CN101327520A - Method for preparing molybdenum alloy powder containing nano rare-earth oxides - Google Patents
Method for preparing molybdenum alloy powder containing nano rare-earth oxides Download PDFInfo
- Publication number
- CN101327520A CN101327520A CNA2008101504626A CN200810150462A CN101327520A CN 101327520 A CN101327520 A CN 101327520A CN A2008101504626 A CNA2008101504626 A CN A2008101504626A CN 200810150462 A CN200810150462 A CN 200810150462A CN 101327520 A CN101327520 A CN 101327520A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- molybdenum alloy
- molybdenum
- earth oxides
- alloy powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a preparation method of molybdenum alloy powder containing nanometer rare earth oxides. The method uses rare earth ammonium dimolybdate crystals as the material, and adopts the methods of roasting and hydrogen reduction to produce powder mixture containing nanoscale rare earth oxides and molybdenum metal, wherein, the scale range of the rare earth oxides in the molybdenum alloy powder is from 30 to 80 nanometers, and the rare earth oxides are all evenly dispersed on molybdenum powder matrix; the molybdenum granules are very fine, wherein, the Fisher particle size of the crystals is 1.0 to 4.0 um. The invention to prepare molybdenum alloy powder containing nanometer rare earth oxides has the characteristics of simple structure, low cost, small particle size and even distribution of the rare earth oxides, etc, and ensures the high strength and high flexibility of the molybdenum alloy material prepared in the method.
Description
Technical field
The invention belongs to field of powder metallurgy, particularly contain the molybdenum alloy powder preparation method of oxide nano rare earth.
Background technology
At present, the research and development emphasis of molybdenum alloy Strengthening and Toughening and developing direction are how second mutually dispersed particle-strengthened to mix, and are hot fields with the research of adding rare earth oxide especially.Wherein oxide-doped molybdenum alloy is present most widely used molybdenum alloy.This type of dipping molybdenum alloy preparation prepares simple and convenient than ASK dipping molybdenum alloy, effect is more obvious.Existing result of study shows that the purer molybdenum filament of the molybdenum filament of rare earth doped oxide has higher recrystallization temperature and room temperature strength, and has better high temperature sink-resistance performance; In certain interpolation scope, along with the increase of rare earth oxide content, the prepared molybdenum alloy strength of materials increases, and recrystallization temperature also is improved; Add rare earth oxide molybdenum alloy also show fabulous creep-resistant property and ductility.
Although the succeeding in developing of rare-earth oxide doping molybdenum alloys material solved the problem of molybdenum alloy material deep processing difficulty and undercapacity to a certain extent, but it is wayward because of the yardstick that has the second phase particle that present liquid-solid doping method is produced in the rare-earth oxide doping molybdenum alloys materials process, basic is micron dimension, be difficult to obtain the problems such as the second phase particle of equally distributed nanometer scale, therefore limited to the Strengthening and Toughening effect of molybdenum alloy, and, use the volume fraction that increases by second phase in this preparation method's process then will inevitably cause the reunion of the second phase particle, cause the molybdenum alloy toughness of material to reduce, the deep processing performance obviously descends, limit high-performance molybdenum alloy material to a great extent and on the preparation key technology, obtained to break through, also restricted the exploitation and the extensive use of the high added value molybdenum alloy deep processed product of market active demand.
Therefore be the obdurability that further improves molybdenum alloy, press for exploitation and a kind ofly can in the molybdenum alloy matrix, obtain tiny (especially nanoscale) second phase particle, to guarantee also that simultaneously molybdenum alloy has the technology of tiny crystal grain with the toughness that do not reduce material, for solving this difficult problem, the key technology that at first needs to solve is exactly the technology of preparing that will obtain to contain the tiny molybdenum alloy powder of oxide nano rare earth.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who contains the molybdenum alloy powder of oxide nano rare earth, because traditional rare earth oxide-doped molybdenum alloy powder middle rare earth oxide and molybdenum crystallite dimension are big, adopt prepared molybdenum alloy intensity and the low technical barrier of toughness of this powder to solve and cause.The rare earth oxide that contains in the molybdenum alloy powder of the present invention's preparation is a nanoscale, is evenly distributed, and the molybdenum powder crystallite dimension is also tiny simultaneously.
Technical scheme of the present invention is achieved in that
The molybdenum alloy powder preparation method who contains oxide nano rare earth provided by the present invention, step is as follows:
With the rare earth ammonium dimolybdate is that (preparation method of this raw material please refer to national inventing patent to raw material: ZL0410073414.3), take by weighing corresponding rare earth ammonium dimolybdate powder according to the final rare-earth oxidation species and the mass fraction that contain in the molybdenum alloy of will preparing;
With rare earth ammonium dimolybdate powder calcination, calcination carries out in the hydrogen shield atmosphere furnace, and temperature is: 360-390 ℃, time 1-3h, the pressure of logical hydrogen be 0.3-0.5Pa, flow is 0.5-1.0m
3/ h;
To the material behind the calcination carry out ball milling, the processing of sieving, require powder size less than 60 μ m;
Powder after calcination sieved carries out two sections reduction to be handled, and the temperature of a section of reduction is 430-530 ℃, time 1-1.5h,, the temperature of two sections reduction is 900-1100 ℃, the time is 1-1.5h, in the reduction process the pressure of logical hydrogen be 0.3-0.5Pa, flow is 0.5-1.0m
3/ h can obtain containing the molybdenum alloy powder of oxide nano rare earth.
Contain lanthana La in the molybdenum alloy powder that contains oxide nano rare earth that the present invention is prepared
2O
3, cerium oxide CeO
2, yittrium oxide Y
2O
3Wherein a kind of or its make up or three kinds of combinations in twos, and the average dimension of the rare earth oxide particles that disperse distributes in the molybdenum alloy is 30-80nm, and molybdenum crystal grain Fisher particle size is 1.0-4.0 μ m, and wherein the mass percent scope of rare earth oxide is 0.2-4.0%.
It is the molybdenum alloy powder that raw material preparing contains oxide nano rare earth that the key problem in technology that the present invention solves is to select the rare earth ammonium dimolybdate, the i.e. realization of the molecule rank doping techniques by rare earth oxide and molybdenum, make that prepared molybdenum alloy powder middle rare earth oxide particle is tiny and be evenly distributed, thus for further obtain having high strength, the molybdenum alloy material and the product of high tenacity provide assurance.
Effect of the present invention is embodied in:
(1) the molybdenum alloy powder preparation method who contains oxide nano rare earth of the present invention's proposition is raw material with the rare earth ammonium dimolybdate, and technology is simple and direct, and equipment requires low, has avoided bringing into of impurity element, and production cost is low, and output is big, can realize industrialization production.
(2) adopt the prepared molybdenum alloy powder middle rare earth oxide size that contains oxide nano rare earth of the technology of the present invention evenly tiny and and molybdenum mix, the distribution disperse, average particle size particle size is 30-80nm.
(3) adopt in the prepared molybdenum alloy powder that contains oxide nano rare earth of the technology of the present invention the molybdenum crystallite dimension tiny, Fisher particle size is 1.0-4.0 μ m.
(4) the molybdenum alloy product of high-strength tenacity provides possibility to the molybdenum alloy powder that contains oxide nano rare earth that the present invention is prepared in order to obtain more.
The specific embodiment
Embodiment one:
Take by weighing rare earth ammonium dimolybdate powder 1000 gram that contains the 0.2wt% lanthana, under 360 ℃, carry out calcination, calcination time 1.5h, the calcination process is led to hydrogen shield, the pressure of logical hydrogen be 0.3Pa, flow is 0.5m
3/ h, to the material behind the calcination carry out ball milling, the processing of sieving, require powder size less than 50 μ m, reduce at 450 ℃ earlier afterwards, time 1h reduces at 950 ℃ then, recovery time 1.5h, in the reduction process the pressure of logical hydrogen be 0.3Pa, flow is 0.5m
3/ h.The average-size that can obtain containing the lanthana particle is 36nm, and molybdenum crystal grain Fisher particle size is the molybdenum alloy powder of 2.3 μ m.
Embodiment two:
Take by weighing rare earth ammonium dimolybdate powder 1000 gram that contains the 0.9wt% lanthana, under 370 ℃, carry out calcination, calcination time 1.5h, the calcination process is led to hydrogen shield, the pressure of logical hydrogen be 0.3Pa, flow is 0.6m
3/ h, to the material behind the calcination carry out ball milling, the processing of sieving, require powder size less than 45 μ m, reduce at 480 ℃ earlier afterwards, time 1.1h reduces at 1050 ℃ then, recovery time 1.4h, in the reduction process the pressure of logical hydrogen be 0.4Pa, flow is 0.6m
3/ h.The average-size that can obtain containing the lanthana particle is 54nm, and molybdenum crystal grain Fisher particle size is the molybdenum alloy powder of 1.3 μ m.
Embodiment three:
Take by weighing rare earth ammonium dimolybdate powder 1000 gram that contains 1.2wt% lanthana and 1.2wt% cerium oxide, under 390 ℃, carry out calcination, calcination time 1.5h, the calcination process is led to hydrogen shield, the pressure of logical hydrogen be 0.3Pa, flow is 0.8m
3/ h, to the material behind the calcination carry out ball milling, the processing of sieving, require powder size less than 60 μ m, reduce at 500 ℃ earlier afterwards, time 1.2h reduces at 1000 ℃ then, recovery time 1.3h, in the reduction process the pressure of logical hydrogen be 0.4Pa, flow is 0.8m
3/ h.The average-size that can obtain containing the lanthana particle is 63nm, and molybdenum crystal grain Fisher particle size is the molybdenum alloy powder of 3.0 μ m.
Embodiment four:
Take by weighing rare earth ammonium dimolybdate powder 1000 gram that contains 1.2wt% lanthana, 1.2wt% cerium oxide and 1.2wt% yittrium oxide, under 380 ℃, carry out calcination, calcination time 1.5h, the calcination process is led to hydrogen shield, the pressure of logical hydrogen be 0.3Pa, flow is 1.0m
3/ h, to the material behind the calcination carry out ball milling, the processing of sieving, require powder size less than 50 μ m, reduce at 530 ℃ earlier afterwards, time 1.5h reduces at 1100 ℃ then, recovery time 1.5h, in the reduction process the pressure of logical hydrogen be 0.5Pa, flow is 1.0m
3/ h.The average-size that can obtain containing the lanthana particle is 73nm, and molybdenum crystal grain Fisher particle size is the molybdenum alloy powder of 2.5 μ m.
Claims (1)
1, a kind of preparation method who contains the oxide nano rare earth molybdenum alloy powder is characterized in that step is as follows:
With rare earth ammonium dimolybdate crystal powder calcination, calcination carries out in the hydrogen shield atmosphere furnace, and temperature is: 360-390 ℃, time 1-3h, the pressure of logical hydrogen be 0.3-0.5Pa, flow is 0.5-1.0m
3/ h;
To the material behind the calcination carry out ball milling, the processing of sieving, require the mixed-powder granularity less than 60 μ m;
Powder after calcination sieved carries out two sections reduction to be handled, and the temperature of a section of reduction is 430-530 ℃, time 1-1.5h, the pressure of logical hydrogen be 0.3-0.5Pa, flow is 0.5-1.0m
3/ h; The temperature of two sections reduction is 900-1100 ℃, the pressure of logical hydrogen be 0.3-0.5Pa, flow is 0.5-1.0m
3/ h, time 1-1.5h promptly obtains containing the molybdenum alloy powder of oxide nano rare earth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101504626A CN101327520B (en) | 2008-07-25 | 2008-07-25 | Method for preparing molybdenum alloy powder containing nano rare-earth oxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101504626A CN101327520B (en) | 2008-07-25 | 2008-07-25 | Method for preparing molybdenum alloy powder containing nano rare-earth oxides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101327520A true CN101327520A (en) | 2008-12-24 |
| CN101327520B CN101327520B (en) | 2011-06-01 |
Family
ID=40203656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101504626A Expired - Fee Related CN101327520B (en) | 2008-07-25 | 2008-07-25 | Method for preparing molybdenum alloy powder containing nano rare-earth oxides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101327520B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251162A (en) * | 2011-07-07 | 2011-11-23 | 西安交通大学 | Preparation method of high performance nanometer lanthanide oxide doped molybdenum-silicon-boron alloy |
| CN102373356A (en) * | 2011-11-01 | 2012-03-14 | 西安交通大学 | Composite reinforced long-service-life high-temperature molybdenum alloy boat for molybdenum powder reduction and preparation method thereof |
| CN103639417A (en) * | 2013-11-26 | 2014-03-19 | 金堆城钼业股份有限公司 | Preparation method for molybdenum powder with high surface activity |
| CN111730062A (en) * | 2020-08-24 | 2020-10-02 | 自贡硬质合金有限责任公司 | Preparation method of fine-particle molybdenum powder |
| CN114160789A (en) * | 2021-12-09 | 2022-03-11 | 西安交通大学 | Method for enhancing performance of 3D printed metal product through surface coating of printing raw material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430610B (en) * | 2011-10-26 | 2014-01-29 | 西安交通大学 | Preparation method for molybdenum alloy wires doped with nanometer rare earth oxides |
-
2008
- 2008-07-25 CN CN2008101504626A patent/CN101327520B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251162A (en) * | 2011-07-07 | 2011-11-23 | 西安交通大学 | Preparation method of high performance nanometer lanthanide oxide doped molybdenum-silicon-boron alloy |
| CN102251162B (en) * | 2011-07-07 | 2013-01-02 | 西安交通大学 | Preparation method of high performance nanometer lanthanide oxide doped molybdenum-silicon-boron alloy |
| CN102373356A (en) * | 2011-11-01 | 2012-03-14 | 西安交通大学 | Composite reinforced long-service-life high-temperature molybdenum alloy boat for molybdenum powder reduction and preparation method thereof |
| CN103639417A (en) * | 2013-11-26 | 2014-03-19 | 金堆城钼业股份有限公司 | Preparation method for molybdenum powder with high surface activity |
| CN103639417B (en) * | 2013-11-26 | 2015-12-09 | 金堆城钼业股份有限公司 | There is the preparation method of high surface molybdenum powder |
| CN111730062A (en) * | 2020-08-24 | 2020-10-02 | 自贡硬质合金有限责任公司 | Preparation method of fine-particle molybdenum powder |
| CN114160789A (en) * | 2021-12-09 | 2022-03-11 | 西安交通大学 | Method for enhancing performance of 3D printed metal product through surface coating of printing raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101327520B (en) | 2011-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101327520B (en) | Method for preparing molybdenum alloy powder containing nano rare-earth oxides | |
| CN105088048A (en) | High-entropy alloy for sewage degradation and preparing method thereof | |
| CN100589902C (en) | Ultra-fine or nanometer molybdenum cuprum composite powder and method of producing the alloy thereof | |
| CN100567530C (en) | A kind of preparation method of high performance sinter Mo-Ti-Zr molybdenum alloy | |
| CN101397617B (en) | Method for preparing alloy nano rare-earth oxide doping molybdenum-silicium-boron alloy | |
| CN101628338A (en) | Superfine iron-copper alloy powder and preparation method thereof | |
| WO2015032158A1 (en) | Magnesium-based hydrogen storage material and preparation method therefor | |
| CN104651703A (en) | Method for preparing oxide dispersion strengthened iron-based alloy | |
| CN103862038A (en) | Extra-coarse hard alloy parcel powder and preparation method thereof | |
| CN102909030B (en) | Ferrous oxide-based ammonia synthesis catalyst | |
| CN108788173B (en) | Hydrothermal preparation method of superfine yttrium oxide doped tungsten composite powder | |
| CN101328550B (en) | Preparation of nano rare-earth oxide doping molybdenum alloys | |
| CN102260071A (en) | Method for preparing high-dispersion quasi-spherical M type barium ferrite | |
| CN109778046B (en) | Preparation method of low-cost high-performance WC-Co hard alloy with mixed crystal structure | |
| CN101633990B (en) | Al-Mo-W-Ti quaternary alloy for titanium alloy production | |
| CN104148022B (en) | Amine-modified persimmon tannin adsorbent, and preparation method and application thereof | |
| CN104985194A (en) | Preparation method for oxide dispersion strengthening ferrite-cobalt nano-composite powder | |
| CN101837466B (en) | Method for preparing nano aluminum oxide dispersion iron powder | |
| CN101956118A (en) | Preparation method of magnesium-based composite material containing various in-situ enhancing particles of rare earth | |
| CN102400013A (en) | Low-cost beta titanium alloy | |
| CN103789586A (en) | Novel moderate-strength high-conductivity aluminum alloy electrician round bar | |
| CN102703740A (en) | Preparation method for Cu-Cr-Zr alloy | |
| CN112355323B (en) | Ultrafine oxide particle silver ferric oxide electric contact material and preparation method thereof | |
| CN105692677B (en) | Method for preparing neodymium oxide with large specific surface area through compound precipitation method | |
| CN102367531A (en) | Zinc alloy special for zipper industry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160414 Address after: 276017 west end of the 1 Industrial Park, Linyi hi tech Zone, Shandong Patentee after: Linyi Minghua Pipe Industry Co., Ltd. Address before: 710049 Xianning Road, Shaanxi, China, No. 28, No. Patentee before: Xi'an Jiaotong University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110601 Termination date: 20180725 |