CN112126837A - Preparation method of high-performance tungsten-rhenium alloy heating wire - Google Patents
Preparation method of high-performance tungsten-rhenium alloy heating wire Download PDFInfo
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
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- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
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- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
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- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R27/00—Arrangements for measuring resistance, reactance, impedance, or electric characteristics derived therefrom
- G01R27/02—Measuring real or complex resistance, reactance, impedance, or other two-pole characteristics derived therefrom, e.g. time constant
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Abstract
The invention relates to the field of metal materials, in particular to a preparation method of a high-performance tungsten-rhenium alloy heating wire, which comprises the steps of preparing rare earth ammonium rhenate → mixing, roasting and reducing → powder spheroidizing → blank pressing → vertical sintering → rotary forging and cogging → drawing processing → constant-temperature electrolytic polishing → sizing and resistance adjusting → stabilizing and annealing, and optimizing the process by adding rare earth elements such as lanthanum or/and cerium, so that the mechanical properties such as bending resistance and the like of the prepared high-performance tungsten-rhenium alloy heating wire are obviously improved, the service life is long, the reliability is high, the problems of wire splitting, brittle fracture and the like are solved, and a meter resistance continuous testing method and constant-temperature electrolytic polishing are combined, so that the meter resistance of the prepared tungsten-rhenium alloy heating wire has high uniformity, and the recrystallization temperature is also improved.
Description
Technical Field
The invention relates to the field of metal materials, in particular to a preparation method of a high-performance tungsten-rhenium alloy heating wire.
Background
With the development of modern technologies such as high vacuum electron tubes, high precision detection and electronic imaging, more rigorous requirements are provided for the resistance uniformity, high temperature mechanical property and high temperature stability of the electron tube heating wire material, and higher requirements are provided for the precise control of the material preparation process.
Aiming at the application requirement and the quality problems of easy splitting, brittle fracture and the like of the wire, scientific research personnel mainly add elements such as silicon, aluminum, potassium and the like to improve the recrystallization temperature and the anti-seismic performance of the alloy, but the phenomena of splitting, brittle fracture and the like in the alloy wire processing process and after high-temperature treatment are still serious, the meter resistance is greatly dispersed, and the application of the tungsten-rhenium alloy wire is seriously influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a high-performance tungsten-rhenium alloy heating wire aiming at the corresponding defects of the prior art, the process is optimized by adding rare earth elements such as lanthanum or/and cerium, the mechanical properties such as bending resistance and the like of the prepared tungsten-rhenium alloy heating wire are obviously improved, the service life is long, the reliability is high, the problems of wire splitting, brittle fracture and the like are solved, and the meter resistance continuous testing method and constant-temperature electrolytic polishing are combined, so that the meter resistance of the prepared tungsten-rhenium alloy heating wire has high uniformity, and the recrystallization temperature is also improved.
The purpose of the invention is realized by adopting the following scheme: a preparation method of a high-performance tungsten-rhenium alloy heating wire comprises the following steps:
1) the high-performance tungsten-rhenium alloy heating wire comprises the following components in percentage by weight: rhenium accounts for 3-26%, rare earth elements account for 0.03-0.20%, and the balance is tungsten;
wherein, rhenium element adopts ammonium perrhenate, and rare earth element is nitrate of corresponding element;
2) preparing rare earth ammonium rhenate: dissolving ammonium perrhenate and nitrate in deionized water according to each component in the high-performance tungsten-rhenium alloy heating wire in the step 1), stirring and heating until powder is crystallized, evaporating to remove water, drying the powder in an oven at 50-60 ℃ for 36-72 hours to obtain dried ammonium rare earth rhenate powder, and uniformly mixing;
3) mixing materials: adding tungsten powder into the rare earth ammonium rhenate powder in the step 2) to form mixed powder, adding grinding balls according to the ball-to-ball ratio of 1: 0.4-1: 0.6, and dispersing the mixed powder for 12-16 h by using a ball mill;
4) roasting and reducing: roasting the dispersed mixed powder for 1h at 300 ℃, reducing for 1h at 400 ℃, sieving with a 60-mesh sieve, reducing for 2 h-4 h at 900-1200 ℃, and sieving with a 120-mesh sieve;
5) spheroidizing powder: carrying out powder spheroidizing treatment on the calcined and reduced mixed powder on plasma spheroidizing equipment to obtain pre-alloyed powder; the spheroidizing power adopted by the plasma spheroidizing equipment is 40kw, and the argon flow is 6L-18L/min, so that the sphericity of the pre-alloyed powder can be ensured to be more than 90%.
6) Blank pressing: preparing the pre-alloyed powder into a blank by adopting an isostatic pressing process, wherein the pressure is 190-270 MPa, and the time is 15-20 min;
7) vertical melting and sintering: pre-sintering the blank at 1300-1400 ℃ for 2-4 h, wherein the density of the sintered blank is more than or equal to 18g/cm3；
8) Rotary swaging and cogging: heating the sintered blank to 1650-1400 ℃, preserving heat for 30min, and forging the blank into wire by using a rotary forging machine, wherein the pass reduction rate is 20-25%, and the processing size range is phi 13-phi 3 mm;
9) drawing and processing: drawing the wire material on a wire drawing machine, wherein the heating furnace temperature is 1300-700 ℃, the pass compression ratio is 15-20%, the processing size range is phi 3-phi 0.08mm, and the annealing treatment is carried out after the accumulated deformation of the wire material reaches 60-70%, and the annealing temperature is 1200-900 ℃;
10) constant-temperature electrolytic polishing: adopting alkali liquor to electrolytically clean the annealed wire, wherein the temperature of the electrolyte is 30 +/-5 ℃, the concentration of the alkali liquor is 15-25%, the cleaning electrolytic voltage is 20-90V, and the wire moving speed is 25-60 m/min, so as to obtain a polished wire;
11) sizing and resistance adjustment: testing the rice resistance of the wire obtained in the step 10) by using a rice resistance continuous testing method, and repeatedly adopting the constant-temperature electrolytic polishing in the step 10) to perform fixed-diameter resistance adjustment on the wire according to a test result until the fluctuation of the rice resistance of the wire is less than 2%;
the meter resistance continuous test method disclosed by the invention is disclosed in the invention patent with the publication number of CN108181509A, and relates to a continuous and precise test device and a test method for meter resistance of metal wires, which can realize continuous test of meter resistance of the whole wire, have high test efficiency, and ensure the uniformity of the whole meter resistance of the wires, and the precision can reach more than 0.2% by adopting a 6-bit half-digital multimeter and combining a four-wire test method.
12) And (3) stabilizing annealing: and (3) carrying out stabilizing annealing on the wire subjected to sizing and resistance adjustment, wherein the annealing temperature is 1000-1450 ℃, and the annealing time is 10-40 min, so that the resistance stability of the wire subjected to sizing and resistance adjustment is ensured.
In the step 1), the rare earth element is one or two of lanthanum and/or cerium.
The grinding ball in the step 3) is a mixed grinding ball containing a tungsten ball or a tungsten-rhenium alloy ball.
The meter resistance of the wire in the step 11) is adjusted according to the cleaning electrolytic voltage and the wire moving speed of the constant-temperature electrolytic polishing.
The sphericity of the pre-alloyed powder in the step 5) is more than or equal to 90%.
The vertical melting sintering in the step 7) is implemented in two sections, wherein the first section comprises the following steps: 1800A-2200A × 20 min; and a second stage: 2800A-3200A × 40min.
The performance test of the high-performance tungsten-rhenium alloy heating wire prepared by the invention is as follows:
the high-performance tungsten-rhenium alloy heating wire is subjected to heat treatment at 1600-1650 ℃ for 10-15min and then is bent at 90 ℃ without brittle fracture, 20 circles of wire rods with the diameter 5 times of the wire diameter are wound without brittle fracture, the meter resistance of the whole wire is measured, and the maximum fluctuation range of the meter resistance is not more than 2% of the theoretical meter resistance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the rare earth lanthanum or cerium is beneficial to purifying crystal boundary, refining crystal grains, improving the strength and recrystallization temperature of the alloy, reducing splitting and brittle fracture of the tungsten-rhenium alloy wire, has small influence on the resistivity of the material and obviously improves the properties of bending, tensile strength and the like of the material compared with the traditional doping of silicon, aluminum and potassium, and the addition mode of the rare earth element can ensure the uniformity of the components.
(2) The strength of the pressed blank of the spherical powder is improved by more than 100 percent compared with that of the blank of the non-spherical powder, and the compactness and the mechanical property of the tungsten-rhenium alloy heating wire are improved by adopting the spherical powder to press the blank;
(3) by using a meter resistance continuous testing method and constant-temperature electrolytic polishing, the meter resistance uniformity of the high-performance tungsten-rhenium alloy heating wire is ensured, the meter resistance fluctuation of the high-performance tungsten-rhenium alloy heating wire is less than 2%, and missing detection is prevented.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a graph showing the comparison of tensile strength between rare earth-doped wire and non-rare earth-doped wire;
FIG. 3 is a diagram of a high-performance W-Re alloy heating wire prepared by the invention after being bent for multiple times;
FIG. 4 is a meter resistance continuous test curve diagram of the high-performance tungsten-rhenium alloy heating wire prepared by the invention;
Detailed Description
As shown in fig. 1 to 4, a method for preparing a high-performance tungsten-rhenium alloy heating wire comprises the following steps:
1) the high-performance tungsten-rhenium alloy heating wire comprises the following components in percentage by weight: rhenium accounts for 3-26%, rare earth elements account for 0.03-0.20%, and the balance is tungsten;
wherein, rhenium element adopts ammonium perrhenate, and rare earth element is nitrate of corresponding element;
in the step 1), the rare earth element is one or two of lanthanum and/or cerium.
2) Preparing rare earth ammonium rhenate: dissolving ammonium perrhenate and nitrate in deionized water according to each component in the high-performance tungsten-rhenium alloy heating wire in the step 1), stirring and heating until powder is crystallized, evaporating to remove water, drying the powder in an oven at 50-60 ℃ for 36-72 hours to obtain dried ammonium rare earth rhenate powder, and uniformly mixing;
3) mixing materials: adding tungsten powder into the rare earth ammonium rhenate powder in the step 2) to form mixed powder, adding grinding balls according to the ball-to-ball ratio of 1: 0.4-1: 0.6, and dispersing the mixed powder for 12-16 h by using a ball mill;
the grinding ball in the step 3) is a mixed grinding ball containing a tungsten ball or a tungsten-rhenium alloy ball.
4) Roasting and reducing: roasting the dispersed mixed powder for 1h at 300 ℃, reducing for 1h at 400 ℃, sieving with a 60-mesh sieve, reducing for 2 h-4 h at 900-1200 ℃, and sieving with a 120-mesh sieve;
5) spheroidizing powder: carrying out powder spheroidizing treatment on the calcined and reduced mixed powder on plasma spheroidizing equipment to obtain pre-alloyed powder; the spheroidizing power adopted by the plasma spheroidizing equipment is 40kw, and the argon flow is 6L-18L/min, so that the sphericity of the pre-alloyed powder can be ensured to be more than 90%.
The sphericity of the pre-alloyed powder in the step 5) is more than or equal to 90%.
6) Blank pressing: preparing the pre-alloyed powder into a blank by adopting an isostatic pressing process, wherein the pressure is 190-270 MPa, and the time is 15-20 min;
7) vertical melting and sintering: pre-sintering the blank at 1300-1400 ℃ for 2-4 h, wherein the density of the sintered blank is more than or equal to 18g/cm3；
The vertical melting sintering in the step 7) is implemented in two sections, wherein the first section comprises the following steps: 1800A-2200A × 20 min; and a second stage: 2800A-3200A × 40min.
8) Rotary swaging and cogging: heating the sintered blank to 1650-1400 ℃, preserving heat for 30min, and forging the blank into wire by using a rotary forging machine, wherein the pass reduction rate is 20-25%, and the processing size range is phi 13-phi 3 mm;
9) drawing and processing: drawing the wire material on a wire drawing machine, wherein the heating furnace temperature is 1300-700 ℃, the pass compression ratio is 15-20%, the processing size range is phi 3-phi 0.08mm, and the annealing treatment is carried out after the accumulated deformation of the wire material reaches 60-70%, and the annealing temperature is 1200-900 ℃;
10) constant-temperature electrolytic polishing: adopting alkali liquor to electrolytically clean the annealed wire, wherein the temperature of the electrolyte is 30 +/-5 ℃, the concentration of the alkali liquor is 15-25%, the cleaning electrolytic voltage is 20-90V, and the wire moving speed is 25-60 m/min, so as to obtain a polished wire;
11) sizing and resistance adjustment: testing the rice resistance of the wire obtained in the step 10) by using a rice resistance continuous testing method, and repeatedly adopting the constant-temperature electrolytic polishing in the step 10) to perform fixed-diameter resistance adjustment on the wire according to a test result until the fluctuation of the rice resistance of the wire is less than 2%;
the meter resistance of the wire in the step 11) is adjusted according to the cleaning electrolytic voltage and the wire moving speed of the constant-temperature electrolytic polishing.
The meter resistance continuous test method disclosed by the invention is disclosed in the invention patent with the publication number of CN108181509A, and relates to a continuous and precise test device and a test method for meter resistance of metal wires, which can realize continuous test of meter resistance of the whole wire, have high test efficiency, and ensure the uniformity of the whole meter resistance of the wires, and the precision can reach more than 0.2% by adopting a 6-bit half-digital multimeter and combining a four-wire test method.
12) And (3) stabilizing annealing: and (3) carrying out stabilizing annealing on the wire subjected to sizing and resistance adjustment, wherein the annealing temperature is 1000-1450 ℃, and the annealing time is 10-40 min, so that the resistance stability of the wire subjected to sizing and resistance adjustment is ensured.
The technical solution of the present invention will be described with reference to the following examples 1 to 3.
Material purity:
the purity of the tungsten powder is more than or equal to 99.95 percent (sold in the market), the Fisher particle size is 2.0-5.0 mu m, the particle size is in normal mass distribution, and the shape is polygonal.
Rhenium element as NH4ReO4Form addition of NH4ReO4The purity of the product is more than or equal to 99.99 percent.
Lanthanum as rare earth element La (NO)3)3·6H2Adding in the form of O;
rare earth element cerium with Ce (NO)3)3·6H2Adding in the form of O;
EXAMPLE 1 weighing 2.6 g La (NO)3)3·6H2O and 300 g NH4ReO4Dissolving the mixture in 800ml deionized water, heating, stirring and concentrating to obtain fine powder, drying in 60 deg.C oven for 36 hr, adding dried powder into ball mill, adding 825 g tungsten powder, adding 450 g grinding ball, dispersing in ball mill at 150r/min for 12 hr, taking out the mixed powder, and placing in H at 300 deg.C and 400 deg.C2Respectively reducing for 1 hour under atmosphere, sieving with 60 mesh sieve, dispersing again in ball mill, adding 450 g grinding ball, dispersing at 150r/min for 12 hours, and H at 1100 deg.C2Reducing for 3 hours in the atmosphere to obtain the tungsten-rhenium pre-alloy powder.
Preparing spherical powder at an argon flow rate of 6L/min, pressing the tungsten-rhenium pre-alloy powder on an isostatic press at a pressure of 240MPa for 20min to form a blank strip with the diameter of phi 12mm multiplied by 300mm, presintering at 1400 ℃ for 2h, vertically melting at 2100A for 20min, vertically melting at 3050A for 40min, processing the blank strip by 20% of pass, performing rotary swaging to phi 3mm, and drawing to form a filament with the diameter of 0.1mm according to the pass processing rate of 20%. Cleaning oxide skin and graphite emulsion on the surface of the wire material at the concentration of 25% of alkali liquor, cleaning the electrolytic voltage of 90V and the wire running speed of 60m/min, cleaning the wire material at the speed of 25m/min, testing the meter resistance of the obtained wire material by a meter resistance continuous test method, repeatedly carrying out constant-temperature electrolytic polishing according to the test result to carry out sizing and resistance adjustment on the wire material until the meter resistance fluctuation of the wire material is less than 2%, annealing the wire material at 1000 ℃ for 40 minutes, carrying out performance test, bending the wire material for 90 degrees, unfolding the wire material for 90 degrees, tightly winding the wire material for 20 circles on a core rod with the diameter of 5 times of the wire diameter, and not cracking and brittle fracture, wherein the whole wire has the meter resistance fluctuation of less than 2%, and bending the wire material for 90 degrees after being.
Example 2 weigh 7.6 grams of Ce (NO)3)3·6H2O and 700 g NH4ReO4Dissolving the powder in 2000ml of deionized water completely, continuously heating, stirring and concentrating the solution to form fine powder, transferring the powder into a 50 ℃ oven for drying for 72 hours, transferring the dried powder into a ball mill, adding 1945 g of tungsten powder, adding 1400 g of grinding balls, and placing the powder on the ball mill for dispersing for 16 hours at the speed of 150r/min. Taking out the mixed powder at H of 300 ℃ and 400 DEG C2Respectively reducing for 1 hour under atmosphere, sieving with 60 mesh sieve, dispersing again in ball mill, adding 880 g of grinding ball, dispersing at 150r/min for 14 hours, and maintaining at 1200 deg.C in H2Reducing for 2 hours under the atmosphere to obtain the tungsten-rhenium prealloy powder.
Preparing spherical powder at an argon flow rate of 18L/min, pressing the tungsten-rhenium pre-alloy powder on an isostatic press at a pressure of 270MPa for 15min to form a blank strip with a diameter of 12mm multiplied by 300mm, pre-sintering at 1350 ℃ for 3h, vertically melting at 1800A for 20min, vertically melting at 3200A for 40min, processing the blank strip by 25% of rotary swaging and cogging by passes, gradually forging the blank strip to a diameter of 3mm, and drawing the blank strip to a filament with a diameter of 0.3mm according to a pass processing rate of 10%. Cleaning oxide skin and graphite emulsion on the surface of the wire material at the concentration of 15% of alkali liquor, cleaning the electrolytic voltage of 60V and the wire running speed of 40m/min, cleaning the wire material at the speed of 30V and the speed of 50m/min, testing the meter resistance of the obtained wire material by a meter resistance continuous test method, repeatedly carrying out constant-temperature electrolytic polishing according to the test result to carry out sizing and resistance adjustment on the wire material until the meter resistance fluctuation of the wire material is less than 2%, annealing the wire material at 1450 ℃ for 10 minutes, carrying out performance test, bending the wire material for 90 degrees to expand, tightly winding the wire material on a core rod with the diameter of 5 times for 20 circles, and carrying out non-cracking and non-brittle fracture on the whole wire, wherein the meter resistance fluctuation of the whole wire is less than 2%.
Example 3.6 g of Ce (NO) are weighed3)3·6H2O, 4 g La (NO)3)3·6H2O and 700 g NH4ReO4Completely dissolving the powder in 2000ml of deionized water, continuously heating, stirring and concentrating the solution to be fine powder, transferring the powder into a 55 ℃ oven for drying for 48 hours, transferring the dried powder into a ball mill tank, adding 1945 g of tungsten powder, adding 1400 g of grinding balls, and placing the powder on a high-energy dispersion machine for dispersing for 15 hours at the speed of 150r/min. Taking out the mixed powder at H of 300 ℃ and 400 DEG C2Respectively reducing for 1 hour under atmosphere, sieving with 60 mesh sieve, dispersing again on high energy disperser, adding 870 g tungsten ball, dispersing at 150r/min for 13 hours, and dispersing at 1200 deg.C in H2Reducing for 2 hours under the atmosphere to obtain the tungsten-rhenium prealloy powder.
Preparing spherical powder at an argon flow rate of 11L/min, pressing the tungsten-rhenium pre-alloy powder on an isostatic press at a pressure of 260MPa and a pressure of 17min to form a blank strip with a diameter of 12mm multiplied by 300mm, presintering at 1300 ℃ for 4h, vertically melting at 1800A for 20min, vertically melting at 3200A for 40min, processing the blank strip by 25% of rotary swaging and cogging by pass, gradually forging the blank strip to a diameter of 3mm, and drawing the blank strip to a filament with a diameter of 0.3mm according to a pass processing rate of 10%. Cleaning oxide skin and graphite emulsion on the surface of the wire material at the concentration of 15% of alkali liquor, cleaning electrolytic voltage of 70V and the wire running speed of 50m/min, cleaning at the electrolytic voltage of 30V and the wire running speed of 5m/min, testing the meter resistance of the obtained wire material by a meter resistance continuous test method, repeatedly carrying out constant-temperature electrolytic polishing according to the test result to carry out sizing and resistance adjustment on the wire material until the meter resistance fluctuation of the wire material is less than 2%, then carrying out performance test after annealing the wire material for 30 minutes at 1250 ℃, bending the wire material for 90 degrees and spreading the wire material for 20 circles on a core rod with 5 times of wire diameter, and carrying out treatment at 1630 ℃ for 13 minutes without cracking and brittle fracture.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and those skilled in the art can make modifications without departing from the spirit of the present invention.
Claims (6)
1. The preparation method of the high-performance tungsten-rhenium alloy heating wire is characterized by comprising the following steps of:
1) the high-performance tungsten-rhenium alloy heating wire comprises the following components in percentage by weight: rhenium accounts for 3-26%, rare earth elements account for 0.03-0.20%, and the balance is tungsten;
wherein, rhenium element adopts ammonium perrhenate, and the rare earth element adopts nitrate of corresponding element;
2) preparing rare earth ammonium rhenate: dissolving ammonium perrhenate and nitrate in the step 1) into deionized water according to each component in the high-performance tungsten-rhenium alloy heating wire in the step 1), stirring and heating until powder is crystallized, drying the powder by distillation for 36-72 hours, putting the powder into an oven at 50-60 ℃ to obtain dry ammonium rare earth rhenate powder, and uniformly mixing;
3) mixing materials: adding tungsten powder into the rare earth ammonium rhenate powder in the step 2) to form mixed powder, adding grinding balls according to the ball-to-ball ratio of 1: 0.4-1: 0.6, and dispersing the mixed powder for 12-16 h by using a ball mill;
4) roasting and reducing: roasting the dispersed mixed powder for 1h at 300 ℃, reducing for 1h at 400 ℃, sieving with a 60-mesh sieve, reducing for 2 h-4 h at 900-1200 ℃, and sieving with a 120-mesh sieve;
5) spheroidizing powder: carrying out powder spheroidizing treatment on the calcined and reduced mixed powder on plasma spheroidizing equipment to obtain pre-alloyed powder;
6) blank pressing: preparing the pre-alloyed powder into a blank by adopting an isostatic pressing process, wherein the pressure is 190-270 MPa, and the time is 15-20 min;
7) vertical melting and sintering: pre-sintering the blank at 1300-1400 ℃ for 2-4 h, wherein the density of the sintered blank is more than or equal to 18g/cm3；
8) Rotary swaging and cogging: heating the sintered blank to 1650-1400 ℃, preserving heat for 30min, and forging the blank into wire by using a rotary forging machine, wherein the pass reduction rate is 20-25%, and the processing size range is phi 13-phi 3 mm;
9) drawing and processing: drawing the wire material on a wire drawing machine, wherein the heating furnace temperature is 1300-700 ℃, the pass compression ratio is 15-20%, the processing size range is phi 3-phi 0.08mm, and the annealing treatment is carried out after the accumulated deformation of the wire material reaches 60-70%, and the annealing temperature is 1200-900 ℃;
10) constant-temperature electrolytic polishing: adopting alkali liquor to electrolytically clean the annealed wire, wherein the temperature of the electrolyte is 30 +/-5 ℃, the concentration of the alkali liquor is 15-25%, the cleaning electrolytic voltage is 20-90V, and the wire moving speed is 25-60 m/min, so as to obtain a polished wire;
11) sizing and resistance adjustment: testing the rice resistance of the wire obtained in the step 10) by using a rice resistance continuous testing method, and repeatedly adopting the constant-temperature electrolytic polishing in the step 10) to perform fixed-diameter resistance adjustment on the wire according to a test result until the fluctuation of the rice resistance of the wire is less than 2%;
12) and (3) stabilizing annealing: and (3) carrying out stabilizing annealing on the wire subjected to sizing and resistance adjustment, wherein the annealing temperature is 1000-1450 ℃, and the time is 10-40 min.
2. The preparation method of the high-performance tungsten-rhenium alloy heating wire according to claim 1, characterized in that: in the step 1), the rare earth element is one or two of lanthanum and/or cerium.
3. The preparation method of the high-performance tungsten-rhenium alloy heating wire according to claim 1, characterized in that: the grinding ball in the step 3) is a mixed grinding ball containing a tungsten ball or a tungsten-rhenium alloy ball.
4. The preparation method of the high-performance tungsten-rhenium alloy heating wire according to claim 1, characterized in that: the meter resistance of the wire in the step 11) is adjusted according to the cleaning electrolytic voltage and the wire moving speed of the constant-temperature electrolytic polishing.
5. The preparation method of the high-performance tungsten-rhenium alloy heating wire according to claim 1, characterized in that: the sphericity of the pre-alloyed powder in the step 5) is more than or equal to 90%.
6. The preparation method of the high-performance tungsten-rhenium alloy heating wire according to claim 1, characterized in that: the vertical melting sintering in the step 7) is implemented in two sections, wherein the first section comprises the following steps: 1800A-2200A × 20 min; and a second stage: 2800A-3200A × 40min.
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| CN113604719A (en) * | 2021-06-17 | 2021-11-05 | 重庆材料研究院有限公司 | Preparation method of high-performance tungsten-rhenium thermocouple wire |
| CN114381643A (en) * | 2021-12-30 | 2022-04-22 | 镇江原轼新型材料有限公司 | High-density tungsten alloy wire and preparation method thereof |
| CN114888292A (en) * | 2022-05-11 | 2022-08-12 | 陕西汇联聚合新材料有限公司 | Preparation method of high-strength superfine tungsten alloy wire for cutting |
| CN115229700A (en) * | 2022-07-27 | 2022-10-25 | 镇江原轼新型材料有限公司 | Tungsten wire and saw wire |
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