CN1594098A - Synthesis of micron and nano zinc oxide fiber by alloy gas controllable evaporation method - Google Patents
Synthesis of micron and nano zinc oxide fiber by alloy gas controllable evaporation method Download PDFInfo
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- CN1594098A CN1594098A CN 200410013391 CN200410013391A CN1594098A CN 1594098 A CN1594098 A CN 1594098A CN 200410013391 CN200410013391 CN 200410013391 CN 200410013391 A CN200410013391 A CN 200410013391A CN 1594098 A CN1594098 A CN 1594098A
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Abstract
本发明提供一种合金气体可控蒸发法合成氧化锌微米、纳米纤维的方法。该方法利用铜锌混合粉末或者直接用商业纯度的黄铜块作为反应物，在空气中高温下直接氧化熔融反应物释放的金属锌蒸气。合成的氧化锌微米纤维的维度在0.1μm－0.6μm，单针长度1μm－3μm，合成的氧化锌纳米线纤维的维度在10－150nm，大多数的维度在50－100nm，长度在3－8μm。
The invention provides a method for synthesizing zinc oxide micron and nanofibers by an alloy gas controllable evaporation method. The method utilizes copper-zinc mixed powder or directly uses commercially pure brass blocks as reactants, and directly oxidizes metal zinc vapor released from molten reactants at high temperature in air. The dimension of the synthesized zinc oxide microfiber is 0.1μm-0.6μm, the length of a single needle is 1μm-3μm, the dimension of the synthesized zinc oxide nanowire fiber is 10-150nm, most of the dimensions are 50-100nm, and the length is 3-8μm .
Description
Affiliated technical field
The invention belongs to the synthetic method of zinc oxide micrometer and nanofiber.
Background technology
Zinc oxide fiber is used as enhancing, the toughner of matrix material, damping, anti-impact and sound-proof material, wear-resisting and anti-slip material, coating, antistatic material, absorbing material widely.In fields such as national defence, electronics, chemical industry, traffic performance enormous function.At present, being used for the methods of a large amount of synthetic microns, nano zine oxide fiber mainly contains two kinds: zinc powder mechanize preoxidation (oxidizing roasting method) and metal zinc direct oxidation roasting method.
The former is that Japanese Matsushita Electric Industrial company developed the end of the eighties, principle technology is: earlier the raw material zinc powder is mixed according to a certain percentage with deionized water, activation treatment in punching press or vortex cutting grinding machine, " ageing makes the zinc powder surface form one deck dense oxidation film after handling; the zinc powder surface film oxide can not get needle-shape zinc oxide crystal whisker when too thin; be the raw material as the gasification oxidation after this preoxidation zinc powder drying; it is gasification oxidation certain hour (heat treatment time is relevant with temperature) and process aftertreatment under the high temperature in particular device, promptly obtains the ZnOw product will to activate the water that material places certain temperature then.Wherein the gasification oxidation furnaces of preoxidation of zinc powder mechanochemistry and preoxidation zinc powder is the key that technology realizes.On this basis, PANASONIC has successively realized that again the direct recycling of continuous production, crystal whisker products large sizeization and non-whisker zinc oxide product of automatic control, the whisker of roasting gasification oxidising process has improved product yield, the whisker outward appearance that technology makes is loose, density is less, the needle-shape zinc oxide crystal whisker productive rate is higher to be more than 40% of initial zinc powder quality, can reach 80%-86% in the time of better, the zinc oxide fiber that makes has different size, can adopt the fractionated method to separate.Weak point is that zinc powder mechanochemistry pretreatment time is longer, and processing condition are complicated.
The latter is by Southwest Jiaotong University and Tsing-Hua University's exploitation.Principle technology is: be raw material with the metal zinc, coke powder is a solid reductant, and both are mixed in proportion in the opening resistance furnace, make ZnOw through roasting oxidation under the high temperature.Shortcomings such as after this " investigator controls at its atmosphere is difficult, and productive rate is low have been done many improvement, have realized the continuous production of ZnOw.This is simple for process, but there is certain gap in the product of quality product and Japanese Matsushita Electric Industrial company, and productive rate is on the low side, produces to be difficult to the formation scale.
Summary of the invention
The objective of the invention is in order to overcome low, the difficult deficiency on a large scale of the long pre-treatment, complex process, the productive rate that exist in the above-mentioned production zinc oxide fiber.Provide a kind of simple, the method for fast a large amount of controlledly synthesis high purity microns, nano zine oxide fiber.This method need not the complicated mechanical Chemical Pretreatment, and processing condition are simple.Production process forms large-scale production rapidly, continuously, easily.
For realizing the object of the invention, we propose the method for alloy gas controlled evaporation method synthesizing zinc oxide micron and nanofiber,
Principle of the present invention: studies show that the steam of direct oxidation metallic zinc at high temperature can obtain zinc oxide micrometer, nanofiber.Its form can be controlled by oxygen bias voltage in the reactant gases or metallic zinc steam.Common to the difficult realization of oxygen bias voltage in the reactant gases, and make reaction process complicated, and prolonged the reaction times, be difficult for realizing the continuity of building-up process, and the control of metallic zinc steam bias voltage there is not good solution at present yet.Yet our the alloy gas controlled evaporation method that proposes has realized the control of metallic zinc steam bias voltage here.Alloy gas controlled evaporation method mainly is to form a certain proportion of metal alloy by high-melting point metal and low-melting metal.Make the liquefaction temperature of low-melting metal bring up to the temperature of fusion of alloy, thereby can slowly discharge the steam bias voltage that obtains.The alloy here is a notion widely, and this method is equally applicable in the control of nonmetallic steam bias voltage.Specifically in the present invention according to copper zinc binary alloy phase diagram (referring to Fig. 1), the fusing point of copper zinc alloy increases along with the increase of copper component, the release temperature of the zinc fume in the alloy also improves, and owing to form alloy with copper, it at high temperature can slowly discharge, and the steam bias voltage can be regulated by the ratio of alloy.Under suitable high temperature, the slowly stable zinc fume that discharges from the fused alloy assembles forming zinc micron, many twins of nanometer particle in air.The oxidation in air of many twins particle also absorbs the zinc composition in the atmosphere simultaneously, each twin particle forms an independently acicular structure to outgrowth, last whole many twins particle develops into the zinc oxide fiber structure (referring to Fig. 2, having shown among the figure that many twins develop into the fibrous texture process of spininess) of spininess.The size of zinc oxide fiber can be by the many twins particulate size adjustment that forms, and many twins particulate size is by the control of the zinc fume bias voltage in the reaction atmosphere, and finally the copper zinc ratio by the beginning reactant is determined.
The scheme that realizes the object of the invention is: the method for a kind of alloy gas controlled evaporation method synthesizing zinc oxide micron and nanofiber, and the step of this method is:
(1) with copper zinc powder mix art or the brass ingot of directly using commercial purity as reactant feed, copper content is 10wt%-95wt% in the reactant feed;
(2) reactant is placed opening high temperature silicon molybdenum bar temperature programmed control Reaktionsofen under 1100 ℃ of-1450 ℃ of temperature of reaction, make its own oxidation fusion discharge the metallic zinc steam, the reaction times is 5-15min;
(3) directly near the following wind direction of air-flow and reactant, directly collect and react synthetic product zinc oxide, collected synthetic zinc oxide micrometer fiber is a synthetic zinc oxide micrometer fiber, its dimension is at 0.1 μ m-0.6 μ m, single needle length 1 μ m-3 μ m, collected synthetic zinc-oxide nano line fiber, be synthetic zinc oxide micrometer fiber, its dimension is at 10-150nm, and length is at 3-8 μ m.
In the above-mentioned reaction, reasonable as copper content in the copper zinc mixed powder of reactant or the brass is 40wt%-70wt%.
In the above-mentioned reaction, temperature of reaction is 1200 ℃-1300 ℃ preferably.
In the above-mentioned reaction, the product of leaving over of reactant is that the brass of low levels can reclaim again and uses.
The invention has the beneficial effects as follows that product pattern, dimension are controlled, production process realizes the mass-producing continuous production fast, simply, easily.
Description of drawings
Fig. 1 is the binary phase diagram of copper zinc alloy.
Fig. 2 is the transmission electron microscope picture of the process of growth of many contractions of zinc oxide crystal orientation spininess shape fiber.
Fig. 3 is that copper zinc weight ratio is 50% the mixed powder fiber scanning electron microscope picture as reactant synthetic zinc oxide.
Fig. 4 is as scanning of reactant synthetic zinc oxide nano fiber and transmission electron microscope picture with the business level brass ingot.
Embodiment
Embodiment 1: in opening high temperature silicon molybdenum bar temperature programmed control Reaktionsofen (GWDL-1KY, high temperature Instr Ltd. of Luoyang Weida), under 1250 ℃, the copper zinc powder mix art with copper zinc weight ratio 50% in air places the reaction warm area, reacts end in 10 minutes.Can receive a large amount of white cotton-shaped products on the leeward.
Show that with the XRD diffraction analysis white cotton-shaped product is the fabulous zinc oxide of crystallization degree, does not have the appearance mutually of other copper or cupric oxide.The zinc oxide that gets with scanning electron microscope (SEM) observation post is uniform three pins or four acicular fiber (see figure 3)s.The single needle dimension is at 100nm, and length is at 1.5um.
Embodiment 2: in opening high temperature silicon molybdenum bar temperature programmed control Reaktionsofen, under 1250 ℃, the brass ingot (copper content 50wt%-65wt%) with commercial purity in air places the reaction warm area, reacts end in 15 minutes.Can receive a large amount of white cotton-shaped products on the leeward.
Show that with the XRD diffraction analysis white cotton-shaped product is the fabulous zinc oxide of crystallization degree, does not have the appearance mutually of other copper or cupric oxide.With scanning electron microscope (SEM) (Fig. 4 a) and the zinc oxide that gets of transmission electron microscope (TEM) (Fig. 4 b) observation post be the wire product of 1-dimention nano dimension.The dimension of zinc oxide nanowire changes from 10-150nm, and still most dimension is at 50-100nm, and the distribution of dimension is more even, and length is at 3-8um.
Hangover behind the above-mentioned reactant reaction is the brass alloys of low levels, can directly recycle.
Claims (3)
1, the method for a kind of alloy gas controlled evaporation method synthesizing zinc oxide micron and nanofiber is characterized in that synthesis step is
(1) with copper zinc mixed powder or brass ingot as reactant feed, copper content is 10wt%-95wt% in its reactant feed;
(2) reactant is placed opening high temperature silicon molybdenum bar temperature programmed control Reaktionsofen under 1100 ℃ of-1450 ℃ of temperature of reaction, make its own oxidation fusion discharge the metallic zinc steam, the reaction times is 5-15min;
(3) near the following wind direction of air-flow and reactant, directly collect reaction synthetic product zinc oxide, collected synthetic zinc oxide micrometer fiber is a synthetic zinc oxide micrometer fiber, its dimension is at 0.1 μ m-0.6 μ m, single needle length 1 μ m-3 μ m, collected synthetic zinc-oxide nano line fiber, be synthetic zinc oxide micrometer fiber, its dimension is at 10-150nm, and length is at 3-8 μ m.
2, the method for claim 1, it is characterized in that being used as in the copper-zinc powder of reactant or the brass ingot copper content be 40wt%-70wt%.
3, the method for claim 1 is characterized in that described temperature of reaction is 1200 ℃-1300 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381360C (en) * | 2006-05-15 | 2008-04-16 | 南京大学 | Method of growing ZnO mono-dimension nanometer material directly on zine containing alloy material |
| CN100417753C (en) * | 2006-11-07 | 2008-09-10 | 北京矿冶研究总院 | Preparation of Tetraacicular Zinc Oxide Whiskers by Atmospheric Pressure Zinc Vapor Oxidation |
| CN101665984B (en) * | 2008-09-01 | 2012-07-25 | 西北工业大学 | Copper zinc alloy nanowire and preparation method thereof |
| CN104906816A (en) * | 2015-06-01 | 2015-09-16 | 上海交通大学 | Controllable liquid evaporation method based on porous composite material |
| CN104941227A (en) * | 2015-06-05 | 2015-09-30 | 上海交通大学 | Method for evaporation separation of liquid state mixture based on porous composite |
-
2004
- 2004-06-29 CN CN 200410013391 patent/CN1260131C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381360C (en) * | 2006-05-15 | 2008-04-16 | 南京大学 | Method of growing ZnO mono-dimension nanometer material directly on zine containing alloy material |
| CN100417753C (en) * | 2006-11-07 | 2008-09-10 | 北京矿冶研究总院 | Preparation of Tetraacicular Zinc Oxide Whiskers by Atmospheric Pressure Zinc Vapor Oxidation |
| CN101665984B (en) * | 2008-09-01 | 2012-07-25 | 西北工业大学 | Copper zinc alloy nanowire and preparation method thereof |
| CN104906816A (en) * | 2015-06-01 | 2015-09-16 | 上海交通大学 | Controllable liquid evaporation method based on porous composite material |
| CN104941227A (en) * | 2015-06-05 | 2015-09-30 | 上海交通大学 | Method for evaporation separation of liquid state mixture based on porous composite |
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| CN1260131C (en) | 2006-06-21 |
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