CN110257745B - White tungsten wire and preparation method thereof - Google Patents

White tungsten wire and preparation method thereof Download PDF

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Publication number
CN110257745B
CN110257745B CN201910680942.1A CN201910680942A CN110257745B CN 110257745 B CN110257745 B CN 110257745B CN 201910680942 A CN201910680942 A CN 201910680942A CN 110257745 B CN110257745 B CN 110257745B
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wire
filament
wire drawing
temperature
tungsten
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CN110257745A (en
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徐福生
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Liaoning dongdaihe New District Xingyuan Technology Co.,Ltd.
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Langfang Huaxing Tungsten Molybdenum Industry Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/02—Drawing metal wire or like flexible metallic material by drawing machines or apparatus in which the drawing action is effected by drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C51/00—Measuring, gauging, indicating, counting, or marking devices specially adapted for use in the production or manipulation of material in accordance with subclasses B21B - B21F
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals
    • C25F3/26—Polishing of heavy metals of refractory metals

Abstract

The invention provides a preparation method of a tungsten filament, belonging to the technical field of photocopiers. The preparation method comprises the following steps: (1) sequentially performing filament unwinding, annealing, graphite emulsion attaching, heating, wire drawing and filament winding on a tungsten filament precursor to obtain a black tungsten filament; repeating the processes of attaching the graphite emulsion, heating and drawing N times; wherein N is more than or equal to 4 and less than or equal to 12; the annealing time is after the wire drawing for the Nth time to 4 times and before the graphite emulsion is attached for the N times to 3 times; (2) and (2) sequentially carrying out continuous electrolysis and stress homogenization on the black tungsten wire obtained in the step (1) to obtain a white tungsten wire with the specification of 28-420 mg/200 mm. By optimizing the parameters in the step (1) and the step (2), when the obtained white tungsten filament is used for loose core winding and rodless setting of a heating lamp of a photocopier, the deformation rate of the tungsten filament is reduced to below 1%, and the defect of penetrating rod setting is overcome. The production cost of heating lamp manufacturing enterprises is reduced by more than 20%.

Description

White tungsten wire and preparation method thereof
Technical Field
The invention relates to the technical field of photocopiers, in particular to a white tungsten wire and a preparation method thereof.
Background
Since photocopier manufacturers have high requirements for the heating lamps, in addition to the photoelectric indicators, the shock resistance is a key quality indicator for the heating lamps, and the filament breakage rate of the heating lamps is less than one ten thousandth under normal transport and use conditions of the photocopiers throughout the life of the heating lamps. Under the high requirement, the existing rod penetrating and shaping method cannot achieve the purpose even if the tungsten wire material with the best shock resistance is selected. The reason is that the through rod shaping can cause the filament to generate brittle points, which affects the shock resistance. The use of rodless sizing can solve this problem. However, the filament can be deformed during the rodless shaping, and the stress in different directions generated in the tungsten filament production process must be consistent to solve the problem of filament deformation. In order to achieve the purpose, the method commonly used by tungsten wire production enterprises at present is as follows: selecting the best raw material, and eliminating stress generated in the drawing process as much as possible by selecting different annealing points, even increasing the annealing times, increasing the annealing temperature, prolonging the annealing time and the like in the drawing process of the black tungsten wire; in the production process of the white yarn, an electrolysis method and a hydrogen burning method are adopted, and when the electrolysis method is adopted, the polarization is reduced as much as possible by changing parameters such as electrolyte formula, concentration, temperature, current, speed, electrolyte flow rate and the like. Although tungsten wire production enterprises use the methods at present, the tungsten wire production enterprises do not achieve the optimal combination, and the qualified rate of the produced tungsten wire for loose core winding and rodless shaping is only 85 percent at most.
Disclosure of Invention
In view of the above, the present invention aims to provide a white tungsten filament and a preparation method thereof, wherein when the white tungsten filament obtained by the preparation method of the present invention is used for loose core winding and rodless setting of a heating lamp of a photocopier, a tungsten filament deformation rate is reduced to below 1%, and meanwhile, the defect of rod penetration setting is solved. The production cost of heating lamp manufacturing enterprises is reduced by more than 20%.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a white tungsten wire, which comprises the following steps:
(1) sequentially performing filament unwinding, annealing, graphite emulsion attaching, heating, wire drawing and filament winding on a tungsten filament precursor to obtain a black tungsten filament;
repeating the processes of attaching the graphite emulsion, heating and drawing N times;
wherein N is more than or equal to 4 and less than or equal to 12;
the annealing time is after the wire drawing for the Nth time to 4 times and before the graphite emulsion is attached for the N times to 3 times;
the tungsten filament comprises a phi 0.39-0.60A grade material which meets the W91 or W61 mark specified in GB/T23272-2009;
when N is 4, the parameters in step (1) include: the back tension of the wire drawing is 4.7-6.7 g/mg, the annealing temperature is 1200-1300 ℃, the annealing time is 10-14 s, the baume degree of the quartic graphite emulsion is 5.0 independently, the quartic heating temperature is 900-1000 ℃, the temperature of the quartic wire drawing die is 350-370 ℃, the quartic wire drawing compression ratio is 20-22% independently, the wire drawing speed is 8-12 m/min, and the wire drawing torque is 1.1-1.3 N.m; the black tungsten wire has the specification of 185-460 mg/200mm and the tensile strength of 2000-2150N/mm2Other items are tested to meet the national standard qualification index;
(2) carrying out continuous electrolysis and stress homogenization on the black tungsten wire obtained in the step (1) in sequence to obtain a white tungsten wire, wherein the specification of the white tungsten wire is 165-420 mg/200mm, and the tensile strength is 2080-2230N/mm2。
Preferably, when N ═ 5 or 6, the parameters in step (1) include: silk-releasing counter-pulling force of 5.0 &7.0g/mg, the annealing temperature is 1200-1300 ℃, the annealing time is 8-11 s, the baume degrees of the five or six graphite latexes are independently 5.0, the heating temperature of the five or six times is independently 800-900 ℃, the temperature of the five or six wire drawing dies is independently 350-370 ℃, the wire drawing compression ratio of the five or six times is independently 18-21%, the wire drawing speed is 13-17 m/min, and the wire drawing torque is 0.8-1.0 N.m; the black tungsten wire has the specification of 125-180 mg/200mm and the tensile strength of 2120-2200N/mm2Other items are tested to meet the national standard qualification index;
the black tungsten wire is subjected to continuous electrolysis and stress homogenization in sequence to obtain a white tungsten wire; the specification of the white tungsten filament is 105-165 mg/200mm, and the tensile strength is 2230-2310N/mm2。
Preferably, when N ═ 7 or 8, the parameters of step (1) include; the wire-drawing back tension is 6.0-8.0 g/mg, the annealing temperature is 1250-1350 ℃, and the annealing time is 6.0-7.5 s; the baume degree of the seven-time or eight-time graphite emulsion is independently 5.0, the heating temperature of the seven-time or eight-time graphite emulsion is independently 750-850 ℃, the temperature of the seven-time or eight-time wire drawing die is independently 350-370 ℃, the wire drawing compression ratio of the seven-time or eight-time wire drawing die is independently 17-20%, the wire drawing speed is 18-22 m/min, and the wire drawing torque is 0.4-0.6 N.m; the specification of the black tungsten wire is 95-125 mg/200mm, and the tensile strength is 2190-2270N/mm2Other items are tested to meet the national standard qualification index;
the black tungsten wire is subjected to continuous electrolysis and stress homogenization in sequence to obtain a white tungsten wire; the white tungsten wire has the specification of 80-105 mg/200mm and the tensile strength of 2230-2380N/mm2。
Preferably, when N is 9, 10, 11 or 12, the parameters of step (1) include: the back tension of the wire drawing is 6.0-8.0 g/mg, the annealing temperature is 1250-1350 ℃, the annealing time is 4-5.5 s, the baume degrees of the graphite milk of the last four times are independently 3.5, the heating temperature of the last four times is independently 600-620 ℃, the temperature of the wire drawing die of the last four times is independently 380-420 ℃, the wire drawing compression ratio of the last four times is independently 17-19%, the wire drawing speed is 23-30 m/min, and the wire drawing torque is 0.25-0.35 N.m; of the black tungsten wireThe specification is 38-95 mg/200mm, and the tensile strength is 2270-2500N/mm2Other items are tested to meet the national standard qualification index;
the black tungsten wire is subjected to continuous electrolysis and stress homogenization in sequence to obtain a white tungsten wire; the white tungsten wire has the specification of 28-80 mg/200mm and the tensile strength of 2380-2570N/mm2。
Preferably, the continuous electrolysis comprises four electrolysis processes.
Preferably, the primary electrolysis process parameters include: the electrolyte is NaOH and H2O is mixed according to the weight ratio of 11: 100, mixing, wherein the temperature of an electrolyte is 20-35 ℃, the flow rate of the electrolyte is 17-23L/min, the current is 9-11A, the filament winding speed is 14-17 m/min, and the back tension of the filament is 3.7-4.3 g/mg;
the secondary electrolysis process parameters comprise: the electrolyte is NaOH and H2O is mixed according to the weight ratio of 11: 100, mixing, wherein the temperature of electrolyte is 20-35 ℃, the flow rate of the electrolyte is 17-23L/min, the current is 10-17A, the filament winding speed is 14-17 m/min, and the back tension of the filament is 3.7-4.3 g/mg;
the parameters of the third electrolysis process comprise: the electrolyte is NaOH and H2O is mixed according to the weight ratio of 7: 100, mixing, wherein the temperature of an electrolyte is 20-35 ℃, the flow rate of the electrolyte is 17-23L/min, the current is 10-17A, the filament winding speed is 9-17 m/min, and the back tension of the filament is 3.7-4.3 g/mg;
the parameters of the four electrolysis processes comprise: the electrolyte is NaOH and H2O is mixed according to the weight ratio of 7: 100, the temperature of the electrolyte is 20-35 ℃, the flow rate of the electrolyte is 17-23L/min, the current is 25-30A, the filament winding speed is 6-17 m/min, and the back tension of the filament is 3.7-4.3 g/mg.
Preferably, the wet hydrogen annealing temperature of the stress homogenization is 1200-1300 ℃, the dry hydrogen annealing temperature is 1400-1500 ℃, the wire unwinding counter-tension is 2.7-3.3 g/mg, and the wire winding speed is 2-12 m/min.
The invention also provides the white tungsten wire prepared by the technical scheme, and the tensile strength of the white tungsten wire is 2000-2600N/mm2。
The invention provides (1) tungsten filament precursor sequentially subjected to filament discharge, annealing, graphite emulsion attachment, heating, wire drawing and collectionFilament to obtain black tungsten filament; repeating the processes of attaching the graphite emulsion, heating and drawing N times; wherein N is more than or equal to 4 and less than or equal to 12; the annealing time is after the wire drawing for the Nth time to 4 times and before the graphite emulsion is attached for the N times to 3 times; the tungsten filament comprises a phi 0.39-0.60A grade material which meets the W91 or W61 mark specified in GB/T23272-2009; the specification of the black tungsten wire obtained after N times of wire drawing is 38-460 mg/200mm, and the tensile strength is 2000-2600N/mm2Other items are tested to meet the national standard qualification index; (2) carrying out continuous electrolysis and stress homogenization on the black tungsten wire obtained in the step (1) in sequence to obtain a white tungsten wire, wherein the specification of the white tungsten wire is 28-420 mg/200mm, and the tensile strength is 2000-2600N/mm2. The invention obtains the black tungsten filament with excellent performance by strictly controlling the specification of the tungsten filament precursor, the counter-pulling force of filament unwinding, the baume degree of graphite emulsion, the heating temperature, the wiredrawing compression ratio, the wiredrawing speed, the torque of filament winding, the annealing temperature and the annealing time; and then electrolytic and stress homogenization treatment is combined, so that the stress of the tungsten wire is reduced, and the white tungsten wire meeting the requirements is obtained. The tensile strength of the white tungsten wire obtained by the method is 2000-2600N/mm2(ii) a When the tungsten filament is used for core-pulling winding and rodless setting of a heating lamp of a photocopier, the deformation rate of the tungsten filament is reduced to below 1%, and the defect of rod penetrating setting is overcome. The production cost of heating lamp manufacturing enterprises is reduced by more than 20%.
Drawings
FIG. 1 is a schematic drawing of a drawing apparatus;
FIG. 2 is a schematic view of a continuous electrolytic apparatus;
FIG. 3 is a schematic view of a TO furnace high temperature stress homogenizing apparatus.
Detailed Description
The invention provides a preparation method of a white tungsten wire, which comprises the following steps:
(1) sequentially performing filament unwinding, annealing, graphite emulsion attaching, heating, wire drawing and filament winding on a tungsten filament precursor to obtain a black tungsten filament;
repeating the processes of attaching the graphite emulsion, heating and drawing N times;
wherein N is more than or equal to 4 and less than or equal to 12;
the annealing time is after the wire drawing for the Nth time to 4 times and before the graphite emulsion is attached for the N times to 3 times;
the tungsten filament comprises a phi 0.39-0.60A grade material which meets the W91 or W61 mark specified in GB/T23272-2009;
when N is 4, the parameters in step (1) include: the back tension of the wire drawing is 4.7-6.7 g/mg, the annealing temperature is 1200-1300 ℃, the annealing time is 10-14 s, the baume degree of the quartic graphite emulsion is 5.0 independently, the quartic heating temperature is 900-1000 ℃, the temperature of the quartic wire drawing die is 350-370 ℃, the quartic wire drawing compression ratio is 20-22% independently, the wire drawing speed is 8-12 m/min, and the wire drawing torque is 1.1-1.3 N.m; the black tungsten wire has the specification of 185-460 mg/200mm and the tensile strength of 2000-2150N/mm2Other items are tested to meet the national standard qualification index;
(2) carrying out continuous electrolysis and stress homogenization on the black tungsten wire obtained in the step (1) in sequence to obtain a white tungsten wire, wherein the specification of the white tungsten wire is 165-420 mg, and the tensile strength is 2080-2230N/mm2。
The method comprises the following steps of sequentially performing filament unwinding, annealing, graphite emulsion attaching, heating, wire drawing and filament winding on a tungsten filament precursor to obtain a black tungsten filament; the process of attaching the graphite emulsion, heating and drawing was repeated N times. In the invention, N is more than or equal to 4 and less than or equal to 12. In the invention, the annealing time is after the Nth-4 th wire drawing and before the Nth-3 th attachment of the graphite emulsion.
In the invention, when N is 4, the annealing time is that the tungsten filament is directly annealed after being unreeled; and (3) repeatedly attaching graphite emulsion to the annealed tungsten filament precursor, heating and drawing for 4 times, and collecting the filament to obtain the black tungsten filament.
In the invention, the back tension of the filament is 4.7-6.7 g/mg, preferably 5.0-6.5 g/mg, and more preferably 5.5-6.0 g/mg. In the invention, the wire releasing counter-tension keeps the stability of the tungsten filament precursor entering the wire drawing die, thereby reducing the generation of irregular stress.
In the invention, the annealing temperature is 1200-1300 ℃, preferably 1220-280 ℃, and more preferably 1240-1260 ℃; the annealing time is 10-14 s, preferably 11-13 s, and more preferably 11.5-12.5 s. In the invention, the annealing can eliminate the internal stress of the black tungsten wire and ensure the quality of the final white tungsten wire.
In the present invention, the 4-fold graphitic breast baume is independently 5.0. In the invention, the graphite emulsion plays a role in lubrication, and ensures that the tungsten filament precursor can smoothly pass through a wire drawing die under the action of small deformation force.
In the invention, the heating temperature for 4 times is 900-1000 ℃, preferably 920-980 ℃, and more preferably 940-960 ℃. In the invention, the heating can dry the graphite emulsion attached to the tungsten filament precursor, and the tungsten filament precursor reaches the plastic deformation temperature of over 600 ℃, thereby improving the quality of the black tungsten filament.
In the invention, the temperature of the 4-time wire-drawing die is 350-370 ℃, preferably 355-365 ℃, more preferably 358-362 ℃; the 4-time drawing compression ratio is 20-22% independently, preferably 20.5-21.5%, and more preferably 20.8-21.2%; the drawing speed is 8 to 12m/min, preferably 9 to 11m/min, and more preferably 9.5 to 10.5 m/min. In the invention, the wire drawing can thin the tungsten filament precursor to obtain the black tungsten filament with each index meeting the requirement.
In the present invention, the yarn take-up torque is 1.1 to 1.3 N.m, preferably 1.15 to 1.25 N.m, and more preferably 1.18 to 1.22 N.m. In the invention, the filament winding can ensure that the black tungsten filament has certain tension, and can avoid filament bending and filament pressing. In the invention, when N is 4, the black tungsten filament obtained in the step (1) has the specification of 185-460 mg/200mm and the tensile strength of 2000-2150N/mm2And other items of inspection accord with the national standard qualification index.
In the invention, when N is 5, the annealing time is that the tungsten filament is subjected to filament discharge, primary attachment of graphite emulsion, primary heating and primary wire drawing; annealing is carried out; and (3) repeatedly attaching graphite emulsion to the annealed tungsten filament precursor, heating and drawing for 4 times, and then collecting the filament to obtain the black tungsten filament: when N is 6, the annealing time is that the tungsten filament is subjected to filament discharge and repeated attachment of the graphite emulsion, heating and wire drawing for 2 times; annealing is carried out; and repeating the processes of attaching the graphite emulsion to the annealed tungsten filament precursor, heating and drawing for 4 times, and collecting the filament to obtain the black tungsten filament. In the present invention, when N is 5 or 6, the other parameters in step (1) are selected in the same range except for different annealing timings. The method specifically comprises the following steps: the counter-pulling force of the filament is preferably 5.0-7.0 g/mg, more preferably 5.5-6.5 g/mg, and most preferably 5.8-6.2 g/mg.
In the invention, the annealing temperature is preferably 1200-1300 ℃, more preferably 1220-1280 ℃, and most preferably 1240-1260 ℃; the annealing time is preferably 8 to 11 seconds, more preferably 8.5 to 10.5 seconds, and most preferably 9.0 to 10.0 seconds.
In the present invention, the baume degree of the graphite emulsion is preferably 5.0 independently for 5 or 6 times.
In the invention, the heating temperature of 5 times or 6 times is preferably 800-900 ℃, more preferably 820-880 ℃, and most preferably 840-860 ℃.
In the invention, the temperature of the wire-drawing die for 5 times or 6 times is preferably 350-370 ℃, more preferably 355-365 ℃ and most preferably 358-362 ℃; the drawing compression ratio of 5 times or 6 times is independently preferably 18-21%, more preferably 18.5-20.5%, and most preferably 19-20%; the drawing speed is preferably 13 to 17m/min, more preferably 14 to 16m/min, and most preferably 14.5 to 15.5 m/min.
In the present invention, the torque of the yarn take-up is preferably 0.8 to 1.0 N.m, more preferably 0.85 to 0.98 N.m, and most preferably 0.9 to 0.95 N.m. In the invention, when N is 5 or 6, the black tungsten wire obtained in the step (1) has the specification of 125-180 mg/200mm and the tensile strength of 2120-2200N/mm2And other items of inspection accord with the national standard qualification index.
In the invention, when N is 7, the annealing time is that the tungsten filament is subjected to filament discharge, and the processes of graphite emulsion adhesion, heating and wire drawing are repeated for 3 times; annealing is carried out; and (3) repeatedly attaching graphite emulsion to the annealed tungsten filament precursor, heating and drawing for 4 times, and collecting the filament to obtain the black tungsten filament. When N is 8, the annealing time is that the tungsten filament is subjected to filament discharge, and the processes of graphite emulsion attachment, heating and wire drawing are repeated for 4 times; annealing is carried out; and (3) repeatedly attaching graphite emulsion to the annealed tungsten filament precursor, heating and drawing for 4 times, and collecting the filament to obtain the black tungsten filament. In the present invention, when N is 7 or 8, the other parameters in step (1) are selected in the same range except for different annealing timings. The method specifically comprises the following steps: the back tension of the wire releasing is preferably 6.0-8.0 g/mg, more preferably 6.5-7.5 g/mg, and most preferably 6.8-7.2 g/mg.
In the invention, the annealing temperature is preferably 1250-1350 ℃, more preferably 1270-1330 ℃, and most preferably 1290-1310 ℃; the annealing time is preferably 6 to 7.5s, more preferably 6.2 to 7.3s, and most preferably 6.5 to 7.0 s.
In the present invention, the baume degree of the graphite emulsion of 7 or 8 times is independently preferably 5.0.
In the present invention, the heating temperature of 7 or 8 times is preferably 750 to 850 ℃, more preferably 770 to 830 ℃, and most preferably 790 to 820 ℃.
In the invention, the temperature of the wire-drawing die is preferably 350-370 ℃ independently for 7 times or 8 times, more preferably 355-365 ℃ and most preferably 358-362 ℃; the drawing compression ratio of 7 times or 8 times is independently preferably 17-20%, more preferably 18-19%, and most preferably 18.4-18.8%; the drawing speed is preferably 18 to 22m/min, more preferably 19 to 21m/min, and most preferably 19.5 to 20.5 m/min.
In the present invention, the yarn take-up torque is preferably 0.4 to 0.6 N.m, more preferably 0.45 to 0.55 N.m, and most preferably 0.48 to 0.52 N.m. In the invention, when N is 7 or 8, the specification of the black tungsten wire obtained in the step (1) is 95-125 mg/200mm, and the tensile strength is 2190-2270N/mm2And other items of inspection accord with the national standard qualification index.
In the embodiment of the invention, the adopted wire drawing device can only carry out wire drawing for 8 times, so when N is more than or equal to 4 and less than or equal to 8, the wire drawing can be finished for 8 times in one wire drawing device. When N is more than or equal to 9 and less than or equal to 12, two wire drawing devices are needed to finish wire drawing. In the invention, the first wire drawing device is preferably used for drawing wires, the operations of attaching the graphite emulsion, heating and drawing the wires are repeated for N-4 times, and the wires are collected to obtain the black tungsten wires; drawing wires for 4 times in a second wire drawing device; and (3) annealing the black tungsten wire obtained after N-4 times of wire drawing in a second wire drawing device immediately after wire drawing, then repeating the processes of attaching the graphite emulsion, heating and wire drawing for 4 times, and collecting the black tungsten wire.
In the present invention, when N is 9, 10, 11, 12, the adhesion of the graphite emulsion-heating-drawing process is repeated 5 times, 6 times, 7 times, and 8 times, respectively, in the first drawing device. When the first wire drawing device repeats the attachment of the graphite emulsion-heating-wire drawing process 5 times or 6 times, the parameters of the step (1) are selected to be the same as those of the step (1) when N is 5 or 6; when the emulsion-heating-drawing of graphite is repeatedly carried out 7 or 8 times in the first drawing device, the parameters in the step (1) are selected in the same range as those in the step (1) when N is 7 or 8.
In the present invention, when N is 9, 10, 11 or 12, the parameter ranges in the step (1) are selected to be the same when the second drawing device repeats the attachment of the graphite emulsion-heating-drawing process 4 times; the method specifically comprises the following steps: the back tension of the wire releasing is preferably 6.0-8.0 g/mg, more preferably 6.5-7.5 g/mg, and most preferably 6.8-7.2 g/mg.
In the invention, the annealing temperature is preferably 1250-1350 ℃, more preferably 1280-1330 ℃, and most preferably 1290-1320 ℃; the annealing time is preferably 4.0 to 5.5s, more preferably 4.2 to 5.2s, and most preferably 4.5 to 5.0 s.
In the present invention, the baume degree of the last 4 graphite latexes is independently preferably 3.5.
In the present invention, the heating temperature of the last 4 times is independently preferably 600 to 620 ℃, more preferably 605 to 615 ℃, and most preferably 608 to 613 ℃.
In the invention, the temperature of the wire-drawing die in the last 4 times is preferably 380-420 ℃, more preferably 390-410 ℃, and most preferably 395-405 ℃; the drawing compression ratio of the last 4 times is independently preferably 17-19%, more preferably 17.4-18.6%, and most preferably 17.5-18.5%; the drawing speed is preferably 23-30 m/min, more preferably 25-28 m/min, and most preferably 26-27 m/min.
In the present invention, the yarn take-up torque is preferably 0.25 to 0.35 N.m, more preferably 0.27 to 0.33 N.m, and most preferably 0.29 to 0.31 N.m.
In the present invention, the baume degree of the last N-8 times of the graphite emulsion is independently preferably 3.5.
In the invention, the heating temperature of the last N-8 times is independently preferably 600-620 ℃, more preferably 605-615 ℃, and most preferably 608-613 ℃.
In the invention, the temperature of the back N-8 times of wire-drawing dies is preferably 380-420 ℃, more preferably 390-410 ℃, and most preferably 395-405 ℃; the drawing compression ratio of the last N-8 times is independently preferably 16-19%, more preferably 16.5-18.5%, and most preferably 17-18%; the drawing speed is preferably 32-45 m/min, more preferably 35-43 m/min, and most preferably 38-40 m/min.
In the present invention, the torque of the yarn take-up is preferably 0.1 to 0.2 N.m, more preferably 0.12 to 0.18 N.m, and most preferably 0.14 to 0.16 N.m. In the invention, when N is 9, 10, 11 or 12, the black tungsten wire obtained in the step (1) has the specification of 38-95 mg/200mm and the tensile strength of 2270-2500N/mm2And other items of inspection accord with the national standard qualification index.
In the invention, the tungsten filament comprises a phi 0.39-0.60A grade material which conforms to the W91 or W61 mark specified in GB/T23272-2009.
In the invention, the tensile strength of the black tungsten wire is preferably 2000-2600N/mm2. The invention does not specially limit the repetition times of the step (1), as long as the tungsten filament precursor is drawn into the black tungsten filament with the desired size and the tensile strength is 2000-2600N/mm2And (4) finishing.
In the embodiment of the invention, the tungsten filament is prepared into the black tungsten filament by using the wire drawing device. In the present invention, the drawing apparatus is shown in FIG. 1. In fig. 1: 1 is a tungsten filament unwinding device: comprises a wire releasing frame and a counter-pull device; 2 is a tungsten filament, 3 is a tower-shaped eight-guide wheel set, 4 is a graphite emulsion groove, 5 is a heating furnace, 6 is an electric heating die set and a die which can simultaneously place eight drawing dies, 7 is a tower-shaped eight-pass drawing wheel, 8 is a wire winding and arranging device, and 9 is a gas annealing furnace. In the invention, the tungsten filament precursor is fed by a tungsten filament feeding device 1, poured out through a tower-shaped eight-guide wheel 3, and enters a graphite emulsion groove 4 to be adhered with graphite emulsion, and a heating furnace 5 heats the tungsten filament precursor adhered with the graphite emulsion and dries the graphite emulsion adhered on the tungsten filament precursor; the heated tungsten filament precursor enters a die 6 on an electric heating die frame for wire drawing; the tungsten filament precursor after wire drawing is led into the tower-shaped eight-guide wheel 3 through the tower-shaped eight-pass wire drawing wheel 7, and then enters the tower-shaped eight-guide wheel 3 through the graphite emulsion groove 4, the heating furnace 5, the die 6 on the electric heating die frame and the tower-shaped wire drawing wheel 7, and the repetition frequency is determined according to the requirement; after the black tungsten filament with the target size is obtained, the black tungsten filament is collected by a filament collecting and arranging device 8; the gas annealing furnace 9 is movable, and a person skilled in the art can place the gas annealing furnace 9 at a designated position according to the annealing time.
After the black tungsten filament is obtained, the invention sequentially carries out continuous electrolysis and stress homogenization on the black tungsten filament to obtain the white tungsten filament.
In the present invention, the continuous electrolysis preferably includes four electrolysis processes. In the invention, the electrolysis process preferably comprises the steps of unwinding, electrolyzing, neutralizing, cleaning, dehydrating, drying and winding the black tungsten wire to obtain the white tungsten wire.
In the invention, the electrolyte of the primary electrolysis process is preferably NaOH and H2O is mixed according to the weight ratio of 11: 100, and mixing. In the invention, the temperature of the electrolyte in one electrolysis process is preferably 20-35 ℃, more preferably 23-33 ℃, and most preferably 25-30 ℃. In the invention, the flow rate of the electrolyte in the primary electrolysis process is preferably 17-23L/min, more preferably 18-22L/min, and most preferably 19-21L/min. In the invention, the current in the primary electrolysis process is preferably 9-11A, more preferably 9.5-10.5A, and most preferably 9.8-10.2A. In the invention, the filament winding speed in the primary electrolysis process is preferably 14-17 m/min, more preferably 14.5-16.5 m/min, and most preferably 15-16 m/min. In the invention, the back tension of the wire unwinding in the primary electrolysis process is preferably 3.7-4.3 g/mg, more preferably 3.8-4.2 g/mg, and most preferably 3.9-4.1 g/mg.
In the invention, the electrolyte of the secondary electrolysis process is preferably NaOH and H2O is mixed according to the weight ratio of 11: 100. in the invention, the temperature of the electrolyte in the secondary electrolysis process is preferably 20-35 ℃, more preferably 23-33 ℃, and most preferably 25-30 ℃. In the invention, the flow rate of the electrolyte in the secondary electrolysis process is preferably 17-23L/min, more preferably 18-22L/min, and most preferably 19-21L/min. In the invention, the current of the secondary electrolysis process is preferably 10-17A, more preferably 12-16A, and most preferably 14-15A. In the invention, the filament winding speed in the secondary electrolysis process is preferably 14-17 m/min, more preferably 15.5E to E16.5m/min, preferably 15.8-16.2 m/min. In the invention, the wire-releasing back tension in the secondary electrolysis process is preferably 3.7-4.3 g/mg, more preferably 3.8-4.2 g/mg, and most preferably 3.9-4.1 g/mg.
In the invention, the electrolyte of the three electrolysis processes is preferably NaOH and H2O is mixed according to the weight ratio of 7: 100, and mixing. In the invention, the temperature of the electrolyte in the three electrolysis processes is preferably 20-35 ℃, more preferably 23-32 ℃, and most preferably 25-30 ℃. In the invention, the flow rate of the electrolyte in the three electrolysis processes is preferably 17-23L/min, more preferably 18-22L/min, and most preferably 19-21L/min. In the invention, the current of the three electrolysis processes is preferably 10-17A, more preferably 12-16A, and most preferably 13-15A. In the invention, the filament winding speed in the three electrolysis processes is preferably 9-17 m/min, more preferably 11-15 m/min, and most preferably 12-14 m/min. In the invention, the counter-pulling force of the tertiary yarn unwinding is preferably 3.7-4.3 g/mg, more preferably 3.8-4.2 g/mg, and most preferably 3.9-4.1 g/mg.
In the invention, the electrolyte of the four electrolysis processes is preferably NaOH and H2O is mixed according to the weight ratio of 7: 100, and mixing. In the invention, the temperature of the electrolyte in the four electrolysis processes is preferably 20-35 ℃, more preferably 23-33 ℃, and most preferably 25-30 ℃. In the invention, the flow rate of the electrolyte in the four electrolysis processes is preferably 17-23L/min, more preferably 18-22L/min, and most preferably 19-21L/min. In the invention, the current of the four times of electrolysis process is preferably 25-30A, more preferably 26-29A, and most preferably 27-28A. In the invention, the filament winding speed in the four electrolysis processes is preferably 6-17 m/min, more preferably 8-15 m/min, and more preferably 10-12 m/min. In the invention, the back tension of the wire unwinding in the four electrolysis processes is preferably 3.7-4.3 g/mg, more preferably 3.8-4.2 g/mg, and most preferably 3.9-4.1 g/mg.
The invention has no special limitation on the neutralization, cleaning, dehydration and drying in the electrolysis process, and the operation well known by the technicians in the field can be adopted, specifically, the black tungsten wire after four times of electrolysis is treated by oxalic acid: water 3L: neutralizing in 100L of solution, washing with city tap water, dehydrating with absolute ethyl alcohol with purity of more than or equal to 95%, and drying at 300-400 ℃.
The apparatus used for continuous electrolysis in the present invention is not particularly limited, and a continuous electrolysis apparatus known to those skilled in the art may be used. In the present example, a continuous electrolytic apparatus was used in the configuration shown in FIG. 2. In fig. 2: the device comprises a tungsten filament unwinding mechanism and a counter-tension adjusting mechanism 1, 10-20 groups of electrolytic tanks 2, an electrolyte liquid separating pipe 3, a neutralizing tank 4, a water purifying cleaning tank 5, a dewatering tank 6, a drying device 7, a speed-adjustable filament winding and arranging mechanism 8 and a black tungsten filament 9. In the invention, the black tungsten wire is discharged through a tungsten wire discharging mechanism and a counter-tension adjusting mechanism 1; entering an electrolytic cell 2 for electrolysis; then the wastewater enters a neutralization tank 4 for neutralization and then enters a clean water cleaning tank 5 for cleaning; then enters a dehydration tank 6 for dehydration; then the filament is dried in a drying device 7 and is wound by a speed-adjustable filament winding and arranging structure 8 to obtain the electrolytic white tungsten filament.
In the invention, the electrolysis can remove impurities such as graphite lubricant, oxide and the like on the surface of the black tungsten wire, and simultaneously can improve the roughness of the surface of the tungsten wire, so that the tungsten wire is clean and bright. In the present invention, the tensile strength of the tungsten wire after electrolysis is preferably 2000 to 2600N/mm2。
After the electrolytic white tungsten filament is obtained, the invention carries out stress homogenization on the electrolytic white tungsten filament to obtain the white tungsten filament. In the present invention, the stress homogenization preferably comprises subjecting the electrolytic white tungsten wire to wire unwinding, wet hydrogen annealing, dry hydrogen annealing and wire winding. In the invention, the wet hydrogen annealing temperature is preferably 1200-1300 ℃, more preferably 1220-1280 ℃, and most preferably 1240-1260 ℃. In the invention, the wet hydrogen annealing can remove impurities on the surface of the tungsten wire and reduce stress. In the invention, the dry hydrogen annealing temperature is preferably 1400-1500 ℃, more preferably 1420-1480 ℃, and most preferably 1440-1460 ℃. In the invention, the dry hydrogen annealing is that the electrolytic white tungsten wire is protected by the dry hydrogen with the purity of 99.999, and the tungsten wire stress is reduced by non-contact 360-degree electric heating in the circular molybdenum tube. In the invention, the back tension of the filament is preferably 2.7-3.3 g/mg, more preferably 2.8-3.2 g/mg, and most preferably 2.9-3.1 g/mg. In the invention, the speed of the filament winding is preferably 2-12 m/min, more preferably 4-10 m/min, and most preferably 6-8 m/min. In the invention, the time of the wet hydrogen annealing and the time of the dry hydrogen return annealing are both determined by the wire receiving speed.
In the embodiment of the invention, the TO furnace high-temperature stress homogenizing device is preferably used for stress homogenization. In the present invention, the structure of the TO furnace high temperature stress homogenizing device is shown in FIG. 3. In fig. 3: 1 is a tungsten filament pay-off device and a counter-tension adjusting device, 2 is an electrolytic white tungsten filament, 3 is a wet hydrogen annealing furnace, 4 is a dry hydrogen annealing furnace, 5 is a filament-receiving speed guide wheel, and 6 is a filament-receiving and wire-arranging device. In the invention, the electrolytic white tungsten filament is discharged through a tungsten filament pay-off device and a back tension adjusting device 1; annealing in a wet hydrogen annealing furnace 3; then the annealing furnace enters a dry hydrogen annealing furnace 4 for annealing; the white tungsten wires obtained by annealing are loaded into a wire collecting and arranging device 6 after being collected by a wire collecting speed guide wheel 5.
In the invention, the stress homogenization can eliminate the stress of the tungsten wire in different directions and reduce the failure rate of the tungsten wire in application.
The invention also provides the white tungsten wire obtained by the preparation method of the technical scheme. In the invention, the tensile strength of the white tungsten wire is 2000-2600N/mm2(ii) a When the method is used for core-pulling winding and rodless setting of a heating lamp of a photocopier, the deformation rate of the white tungsten filament is reduced to below 1%, and the defect of rod-penetrating setting is overcome. The production cost of heating lamp manufacturing enterprises is reduced by more than 20%.
The white tungsten wire and the method for producing the same according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
The diameter of the tungsten filament is 0.50mm
A preparation method of a white tungsten wire comprises the following steps:
(1) sequentially performing filament unwinding, annealing, graphite emulsion attaching, heating, wire drawing and filament winding on a tungsten filament precursor to obtain a black tungsten filament; repeating the process of attaching the graphite emulsion, heating and drawing for 4 times;
the annealing time is that the tungsten filament is directly annealed after being unreeled; repeatedly attaching the graphite emulsion, heating and drawing for four times, and collecting the filament to obtain the black tungsten filament;
the parameters in the step (1) comprise: the back tension of wire drawing is 5.5g/mg, the annealing temperature is 1250 ℃, the annealing time is 12.8s, the baume degree of the quartic graphite emulsion is 5.0 independently, the quartic heating temperature is 950 ℃, the temperature of the quartic wire drawing die is 360 ℃, the compression ratio of quartic wire drawing is 20-22 independently, the wire drawing speed is 12m/min, and the wire drawing torque is 1.1 N.m; obtaining the black tungsten wire with the specification of 295 plus or minus 3mg/200mm and the tested tensile strength of 2043N/mm2And other items of inspection accord with the national standard qualification index.
(2) Carrying out continuous electrolysis and stress homogenization on the black tungsten wire obtained in the step (1) in sequence to obtain a tungsten wire;
the continuous electrolysis comprises four electrolysis processes: the primary electrolysis process parameters include: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 11: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 10A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg;
the secondary electrolysis process parameters comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 11: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 12A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg;
the parameters of the third electrolysis process comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 7: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 15A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg;
the parameters of the four electrolysis processes comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 7: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 30A, the filament winding speed is 8m/min, and the back tension of the filament is 4 g/mg; the electrolytic white tungsten wire with the specification of 270 +/-2 mg/200mm is obtained. The test tensile strength is 2270N/mm2；
The wet hydrogen annealing temperature of the stress homogenization is 1250 ℃, the wet hydrogen annealing time is 7.5s, the dry hydrogen annealing temperature is 1400 ℃, the dry hydrogen annealing time is 7.5s, the wire unwinding counter-tension is 3.0g/mg, and the wire winding speed is 4 m/min.
The tensile strength of the obtained white tungsten wire is measured by adopting an annex B method in GB/T23272-2009, and the result is as follows: the tensile strength of the white tungsten wire is 2195N/mm2. Other items meet the national standard qualification index.
Example 2
The diameter of the tungsten filament is 0.39mm
A preparation method of a white tungsten wire comprises the following steps:
(1) sequentially performing filament unwinding, annealing, graphite emulsion attaching, heating, wire drawing and filament winding on a tungsten filament precursor to obtain a black tungsten filament; repeating the process of attaching the graphite emulsion, heating and drawing 6 times; obtaining a black tungsten wire with the specification of 125 +/-1.5 mg/200mm, and measuring the tensile strength of the obtained tungsten wire to be 2230N/mm2And other items of inspection accord with the national standard qualification index. After the tungsten filament is discharged, the process of attaching the graphite emulsion, heating and drawing is repeated for 2 times, then annealing is carried out, after annealing, the process of attaching the graphite emulsion, heating and drawing is repeated for 4 times, and the black tungsten filament is obtained after filament winding;
the parameters in the step (1) comprise: the back tension of the wire drawing is 6g/mg, the baume degrees of the graphite emulsion for 6 times are independently 5.0, the heating temperature for 6 times is independently 850 ℃, the wire drawing die temperature for 6 times is independently 360 ℃, the wire drawing compression ratio for 6 times is independently 18-21%, the wire drawing speed is 17m/min, and the wire drawing torque is 0.8 N.m; the annealing temperature was 1280 ℃ and the annealing time was 8.6 s.
(2) Carrying out continuous electrolysis and stress homogenization on the black tungsten wire obtained in the step (1) in sequence to obtain a white tungsten wire;
the continuous electrolysis comprises four electrolysis processes: the primary electrolysis process parameters include: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 11: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 9A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg;
the secondary electrolysis process parameters comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 11: 100, the temperature of the electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 10A, the filament winding speed is 17m/min,the back tension of the wire unwinding is 4 g/mg;
the parameters of the third electrolysis process comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 7: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 10A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg;
the parameters of the four electrolysis processes comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 7: 100, the temperature of the electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 25A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg. Obtaining the electrolytic white tungsten wire with the specification of 115 +/-1 mg/200 mm; the tensile strength is 2340N/mm2。
The wet hydrogen annealing temperature of the stress homogenization is 1200 ℃, the wet hydrogen annealing time is 3.75s, the dry hydrogen annealing temperature is 1450 ℃, the dry hydrogen annealing time is 3.75s, the wire unwinding counter-tension is 3g/mg, and the wire winding speed is 8 m/min.
The tensile strength of the obtained white tungsten wire is measured by adopting an annex B method in GB/T23272-2009, and the result is as follows: the tensile strength of the white tungsten wire is 2230N/mm2(ii) a Other items meet the national standard qualification index.
Example 3
The diameter of the tungsten filament is 0.39mm
A preparation method of a white tungsten wire comprises the following steps:
(1) sequentially performing filament unwinding, annealing, graphite emulsion attaching, heating, wire drawing and filament winding on a tungsten filament precursor to obtain a black tungsten filament; repeating the process of attaching the graphite emulsion, heating and drawing for 10 times; obtaining a black tungsten wire with the specification of 63 +/-1.0 mg/200mm, and measuring the tensile strength of the obtained black tungsten wire to be 2410N/mm2And other items of inspection accord with the national standard qualification index.
Because the drawing times exceed 8, drawing is carried out in two drawing devices; drawing for six times in a first drawing device to obtain a black tungsten wire with the specification of 157 +/-2 mg/200mm, and measuring the tensile strength of the obtained tungsten wire to be 2570N/mm2Other items are tested to meet the national standard qualification index; drawing the wire for the last four times in a second wire drawing device; the annealing time is that annealing is carried out immediately after wire drawing in the second wire drawing device, and then annealing is carried outRepeatedly attaching the graphite emulsion, heating and drawing the wire for 4 times, and collecting the wire to obtain the black tungsten wire;
the parameters in the step (1) comprise: the back tension of the wire drawing of the first wire drawing device is 7g/mg, the baume degrees of the six times of graphite emulsion of the first wire drawing device are independently 5.0, the heating temperatures of the six times of the first wire drawing device are independently 850 ℃, the temperatures of the six times of the wire drawing die are independently 360 ℃, the compression ratios of the six times of the wire drawing are independently 18-21%, the wire drawing speed is 17m/min, and the wire drawing torque is 0.8 N.m; the annealing temperature is 1300 ℃, the annealing time is 4.1s, the four-time graphite emulsion baume degree of the second wire drawing device is independently 3.5, the four-time heating temperature is independently 600 ℃, the four-time wire drawing die temperature is independently 400 ℃, the four-time wire drawing compression ratio is independently 17-19%, the wire drawing speed is 27m/min, and the wire drawing torque is 0.3 N.m;
(2) carrying out continuous electrolysis and stress homogenization on the black tungsten wire obtained in the step (1) in sequence to obtain a tungsten wire;
the continuous electrolysis comprises four electrolysis processes: the primary electrolysis process parameters include: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 11: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 9A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg;
the secondary electrolysis process parameters comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 11: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 10A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg;
the parameters of the third electrolysis process comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 7: 100, mixing, wherein the temperature of electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 10A, the filament winding speed is 17m/min, and the back tension of the filament is 4 g/mg;
the parameters of the four electrolysis processes comprise: the electrolyte is NaOH and H2O is mixed according to the mass ratio of 7: 100, mixing, wherein the temperature of an electrolyte is 25 ℃, the flow rate of the electrolyte is 20L/min, the current is 25A, the filament winding speed is 17m/min, and the back tension of the filament unwinding is 4 g/mg; obtaining an electrolytic white tungsten wire with the specification of 55 +/-0.5 mg/200 mm; the test tensile strength is 2530N/mm2。
The wet hydrogen annealing temperature of the stress homogenization is 1200 ℃, the wet hydrogen annealing time is 2.5s, the dry hydrogen annealing temperature is 1450 ℃, the dry hydrogen annealing time is 2.5s, the wire unwinding counter-tension is 3g/mg, and the wire winding speed is 12 m/min.
The tensile strength of the obtained white tungsten wire is measured by adopting an annex B method in GB/T23272-2009, and the result is that the tensile strength of the white tungsten wire is 2380N/mm2。
As can be seen from the examples: the tensile strength of the white tungsten wire is 2000-2600N/mm by strictly controlling the parameters in the step (1) and combining continuous electrolysis and stress homogenization parameters2When the tungsten filament is used for core-pulling winding and rodless setting of a heating lamp of a photocopier, the deformation rate of the tungsten filament is reduced to below 1%, and the production cost of heating lamp production enterprises is reduced by more than 20%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A preparation method of a white tungsten wire comprises the following steps:
(1) sequentially performing filament unwinding, annealing, graphite emulsion attaching, heating, wire drawing and filament winding on a tungsten filament precursor to obtain a black tungsten filament;
repeating the processes of attaching the graphite emulsion, heating and drawing N times;
wherein N is more than or equal to 4 and less than or equal to 12;
the annealing time is after the wire drawing for the Nth time to 4 times and before the graphite emulsion is attached for the N times to 3 times;
the tungsten filament comprises a phi 0.39-0.60A grade material which meets the W91 or W61 mark specified in GB/T23272-2009;
when N is 4, the parameters in step (1) include: the back tension of the wire drawing is 4.7-6.7 g/mg, the annealing temperature is 1200-1300 ℃, the annealing time is 10-14 s, the baume degree of the quartic graphite emulsion is 5.0 independently, the quartic heating temperature is 900-1000 ℃, the temperature of the quartic wire drawing die is 350-370 ℃, the compression ratio of the quartic wire drawing is 20-22% independently, and the wire drawing speed is 8-1300%12m/min, and the filament winding moment is 1.1-1.3 Nm; the black tungsten wire has the specification of 185-460 mg/200mm and the tensile strength of 2000-2150N/mm2Other items are tested to meet the national standard qualification index;
(2) carrying out continuous electrolysis and stress homogenization on the black tungsten wire obtained in the step (1) in sequence to obtain a white tungsten wire; the specification of the white tungsten wire is 28-420 mg/200 mm;
the continuous electrolysis comprises four electrolysis processes; the primary electrolysis process parameters include: the electrolyte is NaOH and H2O is mixed according to the weight ratio of 11: 100, mixing, wherein the temperature of an electrolyte is 20-35 ℃, the flow rate of the electrolyte is 17-23L/min, the current is 9-11A, the filament winding speed is 14-17 m/min, and the back tension of the filament is 3.7-4.3 g/mg;
the secondary electrolysis process parameters comprise: the electrolyte is NaOH and H2O is mixed according to the weight ratio of 11: 100, mixing, wherein the temperature of electrolyte is 20-35 ℃, the flow rate of the electrolyte is 17-23L/min, the current is 10-17A, the filament winding speed is 14-17 m/min, and the back tension of the filament is 3.7-4.3 g/mg;
the parameters of the third electrolysis process comprise: the electrolyte is NaOH and H2O is mixed according to the weight ratio of 7: 100, mixing, wherein the temperature of an electrolyte is 20-35 ℃, the flow rate of the electrolyte is 17-23L/min, the current is 10-17A, the filament winding speed is 9-17 m/min, and the back tension of the filament is 3.7-4.3 g/mg;
the parameters of the four electrolysis processes comprise: the electrolyte is NaOH and H2O is mixed according to the weight ratio of 7: 100, mixing, wherein the temperature of an electrolyte is 20-35 ℃, the flow rate of the electrolyte is 17-23L/min, the current is 25-30A, the filament winding speed is 6-17 m/min, and the back tension of the filament is 3.7-4.3 g/mg;
the wet hydrogen annealing temperature of the stress homogenization is 1200-1300 ℃, the dry hydrogen annealing temperature is 1400-1500 ℃, the wire unwinding counter-tension is 2.7-3.3 g/mg, and the wire winding speed is 2-12 m/min.
2. The method according to claim 1, wherein when N-4, the parameters in step (1) include: the back tension of the wire is 4.7-6.7 g/mg, the annealing temperature is 1200-1300 ℃, the annealing time is 10-14 s, the baume degree of the four-time graphite emulsion is 5.0 independently, and the four-time heating temperature is 5.7 independentlyThe temperature of the four-time wire drawing die is 900-1000 ℃ in a vertical place, the temperature of the four-time wire drawing die is 350-370 ℃ independently, the four-time wire drawing compression ratio is 20-22% independently, the wire drawing speed is 8-12 m/min, and the wire winding torque is 1.1-1.3 Nm; the black tungsten wire has the specification of 185-460 mg/200mm and the tensile strength of 2000-2150N/mm2Other items are tested to meet the national standard qualification index;
the black tungsten wire is subjected to continuous electrolysis and stress homogenization in sequence to obtain a white tungsten wire; the specification of the white tungsten wire is 165-420 mg/200mm, and the tensile strength is 2080-2230N/mm2。
3. The method according to claim 1, wherein when N-5 or 6, the parameters in step (1) include: the back tension of the wire drawing is 5.0-7.0 g/mg, the annealing temperature is 1200-1300 ℃, the annealing time is 8-11 s, the baume degrees of the fifth or sixth graphite emulsion are independently 5.0, the heating temperature of the fifth or sixth heating temperature is independently 800-900 ℃, the temperature of the fifth or sixth wire drawing die is independently 350-370 ℃, the wire drawing compression ratio of the fifth or sixth wire drawing is independently 18-21%, the wire drawing speed is 13-17 m/min, and the wire winding torque is 0.8-1.0 N.m; the black tungsten wire has the specification of 125-180 mg/200mm and the tensile strength of 2120-2200N/mm2Other items are tested to meet the national standard qualification index;
the black tungsten wire is subjected to continuous electrolysis and stress homogenization in sequence to obtain a white tungsten wire; the specification of the white tungsten filament is 105-165 mg/200mm, and the tensile strength is 2230-2310N/mm2。
4. The method according to claim 1, wherein when N-7 or 8, the parameters of step (1) include; the wire-drawing back tension is 6.0-8.0 g/mg, the annealing temperature is 1250-1350 ℃, and the annealing time is 6.0-7.5 s; the baume degree of the seven-time or eight-time graphite emulsion is independently 5.0, the heating temperature of the seven-time or eight-time graphite emulsion is independently 750-850 ℃, the temperature of the seven-time or eight-time wire drawing die is independently 350-370 ℃, the wire drawing compression ratio of the seven-time or eight-time wire drawing die is independently 17-20%, the wire drawing speed is 18-22 m/min, and the wire drawing torque is 0.4-0.6 N.m; the specification of the black tungsten wire is 95-125 mg200mm and the tensile strength of 2190-2270N/mm2Other items are tested to meet the national standard qualification index;
the black tungsten wire is subjected to continuous electrolysis and stress homogenization in sequence to obtain a white tungsten wire; the white tungsten wire has the specification of 80-105 mg/200mm and the tensile strength of 2230-2380N/mm2。
5. The method according to claim 1, wherein when N-9, 10, 11 or 12, the parameters of step (1) include: the back tension of the wire drawing is 6.0-8.0 g/mg, the annealing temperature is 1250-1350 ℃, the annealing time is 4-5.5 s, the baume degrees of the graphite milk of the last four times are independently 3.5, the heating temperature of the last four times is independently 600-620 ℃, the temperature of the wire drawing die of the last four times is independently 380-420 ℃, the wire drawing compression ratio of the last four times is independently 17-19%, the wire drawing speed is 23-30 m/min, and the wire drawing torque is 0.25-0.35 N.m; the black tungsten wire has the specification of 38-95 mg/200mm and the tensile strength of 2270-2500N/mm2Other items are tested to meet the national standard qualification index;
the black tungsten wire is subjected to continuous electrolysis and stress homogenization in sequence to obtain a white tungsten wire; the white tungsten wire has the specification of 28-80 mg/200mm and the tensile strength of 2380-2570N/mm2。
6. The scheelite wire obtained by the preparation method according to any one of claims 1 to 5, wherein the scheelite wire has a tensile strength of 2000 to 2600N/mm2。
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