design carbon
Nitride grains are grown up and inhibitor or are applied in combination grain growth inhibitor and prepare hard alloy and compare, and can preferably improve hard
The comprehensive mechanical performance (see the comparative example in specification) of matter alloy.
5th, the method for the invention process is simple, it is low for equipment requirements, it is easy to industrialized production.
Brief description of the drawings
Fig. 1 is hard alloy X-ray diffraction (XRD) figure of nitrogenous foundry alloy Binder Phase of the preparation of embodiment 1.
Specific embodiment
By the following examples to hard alloy of the present invention nitrogenous foundry alloy Binder Phase powder and preparation method thereof
It is described further.
Embodiment 1
Hard alloy prepared by the present embodiment is Co-15% (Cr with nitrogenous foundry alloy Binder Phase powder0.8,V0.2)2
(C0.5,N0.5), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 8.5Kg Co powder and 1.5Kg (Cr0.8,V0.2)2(C0.5,N0.5) powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 8L wine to ball grinder
Essence, ball milling obtains compound in 5 hours in 24 hours after drying in baking oven 60 DEG C；
(3) sinter
Sintered in confined reaction stove：
Compound prepared by step (2) is placed in the inflatable tube furnace of vacuum, reacting furnace is evacuated to 1 × 10-2Pa
After begin to warm up and continue to vacuumize, when reacting in-furnace temperature and rising to 600 DEG C, protected in this temperature and under continuing vacuumized conditions
Temperature sintering 6 hours, heat preservation sintering cools to temperature with the furnace and is come out of the stove less than 100 DEG C after terminating；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 300 mesh sieves, that is, Co-15% (Cr are obtained0.8,V0.2)2(C0.5,
N0.5) with nitrogenous foundry alloy Binder Phase powder, its X-ray diffractogram is shown in Fig. 1 to hard alloy.As shown in Figure 1, the nitrogenous foundry alloy
Be with Co as solvent, (Cr0.8,V0.2)2(C0.5,N0.5) it is the single-phase solid solution of solute.
Embodiment 2
Novel hard alloy prepared by the present embodiment is Co-15%Ni-5%Fe- with nitrogenous foundry alloy Binder Phase powder
18% (Cr0.85,V0.025,Ti0.025,Mo0.025,Ta0.025,Nb0.025,Zr0.025)2(C0.9,N0.1), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 6.2Kg Co powder, 1.5Kg Ni powder, 0.5Kg Fe powder and 1.8Kg (Cr0.85,V0.025,Ti0.025,Mo0.025,Ta0.025,
Nb0.025,Zr0.025)2(C0.9,N0.1) powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 8L wine to ball grinder
Essence, ball milling obtains compound in 24 hours after being dried 4 hours in baking oven 70 DEG C；
(3) sinter
Sintered in confined reaction stove：
Compound prepared by step (2) is placed in microwave agglomerating furnace, reacting furnace is evacuated to 1 × 10-2Start after Pa
Heat and continue to vacuumize, when reaction in-furnace temperature rises to 1000 DEG C, be incubated in this temperature and under continuing vacuumized conditions and burnt
Knot 1.5 hours, heat preservation sintering cools to temperature with the furnace and is come out of the stove less than 100 DEG C after terminating；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 500 mesh sieves, that is, Co-15%Ni-5%Fe-18% is obtained
(Cr0.85,V0.025,Ti0.025,Mo0.025,Ta0.025,Nb0.025,Zr0.025)2(C0.9,N0.1) hard alloy bonds with nitrogenous foundry alloy
Phase powder.
Embodiment 3
Hard alloy prepared by the present embodiment is Co-20%Ni-50% (V with nitrogenous foundry alloy Binder Phase powder0.9,
Ti0.1)(C0.1,N0.9), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 30g Co powder, 20g Ni powder and 50g (V0.9,Ti0.1)(C0.1,N0.9) powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 8:1 ratio of grinding media to material loads abrading-ball, and adds 100ml to ball grinder
Alcohol, ball milling obtains compound in 36 hours after being dried 4 hours in oven for drying 80 DEG C；
(3) sinter
Sintered in confined reaction stove：
Compound prepared by step (2) is placed in the inflatable tube furnace of vacuum, reacting furnace is evacuated to 1 × 10-1Pa
After begin to warm up and continue to vacuumize, when reacting in-furnace temperature and rising to 1350 DEG C, in this temperature and continue under vacuumized conditions
Heat preservation sintering 0.5 hour, heat preservation sintering cools to temperature with the furnace and is come out of the stove less than 100 DEG C after terminating；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 200 mesh sieves, that is, Co-20%Ni-50% (V are obtained0.9,Ti0.1)
(C0.1,N0.9) hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Embodiment 4
Hard alloy prepared by the present embodiment is Co-10%Fe-5% (V with nitrogenous foundry alloy Binder Phase powder0.75,
Cr0.05,Ti0.05,Mo0.05,Ta0.05,Nb0.025,Zr0.025)(C0.9,N0.1) -0.1%WC, processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 84.9g Co powder, 10g Fe powder, 5g (V0.75,Cr0.05,Ti0.05,Mo0.05,Ta0.05,Nb0.025,Zr0.025)(C0.9,N0.1)
Powder and 0.1g WC powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 4:1 ratio of grinding media to material loads abrading-ball, and adds 120ml to ball grinder
Alcohol, ball milling obtains compound in 4 hours in 48 hours after drying in oven for drying 70 DEG C；
(3) sinter
Sintered in confined reaction stove：
Compound prepared by step (2) is placed in induction heater, is begun to warm up simultaneously after reacting furnace is evacuated into 1Pa
Continue to vacuumize, when reaction in-furnace temperature rises to 900 DEG C, the heat preservation sintering 2 hours at this temperature and continuation vacuumized conditions,
Heat preservation sintering cools to temperature with the furnace and is come out of the stove less than 100 DEG C after terminating；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 500 mesh sieves, that is, Co-10%Fe-5% (V are obtained0.75,Cr0.05,
Ti0.05,Mo0.05,Ta0.05,Nb0.025,Zr0.025)(C0.9,N0.1) -0.1%WC hard alloy is with nitrogenous foundry alloy Binder Phase powder
Body.
Embodiment 5
Novel hard alloy prepared by the present embodiment is Co-26% (Cr with nitrogenous foundry alloy Binder Phase powder0.85,
Ta0.15)2(C0.5,N0.5) -1%WC-1%TiC-1%TaC-1%NbC, processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 70g Co powder, 26g (Cr0.85,Ta0.15)2(C0.5,N0.5) powder, 1g WC powder, 1g TiC powder, 1g TaC powder and 1g NbC powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 80ml wine to ball grinder
Essence, ball milling obtains compound in 24 hours after being dried 4 hours in oven for drying 70 DEG C；
(3) sinter
Sintered in open reactive stove：
Push boat type controlled atmosphere tube furnace gas outlet open in the state of heating reaction furnace and to reacting furnace in be passed through stream
Dynamic argon gas, when the temperature that region is sintered in reacting furnace rises to 600 DEG C, reaction is continuously introduced into by step (2) gained compound
The sintering region of stove heat preservation sintering under mobile status, compound moves out sintering region for 6 hours and enters in sintering zone sintering
The cooled region of reacting furnace is cooled below 100 DEG C and comes out of the stove；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 500 mesh sieves, that is, Co-26% (Cr are obtained0.85,Ta0.15)2(C0.5,
N0.5) -1%WC-1%TiC-1%TaC-1%NbC hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Embodiment 6
Novel hard alloy prepared by the present embodiment is Co-30% (Cr with nitrogenous foundry alloy Binder Phase powder0.8,V0.1,
Mo0.1)2(C0.4,N0.6), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 70g Co powder and 30g (Cr0.8,V0.1,Mo0.1)2(C0.4,N0.6) powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 8:1 ratio of grinding media to material loads abrading-ball, and adds 100ml to ball grinder
Alcohol, ball milling obtains compound in 36 hours after being dried 4 hours in oven for drying 70 DEG C；
(3) sinter
Sintered in open reactive stove：
Push boat type controlled atmosphere tube furnace gas outlet open in the state of heating reaction furnace and to reacting furnace in be passed through stream
Dynamic argon gas and hydrogen are with volume ratio 60:The mixed gas of 40 mixing, when the temperature that region is sintered in reacting furnace rises to 1300 DEG C
When, step (2) gained compound is continuously introduced into the sintering region of the reacting furnace heat preservation sintering under mobile status, compound is burning
Tie region sintering moves out sintering region for 0.5 hour and is cooled below 100 DEG C into the cooled region of reacting furnace and comes out of the stove；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 300 mesh sieves, that is, Co-30% (Cr are obtained0.8,V0.1,Mo0.1)2
(C0.4,N0.6) hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Embodiment 7
Novel hard alloy prepared by the present embodiment is Co-10%Ni-15% with nitrogenous foundry alloy Binder Phase powder
(V0.75,Nb0.15,Zr0.1)(C0.7,N0.3), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase and the content dispensing of each component, weigh
75g Co powder, 10g Ni powder and 15g (V0.75,Nb0.15,Zr0.1)(C0.7,N0.3) powder, it is fitted into ball grinder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 8:1 ratio of grinding media to material loads abrading-ball, and adds 100ml to ball grinder
Alcohol, ball milling obtains compound in 36 hours after being dried 4 hours in oven for drying 70 DEG C；
(3) sinter
Sintered in open reactive stove：
Push boat type controlled atmosphere tube furnace gas outlet open in the state of heating reaction furnace and to reacting furnace in be passed through stream
Dynamic nitrogen, when the temperature that region is sintered in reacting furnace rises to 1100 DEG C, reaction is continuously introduced into by step (2) gained compound
The sintering region of stove heat preservation sintering under mobile status, compound moves out sintering region for 1 hour and enters in sintering zone sintering
The cooled region of reacting furnace is cooled below 100 DEG C and comes out of the stove；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 200 mesh sieves, that is, Co-10Ni-15% (V are obtained0.75,Nb0.15,
Zr0.1)(C0.7,N0.3) hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Embodiment 8
Novel hard alloy manufactured in the present embodiment is Co-20% (Ti with nitrogenous foundry alloy Binder Phase powder0.4,V0.3,
Ta0.1)2(C0.5,N0.5), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 80g Co powder and 20g (Ti0.4,V0.3,Ta0.1)2(C0.5,N0.5) powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 80ml wine to ball grinder
Essence, ball milling obtains compound in 24 hours after being dried 4 hours in oven for drying 70 DEG C；
(3) sinter
Sintered in open reactive stove：
The ammonia of flowing is passed through in heating reaction furnace in the state of tube type resistance furnace gas outlet is opened and to reacting furnace, when
When the temperature in sintering region rises to 1000 DEG C in reacting furnace, step (2) gained compound is continuously introduced into the sintering zone of reacting furnace
Domain heat preservation sintering under mobile status, compound moves out sintering region for 1 hour and enters the cold of reacting furnace in sintering zone sintering
But region is cooled below 100 DEG C and comes out of the stove；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 500 mesh sieves, that is, Co-20% (Ti are obtained0.4,V0.3,Ta0.1)2
(C0.5,N0.5) hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Embodiment 9
Hard alloy prepared by the present embodiment is Co-15% (Cr with nitrogenous foundry alloy Binder Phase powder0.9,Ta0.1)2
(C0.5,N0.5) -5% (V0.8,Ti0.2)(C0.5,N0.5) -5% (Ti0.9,Mo0.1)(C0.5,N0.5) -2%NbC, processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 75g Co powder, 15g (Cr0.9,Ta0.1)2(C0.5,N0.5) powder, 5g (V0.8,Ti0.2)(C0.5,N0.5) powder, 5g (Ti0.9,Mo0.1)
(C0.5,N0.5) powder and 2g NbC powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 80ml wine to ball grinder
Essence, ball milling obtains compound in 24 hours after being dried 4 hours in oven for drying 70 DEG C；
(3) sinter
Sintered in confined reaction stove：
Compound prepared by step (2) is placed in the inflatable tube furnace of vacuum, reacting furnace is evacuated to 1 × 10-2Pa
After begin to warm up and continue to vacuumize, when reacting in-furnace temperature and rising to 1350 DEG C, in this temperature and continue under vacuumized conditions
Heat preservation sintering 0.5 hour, heat preservation sintering cools to temperature with the furnace and is come out of the stove less than 100 DEG C after terminating；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 500 mesh sieves, that is, Co-15% (Cr are obtained0.9,Ta0.1)2(C0.5,
N0.5) -5% (V0.8,Ti0.2)(C0.5,N0.5) -5% (Ti0.9,Mo0.1)(C0.5,N0.5) -2%NbC hard alloy female closes with nitrogenous
Golden Binder Phase powder.
Embodiment 10
Novel hard alloy prepared by the present embodiment is Co-10% (V with nitrogenous foundry alloy Binder Phase powder0.8,Cr0.2)
(C0.5,N0.5), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 75.21g cobaltosic oxides, 5.80g vanadium trioxides powder, 1.47g chrome greens powder and 17.52g graphite powders；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 100ml to ball grinder
Alcohol, ball milling obtains compound in 4 hours in 36 hours after drying in oven for drying 70 DEG C；
(3) sinter
Sintered in confined reaction stove：
Compound prepared by step (2) is placed in microwave agglomerating furnace, reacting furnace is evacuated to 1 × 10-2Start after Pa
Heat and continue to vacuumize, when reacting in-furnace temperature and rising to 800 DEG C, stopping is vacuumized and to being passed through nitrogen to nitrogen in reacting furnace
Air pressure is 0.01MPa, the heat preservation sintering 6 hours at this nitrogen pressure and 800 DEG C, and it is low that heat preservation sintering cools to temperature with the furnace after terminating
Come out of the stove in 100 DEG C；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 500 mesh sieves, that is, Co-10% (V are obtained0.8,Cr0.2)(C0.5,
N0.5) hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Embodiment 11
Novel hard alloy prepared by the present embodiment is Co-5%Fe-15% with nitrogenous foundry alloy Binder Phase powder
(Cr0.85,V0.1,Ta0.05)2(C0.5,N0.5), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 329.97g cobalt sesquioxides powder, 20.69g ferric oxide powders, 43.80g chrome greens powder, 6.17g vanadic anhydrides
Powder, 7.49g tantalum pentoxides powder and 91.88g carbon powders；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 600ml to ball grinder
Alcohol, ball milling obtains compound in 24 hours after being dried 4 hours in oven for drying 70 DEG C；
(3) sinter
Sintered in confined reaction stove：
Compound prepared by step (2) is placed in microwave agglomerating furnace, reacting furnace is evacuated to 1 × 10-1Start after Pa
Heat and continue to vacuumize, when reacting in-furnace temperature and rising to 1600 DEG C, stopping is vacuumized and to being passed through nitrogen in reacting furnace extremely
Nitrogen pressure is 0.1MPa, the heat preservation sintering 1 hour at this nitrogen pressure and 1600 DEG C, and heat preservation sintering cools to temperature with the furnace after terminating
Come out of the stove less than 100 DEG C；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 200 mesh sieves, that is, Co-5%Fe-15% (Cr are obtained0.85,V0.1,
Ta0.05)2(C0.5,N0.5) hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Embodiment 12
Novel hard alloy prepared by the present embodiment is Ni-20% (V with nitrogenous foundry alloy Binder Phase powder0.6,Ti0.1,
Mo0.1,Nb0.1,Zr0.1)(C0.1,N0.9), processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase powder and the content dispensing of each component,
Weigh 328.06g nickel sesquioxides powder, 41.18g vanadic anhydrides powder, 6.02g titanium dioxide powders, 10.86g molybdenum trioxides powder,
10.02g niobium pentaoxides powder, 9.29g titanium dioxides zirconium powder, 54.57g graphite powders and 40g activated carbon powders；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 600ml to ball grinder
Alcohol, ball milling obtains compound in 24 hours after being dried 4 hours in oven for drying 70 DEG C；
(3) sinter
Sintered in confined reaction stove：
Compound prepared by step (2) is placed in microwave agglomerating furnace, is begun to warm up simultaneously after reacting furnace is evacuated into 1Pa
Continue to vacuumize, when reacting in-furnace temperature and rising to 1200 DEG C, stopping is vacuumized and to being passed through nitrogen to nitrogen pressure in reacting furnace
It is 0.06MPa, the heat preservation sintering 2 hours at this nitrogen pressure and 1200 DEG C, heat preservation sintering cools to temperature with the furnace and is less than after terminating
100 DEG C are come out of the stove；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 300 mesh sieves, that is, Ni-20% (V are obtained0.6,Ti0.1,Mo0.1,
Nb0.1,Zr0.1)(C0.1,N0.9) hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Embodiment 13
Novel hard alloy prepared by the present embodiment is Co-15% (Ti with nitrogenous foundry alloy Binder Phase powder0.9,
Mo0.1)(C0.1,N0.9) -5%TaC, processing step is as follows：
(1) dispensing
According to prepared the hard alloy chemical formula of nitrogenous foundry alloy Binder Phase and the content dispensing of each component, weigh
336.13g cobalt sesquioxides powder, 48.42g titanium dioxide powders, 9.70g molybdenum trioxides powder, 50g graphite powders, 40.82g activated carbon powders
With 14.93g TaC powder；
(2) batch mixing and drying
The raw material that will be prepared is fitted into ball grinder, according to 6:1 ratio of grinding media to material loads abrading-ball, and adds 600ml to ball grinder
Alcohol, ball milling obtains compound in 24 hours after being dried 4 hours in oven for drying 70 DEG C；
(3) sinter
Sintered in open reactive stove：
Push boat type controlled atmosphere tube furnace gas outlet open in the state of heating reaction furnace and to reacting furnace in be passed through stream
Dynamic nitrogen, when the temperature that region is sintered in reacting furnace rises to 1600 DEG C, reaction is continuously introduced into by step (2) gained compound
The sintering region of stove heat preservation sintering under mobile status, compound moves out sintering region for 0.5 hour and enters in sintering zone sintering
The cooled region for entering reacting furnace is cooled below 100 DEG C and comes out of the stove；
(4) crush
By the product after coming out of the stove is by ball mill crushing and crosses 300 mesh sieves, that is, Ni-20% (V are obtained0.6,Ti0.1,Mo0.1,
Nb0.1,Zr0.1)(C0.1,N0.9) hard alloy is with nitrogenous foundry alloy Binder Phase powder.
Comparative example 1
Nitrogenous foundry alloy Binder Phase powder Co-15% (Cr prepared by embodiment 10.8,V0.2)2(C0.5,N0.5) for making
Standby hard alloy.
Nitrogenous foundry alloy Binder Phase powder prepared by 90g WC powder, 5g Co powder and 5g embodiments 1 is weighed respectively, then will
The above-mentioned material powder for measuring loads ball grinder, according to 8:1 ratio of grinding media to material loads abrading-ball, pours into 100mL alcohol, and ball milling 48 is small
When obtain compound, add colloid forming agent polyethylene glycol and granulating after compound is dried, granular material is obtained；
The granular material for weighing constant weight loads in mould, is pressed into hard alloy blank, is then loaded into low
In pressure sintering furnace, 1 × 10 is evacuated to-1Pa, protects when reacting in-furnace temperature and rising to 600 DEG C at the temperature and vacuumized conditions
Colloid in 2 hours removing hard alloy blanks of temperature, is then warming up to 1400 DEG C under vacuumized conditions, in the temperature and takes out true
Lower 1 hour of empty condition, insulation stops vacuumizing after terminating, to being passed through argon gas in sintering furnace to 2MPa and maintain in-furnace temperature to exist
1400 DEG C are continued to be incubated 0.5 hour, and insulation cools to room temperature with the furnace and obtains the hard based on nitrogenous foundry alloy Binder Phase after terminating
Alloy, after testing, the bending strength of the hard alloy is 4350MPa, and dimension formula hardness is 1610, and fracture toughness is 16.3MPa
m1/2。
Comparative example 2
By multi-element composite carbon nitride thing (grain growth inhibitor) (Cr0.8,V0.2)2(C0.5,N0.5) for preparing hard conjunction
Gold.
Weighing 90g WC powder, 9.25g Co powder and 0.75g multi-element composite carbon nitride thing powder respectively (can be by patent application
CN104046828A methods describeds are prepared and obtained), the above-mentioned material powder for measuring then is loaded into ball grinder, according to 8:1
Ratio of grinding media to material loads abrading-ball, pours into 100mL alcohol, and ball milling obtains compound in 48 hours, and colloid shaping is added after compound is dried
Agent polyethylene glycol is simultaneously granulated, and granular material is obtained；
The granular material for weighing constant weight loads in mould, is pressed into hard alloy blank, then loads blank
In low-pressure sintering furnace, 1 × 10 is evacuated to-1Pa, when reacting in-furnace temperature and rising to 600 DEG C at the temperature and vacuumized conditions
Colloid in 2 hours removing hard alloy blanks of insulation, is then warming up to 1400 DEG C under vacuumized conditions, the temperature and is taking out
1 hour is incubated under vacuum condition, insulation stops vacuumizing after terminating, to being passed through argon gas in sintering furnace to 2MPa and remain in stove warm
Degree continues to be incubated 0.5 hour at 1400 DEG C, and insulation cools to room temperature with the furnace after terminating, and obtains thing containing multi-element composite carbon nitride (brilliant
The big inhibitor of grain length) hard alloy.After testing, the bending strength of the hard alloy is 3960MPa, and dimension formula hardness is 1550,
Fracture toughness is 13.2MPam1/2。
Comparative example 3
By grain growth inhibitor Cr3C2It is used to prepare hard alloy with VC.
90g WC powder, 9.25g Co powder, 0.59g Cr are weighed respectively3C2Powder and 0.16g VC powder, then measure above-mentioned
Material powder load ball grinder, according to 8:1 ratio of grinding media to material loads abrading-ball, pours into 100mL alcohol, and ball milling is mixed for 48 hours
Material, adds colloid forming agent polyethylene glycol and granulates after compound is dried, granular material is obtained；
The granular material for weighing constant weight loads in mould, is pressed into hard alloy blank, is then loaded into low
In pressure sintering furnace, 1 × 10 is evacuated to-1Pa, protects when reacting in-furnace temperature and rising to 600 DEG C at the temperature and vacuumized conditions
Colloid in 2 hours removing hard alloy blanks of temperature, is then warming up to 1400 DEG C under vacuumized conditions, in the temperature and takes out true
1 hour is incubated under empty condition, insulation stops vacuumizing after terminating, to being passed through argon gas in sintering furnace to 2MPa and and remain in stove warm
Degree continues to be incubated 0.5 hour at 1400 DEG C, and insulation cools to room temperature with the furnace after terminating, and obtains containing combination grain growth inhibitor
Hard alloy.After testing, the bending strength of the hard alloy is 3310MPa, and dimension formula hardness is 1496, and fracture toughness is
10.1MPa·m1/2。
Be can be seen that from above-mentioned comparative example and prepare hard alloy and use using nitrogenous foundry alloy Binder Phase of the present invention
Multi-element composite carbon nitride thing (grain growth inhibitor) is applied in combination grain growth inhibitor and prepares hard alloy and compares, can
Preferably improve the comprehensive mechanical performance of hard alloy.
Claims (6)
1. a kind of hard alloy is with nitrogenous foundry alloy Binder Phase powder, it is characterised in that by mass fraction be 5%~50% it is many
The compound carbonitride of unit and the Binder Phase metal composition that mass fraction is 50%~95%, structure is with Binder Phase metal as molten
Agent, the solid solution phase with multi-element composite carbon nitride thing as solute, or structure are with Binder Phase metal as solvent, with multiple elements design carbon nitrogen
Compound is the solid solution phase of solute and the compound phase of multi-element composite carbon nitride thing composition；
The multi-element composite carbon nitride thing is carbon chromium nitride based solid solution (Cry,M11-y)2(Cx,N1-x), vanadium carbide nitride based solid solution
(Vy,M21-y)(Cx,N1-x), titanium carbonitride based solid solution (Tiy,M31-y)(Cx,N1-x) at least one, Binder Phase gold
It is at least one in cobalt, nickel, iron to belong to；
(the Cry,M11-y)2(Cx,N1-x) in, constituent element M1 be vanadium, titanium, molybdenum, tantalum, niobium, zirconium at least one, 0.1≤x≤
0.9,0.5 ＜ y≤0.95；(the Vy,M21-y)(Cx,N1-x) in, constituent element M2 is at least in chromium, titanium, molybdenum, tantalum, niobium, zirconium
Kind, 0.1≤x≤0.9,0.5 ＜ y≤0.95；(the Tiy,M31-y)(Cx,N1-x) in, M3 is in vanadium, chromium, molybdenum, tantalum, niobium, zirconium
At least one, 0.1≤x≤0.9,0.5 ＜ y≤0.95.
2. a kind of hard alloy is with nitrogenous foundry alloy Binder Phase powder, it is characterised in that by mass fraction be 5%~49.9%
Multi-element composite carbon nitride thing, mass fraction are 50%~90% Binder Phase metal and the additive of mass fraction 0.1%~5%
Composition, structure is the solid solution phase with Binder Phase metal as solvent, with multi-element composite carbon nitride thing and additive as solute, or structure
It is the solid solution phase and multi-element composite carbon nitride with Binder Phase metal as solvent, with multi-element composite carbon nitride thing and additive as solute
The compound phase of thing, additive composition；
The multi-element composite carbon nitride thing is carbon chromium nitride based solid solution (Cry,M11-y)2(Cx,N1-x), vanadium carbide nitride based solid solution
(Vy,M21-y)(Cx,N1-x), titanium carbonitride based solid solution (Tiy,M31-y)(Cx,N1-x) at least one, Binder Phase gold
It is at least one in cobalt, nickel, iron to belong to, and the additive is at least one in WC, TiC, TaC, NbC；
(the Cry,M11-y)2(Cx,N1-x) in, constituent element M1 be vanadium, titanium, molybdenum, tantalum, niobium, zirconium at least one, 0.1≤x≤
0.9,0.5 ＜ y≤0.95；(the Vy,M21-y)(Cx,N1-x) in, constituent element M2 is at least in chromium, titanium, molybdenum, tantalum, niobium, zirconium
Kind, 0.1≤x≤0.9,0.5 ＜ y≤0.95；(the Tiy,M31-y)(Cx,N1-x) in, M3 is in vanadium, chromium, molybdenum, tantalum, niobium, zirconium
At least one, 0.1≤x≤0.9,0.5 ＜ y≤0.95.
3. hard alloy described in claim 1 is with nitrogenous foundry alloy Binder Phase raw powder's production technology, it is characterised in that technique is walked
It is rapid as follows：
(1) dispensing
Raw material is at least one in cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,N1-x) powder,
(Tiy,M31-y)(Cx,N1-x) at least one in powder；
Or raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,N1-x)
The oxide and carbon source, (V of middle metal constituent elementy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,M31-y)
(Cx,N1-x) in metal constituent element oxide and carbon source at least one；
(the Cry,M11-y)2(Cx,N1-x) in, constituent element M1 be vanadium, titanium, molybdenum, tantalum, niobium, zirconium at least one, 0.1≤x≤
0.9,0.5 ＜ y≤0.95；(the Vy,M21-y)(Cx,N1-x) in, constituent element M2 is at least in chromium, titanium, molybdenum, tantalum, niobium, zirconium
Kind, 0.1≤x≤0.9,0.5 ＜ y≤0.95；(the Tiy,M31-y)(Cx,N1-x) in, M3 is in vanadium, chromium, molybdenum, tantalum, niobium, zirconium
At least one, 0.1≤x≤0.9,0.5 ＜ y≤0.95；
According to hard alloy described in claim 1 component of nitrogenous foundry alloy Binder Phase powder and the mass fraction meter of each component
Measure various raw materials；
(2) batch mixing and drying
Each raw material is uniform by ball milling mixing, then dry to obtain compound；
(3) sinter
Sintered in confined reaction stove：
At least one in raw material is cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,N1-x)
Powder, (Tiy,M31-y)(Cx,N1-x) at least one in powder when, use first method：Compound prepared by step (2) is placed in
In reacting furnace, reacting furnace is evacuated to 1~1 × 10-2Begin to warm up and continue to vacuumize after Pa, when reaction in-furnace temperature rises to
At 600~1350 DEG C, the heat preservation sintering 0.5~6 hour at this temperature and continuation vacuumized conditions, heat preservation sintering is being taken out after terminating
Temperature is cooled under vacuum condition with the furnace to be come out of the stove less than 100 DEG C；
When raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,N1-x) in
The oxide and carbon source of metal constituent element, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,M31-y)
(Cx,N1-x) in metal constituent element oxide and carbon source in it is at least one when, use second method：It is prepared by step (2)
Compound is placed in reacting furnace, and reacting furnace is evacuated into 1~1 × 10-2Begin to warm up and continue to vacuumize after Pa, when temperature liter
It is 0.01~0.1MPa to nitrogen to nitrogen pressure is passed through in reacting furnace, in this nitrogen pressure to stopping vacuumizing at 800~1600 DEG C
With 800~1600 DEG C at heat preservation sintering 1~6 hour, heat preservation sintering cools to temperature with the furnace and is come out of the stove less than 100 DEG C after terminating；
Or sintered in open reactive stove：
Protective gas or the reaction of flowing are passed through in heating reaction furnace in the state of reacting furnace gas outlet is opened and to reacting furnace
Gas, when the temperature that region is sintered in reacting furnace rises to 600~1600 DEG C, step (2) gained compound is continuously introduced into instead
The sintering region of the stove heat preservation sintering under mobile status, compound is answered to move out sintering zone within 0.5~6 hour in sintering zone sintering
Domain is cooled below 100 DEG C and comes out of the stove into the cooled region of reacting furnace；
At least one in raw material is cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,N1-x)
Powder, (Tiy,M31-y)(Cx,N1-x) at least one in powder when, to the protective gas that flowing is passed through in reacting furnace；
When raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,N1-x) in
The oxide and carbon source of metal constituent element, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,M31-y)
(Cx,N1-x) in metal constituent element oxide and carbon source in it is at least one when, to the reacting gas that flowing is passed through in reacting furnace；
(4) crush
By the product after coming out of the stove is by ball mill crushing and sieves, that is, the nitrogenous foundry alloy Binder Phase powder of hard alloy is obtained.
4. hard alloy described in claim 2 is with nitrogenous foundry alloy Binder Phase raw powder's production technology, it is characterised in that technique is walked
It is rapid as follows：
(1) dispensing
Raw material is at least one in cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,N1-x) powder,
(Tiy,M31-y)(Cx,N1-x) at least one in powder, at least one in WC powder, TiC powder, TaC powder, NbC powder；
Or raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,N1-x)
The oxide and carbon source, (V of middle metal constituent elementy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,M31-y)
(Cx,N1-x) in metal constituent element oxide and carbon source at least one, in WC powder, TiC powder, TaC powder, NbC powder at least one
Kind；
(the Cry,M11-y)2(Cx,N1-x) in, constituent element M1 be vanadium, titanium, molybdenum, tantalum, niobium, zirconium at least one, 0.1≤x≤
0.9,0.5 ＜ y≤0.95；(the Vy,M21-y)(Cx,N1-x) in, constituent element M2 is at least in chromium, titanium, molybdenum, tantalum, niobium, zirconium
Kind, 0.1≤x≤0.9,0.5 ＜ y≤0.95；(the Tiy,M31-y)(Cx,N1-x) in, M3 is in vanadium, chromium, molybdenum, tantalum, niobium, zirconium
At least one, 0.1≤x≤0.9,0.5 ＜ y≤0.95；
According to hard alloy described in claim 2 component of nitrogenous foundry alloy Binder Phase powder and the mass fraction meter of each component
Measure various raw materials；
(2) batch mixing and drying
Each raw material is uniform by ball milling mixing, then dry to obtain compound；
(3) sinter
Sintered in confined reaction stove：
At least one in raw material is cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,N1-x)
Powder, (Tiy,M31-y)(Cx,N1-x) at least one in powder, during at least one in WC powder, TiC powder, TaC powder, NbC powder, use
First method：Compound prepared by step (2) is placed in reacting furnace, reacting furnace is evacuated to 1~1 × 10-2Opened after Pa
Beginning heats and continues to vacuumize, when reaction in-furnace temperature rises to 600~1350 DEG C, at this temperature and continuation vacuumized conditions
Heat preservation sintering 0.5~6 hour, heat preservation sintering cools to temperature with the furnace under vacuumized conditions and is come out of the stove less than 100 DEG C after terminating, i.e.,
Obtain the nitrogenous foundry alloy Binder Phase of hard alloy；
When raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,N1-x) in
The oxide and carbon source of metal constituent element, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,M31-y)
(Cx,N1-x) in metal constituent element oxide and carbon source at least one, in WC powder, TiC powder, TaC powder, NbC powder at least one
When planting, second method is used：Compound prepared by step (2) is placed in reacting furnace, reacting furnace is evacuated to 1~1 ×
10-2Begin to warm up and continue to vacuumize after Pa, stop vacuumizing when temperature rises to 800~1600 DEG C, to being passed through in reacting furnace
Nitrogen to nitrogen pressure is 0.01~0.1MPa, heat preservation sintering 1~6 hour, heat preservation sintering at this nitrogen pressure and 800~1600 DEG C
Cool to temperature after end with the furnace to be come out of the stove less than 100 DEG C, obtain final product hard alloy with nitrogenous foundry alloy Binder Phase；
Or sintered in open reactive stove：
Protective gas or the reaction of flowing are passed through in heating reaction furnace in the state of reacting furnace gas outlet is opened and to reacting furnace
Gas, when the temperature that region is sintered in reacting furnace rises to 600~1600 DEG C, step (2) gained compound is continuously introduced into instead
The sintering region of the stove heat preservation sintering under mobile status, compound is answered to move out sintering zone within 0.5~6 hour in sintering zone sintering
Domain is cooled below 100 DEG C and comes out of the stove into the cooled region of reacting furnace, that is, hard alloy is obtained and is bonded with nitrogenous foundry alloy
Phase；
At least one in raw material is cobalt powder, nickel powder, iron powder, (Cry,M11-y)2(Cx,N1-x) powder, (Vy,M21-y)(Cx,N1-x)
Powder, (Tiy,M31-y)(Cx,N1-x) at least one in powder, during at least one in WC powder, TiC powder, TaC powder, NbC powder, to anti-
Answer the protective gas that flowing is passed through in stove；
When raw material is at least one in oxide, the oxide of nickel, the oxide of iron of cobalt, (Cry,M11-y)2(Cx,N1-x) in
The oxide and carbon source of metal constituent element, (Vy,M21-y)(Cx,N1-x) in metal constituent element oxide and carbon source, (Tiy,M31-y)
(Cx,N1-x) in metal constituent element oxide and carbon source at least one, in WC powder, TiC powder, TaC powder, NbC powder at least one
When planting, to the reacting gas that flowing is passed through in reacting furnace；
(4) crush
By the product after coming out of the stove is by ball mill crushing and sieves, that is, the nitrogenous foundry alloy Binder Phase powder of hard alloy is obtained.
5. hard alloy described in claim 3 or 4 is with nitrogenous foundry alloy Binder Phase raw powder's production technology, it is characterised in that described
The oxide of cobalt is at least one in cobalt black, cobalt sesquioxide, cobaltosic oxide；The oxide of nickel be nickel monoxide,
At least one in nickel sesquioxide；The oxide of iron is at least one in di-iron trioxide, ferroso-ferric oxide；
(the Cry,M11-y)2(Cx,N1-x) in metal constituent element oxide and carbon source, (Vy,M21-y)(Cx,N1-x) in metal constituent element
Oxide and carbon source, (Tiy,M31-y)(Cx,N1-x) in metal constituent element oxide and carbon source in, the oxide of metal constituent element is such as
Under：The oxide of vanadium is at least one in vanadic anhydride, vanadium trioxide；The oxide of chromium is chrome green；Titanium
Oxide is titanium dioxide；The oxide of molybdenum is molybdenum trioxide；The oxide of tantalum is tantalum pentoxide；The oxide of niobium is five oxygen
Change two niobiums；The oxide of zirconium is zirconium dioxide；Carbon source is at least one in carbon black, activated carbon, graphite.
6. according to claim 3 or 4 hard alloy with nitrogenous foundry alloy Binder Phase raw powder's production technology, it is characterised in that
When step (3) is sintered in open reactive stove, the protective gas is at least one in argon gas, hydrogen, nitrogen；It is described
Reacting gas is at least one in nitrogen, ammonia.
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