CN104841943A - Method for making refractory metal microcrystalline nanometer material through electric arc, capillary and seed crystal method - Google Patents
Method for making refractory metal microcrystalline nanometer material through electric arc, capillary and seed crystal method Download PDFInfo
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- CN104841943A CN104841943A CN201510245958.1A CN201510245958A CN104841943A CN 104841943 A CN104841943 A CN 104841943A CN 201510245958 A CN201510245958 A CN 201510245958A CN 104841943 A CN104841943 A CN 104841943A
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Abstract
The invention discloses a method for making a refractory metal microcrystalline nanometer material through an electric arc, capillary and seed crystal method. Refractory metal is rapidly sublimed at the high temperature generated by electric arcs, gaps are formed in an adopted crucible, the crucible is made of metal crystals with an induction function, the refractory metal can crystallize in the gaps of the crucible and permeates to the outer surface of the crucible, and crystallization is accomplished. The working principle and the making structure are quite simple, and compared with a conventional technology, the method has the advantages that the production pollution is reduced, environmental protection and simpleness are achieved, and the method has the good popularization prospect.
Description
Technical field
The present invention relates to micro-nano material preparing technical field, especially relate to a kind of electric arc, capillary, seed-grain method prepare Jin Shu Molybdenum hard to tolerate, the preparation method of the microcrystal nanometer material of tungsten.
Background technology
Nano material refers to that grain size number is nano level polycrystalline material, and structurally belonging to the transitional region of cluster and macro object boundary, is by the little atom of number or molecular aggregation.Particle has shell structurre, and its top layer atom accounts for very large ratio, and is unordered class gas shape, exists in order at inside particles---disordered structure, from crystals phase basic unit to grow up to ordered structure completely different.The structural particularity of nano particle makes them have the many special natures different from conventional solid material, thus becomes the heat subject of new material scientific domain, will produce significant impact to national development strategy.
The preparation method of existing polycrystalline material generally adopts the preparations such as sol-gel process, the precipitation method, hydro-thermal method, but this preparation method all belongs to wet-chemical category, need a large amount of acid, alkali, water, in preparation process, waste water can serious environment pollution, and all exist in preparation process high to equipment requirement, condition is harsh, complex process, preparation time long, the not high weak point of productivity ratio.And at present basic research work is only limitted to for the preparation of microcrystal nanometer material, prepare in laboratory small lot.Also be not enough to be applied to industry manufacture.
Summary of the invention
The object of this invention is to provide a kind of electric arc hot melt, capillary condensation, the self assembly of capillary particulate, seed crystal induced crystallization technical method produce hard to tolerate gold belong to Molybdenum, tungsten microcrystal nanometer material.Completely different from Xian You Molybdenum, tungsten microcrystal nanometer material preparation method.
To achieve these goals, the present invention adopts following technical scheme:
Electric arc, capillary, seed-grain method produce a method for refractory metal microcrystal nanometer material, comprise the following steps:
1), take refractory metal as raw material, be positioned in crucible, unsettled in described crucible a carbon electrode bar is set, carbon resistance rod rod connects the positive pole of high voltage source, described crucible is spliced by the crystalline material of some pieces of sheets and forms, have some gaps from crucible outer surface to inner surface, and crucible is external surface grounded;
2), to carbon electrode energising, produce high-voltage arc between carbon electrode and crucible, high-voltage arc produces high temperature and makes Jin Shu Molybdenum liquefy rapidly or distil;
3), the refractory metal of liquefaction by the popular crucible surface in the gap on crucible, the refractory metal part gas simultaneously after distillation enters gap place in crucible crucible body and produces the appearance that coacervation arrives crucible under van der Waals interaction;
4), stop powering to carbon electrode, crucible cool, when crucible hull-skin temperature is at 600 ~ 900 DEG C, crucible exterior slots place grows crystal rapidly, to be crystallized stop growing after collect crystallite;
Described raw metal hard to tolerate includes but not limited to Jin Shu Molybdenum, Jin Shu Molybdenum tungsten.
In technique scheme, each block profile of the crystalline material of described some sheets is all not identical, and spliced gap is irregularly shaped.
In technique scheme, described crystalline material be the crystalline solid of raw metal hard to tolerate.
In technique scheme, described crucible has inducing function in the process of crystallization, when crucible is Shi Molybdenum crystalline material, has the function of induction MoO3 crystallization, when crucible is tungsten crystalline material, has the function of induction WO3 crystallization.
In technique scheme, the outer setting of crucible has air bell, and air bell comprises air bell outer wall and air bell inwall, and the outer surface of air bell inwall and crucible forms seal cavity, and the bottom of air bell is provided with retracting device.
In technique scheme, the upper end of described air bell and crucible is provided with blower fan, and blower fan is just dried to crucible.
In technique scheme, after the raw material distillation in crucible, a part of metal gas rising to air bell, is realized the recovery to metal by the wind of blower fan.
Yi Jin Shu Molybdenum of the present invention is raw material, adopts the method for electric arc melting, capillary condensation, the self assembly of capillary particulate, seed crystal induced crystallization.Prepare the sheet two dimension crystallite that thickness is about 30nm nanometer.Namely crystallite refinement is obtained the MoO3 powder that particle diameter is less than 100nm.
Add the refractory materials such as tungsten, silicon, aluminium oxide in a device Yu also crystallite can be grown after Molybdenum congruent melting.Make XRF analysis, containing the composition participating in congruent melting material to some extent in crystallite composition.Namely, after can realizing the material participation congruent melting of the multiple different melting points such as tungsten Molybdenum nickel, the chemical combination crystallite of multielement is grown up to.
Principle of the present invention is: Molybdenum, and silvery white has the refractory metal of metallic luster, and the Molybdenum of powder powder is black, fusing point 2620 DEG C, boiling point 5560 DEG C. under the temperature of room, Molybdenum is very stable in atmosphere.When temperature rises to 600 DEG C rapidly and oxygen react and generate MoO3.Jin Shu Molybdenum can be obtained with hydrogen reduction MoO3 500 ~ 1150 DEG C time.
MoO3 molecular weight 143.94, white clear rhomboidal crystal, fusing point 795 DEG C, boiling point 1155 DEG C, easily distil, water insoluble, dissolves in ammoniacal liquor and Cheng Molybdenum hydrochlorate with highly basic Sheng.
Arcing device hot melting temperature, up to more than 3000 ~ 3700 DEG C, can make solid-state Jin Shu Molybdenum or molybdenum powder fast melt become liquid to be exuded to the crystallization of crucible appearance through crucible gap or micropore.Also have partial sublimation to become gaseous state MoO3 simultaneously.And gaseous state MoO3 is by van der Waals interaction, molecule also can produce by the gap on crucible or micropore the appearance that capillary condensation phenomenon (namely steam condenses into the phenomenon of liquid in capillary) arrives crucible, and crystallization at a suitable temperature.Crucible gap has capillary particulate self-assembling function simultaneously: namely gap capillarity can drive particles agglomerate to be arranged in two-dimensional material.So the crystallite slabbing prepared by gap capillarity, thickness is less than 30nm.Belong to two-dimensional material.The crystal prepared by micropore capillarity becomes threadiness.
Crystallization: the method obtaining hypersaturated state by solution can be divided into evaporative crystallization and crystallisation by cooling.Crystallization generally needs crystal seed, cries again young brilliant.Caing be compared to cultivation mushroom needs bacterial classification the same.Molybdenum crucible Shi Molybdenum crystalline material, has the function of induction MoO3 crystallization.Tungsten crucible is tungsten crystalline material, has the function of induction WO3 crystallization.Visual rapid crystallization phenomenon will be there is above when crucible external skin temperatures is at 600 ~ 900 DEG C.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows: compared with conventional method, the arc heat fusant material that the present invention utilizes energy efficient to concentrate, high temperature resistant and there is capillary condensation, the crucible of capillary particulate self-assembled structures and crucible appearance has again the seed crystal function that induction is produced thing crystallization.This method technique, do not need with water and chemical engineering industry raw material in whole preparation process, whole process also can not bring pollution, trade effluent can not be produced, whole preparation technology only needs a few minutes just can complete once, and device structure is simple, cheap, convenient later maintenance, is very applicable to industrialization.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is structural representation of the present invention;
Wherein: 1 is blower fan, 2 is air bell inwalls, and 3 is air bell outer walls, and 4 is crucibles, and 5 is retracting devices, and 6 is carbon electrodes, and 7 is electric arc machine electrode lines.
Detailed description of the invention
As shown in Fig. 1, device of the present invention mainly comprises air bell, crucible, retracting device and a carbon electrode, air bell comprises air bell inwall and air-flow cover outer wall, be hollow between inwall and outer wall, the bottom of air bell connects a retracting device, blower fan is arranged on the top of air bell, and the wind object gas flow cover of blower fan blows, and gas is flowed in air bell.Crucible is arranged on air bell outside, forms enclosure space between the outer wall of crucible and the inwall of air bell, and time the wind of blower fan is to air bell and crucible, gas can not blow to the outer surface of crucible.Heater is arranged in crucible.Crucible is made up of some pieces of crucible discs or micropore, is provided with gap between crucible disc and crucible disc.Be positioned in crucible by fritter raw material, utilize the high temperature that electric arc produces, make raw material distil rapidly or melt, the metal gas of distillation is blowed to crucible by blower fan and carry out capillary condensation together with thawing liquid.Another part enters retracting device by the space of air bell inside and outside wall and reclaims.Controlled by crucible external skin temperatures at 600 ~ 900 DEG C, crucible appearance will grow crystallite rapidly.Because crystallite only has length and width, the two-dimensional material that thickness can be ignored (being less than 30nm) disregards, is easy to fragmentation and is refined into the dusty material being less than 100nm.
Embodiment one:
Carbon electrode connects electric arc machine positive pole, and crucible connects negative pole, and mobile carbon electrode makes to form an arc zone between crucible and electrode bar, is melted into liquid or gas by needing the material of preparation.
After stockpile is put well, be energized to electric arc machine, can produce powerful electric arc between electrode bar and crucible, the temperatures as high of electric arc 3000 ~ 3700 DEG C, high temperature makes solid-state metal raw material Molybdenum or molybdenum powder fast melt become liquid to be exuded to the crystallization of crucible appearance through crucible gap or micropore.Also have partial sublimation to become gaseous state MoO3 simultaneously.And gaseous state MoO3 is by van der Waals interaction, molecule also can produce by the gap on crucible or micropore the appearance that capillary condensation phenomenon (namely steam condenses into the phenomenon of liquid in capillary) arrives crucible; Electric arc is closed down when crucible external skin temperatures is raised to about 2000 DEG C.Make crucible cool 900 ~ 600 DEG C time, crystal will be grown rapidly at crucible exterior slots or micropore place; Crucible gap has capillary particulate self-assembling function simultaneously: namely gap capillarity can drive particles agglomerate to be arranged in two-dimensional material.So the crystallite slabbing utilizing gap capillarity to prepare, and thickness is less than 30nm.Belong to two-dimensional material.The crystal prepared by micropore capillarity then becomes threadiness.
The present invention is not limited to aforesaid detailed description of the invention.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (7)
1. electric arc, capillary, seed-grain method produce a method for refractory metal microcrystal nanometer material, it is characterized in that comprising the following steps:
1), take refractory metal as raw material, be positioned in crucible, unsettled in described crucible a carbon electrode bar is set, carbon resistance rod rod connects the positive pole of high voltage source, described crucible is spliced by the crystalline material of some pieces of sheets and forms, have some gaps from crucible outer surface to inner surface, and crucible is external surface grounded;
2), to carbon electrode energising, produce high-voltage arc between carbon electrode and crucible, high-voltage arc produces high temperature and makes Jin Shu Molybdenum liquefy rapidly or distil;
3), the refractory metal of liquefaction by the popular crucible surface in the gap on crucible, the refractory metal part gas simultaneously after distillation enters gap place in crucible crucible body and produces the appearance that coacervation arrives crucible under van der Waals interaction;
4), stop powering to carbon electrode, crucible cool, when crucible hull-skin temperature is at 600 ~ 900 DEG C, crucible exterior slots place grows crystal rapidly, to be crystallized stop growing after collect crystallite;
Described raw metal hard to tolerate includes but not limited to Jin Shu Molybdenum, Jin Shu Molybdenum tungsten.
2. a kind of electric arc according to claim 1, capillary, seed-grain method produce the method for refractory metal microcrystal nanometer material, and it is characterized in that each block profile of crystalline material of described some sheets is all not identical, spliced gap is irregularly shaped.
3. a kind of electric arc according to claim 2, capillary, seed-grain method produce the method for refractory metal microcrystal nanometer material, and what it is characterized in that described crystalline material is the crystalline solid of raw metal hard to tolerate.
4. a kind of electric arc according to claim 3, capillary, seed-grain method produce the method for refractory metal microcrystal nanometer material, it is characterized in that described crucible has inducing function in the process of crystallization, when crucible Wei Shi Molybdenum crystalline material, have induction MoO
3the function of crystallization, when crucible is tungsten crystalline material, has induction WO
3the function of crystallization.
5. a kind of electric arc according to claim 1, capillary, seed-grain method produce the method for refractory metal microcrystal nanometer material, it is characterized in that the outer setting of crucible has air bell, air bell comprises air bell outer wall and air bell inwall, the outer surface of air bell inwall and crucible forms seal cavity, and the bottom of air bell is provided with retracting device.
6. a kind of electric arc according to claim 5, capillary, seed-grain method produce the method for refractory metal microcrystal nanometer material, and it is characterized in that the upper end of described air bell and crucible is provided with blower fan, blower fan is just dried to crucible.
7. a kind of electric arc, capillary, seed-grain method produce the method for refractory metal microcrystal nanometer material according to claim 1 or 5, after it is characterized in that the raw material distillation in crucible, the rising of part metal gas to air bell, is realized the recovery to metal by the wind of blower fan.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5368657A (en) * | 1993-04-13 | 1994-11-29 | Iowa State University Research Foundation, Inc. | Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions |
| CN101269834A (en) * | 2008-05-19 | 2008-09-24 | 昆明理工大学 | Method for producing nano-ITO powder with plasma electrical arc one-step method |
| CN102615289A (en) * | 2011-01-28 | 2012-08-01 | 杭州华纳塔器科技有限公司 | Evaporation-condensation method for preparing superfine metal powder |
| CN204039551U (en) * | 2014-09-11 | 2014-12-24 | 北京首量科技有限公司 | A kind of plumbago crucible |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5368657A (en) * | 1993-04-13 | 1994-11-29 | Iowa State University Research Foundation, Inc. | Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions |
| CN101269834A (en) * | 2008-05-19 | 2008-09-24 | 昆明理工大学 | Method for producing nano-ITO powder with plasma electrical arc one-step method |
| CN102615289A (en) * | 2011-01-28 | 2012-08-01 | 杭州华纳塔器科技有限公司 | Evaporation-condensation method for preparing superfine metal powder |
| CN204039551U (en) * | 2014-09-11 | 2014-12-24 | 北京首量科技有限公司 | A kind of plumbago crucible |
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Effective date of registration: 20230629 Address after: No. 175-1, Lanjin Road, Jinnan Street, Lin'an District, Hangzhou, Zhejiang 310000 Patentee after: Hangzhou Lin'an Fukun Decoration Engineering Co.,Ltd. Address before: 621000 Unit 1, Building 1, Zijincheng Community, No. 3, Xiantong Street, Youxian District, Mianyang City, Sichuan Province Patentee before: Jiang Dexin |