CN100554469C - A kind of preparation method of Mo-Si-Al-K cold-rolling thin molybdenum plate band - Google Patents
A kind of preparation method of Mo-Si-Al-K cold-rolling thin molybdenum plate band Download PDFInfo
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- CN100554469C CN100554469C CNB2007101796649A CN200710179664A CN100554469C CN 100554469 C CN100554469 C CN 100554469C CN B2007101796649 A CNB2007101796649 A CN B2007101796649A CN 200710179664 A CN200710179664 A CN 200710179664A CN 100554469 C CN100554469 C CN 100554469C
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Abstract
The present invention relates to a kind of Mo-Si-Al-K cold-rolling thin molybdenum plate band and preparation method thereof.It is characterized in that its preparation process is with Mo-Si-Al-K sintering high temperature molybdenum base, be rolled preceding preannealing under 1300～1400 ℃, it is the processing of 20%～30% hot rolling cogging that high temperature molybdenum base is made first pass deformation; When rolling total deformation reaches 70%～75%, under 900～1100 ℃ of temperature, carry out process annealing, alkali cleaning, warm-rolling be in thick molybdenum plate; The thick molybdenum plate of centering is cold-rolled to the final finished specification, finished product is carried out the annealing of 800～850 ℃ of vacuum stress-removals after, obtain high temperature cold-rolling thin molybdenum plate band required for the present invention.The hot strength height of the inventive method products obtained therefrom, the recrystallization temperature height, cold-rolling thin molybdenum plate, strip product have premium propertiess such as surface quality is good, dimensional precision is high, hot strength is high, plasticity is good, long service life, can be widely used for making the molybdenum crucible, burn boat, high-power transmitting tube anode (U type), gate molybdenum tube, heating element, thermoscreen and other structural parts.
Description
Technical field
The present invention relates to a kind of Mo-Si-Al-K cold-rolling thin molybdenum plate band and preparation method thereof.
Background technology
Because refractory metal molybdenum has higher high temperature strength, favorable conductive thermal conductivity, the lower coefficient of expansion and workability, thereby in special bulb such as automobile halogen tungsten lamp, high-pressure mercury lamp, tubular halogen tungsten lamp and electric lighting device, be extensive use of the molybdenum filament material make their required bulbs hook, around filament with component such as heart yearn, guide rod, outlet line and plasticity supports, in the metal processing industry, be widely used as line cutting molybdenum filament, be used as the hydrogen furnace heating unit in the kiln industry.
Cold-rolling thin molybdenum plate, band, be mainly used in electrovacuum, the electric light source industry, through secondary forming process such as deep-draw, drawing, spinning, be processed into the goods of different shape, specification by thin molybdenum plate, band, as molybdenum crucible, burning boat, high-power transmitting tube anode (U type), gate molybdenum tube etc.If in above-mentioned industry, use, all require thin molybdenum plate, band to have good low-temperature plasticity and good high-temperature use properties, the recrystallization temperature of pure molybdenum plate has only 1000～1200 ℃, thereby fragility and fracture often appear, its hot strength is also low and yielding, can not satisfy the service requirements of these industries far away.And the recrystallization temperature of the thin molybdenum plate of ASK high temperature, band is more than 1650 ℃, this be because this moment its recrystal grain grow up and behind recrystallize, form due to the crystalline-granular texture of overlap joint mutually and interlocking, and because microstructure still keeps tangible directivity after perfect recrystallization, so the high temperature molybdenum plate of recrystallize still can keep good plasticity.
Summary of the invention
The object of the present invention is to provide a kind of good processability, surface quality is good, dimensional precision is high, hot strength is high, recrystallization temperature is high, technology simply, the Mo-Si-Al-K cold-rolling thin molybdenum plate band of not flexible brittle failure, yield rate height, material high conformity, long service life and preparation method thereof.
The objective of the invention is to be achieved through the following technical solutions.
A kind of preparation method of Mo-Si-Al-K cold-rolling thin molybdenum plate band, it is characterized in that its preparation process is with Mo-Si-Al-K high temperature sintering molybdenum base, be rolled preceding preannealing under 1300～1400 ℃, it is the processing of 20%～30% hot rolling cogging that high temperature molybdenum base is made first pass deformation; When rolling total deformation reached 70%～75%, rolling interruption made them under 900～1100 ℃ of temperature, carries out process annealing, and annealing time is 60min; Carry out alkali cleaning after the annealing, and warm-rolling become δ=1.0mm in thick molybdenum plate; Thick molybdenum plate among the 1.0mm is carried out cold rolling, the final finished specification is δ=0.2～0.5mm; After finished product carried out the annealing of 800～850 ℃ of vacuum stress-removals, obtain the high temperature cold-rolling thin molybdenum plate band.
A kind of Mo-Si-Al-K cold-rolling thin molybdenum plate band preparation method of the present invention, the preparation process that it is characterized in that described Mo-Si-Al-K high temperature sintering molybdenum base are to be that raw material adds hydrogen and once reduces and obtain molybdenum dioxide with the ammonium dimolybdate; Take by weighing K according to weight percent
2SiO
3And Al (NO
3)
3Dissolve standby; With molybdenum dioxide and K
2SiO
3, Al (NO
3)
3Solution mixes, dries in pot is mixed in bipyramid vacuum-drying; To mix, dry the back molybdenum dioxide again and in four pipe high temperature retort furnaces, carry out the secondary hydrogen reducing; The Mo-Si-Al-K doped molybdenum that reduction is obtained sinters the molybdenum base into after carrying out the isostatic cool pressing compacting.
A kind of Mo-Si-Al-K cold-rolling thin molybdenum plate band preparation method of the present invention is characterized in that containing the weight percent that accounts for molybdenum in the described Mo-Si-Al-K high temperature sintering molybdenum base is K
2O:0.01%～0.08%, SiO
2: 0.02%～0.05%, Al
2O
3: 0%～0.005% oxide compound.
Method of the present invention, adopt traditional powder metallurgical production technique, difference is to carry out the liquid-solid doping of bipyramid vacuum-drying in the molybdenum dioxide stage, then carry out secondary reduction and produce the Si-Al-K doped molybdenum, it is δ 0.1～0.5mmMo-Si-Al-K cold-rolling thin molybdenum plate, band that operation such as repressed again, sintering, hot rolling, warm-rolling, cold rolling, alkali cleaning, annealing is prepared specification.Raw material cheapness of the present invention, be easy to get, prepared thin molybdenum plate, the strip surface quality is good, dimensional precision is high, hot strength is high, recrystallization temperature is high, technology simply, not flexible brittle failure, yield rate height, material high conformity, long service life, can be widely used for making the molybdenum crucible, burn boat, high-power transmitting tube anode (U type), gate molybdenum tube, heating element, thermoscreen and other structural parts.
Method of the present invention, it is cheap and easy to get to have following process characteristic (a 1) raw material: the molybdenum source is an ammonium dimolybdate; (2) employed additive K
2SiO
3, Al (NO
3)
3Cheap, to operator's not injury of health; (3) production technique is easy to control, and is easy and simple to handle, safe, reliable, need not big input and transformation on equipment, is suitable for scale operation; (4) Gu adopt liquid-solid adulterating method and solid-adulterating method to compare the alloying element that is added being evenly distributed in material, good product consistency; (5) be rolled heating under 1300～1500 ℃, it is 20～30% hot rolling cogging that the molybdenum base is made first pass deformation; (6) when rolling total deformation reaches 70～75%, rolling interruption makes it carry out process annealing between 900～1100 ℃; (7) annealing after carry out alkali cleaning, and warm-rolling be δ=1.0mm in thick molybdenum plate; (8) thick molybdenum plate among the 1.0m is carried out cold rolling, the final finished specification is δ=0.1～0.5m; (9) finished product is carried out 800～850 ℃ of vacuum annealings.
Method of the present invention, the Mo-Si-Al-K high temperature molybdenum alloy sheet material of preparation contains K in its alloy
2O, SiO
2And Al
2O
3The weight percent that three kinds of oxide compounds, three kinds of oxide compounds account for molybdenum is K
2O:0.01%～0.08%, SiO
2: 0.02%～0.05%, Al
2O
3: 0%～0.005%.Compare with pure molybdenum, the hot strength height of the inventive method products obtained therefrom, the recrystallization temperature height, 500～600 ℃ have been improved than pure molybdenum, the cold-rolling thin molybdenum plate of gained of the present invention, strip product have premium propertiess such as surface quality is good, dimensional precision is high, hot strength is high, plasticity is good, long service life, can be widely used for making the molybdenum crucible, burn boat, high-power transmitting tube anode (U type), gate molybdenum tube, heating element, thermoscreen and other structural parts.
Embodiment
Be that raw material adds hydrogen and once reduces and obtain molybdenum dioxide with the ammonium dimolybdate; Take by weighing K according to weight percent
2SiO
3And Al (NO
3)
3Dissolve standby; With molybdenum dioxide and K
2SiO
3, Al (NO
3)
3Solution mixes in pot is mixed in bipyramid vacuum-drying, and wherein the pressure of air compressor pump is 0.2MPa, and the bake out temperature of the pot that mixes is 70 ℃, and the inner vacuum tightness of pot of mixing need be controlled at more than the 0.06MPa; Molybdenum dioxide is carried out the secondary hydrogen reducing in four pipe high temperature retort furnaces, hydrogen flowing quantity is 5.0M
3/ H, boat charge is the 1.0kg/ boat, pushing away boat speed is 4 boats/60min; The Mo-Si-Al-K doped molybdenum is carried out isostatic cool pressing be pressed into, obtain substance 9.0kg Mo-Si-Al-K high temperature molybdenum base, the pressing pressure of isostatic cool pressing is 175MPa, and the dwell time is 10min, and a release time is 45s, and the secondary release time is 5s; And carry out 1250 ℃ of retort furnace presintering and 1900 ℃ of intermediate frequency high temperature sinterings obtain substance 9.0kg thickness 24～30mmMo-Si-Al-K sintering high temperature molybdenum base; Mo-Si-Al-K sintering high temperature molybdenum base is rolled preceding heating under 1300～1500 ℃, it is the processing of 20～30% hot rolling cogging that high temperature molybdenum base is made first pass deformation; When rolling total deformation reached 70～75%, rolling interruption made it carry out process annealing between 900～1100 ℃, and annealing time is 60min; Carry out alkali cleaning after the annealing, and warm-rolling be δ=1.0mm in thick molybdenum plate; Thick molybdenum plate among the 1.0mm is carried out cold rolling, the final finished specification is δ=0.1～0.5mm; Finished product is carried out obtaining high temperature cold-rolling thin molybdenum plate, band required for the present invention after 800～850 ℃ of vacuum stress-removal annealing.
Embodiment 1
Be that raw material adds hydrogen and once reduces and obtain molybdenum dioxide with the ammonium dimolybdate, it is standby to get molybdenum dioxide 30kg; According to weight percent is 0.2%K
2O, 0.13%SiO
2, Al
2O
30.001% takes by weighing 100gK
2SiO
3, 6.5g Al (NO
3)
39H
2O dissolves standby; With molybdenum dioxide and K
2SiO
3, Al (NO
3)
3Solution mixes in pot is mixed in bipyramid vacuum-drying, and wherein the pressure of air compressor pump is 0.2MPa, and the bake out temperature of the pot that mixes is 70 ℃, and the inner vacuum tightness of pot of mixing need be controlled at more than the 0.06MPa, obtains molybdenum dioxide 29.0kg after the doping; Molybdenum dioxide is carried out the secondary hydrogen reducing in four pipe high temperature retort furnaces, hydrogen flowing quantity is 5.0M
3/ H, boat charge is the 1.0kg/ boat, pushing away boat speed is 4 boats/60min, obtains Mo-Si-Al-K doped molybdenum 21.0kg; The Mo-Si-Al-K doped molybdenum is carried out isostatic cool pressing be pressed into, obtain substance 9.0kgMo-Si-Al-K high temperature molybdenum base, the pressing pressure of isostatic cool pressing is 175MPa, and the dwell time is 10min, and a release time is 45s, and the secondary release time is 5s; And carry out 1250 ℃ of retort furnace presintering and 1900 ℃ of intermediate frequency high temperature sinterings obtain substance 9.0kg thickness 24～30mmMo-Si-Al-K sintering high temperature molybdenum base; Mo-Si-Al-K sintering high temperature molybdenum base is rolled preceding heating under 1450 ℃, soaking time is 60min; It is the processing of 20～30% hot rolling cogging that high temperature molybdenum base is made first pass deformation; When rolling total deformation reached 70～75%, rolling interruption made it carry out process annealing at 1000 ℃, and annealing time is 60min; Carry out alkali cleaning after the annealing, and warm-rolling is the middle thickness molybdenum plate of δ=1.0mm; Thick molybdenum plate among the 1.0mm is carried out cold rolling, the final finished specification is δ=0.3,0.4mm; Finished product is carried out obtaining high temperature cold-rolling thin molybdenum plate, band required for the present invention after 820 ℃ of vacuum stress-removal annealing.Shown in detection data in the process see the following form.
Table 1 Mo-Si-Al-K doped molybdenum physical and chemical index
The physicochemical property of table 2 Mo-Si-Al-K high temperature molybdenum base
Mechanical property after table 3 δ=0.3,820 ℃ of vacuum annealings of 0.4mmMo-Si-Al-K cold-rolling thin molybdenum plate
Cupping performance after table 4 δ=0.3,820 ℃ of vacuum annealings of 0.4mmMo-Si-Al-K cold-rolling thin molybdenum plate
Claims (3)
1. the preparation method of a Mo-Si-Al-K cold-rolling thin molybdenum plate band, it is characterized in that its preparation process is with Mo-Si-Al-K high temperature sintering molybdenum base, be rolled preceding preannealing under 1300～1400 ℃, it is the processing of 20%～30% hot rolling cogging that high temperature molybdenum base is made first pass deformation; When rolling total deformation reached 70%～75%, rolling interruption made them under 900～1100 ℃ of temperature, carries out process annealing, and annealing time is 60min; Carry out alkali cleaning after the annealing, and warm-rolling become δ=1.0mm in thick molybdenum plate; Thick molybdenum plate among the 1.0mm is carried out cold rolling, the final finished specification is δ=0.2～0.5mm; After finished product carried out the annealing of 800～850 ℃ of vacuum stress-removals, obtain the high temperature cold-rolling thin molybdenum plate band.
2. a kind of Mo-Si-Al-K cold-rolling thin molybdenum plate band preparation method according to claim 1, the preparation process that it is characterized in that described Mo-Si-Al-K high temperature sintering molybdenum base are to be that raw material adds hydrogen and once reduces and obtain molybdenum dioxide with the ammonium dimolybdate; Take by weighing K according to weight percent
2SiO
3And Al (NO
3)
3Dissolve standby; With molybdenum dioxide and K
2SiO
3, Al (NO
3)
3Solution mixes, dries in pot is mixed in bipyramid vacuum-drying; To mix, dry the back molybdenum dioxide again and in four pipe high temperature retort furnaces, carry out the secondary hydrogen reducing; The Mo-Si-Al-K doped molybdenum that reduction is obtained sinters the molybdenum base into after carrying out the isostatic cool pressing compacting.
3. a kind of Mo-Si-Al-K cold-rolling thin molybdenum plate band preparation method according to claim 1 is characterized in that containing the weight percent that accounts for molybdenum in the described Mo-Si-Al-K high temperature sintering molybdenum base is K
2O:0.01%～0.08%, SiO
2: 0.02%～0.05%, Al
2O
3: 0%～0.005% oxide compound.
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| CN106399787B (en) * | 2016-08-31 | 2018-06-01 | 安泰天龙（天津）钨钼科技有限公司 | A kind of high temperature and creep resistance molybdenum plate for adulterating K, Si element and preparation method thereof |
| CN106521202B (en) * | 2016-11-10 | 2018-05-18 | 洛阳科威钨钼有限公司 | A kind of preparation method of molybdenum hafnium alloy plate |
| CN109317679B (en) * | 2018-09-12 | 2019-12-24 | 中南大学 | Production method of aluminum alloy sheet |
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| CN110846544A (en) * | 2019-11-25 | 2020-02-28 | 江苏峰峰钨钼制品股份有限公司 | Rhenium-aluminum-potassium-molybdenum alloy rod for electrode for illumination and preparation method thereof |
| CN115449686B (en) * | 2022-10-12 | 2023-03-24 | 如皋市电光源钨钼制品有限公司 | Wire-electrode cutting molybdenum wire with high tensile strength and production method thereof |
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| CN1163173A (en) * | 1996-04-23 | 1997-10-29 | 中南工业大学 | Powder metellurgical method for producing molybdenum wafer |
| CN101045257A (en) * | 2006-07-10 | 2007-10-03 | 孙昭虹 | Method for rolling molybdenum sheet by powder metallurgic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163173A (en) * | 1996-04-23 | 1997-10-29 | 中南工业大学 | Powder metellurgical method for producing molybdenum wafer |
| CN101045257A (en) * | 2006-07-10 | 2007-10-03 | 孙昭虹 | Method for rolling molybdenum sheet by powder metallurgic |
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