CN108359873A - A kind of low-density tungsten alloy and preparation method thereof - Google Patents
A kind of low-density tungsten alloy and preparation method thereof Download PDFInfo
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- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 38
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 32
- 238000003825 pressing Methods 0.000 claims abstract description 22
- 239000007790 solid phase Substances 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 230000002706 hydrostatic effect Effects 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 55
- 239000000956 alloy Substances 0.000 claims description 55
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 20
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000035515 penetration Effects 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 239000012071 phase Substances 0.000 description 15
- 229910052721 tungsten Inorganic materials 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 238000000280 densification Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/001—Starting from powder comprising reducible metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1035—Liquid phase sintering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a kind of low-density tungsten alloys and preparation method thereof, are formed by restoring W powder, carbonyl Ni and carbonyl Fe, using solid-phase sintering process and liquid sintering technology, technological process is：Batch mixing, ball milling, hydrostatic pressing, sintering.Prepared low-density tungsten alloy body will not destroy after penetration, and be suitable as body prepares material.
Description
Technical field
The present invention relates to technical field of alloy, and in particular to a kind of low-density tungsten alloy and preparation method thereof.
Background technology
Tungsten alloy has the excellent performances such as density is high, intensity is high, plasticity is strong, is the main material for preparing kinetic energy penetrator at present
Material.For howitzer, traditional tungsten alloy kinetic energy penetrator has stronger axial collapse characteristic, but not preferable to target
Fragmentation effect.The characteristic that this low density material has is lower than conventional tungsten alloy density, and density is in 9-12g/cm3Have
High tenacity, tensile strength 600-800MPa, elongation percentage are more than 30%.
Low-density tungsten alloy has the armor-piercing action of tungsten alloy, while its super toughening type can preferably be held with elongation percentage
By quick-fried wind-driven power of explosive wastewater, common tungsten alloy is difficult to bear superpower quick-fried wind driving force（The meeting after being loaded by quick-fried wind
It is broken）.
Tungsten alloy should have lower tensile strength.Enough compression strength is needed again and is stretched for guarantee emissive porwer simultaneously
Long rate under the premise of ensureing certain plasticity, there is larger pressure Lapie.A variety of fragile tungsten heavy alloys are had been developed that both at home and abroad, however
Most fragile tungsten heavy alloys such as W-Ni-Fe (Al2O3), W-Ni-Al-Fe etc. have that tensile strength is excessively high to cause brokenness insufficient,
The problems such as Lapie is too low and elongation is too low is pressed, actual demand is cannot be satisfied.Therefore, the brokenness of tungsten alloy is improved, and is protected
It is the key that prepare tungsten alloy to demonstrate,prove tungsten alloy to have certain compressive strength and plasticity.And ensure tungsten alloy body after penetration
Body cannot be destroyed, and ensure that explosion is occurring after penetration, and highdensity tungsten alloy body is split into four sections after penetration,
Apparent destruction occurs in the middle part of body, therefore, although the Penetration Ability of body can be enhanced by increasing tungsten alloy density, is invading
It is easier to destroy during thorough.
Invention content
In order to solve the problems of the above-mentioned prior art, it is an object of the invention to propose a kind of low-density tungsten alloy and
Preparation method.
A kind of low-density tungsten alloy is formed by restoring W powder, carbonyl Ni and carbonyl Fe, reduction W powder, carbonyl Ni and carbonyl Fe
It is matched according to mass fraction ratio, by 60W-28Ni-12Fe, 65W-24.5Ni-10.5Fe, 70W-21Ni-9Fe, 75W-
17.5Ni-7.5Fe, 80W-14Ni-6Fe5 kind ingredient composition.
In this low-density tungsten alloy of the present invention, the formula granularity of taking of the reduction W powder is 2.8 μm, and purity is
99.9%。
In this low-density tungsten alloy of the present invention, the average Fisher particle size of the carbonyl Ni powder is 2.5 μm, and purity is
99.7%。
In this low-density tungsten alloy of the present invention, the average Fisher particle size of the carbonyl Fe powder is 3.0 μm, and purity is
99.9%。
The present invention also provides a kind of preparation methods of low-density tungsten alloy, include the following steps：
Step 1: batch mixing, reduction W powder, carbonyl Ni powder and carbonyl Fe powder is matched according to mass fraction ratio, by 60W-
28Ni-12Fe, 65W-24.5Ni-10.5Fe, 70W-21Ni-9Fe, 75W-17.5Ni-7.5Fe, 80W-14Ni-6Fe5 kind ingredient
Dispensing is put into three-dimensional mixer and mixes；
Step 2: ball milling is uniformly mixed, quality of the ball mill ratio is under the protection of absolute ethyl alcohol by ball mill ball milling 10h-20H
5: 1, rotating speed 250r/min；
Step 3: hydrostatic pressing, by the good mixed-powder of ball milling it is vacuum dried after carrying out hydrostatic pressing, pressing pressure
For 250MPa；
Step 4: sintering, the molding tungsten alloy suppressed is placed in sintering furnace and is sintered, hydrogen is passed through, heating rate is
450 DEG C/h, 900 DEG C are warming up to, keeps the temperature 4h, is passing through solid-phase sintering and liquid-phase sintering, is being cooled to 1100 DEG C, then be passed through nitrogen,
It waits for Temperature fall, obtains W-Ni-Fe alloys.
In the preparation method of this low-density tungsten alloy of the present invention, the heating rate of the solid-phase sintering is 75 DEG C/
H, temperature are 1400 DEG C, keep the temperature 4h.
In the preparation method of this low-density tungsten alloy of the present invention, the heating rate of the liquid-phase sintering is 45 DEG C/
H, temperature are 1440 DEG C, keep the temperature 1h.
The beneficial effects of the invention are as follows：（1）, with solid-phase sintering process prepare W content mass fraction be 60%-80%'s
W content W-Ni-Fe alloys are porous structure, increase with W content, porosity and average pore size all increase.
（2）, the tensile strength of W-Ni-Fe alloys it is relatively low, wherein W content is the W-Ni-Fe alloys of 60%-80%, and tension is strong
Degree is 230-260MPa, elongation 0.3%-2.3%, compression strength 2450-2550MPa, and pressure Lapie is 9.45-11.04, close
In 8.2MPa-11.5MPa, tungsten alloy body will not destroy degree after penetration, more close with initial shape, only exist
Slight damage occurs for tail portion, and be suitable as body prepares material.
（3）, increase with W content, the tensile strength of alloy declines, and elongation is obviously reduced, 70W-21Ni-9Fe alloys
Elongation is 1.8% or more.There are not W grain cleavage fractures in the fracture mode of alloy, mainly with W-W granular boundaries point
It coheres based on boundary fracture, increases with W content, W- coheres the ratio that accounts for of boundary fracture and increases, mechanical property from W-
Enhancing.
Description of the drawings
Fig. 1 is the SEM shape appearance figures of 60W-28Ni-12Fe alloys of the present invention；
Fig. 2 is the SEM shape appearance figures of 70W-21Ni-9Fe alloys；
Fig. 3 is the SEM shape appearance figures of 80W-14Ni-6Fe alloys；
Fig. 4 be W-Ni-Fe alloys tensile strength and elongation with W content variation relation schematic diagram；
Fig. 5 is the micro-structure diagram of 60W-28Ni-12Fe alloys；
Fig. 6 is the micro-structure diagram of 70W-21Ni-9Fe alloys；
Fig. 7 is the micro-structure diagram of 80W-14Ni-6Fe alloys；
Fig. 8 is variation relation schematic diagram of the tensile strength of W-Ni-Fe alloys with compression strength with W content.
Specific implementation mode
The present invention is described further with reference to embodiment.
This low-density tungsten alloy, by restoring W powder, carbonyl Ni powder and carbonyl Fe powder.Wherein reduction W powder expense formula granularity be
2.8 μm, purity 99.9%；The average Fisher particle size of carbonyl Ni powder is 2.5 μm, purity 99.7%；Average the taking of carbonyl Fe powder
Family name's granularity is 3.0 μm, purity 99.9%.
It is 7 according to the content mass fraction ratio of nickel in W-Ni-Fe alloys and iron:Raw material is pressed 60W-28Ni- by 3 ratio
12Fe, 65W-24.5Ni-10.5Fe, 70W-21Ni-9Fe, 75W-17.5Ni-7.5Fe, 80W-14Ni-6Fe5 kind ingredient composition.
Embodiment one
The ratio that mass fraction ratio according to reduction W powder, carbonyl Ni powder and carbonyl Fe powder is 80%: 28%: 12% mixes, anhydrous
It under the protection of ethyl alcohol, is uniformly mixed by ball mill ball milling 10h-20h, quality of the ball mill ratio is 5: 1, rotating speed 250r/min.
Hydrostatic pressing, by the good mixed-powder of ball milling it is vacuum dried after carrying out hydrostatic pressing, pressing pressure is
250MPa。
Sintering, the molding tungsten alloy suppressed is placed in sintering furnace and is sintered, with the liter that heating rate is 450 DEG C/h
Warm speed rises to 900 DEG C, 4h is kept the temperature at a temperature of 900 DEG C, then be warming up to 1400 DEG C by 900 DEG C, and heating rate is 75 DEG C/h,
4h is kept the temperature, the sintering process of this period is solid-phase sintering process；1440 DEG C are warming up to by 1400 DEG C again, heating rate 40
DEG C/h, 1h is kept the temperature, the sintering process of this period is liquid sintering technology；Above sintering stage is in the case where being continually fed into hydrogen
It carries out.Finally drop to 1100 DEG C by 1440 DEG C of temperature, hydrogen be converted into nitrogen at 1100 DEG C, by 1100 DEG C until to
Natural temperature takes out by the tungsten alloy prepared, obtains 60W-28Ni-12Fe alloys.
Embodiment two
The ratio that mass fraction ratio according to reduction W powder, carbonyl Ni powder and carbonyl Fe powder is 65%: 24.5%: 10.5% mixes,
It under the protection of absolute ethyl alcohol, is uniformly mixed by ball mill ball milling 10h-20h, quality of the ball mill ratio is 5: 1, rotating speed 250r/min.
Hydrostatic pressing, by the good mixed-powder of ball milling it is vacuum dried after carrying out hydrostatic pressing, pressing pressure is
250MPa。
Sintering, the molding tungsten alloy suppressed is placed in sintering furnace and is sintered, with the liter that heating rate is 450 DEG C/h
Warm speed rises to 900 DEG C, 4h is kept the temperature at a temperature of 900 DEG C, then be warming up to 1400 DEG C by 900 DEG C, and heating rate is 75 DEG C/h,
4h is kept the temperature, the sintering process of this period is solid-phase sintering process；1440 DEG C are warming up to by 1400 DEG C again, heating rate 40
DEG C/h, 1h is kept the temperature, the sintering process of this period is liquid sintering technology；Above sintering stage is in the case where being continually fed into hydrogen
It carries out.Finally drop to 1100 DEG C by 1440 DEG C of temperature, hydrogen be converted into nitrogen at 1100 DEG C, by 1100 DEG C until to
Natural temperature takes out by the tungsten alloy prepared, obtains 65W-24.5Ni-10.5Fe alloys.
Embodiment three
The ratio that mass fraction ratio according to reduction W powder, carbonyl Ni powder and carbonyl Fe powder is 70%: 21%: 9% mixes, in anhydrous second
It under the protection of alcohol, is uniformly mixed by ball mill ball milling 10h-20h, quality of the ball mill ratio is 5: 1, rotating speed 250r/min.
Hydrostatic pressing, by the good mixed-powder of ball milling it is vacuum dried after carrying out hydrostatic pressing, pressing pressure is
250MPa。
Sintering, the molding tungsten alloy suppressed is placed in sintering furnace and is sintered, with the liter that heating rate is 450 DEG C/h
Warm speed rises to 900 DEG C, 4h is kept the temperature at a temperature of 900 DEG C, then be warming up to 1400 DEG C by 900 DEG C, and heating rate is 75 DEG C/h,
4h is kept the temperature, the sintering process of this period is solid-phase sintering process；1440 DEG C are warming up to by 1400 DEG C again, heating rate 40
DEG C/h, 1h is kept the temperature, the sintering process of this period is liquid sintering technology；Above sintering stage is in the case where being continually fed into hydrogen
It carries out.Finally drop to 1100 DEG C by 1440 DEG C of temperature, hydrogen be converted into nitrogen at 1100 DEG C, by 1100 DEG C until to
Natural temperature takes out by the tungsten alloy prepared, obtains 70W-21Ni-9Fe alloys.
Example IV
The ratio that mass fraction ratio according to reduction W powder, carbonyl Ni powder and carbonyl Fe powder is 75%: 17.5%: 7.5% mixes, in nothing
It under the protection of water-ethanol, is uniformly mixed by ball mill ball milling 10h-20h, quality of the ball mill ratio is 5: 1, rotating speed 250r/min.
Hydrostatic pressing, by the good mixed-powder of ball milling it is vacuum dried after carrying out hydrostatic pressing, pressing pressure is
250MPa。
Sintering, the molding tungsten alloy suppressed is placed in sintering furnace and is sintered, with the liter that heating rate is 450 DEG C/h
Warm speed rises to 900 DEG C, 4h is kept the temperature at a temperature of 900 DEG C, then be warming up to 1400 DEG C by 900 DEG C, and heating rate is 75 DEG C/h,
4h is kept the temperature, the sintering process of this period is solid-phase sintering process；1440 DEG C are warming up to by 1400 DEG C again, heating rate 40
DEG C/h, 1h is kept the temperature, the sintering process of this period is liquid sintering technology；Above sintering stage is in the case where being continually fed into hydrogen
It carries out.Finally drop to 1100 DEG C by 1440 DEG C of temperature, hydrogen be converted into nitrogen at 1100 DEG C, by 1100 DEG C until to
Natural temperature takes out by the tungsten alloy prepared, obtains 75W-17.5Ni-7.5Fe alloys.
Embodiment five
The ratio that mass fraction ratio according to reduction W powder, carbonyl Ni powder and carbonyl Fe powder is 80%: 14%: 6% mixes, in anhydrous second
It under the protection of alcohol, is uniformly mixed by ball mill ball milling 10h-20h, quality of the ball mill ratio is 5: 1, rotating speed 250r/min.
Hydrostatic pressing, by the good mixed-powder of ball milling it is vacuum dried after carrying out hydrostatic pressing, pressing pressure is
250MPa。
Sintering, the molding tungsten alloy suppressed is placed in sintering furnace and is sintered, with the liter that heating rate is 450 DEG C/h
Warm speed rises to 900 DEG C, 4h is kept the temperature at a temperature of 900 DEG C, then be warming up to 1400 DEG C by 900 DEG C, and heating rate is 75 DEG C/h,
4h is kept the temperature, the sintering process of this period is solid-phase sintering process；1440 DEG C are warming up to by 1400 DEG C again, heating rate 40
DEG C/h, 1h is kept the temperature, the sintering process of this period is liquid sintering technology；Above sintering stage is in the case where being continually fed into hydrogen
It carries out.Finally drop to 1100 DEG C by 1440 DEG C of temperature, hydrogen be converted into nitrogen at 1100 DEG C, by 1100 DEG C until to
Natural temperature takes out by the tungsten alloy prepared, obtains 80W-14Ni-6Fe alloys.
Performance detection is carried out to the above embodiments one, embodiment two, embodiment three, example IV and embodiment five, is used
Drainage measures the density of W-Ni-Fe alloys, calculates porosity.With 10t universal tensile testing machines measure alloy tensile strength,
Compression strength and elongation, strain rate when measurement are 0.5mm/min.With Jeol-6360LV type scanning electron microscopic observation alloys
Microscopic appearance, and according to SEM photograph, the diameter of alloy hole is calculated with Image-Pro Plus softwares.
| Alloy | Porosity/% | Average pore size/μm | Shrinking percentage/% |
| 60W-28Ni-12Fe | 12.8 | 3.7 | 26.8 |
| 65W-24.5Ni-10.5Fe | 13.4 | 4.2 | 24.6 |
| 70W-21Ni-9Fe | 14.2 | 5.3 | 23.7 |
| 75W-17.5Ni-7.5Fe | 16.2 | 6.6 | 21.5 |
| 80W-14Ni-6Fe | 17.0 | 8.5 | 20.7 |
Upper table is classified as porosity, average pore size and the shrinking percentage of the W-Ni-Fe alloys of 5 kinds of different W contents.It can from table
To find out, increase with W content, the porosity of tungsten alloy gradually increases, and aperture increases, shrinking percentage is gradually reduced.Tungsten-bast alloy exists
The solid-phase sintering stage can complete most densification.The densification in solid-phase sintering stage, body of powder is mainly solid-state diffusion.
In W-Ni-Fe systems, the mutual solubility of Ni and Fe are big, can form complete solid solution, and solubility of the W in Ni, Fe is big, are formed
γ-(Ni, Fe, W) matrix phase.The tungsten alloy of solid-phase sintering, since sintering temperature is relatively low, this chemistry counterdiffusion can form solid solution
Body and cenotype are the principal elements of densification to make the free energy of system reduce.Under 1400 DEG C of liquid phase sintering conditions,
Ni, Fe fusing point are low and mutual solubility is big, can preferentially form solid solution.But increase with W content, Ni, Fe powder is separated by a large amount of W powder
It opens, Ni, the counterdiffusion of Fe is hindered to be unfavorable for forming uniform γ-(Ni, Fe, W) matrix phase, to inhibit densification process, institute
Gradually increased with the porosity of tungsten alloy, shrinking percentage is gradually reduced
For 60W-28Ni-12Fe alloys shown in Fig. 1, Fig. 2 and Fig. 3 since W content is relatively low, the volume fraction for cohering phase is larger, W particles
It is mutually obstructed by largely cohering, thus is distributed and relatively disperses, the intergranular Connected degree very littles of W；And the hole in 60W-28Ni-12Fe alloys
Gap negligible amounts, pore shape are mostly circular hole.When W content increases to 80%, W particles multiple aggregation forms big group together
Aggressiveness, hole quantity showed increased, certain holes are in irregular shape.In solid-phase sintering process, pass through diffusion between different elements
Solid solution phase and cenotype are formed, the formation of cenotype is alloy densification and the main drive that hole disappears.In solid-phase sintering early stage
Stage, Ni, Fe in mixed-powder mutually diffuse to form γ-(Ni, Fe) phase, are increased with temperature first, part W to γ-(Ni,
Fe it) is spread in phase, the hole between powder is caused to start zooming out, alloy is finally made to generate contraction.When W content is smaller, W particles are equal
Even be distributed in is cohered in phase, and the diffusion into γ-(Ni, Fe) phase is easier, and the driving force of alloy densification is larger.Therefore, compared with
The porosity and pore-size smaller of the W-Ni-Fe alloys of low W content.
It is respectively the microscopic structure of 60%, 70% and 80% W-Ni-Fe alloys for W content as shown in Figure 1, it can from figure
Go out, most of tungsten particle is reunited together, and the tungsten particle of apparent rounding is not present in only a small amount of tungsten particle.This is because preceding
Phase sintering temperature is relatively low, liquid phase does not occur, it is more difficult to intergranular relative motion occur, therefore tungsten particle is indirect after solid-phase sintering
It is larger to touch degree, and is unevenly distributed, is in granular form or block distribution.
As shown in figure 4, increasing with W content, the tensile strength of alloy declines, and elongation is obviously reduced.60W-28Ni-
The tensile strength of 12Fe reaches 260MPa, elongation 2.3%；When W content is more than 70%, tensile strength is declined, 75W-
The tensile strength of 17.5Ni-7.5Fe is 242MPa, elongation 0.8%, and the elongation of 80W-14Ni-6Fe is close to zero.It passes
The high-compactness tungsten alloy of system, W content 88%-97%, consistency are 99% or more, tensile strength 870-1000MPa, elongation
Rate is 20%-30%.W content prepared by the technique is relatively low for the tensile strength and elongation of the low W content alloy of 60%-80%,
Tensile strength is 230-260MPa, and elongation 0.3%-2.3%, main cause is the presence of a large amount of holes, the ductility of tungsten alloy
Very sensitive to porosity with intensity, hole is the fracture origin of stress concentration in tungsten alloy.
When the porosity of W-Ni-Fe alloys be more than 1% when, the ductility of alloy drastically declines, elongation drop to close in
Zero.The elongation that W content helps to improve solid-phase sintering tungsten alloy is reduced, is increased with W content, the elongation of alloy reduces,
But it is not reduced to zero, the elongation of 60W-28Ni-12Fe alloys is 2.3%.Simultaneously as can be seen from the above table, W content subtracts
Small, the porosity of alloy reduces, and effectively reduces the intergranular Connected degrees of W-W, and W-W interface binding powers are most weak, when there are holes
When gap, easy tos produce crackle and along W-W interface growths, so that tungsten alloy is broken under smaller stress, so W content
For 60% alloy, wax-anti dispersant is all maximum.
If Fig. 5, Fig. 6 and Fig. 7 show the microstructure of the tungsten alloy of different W contents, wherein white area is tungsten
Grain, gray area are to cohere phase, and black circular hole is hole.The tungsten particle order of contact of 60W-28Ni-12Fe is bright as can be seen from Figure
It is aobvious to be less than 80W-14Ni-6Fe.When W content is more than 70%, all W particles contact with each other in green compact.When reducing W content,
It coheres and is mutually evenly distributed between tungsten particle, the intergranular contacts of W-W are reduced.It can be seen that, closed when W content is 60% in Fig. 5
Hole in gold, which more appears in, to be cohered in phase, and hole is mostly contacted with tungsten particle (see figure when W content increases to 80%
7).Therefore, the content for cohering phase is improved, alloy porosity can be reduced, inhibits the extension of crackle at hole, to improve alloy
Ductility.The intergranular binding forces of W-W are small more than alternate binding force is cohered, so when tensile stress acts on hole, first
Between W-W particles and W- coheres alternate cracked, and rapid crack leads to alloy fracture.And cohere mutually be γ-(Ni, Fe,
W) matrix phase, this is mutually soft tough phase, when hole, which appears in, to be cohered in phase, coheres the extension that can mutually hinder crackle and hole, from
And improve the elongation of W-Ni-Fe alloys.This also illustrates that the higher W-Ni-Fe alloys of W content can be with the presence of a large amount of holes
In the case of, still there is certain elongation.
It is variation relation of the tensile strength of W-Ni-Fe alloys with compression strength with W content as shown in Figure 8.It can from figure
Find out, the compression strength of alloy apparent changing rule, amplitude of variation very little does not occur between 2450-2550MPa.It says
Bright porosity influences the compression performance of tungsten alloy little.This may be to be not easy to produce because hole can be closed when alloy is pressurized
Raw crackle, existing crackle probably because compressed load and be closed.Compared with traditional tungsten alloy, solid-phase sintering tungsten alloy
Compression strength be not decreased obviously.The pressure Lapie (i.e. the ratio of compression strength and tensile strength) of tungsten alloy is 9.45-
11.04, it disclosure satisfy that the requirement of fragile type penetrators.
In short, the foregoing is merely presently preferred embodiments of the present invention, it is all according to impartial made by scope of the present invention patent
Variation and modification, should all belong to the covering scope of patent of the present invention.
Claims (7)
1. a kind of low-density tungsten alloy is formed by restoring W powder, carbonyl Ni and carbonyl Fe, reduction W powder, carbonyl Ni and carbonyl Fe are pressed
It is matched according to mass fraction ratio, by 60W-28Ni-12Fe, 65W-24.5Ni-10.5Fe, 70W-21Ni-9Fe, 75W-
17.5Ni-7.5Fe, 80W-14Ni-6Fe5 kind ingredient composition.
2. low-density tungsten alloy according to claim 1, it is characterised in that：The formula granularity of taking of the reduction W powder is 2.8 μ
M, purity 99.9%.
3. low-density tungsten alloy according to claim 1, it is characterised in that：The average Fisher particle size of the carbonyl Ni is
2.5 μm, purity 99.7%.
4. low-density tungsten alloy according to claim 1, it is characterised in that：The average Fisher particle size of the carbonyl Fe is
3.0 μm, purity 99.9%.
5. a kind of preparation method of low-density tungsten alloy, which is characterized in that be as follows：
Step 1: batch mixing, reduction W powder, carbonyl Ni and carbonyl Fe is matched according to mass fraction ratio, by 60W-28Ni-
12Fe, 65W-24.5Ni-10.5Fe, 70W-21Ni-9Fe, 75W-17.5Ni-7.5Fe, 80W-14Ni-6Fe5 kind ingredient composition,
It is put into three-dimensional mixer and mixes；
Step 2: ball milling is uniformly mixed, quality of the ball mill ratio is under the protection of absolute ethyl alcohol by ball mill ball milling 10h-20H
5: 1, rotating speed 250r/min；
Step 3: hydrostatic pressing, by the good mixed-powder of ball milling it is vacuum dried after carrying out hydrostatic pressing, pressing pressure
For 250MPa；
Step 4: sintering, the molding tungsten alloy suppressed is placed in sintering furnace and is sintered, hydrogen is passed through, heating rate is
450 DEG C/h, 900 DEG C are warming up to, keeps the temperature 4h, is passing through solid-phase sintering and liquid-phase sintering, is being cooled to 1100 DEG C, then be passed through nitrogen,
It waits for Temperature fall, obtains W-Ni-Fe alloys.
6. the preparation method of low-density tungsten alloy according to claim 5, it is characterised in that：The heating speed of the solid-phase sintering
Rate is 75 DEG C/h, and temperature is 1400 DEG C, keeps the temperature 4h.
7. the preparation method of low-density tungsten alloy according to claim 5, it is characterised in that：The heating speed of the liquid-phase sintering
Rate is 45 DEG C/h, and temperature is 1440 DEG C, keeps the temperature 1h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108315626A (en) * | 2018-03-27 | 2018-07-24 | 江西澳科新材料科技有限公司 | Novel tungsten alloy material and preparation method thereof |
| CN108315627A (en) * | 2018-03-27 | 2018-07-24 | 江西澳科新材料科技有限公司 | Modified tungsten alloy and preparation method thereof |
| CN112442610A (en) * | 2020-11-24 | 2021-03-05 | 深圳市注成科技股份有限公司 | Preparation method of nano tungsten alloy |
| CN117620181A (en) * | 2023-11-02 | 2024-03-01 | 重庆材料研究院有限公司 | Preparation method of powder metallurgy high specific gravity alloy element with layers of different densities |
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| CN102787249A (en) * | 2012-09-07 | 2012-11-21 | 洛阳高新四丰电子材料有限公司 | Sintering process for preparing high-density tungsten ferro-nickel alloy |
| CN108315626A (en) * | 2018-03-27 | 2018-07-24 | 江西澳科新材料科技有限公司 | Novel tungsten alloy material and preparation method thereof |
| CN108315627A (en) * | 2018-03-27 | 2018-07-24 | 江西澳科新材料科技有限公司 | Modified tungsten alloy and preparation method thereof |
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| EP0326713A1 (en) * | 1988-01-04 | 1989-08-09 | GTE Products Corporation | Improved tungsten nickel iron alloys |
| CN102787249A (en) * | 2012-09-07 | 2012-11-21 | 洛阳高新四丰电子材料有限公司 | Sintering process for preparing high-density tungsten ferro-nickel alloy |
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| CN108315626A (en) * | 2018-03-27 | 2018-07-24 | 江西澳科新材料科技有限公司 | Novel tungsten alloy material and preparation method thereof |
| CN108315627A (en) * | 2018-03-27 | 2018-07-24 | 江西澳科新材料科技有限公司 | Modified tungsten alloy and preparation method thereof |
| CN112442610A (en) * | 2020-11-24 | 2021-03-05 | 深圳市注成科技股份有限公司 | Preparation method of nano tungsten alloy |
| CN117620181A (en) * | 2023-11-02 | 2024-03-01 | 重庆材料研究院有限公司 | Preparation method of powder metallurgy high specific gravity alloy element with layers of different densities |
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