CN1616185A - High-content multi-element composite rare earth tungsten electrode material and preparation method thereof - Google Patents
High-content multi-element composite rare earth tungsten electrode material and preparation method thereof Download PDFInfo
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- CN1616185A CN1616185A CN 200410080296 CN200410080296A CN1616185A CN 1616185 A CN1616185 A CN 1616185A CN 200410080296 CN200410080296 CN 200410080296 CN 200410080296 A CN200410080296 A CN 200410080296A CN 1616185 A CN1616185 A CN 1616185A
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Abstract
A high-content multi-element composite rare earth tungsten electrode material and a preparation method thereof belong to the field of rare earth refractory metal cathode materials. Aiming at the poor processing performance and in-situ processing of the existing tungsten electrode materialThe problem that the yield in industrial production is low and the production cost is increased is solved2O3、Y2O3And CeO2The content of each rare earth oxide is 0.6-1.98%, the total content is 3.0-3.3%, and the balance is the weight of tungsten. The preparation method comprises the following steps: weighing lanthanum nitrate, yttrium nitrate and cerium nitrate according to the weight of each rare earth oxide, preparing a mixed solution, converting the weight content of tungsten into the weight of APT (ammonium paratungstate), weighing APT, adding deionized water, stirring to obtain a uniform suspension, adding the rare earth nitrate solution, stirring, evaporating and drying; after drying, carrying out primary hydrogen reduction at the temperature of 550-700 ℃; secondary hydrogen reduction is carried out at 850-1000 ℃ and the average particle size is 1.2-1.4 mu m. The process of APT calcination is omitted, the process is simplified, economy and energy conservation are realized, and the yield and the production stability are improved.
Description
Technical field:
High content poly-component composite rare-earth tungsten electrode material and preparation method thereof belongs to rare earth refractory metal cathode material technical field.
Background technology:
Tungsten electrode is as the critical component in fields such as inert gas-shielded arc welding and plasma spray coating, melting, cutting; be widely used in industries such as machinery, shipbuilding, building, metallurgy, electric power, Aero-Space; the tungsten electrode of using is based on thorium tungsten electrode at present; account for more than 80% of entire electrode product; because thorium has naturally radioactive, its Alpha-ray half-life reaches 1.4 * 10
13Year, the thoriatde-tungsten wire of production contains 1.5%ThO
2The time, its alpha ray dosage is 1.35 * 10
5Bq/Kg, therefore, thorium tungsten material causes the cumulative bad radiological hazard in long-term production and use human body and environment, being badly in need of the novel electrode material replaces, rare-earth tungsten electrode presses for research and development down at this and comes out, this class rare-earth tungsten electrode has the welding performance that compares favourably with thorium tungsten electrode under different operating modes, and begin among a small circle, to substitute thorium tungsten and used, yet thorium tungsten electrode since its to have a starting the arc easy, durable electric current is big, advantages such as long service life, although thorium wherein has cumulative radiological hazard, but there is not the more excellent industrial electrode product of combination property to replace it fully so far, therefore, thorium tungsten electrode occupies leading position always in numerous tungsten electrodes.The electrode material that research and development have the superior weldability energy still is the focus of present electrode material research.
Original application patent (CN1204696A, CN1203136A) middle rare earth oxide total content is 2.0-2.2% (percentage by weight), and the preparation technology of electrode is: WO
3With rare earth nitrate doping, behind evaporation drying, twice hydrogen reducing, incipient fusion sintering, be processed into the electrode of all size, this patent has improved the content of rare earth element, and, successfully prepared high content poly-component composite rare-earth tungsten electrode by improving the problem that critical process has solved high content poly-component composite rare-earth tungsten electrode processing and preparing difficulty.
Summary of the invention:
The objective of the invention is,, thereby improve content of rare earth, improve the welding performance of electrode, a kind of high content poly-component composite rare-earth tungsten electrode material and preparation method thereof is provided in view of rare earth is the main active that reduces the electrode work function.
A kind of high content poly-component composite rare-earth tungsten electrode material is characterized in that:
La
2O
3, Y
2O
3And CeO
2Every kind of rare earth oxide content is 0.6-1.98%, and the total content of these three kinds of rare earth oxides is 3.0-3.3%.All the other are the weight of tungsten.
Above-mentioned a kind of high content poly-component composite rare-earth tungsten electrode material preparation method is characterized in that, is made up of following steps:
1, takes by weighing corresponding lanthanum nitrate, yttrium nitrate, cerous nitrate and be made into mixed solution by every kind of rare earth oxide weight, weight content by tungsten is converted into corresponding APT (para-tungstic acid ammonia) weight, take by weighing APT and add deionized water and stirring and obtain uniform suspension, the back adds above-mentioned rare earth nitrate solution, stirring, evaporation drying;
2) after the evaporation drying through a hydrogen reducing, temperature is 550 ℃-700 ℃; Secondary hydrogen reducing, temperature are 850 ℃-1000 ℃ and make multicomponent composite rare-earth-tungsten electrode material that particle mean size is controlled at 1.2-1.4 μ m.
With the mixed-powder preparation processing method of tungsten routinely of reduction gained, carry out sintering, plastic working, be processed into the electrode of all size at last.That the conventional preparation of tungsten manufacturing procedure is that compacting, pre-burning, incipient fusion sintering, cogging, 203,202,201, chain are drawn, twisted is straight, cut-out, polishing etc., obtains finished electrode at last.
Above-mentioned preparation method has changed the doped raw material in the traditional electrode preparation process, and it is WO that traditional handicraft is mixed
3, WO
2.9Mix Deng with rare earth nitrades, and WO
3, WO
2.9Deng being APT calcining gained, this preparation method directly with APT as doped raw material, omitted the APT calcine technology, economical and energy saving.
In reduction process, change and to go back (one time hydrogen reducing: 500-540 ℃ of raw parameter in the original application patent; Secondary hydrogen reducing: 640-920 ℃), make reduction back powder size be controlled at 1.2-1.4 μ m, simultaneously adjust the following process parameter a little, drawing abillity is improved, can not be thereby broken through electrode industry multielement rare earth content above the constraint of 2.2% (percentage by weight).
Active material when rare earth element is worked as electrode can improve the welding performance of electrode, and the prepared electrode welding performance of the present invention is good, and its anti-scorching performance is particularly outstanding, and machinability is good.
Description of drawings
Fig. 1: static characteristic of arc curve
The specific embodiment.
Example 1:
Whenever get APT powder 1Kg, add deionized water 1000ml, stir, put into the pot that mixes, add and press the 0.6%La of final products weight
2O
3, 1.8%Y
2O
3, 0.6%CeO
2Take by weighing the mixed solution of lanthanum nitrate, yttrium nitrate, cerous nitrate (according to oxide weight conversion nitrate amount) preparation, after fully stirring evaporate to dryness and drying, obtain mixed-powder, mixed-powder is once reduced in reduction furnace (temperature: 550 ℃), behind the secondary reduction (temperature: 1000 ℃), make the mixed-powder of rare earth oxide and tungsten powder, particle mean size is 1.4 μ m.After powder after the reduction added glycerine, alcohol mixings 1h by a certain percentage,, suppress (filling amount: 680g; Compacting pressure: 6.5MPa), after the pre-burning (temperature: 1150 ℃), incipient fusion sintering (being incubated 30min under 90% blowout current), that the processing of swaging, chain draw, twist is straight, be processed into all size tungsten electrode after cutting off and polishing.Obtaining diameter at last is Φ 2.4 finished electrode.
Example 2:
Whenever get APT powder 1Kg, add deionized water 1000ml, stir, put into the pot that mixes, add and press the 0.64%La of final products weight
2O
3, 1.92%Y
2O
3, 0.64%CeO
2Take by weighing the mixed solution of lanthanum nitrate, yttrium nitrate, cerous nitrate (according to oxide weight conversion nitrate amount) preparation, after fully stirring evaporate to dryness and drying, obtain mixed-powder, mixed-powder is once reduced in reduction furnace (temperature: 650 ℃), behind the secondary reduction (temperature: 900 ℃), make the mixed-powder of rare earth oxide and tungsten powder, particle mean size is 1.3 μ m.After powder after the reduction added glycerine, alcohol mixings 1h by a certain percentage,, suppress (filling amount: 680g; Compacting pressure: 6.5MPa), after the pre-burning (temperature: 1150 ℃), incipient fusion sintering (being incubated 30min under 90% blowout current), that the processing of swaging, chain draw, twist is straight, be processed into all size tungsten electrode after cutting off and polishing.Obtaining diameter at last is Φ 2.4 finished electrode
Example 3:
Whenever get APT powder 1Kg, add deionized water 1000ml, stir, put into the pot that mixes, add and press the 0.66%La of final products weight
2O
3, 1.98%Y
2O
3, 0.66%CeO
2Take by weighing the mixed solution of lanthanum nitrate, yttrium nitrate, cerous nitrate (according to oxide weight conversion nitrate amount) preparation, after fully stirring evaporate to dryness and drying, obtain mixed-powder, mixed-powder is once reduced in reduction furnace (temperature: 700 ℃), behind the secondary reduction (temperature: 850 ℃), make the mixed-powder of rare earth oxide and tungsten powder, particle mean size is 1.2 μ m.After powder after the reduction added glycerine, alcohol mixings 1h by a certain percentage,, suppress (filling amount: 680g; Compacting pressure: 6.5MPa), after the pre-burning (temperature: 1150 ℃), incipient fusion sintering (being incubated 30min under 90% blowout current), that the processing of swaging, chain draw, twist is straight, be processed into all size tungsten electrode after cutting off and polishing.Obtaining diameter at last is Φ 2.4 finished electrode
Sample in the above-mentioned example has been carried out the welding performance test,, also the thorium tungsten electrode commonly used both at home and abroad of same size has been tested simultaneously in order to compare; Test job detects inspection and supervision center-Harbin institute of welding in country's welding to be carried out, and its result is as follows:
1. electrode is numbered:
Electrode numbering 1#: contain 0.60% (weight) La
2O
3, 1.80% (weight) Y
2O
3, 0.60% (weight) CeO
2, all the other are W.
Electrode numbering 2#: contain 0.64% (weight) La
2O
3, 1.92% (weight) Y
2O
3, 0.64% (weight) CeO
2, all the other are W.
Electrode numbering 3#: contain 0.66% (weight) La
2O
3, 1.98% (weight) Y
2O
3, 0.66% (weight) CeO
2, all the other are W.
Electrode numbering 4#: contain 2.2% (weight) ThO
2Thorium tungsten electrode (Beijing Tungsten and Molybdenum Materials Factory's product), this electrode is electrode as a comparison.
2. striking performance:
(1) experiment condition
The tungsten filament diameter is Φ 2.41mm, tip cone angle 45 degree, and argon flow amount is 8L/min, electrode extension 3mm, arc length 3mm.Adopt the straight polarity direct current mode, tungsten filament is a negative electrode, and anode is the water-cooled red copper.
(2) experimental facilities
IGCT control DC TIG welding connects power supply, model YC-300TSPVTA.Digital multimeter, model Bestillingsnr is numbered 1287.Electronic balance AEL-200.
(3) experimental result
The test result of 1#, 2#, 3#, 4# electrode: when 30A, 80A, 150A welding current, each repeats striking 30 times, and arcing initiation success rate reaches 100%, the striking function admirable.
3. anti-scorching performance:
(1) experiment condition
Electrode diameter is Φ 2.4mm, and used anode is the water-cooled red copper in the test, welding current 180A, and arc duration 20min, electrode extension 3mm, arc length 3mm, argon flow amount 8L/min, current type and polarity are straight polarity direct current.
(2) experimental facilities
IGCT control DC TIG welding connects power supply, model YC-300TSPVTA.Slide measure, model 025, numbering 096583.Electronic balance AEL-200.
(3) result of the test
Test result sees Table 3.
The anti-scorching performance of table 3. tungsten electrode
| Sample number | ????1# | ???2# | ????3# | ????4# |
| Average scaling loss amount (mg) | ????0.95 | ???0.80 | ????0.87 | ????1.65 |
Wherein the average scaling loss amount of 1#, 2#, 3# tungsten electrode all is lower than the 4# thorium tungsten electrode, has good anti-scorching performance.
4. static characteristic of arc curve
(1) experiment condition
The tungsten filament diameter is Φ 2.4mm, tip cone angle 45 degree, and argon flow amount is 8L/min, electrode extension 3mm, arc length 3mm.Adopt the straight polarity direct current mode, tungsten filament is a negative electrode, and anode is the water-cooled red copper.
(2) experimental facilities
IGCT control DC TIG welding connects power supply, model YC-300TSPVTA.Digital multimeter, model Bestillingsnr is numbered 1287.Electronic balance AEL-200.
(3) experimental technique and result
After the arcing, rapidly loop current being transferred to 20A, is 20A at electric current by from small to large order successively, 30A, 40A, 50A, 60A, 80A, 100A is during 140A, after treating that arc burning is stable, measure pairing steady-state current, magnitude of voltage, according to the voltage that records, current value make respectively 1#, 2#,, the static characteristic of arc curve (VA characteristic curve) of 3#, 4# electrode, as shown in Figure 1.
As can see from Figure 1, the transfer curve and the thorium tungsten electrode transfer curve of 1#, 2#, 3# electrode are similar, and when showing these two kinds of electrode welding, arc stability is more or less the same.
Test result above comprehensive can be seen that 1#, 2#, 3# electrode have reached the welding performance of 4# thorium tungsten electrode, and be better than thorium tungsten electrode in some aspects.
Claims (2)
1, high content poly-component composite rare-earth tungsten electrode material is characterized in that, is grouped into by following one-tenth:
La
2O
3, Y
2O
3And CeO
2Every kind of rare earth oxide content is 0.6-1.98%, the total content of these three kinds of rare earth oxides be 3.0-3.3%. all the other be the weight of tungsten.
2, high content poly-component composite rare-earth tungsten electrode material preparation method according to claim 1 is characterized in that, is made up of following steps:
1) takes by weighing corresponding lanthanum nitrate, yttrium nitrate, cerous nitrate and be made into mixed solution by every kind of rare earth oxide weight, being converted into corresponding APT by the weight content of tungsten is para-tungstic acid ammonia weight, take by weighing APT and add deionized water and stirring and obtain uniform suspension, add above-mentioned rare earth nitrate solution, stirring, evaporation drying;
2) after the evaporation drying through a hydrogen reducing, temperature is 550 ℃-700 ℃; Secondary hydrogen reducing, temperature are 850 ℃-1000 ℃ and make multicomponent composite rare-earth-tungsten electrode material that particle mean size is controlled at 1.2-1.4 μ m.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000923A (en) * | 2010-09-20 | 2011-04-06 | 天津市春风钨业有限公司 | Multi-element composite rare earth tungsten electrode material and preparation method thereof |
| CN103045886A (en) * | 2012-12-27 | 2013-04-17 | 大连理工大学 | Method for preparing rare-earth-tungsten electrode material |
| CN104439763A (en) * | 2014-11-06 | 2015-03-25 | 北矿新材科技有限公司 | Preparation method of multi-element composite rare earth doped tungsten powder |
| CN105518169A (en) * | 2014-10-20 | 2016-04-20 | 中南大学 | Method for preparing rare-earth oxide dispersion strengthened fine-grained tungsten material |
| CN110407254A (en) * | 2018-04-26 | 2019-11-05 | 南昌大学 | A kind of preparation method of the ammonium paratungstate composite powder containing yttrium |
| CN111041315A (en) * | 2019-11-27 | 2020-04-21 | 洛阳爱科麦钨钼科技股份有限公司 | Quaternary composite rare earth tungsten alloy electrode material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716708B (en) * | 2009-12-23 | 2012-11-14 | 北京钨钼材料厂 | Method and device for annealing and rotary swaging multiplex composite rare-earth tungsten electrode |
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2004
- 2004-09-30 CN CN 200410080296 patent/CN1287947C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000923A (en) * | 2010-09-20 | 2011-04-06 | 天津市春风钨业有限公司 | Multi-element composite rare earth tungsten electrode material and preparation method thereof |
| CN103045886A (en) * | 2012-12-27 | 2013-04-17 | 大连理工大学 | Method for preparing rare-earth-tungsten electrode material |
| CN105518169A (en) * | 2014-10-20 | 2016-04-20 | 中南大学 | Method for preparing rare-earth oxide dispersion strengthened fine-grained tungsten material |
| WO2016061721A1 (en) * | 2014-10-20 | 2016-04-28 | 中南大学 | Method for preparing rare-earth oxide dispersion strengthened fine-grained tungsten material |
| CN104439763A (en) * | 2014-11-06 | 2015-03-25 | 北矿新材科技有限公司 | Preparation method of multi-element composite rare earth doped tungsten powder |
| CN110407254A (en) * | 2018-04-26 | 2019-11-05 | 南昌大学 | A kind of preparation method of the ammonium paratungstate composite powder containing yttrium |
| CN111041315A (en) * | 2019-11-27 | 2020-04-21 | 洛阳爱科麦钨钼科技股份有限公司 | Quaternary composite rare earth tungsten alloy electrode material and preparation method thereof |
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