CN100402682C - Fine crystal rare earth oxide molybdenum alloy-doped and its preparation method - Google Patents
Fine crystal rare earth oxide molybdenum alloy-doped and its preparation method Download PDFInfo
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Abstract
The present invention provides a fine crystal rare earth oxide doped molybdenum alloy and a preparation method thereof. The present invention uses molybdenum dioxide as raw material and uses atomization to dope rare earth oxide; reducing treatment is carried out to doped molybdenum alloy powder by hydrogen gas in a multistage muffle furnace with the temperature of 800 to 1100DEG. C after ball milling and sieving treatment of the doped molybdenum alloy powder; reduced powder is shaped by pressing in a cold isostatic pressing mode under the pressure of 150 to 200MPa; shaped blanks are sintered by stages in a middle frequency induction sintering furnace for 16 to 24 hours. Sintered material uses a conventional machine work method to prepare molybdenum alloy bar material or sheet material, etc. after 75%-97% deformation processing. The molybdenum alloy of the present invention has minute grain structure, and the average width of the crystal grains is from 0.5 to 1.2 mum; minute rare earth oxide with the average size of less than 300 nm is uniformly dispersed and distributed on a molybdenum alloy basal body; compared with the common coarse crystal molybdenum alloy, the fine crystal rare earth oxide has the advantages of higher strength, ductility and toughness and broader application.
Description
Technical field
The present invention relates to rare-earth oxide doping molybdenum alloys material and preparation method thereof, particularly a kind of thin brilliant molybdenum alloy material and preparation method thereof.
Background technology
Molybdenum has high-melting-point (2620 ℃), high elastic coefficient (320GPa～350GPa), high-wearing feature, favorable conductive heat conductivility, low-expansion coefficient (5.03 * 10
-6/ K), and the performances such as corrosion of good acid and alkali-resistance and anti-liquid metal, and earth reserves are abundanter.But the molybdenum material has the intrinsic property of bcc metals institute inherent tough-brittle transition and low temperature brittleness, make the plasticity of pure Mo at room temperature just be reduced to the fragility category, this fragility is the essential reason that pure Mo deep processing difficulty and converted products quality do not pass a test.In addition, the deficiency on the pure Mo intensity also is one of limited major reason of pure Mo Application Areas.Therefore, the highly malleablized of pure Mo is to improve the essential measure and the means in deep processing performance and broadened application field.
Molybdenum alloy, especially the rare-earth oxide doping molybdenum alloys material succeeds in developing, not only obviously improve the deep processing performance of molybdenum, also improved the intensity of molybdenum, becoming the refractory metal material of all being used widely at each industrial sector, is the indispensable high-temperature material of national economy and military field.In mechanical industry, molybdenum alloy top head is the important materials that pierces stainless-steel pipe, or the main raw of mfg. moulding die, as the mould as cast aluminium, brass and zinc, also can be as the ferrous metal die casting die material, as parts such as die casting instruments cutter, turbine blades; In electronic industry, it is a kind of very important electrode and cathode emission material; In metallurgical industry, molybdenum alloy can be used as the heating element of High Temperature Furnaces Heating Apparatus, structural part, thermoscreen and the high temperature vessel etc. of resting support.In aerospace, war industry, make high temperature, the high pressure rocket apparatus and the airplane parts of work down with molybdenum alloy, be mainly used in rocket, missile component, as combustion gas wheel sheet, punching engine jet pipe, flame deflector and the combustion chamber etc. of nozzle, engine, for example widely-used metal molybdenum and molybdenum alloy are made combustion chamber, throat's ferrule sleeve on the liquid fuel within rocket engine; Particularly spaceship emission and when returning by atmospheric layer because speed is very fast, be exposed to airborne part temperatures up to 1482 ℃～1646 ℃, thereby to adopt molybdenum to do covering, jet pipe, flame seal, aerofoil be turning vane etc.; In nuclear power industry, it is less that molybdenum has thermal-neutron capture cross-section, the creep rupture strength height, to the characteristics such as corrosion of the stability of nuclear fuel and opposing liquid metal, so molybdenum and molybdenum alloy are as the fuel sheath element of the structured material of nuclear reactor, Gas-Cooled Reactor and releasing member etc.
At present, develop rapidly along with technology such as aerospace, various device shape are more complicated, working accuracy is higher, this processing characteristics to molybdenum alloy has proposed new requirement, not only require molybdenum alloy that high strength will be arranged, also high ductibility and fracture toughness property will be arranged, undoubtedly, common coarse-grain rare-earth oxide doping molybdenum alloys will be difficult to satisfy these requirements, have only thin brilliant coarse-grain rare-earth oxide doping molybdenum alloys could satisfy these requirements, this is because crystal grain is thin more, and crystal grain boundary is many more in the unit volume, and then effective obstacle of dislocation moving is many more, cause the material viscous deformation to trigger the required drag of dislocation motion and increase, improved the strength of materials.Simultaneously, crystal grain is thin more, number of dies in the unit volume is many more, under same deflection condition, distortion can be carried out at more intragranular, causes deformation distribution even, the piling up of dislocations degree is low, the cracking chance that stress concentration causes is few, causes material can bear bigger deflection before fracture, and this makes material have higher ductility and toughness.Therefore, preparation is fine crystal rare earth oxide molybdenum alloy-doped will be one of the method that obtains the molybdenum alloy material of high strength, high ductibility and high tenacity.
Summary of the invention
The object of the present invention is to provide a kind of fine crystal rare earth oxide molybdenum alloy-doped and preparation method thereof, fine crystal rare earth oxide molybdenum alloy-doped with method of the present invention preparation, not only have high strength and the high ductibility better, and have heterogeneous microstructure very uniformly than common coarse-grain molybdenum alloy.
A kind of fine crystal rare earth oxide molybdenum alloy-doped preparation method provided by the present invention, preparation process is as follows:
The first step, following optional approach are determined lanthanum cerium yttrium rare earth oxide,
(1) lanthanum trioxide La
2O
3, cerium oxide CeO
2, yttrium oxide Y
2O
3According to the mass percent ratio is to mix at 1: 1: 1,
(2) cerium oxide CeO
2, yttrium oxide Y
2O
3According to the mass percent ratio is to mix at 1: 3, or lanthanum trioxide La
2O
3, cerium oxide CeO
2According to the mass percent ratio is to mix at 1: 1,
(3) lanthanum trioxide La
2O
3, cerium oxide CeO
2, yttrium oxide Y
2O
3Any,
Second step was that 0.5-3.5% takes by weighing lanthanum cerium yttrium rare earth oxide according to the mass percent scope, and all the other compositions are the molybdenum dioxide powder,
The 3rd goes on foot, and lanthanum cerium yttrium rare earth oxide is dissolved in makes lanthanum cerium yttrium rare earth nitrate solution in the dilute nitric acid solution that mass percent concentration is 5%-10%;
In the 4th step, in the molybdenum dioxide powder that is taken by weighing, add above-mentioned prepared lanthanum cerium yttrium rare earth nitrate solution with atomization, at room temperature stir, stirring velocity is 5-10rpm, makes it uniform doping, dry under 100-125 ℃ then, drying time is 1-3h;
In the 5th step, with the powder roasting after the oven dry, roasting is carried out in the hydrogen shield atmosphere furnace, and temperature is: 500-650 ℃, and time 1-3h;
The 6th step, material after the roasting is carried out ball milling, the processing of sieving, ball-milling technology is that material and spheroid mass ratio are between 3: 2 to 1: 1, time is 1-2h, make raw meal particle size less than 90 μ m, using hydrogen to carry out the multistage reduction then in 800-1100 ℃ retort furnace handles, concrete reducing process is: be incubated 0.3-0.5h earlier under 900-1000 ℃ of temperature, under 1000-1100 ℃ of temperature, be incubated 0.5-1.0h successively afterwards, be incubated 0.3-0.5h under the 1000-900 ℃ of temperature, under 900-800 ℃ of temperature, be incubated 0.3-0.5h at last, in the reduction process the pressure of logical hydrogen be 0.3-0.5Pa, flow is 0.5-1.0m
3MoO takes place in/h
2+ H
2→ Mo+H
2O reaction, the molybdenum alloy powder of the lanthanum cerium yttrium rare earth oxide that obtains mixing;
The 7th step, molybdenum alloy powder isostatic cool pressing compression moulding under 150-200MPa of doping lanthanum cerium yttrium rare earth oxide, the blank after the moulding is multi-steps sintering in 1200-1800 ℃ vacuum Medium frequency induction sintering oven, sintering time 16-24 hour;
In the 8th step, the blank behind the sintering is carried out press working, and to make it total deformation be 75%-97%, carries out stress relief annealing after the distortion and handle, and annealing temperature: 1100-1300 ℃, soaking time 0.5-1 hour, obtains fine crystal rare earth oxide molybdenum alloy-doped.
Blank after the moulding is multi-steps sintering in 1200-1800 ℃ vacuum Medium frequency induction sintering oven, and sintering time 16-24 hour, concrete sintering process was as follows:
Earlier in 2.0-3.0 hour time, blank is warming up to 1200-1300 ℃ gradually by room temperature, and under this temperature, be incubated 1-2 hour, be warming up to 1400-1500 ℃ and be incubated 2-3 hour 2.0-3.0 hour time then, then be warming up to 1600-1700 ℃ and be incubated 2-3 hour, be warming up to 1700-1800 ℃ and be incubated 5-10 hour 1.0-1.5 hour time at last 1.0-1.5 hour time.
Adopt difform materials such as molybdenum alloy bar material that the preparation of conventional machine-tooled method satisfies the demand, sheet material.
The key problem in technology that the present invention solves is to select the proper amount of rare-earth oxide-doped molybdenum alloy, control the globule size and the size-grade distribution of powder simultaneously, make that prepared molybdenum alloy middle-weight rare earths oxide particle is tiny and be evenly distributed, the grain-size of molybdenum alloy is also extremely tiny and even, thereby has guaranteed that resulting material has high-intensity also have simultaneously high ductility and toughness.
In sum, advantage of the present invention and positively effect are embodied in:
(1) adopt the grain structure of the prepared rare-earth oxide doping molybdenum alloys material of the technology of the present invention tiny, the average crystal grain width is: 0.5-1.2 μ m.
(2) owing to adopt the rare earth doped oxide compound of atomization drying method, make the rare earth oxide size evenly tiny and and molybdenum mix, the distribution disperse, mean grain size is less than 300nm.
(3) prepared fine crystal rare earth oxide molybdenum alloy-doped of the present invention has excellent mechanical property, and its tensile strength can reach 700-850MPa, and tension set can reach 20-45%, and the purer Mo of room temperature fracture toughness property has improved more than 3 times.
(4) this fine crystal rare earth oxide molybdenum alloy-dopedly has a good deep processing performance, for further improve its deformation processing degree provide may, be suitable for preparing complex-shaped, the material that deformation extent is high.
(5) the fine crystal rare earth oxide molybdenum alloy-doped preparation method of the present invention's proposition, equipment used can all domesticize, and technology is simple and direct, and output is big, is easy to realize industrialization production.
Specific embodiment
Embodiment one:
Take by weighing 38.46 gram lanthanum trioxides and 2000 gram molybdenum dioxide powder respectively, it is in rare nitric acid of 5% that 38.46 gram lanthanum trioxides are dissolved in mass percent concentration, the preparation lanthanum nitrate hexahydrate;
Adopt atomization that this lanthanum nitrate hexahydrate is joined in the 2000 gram molybdenum dioxide powder, wherein the lanthanum trioxide mass percent is 2.5%, at room temperature stirs and makes it uniform doping, and stirring velocity is 5rpm, dry under 120 ℃ then, drying time is 1.5 hours;
To the powder roasting after the oven dry, roasting is carried out in the hydrogen shield atmosphere furnace, and maturing temperature is 500 ℃, and the time is 1h;
Material after the roasting is carried out ball milling make it by 170 mesh sieve, ball-milling technology is: powder: spheroid=3: 2 (mass ratio), the time is 1h.Powder after sieving uses hydrogen to carry out multistage reduction in retort furnace and handles, the pressure of logical hydrogen be 0.5Pa, flow is 0.7m
3/ h, concrete reducing process is: 900 ℃ * 0.3h, 1050 ℃ * 1h, 900 ℃ * 0.3h, 850 ℃ * 0.3h, obtain the molybdenum powder of lanthanum oxide doping.
This mix molybdenum powder mean grain size less than 1 μ m.This powder is carried out the excellent base that cold isostatic compaction is φ 52mm under 185MPa, carry out multi-steps sintering in the blank Medium frequency induction sintering oven after the moulding, concrete technology is: in 2.0 hour time blank is warming up to 1200 ℃ gradually by room temperature earlier, and under this temperature, be incubated 1 hour, be warming up to 1400 ℃ and be incubated 2 hours 2.0 hour time then, then be warming up to 1600 ℃ and be incubated 2 hours, be warming up to 1700 ℃ 1.0 hour time at last, and be incubated 10 hours 1.0 hour time.Excellent base after adopting the stepped start-stop system milling train with sintering finally is rolled into the molybdenum alloy bar material of φ 17mm.In the hydrogen shield stove, this molybdenum alloy bar is carried out anneal, 1200 ℃ of annealing temperatures, soaking time 1 hour.The average crystal grain width of prepared molybdenum alloy material is 0.63 μ m, and tiny lanthanum trioxide particulate mean sizes is 206nm.According to standard GB 228-87, GB 2.38-91 and GB2106-80 process respectively and room temperature tensile, room temperature fracture toughness and room temperature impelling strength experiment test resulting molybdenum alloy bar, experimental result shows that the tensile strength of material is 739MPa, yield strength is 631MPa, tension set is 38.5%, and fracture toughness is 125.36MPam
1/2(pure molybdenum is 27.6MPam
1/2).
Embodiment two:
Take by weighing 7.69 gram cerium oxide and 2000 gram molybdenum dioxide powder respectively, it is in rare nitric acid of 10% that 7.69 gram cerium oxide are dissolved in mass percent concentration, the preparation cerous nitrate solution, adopt atomization that this cerous nitrate solution is joined in the 2000 gram molybdenum dioxide powder, wherein the cerium oxide mass percent is 0.5%, at room temperature stir and make it uniform doping, stirring velocity is 10rpm, dries under 120 ℃ then, and drying time is 1.5 hours, to the powder roasting after the oven dry, maturing temperature is 650 ℃, and the time is 3h, the material after the oven dry is carried out ball milling make it by 170 mesh sieve, ball-milling technology is: powder: spheroid=3: 2 (quality), the time is 1h.Powder after sieving uses hydrogen to carry out multistage reduction in retort furnace and handles, the pressure of logical hydrogen be 0.5Pa, flow is 0.7m
3/ h, concrete reducing process is: 950 ℃ * 0.3h, 1100 ℃ * 0.5h, 950 ℃ * 0.5h, 850 ℃ * 0.5h, obtain the adulterated molybdenum powder of cerium oxide.
This mix molybdenum powder mean grain size less than 1 μ m.This powder is carried out the excellent base that cold isostatic compaction is φ 17mm under 195MPa, blank after the moulding carries out multi-steps sintering in the Medium frequency induction sintering oven, concrete technology is: in 2.0 hour time blank is warming up to 1200 ℃ gradually by room temperature earlier, and under this temperature, be incubated 1 hour, be warming up to 1400 ℃ and be incubated 2 hours 2.0 hour time then, then be warming up to 1600 ℃ and be incubated 2 hours, be warming up to 1700 ℃ 1.0 hour time at last, and be incubated 10 hours 1.0 hour time.Excellent base after adopting the stepped start-stop system milling train with sintering finally is rolled into the molybdenum alloy bar material of φ 7.8mm.In the hydrogen shield stove, this molybdenum alloy bar is carried out anneal, annealing temperature: 1250 ℃, soaking time 1 hour.The average crystal grain width of prepared molybdenum alloy material is 0.58 μ m, tiny cerium oxide particle mean sizes be 214nm.According to standard GB 228-87, GB 2.38-91 and GB 2106-80 process respectively and room temperature tensile, room temperature fracture toughness and room temperature impelling strength experiment test resulting molybdenum alloy bar, experimental result shows that the tensile strength of material is 754MPa, yield strength is 722MPa, tension set is 41.3%, and fracture toughness is 138.9MPam
1/2
Embodiment three:
Take by weighing 3.02 gram cerium oxide respectively, 9.06 gram yttrium oxide and 2000 gram molybdenum dioxide powder, it is in rare nitric acid of 5% that 3.02 gram cerium oxide and 9.06 gram yttrium oxide are dissolved in mass percent concentration, preparation cerous nitrate and Yttrium trinitrate mixing solutions, adopt atomization that this nitrate solution is joined in the 2000 gram molybdenum dioxide powder, wherein the cerium oxide mass percent is 0.2%, the yttrium oxide mass percent is 0.6%, at room temperature stir and make it uniform doping, stirring velocity is 5rpm, under 120 ℃, dry then, drying time is 1.5 hours, and to the powder roasting after the oven dry, maturing temperature is 600 ℃, time is 2h, material after the oven dry is carried out ball milling make it by 170 mesh sieve, ball-milling technology is: powder: spheroid=3: 2 (quality), the time is 1h.Powder after sieving uses hydrogen to carry out multistage reduction in retort furnace and handles, the pressure of logical hydrogen be 0.3Pa, flow is 0.8m
3/ h, concrete reducing process is: 900 ℃ * 0.3h, 1050 ℃ * 0.5h, 1000 ℃ * 0.5h, 850 ℃ * 0.3h, obtain cerium oxide and the adulterated molybdenum powder of yttrium oxide thing.
This mean grain size of mixing molybdenum powder is less than 1 μ m.This powder is carried out the excellent base that cold isostatic compaction is φ 17mm under 190MPa, blank after the moulding carries out multi-steps sintering in the Medium frequency induction sintering oven, concrete technology is: in 3.0 hour time blank is warming up to 1200 ℃ gradually by room temperature earlier, and under this temperature, be incubated 2 hours, be warming up to 1500 ℃ and be incubated 3 hours 3.0 hour time then, then be warming up to 1700 1.5 hour time) ℃ and be incubated 3 hours, be warming up to 1800 ℃ and be incubated 5 hours 1.5 hour time at last.Excellent base after adopting the stepped start-stop system milling train with sintering finally is rolled into the molybdenum alloy bar material of φ 7.8mm.In the hydrogen shield stove, this molybdenum alloy bar is carried out anneal, annealing temperature: 1200 ℃, soaking time 1 hour.The average crystal grain width of prepared molybdenum alloy material is 0.67 μ m, and the mean sizes of tiny cerium oxide and yttria particles is 91.6nm.According to standard GB 228-87, GB 2.38-91 and GB 2106-80 process respectively and room temperature tensile, room temperature fracture toughness and room temperature impelling strength experiment test resulting molybdenum alloy bar, experimental result shows that the tensile strength of material is 818MPa, yield strength is 747MPa, tension set is 38.5%, and fracture toughness is 135.0MPam
1/2
Embodiment four:
Take by weighing 3.6 gram cerium oxide respectively, 3.6 gram lanthanum trioxide, 3.6 gram yttrium oxide and 2000 gram molybdenum dioxide powder, with 3.6 gram cerium oxide, 3.6 it is in rare nitric acid of 10% that gram lanthanum trioxide and 3.6 gram yttrium oxide are dissolved in mass percent concentration, the preparation cerous nitrate, lanthanum nitrate and Yttrium trinitrate mixing solutions, adopt atomization nitrate solution should be joined in the 2000 gram molybdenum dioxide powder, wherein the cerium oxide mass percent is 0.18%, the lanthanum trioxide mass percent is 0.18%, the yttrium oxide mass percent is 0.18%, at room temperature stir and make it uniform doping, stirring velocity is 5rpm, under 120 ℃, dry then, drying time is 1.5 hours, to the powder roasting after the oven dry, maturing temperature is 500 ℃, and the time is 1.5h, the material after the oven dry is carried out ball milling make it by 170 mesh sieve, ball-milling technology is: powder: spheroid=3: 2 (quality), the time is 1h.Powder after sieving uses hydrogen to carry out multistage reduction in retort furnace and handles, the pressure of logical hydrogen be 0.3Pa, flow is 0.7m
3/ h, concrete reducing process is: 950 ℃ * 0.5h, 1050 ℃ * 0.6h, 950 ℃ * 0.4h, 800 ℃ * 0.5h, obtain the molybdenum powder of cerium oxide, lanthanum trioxide and Yttrium oxide doping.
This mean grain size of mixing molybdenum powder is less than 1 μ m.This powder is carried out the excellent base that cold isostatic compaction is φ 17mm under 190MPa, blank after the moulding carries out multi-steps sintering in the Medium frequency induction sintering oven, concrete technology is: in 3.0 hour time blank is warming up to 1200 ℃ gradually by room temperature earlier, and under this temperature, be incubated 2 hours, be warming up to 1500 ℃ and be incubated 3 hours 3.0 hour time then, then be warming up to 1700 1.5 hour time) ℃ and be incubated 3 hours, be warming up to 1800 ℃ and be incubated 5 hours 1.5 hour time at last.Excellent base after adopting the stepped start-stop system milling train with sintering finally is rolled into the molybdenum alloy bar material of φ 6.5mm.In the hydrogen shield stove, this molybdenum alloy bar is carried out anneal, annealing temperature: 1250 ℃, soaking time 1 hour.The average crystal grain width of prepared molybdenum alloy material is 0.73 μ m, and the mean sizes of tiny rare earth oxide particles is: 109.8nm.According to standard GB 228-87, GB 2.38-91 and GB 2106-80 process respectively and room temperature tensile, room temperature fracture toughness and room temperature impelling strength experiment test resulting molybdenum alloy bar, experimental result shows that the tensile strength of material is 742MPa, yield strength is 717MPa, tension set is 20.1%, and fracture toughness is 106.8.0MPam
1/2
Embodiment five:
Take by weighing 22.8 gram lanthanum trioxides and 2000 gram molybdenum dioxide powder respectively, it is in rare nitric acid of 7% that 22.8 gram lanthanum trioxides are dissolved in mass percent concentration, the preparation lanthanum nitrate hexahydrate, adopt atomization that this lanthanum nitrate hexahydrate is joined in the 2000 gram molybdenum dioxide powder, wherein the lanthanum trioxide mass percent is 1.5%, at room temperature stir and make it uniform doping, stirring velocity is 7rpm, dries under 120 ℃ then, and drying time is 1.5 hours, to the powder roasting after the oven dry, maturing temperature is 500 ℃, and the time is 1h, the material after the oven dry is carried out ball milling make it by 170 mesh sieve, ball-milling technology is: powder: spheroid=3: 2 (quality), the time is 1h.Powder after sieving uses hydrogen to carry out multistage reduction in retort furnace and handles, the pressure of logical hydrogen be 0.4Pa, flow is 0.5m
3/ h, concrete reducing process is: 900 ℃ * 0.3h, 1050 ℃ * 0.8h, 950 ℃ * 0.5h, 850 ℃ * 0.3h, obtain the molybdenum powder of lanthanum oxide doping.
This mean grain size of mixing molybdenum powder is less than 1 μ m.This powder is carried out the excellent base that cold isostatic compaction is φ 52mm under 185MPa, blank after the moulding carries out multi-steps sintering in the Medium frequency induction sintering oven, concrete technology is: in 2.5 hour time blank is warming up to 1250 ℃ gradually by room temperature earlier, and under this temperature, be incubated 1.5 hours, be warming up to 1500 ℃ and be incubated 2 hours 2.5 hour time then, then be warming up to 1700 ℃ and be incubated 2.5 hours, be warming up to 1770 ℃ and be incubated 8 hours 1.0 hour time at last 1.0 hour time.Excellent base after adopting the stepped start-stop system milling train with sintering finally is rolled into the molybdenum alloy bar material of φ 17mm.In the hydrogen shield stove, this molybdenum alloy bar is carried out anneal, 1200 ℃ of annealing temperatures, soaking time 1 hour.The average crystal grain width of prepared molybdenum alloy material is 0.91 μ m, and tiny lanthanum trioxide particulate mean sizes is 137nm.According to standard GB 228-87, GB 2.38-91 and GB 2106-80 process respectively and room temperature tensile, room temperature fracture toughness and room temperature impelling strength experiment test resulting molybdenum alloy bar, experimental result shows that the tensile strength of material is 702MPa, yield strength is 618MPa, tension set is 21.2%, and fracture toughness is 111.8MPam
1/2
Embodiment six:
Take by weighing 18.22 gram cerium oxide and 2000 gram molybdenum dioxide powder respectively, to be dissolved in mass percent concentration be in rare nitric acid of 5% with adding in the 18.22 gram cerium oxide, the preparation cerous nitrate solution, adopt atomization that this cerous nitrate solution is joined in the 2000 gram molybdenum dioxide powder, wherein the cerium oxide mass percent is 1.2%, at room temperature stir and make it uniform doping, stirring velocity is 5rpm, under 120 ℃, dry then, drying time is 1.5 hours, to the powder roasting after the oven dry, maturing temperature is 550 ℃, and the time is 2h, the material after the oven dry is carried out ball milling make it by 170 mesh sieve, ball-milling technology is: powder: spheroid=3: 2 (quality), the time is 1h.Powder after sieving uses hydrogen to carry out multistage reduction in retort furnace and handles, the pressure of logical hydrogen be 0.3Pa, flow is 0.8m
3/ h, concrete reducing process is: 900 ℃ * 0.3h, 1100 ℃ * 0.5h, 950 ℃ * 0.3h, 850 ℃ * 0.3h, obtain the adulterated molybdenum powder of cerium oxide.
This mean grain size of mixing molybdenum powder is less than 1 μ m.This powder is carried out the excellent base that cold isostatic compaction is φ 17mm under 195MPa, blank after the moulding carries out multi-steps sintering in the Medium frequency induction sintering oven, concrete technology is: in 2.0 hour time blank is warming up to 1300 ℃ gradually by room temperature earlier, and under this temperature, be incubated 2 hours, be warming up to 1450 ℃ and be incubated 3 hours 2.5 hour time then, then be warming up to 1600 ℃ and be incubated 2 hours, be warming up to 1770 ℃ and be incubated 6 hours 1.5 hour time at last 1.0 hour time.Excellent base after adopting the stepped start-stop system milling train with sintering finally is rolled into the molybdenum alloy bar material of φ 7.8mm.In the hydrogen shield stove, this molybdenum alloy bar is carried out anneal, 1250 ℃ of annealing temperatures, soaking time 1 hour.The average crystal grain width of prepared molybdenum alloy material is 1.05 μ m, tiny cerium oxide particle mean sizes be 113nm.According to standard GB 228-87, GB 2.38-91 and GB2106-80 process respectively and room temperature tensile, room temperature fracture toughness and room temperature impelling strength experiment test resulting molybdenum alloy bar, experimental result shows that the tensile strength of material is 711MPa, yield strength is 647MPa, tension set is 33.7%, and fracture toughness is 135.7MPam
1/2
Embodiment seven:
Take by weighing 5.53 gram lanthanum trioxides respectively, 5.53 gram cerium oxide and 2000 gram molybdenum dioxide powder, it is in rare nitric acid of 10% that 5.53 gram lanthanum trioxides and 5.53 gram cerium oxide are dissolved in mass percent concentration, preparation lanthanum trioxide and cerium oxide mixing solutions, adopt atomization that this nitrate solution is joined in the 2000 gram molybdenum dioxide powder, wherein the lanthanum trioxide mass percent is 0.28%, the cerium oxide mass percent is 0.28%, at room temperature stir and make it uniform doping, stirring velocity is 5rpm, under 120 ℃, dry then, drying time is 1.5 hours, and to the powder roasting after the oven dry, maturing temperature is 500 ℃, time is 1h, material after the oven dry is carried out ball milling make it by 170 mesh sieve, ball-milling technology is: powder: spheroid=3: 2 (quality), the time is 1h.Powder after sieving uses hydrogen to carry out multistage reduction in retort furnace and handles, the pressure of logical hydrogen be 0.3Pa, flow is 0.7m
3/ h, concrete reducing process is: 900 ℃ * 0.5h, 1080 ℃ * 0.6h, 950 ℃ * 0.3h, 800 ℃ * 0.3h, obtain the adulterated molybdenum powder of lanthanum trioxide and cerium oxide.
This mean grain size of mixing molybdenum powder is less than 1 μ m.This powder is carried out the excellent base that cold isostatic compaction is φ 17mm under 190MPa, blank after the moulding carries out multi-steps sintering in the Medium frequency induction sintering oven, concrete technology is: in 3.0 hour time blank is warming up to 1300 ℃ gradually by room temperature earlier, and under this temperature, be incubated 2 hours, be warming up to 1450 ℃ and be incubated 2.5 hours 3.0 hour time then, then be warming up to 1650 ℃ and be incubated 2.5 hours, be warming up to 1700 ℃ and be incubated 10 hours 1.0 hour time at last 1.5 hour time.Excellent base after adopting the stepped start-stop system milling train with sintering finally is rolled into the molybdenum alloy bar material of φ 7.8mm.In the hydrogen shield stove, this molybdenum alloy bar is carried out anneal, 1200 ℃ of annealing temperatures, soaking time 1 hour.The average crystal grain width of prepared molybdenum alloy material is 1.12 μ m, and the mean sizes of tiny lanthanum trioxide and cerium oxide particle is respectively 86.7 and 90.7nm.According to standard GB 228-87, GB 2.38-91 and GB 2106-80 process respectively and room temperature tensile, room temperature fracture toughness and room temperature impelling strength experiment test resulting molybdenum alloy bar, experimental result shows that the tensile strength of material is 713MPa, yield strength is 701MPa, tension set is 22.7%, and fracture toughness is 120.6MPam
1/2
Embodiment eight:
Take by weighing 38.46 gram yttrium oxide and 2000 gram molybdenum dioxide powder respectively, it is in rare nitric acid of 8% that 38.46 gram yttrium oxide are dissolved in mass percent concentration, the preparation cerous nitrate solution, adopt atomization that this cerous nitrate solution is joined in the 2000 gram molybdenum dioxide powder, wherein the yttrium oxide mass percent is 2.5%, at room temperature stir and make it uniform doping, stirring velocity is 10rpm, dries under 120 ℃ then, and drying time is 1.5 hours, to the powder roasting after the oven dry, maturing temperature is 500 ℃, and the time is 1h, the material after the oven dry is carried out ball milling make it by 170 mesh sieve, ball-milling technology is: powder: spheroid=3: 2 (quality), the time is 1h.Powder after sieving uses hydrogen to carry out multistage reduction in retort furnace and handles, the pressure of logical hydrogen be 0.5Pa, flow is 0.6m
3/ h, concrete reducing process is: 900 ℃ * 0.5h, 1100 ℃ * 0.6h, 1000 ℃ * 0.3h, 850 ℃ * 0.5h, obtain the molybdenum powder of Yttrium oxide doping.
This mean grain size of mixing molybdenum powder is less than 1 μ m.This powder is carried out the excellent base that cold isostatic compaction is φ 17mm under 195MPa, blank after the moulding carries out multi-steps sintering in the Medium frequency induction sintering oven, concrete technology is: in 3.0 hour time blank is warming up to 1300 ℃ gradually by room temperature earlier, and under this temperature, be incubated 2 hours, be warming up to 1500 ℃ and be incubated 2 hours 2.0 hour time then, then be warming up to 1600 ℃ ℃ and be incubated 2 hours, be warming up to 1750 ℃ and be incubated 9 hours 1.0 hour time at last 1.5 hour time.Excellent base after adopting the stepped start-stop system milling train with sintering finally is rolled into the molybdenum alloy bar material of φ 7.8mm.In the hydrogen shield stove, this molybdenum alloy bar is carried out anneal, annealing temperature: 1250 ℃, soaking time 1 hour.The average crystal grain width of prepared molybdenum alloy material is 0.58 μ m, and the mean sizes of tiny yttria particles is 214nm.According to standard GB 228-87, GB 2.38-91 and GB2106-80 process respectively and room temperature tensile, room temperature fracture toughness and room temperature impelling strength experiment test resulting molybdenum alloy bar, experimental result shows that the tensile strength of material is 724MPa, yield strength is 709MPa, tension set is 39.3%, and fracture toughness is 121.9MPam
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Claims (2)
1. fine crystal rare earth oxide molybdenum alloy-doped preparation method is characterized in that preparation process is as follows:
The first step, following optional approach are determined lanthanum cerium yttrium rare earth oxide,
(1) lanthanum trioxide La
2O
3, cerium oxide CeO
2, yttrium oxide Y
2O
3According to the mass percent ratio is to mix at 1: 1: 1,
(2) cerium oxide CeO
2, yttrium oxide Y
2O
3According to the mass percent ratio is to mix at 1: 3, or lanthanum trioxide La
2O
3, cerium oxide CeO
2According to the mass percent ratio is to mix at 1: 1,
(3) lanthanum trioxide La
2O
3, cerium oxide CeO
2, yttrium oxide Y
2O
3Any,
Second step was that 0.5-3.5% takes by weighing lanthanum cerium yttrium rare earth oxide according to the mass percent scope, and all the other compositions are the molybdenum dioxide powder,
The 3rd goes on foot, and lanthanum cerium yttrium rare earth oxide is dissolved in makes lanthanum cerium yttrium rare earth nitrate solution in the dilute nitric acid solution that mass percent concentration is 5%-10%;
In the 4th step, in the molybdenum dioxide powder that is taken by weighing, add above-mentioned prepared lanthanum cerium yttrium rare earth nitrate solution with atomization, at room temperature stir, stirring velocity is 5-10rpm, makes it uniform doping, dry under 100-125 ℃ then, drying time is 1-3h;
In the 5th step, with the powder roasting after the oven dry, roasting is carried out in the hydrogen shield atmosphere furnace, and temperature is: 500-650 ℃, and time 1-3h;
The 6th step, material after the roasting is carried out ball milling, the processing of sieving, ball-milling technology is that material and spheroid mass ratio are between 3: 2 to 1: 1, time is 1-2h, make raw meal particle size less than 90 μ m, using hydrogen to carry out the multistage reduction then in 800-1100 ℃ retort furnace handles, concrete reducing process is: be incubated 0.3-0.5h earlier under 900-1000 ℃ of temperature, under 1000-1100 ℃ of temperature, be incubated 0.5-1.0h successively afterwards, be incubated 0.3-0.5h under the 1000-900 ℃ of temperature, under 900-800 ℃ of temperature, be incubated 0.3-0.5h at last, in the reduction process the pressure of logical hydrogen be 0.3-0.5Pa, flow is 0.5-1.0m
3MoO takes place in/h
2+ H
2→ Mo+H
2O reaction, the molybdenum alloy powder of the lanthanum cerium yttrium rare earth oxide that obtains mixing;
The 7th step, molybdenum alloy powder isostatic cool pressing compression moulding under 150-200MPa of doping lanthanum cerium yttrium rare earth oxide, the blank after the moulding is multi-steps sintering in 1200-1800 ℃ vacuum Medium frequency induction sintering oven, sintering time 16-24 hour;
In the 8th step, the blank behind the sintering is carried out press working, and to make it total deformation be 75%-97%, carries out stress relief annealing after the distortion and handle, and annealing temperature: 1100-1300 ℃, soaking time 0.5-1 hour, obtains fine crystal rare earth oxide molybdenum alloy-doped.
2. fine crystal rare earth oxide molybdenum alloy-doped preparation method according to claim 1 is characterized in that, the blank after the moulding is multi-steps sintering in 1200-1800 ℃ vacuum Medium frequency induction sintering oven, and sintering time 16-24 hour, concrete sintering process was as follows:
Earlier in 2.0-3.0 hour time, blank is warming up to 1200-1300 ℃ gradually by room temperature, and under this temperature, be incubated 1-2 hour, be warming up to 1400-1500 ℃ and be incubated 2-3 hour 2.0-3.0 hour time then, then be warming up to 1600-1700 ℃ and be incubated 2-3 hour, be warming up to 1700-1800 ℃ and be incubated 5-10 hour 1.0-1.5 hour time at last 1.0-1.5 hour time.
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| CN100417738C (en) * | 2006-11-10 | 2008-09-10 | 金堆城钼业股份有限公司 | High temperature resistant, anti electric arc corrosion composite rare earth molybdenum alloy and its preparation method |
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| CN110804709B (en) * | 2019-11-21 | 2020-08-18 | 西安交通大学 | Method for preparing molybdenum alloy with different components in high flux and characterizing molybdenum alloy with different components in high flux |
| CN112207287B (en) * | 2020-12-07 | 2021-03-16 | 西安稀有金属材料研究院有限公司 | Preparation method and application of yttrium oxide nanoparticle-doped nano molybdenum powder |
| CN113414386B (en) * | 2021-05-28 | 2022-12-06 | 中南大学 | Method for preparing block alloy by gradient reduction of oxide at low temperature |
| CN114850473B (en) * | 2022-04-13 | 2024-02-02 | 金堆城钼业股份有限公司 | Sintering method and application of molybdenum and molybdenum alloy material |
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