CN115305399A - Rare earth tungsten electrode material and preparation method thereof - Google Patents
Rare earth tungsten electrode material and preparation method thereof Download PDFInfo
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 55
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 49
- 239000010937 tungsten Substances 0.000 title claims abstract description 49
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 48
- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 32
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- 239000006104 solid solution Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 40
- 238000005245 sintering Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 239000011812 mixed powder Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 229910001080 W alloy Inorganic materials 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001238 wet grinding Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims 1
- 239000003870 refractory metal Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 15
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- -1 rare earth nitrate Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- WLTSUBTXQJEURO-UHFFFAOYSA-N thorium tungsten Chemical compound [W].[Th] WLTSUBTXQJEURO-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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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
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- 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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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1053—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by induction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The invention relates to the technical field of rare earth refractory metal materials, and particularly discloses a rare earth tungsten electrode material and a preparation method thereof, wherein the rare earth tungsten electrode material comprises a rare earth oxide, solid-solution element carbon and tungsten, wherein the mass percent of the rare earth oxide is 0.1-3.0%, the mass percent of the carbon is 0.01-0.30%, and the balance is tungsten; the rare earth oxide is one or more of lanthanum oxide, cerium oxide, zirconium oxide and yttrium oxide; and a preparation method of the material is disclosed; the invention has no radioactivity and toxic pollution, the rare earth oxide is uniformly distributed, and the tungsten electrode has good performance.
Description
Technical Field
The invention relates to the technical field of rare earth refractory metal materials, in particular to a rare earth tungsten electrode material and a preparation method thereof.
Background
Tungsten has the advantages of high melting point, high strength, low vapor pressure, strong electron emission capability and the like, and is widely applied to the fields of inert gas shielded welding, plasma welding, cutting, smelting, electric vacuum and the like. Thorium-tungsten electrodes have been used in the field of thermionic emission materials, but the radioactive influence of thorium can harm human health and pollute the environment. The tungsten-based rare earth oxide doped with rare earth oxide with low electron work function, such as lanthanum oxide, cerium oxide, zirconium oxide, yttrium oxide and the like, not only can play a role of dispersion strengthening, but also can improve the recrystallization temperature and activate electron emission, and becomes a development direction for replacing the traditional radioactive thorium tungsten electrode material, but still none of the rare earth tungsten electrodes has comprehensive performance comparable to that of the thorium tungsten electrode.
The doping method of the rare earth tungsten electrode is a liquid-liquid doping method in the patent publication (CN 1616185), APT is added into deionized water and stirred to obtain uniform suspension, and then rare earth nitrate solution is added into the suspension, and stirring, evaporation and drying are carried out; there is also a solid-liquid doping method disclosed in the patent publication (CN 1203136, CN103862196 a), in which rare earth nitrates corresponding to each kind of rare earth tungsten oxide are prepared into a solution, and the solution is doped into tungsten trioxide, blue tungsten, tungsten powder or ammonium paratungstate powder, and the solution is stirred uniformly and heated and dried to obtain a mixed powder; there is also a solid-solid doping method in the patent publication (CN 109226748A, CN110788318A, CN111850331 a), in which tungsten powder and rare earth oxide powder are directly and fully mixed to obtain mixed powder. Wherein, the solid-solid doping method has simple process, but the mixing uniformity is poor, and the rare earth oxide is easy to agglomerate into large particles; the solid-liquid doping method and the liquid-liquid doping method have good doping uniformity, but the decomposition of the rare earth nitrate can generate toxic and harmful nitrogen oxide gas, and the purification treatment is needed, so the cost is high. With the enhancement of environmental protection control in industrial production in recent years, the development of an environment-friendly and pollution-free doping method with good doping uniformity gradually becomes the key point of rare earth refractory metal production enterprises.
Disclosure of Invention
The invention aims to solve the technical problem of providing a rare earth tungsten electrode material and a preparation method thereof, which have the advantages of no radioactivity and toxic pollution, uniform distribution of rare earth oxides and good performance of a tungsten electrode.
The technical problem to be solved by the invention is as follows:
on the one hand, the method comprises the following steps of,
the invention discloses a rare earth tungsten electrode material, which comprises rare earth oxide, solid solution element carbon and tungsten, wherein the mass percentage of the rare earth oxide is 0.1-3.0%, the mass percentage of the carbon is 0.01-0.30%, and the balance is tungsten; the rare earth oxide is one or more of lanthanum oxide, cerium oxide, zirconium oxide and yttrium oxide.
On the other hand, in the case of a liquid,
a preparation method of a rare earth tungsten electrode material specifically comprises the following steps:
s1, weighing rare earth oxide according to the mass percent of the rare earth tungsten electrode material, and putting the rare earth oxide into a ball mill for wet milling, wherein the ball milling time is not less than 10h, the ball-to-material ratio is 1:1-10, 1, and the solid-to-liquid ratio is 5:1-1:5;
s2, adding a ball-milling liquid medium into the rare earth oxide slurry ball-milled in the step S1 to prepare a suspension liquid which is uniformly distributed;
s3, adding blue tungsten powder and carbon powder into the suspension, uniformly mixing, and heating and drying to obtain mixed powder;
s4, introducing hydrogen into the mixed powder in a reduction furnace for reduction at the temperature of 600-1000 ℃ to obtain rare earth tungsten alloy powder;
and S5, performing press forming, pre-sintering and sintering on the rare earth tungsten alloy powder to obtain the rare earth tungsten electrode, thus completing preparation.
In some possible embodiments, the rare earth oxide has a powder particle size of 0.1 μm to 3.0 μm.
In some possible embodiments, the ball milling liquid medium is water or alcohol.
In some possible embodiments, the pre-sintering step is carried out at a temperature of 1200 ℃ to 1400 DEG C
In some possible embodiments, the sintering is a vertical sintering or an intermediate frequency induction sintering, and the sintering temperature is 2000 ℃ to 2500 ℃.
In some possible embodiments, the pre-sintering and sintering atmosphere is hydrogen.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the rare earth oxide powder is subjected to wet grinding, so that the particle size of the powder is reduced to obtain submicron or even nanoscale powder, and the powder agglomeration can be effectively prevented.
According to the invention, the wet-milled rare earth oxide is prepared into turbid liquid, the turbid liquid is added into the blue-tungsten powder in a solid-liquid doping mode, the blue-tungsten powder or the mixed powder obtained by directly mixing the blue-tungsten powder or the tungsten powder and the rare earth oxide powder is better in distribution uniformity compared with the solid-solid doping mode, and the rare earth oxide turbid liquid is doped in a mode of replacing rare earth nitrate, so that the rare earth doping process is environment-friendly and pollution-free due to the absence of nitrate, and the environment-friendly effect is realized.
According to the invention, by adding the carbon element into the rare earth tungsten electrode, on one hand, the carbon element can be dissolved in the tungsten matrix in a solid solution manner to form solid solution strengthening so as to improve the strength of the tungsten electrode, and on the other hand, the carbon element can promote the diffusion of the rare earth element in the tungsten, so that the performance of the tungsten electrode is improved.
Drawings
FIG. 1 is a gold phase diagram of a rare earth tungsten electrode prepared in example 1 of the present invention;
FIG. 2 is a histogram of the second phase particle distribution of FIG. 1;
FIG. 3 is a gold phase diagram of a rare earth tungsten electrode prepared in example 2 of the present invention;
FIG. 4 is a histogram of the second phase particle distribution of FIG. 3;
Detailed Description
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; either directly or indirectly through intervening media, either internally or in any other relationship. Reference herein to "first," "second," and similar words, does not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Also, the use of the terms "a" or "an" and the like do not denote a limitation of quantity, but rather denote the presence of at least one. In the implementation of the present application, "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. In the description of the embodiments of the present application, the meaning of "a plurality" means two or more unless otherwise specified. For example, the plurality of positioning pillars refers to two or more positioning pillars. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The present invention will be described in detail below.
Example 1:
selecting cerium oxide powder with the powder particle size of 1.8 mu m as a raw material, weighing 160.25g of cerium oxide powder, 160.25g of water and 320.50g of grinding balls, putting the mixture into a ball mill, ball-milling for 24 hours, adding 1000g of water to prepare uniform suspension of the cerium oxide after wet grinding, weighing 4.01g of carbon powder and 9835.74g of blue tungsten powder, adding the mixture into the suspension, fully mixing uniformly, heating and drying to obtain mixed powder;
putting the obtained mixed powder into a reduction boat, putting the boat into a five-temperature-zone hydrogen reduction furnace for primary reduction, wherein the temperature of each temperature zone is 800 ℃, 840 ℃, 870 ℃, 900 ℃ and 930 ℃ in sequence, and sieving to obtain the rare earth tungsten alloy powder with the cerium oxide content of 2.0% and the carbon content of 0.05%;
weighing 3000g of prepared rare earth tungsten alloy powder, filling the rare earth tungsten alloy powder into a rubber sleeve, sealing the rubber sleeve, putting the rubber sleeve into a cold isostatic press, and pressing the rubber sleeve into a rod-shaped pressed blank with the pressing pressure set to be 2000Kg/cm 2 ；
Presintering the pressed blank under the protection of hydrogen, wherein the sintering temperature is 1300 ℃;
placing the pre-sintered billet in a medium-frequency induction sintering device under hydrogen protection, keeping the sintering temperature at 2300 ℃, and cooling after keeping the temperature for 4 hours to finish the preparation;
when the rare earth tungsten electrode material of the embodiment is detected, the compactness is 98.04%, the gold phase diagram and the size distribution of the second phase particles are shown in fig. 1 and 2, and the average size of the second phase particles is 2.04 μm.
Example 2:
selecting lanthanum oxide powder with the powder particle size of 0.6 mu m as a raw material, weighing 95.94g of lanthanum oxide powder, 191.88g of water and 287.82g of grinding balls, putting the materials into a ball mill, carrying out ball milling for 24h, then adding 1000g of water to prepare uniform suspension of the lanthanum oxide after wet grinding, weighing 8.00g of carbon powder and 9896.06g of blue tungsten powder, adding the mixture into the suspension, fully mixing uniformly, heating and drying to obtain mixed powder;
putting the mixed powder into a reduction boat, putting the boat into a five-temperature-zone hydrogen reduction furnace for primary reduction, wherein the temperature of each temperature zone is 780 ℃, 820 ℃, 860 ℃, 890 ℃ and 910 ℃ in sequence, and sieving to obtain the rare earth tungsten alloy powder with the lanthanum oxide content of 1.2% and the carbon content of 0.1%;
weighing 3000g of the prepared rare earth tungsten alloy powder, filling the powder into a rubber sleeve, sealing the rubber sleeve, putting the rubber sleeve into a cold isostatic press, and pressing the rubber sleeve into a rod-shaped pressed blank with the pressing pressure set to be 2000Kg/cm 2 ；
Presintering the pressed blank under the protection of hydrogen, wherein the sintering temperature is 1200 ℃;
placing the pre-sintered billet in hydrogen-protected medium-frequency induction sintering equipment, wherein the sintering temperature is 2200 ℃, and cooling is carried out after heat preservation is carried out for 5 hours;
the rare earth tungsten electrode material of the present example was examined, and the degree of densification was 97.92%, the gold phase diagram and the size distribution of the second phase particles are shown in fig. 3 and 4, and the average size of the second phase particles was 2.03 μm.
Example 3:
selecting lanthanum oxide with the powder granularity of 0.6 mu m, yttrium oxide with the powder granularity of 2.0 mu m and zirconium oxide powder with the powder granularity of 0.8 mu m as raw materials, weighing 95.94g of lanthanum oxide powder, 39.98g of yttrium oxide powder, 23.99g of zirconium oxide powder, 159.91g of alcohol and 799.5g of grinding balls, putting the raw materials into a ball mill for ball milling for 24 hours, adding 500g of alcohol to prepare uniform suspension of rare earth oxide after wet milling, weighing 4.80g of carbon powder, 9835.29g of blue tungsten powder, adding the suspension, fully mixing uniformly, heating and drying to obtain mixed powder;
putting the prepared mixed powder into a reduction boat, putting the boat into a five-temperature-zone hydrogen reduction furnace for primary reduction, and sieving at 830 ℃, 860 ℃, 890 ℃, 920 ℃ and 950 ℃ in sequence to obtain rare earth tungsten alloy powder with the lanthanum oxide content of 1.2%, the yttrium oxide content of 0.5%, the zirconium oxide content of 0.3% and the carbon content of 0.06%;
weighing 3000g of the prepared rare earth tungsten alloy powder, filling the powder into a rubber sleeve, sealing the rubber sleeve, putting the rubber sleeve into a cold isostatic press, and pressing the rubber sleeve into a rod-shaped pressed blank with the pressing pressure set to be 2000Kg/cm 2 ；
Presintering the pressed blank under the protection of hydrogen, wherein the sintering temperature is 1300 ℃;
placing the pre-sintered billet into medium-frequency induction sintering equipment under the protection of hydrogen, wherein the sintering temperature is 2400 ℃, and cooling is carried out after heat preservation is carried out for 5 hours;
the density of the rare earth tungsten electrode material of the embodiment is detected to be 98.23%.
From examples 1 to 3, it is understood that the rare earth tungsten electrode material of the present invention has good uniformity, and no radioactive material and nitrate solution are added, and the prepared rare earth tungsten electrode material is non-radioactive, non-toxic and harmless.
According to the invention, the rare earth oxide powder is subjected to wet grinding, so that the particle size of the powder is reduced to obtain submicron or even nanoscale powder, and the powder agglomeration can be effectively prevented. The wet-milled rare earth oxide is prepared into turbid liquid, the turbid liquid is added into blue tungsten powder in a solid-liquid doping mode, the turbid liquid is better in distribution uniformity compared with a solid-solid doping mode of directly mixing the blue tungsten powder or the tungsten powder with the rare earth oxide powder to obtain mixed powder, and the rare earth oxide turbid liquid is doped in a mode of replacing rare earth nitrate, so that the rare earth doping process is environment-friendly and pollution-free due to the fact that nitrate does not exist, and the environment-friendly rare earth doping method is environment-friendly. By adding some carbon elements into the rare earth tungsten electrode, on one hand, the carbon elements can be dissolved in a tungsten matrix in a solid manner to form solid solution strengthening so as to improve the strength of the tungsten electrode, and on the other hand, the carbon elements can promote the diffusion of the rare earth elements in tungsten, so that the performance of the tungsten electrode is improved.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (7)
1. The rare earth tungsten electrode material is characterized by comprising rare earth oxide, solid solution element carbon and tungsten, wherein the mass percent of the rare earth oxide is 0.1-3.0%, the mass percent of the carbon is 0.01-0.30%, and the balance is tungsten; the rare earth oxide is one or more of lanthanum oxide, cerium oxide, zirconium oxide and yttrium oxide.
2. The preparation method of the rare earth tungsten electrode material according to claim 1, which is characterized by comprising the following steps:
s1, weighing rare earth oxide according to the mass percent of the rare earth tungsten electrode material, and putting the rare earth oxide into a ball mill for wet milling, wherein the ball milling time is not less than 10h, the ball-to-material ratio is 1:1-10, 1, and the solid-to-liquid ratio is 5:1-1:5;
s2, adding a ball-milling liquid medium into the rare earth oxide slurry ball-milled in the step S1 to prepare a suspension liquid which is uniformly distributed;
s3, adding blue tungsten powder and carbon powder into the suspension, uniformly mixing, and heating and drying to obtain mixed powder;
s4, introducing hydrogen into the mixed powder in a reduction furnace for reduction at the temperature of 600-1000 ℃ to obtain rare earth tungsten alloy powder;
and S5, performing compression molding, pre-sintering and sintering on the rare earth tungsten alloy powder to obtain the rare earth tungsten electrode, and finishing the preparation.
3. The rare earth tungsten electrode material and the preparation method thereof according to claim 2, wherein the powder particle size of the rare earth oxide is 0.1 μm to 3.0 μm.
4. The rare earth tungsten electrode material and the preparation method thereof according to claim 2, wherein the ball milling liquid medium is water or alcohol.
5. The rare earth tungsten electrode material and the preparation method thereof according to claim 2, wherein the temperature in the pre-sintering step is 1200 ℃ to 1400 ℃.
6. The rare earth tungsten electrode material and the preparation method thereof according to claim 2, wherein the sintering is sintered by vertical melting or medium frequency induction sintering, and the sintering temperature is 2000-2500 ℃.
7. The rare earth tungsten electrode material and the preparation method thereof according to claim 2, wherein the presintering and sintering atmosphere is hydrogen.
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| WO2025087091A1 (en) * | 2023-10-25 | 2025-05-01 | 厦门虹鹭钨钼工业有限公司 | Tungsten carbide alloy filament and preparation method therefor, and heating device |
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