CN105219997A - Wimet nitrogenous mother alloy Binder Phase powder and preparation method thereof - Google Patents
Wimet nitrogenous mother alloy Binder Phase powder and preparation method thereof Download PDFInfo
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Abstract
The nitrogenous mother alloy Binder Phase powder of the first Wimet of the present invention, by massfraction be 5% ~ 50% multiple elements design grain growth inhibitor and massfraction be 50% ~ 95% Binder Phase metal form.The nitrogenous mother alloy Binder Phase powder of described the second Wimet, the multiple elements design grain growth inhibitor, the massfraction that are 5% ~ 49.9% by massfraction are that the Binder Phase metal of 50% ~ 90% and the additive of massfraction 0.1% ~ 5% form.Present invention also offers the nitrogenous mother alloy Binder Phase raw powder's production technology of above-mentioned two kinds of Wimet, step is: (1) prepares burden; (2) batch mixing and drying; (3) sinter, (4) are broken.The preparation that the present invention is Wimet provides new bonding phase raw material, provides new way, thus be conducive to preparing the better Wimet of comprehensive mechanical performance such as hardness, intensity and toughness for introducing nitrogen element in Wimet.
Description
Technical field
The invention belongs to Wimet field, particularly relate to Wimet Binder Phase powder and preparation method thereof.
Background technology
Wimet, because having a series of excellent properties such as high hardness, wear resistance, red hardness and good toughness, is widely used in preparing cutting tool, mining and wear parts.Usual alloy rigidity is higher, and its wear resistance is better, and the obdurability (intensity and toughness) of alloy is higher, and its shock resistance is better.Therefore, hardness and obdurability have become the important indicator evaluating Cemented Carbide Properties.The regulation and control hardness of alloy and obdurability, mainly comprise the means such as the homogeneity that the content, hard-phase particles size, hard phase and the Binder Phase that control Binder Phase distribute.The particle size reducing Binder Phase content or reduction hard phase WC is conducive to putting forward heavy alloyed hardness, but can cause the reduction of alloy obdurability; Otherwise the particle size improving Binder Phase content or increase hard phase WC is then conducive to the raising of obdurability, but alloy rigidity can be caused to reduce.Therefore, the hardness of Wimet, intensity and toughness are difficult to be improved simultaneously, and this contradiction limits the further application of Wimet.
In the liquid phase sintering step of conventional rigid reasonable offer process, hard phase grain growth is the important factor affecting Cemented Carbide Hardness, intensity and toughness.Due to Ostwald slaking mechanism, liquid phase sintering must cause WC average particle size particle size in sintered compact to be greater than the average original dimension of its raw material, and namely sintering result in hard phase grain growth.Particularly preparing in ultra-fine cemented carbide process, be easy to cause grain discontinuity to grow up.In order to control growing up of crystal grain, in industrial production, the normal a small amount of grain growth inhibitor (grain-refining agent) that adds is (as VC, Cr
3c
2, TaC etc.) to obtain the tiny and uniform Wimet of granularity.But, existing commercially available conventional inhibitor granularity comparatively large (mostly more than micron level), do not mate with the granularity of raw material WC, cause preparing Wimet, when particularly preparing ultra-fine cemented carbide, inhibitor is difficult to be uniformly distributed in carbide alloy mixture, affects the effect of its inhibiting grain growth.Although it is better to combinationally use two kinds and above inhibitor effect, this improves the mixed uniformly difficulty of compound further, thus increases cost.Chinese patent CN102828061A, CN103343257A, CN104046828A discloses multiple elements design grain-refining agent and preparation method thereof, although solve the problem that need combinationally use two kinds and above inhibitor for improving thinning effect, but because the addition of inhibitor in Wimet is very low, general control at 1% (weight percentage) below, under existing working condition, by common mechanically mixing, still the homogeneity ensureing that the inhibitor of few additive like this distributes in compound is difficult to, finally be difficult to ensure the inhibition to hard phase grain growth.In addition, in existing preparation method, sintering temperature is very high, and then accelerates growing up of hard phase crystal grain, and Binder Phase occur the temperature of liquid phase too high be the first cause causing this problem.
Usually, in Wimet, introduce nitrogen unit have two kinds of approach: 1) by sintering in nitrogen atmosphere, nitrogen element is introduced to Wimet, the people such as N.G.Hashe (Int.J.Refract.Met. & HardMater.27 (2009) 20-25) have studied sintered hard alloy in a nitrogen atmosphere, result shows that N effectively can control grain growth, and the hard-phase particles size distribution ranges that narrows, the people such as C.Buchegger (Int.J.Refract.Met. & HardMater.49 (2015) 67-74) research shows sintered hard alloy under condition of nitrogen gas, the spread coefficient of inhibitor can be affected, 2) to add the mode of nitride/carbonitride, nitrogen element is introduced to Wimet, Chinese patent CN102534340B introduces nitrogen with multi-element composite titanium carbonitride solid solution in Wimet, effectively can improve interface wet ability, strengthening Binder Phase, crystal grain thinning, improve alloy property.As can be seen here, suitable introducing nitrogen element can produce obvious beneficial effect to Wimet, but all there is limitation in existing two kinds of modes introducing nitrogen element: the former only can introduce nitrogen element in alloy surface certain depth, and there is gradient, cannot obtain the Wimet that performance is homogeneous; Though the latter solves the gradient problem of nitrogen distribution to a certain extent, but nitrogen element is by the confinement of nitride/carbonitride particle, and its distributing homogeneity is affected.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, Wimet nitrogenous mother alloy Binder Phase powder and preparation method thereof is provided, so that the preparation for Wimet provides new bonding phase raw material, there is provided new way for introducing nitrogen element in Wimet, thus prepare the better Wimet of comprehensive mechanical performance such as hardness, intensity and toughness.
Wimet of the present invention is in conventional adhesive phase cobalt metal, nickel and iron, introduce multi-element composite carbon nitride thing formed with nitrogenous mother alloy Binder Phase powder, can be divided into two kinds according to whether adding additive.
The nitrogenous mother alloy Binder Phase powder of the first Wimet of the present invention, by massfraction be 5% ~ 50% multi-element composite carbon nitride thing and massfraction be 50% ~ 95% Binder Phase metal form, described multi-element composite carbon nitride thing is carbon chromium nitride based solid solution (Cr
y, M1
1-y)
2(C
x, N
1-x), vanadium carbide nitride based solid solution (V
y, M2
1-y) (C
x, N
1-x), titanium carbonitride based solid solution (Ti
y, M3
1-y) (C
x, N
1-x) at least one, described Binder Phase metal is at least one in cobalt, nickel, iron; Described (Cr
y, M1
1-y)
2(C
x, N
1-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; Described (V
y, M2
1-y) (C
x, N
1-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; Described (Ti
y, M3
1-y) (C
x, N
1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5 < y≤0.95.
The nitrogenous mother alloy Binder Phase powder of the first Wimet above-mentioned, structure be with Binder Phase metal be solvent, the solid solution phase that is solute with multi-element composite carbon nitride thing, or structure be with Binder Phase metal be solvent, the compound phase that forms with the multi-element composite carbon nitride thing solid solution phase that is solute and multi-element composite carbon nitride thing.
The nitrogenous mother alloy Binder Phase powder of the second Wimet of the present invention, the multi-element composite carbon nitride thing, the massfraction that are 5% ~ 49.9% by massfraction are that the Binder Phase metal of 50% ~ 90% and the additive of massfraction 0.1% ~ 5% form, and described multi-element composite carbon nitride thing is carbon chromium nitride based solid solution (Cr
y, M1
1-y)
2(C
x, N
1-x), vanadium carbide nitride based solid solution (V
y, M2
1-y) (C
x, N
1-x), titanium carbonitride based solid solution (Ti
y, M3
1-y) (C
x, N
1-x) at least one, described Binder Phase metal is at least one in cobalt, nickel, iron, and described additive is at least one in WC, TiC, TaC, NbC; Described (Cr
y, M1
1-y)
2(C
x, N
1-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; Described (V
y, M2
1-y) (C
x, N
1-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; Described (Ti
y, M3
1-y) (C
x, N
1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5 < y≤0.95.
Above-mentioned the second states the nitrogenous mother alloy Binder Phase powder of Wimet, structure be with Binder Phase metal be solvent, the solid solution phase that is solute with multi-element composite carbon nitride thing and additive, or structure be with Binder Phase metal be solvent, with the compound phase of multi-element composite carbon nitride thing and the additive solid solution phase that is solute and multi-element composite carbon nitride thing, additive.
The nitrogenous mother alloy Binder Phase raw powder's production technology of the first Wimet above-mentioned provided by the invention, processing step is as follows:
(1) prepare burden
Raw material is at least one in the oxide compound of cobalt powder, nickel powder, iron powder, the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source;
Described (Cr
y, M1
1-y)
2(C
x, N
1-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; Described (V
y, M2
1-y) (C
x, N
1-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; Described (Ti
y, M3
1-y) (C
x, N
1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5 < y≤0.95;
Various raw material is measured according to the first Wimet above-mentioned nitrogenous component of mother alloy Binder Phase powder and the massfraction of each component;
(2) batch mixing and drying
Each raw material is mixed by ball milling, then dries to obtain compound;
(3) sinter
Sinter in confined reaction stove:
When at least one that raw material is in cobalt powder, nickel powder, iron powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in powder time, use first method: compound prepared by step (2) is placed in Reaktionsofen, Reaktionsofen is evacuated to 1 ~ 1 × 10
-2start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 600 ~ 1350 DEG C, at this temperature and continuation vacuumized conditions, heat preservation sintering 0.5 ~ 6 hour, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C under vacuumized conditions after heat preservation sintering terminates;
When at least one that raw material is in the oxide compound of the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source time, use second method: compound prepared by step (2) is placed in Reaktionsofen, Reaktionsofen is evacuated to 1 ~ 1 × 10
-2start after Pa to heat and continue to vacuumize, stop vacuumizing when temperature rises to 800 ~ 1600 DEG C, in Reaktionsofen, pass into nitrogen to nitrogen pressure is 0.01 ~ 0.1MPa, heat preservation sintering 1 ~ 6 hour at this nitrogen pressure and 800 ~ 1600 DEG C, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C after heat preservation sintering terminates;
Or sinter in open reactive stove:
Heating reaction furnace under the state that Reaktionsofen air outlet is opened also passes into shielding gas or the reactant gases of flowing in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 600 ~ 1600 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 0.5 ~ 6 hour and is cooled to temperature and comes out of the stove lower than 100 DEG C;
When at least one that raw material is in cobalt powder, nickel powder, iron powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in powder time, in Reaktionsofen, pass into the shielding gas of flowing;
When at least one that raw material is in the oxide compound of the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source time, in Reaktionsofen, pass into the reactant gases of flowing;
(4) broken
Product after coming out of the stove is sieved by ball mill crushing, i.e. the obtained nitrogenous mother alloy Binder Phase powder of Wimet.
Above-mentioned the second provided by the invention states the nitrogenous mother alloy Binder Phase raw powder's production technology of Wimet, and processing step is as follows:
(1) prepare burden
Raw material is at least one in the oxide compound of cobalt powder, nickel powder, iron powder, the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source, at least one in WC powder, TiC powder, TaC powder, NbC powder;
Described (Cr
y, M1
1-y)
2(C
x, N
1-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; Described (V
y, M2
1-y) (C
x, N
1-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; Described (Ti
y, M3
1-y) (C
x, N
1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5 < y≤0.95;
Various raw material is measured according to above-mentioned the second Wimet nitrogenous component of mother alloy Binder Phase powder and the massfraction of each component;
(2) batch mixing and drying
Each raw material is mixed by ball milling, then dries to obtain compound;
(3) sinter
Sinter in confined reaction stove:
When at least one that raw material is in cobalt powder, nickel powder, iron powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-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 Reaktionsofen, Reaktionsofen is evacuated to 1 ~ 1 × 10
-2start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 600 ~ 1350 DEG C, heat preservation sintering 0.5 ~ 6 hour at this temperature and continuation vacuumized conditions, under vacuumized conditions, cool to temperature after heat preservation sintering terminates with the furnace come out of the stove lower than 100 DEG C, obtain the nitrogenous mother alloy Binder Phase of Wimet;
When at least one that raw material is in the oxide compound of the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source, during at least one in WC powder, TiC powder, TaC powder, NbC powder, use second method: compound prepared by step (2) is placed in Reaktionsofen, Reaktionsofen is evacuated to 1 ~ 1 × 10
-2start after Pa to heat and continue to vacuumize, stop vacuumizing when temperature rises to 800 ~ 1600 DEG C, in Reaktionsofen, pass into nitrogen to nitrogen pressure is 0.01 ~ 0.1MPa, heat preservation sintering 1 ~ 6 hour at this nitrogen pressure and 800 ~ 1600 DEG C, cool to temperature after heat preservation sintering terminates with the furnace to come out of the stove lower than 100 DEG C, obtain the nitrogenous mother alloy Binder Phase of Wimet;
Or sinter in open reactive stove:
Heating reaction furnace under the state that Reaktionsofen air outlet is opened also passes into shielding gas or the reactant gases of flowing in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 600 ~ 1600 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 0.5 ~ 6 hour and is cooled to temperature and comes out of the stove lower than 100 DEG C, i.e. the obtained nitrogenous mother alloy Binder Phase of Wimet;
When at least one that raw material is in cobalt powder, nickel powder, iron powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in powder, during at least one in WC powder, TiC powder, TaC powder, NbC powder, in Reaktionsofen, pass into the shielding gas of flowing;
When at least one that raw material is in the oxide compound of the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source, during at least one in WC powder, TiC powder, TaC powder, NbC powder, in Reaktionsofen, pass into the reactant gases of flowing.
(4) broken
Product after coming out of the stove is sieved by ball mill crushing, i.e. the obtained nitrogenous mother alloy Binder Phase powder of Wimet.
The nitrogenous mother alloy Binder Phase raw powder's production technology of above-mentioned two kinds of Wimet, the oxide compound of described cobalt is at least one in cobalt monoxide, cobalt sesquioxide, tricobalt tetroxide; The oxide compound of nickel is at least one in nickel protoxide, nickel sesquioxide; The oxide compound of iron is at least one in ferric oxide, Z 250;
Described (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, the oxide compound of metal constituent element is as follows: the oxide compound of vanadium is at least one in Vanadium Pentoxide in FLAKES, vanadous oxide; The oxide compound of chromium is chromium sesquioxide; Titanyl compound is titanium dioxide; The oxide compound of molybdenum is molybdic oxide; The oxide compound of tantalum is tantalum pentoxide; The oxide compound of niobium is Niobium Pentxoxide; The oxide compound of zirconium is zirconium dioxide; Carbon source is at least one in carbon black, gac, graphite.
The nitrogenous mother alloy Binder Phase raw powder's production technology of above-mentioned two kinds of Wimet, when step (3) sinters in open reactive stove, described shielding gas is at least one in argon gas, hydrogen, nitrogen; Described reactant gases is at least one in nitrogen, ammonia.
The nitrogenous mother alloy Binder Phase raw powder's production technology of above-mentioned two kinds of Wimet, described (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder by " the multi-component nanograin growth inhibitor preparation method containing high-energy-milling " disclosed in patent application CN104046828A obtain, described (Ti
y, M3
1-y) (C
x, N
1-x) powder obtains by method disclosed in paper the research of CRN method preparation (Ti, W, Mo, V) CN solid-solution powder " under the open system " (Zhu Yunfeng etc., functional materials, the 17th phase 43 volume in 2012).
Compared with prior art, the present invention has following beneficial effect:
1, the present invention is that the preparation of Wimet provides new bonding phase raw material, and in Binder Phase, introduces nitrogen element first, provides a kind of new way for introducing nitrogen element in Wimet.
2, the method of the invention prepares nitrogenous mother alloy Binder Phase powder by being evenly spread in Binder Phase with vast scale by multi-element composite carbon nitride thing (grain growth inhibitor), realize in Wimet, adding multi-element composite carbon nitride thing with the form of mother alloy, because the content of multi-element composite carbon nitride thing in Binder Phase is far away higher than content when being directly added in hard phase, compare and be directly added in hard phase, it is added in Binder Phase and more easily fully mixes, when again the Binder Phase that multi-element composite carbon nitride thing has mixed being mixed with hard phase, the homogeneity that multi-element composite carbon nitride thing distributes in Wimet can be significantly improved.Moreover, the nitrogenous mother alloy Binder Phase of Wimet of the present invention is compared with iron with Binder Phase cobalt metal, nickel, fusing point is lower, when preparing Wimet, sintering occurs that the temperature of liquid phase significantly reduces, above-mentioned two kinds of factors are all conducive to preparing that crystal grain is tiny, microtexture evenly Wimet.
3, by nitrogenous mother alloy Binder Phase of the present invention, nitrogen element is introduced Wimet, nitrogen element can be made to be more evenly distributed in Wimet, be conducive to the homogeneity of Wimet crystal grain and performance.
4, test shows, using nitrogenous mother alloy Binder Phase of the present invention to prepare Wimet and use multi-element composite carbon nitride thing grain growth inhibitor or combinationally use grain growth inhibitor prepares compared with Wimet, better can improve the comprehensive mechanical performance (comparative example see in specification sheets) of Wimet.
5, the method for the invention technique is simple, low for equipment requirements, is convenient to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the nitrogenous mother alloy Binder Phase of Wimet prepared by embodiment 1.
Embodiment
By the following examples Wimet of the present invention nitrogenous mother alloy Binder Phase powder and preparation method thereof is described further.
Embodiment 1
Wimet prepared by the present embodiment is Co-15% (Cr with nitrogenous mother alloy Binder Phase powder
0.8, V
0.2)
2(C
0.5, N
0.5), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 8.5KgCo powder and 1.5Kg (Cr
0.8, V
0.2)
2(C
0.5, N
0.5) powder;
(2) batch mixing and drying
Load in ball grinder by the raw material prepared, load abrading-ball, and add 8L alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling is dry at 60 DEG C in baking oven after 24 hours obtains compound in 5 hours;
(3) sinter
Sinter in confined reaction stove:
Compound prepared by step (2) is placed in the inflatable tube furnace of vacuum, Reaktionsofen is evacuated to 1 × 10
-2start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 600 DEG C, at this temperature and continuation vacuumized conditions, heat preservation sintering 6 hours, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C after heat preservation sintering terminates;
(4) broken
Product after coming out of the stove also is crossed 300 mesh sieves by ball mill crushing, i.e. obtained Co-15% (Cr
0.8, V
0.2)
2(C
0.5, N
0.5) the nitrogenous mother alloy Binder Phase powder of Wimet, its X-ray diffractogram is shown in Fig. 1.As shown in Figure 1, this nitrogenous mother alloy is be solvent, (Cr with Co
0.8, V
0.2)
2(C
0.5, N
0.5) be the single-phase sosoloid of solute.
Embodiment 2
Novel hard alloy prepared by the present embodiment is Co-15%Ni-5%Fe-18% (Cr with nitrogenous mother alloy Binder Phase powder
0.85, V
0.025, Ti
0.025, Mo
0.025, Ta
0.025, Nb
0.025, Zr
0.025)
2(C
0.9, N
0.1), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 6.2KgCo powder, 1.5KgNi powder, 0.5KgFe powder and 1.8Kg (Cr
0.85, V
0.025, Ti
0.025, Mo
0.025, Ta
0.025, Nb
0.025, Zr
0.025)
2(C
0.9, N
0.1) powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 8L alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling after 24 hours in baking oven at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in confined reaction stove:
Compound prepared by step (2) is placed in microwave agglomerating furnace, Reaktionsofen is evacuated to 1 × 10
-2start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 1000 DEG C, at this temperature and continuation vacuumized conditions, heat preservation sintering 1.5 hours, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C after heat preservation sintering terminates;
(4) broken
Product after coming out of the stove also is crossed 500 mesh sieves by ball mill crushing, i.e. obtained Co-15%Ni-5%Fe-18% (Cr
0.85, V
0.025, Ti
0.025, Mo
0.025, Ta
0.025, Nb
0.025, Zr
0.025)
2(C
0.9, N
0.1) the nitrogenous mother alloy Binder Phase powder of Wimet.
Embodiment 3
Wimet prepared by the present embodiment is Co-20%Ni-50% (V with nitrogenous mother alloy Binder Phase powder
0.9, Ti
0.1) (C
0.1, N
0.9), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 30gCo powder, 20gNi powder and 50g (V
0.9, Ti
0.1) (C
0.1, N
0.9) powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 100ml alcohol to ball grinder according to the ratio of grinding media to material of 8:1, ball milling after 36 hours in oven for drying at 80 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in confined reaction stove:
Compound prepared by step (2) is placed in the inflatable tube furnace of vacuum, Reaktionsofen is evacuated to 1 × 10
-1start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 1350 DEG C, at this temperature and continuation vacuumized conditions, heat preservation sintering 0.5 hour, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C after heat preservation sintering terminates;
(4) broken
Product after coming out of the stove also is crossed 200 mesh sieves by ball mill crushing, i.e. obtained Co-20%Ni-50% (V
0.9, Ti
0.1) (C
0.1, N
0.9) the nitrogenous mother alloy Binder Phase powder of Wimet.
Embodiment 4
Wimet prepared by the present embodiment is Co-10%Fe-5% (V with nitrogenous mother alloy Binder Phase powder
0.75, Cr
0.05, Ti
0.05, Mo
0.05, Ta
0.05, Nb
0.025, Zr
0.025) (C
0.9, N
0.1)-0.1%WC, processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 84.9gCo powder, 10gFe powder, 5g (V
0.75, Cr
0.05, Ti
0.05, Mo
0.05, Ta
0.05, Nb
0.025, Zr
0.025) (C
0.9, N
0.1) powder and 0.1gWC powder;
(2) batch mixing and drying
Load in ball grinder by the raw material prepared, load abrading-ball, and add 120ml alcohol to ball grinder according to the ratio of grinding media to material of 4:1, ball milling is dry at 70 DEG C in oven for drying after 48 hours obtains compound in 4 hours;
(3) sinter
Sinter in confined reaction stove:
Compound prepared by step (2) is placed in induction heater, start to heat after Reaktionsofen being evacuated to 1Pa and continue to vacuumize, when reacting in-furnace temperature and rising to 900 DEG C, at this temperature and continuation vacuumized conditions, heat preservation sintering 2 hours, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C after heat preservation sintering terminates;
(4) broken
Product after coming out of the stove also is crossed 500 mesh sieves by ball mill crushing, i.e. obtained Co-10%Fe-5% (V
0.75, Cr
0.05, Ti
0.05, Mo
0.05, Ta
0.05, Nb
0.025, Zr
0.025) (C
0.9, N
0.1) the nitrogenous mother alloy Binder Phase powder of-0.1%WC Wimet.
Embodiment 5
Novel hard alloy prepared by the present embodiment is Co-26% (Cr with nitrogenous mother alloy Binder Phase powder
0.85, Ta
0.15)
2(C
0.5, N
0.5)-1%WC-1%TiC-1%TaC-1%NbC, processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 70gCo powder, 26g (Cr
0.85, Ta
0.15)
2(C
0.5, N
0.5) powder, 1gWC powder, 1gTiC powder, 1gTaC powder and 1gNbC powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 80ml alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling after 24 hours in oven for drying at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in open reactive stove:
Heating reaction furnace under the state that push boat type controlled atmosphere tube furnace air outlet is opened also passes into the argon gas of flowing in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 600 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 6 hours and is cooled to temperature and comes out of the stove lower than 100 DEG C;
(4) broken
Product after coming out of the stove also is crossed 500 mesh sieves by ball mill crushing, i.e. obtained Co-26% (Cr
0.85, Ta
0.15)
2(C
0.5, N
0.5) the nitrogenous mother alloy Binder Phase powder of-1%WC-1%TiC-1%TaC-1%NbC Wimet.
Embodiment 6
Novel hard alloy prepared by the present embodiment is Co-30% (Cr with nitrogenous mother alloy Binder Phase powder
0.8, V
0.1, Mo
0.1)
2(C
0.4, N
0.6), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 70gCo powder and 30g (Cr
0.8, V
0.1, Mo
0.1)
2(C
0.4, N
0.6) powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 100ml alcohol to ball grinder according to the ratio of grinding media to material of 8:1, ball milling after 36 hours in oven for drying at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in open reactive stove:
Heating reaction furnace under the state that push boat type controlled atmosphere tube furnace air outlet is opened also passes into the mixed gas that the argon gas of flowing and hydrogen mixes with volume ratio 60:40 in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 1300 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 0.5 hour and is cooled to temperature and comes out of the stove lower than 100 DEG C;
(4) broken
Product after coming out of the stove also is crossed 300 mesh sieves by ball mill crushing, i.e. obtained Co-30% (Cr
0.8, V
0.1, Mo
0.1)
2(C
0.4, N
0.6) the nitrogenous mother alloy Binder Phase powder of Wimet.
Embodiment 7
Novel hard alloy prepared by the present embodiment is Co-10%Ni-15% (V with nitrogenous mother alloy Binder Phase powder
0.75, Nb
0.15, Zr
0.1) (C
0.7, N
0.3), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase and the content batching of each component, take 75gCo powder, 10gNi powder and 15g (V
0.75, Nb
0.15, Zr
0.1) (C
0.7, N
0.3) powder, load in ball grinder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 100ml alcohol to ball grinder according to the ratio of grinding media to material of 8:1, ball milling after 36 hours in oven for drying at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in open reactive stove:
Heating reaction furnace under the state that push boat type controlled atmosphere tube furnace air outlet is opened also passes into the nitrogen of flowing in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 1100 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 1 hour and is cooled to temperature and comes out of the stove lower than 100 DEG C;
(4) broken
Product after coming out of the stove also is crossed 200 mesh sieves by ball mill crushing, i.e. obtained Co-10Ni-15% (V
0.75, Nb
0.15, Zr
0.1) (C
0.7, N
0.3) the nitrogenous mother alloy Binder Phase powder of Wimet.
Embodiment 8
Novel hard alloy prepared by the present embodiment is Co-20% (Ti with nitrogenous mother alloy Binder Phase powder
0.4, V
0.3, Ta
0.1)
2(C
0.5, N
0.5), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 80gCo powder and 20g (Ti
0.4, V
0.3, Ta
0.1)
2(C
0.5, N
0.5) powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 80ml alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling after 24 hours in oven for drying at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in open reactive stove:
Heating reaction furnace under the state that tube type resistance furnace air outlet is opened also passes into the ammonia of flowing in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 1000 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 1 hour and is cooled to temperature and comes out of the stove lower than 100 DEG C;
(4) broken
Product after coming out of the stove also is crossed 500 mesh sieves by ball mill crushing, i.e. obtained Co-20% (Ti
0.4, V
0.3, Ta
0.1)
2(C
0.5, N
0.5) the nitrogenous mother alloy Binder Phase powder of Wimet.
Embodiment 9
Wimet prepared by the present embodiment is Co-15% (Cr with nitrogenous mother alloy Binder Phase powder
0.9, Ta
0.1)
2(C
0.5, N
0.5)-5% (V
0.8, Ti
0.2) (C
0.5, N
0.5)-5% (Ti
0.9, Mo
0.1) (C
0.5, N
0.5)-2%NbC, processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 75gCo powder, 15g (Cr
0.9, Ta
0.1)
2(C
0.5, N
0.5) powder, 5g (V
0.8, Ti
0.2) (C
0.5, N
0.5) powder, 5g (Ti
0.9, Mo
0.1) (C
0.5, N
0.5) powder and 2gNbC powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 80ml alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling after 24 hours in oven for drying at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in confined reaction stove:
Compound prepared by step (2) is placed in the inflatable tube furnace of vacuum, Reaktionsofen is evacuated to 1 × 10
-2start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 1350 DEG C, at this temperature and continuation vacuumized conditions, heat preservation sintering 0.5 hour, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C after heat preservation sintering terminates;
(4) broken
Product after coming out of the stove also is crossed 500 mesh sieves by ball mill crushing, i.e. obtained Co-15% (Cr
0.9, Ta
0.1)
2(C
0.5, N
0.5)-5% (V
0.8, Ti
0.2) (C
0.5, N
0.5)-5% (Ti
0.9, Mo
0.1) (C
0.5, N
0.5) the nitrogenous mother alloy Binder Phase powder of-2%NbC Wimet.
Embodiment 10
Novel hard alloy prepared by the present embodiment is Co-10% (V with nitrogenous mother alloy Binder Phase powder
0.8, Cr
0.2) (C
0.5, N
0.5), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 75.21g cobaltosic oxide, 5.80g vanadous oxide powder, 1.47g chromium sesquioxide powder and 17.52g Graphite Powder 99;
(2) batch mixing and drying
Load in ball grinder by the raw material prepared, load abrading-ball, and add 100ml alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling is dry at 70 DEG C in oven for drying after 36 hours obtains compound in 4 hours;
(3) sinter
Sinter in confined reaction stove:
Compound prepared by step (2) is placed in microwave agglomerating furnace, Reaktionsofen is evacuated to 1 × 10
-2start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 800 DEG C, stopping vacuumizing and in Reaktionsofen, passing into nitrogen to nitrogen pressure is 0.01MPa, and heat preservation sintering 6 hours at this nitrogen pressure and 800 DEG C, cools to temperature with the furnace and come out of the stove lower than 100 DEG C after heat preservation sintering terminates;
(4) broken
Product after coming out of the stove also is crossed 500 mesh sieves by ball mill crushing, i.e. obtained Co-10% (V
0.8, Cr
0.2) (C
0.5, N
0.5) the nitrogenous mother alloy Binder Phase powder of Wimet.
Embodiment 11
Novel hard alloy prepared by the present embodiment is Co-5%Fe-15% (Cr with nitrogenous mother alloy Binder Phase powder
0.85, V
0.1, Ta
0.05)
2(C
0.5, N
0.5), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 329.97g cobalt sesquioxide powder, 20.69g ferric oxide powder, 43.80g chromium sesquioxide powder, 6.17g Vanadium Pentoxide in FLAKES powder, 7.49g tantalum pentoxide powder and 91.88g carbon powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 600ml alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling after 24 hours in oven for drying at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in confined reaction stove:
Compound prepared by step (2) is placed in microwave agglomerating furnace, Reaktionsofen is evacuated to 1 × 10
-1start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 1600 DEG C, stopping vacuumizing and in Reaktionsofen, passing into nitrogen to nitrogen pressure is 0.1MPa, and heat preservation sintering 1 hour at this nitrogen pressure and 1600 DEG C, cools to temperature with the furnace and come out of the stove lower than 100 DEG C after heat preservation sintering terminates;
(4) broken
Product after coming out of the stove also is crossed 200 mesh sieves by ball mill crushing, i.e. obtained Co-5%Fe-15% (Cr
0.85, V
0.1, Ta
0.05)
2(C
0.5, N
0.5) the nitrogenous mother alloy Binder Phase powder of Wimet.
Embodiment 12
Novel hard alloy prepared by the present embodiment is Ni-20% (V with nitrogenous mother alloy Binder Phase powder
0.6, Ti
0.1, Mo
0.1, Nb
0.1, Zr
0.1) (C
0.1, N
0.9), processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase powder and the content batching of each component, take 328.06g nickel sesquioxide powder, 41.18g Vanadium Pentoxide in FLAKES powder, 6.02g titanium dioxide powder, 10.86g molybdic oxide powder, 10.02g Niobium Pentxoxide powder, 9.29g titanium dioxide zirconium powder, 54.57g Graphite Powder 99 and 40g activity charcoal powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 600ml alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling after 24 hours in oven for drying at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in confined reaction stove:
Compound prepared by step (2) is placed in microwave agglomerating furnace, start to heat after Reaktionsofen being evacuated to 1Pa and continue to vacuumize, when reacting in-furnace temperature and rising to 1200 DEG C, stopping vacuumizing and in Reaktionsofen, passing into nitrogen to nitrogen pressure is 0.06MPa, heat preservation sintering 2 hours at this nitrogen pressure and 1200 DEG C, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C after heat preservation sintering terminates;
(4) broken
Product after coming out of the stove also is crossed 300 mesh sieves by ball mill crushing, i.e. obtained Ni-20% (V
0.6, Ti
0.1, Mo
0.1, Nb
0.1, Zr
0.1) (C
0.1, N
0.9) the nitrogenous mother alloy Binder Phase powder of Wimet.
Embodiment 13
Novel hard alloy prepared by the present embodiment is Co-15% (Ti with nitrogenous mother alloy Binder Phase powder
0.9, Mo
0.1) (C
0.1, N
0.9)-5%TaC, processing step is as follows:
(1) prepare burden
According to the chemical formula of prepared Wimet with nitrogenous mother alloy Binder Phase and the content batching of each component, take 336.13g cobalt sesquioxide powder, 48.42g titanium dioxide powder, 9.70g molybdic oxide powder, 50g Graphite Powder 99,40.82g activity charcoal powder and 14.93gTaC powder;
(2) batch mixing and drying
The raw material for preparing loaded in ball grinder, load abrading-ball, and add 600ml alcohol to ball grinder according to the ratio of grinding media to material of 6:1, ball milling after 24 hours in oven for drying at 70 DEG C dry 4 hours, obtains compound;
(3) sinter
Sinter in open reactive stove:
Heating reaction furnace under the state that push boat type controlled atmosphere tube furnace air outlet is opened also passes into the nitrogen of flowing in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 1600 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 0.5 hour and is cooled to temperature and comes out of the stove lower than 100 DEG C;
(4) broken
Product after coming out of the stove also is crossed 300 mesh sieves by ball mill crushing, i.e. obtained Ni-20% (V
0.6, Ti
0.1, Mo
0.1, Nb
0.1, Zr
0.1) (C
0.1, N
0.9) the nitrogenous mother alloy Binder Phase powder of Wimet.
Comparative example 1
Nitrogenous mother alloy Binder Phase powder Co-15% (Cr prepared by embodiment 1
0.8, V
0.2)
2(C
0.5, N
0.5) for the preparation of Wimet.
Take the nitrogenous mother alloy Binder Phase powder of 90gWC powder, 5gCo powder and 5g embodiment 1 preparation respectively, then the above-mentioned material powder measured is loaded ball grinder, abrading-ball is loaded according to the ratio of grinding media to material of 8:1, pour 100mL alcohol into, ball milling obtains compound in 48 hours, colloid forming agent polyoxyethylene glycol is added and granulation, obtained granular material by after compound drying;
The granular material taking certainweight loads in mould, is pressed into hard alloy blank, is then loaded in low-pressure sintering furnace, be evacuated to 1 × 10
-1pa, at this temperature and vacuumized conditions, the colloid removed for 2 hours in hard alloy blank is incubated when reacting in-furnace temperature and rising to 600 DEG C, then under vacuumized conditions, 1400 DEG C are warming up to, at this temperature and vacuumized conditions 1 hour, insulation terminates rear stopping and vacuumizing, in sintering oven, passing into argon gas to 2MPa maintains in-furnace temperature and continues insulations 0.5 hour at 1400 DEG C, the Wimet that room temperature obtains based on nitrogenous mother alloy Binder Phase is cooled to the furnace after insulation terminates, after testing, the bending strength of this Wimet is 4350MPa, dimension formula hardness is 1610, fracture toughness property is 16.3MPam
1/2.
Comparative example 2
By multi-element composite carbon nitride thing (grain growth inhibitor) (Cr
0.8, V
0.2)
2(C
0.5, N
0.5) for the preparation of Wimet.
Take 90gWC powder, 9.25gCo powder and 0.75g multi-element composite carbon nitride thing powder (obtaining by method preparation described in patent application CN104046828A) respectively, then the above-mentioned material powder measured is loaded ball grinder, abrading-ball is loaded according to the ratio of grinding media to material of 8:1, pour 100mL alcohol into, ball milling obtains compound in 48 hours, colloid forming agent polyoxyethylene glycol is added and granulation, obtained granular material by after compound drying;
The granular material taking certainweight loads in mould, is pressed into hard alloy blank, then loads in low-pressure sintering furnace by blank, be evacuated to 1 × 10
-1pa, at this temperature and vacuumized conditions, the colloid removed for 2 hours in hard alloy blank is incubated when reacting in-furnace temperature and rising to 600 DEG C, then under vacuumized conditions, 1400 DEG C are warming up to, 1 hour is incubated at this temperature and vacuumized conditions, insulation terminates rear stopping and vacuumizing, in sintering oven, passing into argon gas to 2MPa maintains in-furnace temperature and continues insulations 0.5 hour at 1400 DEG C, cool to room temperature with the furnace after insulation terminates, obtain the Wimet containing multi-element composite carbon nitride thing (grain growth inhibitor).After testing, the bending strength of this Wimet is 3960MPa, and dimension formula hardness is 1550, and fracture toughness property is 13.2MPam
1/2.
Comparative example 3
By grain growth inhibitor Cr
3c
2with VC for the preparation of Wimet.
Take 90gWC powder, 9.25gCo powder, 0.59gCr respectively
3c
2powder and 0.16gVC powder, then load ball grinder by the above-mentioned material powder measured, and loads abrading-ball according to the ratio of grinding media to material of 8:1, pour 100mL alcohol into, ball milling obtains compound in 48 hours, adds colloid forming agent polyoxyethylene glycol and granulation by after compound drying, obtained granular material;
The granular material taking certainweight loads in mould, is pressed into hard alloy blank, is then loaded in low-pressure sintering furnace, be evacuated to 1 × 10
-1pa, at this temperature and vacuumized conditions, the colloid removed for 2 hours in hard alloy blank is incubated when reacting in-furnace temperature and rising to 600 DEG C, then under vacuumized conditions, 1400 DEG C are warming up to, 1 hour is incubated at this temperature and vacuumized conditions, insulation terminates rear stopping and vacuumizing, pass in sintering oven argon gas to 2MPa and and maintain in-furnace temperature and continue insulations 0.5 hour at 1400 DEG C, cool to room temperature with the furnace after insulation terminates, obtain the Wimet containing combination grain growth inhibitor.After testing, the bending strength of this Wimet is 3310MPa, and dimension formula hardness is 1496, and fracture toughness property is 10.1MPam
1/2.
As can be seen from above-mentioned comparative example, using nitrogenous mother alloy Binder Phase of the present invention to prepare Wimet and use multi-element composite carbon nitride thing (grain growth inhibitor) or combinationally use grain growth inhibitor prepares compared with Wimet, better can improve the comprehensive mechanical performance of Wimet.
Claims (8)
1. the nitrogenous mother alloy Binder Phase powder of Wimet, it is characterized in that by massfraction be 5% ~ 50% multi-element composite carbon nitride thing and massfraction be 50% ~ 95% Binder Phase metal form, described multi-element composite carbon nitride thing is carbon chromium nitride based solid solution (Cr
y, M1
1-y)
2(C
x, N
1-x), vanadium carbide nitride based solid solution (V
y, M2
1-y) (C
x, N
1-x), titanium carbonitride based solid solution (Ti
y, M3
1-y) (C
x, N
1-x) at least one, described Binder Phase metal is at least one in cobalt, nickel, iron;
Described (Cr
y, M1
1-y)
2(C
x, N
1-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; Described (V
y, M2
1-y) (C
x, N
1-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; Described (Ti
y, M3
1-y) (C
x, N
1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5 < y≤0.95.
2. the nitrogenous mother alloy Binder Phase powder of Wimet according to claim 1, it is characterized in that structure be with Binder Phase metal be solvent, the solid solution phase that is solute with multi-element composite carbon nitride thing, or structure be with Binder Phase metal be solvent, the compound phase that forms with the multi-element composite carbon nitride thing solid solution phase that is solute and multi-element composite carbon nitride thing.
3. the nitrogenous mother alloy Binder Phase powder of Wimet, multi-element composite carbon nitride thing, massfraction that to it is characterized in that by massfraction be 5% ~ 49.9% are that the Binder Phase metal of 50% ~ 90% and the additive of massfraction 0.1% ~ 5% form, and described multi-element composite carbon nitride thing is carbon chromium nitride based solid solution (Cr
y, M1
1-y)
2(C
x, N
1-x), vanadium carbide nitride based solid solution (V
y, M2
1-y) (C
x, N
1-x), titanium carbonitride based solid solution (Ti
y, M3
1-y) (C
x, N
1-x) at least one, described Binder Phase metal is at least one in cobalt, nickel, iron, and described additive is at least one in WC, TiC, TaC, NbC;
Described (Cr
y, M1
1-y)
2(C
x, N
1-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; Described (V
y, M2
1-y) (C
x, N
1-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; Described (Ti
y, M3
1-y) (C
x, N
1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5 < y≤0.95.
4. the nitrogenous mother alloy Binder Phase powder of Wimet according to claim 3, it is characterized in that structure be with Binder Phase metal be solvent, the solid solution phase that is solute with multi-element composite carbon nitride thing and additive, or structure be with Binder Phase metal be solvent, the compound phase that forms with multi-element composite carbon nitride thing and the additive solid solution phase that is solute and multi-element composite carbon nitride thing, additive.
5. the nitrogenous mother alloy Binder Phase raw powder's production technology of Wimet described in claim 1 or 2, is characterized in that processing step is as follows:
(1) prepare burden
Raw material is at least one in the oxide compound of cobalt powder, nickel powder, iron powder, the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source;
Described (Cr
y, M1
1-y)
2(C
x, N
1-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; Described (V
y, M2
1-y) (C
x, N
1-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; Described (Ti
y, M3
1-y) (C
x, N
1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5 < y≤0.95;
Various raw material is measured according to Wimet described in claim 1 or the 2 nitrogenous component of mother alloy Binder Phase powder and the massfraction of each component;
(2) batch mixing and drying
Each raw material is mixed by ball milling, then dries to obtain compound;
(3) sinter
Sinter in confined reaction stove:
When at least one that raw material is in cobalt powder, nickel powder, iron powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in powder time, use first method: compound prepared by step (2) is placed in Reaktionsofen, Reaktionsofen is evacuated to 1 ~ 1 × 10
-2start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 600 ~ 1350 DEG C, at this temperature and continuation vacuumized conditions, heat preservation sintering 0.5 ~ 6 hour, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C under vacuumized conditions after heat preservation sintering terminates;
When at least one that raw material is in the oxide compound of the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source time, use second method: compound prepared by step (2) is placed in Reaktionsofen, Reaktionsofen is evacuated to 1 ~ 1 × 10
-2start after Pa to heat and continue to vacuumize, stop vacuumizing when temperature rises to 800 ~ 1600 DEG C, in Reaktionsofen, pass into nitrogen to nitrogen pressure is 0.01 ~ 0.1MPa, heat preservation sintering 1 ~ 6 hour at this nitrogen pressure and 800 ~ 1600 DEG C, cools to temperature with the furnace and comes out of the stove lower than 100 DEG C after heat preservation sintering terminates;
Or sinter in open reactive stove:
Heating reaction furnace under the state that Reaktionsofen air outlet is opened also passes into shielding gas or the reactant gases of flowing in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 600 ~ 1600 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 0.5 ~ 6 hour and is cooled to temperature and comes out of the stove lower than 100 DEG C;
When at least one that raw material is in cobalt powder, nickel powder, iron powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in powder time, in Reaktionsofen, pass into the shielding gas of flowing;
When at least one that raw material is in the oxide compound of the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source time, in Reaktionsofen, pass into the reactant gases of flowing;
(4) broken
Product after coming out of the stove is sieved by ball mill crushing, i.e. the obtained nitrogenous mother alloy Binder Phase powder of Wimet.
6. the nitrogenous mother alloy Binder Phase raw powder's production technology of Wimet described in claim 3 or 4, is characterized in that processing step is as follows:
(1) prepare burden
Raw material is at least one in the oxide compound of cobalt powder, nickel powder, iron powder, the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source, at least one in WC powder, TiC powder, TaC powder, NbC powder;
Described (Cr
y, M1
1-y)
2(C
x, N
1-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; Described (V
y, M2
1-y) (C
x, N
1-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; Described (Ti
y, M3
1-y) (C
x, N
1-x) in, M3 is at least one in vanadium, chromium, molybdenum, tantalum, niobium, zirconium, 0.1≤x≤0.9,0.5 < y≤0.95;
Various raw material is measured according to Wimet described in claim 3 or the 4 nitrogenous component of mother alloy Binder Phase powder and the massfraction of each component;
(2) batch mixing and drying
Each raw material is mixed by ball milling, then dries to obtain compound;
(3) sinter
Sinter in confined reaction stove:
When at least one that raw material is in cobalt powder, nickel powder, iron powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-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 Reaktionsofen, Reaktionsofen is evacuated to 1 ~ 1 × 10
-2start after Pa to heat and continue to vacuumize, when reacting in-furnace temperature and rising to 600 ~ 1350 DEG C, heat preservation sintering 0.5 ~ 6 hour at this temperature and continuation vacuumized conditions, under vacuumized conditions, cool to temperature after heat preservation sintering terminates with the furnace come out of the stove lower than 100 DEG C, obtain the nitrogenous mother alloy Binder Phase of Wimet;
When at least one that raw material is in the oxide compound of the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source, during at least one in WC powder, TiC powder, TaC powder, NbC powder, use second method: compound prepared by step (2) is placed in Reaktionsofen, Reaktionsofen is evacuated to 1 ~ 1 × 10
-2start after Pa to heat and continue to vacuumize, stop vacuumizing when temperature rises to 800 ~ 1600 DEG C, in Reaktionsofen, pass into nitrogen to nitrogen pressure is 0.01 ~ 0.1MPa, heat preservation sintering 1 ~ 6 hour at this nitrogen pressure and 800 ~ 1600 DEG C, cool to temperature after heat preservation sintering terminates with the furnace to come out of the stove lower than 100 DEG C, obtain the nitrogenous mother alloy Binder Phase of Wimet;
Or sinter in open reactive stove:
Heating reaction furnace under the state that Reaktionsofen air outlet is opened also passes into shielding gas or the reactant gases of flowing in Reaktionsofen, when the temperature sintering region in Reaktionsofen rises to 600 ~ 1600 DEG C, step (2) gained compound is sent into continuously sintering region heat preservation sintering under mobile status of Reaktionsofen, compound moves out in sintering zone sintering cooled region that sintering region enters Reaktionsofen for 0.5 ~ 6 hour and is cooled to temperature and comes out of the stove lower than 100 DEG C, i.e. the obtained nitrogenous mother alloy Binder Phase of Wimet;
When at least one that raw material is in cobalt powder, nickel powder, iron powder, (Cr
y, M1
1-y)
2(C
x, N
1-x) powder, (V
y, M2
1-y) (C
x, N
1-x) powder, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in powder, during at least one in WC powder, TiC powder, TaC powder, NbC powder, in Reaktionsofen, pass into the shielding gas of flowing;
When at least one that raw material is in the oxide compound of the oxide compound of cobalt, the oxide compound of nickel, iron, (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) at least one in the oxide compound of metal constituent element and carbon source, during at least one in WC powder, TiC powder, TaC powder, NbC powder, in Reaktionsofen, pass into the reactant gases of flowing;
(4) broken
Product after coming out of the stove is sieved by ball mill crushing, i.e. the obtained nitrogenous mother alloy Binder Phase powder of Wimet.
7. the nitrogenous mother alloy Binder Phase raw powder's production technology of Wimet described in claim 5 or 6, is characterized in that the oxide compound of described cobalt is at least one in cobalt monoxide, cobalt sesquioxide, tricobalt tetroxide; The oxide compound of nickel is at least one in nickel protoxide, nickel sesquioxide; The oxide compound of iron is at least one in ferric oxide, Z 250;
Described (Cr
y, M1
1-y)
2(C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (V
y, M2
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, (Ti
y, M3
1-y) (C
x, N
1-x) in the oxide compound of metal constituent element and carbon source, the oxide compound of metal constituent element is as follows: the oxide compound of vanadium is at least one in Vanadium Pentoxide in FLAKES, vanadous oxide; The oxide compound of chromium is chromium sesquioxide; Titanyl compound is titanium dioxide; The oxide compound of molybdenum is molybdic oxide; The oxide compound of tantalum is tantalum pentoxide; The oxide compound of niobium is Niobium Pentxoxide; The oxide compound of zirconium is zirconium dioxide; Carbon source is at least one in carbon black, gac, graphite.
8. the nitrogenous mother alloy Binder Phase raw powder's production technology of Wimet according to claim 5 or 6, when it is characterized in that step (3) sinters in open reactive stove, described shielding gas is at least one in argon gas, hydrogen, nitrogen; Described reactant gases is at least one in nitrogen, ammonia.
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| CN103276270A (en) * | 2013-05-17 | 2013-09-04 | 中南大学 | Ultrafine/nanocrystalline carbide alloy binding phase and preparation and application thereof |
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