CN101550596B - Method for preparing four-needle and multi-needle zinc oxide whiskers from liquid metal zinc - Google Patents
Method for preparing four-needle and multi-needle zinc oxide whiskers from liquid metal zinc Download PDFInfo
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- CN101550596B CN101550596B CN2009101308273A CN200910130827A CN101550596B CN 101550596 B CN101550596 B CN 101550596B CN 2009101308273 A CN2009101308273 A CN 2009101308273A CN 200910130827 A CN200910130827 A CN 200910130827A CN 101550596 B CN101550596 B CN 101550596B
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Abstract
A method for preparing four-needle and multi-needle zinc oxide whiskers by liquid metal zinc belongs to the field of inorganic material preparation technology and non-ferrous metallurgy. The method is characterized in that: the method is characterized in that metal zinc is used as a raw material, the metal zinc is melted into liquid metal zinc in a heating furnace with a lower temperature, then the liquid metal zinc is added into another high-temperature oxidation reaction furnace with a higher temperature, and simultaneously air or oxygen is introduced into the high-temperature oxidation reaction furnace, so that the liquid metal zinc is rapidly oxidized to generate zinc oxide whiskers. By controlling the adding amount and components of liquid metal zinc, four-needle or multi-needle zinc oxide whisker products are generated. The zinc oxide whisker is prepared by directly adopting the molten liquid metal zinc, so that the complex raw material pretreatment process in other preparation methods at present is omitted, the equipment investment and the whisker preparation link are reduced, the preparation process is greatly simplified, the automatic control and the continuous production of the preparation process are facilitated, the preparation method is suitable for large-scale industrial production, the production cost is low, and the product quality is stable and reliable.
Description
Technical field
The present invention relates to the method that liquid metal zinc prepares four needle-likes and spininess shape ZnOw, belong to inorganic materials technology of preparing and Non-ferrous Metallurgy field.Especially relate to by heating of metal zinc, be fused into liquid metal zinc after, at high temperature by oxygen or atmospheric oxidation, prepare the technological method of four needle-likes and spininess shape ZnOw.
Technical background
Compare with other metal oxide, there is the more shape characteristic of horn of plenty in zinc oxide, and its purposes is also very extensive, is one of the research focus in fields such as material, physics, chemistry for a long time always.By adopting different containing the zinc raw material and control the differential responses condition, can obtain the zinc oxide of different-shape.In recent years, with professor Wang Zhonglin of the georgia ,u.s.a Institute of Technology is representative, to adopt zinc oxide etc. be raw material, prepared the oxidized zinc products that the single form such as bar-shaped of nano-comb, nano-rings, nano wire, nanocages, nano belt, nanometer spring, nanotube, nanometer bow, nano four-needle-shape, nanometer is enriched by the gas evaporation method.
ZnOw has monoclinic crystal structure, not only has high mechanical strength and Young's modulus, tensile strength near the calculated value of chemical bond, high temperature resistant characteristics such as (more than 1700 ℃), but also has the performance of many excellences.Compare with common zinc oxide, ZnOw has many advantages, has excellent wear-resisting, anti-skidding, noise reduction, suction ripple, anti-aging, shock resistance, antistatic, anti-algae, antibiotic a, emission etc. as the material with four acicular type zinc oxide crystal whisker preparation.Its main application at present comprises: 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.Because the whisker or the needle point position of four acicular type zinc oxide crystal whisker usually are nano-scale structure, in many investigation of materials and using, show as the characteristic of nano material, therefore the four acicular type zinc oxide crystal whisker of this structure is also referred to as nano four-needle-shape zinc oxide crystal whisker.Because the difference of preparation condition when needles quantity reaches one regularly, shows as spininess shape (or flower-shaped) pattern.
The preparation method of four acicular type zinc oxide crystal whisker mainly contains zinc powder preoxidation, zinc powder direct oxidation method and zinc granule oxidation style.Heating at high temperature or burning zinc powder, zinc granule, wherein the zinc fume of Chan Shenging contacts with air or oxygen, is oxidized into four acicular type zinc oxide crystal whisker, is the quality of controlled oxidation zinc whisker, also normal some catalyzer (as carbon dust, zeolite) etc. that add in preparation process.In addition to the above methods, also zinc oxide can be mixed with carbon dust, be the reactive group bottom material with silicon chip etc., and the zinc fume that high temperature reduction goes out is deposited ZnOw by oxygen or atmospheric oxidation on base material.The zinc fume that perhaps metallic zinc is evaporated output is a raw material, contacts the preparation four acicular type zinc oxide crystal whisker by different way with oxygen or air.Or be raw material with zinc compounds such as zinc oxide, adopt the method for gas evaporation to prepare the zinc oxide of four acicular type zinc oxide crystal whisker or other pattern with the means of physics or chemistry.Because the preparation of ZnOw needs higher temperature, except that only a few had been used for producing in batches, great majority also just were used for scientific experiment research in the aforesaid method, and existing mass production processes output is little, the poor quality.The raw materials pretreatment process of some of them method is cumbersome, and the ZnOw end product quality of output is poor, be mingled with the oxidized zinc products of a large amount of other patterns (as particulate state, bulk), and direct recovery rate is low.And when being raw material with the zinc fume, needed preparation equipment and control process are complicated, and the homogeneity control of product is difficulty also.
Liquid metal zinc disclosed by the invention prepares the method for four needle-likes and spininess shape ZnOw, is to be raw material with plain metal zinc, be fused into liquid metal zinc after, directly at high temperature by oxygen or atmospheric oxidation, obtain four needle-likes or spininess shape ZnOw.
Summary of the invention
The objective of the invention is: provide a kind of liquid metal zinc to prepare the method for four needle-likes and spininess shape ZnOw, reduce the pre-preparation link of raw material in the ZnOw preparation process, shorten preparation process, reduce preparation number of devices and controlling unit, make preparation process be easier to control, thereby improve the quality and the output of ZnOw.Add-on and composition by control liquid metal zinc, make liquid metal zinc oxidized rapidly, avoid the evaporation of at high temperature excessive liquid metal zinc, thereby avoid generation because of zinc fume, and then avoid the product ununiformity that caused by zinc fume and oxygen or air generation oxidizing reaction, guaranteed the quality of ZnOw.
The objective of the invention is to realize by following scheme:
1, with the metallic zinc is raw material, outside the dezincification, other constituent content summation is no more than 6% in the raw material, other element comprises lead, cadmium, copper, tin, arsenic, antimony, indium, bismuth, titanium, aluminium, nickel, cobalt, chromium, calcium, magnesium, manganese, gold and silver, lithium, silicon and phosphorus, and other element also comprises rare earth scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
2, metallic zinc is melted in the process furnace A at a lesser temps, Heating temperature is 450～750 ℃.
3, to join temperature be in 800～1200 ℃ the high temperature oxidation Reaktionsofen B of another comparatively high temps to the liquid metal zinc after the fusing.
4, hold on the inner bottom surface of ware as reaction in high temperature oxidation Reaktionsofen B, the base area that the add-on of liquid metal zinc is held in the ware by reaction is counted 0.02～0.20g/cm
2When the add-on of liquid metal zinc is counted 0.02～0.10g/cm by base area
2The time, product is a four acicular type zinc oxide crystal whisker; When the add-on of liquid metal zinc is counted 0.13～0.20g/cm by base area
2The time, product is a spininess shape ZnOw; When liquid metal zinc by base area at 0.10～0.13g/cm
2Between the time, product is the mixture of four-needle-like zinc oxide and spininess shape ZnOw.
5, behind the adding liquid metal zinc, while aerating oxygen or air in high temperature oxidation Reaktionsofen B, and with nitrogen adjusting oxygen partial pressure, oxygen partial pressure is 10～120KPa.
Advantage and positively effect that the present invention and existing known technology relatively have are: directly adopt the liquid metal zinc after melting to prepare ZnOw, saved raw materials pretreatment process complicated among other preparation method, reduce facility investment and whisker prepares link, simplified preparation process greatly.The preparation method is simple, regulates the pattern of ZnOw by the add-on of control liquid metal zinc, obtains needed product, help the automatic control and the serialization production of preparation process, be suitable for large-scale industrial production, production cost is low, stable and reliable product quality.
Description of drawings
Fig. 1 is for adopting scanning electronic microscope (SEM) photo of the prepared four acicular type zinc oxide crystal whisker pattern of the present invention.
Fig. 2 is for adopting scanning electronic microscope (SEM) photo of the prepared spininess shape ZnOw pattern of the present invention.
Fig. 3 is for adopting the prepared four acicular type zinc oxide crystal whisker of the present invention and scanning electronic microscope (SEM) photo of spininess shape ZnOw mixture pattern.
Embodiment
Embodiment one
Get purity and be 99.9% metallic zinc 14g, in the alumina crucible of packing into, put into electric furnace A.Simultaneously putting into a floorage in another electric furnace B is 280cm
2Silicon carbide crucible, two electric furnaces are heated up.Behind the 110min, electric furnace A temperature rises to 600 ℃, and insulation is fully melted metallic zinc.Behind the 160min, electric furnace B temperature rises to 1050 ℃.Turn-off the electric furnace a-power supply, from electric furnace A, take out alumina crucible, will wherein be fused into rapidly liquid metallic zinc and pour among the electric furnace B in the silicon carbide crucible, be incubated 20min then, and the mixed gas of aerating oxygen and nitrogen, wherein the dividing potential drop of oxygen is 45～50KPa.After reaching soaking time, turn-off the electric furnace B-source, silicon carbide crucible is taken out in the cooling back, with white fluffy zinc oxide taking-up wherein.Through microscopic examination, be four acicular type zinc oxide crystal whisker.
Embodiment two
Get purity and be 98% metallic zinc 42g, in the alumina crucible of packing into, put into electric furnace A.Simultaneously putting into a floorage in another electric furnace B is 280cm
2Silicon carbide crucible, two electric furnaces are heated up.Behind the 120min, electric furnace A temperature rises to 650 ℃, and insulation is fully melted metallic zinc.Behind the 140min, electric furnace B temperature rises to 1000 ℃.Turn-off the electric furnace a-power supply, from electric furnace A, take out alumina crucible, will wherein be fused into liquid metallic zinc rapidly and pour among the electric furnace B in the silicon carbide crucible, be incubated 40min then, and bubbling air.After reaching soaking time, turn-off the electric furnace B-source, silicon carbide crucible is taken out in the cooling back, with white zinc oxide taking-up wherein.Through microscopic examination, be spininess shape ZnOw.
Embodiment three
Get purity and be 97.5% metallic zinc 32g, in the alumina crucible of packing into, put into electric furnace A.Simultaneously putting into a floorage in another electric furnace B is 280cm
2Silicon carbide crucible, two electric furnaces are heated up.Behind the 105min, electric furnace A temperature rises to 560 ℃, and insulation is fully melted metallic zinc.Behind the 135min, electric furnace B temperature rises to 980 ℃.Turn-off the electric furnace a-power supply, from electric furnace A, take out alumina crucible, and will wherein be fused into liquid metallic zinc rapidly and pour among the electric furnace B in the silicon carbide crucible, be incubated 30min then, and aerating oxygen, with the air mixed in the stove, the control oxygen partial pressure is 30～35KPa.After reaching soaking time, turn-off the electric furnace B-source, silicon carbide crucible is taken out in the cooling back, with white zinc oxide taking-up wherein.Through microscopic examination, be the mixture of four needle-likes and spininess shape ZnOw.
Claims (6)
1. liquid metal zinc prepares the method for four needle-likes and spininess shape ZnOw, it is characterized in that: metallic zinc is fused into liquid metal zinc in process furnace A, be poured into then in the high temperature oxidation Reaktionsofen B that is heated to 800～1200 ℃ in advance, while bubbling air or oxygen, make liquid metal zinc oxidized, and generate ZnOw; Outside dezincifying in the metallic zinc raw material, other constituent content summation is no more than 6%, holds on the inner bottom surface of ware as reaction in high temperature oxidation Reaktionsofen B, and the base area that the add-on of liquid metal zinc is held in the ware by reaction is counted 0.02～0.20g/cm
2, generate four needle-likes or spininess shape ZnOw product.
2. the method for preparing four needle-likes and spininess shape ZnOw by the described liquid metal zinc of claim 1, it is characterized in that with the metallic zinc being raw material, outside the dezincification, other constituent content summation is no more than 6% in the raw material, other element comprises lead, cadmium, copper, tin, arsenic, antimony, indium, bismuth, titanium, aluminium, nickel, cobalt, chromium, calcium, magnesium, manganese, gold and silver, lithium, silicon and phosphorus, and other element also comprises rare earth scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
3. the method that is prepared four needle-likes and spininess shape ZnOw by the described liquid metal zinc of claim 1 is characterized in that furnace temp is 450～750 ℃ with metallic zinc A fusing in process furnace.
4. it is in 800～1200 ℃ the high temperature oxidation Reaktionsofen B that the method that is prepared four needle-likes and spininess shape ZnOw by the described liquid metal zinc of claim 1, the liquid metal zinc after it is characterized in that melting join temperature.
5. the method for preparing four needle-likes and spininess shape ZnOw by the described liquid metal zinc of claim 1, it is characterized in that holding on the inner bottom surface of ware as reaction in high temperature oxidation Reaktionsofen B, the base area that the add-on of liquid metal zinc is held in the ware by reaction is counted 0.02～0.20g/cm
2When the add-on of liquid metal zinc is counted 0.02～0.10g/cm by base area
2The time, product is a four acicular type zinc oxide crystal whisker; When the add-on of liquid metal zinc is counted 0.13～0.20g/cm by base area
2The time, product is a spininess shape ZnOw; When liquid metal zinc thickness at 0.10～0.13g/cm
2Between the time, product is the mixture of four-needle-like zinc oxide and spininess shape ZnOw.
6. the method for preparing four needle-likes and spininess shape ZnOw by the described liquid metal zinc of claim 1, after it is characterized in that adding liquid metal zinc, while aerating oxygen or air in high temperature oxidation Reaktionsofen B, and with nitrogen adjusting oxygen partial pressure, oxygen partial pressure is 10～120KPa.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101773147B (en) * | 2010-01-27 | 2012-06-27 | 中南大学 | Modified T-ZnOw antibiotic material and preparation method thereof |
| CN101898788A (en) * | 2010-08-18 | 2010-12-01 | 北京理工大学 | Method for growing nano zinc oxide with aid of metal activation |
| CN101962807B (en) * | 2010-10-15 | 2012-11-28 | 北京北矿锌业有限责任公司 | Equipment and method for producing tetrapod-shaped zinc oxide whiskers |
| CN101967679B (en) * | 2010-10-29 | 2012-04-25 | 北京矿冶研究总院 | Method for regulating and controlling morphology of zinc oxide whisker |
| CN105926029B (en) * | 2016-05-09 | 2018-11-27 | 郑州云江科技有限公司 | A method of utilizing microwave rapid synthesis ZnOw |
| CN113321235A (en) * | 2020-07-31 | 2021-08-31 | 上海交通大学 | Method for preparing zinc oxide ultrafine powder by using zinc skins of waste zinc-manganese batteries |
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| US5066475A (en) * | 1987-12-29 | 1991-11-19 | Matsushita Electric Industrial Co., Ltd. | Zinc oxide whiskers having a novel crystalline form and method for making same |
| US5158643A (en) * | 1988-12-16 | 1992-10-27 | Matsushita Electric Industrial Co., Ltd. | Method for manufacturing zinc oxide whiskers |
| CN1206756A (en) * | 1997-07-24 | 1999-02-03 | 西南交通大学 | Process for preparing zinc oxide crystal whisker |
| CN1384056A (en) * | 2002-06-12 | 2002-12-11 | 云南省冶金研究设计院 | Process and apapratus of producing four-needle zine oxide whisker |
| CN1566417A (en) * | 2003-06-17 | 2005-01-19 | 中南大学 | Process for preparing zinc oxide crystal whisker |
| CN1683603A (en) * | 2005-02-04 | 2005-10-19 | 浙江大学 | Process and its device for preparing fibrous zinc oxide whisker |
| CN101235538A (en) * | 2007-11-16 | 2008-08-06 | 北京矿冶研究总院 | Method for preparing tetrapod-like zinc oxide whisker with assistance of electric arc atomization |
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- 2009-04-16 CN CN2009101308273A patent/CN101550596B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5066475A (en) * | 1987-12-29 | 1991-11-19 | Matsushita Electric Industrial Co., Ltd. | Zinc oxide whiskers having a novel crystalline form and method for making same |
| US5158643A (en) * | 1988-12-16 | 1992-10-27 | Matsushita Electric Industrial Co., Ltd. | Method for manufacturing zinc oxide whiskers |
| CN1206756A (en) * | 1997-07-24 | 1999-02-03 | 西南交通大学 | Process for preparing zinc oxide crystal whisker |
| CN1384056A (en) * | 2002-06-12 | 2002-12-11 | 云南省冶金研究设计院 | Process and apapratus of producing four-needle zine oxide whisker |
| CN1566417A (en) * | 2003-06-17 | 2005-01-19 | 中南大学 | Process for preparing zinc oxide crystal whisker |
| CN1683603A (en) * | 2005-02-04 | 2005-10-19 | 浙江大学 | Process and its device for preparing fibrous zinc oxide whisker |
| CN101235538A (en) * | 2007-11-16 | 2008-08-06 | 北京矿冶研究总院 | Method for preparing tetrapod-like zinc oxide whisker with assistance of electric arc atomization |
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