CN105779799B - A kind of method for preparing Hardmetal materials with diffusion prealloy coated composite powder - Google Patents
A kind of method for preparing Hardmetal materials with diffusion prealloy coated composite powder Download PDFInfo
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- CN105779799B CN105779799B CN201410822913.1A CN201410822913A CN105779799B CN 105779799 B CN105779799 B CN 105779799B CN 201410822913 A CN201410822913 A CN 201410822913A CN 105779799 B CN105779799 B CN 105779799B
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Abstract
The invention discloses a kind of method for preparing Hardmetal materials with diffusion prealloy coated composite powder, comprise the following steps：(1) can be well mixed the hard compounds of refractory metal and binding metal in proportion in three-dimensional material mixer by the compound of hydrogen reduction; then it is diffused processing in hydrogen or under ammonia dissolving atmosphere protection; diffusion temperature is 600 1000 DEG C, and diffusion time is 45 120min；(2) powder after DIFFUSION TREATMENT crushed, sieve and obtain covered composite yarn powder；(3) one or more of covered composite yarn powder are filled in mould, it is compressing under 600 1000MPa pressure, hard alloy green body is made；(4) hard alloy green body is sintered into 30 120min in 1,200 600 DEG C under hydrogen or ammonia dissolving atmosphere, is cooled to room temperature, obtains Hardmetal materials.Have that composition is uniform, wetability is good, hard phase and metal adhesive interface bond strength are big, composition is adjustable using the Hardmetal materials that prepare of the present invention, the superior function such as intensity and hardness height.
Description
Technical field
The present invention relates to a kind of method for preparing Hardmetal materials with diffusion prealloy coated composite powder, belong to hard alloy work
Has manufacturing technology field.
Background technology
Hard alloy has the excellent properties such as hardness and intensity height, wearability and good corrosion resistance, for manufacturing skiver
Tool, cutter, wear-resisting spare part etc., be widely used in military project, space flight and aviation, machining, metallurgy, oil drilling, mine instrument,
The fields such as telecommunications, building.
Hard alloy is made up of two parts, i.e. hard phase and metal adhesive.Hard phase is transition metal carbide, nitridation
Thing, boride, silicide etc., with very high hardness and fusing point.It is very high hard that the presence of hard phase determines that hard alloy has
Degree and wearability.The hardness of hard alloy depends on hard phase content and crystallite size, that is, harden that phase content is higher, crystal grain more
Carefully, then hardness is also bigger.The toughness of hard alloy is determined that binding metal content is higher, and bending strength is bigger by binding metal.It is viscous
Knot metal mainly has the metals such as cobalt, nickel, iron.
Traditional hard alloy preparation method is in composition requirement ratio progress dispensing, by adding by the material powder of selection
The wet-milling in wet ball mill of the media such as water, alcohol, is sufficiently mixed them.Through drying, sieving, classification, addition forming agent etc.
Compound is made in step.Then, mixture granulation, die mould, (sintering temperature is close to binding metal fusing point (1200-1600 for sintering
DEG C), hardening just forms eutectic alloy with binding metal.The problem of this conventional method is present is that binding metal powder is usual very
Difficulty accomplishes several micron-scale sizes, and it is poor to there is the wetability of hard-phase particles and binding metal.
The content of the invention
Based on this, it is an object of the invention to provide a kind of side that Hardmetal materials are prepared with diffusion prealloy coated composite powder
Method, to strengthen the interface bond strength of hard phase and metal adhesive.
To achieve the above object, the present invention uses following technical scheme：
A kind of method for preparing Hardmetal materials with diffusion prealloy coated composite powder, comprises the following steps：
(1) by the hard compounds of refractory metal and binding metal can be mixed in three-dimensional in proportion by the compound of hydrogen reduction
It is well mixed in material machine, is then diffused processing in hydrogen or under ammonia dissolving atmosphere protection, diffusion temperature is 600-1000
DEG C, diffusion time is 45-120min；
(2) powder after DIFFUSION TREATMENT crushed, sieve the covered composite yarn powder for obtaining partially pre-alloying；
(3) one or more of covered composite yarn powder are filled in mould, it is compressing under 600-1000MPa pressure,
Hard alloy green body is made；
(4) hard alloy green body is sintered into 30-120min under vacuum, hydrogen or ammonia dissolving atmosphere in 1200-1600 DEG C,
It is cooled to room temperature, obtains Hardmetal materials.
Wherein, the weight content of hard compounds is 75-95% in gained covered composite yarn powder in the step (2), also
The content of binding metal after original is 5-25%.
In the method, as the optional carbide of hard compounds or nitride of the refractory metal of raw material, such as WC,
TiC、TaC、NbC、HfC、Cr3C2, Ti (C, N) etc., other hard phases can also be selected, its particle size (Fisher particle size) is 1-
30μm。
In the method, binding metal can be the metals such as Co, Ni, Mo, Fe, Cu.It is used as the change of the binding metal of raw material
Compound is the salt or oxide of binding metal, can be by hydrogen reduction, such as cobalt oxalate, molybdenum oxide, its particle size (Fei Shi
Degree) it is 0.5-20 μm.Because the salt and oxide of binding metal are brittlement phases, it is easy to ultra-fine (≤10 μm) powder is made.It is logical
The salt or oxide of reduction binding metal are crossed, the combination of hard-phase particles and binding metal can be strengthened.Because diffusion effect and
Metal obtained by partially-alloyed and salt as binding metal or oxide reduction is attached on hard-phase particles, and being formed has core
With the covered composite yarn powder of clad.
According to actual needs, can be mixed into the powder of other a certain proportion of metals in step (3), such as Co, Ni, Fe,
Cu, Cr, Mo, Ti, Al etc..
The advantage of the invention is that：
To obtain special hard alloy, granularity and Song Bi adjustable by reducing the salt or oxide of binding metal by the present invention
Pre-alloyed covered composite yarn powder, the Hardmetal materials prepared using the covered composite yarn powder have that composition is uniform, wetting
The superior functions such as good, hard phase and metal adhesive interface bond strength are big, composition is adjustable for property, intensity and hardness height.The hard
Alloy material be particularly suitable for military project, space flight and aviation, machining, metallurgy, oil drilling, mine instrument, telecommunications,
The fields such as building.
Embodiment
With reference to embodiment, the present invention will be further described, but the implementation of the present invention is not limited to this.Embodiment 1
Tungsten carbide (WC40) 8.0kg and cobalt oxalate 6.5kg that Fisher particle size size is 4.01-5.00 μm are weighed, in three-dimensional
Batch mixer mixing 60min, in 650 DEG C of temperature diffusion 45min under ammonia dissolving atmosphere protection, crushes, is sieved into part and closes in advance
The WC (core) of aurification/Co (shell) coated composite powder.By the morphology analysis to coated composite powder, the covered effect that display coated composite powder has had, boundary
Face is combined, and powder is in the silver gray of Co metals.Coated composite powder is compressing under 1000MPa, at 1500 DEG C, in ammonia dissolving atmosphere
45min is sintered, room temperature is air-cooled to stove, that is, the WC-Co hard alloy containing 20%Co is made.
Embodiment 2
Titanium carbide 8.5kg and cobalt oxalate 4.8kg of the Fisher particle size size for 3-5 μm of size are weighed, is mixed in three-dimensional material mixer
60min is closed, in 650 DEG C of temperature diffusion 45min under ammonia dissolving atmosphere protection, crushes, is sieved into the TiC of partially pre-alloying
(core)/Co (shell) coated composite powder.By the morphology analysis to coated composite powder, the covered effect that display coated composite powder has had, interface cohesion is good,
Powder is in the silver gray of Co metals.Coated composite powder is compressing under 800MPa, and at 1500 DEG C, 45min is sintered in ammonia dissolving atmosphere,
Room temperature is air-cooled to stove, that is, the TiC-Co hard alloy containing 15%Co is made.
Embodiment 3
TiC (the core)/Co prepared in the WC (core) prepared in Example 1 /Co (shell) coated composite powders 5.0kg, embodiment 2
(shell) coated composite powder 4.7kg and Co powder (granularity≤10 μm) 0.28kg, in three-dimensional material mixer mixing 60min, is suppressed under 1000MPa
Shaping, at 1500 DEG C, sinters 45min, room temperature is air-cooled to stove in ammonia dissolving atmosphere, that is, the WC-TiC-Co containing 20%Co is made
Hard alloy.
Embodiment 4
Titanium carbide 8.0kg and molybdenum oxide 3.0kg of the Fisher particle size size for 3-5 μm of size are weighed, is mixed in three-dimensional material mixer
60min is closed, in 800 DEG C of temperature diffusion 45min under ammonia dissolving atmosphere protection, crushes, is sieved into the TiC of partially pre-alloying
(core)/Mo (shell) coated composite powder.By the morphology analysis to coated composite powder, the covered effect that display coated composite powder has had, interface cohesion is good,
Powder is in the silver gray of Mo metals.Coated composite powder is compressing under 1000MPa, at 1500 DEG C, is sintered in ammonia dissolving atmosphere
45min, room temperature is air-cooled to stove, that is, the TiC-Mo hard alloy containing 20%Mo is made.
The hard alloy of the hard alloy that above example is obtained and the same sample ingredient conventionally prepared is carried out
Contrast, its hardness (HRA) improves 1~4 degree, and bending strength improves 20~50N/cm2。
Claims (5)
1. a kind of method for preparing Hardmetal materials with diffusion prealloy coated composite powder, it is characterised in that comprise the following steps：
(1) by the hard compounds of refractory metal and binding metal can be by the compound of hydrogen reduction in proportion in three-dimensional material mixer
In be well mixed, be then diffused processing in hydrogen or under ammonia dissolving atmosphere protection, diffusion temperature is 600-1000 DEG C, expansion
The time of dissipating is 45-120min；
(2) powder after DIFFUSION TREATMENT crushed, sieve the covered composite yarn powder for obtaining partially pre-alloying, gained cladding
The weight content of hard compounds is 75-85% in composite powder, and the content of the binding metal after reduction is 15-25%；
(3) one or more of covered composite yarn powder are filled in mould, it is compressing under 600-1000MPa pressure, it is made
Hard alloy green body；
(4) hard alloy green body is sintered into 30-120min in 1200-1600 DEG C under vacuum, hydrogen or ammonia dissolving atmosphere, be cooled to
Room temperature, obtains Hardmetal materials.
2. the method according to claim 1 for preparing Hardmetal materials with diffusion prealloy coated composite powder, it is characterised in that
The hard compounds of the refractory metal are the carbide or nitride of refractory metal.
3. the method according to claim 1 or 2 for preparing Hardmetal materials with diffusion prealloy coated composite powder, its feature exists
In the particle size of the hard compounds of the refractory metal is 1-30 μm.
4. the method according to claim 1 for preparing Hardmetal materials with diffusion prealloy coated composite powder, it is characterised in that
The compound of the binding metal is the salt or oxide of binding metal.
5. the method for preparing Hardmetal materials with diffusion prealloy coated composite powder according to claim 1 or 4, its feature exists
In the particle size of the compound of the binding metal is 0.5-20 μm.
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