CN116460295B - Preparation method of tungsten-lanthanum alloy wire - Google Patents
Preparation method of tungsten-lanthanum alloy wire Download PDFInfo
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- CN116460295B CN116460295B CN202310468184.3A CN202310468184A CN116460295B CN 116460295 B CN116460295 B CN 116460295B CN 202310468184 A CN202310468184 A CN 202310468184A CN 116460295 B CN116460295 B CN 116460295B
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- 229910000858 La alloy Inorganic materials 0.000 title claims abstract description 129
- FAYUQEZUGGXARF-UHFFFAOYSA-N lanthanum tungsten Chemical compound [La].[W] FAYUQEZUGGXARF-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 79
- 239000010937 tungsten Substances 0.000 claims abstract description 79
- 239000000835 fiber Substances 0.000 claims abstract description 75
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 238000005242 forging Methods 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 230000005684 electric field Effects 0.000 claims description 10
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003892 spreading Methods 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910001080 W alloy Inorganic materials 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000011882 ultra-fine particle Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000956 alloy Substances 0.000 description 18
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000000280 densification Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/12—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- 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
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
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- B22F9/00—Making metallic powder or suspensions thereof
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Abstract
The invention discloses a preparation method of a tungsten-lanthanum alloy wire in the field of tungsten alloy, which specifically comprises the following steps: s1, preparing tungsten-lanthanum alloy precursor powder; s2, arranging tungsten fibers to obtain a tungsten fiber sheet layer; s3, sequentially stacking tungsten-lanthanum alloy precursor powder and tungsten fiber sheets in a die; s4, presintering, heat treatment, grinding and crushing, and sieving with a 200-mesh sieve to obtain tungsten-lanthanum alloy powder; s5, flash burning treatment; and S6, rolling, annealing and rotary forging to obtain the tungsten-lanthanum alloy wire. According to the invention, the tungsten alloy is reinforced by doping lanthanum element and tungsten fiber, and the relative density of the tungsten-lanthanum alloy is improved by flash burning treatment; during plastic deformation, the motion of dislocation is blocked by the dispersed second-phase ultrafine particles, so that the dislocation density is improved, meanwhile, the addition of the dispersed particles can refine crystal grains, the total number of crystal boundaries is improved, the content of average impurity elements on the crystal boundaries is reduced, and the toughness of the tungsten alloy is improved.
Description
Technical Field
The invention belongs to the technical field of tungsten alloy, and particularly relates to a preparation method of a tungsten lanthanum alloy wire.
Background
The high-density tungsten alloy material is an alloy formed by adding a small amount of Cu, zr, mo, co elements or compounds into a metal tungsten matrix, has the characteristics of high melting point, small thermal expansion coefficient and high strength, can be applied to the fields of bullets, plasma materials and the like, contains nonmetallic impurity elements, causes the problems of larger brittleness and poor toughness of the tungsten material, and limits the application of the tungsten material; the dispersion strengthening tungsten alloy is characterized in that hard particles are added into a uniform material to improve the performance of the material, superfine particles are utilized for blocking dislocation movement of crystal grains in dispersion strengthening, so that the effect of improving the strength is achieved, common dispersion particles are mainly metal carbide and rare earth oxide particles, the strength of the tungsten alloy can be improved by the dispersion particles, interface stress concentration can be caused due to the addition of dispersion active elements, and the heat conducting performance and the heat stabilizing performance of the material are reduced; the flash treatment is a novel rapid sintering process, the rapid reaction sintering can enable the sintered material to achieve full densification in a short time, the sample can be subjected to surface excellent modulus, hardness and fracture toughness, the flash treatment is mainly divided into three processes, the first stage of the flash is a voltage control stage, after the current is electrified, the flash sample generates Joule heat effect, the conductivity of the sample changes, when the current rises to reach a preset value, the second stage of the flash is started, the stage is mainly controlled by the current, the sintering mainly occurs in a few seconds, and the electroluminescence phenomenon is accompanied, so that the sample rapidly completes the densification process, after the voltage and the current power tend to be stable, the sample is immersed in a steady state, namely a third stage of the flash, the external power supply is turned off in the stage, the temperature is reduced, and the sample is cooled.
The existing tungsten alloy technology mainly has the following problems: 1. the dispersion strengthening tungsten alloy is difficult to meet the performance requirements of the tungsten alloy material, and has poor thermal conductivity and thermal stability; 2. the sintering speed in the traditional sintering process is low, which is unfavorable for the growth of crystals all the time, thereby influencing the toughness and strength of the tungsten material.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides a preparation method of a tungsten-lanthanum alloy wire, and in order to solve the problem of uneven comprehensive performance of a tungsten alloy material, the invention provides a method for doping lanthanum element, tungsten fiber and flash burning treatment, so that the comprehensive performance of the tungsten alloy material is improved, and further the technical effects of high thermal conductivity, high toughness and high strength are realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a preparation method of a tungsten-lanthanum alloy wire, which specifically comprises the following steps:
s1, dissolving ammonium paratungstate and lanthanum nitrate in deionized water, adding an organic adhesive, stirring, uniformly mixing, and drying in a vacuum environment to obtain tungsten-lanthanum alloy precursor powder;
s2, carrying out ultrasonic cleaning on the tungsten fibers to remove surface impurities, arranging the tungsten fibers in parallel in the same direction, and then vertically arranging a small amount of fibers to obtain a tungsten fiber sheet layer;
s3, placing the tungsten fiber sheet layer in a die, spreading the tungsten-lanthanum alloy precursor powder prepared in the step S1 on the tungsten fiber sheet layer, and repeating for 3 times to obtain a mixed material of three layers of tungsten fiber sheet layers and tungsten-lanthanum alloy precursor powder which are sequentially laminated;
s4, placing the mixed material powder obtained in the step S3 in a hydrogen atmosphere for pre-sintering heat treatment, grinding and crushing, and sieving with a 200-mesh sieve to obtain tungsten-lanthanum alloy powder;
s5, cold pressing the tungsten-lanthanum alloy powder obtained in the step S4 into a cylindrical sample, placing the cylindrical sample in a flash furnace, performing flash burning and heat preservation, and obtaining a tungsten-lanthanum alloy blank after the flash furnace is cooled to room temperature;
and S6, rolling, annealing and rotary forging the blank for multiple times to obtain the tungsten-lanthanum alloy wire.
Preferably, in S1, the content of ammonium paratungstate in deionized water is 50-400g/L and the content of lanthanum nitrate in deionized water is 2.5-12.5g/L.
Preferably, in S1, the organic binder is at least one of PVA, PVB, PMMA, ethylcellulose; the content of the organic binder in deionized water is 1-5g/L.
Preferably, in S1, the time of vacuum drying is 2 hours and the drying temperature is 40-60 ℃.
Preferably, in S2, the ultrasonic power is 300-500W and the ultrasonic time is 0.5-2h when the tungsten fiber is ultrasonically cleaned.
Preferably, in S3, the mass ratio of the tungsten fiber to the tungsten-lanthanum alloy precursor powder of each layer is 1:3-4.
Preferably, in S4, the parameters of the pre-sintering heat treatment are that the temperature is raised to 600-800 ℃ at 5 ℃/min, the heat is preserved for 2-4 hours after the temperature is raised to the set temperature, and the temperature is naturally lowered to normal temperature after the temperature is lowered to 300 ℃ at 5 ℃/min.
Preferably, in S5, the parameters of the flash firing process are that the preset temperature is 1000-1200 ℃, the temperature is kept for 10-30min, the ac power supply is turned on, the electric field strength is applied, after the preset current is reached, the voltage control of the power supply is changed into the current control, after the battery mode is switched, the power supply is kept for 1-3min, and the cooling is carried out at room temperature.
Preferably, in S5, the first stage of the flash firing is controlled by a voltage, and a preset electric field strength of 150-250V/cm is applied.
Preferably, in S5, the second stage of flash firing is changed from voltage control to current control, and the preset current density is 40-60mA/mm 2 。
Preferably, in S6, the procedure of rolling and annealing the blank is that the blank is subjected to medium-frequency annealing for 2 hours at 1800-2000 ℃ to obtain a second blank, and the second blank is a tungsten-lanthanum alloy rod with the diameter of 5-6 mm; and carrying out medium-frequency annealing on the second blank for 2 hours at 2000-2200 ℃ to obtain a third blank, wherein the third blank is a tungsten-lanthanum alloy rod with the diameter of 2-3 mm.
Preferably, in S6, the step of performing rotary forging on the third blank includes: and heating the tungsten-lanthanum alloy rod to 1500-1700 ℃ under the condition of rotary forging strength, wherein the rotary forging speed is 1.0-1.5m/min, and the reduction rate of single pass of rotary forging is 12-20%.
The beneficial effects obtained by the invention are as follows:
according to the invention, the tungsten alloy is reinforced by doping lanthanum element and tungsten fiber, and the relative density of the tungsten-lanthanum alloy is improved by flash burning treatment; during plastic deformation, the movement of dislocation is blocked by the dispersed second-phase ultrafine particles, so that the dislocation density is improved, meanwhile, the addition of the dispersed particles can refine crystal grains, the total number of crystal boundaries is improved, the content of average impurity elements on the crystal boundaries is reduced, and the toughness of the tungsten alloy is improved; the tungsten fiber is used as the toughening fiber of the tungsten alloy, and the tungsten fiber can be subjected to self-toughening modes such as plastic fracture, fiber bridging, crack deflection and the like, so that the toughness of the tungsten fiber/tungsten alloy composite material is increased, the doping of lanthanum element makes up the pores generated when the tungsten fiber and the tungsten matrix are sintered and assimilated at high temperature, and the fiber toughening effect is further improved; the flash burning treatment can instantly reach high temperature by applying an electric field, so that the sample processing time can be effectively reduced, the instant heating of the flash burning treatment can effectively inhibit the growth of crystal grains, the refined crystal grain structure is obtained, and the compactness of the material is improved.
Drawings
FIG. 1 is a graph showing the strength results of the tungsten-lanthanum alloy produced in examples 1-5 and comparative examples 1-3 of the present invention;
FIG. 2 is a graph showing the results of relative densities and room temperature thermal conductivities of the ullan alloys prepared in examples 1-5 and comparative examples 1-3 of the present invention;
FIG. 3 is a graph showing the tensile stress strain at room temperature of the tungsten lanthanum alloy wires prepared in examples 1-5 and comparative examples 1-3 of the present invention;
FIG. 4 is a graph showing the high temperature tensile stress strain curves of the tungsten lanthanum alloy wires prepared in examples 1-5 and comparative examples 1-3 of the present invention;
FIG. 5 is an XRD pattern of a tungsten lanthanum alloy wire prepared in example 1 of the present invention;
fig. 6 is a schematic view of a tungsten lanthanum alloy wire prepared in example 1 of the present invention.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present invention. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the scope of the present application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials and test strains used in the examples described below, unless otherwise specified, were commercially available.
Example 1
The preparation method of the tungsten-lanthanum alloy wire specifically comprises the following steps:
s1, dissolving 20g of ammonium paratungstate and 0.6g of lanthanum nitrate in 100mL of deionized water, adding 0.3g of PVB, stirring, and drying at 40 ℃ in a vacuum environment after uniformly mixing to obtain tungsten-lanthanum alloy precursor powder;
s2, carrying out ultrasonic cleaning on the tungsten fibers, wherein the ultrasonic power is 300W, the ultrasonic time is 0.5h, removing surface impurities, arranging the tungsten fibers in parallel in the same direction, and then vertically arranging a small amount of fibers to obtain a tungsten fiber sheet layer;
s3, placing the tungsten fiber sheet layer in a die, spreading the tungsten-lanthanum alloy precursor powder prepared in the step S1 on the tungsten fiber sheet layer, and repeating for 3 times to obtain a mixed material of three layers of tungsten fiber sheet layers and tungsten-lanthanum alloy precursor powder which are sequentially laminated; the mass ratio of each layer of tungsten fiber to tungsten lanthanum alloy precursor powder is 1:4, a step of;
s4, placing the mixed material powder obtained in the step S3 in a hydrogen atmosphere for pre-sintering heat treatment, heating to 600 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours after heating to a set temperature, cooling to 300 ℃ at a speed of 5 ℃/min, naturally cooling to normal temperature, grinding and crushing, and sieving with a 200-mesh sieve to obtain tungsten-lanthanum alloy powder;
s5, cold pressing the tungsten-lanthanum alloy powder obtained in the step S4 into a cylindrical sample, wherein the diameter of the cylindrical sample is 10mm, the thickness of the cylindrical sample is 3mm, placing the cylindrical sample in a flash furnace, adjusting the pressure in the flash furnace to keep 5MPa in the whole sintering process, heating the cylindrical sample from room temperature to 1000 ℃ at a heating rate of 5 ℃/min, preserving the heat for 10min, starting an alternating current power supply, applying electric field strength of 150V/cm, and presetting current density of 50mA/mm 2 After the battery mode is switched, maintaining for 3min, turning off a power supply, and cooling the flash furnace to room temperature at 5 ℃/min to obtain a tungsten-lanthanum alloy blank;
s6, carrying out intermediate frequency annealing on the tungsten-lanthanum alloy blank for 2 hours at 1800 ℃ to obtain a second blank tungsten-lanthanum alloy rod with the diameter of 5.4mm, carrying out intermediate frequency annealing on the second blank for 2 hours at 2200 ℃ to obtain a third blank tungsten-lanthanum alloy rod with the diameter of 2.2mm, carrying out rotary forging on the third blank at 1600 ℃ at the rotary forging speed of 1.2m/min and the single-pass reduction rate of 18%, and obtaining the tungsten-lanthanum alloy wire with the diameter of 1+/-0.04 mm; a schematic diagram of the tungsten lanthanum alloy wire is shown in fig. 6.
Example 2
The preparation method of the tungsten-lanthanum alloy wire specifically comprises the following steps:
s1, dissolving 5g of ammonium paratungstate and 0.25g of lanthanum nitrate in 100mL of deionized water, adding 1g of PVA, stirring, and drying at 50 ℃ in a vacuum environment after uniform mixing to obtain tungsten-lanthanum alloy precursor powder;
s2, carrying out ultrasonic cleaning on the tungsten fibers, wherein the ultrasonic power is 400W, the ultrasonic time is 1.5h, removing surface impurities, arranging the tungsten fibers in parallel in the same direction, and then vertically arranging a small amount of fibers to obtain a tungsten fiber sheet layer;
s3, placing the tungsten fiber sheet layer in a die, spreading the tungsten-lanthanum alloy precursor powder prepared in the step S1 on the tungsten fiber sheet layer, and repeating for 3 times to obtain a mixed material of three layers of tungsten fiber sheet layers and tungsten-lanthanum alloy precursor powder which are sequentially laminated; the mass ratio of each layer of tungsten fiber to tungsten lanthanum alloy precursor powder is 1:3, a step of;
s4, placing the mixed material powder obtained in the step S3 in a hydrogen atmosphere for pre-sintering heat treatment, heating to 700 ℃ at a speed of 5 ℃/min, preserving heat for 4 hours after heating to a set temperature, cooling to 300 ℃ at a speed of 5 ℃/min, naturally cooling to normal temperature, grinding and crushing, and sieving with a 200-mesh sieve to obtain tungsten-lanthanum alloy powder;
s5, cold pressing the tungsten-lanthanum alloy powder obtained in the step S4 into a cylindrical sample, wherein the diameter of the cylindrical sample is 10mm, the thickness of the cylindrical sample is 3mm, placing the cylindrical sample in a flash furnace, adjusting the pressure in the flash furnace to keep 5MPa in the whole sintering process, heating the cylindrical sample from room temperature to 1100 ℃ at a heating rate of 5 ℃/min, preserving heat for 20min, starting an alternating current power supply, applying electric field strength of 170V/cm, and presetting current density of 60mA/mm 2 After the battery mode is switched, maintaining for 1min, turning off a power supply, and cooling the flash furnace to room temperature at a speed of 5 ℃/min to obtain a tungsten-lanthanum alloy blank;
s6, carrying out intermediate frequency annealing on the tungsten-lanthanum alloy blank for 2 hours at 1900 ℃ to obtain a second blank tungsten-lanthanum alloy rod with the diameter of 5.7mm, carrying out intermediate frequency annealing on the second blank for 2 hours at 2000 ℃ to obtain a third blank tungsten-lanthanum alloy rod with the diameter of 2.5mm, carrying out rotary forging on the third blank at 1700 ℃ at the rotary forging speed of 1.0m/min and the single-pass reduction ratio of 15%, and obtaining the tungsten-lanthanum alloy wire with the diameter of 1+/-0.05 mm.
Example 3
The preparation method of the tungsten-lanthanum alloy wire specifically comprises the following steps:
s1, dissolving 10g of ammonium paratungstate and 0.3g of lanthanum nitrate in 100mL of deionized water, adding 1.5g of PMMA1, stirring, and drying at 60 ℃ in a vacuum environment after uniformly mixing to obtain tungsten-lanthanum alloy precursor powder;
s2, carrying out ultrasonic cleaning on the tungsten fibers, wherein the ultrasonic power is 500W, the ultrasonic time is 2 hours, removing surface impurities, arranging the tungsten fibers in parallel in the same direction, and then vertically arranging a small amount of fibers to obtain a tungsten fiber sheet layer;
s3, placing the tungsten fiber sheet layer in a die, spreading the tungsten-lanthanum alloy precursor powder prepared in the step S1 on the tungsten fiber sheet layer, and repeating for 3 times to obtain a mixed material of three layers of tungsten fiber sheet layers and tungsten-lanthanum alloy precursor powder which are sequentially laminated; the mass ratio of each layer of tungsten fiber to tungsten lanthanum alloy precursor powder is 1:3, a step of;
s4, placing the mixed material powder obtained in the step S3 in a hydrogen atmosphere for pre-sintering heat treatment, heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours after heating to a set temperature, cooling to 300 ℃ at a speed of 5 ℃/min, naturally cooling to normal temperature, grinding and crushing, and sieving with a 200-mesh sieve to obtain tungsten-lanthanum alloy powder;
s5, cold pressing the tungsten-lanthanum alloy powder obtained in the step S4 into a cylinder sample, wherein the diameter of the cylinder sample is 10mm, the thickness of the cylinder sample is 3.0mm, placing the cylinder sample in a flash furnace, adjusting the pressure in the flash furnace to keep 5MPa in the whole sintering process, heating the cylinder from room temperature to 1000 ℃ at a heating rate of 5 ℃/min, preserving the heat for 10min, starting an alternating current power supply, applying an electric field strength of 200V/cm, and presetting the current density to be 60mA/mm 2 After the battery mode is switched, maintaining for 1min, turning off a power supply, and cooling the flash furnace to room temperature at a speed of 5 ℃/min to obtain a tungsten-lanthanum alloy blank;
s6, carrying out medium-frequency annealing on the tungsten-lanthanum alloy blank for 2 hours at 1900 ℃ to obtain a second blank tungsten-lanthanum alloy rod with the diameter of 5.7mm, carrying out medium-frequency annealing on the second blank for 2 hours at 2000 ℃ to obtain a third blank tungsten-lanthanum alloy rod with the diameter of 2.5mm, carrying out rotary forging on the third blank at 1800 ℃ at the rotary forging speed of 1.0m/min and the single-pass reduction rate of 15%, and obtaining the tungsten-lanthanum alloy wire with the diameter of 1+/-0.05 mm.
Example 4
The preparation method of the tungsten-lanthanum alloy wire specifically comprises the following steps:
s1, dissolving 30g of ammonium paratungstate and 1g of lanthanum nitrate in 100mL of deionized water, adding 5g of ethylcellulose, stirring, and drying at 40 ℃ in a vacuum environment after uniformly mixing to obtain tungsten-lanthanum alloy precursor powder;
s2, carrying out ultrasonic cleaning on the tungsten fibers, wherein the ultrasonic power is 400W, the ultrasonic time is 0.5h, removing surface impurities, arranging the tungsten fibers in parallel in the same direction, and then vertically arranging a small amount of fibers to obtain a tungsten fiber sheet layer;
s3, placing the tungsten fiber sheet layer in a die, spreading the tungsten-lanthanum alloy precursor powder prepared in the step S1 on the tungsten fiber sheet layer, and repeating for 3 times to obtain a mixed material of three layers of tungsten fiber sheet layers and tungsten-lanthanum alloy precursor powder which are sequentially laminated; the mass ratio of each layer of tungsten fiber to tungsten lanthanum alloy precursor powder is 1:4, a step of;
s4, placing the mixed material powder obtained in the step S3 in a hydrogen atmosphere for pre-sintering heat treatment, heating to 650 ℃ at a speed of 5 ℃/min, keeping the temperature for 4 hours after heating to a set temperature, cooling to 300 ℃ at a speed of 5 ℃/min, naturally cooling to normal temperature, grinding and crushing, and sieving with a 200-mesh sieve to obtain tungsten-lanthanum alloy powder;
s5, cold pressing the tungsten-lanthanum alloy powder obtained in the step S4 into a cylinder sample, wherein the diameter of the cylinder sample is 10mm, the thickness of the cylinder sample is 3.0mm, placing the cylinder sample in a flash furnace, adjusting the pressure in the flash furnace to keep 5MPa in the whole sintering process, heating the cylinder sample from room temperature to 1200 ℃ at a heating rate of 5 ℃/min, preserving the temperature for 30min, starting an alternating current power supply, applying an electric field strength of 220V/cm, and presetting the current density to be 40mA/mm 2 After the battery mode is switched, maintaining for 2min, turning off a power supply, and cooling the flash furnace to room temperature at 5 ℃/min to obtain a tungsten-lanthanum alloy blank;
s6, carrying out intermediate frequency annealing on the tungsten-lanthanum alloy blank for 2 hours at 2000 ℃ to obtain a second blank tungsten-lanthanum alloy rod with the diameter of 5.1mm, carrying out intermediate frequency annealing on the second blank for 2 hours at 2100 ℃ to obtain a third blank tungsten-lanthanum alloy rod with the diameter of 2.4mm, carrying out rotary forging on the third blank at 1700 ℃ at the rotary forging speed of 1.5m/min and the single-pass reduction ratio of 20%, and obtaining the tungsten-lanthanum alloy wire with the diameter of 1+/-0.05 mm.
Example 5
The preparation method of the tungsten-lanthanum alloy wire specifically comprises the following steps:
s1, dissolving 40g of ammonium paratungstate and 1.25g of lanthanum nitrate in 100mL of deionized water, adding 6g of PVB, stirring, and drying at 60 ℃ in a vacuum environment after uniformly mixing to obtain tungsten-lanthanum alloy precursor powder;
s2, carrying out ultrasonic cleaning on the tungsten fibers, wherein the ultrasonic power is 500W, the ultrasonic time is 1h, removing surface impurities, arranging the tungsten fibers in parallel in the same direction, and then vertically arranging a small amount of fibers to obtain a tungsten fiber sheet layer;
s3, placing the tungsten fiber sheet layer in a die, spreading the tungsten-lanthanum alloy precursor powder prepared in the step S1 on the tungsten fiber sheet layer, and repeating for 3 times to obtain a mixed material of three layers of tungsten fiber sheet layers and tungsten-lanthanum alloy precursor powder which are sequentially laminated; the mass ratio of each layer of tungsten fiber to tungsten lanthanum alloy precursor powder is 1:4, a step of;
s4, placing the mixed material powder obtained in the step S3 in a hydrogen atmosphere for pre-sintering heat treatment, heating to 700 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours after heating to a set temperature, cooling to 300 ℃ at a speed of 5 ℃/min, naturally cooling to normal temperature, grinding and crushing, and sieving with a 200-mesh sieve to obtain tungsten-lanthanum alloy powder;
s5, cold pressing the tungsten-lanthanum alloy powder obtained in the step S4 into a cylinder sample, wherein the diameter of the cylinder sample is 10mm, the thickness of the cylinder sample is 3.0mm, placing the cylinder sample in a flash furnace, adjusting the pressure in the flash furnace to keep 5MPa in the whole sintering process, heating the cylinder sample from room temperature to 1100 ℃ at a heating rate of 5 ℃/min, preserving the heat for 20min, starting an alternating current power supply, applying electric field strength of 250V/cm, and presetting current density of 60mA/mm 2 After the battery mode is switched, maintaining for 2min, turning off a power supply, and cooling the flash furnace to room temperature at 5 ℃/min to obtain a tungsten-lanthanum alloy blank;
s6, carrying out intermediate frequency annealing on the tungsten-lanthanum alloy blank for 2 hours at 1800 ℃ to obtain a second blank tungsten-lanthanum alloy rod with the diameter of 5.4mm, carrying out intermediate frequency annealing on the second blank for 2 hours at 2200 ℃ to obtain a third blank tungsten-lanthanum alloy rod with the diameter of 2.2mm, carrying out rotary forging on the third blank at 1600 ℃ at the rotary forging speed of 1.2m/min and the single-pass reduction rate of 12%, and obtaining the tungsten-lanthanum alloy wire with the diameter of 1+/-0.01 mm.
Comparative example 1
The comparative example provides a tungsten wire prepared from pure tungsten metal.
Comparative example 2,
this comparative example provides a tungsten lanthanum alloy wire which differs from example 1 only in that the preparation step shown does not include step S3.
Comparative example 3
This comparative example provides a tungsten lanthanum alloy wire which differs from example 1 only in that the sintering method is a spark plasma sintering technique, the sintering pressure is 50MPa, the sintering end temperature is 2000 ℃, and the maximum temperature holding time is 5min.
Experimental example
1. The mass of the tungsten-lanthanum alloy wire samples prepared in the examples 1-5 of the invention in air and water is weighed, the density of the tungsten-lanthanum alloy wire is calculated by the following formula, and the ratio of the actual density to the theoretical density is the relative density.
ρ=ρ
Water and its preparation method
•m
Empty space
/(m
Empty space
-m
Water and its preparation method
)
2. The hardness of the tungsten-lanthanum alloy wire is tested by adopting a Vickers microhardness tester, the diamond pressing head is rectangular pyramid, the load is 00g, and the pressure maintaining time is 10s.
3. The tungsten-lanthanum alloys prepared in examples 1 to 5 and comparative examples 1 to 3 of the present invention were subjected to a room temperature three-point flexural strength test using a microcomputer controlled fine ceramic tester, with a span of 16mm and a strain rate of 0.5mm/min.
4. And measuring the controlled three coefficient and the specific heat capacity of the tungsten-lanthanum alloy wire by using a laser thermal diffusion instrument, and calculating the thermal conductivity of the tungsten-lanthanum alloy wire according to the following formula.
α＝λ/pc
5. The mechanical properties of the tungsten-lanthanum alloy wires prepared in examples 1 to 5 of the present invention were measured by unidirectional tensile testing at room temperature and 500℃and at a tensile strain rate of 0.06mm/min.
6. And observing the surface morphology of the tungsten-lanthanum alloy wire prepared in the embodiment 1-5 by adopting a scanning electron microscope.
Analysis of results
FIG. 1 is a graph showing the results of the strength of the tungsten lanthanum alloy prepared in examples 1-5 and comparative examples 1-3 according to the present invention, wherein the microscopic strength of the tungsten wire prepared in examples 1-5 is 510-530MPa, and the microscopic strength of the tungsten wire prepared from pure tungsten metal is 347MPa, the microscopic strength of the tungsten lanthanum alloy prepared in comparative example 2 is 369MPa, and the microscopic strength of the tungsten lanthanum alloy prepared in comparative example 3 is 354MPa; the bending strength of the tungsten lanthanum alloy wire prepared in examples 1-5 is 740-780MPa, while that of comparative example 1 is 320MPa, that of comparative example 2 is 476MPa, and that of comparative example 3 is 552MPa; since lanthanum element plays a role in dispersing in tungsten metal grains, the strength of the tungsten-lanthanum alloy is clearThe strength of the alloy is obviously higher than that of pure tungsten, and the tungsten fiber can strengthen the strength and toughness of the tungsten-lanthanum alloy so as to improve the mechanical property, and the flash burning treatment can lead the temperature of the calcined alloy to reach 10 in a short time 4 The temperature/min can improve the densification speed in the alloy, and prevent the migration of alloy grains, thereby improving the alloy strength.
FIG. 2 is a graph showing the results of the relative densities and room temperature thermal conductivities of the ullan alloys prepared in examples 1-5 and comparative examples 1-3 according to the present invention, wherein the relative densities of examples 1-5 are significantly higher than those of the tungsten-lanthanum alloy materials prepared in comparative examples 1-3; the pure tungsten metal has higher thermal conductivity, when alloy elements are doped in the pure tungsten, the thermal conductivity is obviously reduced due to the doping among crystal grains, the alloy wires prepared in the examples 1-5 have no obvious reduction compared with the pure tungsten, the doping content of the alloy elements is reduced due to the tungsten fiber serving as a supporting structure, and the lanthanum element content in the tungsten-lanthanum alloy prepared in the comparative example 2 is higher, so that the thermal conductivity is obviously influenced.
FIG. 3 is a graph showing the room temperature tensile stress strain curves of the tungsten-lanthanum alloy wires prepared in examples 1-5 and comparative examples 1-3, wherein the tungsten-lanthanum alloy wires still have obvious brittleness at room temperature, the sample is broken under the state of being in an elastic stage, the peak stress is lower, the peak stress of examples 1-5 is obviously higher than that of comparative examples 1-3, and the sintering mode of tungsten fiber doped tungsten-lanthanum alloy and flash treatment can prove that the toughness of the tungsten-lanthanum alloy is enhanced.
Fig. 4 is a graph showing the high temperature tensile stress strain curves of the tungsten-lanthanum alloy wires prepared in examples 1 to 5 and comparative examples 1 to 3 according to the present invention, wherein the tungsten-lanthanum alloy wire is subjected to yield after elastic deformation at a high temperature of 500 ℃, and the tensile strength and elongation are gradually increased, which indicates that a plastic region appears in the region 2, and the alloy material prepared in the examples has a significant improvement in tensile strength compared with the alloy material prepared in comparative example 1, and the tungsten fiber can have a significant toughening effect in combination with comparative example 2 and comparative example 3, so that the high temperature tensile strength of the material is improved.
Fig. 5 is an XRD image of the tungsten-lanthanum alloy wire prepared in example 1 according to the present invention, and as shown in the figure, the tungsten-lanthanum alloy wire prepared in example 1 has diffraction peaks of metallic tungsten and also shows diffraction peaks of lanthanum oxide, but since the content of tungsten is high, the diffraction peaks of lanthanum oxide are not obvious.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (3)
1. A preparation method of a tungsten-lanthanum alloy wire is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, dissolving ammonium paratungstate and lanthanum nitrate in deionized water, adding an organic adhesive, stirring, and drying for 2 hours at 40-60 ℃ in a vacuum environment after uniformly mixing to obtain tungsten-lanthanum alloy precursor powder; the content of ammonium paratungstate in deionized water is 50-400g/L; the content of lanthanum nitrate in deionized water is 2.5-12.5g/L; the content of the organic adhesive in deionized water is 1-5g/L; the organic binder is at least one of PVA, PVB, PMMA and ethyl cellulose;
s2, carrying out ultrasonic cleaning on the tungsten fibers to remove surface impurities, arranging the tungsten fibers in parallel in the same direction, and then vertically arranging a small amount of fibers to obtain a tungsten fiber sheet layer;
s3, placing the tungsten fiber sheet layer in a die, spreading the tungsten-lanthanum alloy precursor powder prepared in the step S1 on the tungsten fiber sheet layer, and repeating for 3 times to obtain a mixed material of three layers of tungsten fiber sheet layers and tungsten-lanthanum alloy precursor powder which are sequentially laminated; the mass ratio of each layer of tungsten fiber to tungsten-lanthanum alloy precursor powder is 1:3-4;
s4, placing the mixed material powder obtained in the step S3 in a hydrogen atmosphere for pre-sintering heat treatment, grinding and crushing, and sieving with a 200-mesh sieve to obtain tungsten-lanthanum alloy powder;
s5, cold pressing the tungsten-lanthanum alloy powder obtained in the step S4 into a cylindrical sample, placing the cylindrical sample in a flash furnace, performing flash burning and heat preservation, and obtaining a tungsten-lanthanum alloy blank after the flash furnace is cooled to room temperature;
the parameters of the flash firing treatment are that the preset temperature is 1000-1200 ℃, the temperature is kept for 10-30min, an alternating current power supply is started, the electric field strength is applied, after the preset current is reached, the voltage control of the power supply is changed into the current control, after the battery mode is converted, the power supply is kept for 1-3min, the power supply is turned off, and the cooling is carried out at room temperature;
the first stage of flash firing is controlled by voltage, and the preset electric field strength is applied to be 150-250V/cm; the second stage of flash burning is changed from voltage control to current control, and the current density is preset to 40-60mA/mm 2 ；
And S6, rolling, annealing and rotary forging the blank for multiple times to obtain the tungsten-lanthanum alloy wire.
2. The method for preparing the tungsten-lanthanum alloy wire according to claim 1, wherein: in S2, when the tungsten fiber is ultrasonically cleaned, the ultrasonic power is 300-500W, and the ultrasonic time is 0.5-2h.
3. The method for preparing the tungsten-lanthanum alloy wire according to claim 2, wherein: in S6, the rolling and annealing process of the blank is that the blank is subjected to medium-frequency annealing for 2 hours at 1800-2000 ℃ to obtain a second blank, and the second blank is a tungsten-lanthanum alloy rod with the diameter of 5-6 mm; intermediate-frequency annealing is carried out on the second blank for 2 hours at 2000-2200 ℃ to obtain a third blank, wherein the third blank is a tungsten-lanthanum alloy rod with the diameter of 2-3 mm; in S6, the step of performing rotary forging on the third blank includes: and heating the tungsten-lanthanum alloy rod to 1500-1700 ℃ under the condition of rotary forging strength, wherein the rotary forging speed is 1.0-1.5m/min, and the reduction rate of single pass of rotary forging is 12-20%.
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