CN101235538A - Method for preparing tetrapod-like zinc oxide whisker with assistance of electric arc atomization - Google Patents
Method for preparing tetrapod-like zinc oxide whisker with assistance of electric arc atomization Download PDFInfo
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- CN101235538A CN101235538A CNA200710150201XA CN200710150201A CN101235538A CN 101235538 A CN101235538 A CN 101235538A CN A200710150201X A CNA200710150201X A CN A200710150201XA CN 200710150201 A CN200710150201 A CN 200710150201A CN 101235538 A CN101235538 A CN 101235538A
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Abstract
The invention relates to a method for preparing tetrapod-like zinc oxide whiskers by assistance of electric arc atomization. Based on the mixed growth mechanism of tetrapod-like zinc oxide whisker with whisker nucleation and whisker growth divided into two stages, metal zinc ingot, industrial crude zinc, zinc alloy, zinc-containing metal waste, zinc powder and zinc particles are heated or zinc vapor generated in the process of smelting metal zinc and producing metal zinc powder by an indirect method is taken as a raw material, in order to improve the reaction speed and improve the technical conditions of the preparation process, the metal zinc is atomized by electric arc to assist nucleation, and the generated liquid metal zinc mist is mixed with the zinc vapor and oxidized by air or oxygen to obtain the tetrapod-like zinc oxide whisker. The preparation process is simple, high in efficiency and high in whisker product quality. The product can be used as an additive for preparing composite materials and functional materials, and meets the use requirements of different materials.
Description
[technical field]: the invention belongs to inorganic materials technology and Non-ferrous Metallurgy field.Relate to electric arc atomization aid preparation four acicular type zinc oxide crystal whisker technology, relate in particular to the zinc fume or the smelting zinc fume that utilize the heating material containing zinc to produce and be raw material, adopt the auxiliary forming core of electric arc atomization metallic zinc, directly contact also oxidizedly with air or oxygen, prepare the method for four acicular type zinc oxide crystal whisker.
[background technology]: four acicular type zinc oxide crystal whisker (Tetrapod-like Zinc Oxide Whisker, be called for short T-ZnOw) be the single crystal of zinc oxide, can be used for macromolecular material antistatic material, wear-resisting anti-slip material, semi-conductor, piezoelectricity, microwave absorbing material, vibration and noise reducing material, ceramic toughening shatter-resistant material, strongthener, antimicrobial composite material, photocatalyst material etc.The technology of preparing of T-ZnOw ZnOw is mainly divided zinc powder preoxidation and zinc powder direct oxidation method at present.
Method one is in advance with the zinc powder surface oxidation in the zinc powder preoxidation, be about to high-purity zinc powder and place deionized water for stirring, ageing, drying, make its surface generate certain thickness oxide film, more this zinc powder is prepared four needle-like whiskers in about 1000 ℃ heating of high temperature gasification in about 1 hour oxidation.Method two is that the zinc powder that will have oxide film under protection of inert gas is heated to more than the boiling point; be carrier gas then with the rare gas element; zinc fume is introduced oxygen-containing gas or oxygen-containing gas is blown in the zinc fume, zinc is contacted in gas phase with oxygen, generate four acicular type zinc oxide crystal whisker.Method three is with zinc powder and NH
4 +, CO
3 2-(or HCO
3 -) and H
2O mixes by a certain percentage, generates ZnCO under prescribed condition
3, be heated to specified temp then, ZnCO
3Then slowly be decomposed to form four acicular type zinc oxide crystal whisker.Method four is to use the zinc powder through surface oxidation to mix with white carbon black (or clay), and bubbling air carries out oxidation when being heated to 900～1000 ℃, has prepared T-ZnOw.Method five is the zinc powder through surface oxidation to be mixed by suitable proportion with activated carbon be placed in the electric furnace N
2And O
2Feed by a certain percentage in the reaction chamber, controlled temperature obtains four acicular type zinc oxide crystal whisker at 1050～1150 ℃.
The zinc powder direct oxidation method is promptly directly produced T-ZnOw with the zinc powder oxidation.Method one is the metal zinc ingot fusion to be sprayed into make zinc powder in the water, is 5: 1 batchings by zinc powder and coke ratio, is heated to 950～1050 ℃ in the container of packing into after the mixing in atmosphere, and insulation 10～20min makes four acicular type zinc oxide crystal whisker.Method two is a reaction tubes of zinc powder being put into an end opening, and 500～850 ℃ of temperature of reaction are incubated 0.5～2h, make the whisker of two kinds of forms.
Preoxidation prepares purity and the granularity requirements strictness of T-ZnOw to zinc powder, and zinc is by partial oxidation when the preparation raw material, and the recovery rate of whisker is lower, and the pre-oxidation treatment technology of zinc powder is very numerous and diverse, and cost is higher; There is the incomplete problem of part zinc powder oxidation in the direct oxidation rule, and productivity is lower.Adopt the carrier gas of rare gas element, can realize the serialization of production process, but the product that generates usually is the mixture of the zinc oxide of different-shape, is more difficult to get the T-ZnOw of single shape as zinc fume.
Zinc powder preoxidation and zinc powder (grain) direct oxidation method; with zinc powder; zinc granule is feedstock production T-ZnOw; also exist reaction back T-ZnOw and reaction residues to be difficult to isolating problem; behind zinc powder or zinc granule surface formation one deck whisker; the air (or oxygen) of outside is isolated with zinc powder or zinc granule; must pass T-ZnOw whisker upper layer by the zinc fume that continues in zinc powder or the zinc granule to overflow subsequently; concentration is also constantly changing; not to be in steady-state process when reacting with oxygen; further reaction product quality descends; or generate the zinc oxide of other pattern, and the continuity of production process and mass-producing problem also are difficult to resolve and determine.As behind the catalyzer, the T-ZnOw product mixes with catalyzer can't separate or generate other material, has had a strong impact on quality product to add (activated carbon, zeolite, white carbon black, clay).
Unvanquishable problem when directly adopting the method for zinc fume oxidation to prepare T-ZnOw then may to solve with zinc powder or zinc granule preferably to raw material, and can deduct numerous and diverse zinc powder or zinc granule prepares link, the minimizing technological process is improved the quality of products.The inventor has applied for preparing under preparing different shape zinc oxide by vacuum limit oxygen method and the condition of normal pressure method of four acicular type zinc oxide crystal whisker in the past.But the vacuum limit oxygen legal system is equipped with the difficult control of four acicular type zinc oxide crystal whisker process, often forms the mixture of multiple pattern zinc oxide, influences quality product; Zinc fume forming core difficulty in oxidising process particularly, reaction process is slower, and productive rate is low.
[summary of the invention]: the present invention seeks to solve the pre existing oxidation style, to prepare T-ZnOw lower to the recovery rate of the purity of zinc powder and granularity requirements strictness and whisker, and technology is numerous and diverse, and cost is higher; There is the problem that the oxidation of part zinc powder is incomplete, productivity is lower in the direct oxidation rule, and a kind of method of arc oxidation aid preparation four acicular type zinc oxide crystal whisker is provided.
The present invention is in order to accelerate the formation speed of four acicular type zinc oxide crystal whisker, control the different requirements of crystal whisker products quality preferably, improve technical condition of production technology, from whisker forming core and two main phase of whisker growth, summed up based on whisker forming core and whisker growth and divided the T-ZnOw mixed growth mechanism model in two stages, be that zinc fume is in forming the T-ZnOw process, at first form nucleus by gas-liquid-solid (VLS) growth mechanism, four whiskers finally form the T-ZnOw product by the growth of gas-solid (VS) mechanism on nucleus then.Based on this growth mechanism, utilize blasting, the quick-fried method of line, arc-over atomization to prepare the method for nano material, by adopting electric furnace evaporated metal zinc to produce zinc fume, and with arc discharge method atomization metal zinc, under arcing, make metallic zinc moment gasification, and carry a large amount of small liquid metal zinc secretly and sneak in the zinc fume, with reaction chamber that air communicates in oxidizing reaction takes place prepares T-ZnOw.
The concrete preparation method of the present invention is as follows:
The material of metallic zinc or containing metal zinc is put into the process furnace internal heating, Heating temperature reaches 650～1300 ℃, make the metallic zinc evaporation, the zinc fume that produces enters in the reaction chamber, it perhaps directly is raw material with the zinc fume, the tiny liquid zinc mist that produces with the arc-over atomizing in reaction chamber mixes mutually, the zinc mist is 0.1～8: 99.9～92 with the ratio of zinc fume containing metal zinc, under air or purity oxygen effect, at first the zinc mist is oxidized into the whisker core, zinc fume is oxidized subsequently, and grows up in the whisker core, forms four acicular type zinc oxide crystal whisker.
Above-mentioned preparation process can be carried out at normal pressure or under less than 1 atmospheric condition of negative pressure, must adopt pure oxygen as oxidizing gas under condition of negative pressure.
When under being reflected at condition of normal pressure, carrying out, can in air, can in air, feed 0.5～16% rare gas element, CO that content accounts for gas gross
2, CO or SO
2Gas is as assist gas, with the size and the pattern of control four acicular type zinc oxide crystal whisker.
Above-mentioned gas is to send in the reaction chamber in mode continuous or that pulse is interrupted, produces reaction with zinc fume and tiny liquid zinc mist mixture; Perhaps, the tiny liquid zinc mist that is produced by the electric arc atomization effect is sent in the reaction chamber with pulse or successive mode with oxygen or air.
Wherein, the material of described metallic zinc or containing metal zinc is metal zinc ingot, industrial crude zinc, zinc alloy, zinc-containing metal waste material, zinc powder or zinc granule.
Advantage of the present invention and positively effect:
The present invention utilizes chemical industry forming core reaction process principle, introduce superfine little liquid metal zinc, at first oxidation generates zinc oxide, becomes the core that whisker is grown up, under the condition of not introducing impurity, solve forming core difficulty and the unmanageable problem of pattern in the four acicular type zinc oxide crystal whisker preparation process.
The raw material that the present invention prepares T-ZnOw is metal zinc ingot, industrial crude zinc, zinc alloy, zinc-containing metal waste material, zinc powder, zinc granule etc., produce zinc fume by heating evaporation, also can be directly with in the crude zinc refining rectifying tower in the zinc metallurgical process or the zinc fume that produces in the zinc powder production process be zinc fume feedstock production T-ZnOw.Can realize simultaneously effectively separating of four acicular type zinc oxide crystal whisker and zinc residue on evaporation, improve quality product.Raw material sources are wide, simplified the technological process of production, reduced production cost significantly, and the production process serialization is for the broad practice of four needle-like oxidation whiskers provides condition.
The present invention adopts better simply equipment, requirement according to T-ZnOw whisker forming core and two main phase of whisker growth, produce tiny liquid zinc mist by the arc-over atomizing, material and smelting zinc fume with containing metal zinc are raw material, the zinc fume that obtains mixes mutually with vaporific liquid zinc, be oxidized to T-ZnOw at normal pressure with under, improved the productive rate of T-ZnOw significantly, and controlled homogeneity and the quality product of T-ZnOw well less than 1 atmospheric condition of negative pressure.Technology condition of the present invention is simple, and production process is easy to control.
[description of drawings]:
Fig. 1 is the pattern scanning electronic microscope SEM photo that adopts the prepared four acicular type zinc oxide crystal whisker of the present invention.
[embodiment]:
Embodiment 1:
With industrial crude zinc is raw material, and 2kg metal crude zinc is added in the zinc vapourizing furnace, seals the Heating temperature of control zinc vapourizing furnace, the zinc fume of generation different pressures.Zinc fume enters in the vertical oxidizing reaction electric furnace, when temperature reaches 650～1300 ℃, keeps the temperature in the oxidizing reaction electric furnace.
Oxygen infeeds pipe and is connected with the arc-over atomisation unit, import from the upper lateral part pipe of vertical oxidizing reaction electric furnace, the tiny liquid metal zinc mist that the arc-over atomizing produces is blown in the vertical oxidizing reaction electric furnace by pulse oxygen supply, mixes with the zinc fume that the zinc vapourizing furnace produces again.The arc-over atomisation unit adopts the conventional DC arc welding machine, only needs its two electrode is fixed, and is made up of the tungsten electrode and the metallic zinc silk feeding unit of two overcoat alumina insulations of fixed material, and tungsten electrode passes the upper lateral part tube wall, and the termination is fixed in the pipe.Metallic zinc silk feeding unit adopts common electric arc spraying wire feeding machine.Distance between the control tungsten electrode termination, when the metallic zinc silk is fed between the tungsten electrode termination by the tube wall aperture, because the effect of electric arc, metallic zinc will atomize rapidly, or directly the metallic zinc silk is atomized with electric arc spraying equipment, mode by pulse or oxygen supply is continuously sent in the vertical oxidizing reaction electric furnace with air or oxygen, in order to guarantee the needed oxygen amount of oxidizing reaction, from supplemental oxygen pipe of bottom configuration of vertical oxidizing reaction electric furnace tube.Oxygen that feeds and tiny liquid metal zinc mist and zinc fume reaction, control zinc mist is 0.1～8: 99.9～92 with the ratio of zinc fume containing metal zinc, generates the white zinc oxide product, is deposited on vertical oxidizing reaction electric furnace bottom.
With the pattern and the crystalline structure of scanning electronic microscope (SEM) and X-ray diffractometer (XRD) assay products, product is uniform four acicular type zinc oxide crystal whisker.Splash into liquid metal zinc between the tungsten electrode of arc-over atomisation unit, the tiny liquid metal zinc mist of generation is blown in the vertical oxidizing reaction electric furnace by pulse oxygen supply, and is identical with the effect of zinc silk atomizing.
Adopting other material containing zinc, is raw material as industrial zinc ingot metal, zinc alloy, zinc-containing metal waste material, zinc powder, zinc granule etc., with above-mentioned method and apparatus, can obtain four acicular type zinc oxide crystal whisker equally, but the length-to-diameter ratio difference of whisker.When being raw material, can economize dezincify evaporation heating installation, only zinc fume need be fed in the vertical oxidizing reaction electric furnace, and keep certain temperature, adopt aforesaid method, can obtain four acicular type zinc oxide crystal whisker to smelt zinc fume.
Embodiment 2
Less than producing four acicular type zinc oxide crystal whisker under the 1 atmospheric negative pressure air tight condition.Zinc fume system, electric arc atomization system are carried out resistance to air loss handle, first vacuum pump is taken out part air wherein, charges into nitrogen again, and the gaseous tension of system is in less than carrying out under the 1 atmospheric condition of negative pressure.Directly the zinc fume that produces with the zinc distillation tower is a raw material, it is 8.3 kilograms/hour that zinc fume includes the metallic zinc output capacity, with temperature is after 1030～1050 ℃ zinc fume is introduced in the vertical oxidizing reaction electric furnace, open the arc-over atomisation unit, the tiny liquid metal zinc mist that utilizes air or pure oxygen to produce is sent in the vertical oxidizing reaction electric furnace by the mode of pulse or oxygen supply continuously, control zinc mist is 0.1～8: 99.9～92 with the ratio of zinc fume containing metal zinc, mix mutually with zinc fume, and and vertical oxidizing reaction electric furnace in the pure oxygen sent into of bottom react, generate white cotton-shaped four acicular type zinc oxide crystal whisker product.The zinc mist is 3: 97 with the ratio of zinc fume containing metal zinc.When the ratio of zinc mist and zinc fume containing metal zinc is 3: 97,11.05 kilograms/hour of the output capacity average out to of four acicular type zinc oxide crystal whisker.
With metal zinc ingot, industrial crude zinc, zinc alloy, zinc-containing metal waste material, zinc powder, zinc granule is that raw materials evaporate prepares zinc fume, or is raw material to smelt zinc fume directly, adopts aforesaid method all can prepare four acicular type zinc oxide crystal whisker.
Embodiment 3
Produce four acicular type zinc oxide crystal whisker under the condition of normal pressure.Earlier the 2kg metal zinc is added in the zinc vapourizing furnace, the Heating Zn vapourizing furnace, when temperature reaches 900 ℃, the zinc fume that produces overflows in the oxidizing reaction electric furnace, open the arc-over atomisation unit, the tiny liquid metal zinc mist that adopts air or pure oxygen to produce is sent in the vertical oxidizing reaction electric furnace by the mode of pulse or oxygen supply continuously, mixes mutually with zinc fume, and and vertical oxidizing reaction electric furnace in bottom air or the pure oxygen sent into react, generate white cotton-shaped four acicular type zinc oxide crystal whisker product.
With metal zinc ingot, industrial crude zinc, zinc alloy, zinc-containing metal waste material, zinc granule is that raw materials evaporate prepares zinc fume, or is raw material to smelt zinc fume directly, adopts aforesaid method all can prepare four acicular type zinc oxide crystal whisker.
In air or oxygen, feed content and account for 0.5～16% rare gas element, CO, SO of gas gross
2, CO
2Gas forms different oxidizing atmosphere as assist gas, can regulate the pattern (length-to-diameter ratio of whisker) of four acicular type zinc oxide crystal whisker product.
Claims (5)
1, a kind of method of arc oxidation aid preparation four acicular type zinc oxide crystal whisker, it is characterized in that this method adopts the auxiliary forming core of electric arc atomization metallic zinc, the liquid metal zinc mist that produces is mixed with zinc fume, by the air or oxygen oxidation, obtain four acicular type zinc oxide crystal whisker, its concrete grammar is: the material of metallic zinc or containing metal zinc is put into the process furnace internal heating, temperature reaches 650～1300 ℃, the metallic zinc evaporation, the zinc fume that produces enters in the reaction chamber, is raw material with the zinc fume directly perhaps, and the tiny liquid zinc mist that produces with the arc-over atomizing in reaction chamber mixes mutually, the zinc mist is 0.1～8: 99.9～92 with the ratio of zinc fume containing metal zinc, under air or purity oxygen effect, at first the zinc mist is oxidized into the whisker core, and zinc fume is oxidized subsequently, and grow up in the whisker core, form four acicular type zinc oxide crystal whisker.
2, method according to claim 1, the material that it is characterized in that described metallic zinc or containing metal zinc are metal zinc ingot, industrial crude zinc, zinc alloy, zinc-containing metal waste material, zinc powder or zinc granule.
3, method according to claim 1 is characterized in that preparation process carries out at normal pressure or under less than 1 atmospheric condition of negative pressure, adopts pure oxygen as oxidizing gas under less than 1 atmospheric condition of negative pressure.
4, method according to claim 1 when it is characterized in that carrying out, can feed 0.5～16% rare gas element, CO that content accounts for gas gross in air under being reflected at condition of normal pressure
2, CO or SO
2Gas is as assist gas, with the size and the pattern of control four acicular type zinc oxide crystal whisker.
5, method according to claim 1 is characterized in that in mode continuous or that pulse is interrupted air or oxygen being sent in the reaction chamber, produces reaction with zinc fume and tiny liquid zinc mist mixture; Perhaps, the tiny liquid zinc mist that is produced by the electric arc atomization effect is sent in the reaction chamber with pulse or successive mode with oxygen or air.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710150201XA CN101235538B (en) | 2007-11-16 | 2007-11-16 | Method for preparing tetrapod-like zinc oxide whisker with assistance of electric arc atomization |
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| CN200710150201XA CN101235538B (en) | 2007-11-16 | 2007-11-16 | Method for preparing tetrapod-like zinc oxide whisker with assistance of electric arc atomization |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967679A (en) * | 2010-10-29 | 2011-02-09 | 北京矿冶研究总院 | Method for regulating and controlling morphology of zinc oxide whisker |
| CN102139911A (en) * | 2011-03-30 | 2011-08-03 | 瑞安市顺丰塑料助剂有限公司 | Reaction device and method for preparing nano zinc oxide |
| CN101550596B (en) * | 2009-04-16 | 2011-10-05 | 北京矿冶研究总院 | Method for preparing four-needle and multi-needle zinc oxide whiskers from liquid metal zinc |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858001A (en) * | 2005-04-29 | 2006-11-08 | 南京大学 | Method for preparing different shape zinc oxide by vacuum limit oxygen method |
| CN100460330C (en) * | 2006-03-30 | 2009-02-11 | 东南大学 | One-D nano zinc oxide and vacuum electric arc prepn. process |
-
2007
- 2007-11-16 CN CN200710150201XA patent/CN101235538B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550596B (en) * | 2009-04-16 | 2011-10-05 | 北京矿冶研究总院 | Method for preparing four-needle and multi-needle zinc oxide whiskers from liquid metal zinc |
| CN101967679A (en) * | 2010-10-29 | 2011-02-09 | 北京矿冶研究总院 | Method for regulating and controlling morphology of zinc oxide whisker |
| CN102139911A (en) * | 2011-03-30 | 2011-08-03 | 瑞安市顺丰塑料助剂有限公司 | Reaction device and method for preparing nano zinc oxide |
| CN102139911B (en) * | 2011-03-30 | 2013-01-16 | 瑞安市顺丰塑料助剂有限公司 | Reaction device and method for preparing nano zinc oxide |
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Address after: 100160 Beijing City, South West Fourth Ring Road, Fengtai District, No. 188 headquarters base area, building eighteen, No. 23 Patentee after: Beijing General Research Institute of Mining & Metallurgy Address before: 100044, Beijing, Xicheng District, Xizhimen foreign Hing Street, No. 1 Patentee before: Beijing General Research Institute of Mining & Metallurgy |
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