CN104313377B - A kind of high specific gravity tungsten alloy material and preparation method thereof - Google Patents
A kind of high specific gravity tungsten alloy material and preparation method thereof Download PDFInfo
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- CN104313377B CN104313377B CN201410535266.6A CN201410535266A CN104313377B CN 104313377 B CN104313377 B CN 104313377B CN 201410535266 A CN201410535266 A CN 201410535266A CN 104313377 B CN104313377 B CN 104313377B
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- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
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- 239000000843 powder Substances 0.000 claims abstract description 95
- 238000000498 ball milling Methods 0.000 claims abstract description 61
- 238000005245 sintering Methods 0.000 claims abstract description 58
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 35
- 239000010937 tungsten Substances 0.000 claims abstract description 35
- 239000011812 mixed powder Substances 0.000 claims abstract description 30
- 238000000886 hydrostatic extrusion Methods 0.000 claims abstract description 29
- 239000006104 solid solution Substances 0.000 claims abstract description 20
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 15
- 150000003657 tungsten Chemical class 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000003825 pressing Methods 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 230000001681 protective Effects 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 11
- 238000006011 modification reaction Methods 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000000227 grinding Methods 0.000 description 17
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- 239000002131 composite material Substances 0.000 description 10
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
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- 229910045601 alloy Inorganic materials 0.000 description 4
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 4
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Abstract
The present invention provides a kind of high specific gravity tungsten alloy material and preparation method thereof.This preparation method includes: 1) tungsten powder is carried out ball milling, prepares modified tungsten powder；2) carry out ball milling after nikel powder and iron powder being mixed, prepare nanocrystalline ferronickel solid solution；3) it is, after 93:7 mixes powder, to be pressed into blank by modification tungsten powder and nanocrystalline ferronickel solid solution according to quality proportioning；4) blank is carried out liquid-phase sintering, make the sintering blank that relative density is 93.9～99.8%；5) be (60～90) by superfine graphite powder and nano grade silica particles according to quality proportioning: after (20～40) mixed powder, carry out ball milling, suppress to relative density be 80～90% and make lubricant medium；6) sintering blank is placed in lubricant medium carries out hot hydrostatic extrusion, and the sintering blank after hot hydrostatic extrusion is carried out heat treatment, prepare high specific gravity tungsten alloy material.The high specific gravity tungsten alloy material that the method prepares remains to keep good elongation percentage when intensity is greatly improved.
Description
Technical field
The present invention relates to a kind of tungsten alloy material, particularly to a kind of high specific gravity tungsten alloy material and preparation thereof
Method.
Background technology
High-specific gravity tungsten alloy be a class with wolfram element as matrix material (tungstenic amount is 80%～97%), and
It is added with the elementary composition alloy such as Ni, Cu, Fe, Co, Mo, Cr in right amount, owing to which overcoming tungsten
Fragility, and maintain the premium properties such as the high-melting-point of tungsten, high density, low-expansion coefficient, thus in boat
The industries such as empty space flight, military affairs, civilian industry are widely used.
At present, the preparation of high-specific gravity tungsten alloy is mainly by carrying out swaging after sintering.Although rotating forging
Make and can improve tungsten alloy intensity, but plasticity is very poor；It addition, swaging deflection is the least,
Need could obtain bigger deflection through heating for multiple times and forging, not only process cycle length, energy consumption greatly,
Cost is high, and surface quality is poor, allowance compared with big, stock utilization is relatively low.
Hydrostatic extrusion technology is a kind of technique that difficult-to-deformation material carries out plastic working, and it is broadly divided into cold
Hydrostatic extrusion and hot hydrostatic extrusion.Cold hydrostatic extrusion typically uses high pressure or superhigh pressure liquid to pass as pressure
The lubricant medium passed, it makes extrded material be placed in the highly pressurised liquid of sealing, and so when deformation, material begins
It is in eventually under good lubricating condition and favourable three-dimensional compressive stress state, therefore can improve the plasticity of material；
But, use high pressure liquid to know from experience and bring the problem such as die sealing and production safety, and its resistance of deformation is big,
Residual stress is big, and these factors all limit its actual application aborning.
Hot hydrostatic extrusion can overcome the drawbacks described above of cold hydrostatic extrusion, therefore has greatly on producing
Application potential, currently also has a small amount of correlational study.Such as, the invention of Publication No. CN101386947A
Patent discloses a kind of high specific gravity tungsten alloy material and preparation method thereof, first by tungsten powder, nickel by powder,
Make blank after iron powder and cobalt dust mix homogeneously, be then sintered；Meanwhile, by graphite and glass
Powder mixes powder aftershaping, makes lubricant medium；Secondly, blank and the lubricant medium of preheating are put in mould
Extrude, i.e. prepare high specific gravity tungsten alloy material.
Said method sinters to densifie state, yet with raw material tungsten powder after being mixed by each element powders
Granularity is the biggest (3～10um), the thickest (tungsten of tungsten alloy microstructure after high temperature sintering
Particle size 30～40um), easily there is component segregation and serious Collapse Deformation in material, even if after passing through
Continuous working hardening technique also is difficult to be refined, and can produce plasticity reduction while intensity improves.
Additionally, existing tungsten alloy material need at aspects such as deflection, tensile strength and elongation percentage further
Improve.
Summary of the invention
The present invention provides a kind of high specific gravity tungsten alloy material and preparation method thereof, for solving prior art
Tungsten alloy material microstructure is thick, and when intensity improves, plasticity reduces, and alloy material deflection, tension are strong
The technological deficiencies such as degree is limited with elongation percentage.
The present invention provides the preparation method of a kind of high specific gravity tungsten alloy material, comprises the steps:
1) tungsten powder carrying out ball milling, prepared average-size is the modified tungsten powder of submicron order；
2) it is (6～8) by nikel powder and iron powder according to quality proportioning: carry out ball milling after (4～2) mixing, system
Obtain nanocrystalline ferronickel solid solution；
3) it is that 93:7 mixes powder by described modified tungsten powder and described nanocrystalline ferronickel solid solution according to quality proportioning
After, it is pressed into the blank that relative density is 70～85%；
4) described blank is carried out liquid-phase sintering, make the sintering blank that relative density is 93.9～99.8%；
5) it is 500nm by particle diameter～the graphite powder of 2.5 μm and SiO 2 powder that particle diameter is 5～15nm
It is (60～90) according to quality proportioning: carry out ball milling after (20～40) mixed powder, suppress subsequently to the closeest
Degree is 80～90% and make lubricant medium；
6) described sintering blank is placed in described lubricant medium carries out hot hydrostatic extrusion, and hot hydrostatic is squeezed
Sintering blank after pressure carries out heat treatment, prepares high specific gravity tungsten alloy material.
In the present invention, the tungsten powder used is that purity reaches more than 99.9%, mean diameter is that 3 μm are left
Right reduction tungsten powder；Nikel powder is that purity reaches more than 99.5%, mean diameter is the Nickel tetracarbonyl. about 5 μm
Powder；Iron powder is that purity reaches more than 99.5%, mean diameter is the carbonyl iron dust about 5 μm.Further,
The particle size of described modified tungsten powder is 500nm～5 μm, and crystallite dimension is 14nm～117nm；Described
The particle size of nanocrystalline ferronickel solid solution is 0.8～2 μm, and crystallite dimension is 6nm～10nm.
By through the super-refinement of ball milling modification and uniform modified tungsten powder and nanocrystalline ferronickel solid solution through one section time
Between the alloy powder that formed of mixed powder, it is possible to be prevented effectively from tungsten a large amount of diffusions molten in ferronickel solid solution
Solve, thus the plasticity avoiding alloy material reduces；Meanwhile, it can also stop tungsten particle to exist effectively
Grow up during following liquid-phase sintering, therefore, it is possible to reach higher consistency at relatively low temperature, enter
And improve the mechanical property of material.
In a detailed description of the invention, step 1) and step 2) described in ball milling carry out in protective atmosphere,
And the rotating speed controlling described ball milling is 200～350 revs/min, Ball-milling Time is 5～35 hours.Described
Protective atmosphere such as can use purity to reach the high-purity argon gas of more than 99.99% as protective gas, thus
Prevent powder oxidized at mechanical milling process；The quality proportioning of nikel powder and iron powder can be such as 7:3, and
The ball mill that can use routine carries out (such as stirring-type high energy ball mill) described ball milling, grinding ball material
Can be GCr15 (diameter for example, 6mm), ratio of grinding media to material (mass ratio) can be 5:1～15:1.
Further, in order to prevent the excessive slimeball of powder in described mechanical milling process, can add a certain amount of
The process control agent of (such as 0.5～2wt%), such as dehydrated alcohol, stearic acid etc..It is suitable to add
Process control agent can significantly improve the flour extraction of mechanical ball milling, is particularly conducive to commercial production.
Through above-mentioned ball milling modification
In the present invention one concrete scheme, step 3 can be carried out in ball mill) described in mixed powder.Enter
One step ground, rate-determining steps 3) described in time of mixed powder be 50～70 hours, such as 60 hours, this
Outward, described mixed powder can be carried out under rotating speed is 80～120 revs/min；And use isostatic cool pressing to walk
Rapid 3) compacting described in, and the pressure controlling described compacting is 200～350MPa, such as 230～
270MPa.Can obtain that density is higher at this pressure, Density Distribution and porosity are colded pressing more uniformly
Base, it is conducive to even in liquid phase filling pore in follow-up liquid sintering technology, thus does not easily causes into
Divide segregation.
Further, rate-determining steps 4) described in the temperature of liquid-phase sintering be 1445～1530 DEG C, such as
About 1465 DEG C, sintering time is 20～120 minutes, such as 30～60 minutes.Sintering temperature too low or
γ opposite tungsten can be made when sintering time is too short not infiltrate mutually or infiltrate poor, causing two-phase interface combination more weak,
Easily become formation of crack；And when sintering temperature is too high or sintering time is long, then can produce the poly-of tungsten grain
Collection is grown up, and there will be tungsten particle size inequality and Binder Phase skewness in alloy, and it easily makes alloy
Extensibility reduce.
In the present invention, nano level SiO is used2It is that raw material makes hot hydrostatic extrusion with ultra-fine graphite powder
Lubricant medium, it can be formed under thinner micro state and be sufficiently mixed, enter with this lubricant medium
During the hot hydrostatic extrusion of row, melt of si O of refinement2Formed small and uniform power transmission unit and be attracted to stone
In layer of ink, owing to power transmission unit and lubrication unit are all refined to nanoscale, thus can be formed more stable
Hydrostatic power transmission layer, can not only improve extrusion process (such as reducing extruding force), additionally it is possible to significantly effectively
Improve the performance (remaining to keep good elongation percentage when the strength of materials is such as greatly improved) of the material after strengthening
And dimensional accuracy.
Specifically, in step 5) in, described graphite powder and SiO 2 powder are placed in ball mill device
Carry out described mixed powder and ball milling；And before carrying out described mixed powder and ball milling, first described ball mill device is taken out
Vacuum is also filled with 0.5～1.0MPa argon；When carrying out described mixed powder and ball milling, control described mixed powder
Rotating speed is 80～120 revs/min, and the mixed powder time is 40～60 hours, and the rotating speed of described ball milling is 300～450
Rev/min, Ball-milling Time is 10～30 hours.Further, the purity of the graphite powder used is 99.8%
Above, the purity of SiO 2 powder is more than 99.9%.
Further, using colds pressing carries out step 5) described in compacting, and control the pressure of described compacting
Power is 400～1000MPa.The blank formed after compacting can be machined lubrication Jie forming jacket form
Matter, its external diameter can be such as 52mm, and wall thickness can be such as 3～6mm.
In the present invention one concrete scheme, step 6) in described hot hydrostatic extrusion include:
After described sintering blank is placed in described lubricant medium, heat up with the programming rates of 10～20 DEG C/min
To 600～1250 DEG C, after being incubated 30～60 minutes, it is placed in extrusion die and carries out hot hydrostatic extrusion；Its
In, the quality proportioning controlling described sintering blank and described lubricant medium is 2.5～3.5:1, described hot hydrostatic
The extrusion ratio 6～40 of extruding, extruding force 600～800MPa.The preheating temperature of extrusion die can not be the highest,
Can be such as 200 DEG C～350 DEG C.
Reaching more than 85% through the material deflection of above-mentioned hot hydrostatic extrusion, tungsten particle deformation extent strengthens,
Not only the effect of thinning microstructure becomes apparent from, and materials microstructure can be made to be longitudinally formed threadiness point
Cloth, not only contributes to improve the intensity of tungsten alloy material, makes the bullet core armour-piercing capability utilizing this material to make
Strengthen；The residual porosity in sintered body can be reduced or eliminate simultaneously, improve the consistency of material.This
Outward, owing to using the lubricant medium of above-mentioned preparation, hot hydrostatic extrusion working hardening lubricating condition is improved,
The deformation strengthening excellent effect of the material being under three-dimensional compressive stress state, and the cost performance of material is high,
It is particularly suitable for batch production.
Further, step 6) in described heat treatment include:
After sintering blank after hot hydrostatic extrusion is placed in annealing device, described annealing device is carried out
Evacuation, subsequently with the programming rate of 10～30 DEG C/min described sintering blank is warming up to 600～
800 DEG C, after being incubated 2～4 hours, it is cooled to room temperature.
Suitable heat treatment can control crystal grain or the size of subgrain and distribution and the pattern of precipitated phase, big
Little, distribution, improves dislocation distribution and configuration, and eliminates or partially remove residual stress, and it is for improving
The stability playing core size has important function, and then improves the mechanical property of product；But, too high
Heat treatment temperature can cause substantial amounts of tungsten particle to be sticked together and reduce the elongation percentage of material.
The present invention also provides for a kind of high specific gravity tungsten alloy material, according to any of the above-described described preparation method system
?.The deformation quantity of this high specific gravity tungsten alloy material reaches more than 80%, tensile strength reach 1600MP with
On, elongation percentage reaches more than 15%.
The enforcement of the present invention, at least has the advantage that
1, the present invention by carrying out ball milling modification to raw material, thus it is big in ferronickel solid solution to be prevented effectively from tungsten
Amount diffusion also dissolves, it is to avoid the plasticity of alloy material reduces；Meanwhile, it can also stop tungsten effectively
Granule is grown up when following liquid-phase sinters, therefore, it is possible to reach higher densification at relatively low temperature
Degree, so advantageously reduce production cost, Simplified flowsheet, minimizing sintering time pollution and composition transfer.
2, the present invention uses nanoscale SiO2It is the lubrication that raw material makes hot hydrostatic extrusion with superfine graphite powder
Medium, can form more stable hydrostatic power transmission layer when carrying out hot hydrostatic extrusion with this lubricant medium,
Not only contribute to improve extrusion process (such as reducing extruding force), additionally it is possible to greatly improve the material after strengthening
Performance and dimensional accuracy.
3, the deformation quantity of the high specific gravity tungsten alloy material of the present invention reaches more than 80%, and tensile strength reaches
More than 1600MP, elongation percentage reaches more than 15%, and this material has the combination property of excellence, can be used as
The bullet core of armor-piercing weapon, and there is good armour-piercing capability.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the modified tungsten powder of the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope picture of the nanocrystalline ferronickel solid solution of the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of the high-specific gravity tungsten alloy bar longitudinal direction of the embodiment of the present invention 1.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, attached below in conjunction with the present invention
Figure and embodiment, be clearly and completely described the technical scheme in the embodiment of the present invention, it is clear that
Described embodiment is a part of embodiment of the present invention rather than whole embodiments.Based on the present invention
In embodiment, the institute that those of ordinary skill in the art are obtained under not making creative work premise
There are other embodiments, broadly fall into the scope of protection of the invention.
The raw material that the embodiment of the present invention uses is as follows:
Reduction tungsten powder: purity is 99.9%, and mean diameter is 3 μm；
Carbonyl nickel powder: purity is 99.5%, mean diameter is 5 μm；
Carbonyl iron dust: purity is 99.5%, mean diameter is 5 μm；
Graphite powder: purity is 99.8%, particle diameter is 500nm～2.5 μm；
SiO 2 powder: purity is 99.9%, and particle diameter is about 10nm.
Embodiment 1
One, the ball milling modification of raw material
Being inserted by reduction tungsten powder in high-energy stirring formula ball mill and carry out ball milling, when ball milling, employing purity is
The high-purity argon gas of 99.99% is as protective gas, and adds the stearic acid of 1wt% as mechanical milling process control
Agent, grinding ball material selection GCr15, its diameter is about 6mm, and ratio of grinding media to material (mass ratio) is about 15:1,
And controlling drum's speed of rotation is about 350rpm, and Ball-milling Time is about 35h, and prepared average-size is
The modified tungsten powder (flour extraction about 94.3%) of submicron order, its scanning electron microscope result is as shown in Figure 1.By
Fig. 1 understands, and is substantially refined through the tungsten particle of ball milling modification, and grain shape tends to " isometry " shape, flat
All sizes have reached submicron order, about about 500nm, and powder size is at the granularity model of ultra-fine grain
Enclosing, crystallite dimension reaches about 14nm.
Carbonyl nickel powder and carbonyl iron dust, are placed in after about 7:3 is configured to mixed-powder according to quality proportioning
Mix homogeneously in mixed powder machine, then inserts in high-energy stirring formula ball mill and carries out ball milling, uses when ball milling
Purity be the high-purity argon gas of 99.99% as protective gas, grinding ball material selects GCr15, and its diameter is about
6mm, ratio of grinding media to material is about 15:1, and to control drum's speed of rotation be about 350rpm, Ball-milling Time
For about 25h, preparing nanocrystalline ferronickel solid solution, its transmission electron microscope results is as shown in Figure 2.By Fig. 2
Understand, not only refined through the powder microstructure of ball milling modification, and be completely formed nanometer
Brilliant Ni-based solid solution, its particle size is about 2 μm, and crystallite dimension is about 6nm.
Two, isostatic cool pressing and liquid-phase sintering
According to quality proportioning, the modified tungsten powder of above-mentioned preparation and nanocrystalline ferronickel solid solution are that 93:7 makes multiple
After closing powder, it is placed in mixed powder machine and mixes powder about 60h；Then the composite powder of mix homogeneously is put into wall thickness
It is about in the gum cover of 2mm, is subsequently placed in 270MPa supertension indoor and carries out isostatic cool pressing, obtain relatively
Density is the blank of colding pressing of about 77%；Subsequently, above-mentioned blank of colding pressing is put in vacuum heat treatment furnace,
Carrying out liquid-phase sintering at 1460 DEG C, sintering time is 40min, and prepared density reaches 17.69g/cm3, phase
Density is about the sintering blank of 99.8%, and in this sintering blank, the average-size of tungsten particle is less than 20 μm,
And it is spherical in shape is distributed in γ phase, and the distribution of γ phase is the most uniform.
After testing, the tensile strength of this sintering blank reaches about 1024MP, and yield strength reaches 827MP
Left and right, elongation percentage reaches about 23.4%, and toughness reaches 155J/cm2Left and right.
Three, hot hydrostatic extrusion
Graphite powder and SiO 2 powder, are pressed after about 6:4 is configured to composite powder according to quality proportioning
Ratio of grinding media to material is that about 40:1 puts in ball grinder, and ball grinder is evacuated to about 10-2After Pa, to ball grinder
In be filled with the argon of about 1.0MPa, first under the rotating speed of about 100rpm, low speed mixes powder about 50h, mixed
Powder terminate after under the rotating speed of about 400rpm mechanical ball milling about 20h；Composite powder through ball milling is inserted
In punching block, cold pressing under the pressure of about 400MPa, obtain the block that relative density is about 85%
Shape blank, is machined, and makes that external diameter is about 52mm, wall thickness is about the jacket of 6mm and (i.e. lubricates Jie
Matter).
After the sintering blank of above-mentioned preparation is loaded the jacket of above-mentioned preparation, with the heating rate of 15 DEG C/min
It is warming up to about 1200 DEG C, after insulation about 40min, is placed in extrusion die and carries out hot hydrostatic extrusion, its
Middle sintering blank is about 3.5:1 with the quality proportioning of jacket, and the preheating temperature of mould is about 300 DEG C, extruding
Ratio about 27, extruding force is about 800MPa, obtains the bar of a diameter of 10mm through extruding.
Four, heat treatment
After above-mentioned bar is placed in vacuum drying oven, vacuum drying oven is evacuated to 10-2Below Pa, subsequently with
Bar is warming up to 600 DEG C by the speed of 10 DEG C/min, cools to room temperature with the furnace after insulation 4h, i.e. obtains straight
Footpath is the high-specific gravity tungsten alloy bar of 10mm, and its longitudinal scanning Electronic Speculum result is as shown in Figure 3.
From the figure 3, it may be seen that the tungsten particle of this bar is greatly elongated along deformation direction, the deformation of γ phase factor is squeezed
Being pressed into strip, its microscopic structure is obvious filamentary structure, and γ phase is evenly distributed in most of
Between tungsten particle.Owing to the tungsten particle area that contacts with γ increases, the therefore interface knot of tungsten particle and γ phase
Close intensity also dramatically increase, this make the tungsten alloy material with bacillar structure have good intensity and
Plasticity.
After testing, the deformation quantity of the high-specific gravity tungsten alloy bar of above-mentioned preparation reaches about 85%, and tension is strong
Degree reaches about 1650MP, and elongation percentage reaches about 15%.
Embodiment 2
One, the ball milling modification of raw material
Reduction tungsten powder is inserted in high-energy stirring formula ball mill and carry out ball milling, use high-purity argon gas when ball milling
As protective gas, grinding ball material selects GCr15, and its diameter is about 6mm, and ratio of grinding media to material is about 10:1,
And controlling drum's speed of rotation is about 300rpm, and Ball-milling Time is about 25h, prepares modified tungsten powder and (go out
Powder rate about 96.3%), its crystallite dimension reaches about 34nm.
Carbonyl nickel powder and carbonyl iron dust, are placed in after about 6:4 is configured to mixed-powder according to quality proportioning
Mix homogeneously in mixed powder machine, then inserts in high-energy stirring formula ball mill and carries out ball milling, uses when ball milling
High-purity argon gas selects GCr15 as protective gas, grinding ball material, and its diameter is about 6mm, and ratio of grinding media to material is
About 10:1, and to control drum's speed of rotation be about 300rpm, and Ball-milling Time is about 25h, prepares
Nanocrystalline ferronickel solid solution, its particle size is about 2 μm, and crystallite dimension is about 10nm.
Two, isostatic cool pressing and liquid-phase sintering
According to quality proportioning, the modified tungsten powder of above-mentioned preparation and nanocrystalline ferronickel solid solution are that 93:7 makes multiple
After closing powder, it is placed in ball mill under the speed of 100rpm mixed powder about 70h；Then by mix homogeneously
Composite powder put into wall thickness and be about in the gum cover of 2mm, be subsequently placed in 230MPa supertension indoor and carry out
Isostatic cool pressing, obtains the blank of colding pressing that relative density is about 71%；Subsequently, above-mentioned blank of colding pressing is put
Entering in vacuum heat treatment furnace, carry out liquid-phase sintering at 1530 DEG C, sintering time is 70min, prepares phase
Density is about the sintering blank of 98%.
Three, hot hydrostatic extrusion
Graphite powder and SiO 2 powder, are pressed after about 7:3 is configured to composite powder according to quality proportioning
Ratio of grinding media to material is that about 40:1 puts in ball grinder, and ball grinder is evacuated to about 10-2After Pa, to ball grinder
In be filled with the argon of about 0.5MPa, first under the rotating speed of about 80rpm, low speed mixes powder about 60h, mixed
Powder terminate after under the rotating speed of about 450rpm mechanical ball milling about 10h；Composite powder through ball milling is inserted
In punching block, cold pressing under the pressure of about 800MPa, obtain the block that relative density is about 90%
Shape blank, is machined, and makes that external diameter is about 52mm, wall thickness is about the jacket of 6mm and (i.e. lubricates Jie
Matter).
After the sintering blank of above-mentioned preparation is loaded the jacket of above-mentioned preparation, with the heating rate of 20 DEG C/min
It is warming up to about 1000 DEG C, after insulation about 60min, is placed in extrusion die and carries out hot hydrostatic extrusion, its
Middle sintering blank is about 3:1 with the quality proportioning of jacket, and the preheating temperature of mould is about 350 DEG C, extrusion ratio
Being about 20, extruding force is about 700MPa, obtains bar through extruding.
Four, heat treatment
After above-mentioned bar is placed in vacuum drying oven, vacuum drying oven is evacuated to 10-2Below Pa, subsequently with
Bar is warming up to 700 DEG C by the speed of 10 DEG C/min, cools to room temperature with the furnace, i.e. obtain height after insulation 3h
Ratio gravity tungsten alloy bar.
After testing, the deformation quantity of the high-specific gravity tungsten alloy bar of above-mentioned preparation reaches about 80%, and tension is strong
Degree reaches about 1620MP, and elongation percentage reaches about 16%.
Embodiment 3
One, the ball milling modification of raw material
Reduction tungsten powder is inserted in high-energy stirring formula ball mill and carry out ball milling, use high-purity argon gas when ball milling
As protective gas, grinding ball material selects GCr15, and its diameter is about 6mm, and ratio of grinding media to material is about 15:1,
And controlling drum's speed of rotation is about 250rpm, and Ball-milling Time is about 20h, prepare modified tungsten powder,
Its crystallite dimension reaches about 117nm.
Carbonyl nickel powder and carbonyl iron dust, are placed in after about 8:2 is configured to mixed-powder according to quality proportioning
Mix homogeneously in mixed powder machine, then inserts in high-energy stirring formula ball mill and carries out ball milling, uses when ball milling
High-purity argon gas selects GCr15 as protective gas, grinding ball material, and its diameter is about 6mm, and ratio of grinding media to material is
About 15:1, and to control drum's speed of rotation be about 250rpm, and Ball-milling Time is about 20h, prepares
Nanocrystalline ferronickel solid solution, its particle size is about 2 μm, and crystallite dimension is about 10nm.
Two, isostatic cool pressing and liquid-phase sintering
According to quality proportioning, the modified tungsten powder of above-mentioned preparation and nanocrystalline ferronickel solid solution are that 93:7 makes multiple
After closing powder, it is placed in mixed powder machine and mixes powder about 50h；Then the composite powder of mix homogeneously is put into wall thickness
It is about in the gum cover of 2mm, is subsequently placed in 350MPa supertension indoor and carries out isostatic cool pressing, obtain relatively
Density is the blank of colding pressing of about 85%；Subsequently, above-mentioned blank of colding pressing is put in vacuum heat treatment furnace,
Carrying out liquid-phase sintering at 1500 DEG C, sintering time is 100min, and prepared relative density is about the burning of 99%
Knot blank, in this sintering blank, the average-size of tungsten particle is less than 20 μm, and spherical in shape is evenly distributed
In γ phase.
Three, hot hydrostatic extrusion
Graphite powder and SiO 2 powder, are pressed after about 8:2 is configured to composite powder according to quality proportioning
Ratio of grinding media to material is that about 40:1 puts in ball grinder, and ball grinder is evacuated to about 10-2After Pa, to ball grinder
In be filled with the argon of about 1.0MPa, first under the rotating speed of about 120rpm, low speed mixes powder about 40h, mixed
Powder terminate after under the rotating speed of about 300rpm mechanical ball milling about 30h；Composite powder through ball milling is inserted
In punching block, cold pressing under the pressure of about 600MPa, obtain the block that relative density is about 80%
Shape blank, is machined, and makes that external diameter is about 52mm, wall thickness is about the jacket of 6mm and (i.e. lubricates Jie
Matter).
After the sintering blank of above-mentioned preparation is loaded the jacket of above-mentioned preparation, with the heating rate of 20 DEG C/min
It is warming up to about 600 DEG C, after insulation about 30min, is placed in extrusion die and carries out hot hydrostatic extrusion, its
Middle sintering blank is about 3:1 with the quality proportioning of jacket, and the preheating temperature of mould is about 200 DEG C, extrusion ratio
Being about 25, extruding force is about 600MPa, obtains bar through extruding.
Four, heat treatment
After above-mentioned bar is placed in vacuum drying oven, vacuum drying oven is evacuated to 10-2Below Pa, subsequently with
Bar is warming up to 800 DEG C by the speed of 20 DEG C/min, cools to room temperature with the furnace, i.e. obtain height after insulation 2h
Ratio gravity tungsten alloy bar.
After testing, the deformation quantity of the high-specific gravity tungsten alloy bar of above-mentioned preparation reaches about 80%, and tension is strong
Degree reaches about 1600MP, and elongation percentage reaches about 17%.
Reference examples 1
The method using embodiment 1 prepares high specific gravity tungsten alloy material, and except for the difference that, reference examples 1 is the most right
Reduction tungsten powder carries out ball milling modification, but directly by reduction tungsten powder that mean diameter is 3 μm and embodiment 1
The nanocrystalline ferronickel solid solution of preparation is to carry out isostatic cool pressing after 93:7 makes composite powder according to quality proportioning
And liquid-phase sintering, prepared sintering blank, in this sintering blank, the average-size of tungsten particle reaches 40 μm
Left and right, the inhomogeneities that the inhomogeneities of granular size and γ phase are distributed substantially increases, and material easily occurs
Component segregation and serious Collapse Deformation.
After testing, the tensile strength of this sintering blank reaches about 935MP, and it is left that yield strength reaches 762MP
The right side, elongation percentage reaches about 20.0%, and toughness reaches 120J/cm2Left and right, the performance of its each side is all not as adopting
With the sintering blank prepared by the tungsten powder of ball milling modification.
Reference examples 2
The method using embodiment 1 prepares high specific gravity tungsten alloy material, and except for the difference that, reference examples 2 is in system
Use mean diameter to be the graphite powder about 25 μm when making jacket (lubricant medium) and mean diameter is
Glass dust about 2.5 μm, and the quality proportioning of blank and jacket is sintered when carrying out hot hydrostatic extrusion
It is about 2:1.
After testing, the deformation quantity of the final high-specific gravity tungsten alloy bar prepared is about 75%, tensile strength
For about 1450MP, elongation percentage is about 14%, and its tensile strength and elongation percentage are all real not as the present invention
Execute the high-specific gravity tungsten alloy bar prepared by example.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, rather than right
It limits；Although the present invention being described in detail with reference to foregoing embodiments, this area common
Skilled artisans appreciate that the technical scheme described in foregoing embodiments still can be modified by it,
Or the most some or all of technical characteristic is carried out equivalent；And these amendments or replacement, and
The essence not making appropriate technical solution departs from the scope of various embodiments of the present invention technical scheme.
Claims (9)
1. the preparation method of a high specific gravity tungsten alloy material, it is characterised in that comprise the steps:
1) tungsten powder carrying out ball milling, prepared average-size is the modified tungsten powder of submicron order；
2) it is (6～8) by nikel powder and iron powder according to quality proportioning: carry out ball milling after (4～2) mixing, system
Obtain nanocrystalline ferronickel solid solution；
3) it is that 93:7 mixes powder by described modified tungsten powder and described nanocrystalline ferronickel solid solution according to quality proportioning
After, it is pressed into the blank that relative density is 70～85%；
4) described blank is carried out liquid-phase sintering, make the sintering blank that relative density is 93.9～99.8%；
5) it is 500nm by particle diameter～the graphite powder of 2.5 μm and SiO 2 powder that particle diameter is 5～15nm
It is (60～90) according to quality proportioning: carry out ball milling after (20～40) mixed powder, suppress subsequently to the closeest
Degree is 80～90% and make lubricant medium；
6) described sintering blank is placed in described lubricant medium carries out hot hydrostatic extrusion, and hot hydrostatic is squeezed
Sintering blank after pressure carries out heat treatment, prepares high specific gravity tungsten alloy material；
Described hot hydrostatic extrusion includes:
After described sintering blank is placed in described lubricant medium, heat up with the programming rates of 10～20 DEG C/min
To 600～1250 DEG C, after being incubated 30～60 minutes, it is placed in extrusion die and carries out hot hydrostatic extrusion；Its
In, the quality proportioning controlling described sintering blank and described lubricant medium is 2.5～3.5:1, described hot hydrostatic
The extrusion ratio 6～40 of extruding, extruding force 600～800MPa.
Preparation method the most according to claim 1, it is characterised in that the granule of described modified tungsten powder
A size of 500nm～5 μm, crystallite dimension is 14nm～117nm；Described nanocrystalline ferronickel solid solution
Particle size is 0.8～2 μm, and crystallite dimension is 6nm～10nm.
Preparation method the most according to claim 1 and 2, it is characterised in that step 1) and step
2) ball milling described in is carried out in protective atmosphere, and the rotating speed controlling described ball milling be 200～350 turns/
Point, Ball-milling Time is 5～35 hours.
Preparation method the most according to claim 1, it is characterised in that rate-determining steps 3) described in
The time of mixed powder is 50～70 hours；And use isostatic cool pressing to carry out step 3) described in compacting, and
And the pressure controlling described compacting is 200～350MPa.
Preparation method the most according to claim 1, it is characterised in that rate-determining steps 4) described in
The temperature of liquid-phase sintering is 1445～1530 DEG C, and sintering time is 20～120 minutes.
Preparation method the most according to claim 1, it is characterised in that in step 5) in, by institute
State graphite powder and SiO 2 powder is placed in ball mill device and carries out described mixed powder and ball milling；And carry out
Before described mixed powder and ball milling, first to described ball mill device evacuation and be filled with 0.5～1.0MPa argon；?
When carrying out described mixed powder and ball milling, the rotating speed controlling described mixed powder is 80～120 revs/min, and the mixed powder time is
40～60 hours, the rotating speed of described ball milling was 300～450 revs/min, and Ball-milling Time is 10～30 hours.
7. according to the preparation method described in claim 1 or 6, it is characterised in that using colds pressing walks
Rapid 5) compacting described in, and the pressure controlling described compacting is 400～1000MPa.
Preparation method the most according to claim 1, it is characterised in that step 6) in described heat
Process includes:
After sintering blank after hot hydrostatic extrusion is placed in annealing device, described annealing device is carried out
Evacuation, subsequently with the programming rate of 10～30 DEG C/min described sintering blank is warming up to 600～
800 DEG C, after being incubated 2～4 hours, it is cooled to room temperature.
9. a high specific gravity tungsten alloy material, it is characterised in that arbitrary described according to claim 1 to 8
Preparation method prepare.
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|---|---|---|---|---|
| CN101748365A (en) * | 2008-12-19 | 2010-06-23 | 北京有色金属研究总院 | Tungsten titanium target material with high purity and high tungsten-rich phase, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748365A (en) * | 2008-12-19 | 2010-06-23 | 北京有色金属研究总院 | Tungsten titanium target material with high purity and high tungsten-rich phase, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Fracture Behavior of W-Ni-Fe Heavy Alloys;K.S.CHURN等;《METALLURGICAL TRANSACTIONS A》;19840229;第15A卷;第331页试验方法第1段及表1 * |
| 高密度钨合金热静液挤压流动粘度的数值计算;房文斌等;《高密度钨合金热静液挤压流动粘度的数值计算》;20050131;第34卷(第1期);第35页第1段 * |
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