CN1594671A - Process for collimated beam shaped nano zinc oxide crystal whisker - Google Patents
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- CN1594671A CN1594671A CN 200410027783 CN200410027783A CN1594671A CN 1594671 A CN1594671 A CN 1594671A CN 200410027783 CN200410027783 CN 200410027783 CN 200410027783 A CN200410027783 A CN 200410027783A CN 1594671 A CN1594671 A CN 1594671A
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Abstract
The invention relates to a wholly new method for preparing parallel bundle nanometer zinc oxide crystal whisker, which adopts liquid crystal chemical as moulding board, supersonic colloidal sol method as preparation means, and prepare single parallel bundle crystal whisker, average grain size being 50nm zinc oxide powder. The inventive method solves the problem that traditional predecessor sintering method has high energy consumption, shape, grain size and its distribution is controlled difficultly, Quantity is small using microemulsion preparation method, which makes industrialized production difficult. The inventive preparation method saves the process of predecessor high temperature sintering using in the traditional method. The whole reaction time is only 1-2 hours.
Description
Technical field
The present invention relates to a kind of method for preparing parallel pencil nano zinc oxide crystal whisker.
Background technology
Nano zine oxide is a kind of novel high function fine inorganic product, because the granular of particle size, specific surface area is big, distinctive quantum size effect, interfacial effect and coupling effect have a wide range of applications at aspects such as quantum device, extraordinary fine ceramics, sun power utilization, environmental protection catalyst, matrix material, coating, printing ink, medicine, makeup.It has many excellent comprehensive performances, as inhale ripple, absorb infrared rays, the opposing ultraviolet ray, fluoresce, effects such as image recording, gas sensing, piezoelectricity, change resistance, explosion-proof, damping, noise reduction, sterilization, sterilization; Also can be used to make gas sensor, fluor, UV-preventing material varistor, image recording material, piezoelectric, voltage dependent resistor, catalyzer, magneticsubstance, stupalith, high density information storage medium.The type of partly leading of scientist professor Wang Zhonglin initiative of Chinese origin, band shape (Belt) can have been started the new gang functional materials with wide application prospect from the nano zine oxide monocrystalline of spiral assembling.
Because the form of zinc oxide particle, particle diameter and size distribution play decisive role for its various functional performances, therefore the zinc oxide nano-particle preparation method have been proposed the form controlled amount and have prevented higher requirement such as reunion.Particularly thereby the controllability of the structure of material and form has become the controlled deciding factor for preparing corresponding performance function material and device of realization performance.The preparation method of zinc oxide nano-particle mainly contains solid phase method, liquid phase method and vapor phase process three major types at present, have some shortcomings in actually operating and the suitability for industrialized production respectively: 1, vapour deposition process such as laser steam the method for coagulating, complex process, apparatus expensive generally needs comparatively high temps and energy consumption; 2, sluggish precipitation, size distribution broad, morphology Control difficulty; 3, sol-gel method is difficult to avoid reuniting in the gel follow-up sintering process and the problem such as grow up of crystal particles; 4, ultrasonic microemulsion method, preparation output is difficult to industrialization for a short time; 5, solid sintering technology, energy consumption height, severe reaction conditions.Since preparation method's restriction, present nano zine oxide structure and the form poor controllability of producing of China, the big and size distribution broad of particle diameter, product is in low value added state relatively, particularly can not satisfy pressing for of performance function material application.Therefore prepare single form, size distribution is even, has the nano zine oxide of specific function characteristic, improve its value added, and exploitation (as piezoelectricity, is led partly based on the new function material of nano zine oxide, air-sensitive, sensitization) be that China's nanotechnology industry is when last the task of being badly in need of solution.The nano zinc oxide crystal whisker production of present domestic specific form purposes is that (carbonaceous reducing agent control legal system is equipped with the processing method of ZnOw in representative with people's such as the Zhou Zuowan of macromolecular material institute of Southwest Jiaotong University method, patent of invention, 94 1 11823.1) Zhi Bei ZnOw is mainly three-dimensional four acicular twins, association simultaneously has needle-like, torispherical and rod-shaped particle; And only in limited range, reach nano-scale near needle point.The matrix material of being made up of it is isotropy.Other is as the Tian Yajuan of Northeastern University (CN1271786A), the Wu Hua Wu of Tsing-Hua University (CN1031838), and the method for the Dai Ying of University of Science ﹠ Technology, Beijing etc. is close substantially.The NPP rule that Chinese Academy of Sciences's chemical industry metallurgical is developed is to produce spherical product.The Zhang Lingang of Southeast China University (CN1129263) is a target with the preparation ZnO water-sol then, and form is controlled.
The ultrasound templates legal system is equipped with nano zine oxide, mainly be by special template control conversion zone and limit the form and the orientation of product, with different ultrasonic and temperature condition provocative reactions, the control crystalline growth velocity, in the hope of control particle diameter and size distribution, the nano zine oxide that preparation has specific form and performance.
Summary of the invention
The object of the invention is to provide the method for making of a kind of single whisker bunch shape zinc oxide, this single whisker bunch shape zinc oxide form and size distribution homogeneous, and this is the effect that adopts traditional preparation method to be difficult to reach, and technology is simple, energy consumption is low.Another object of the present invention provides a kind of zinc oxide with specific function characteristic, and this kind specific form zinc oxide can be used for preparing functional, as piezo-electricity composite material.
The present invention adopts sonochemical method to be prepared.Ultrasonic with heat energy, luminous energy and ionizing radiation can have significant difference as a kind of special energy form, and they are different with traditional energy at aspects such as action time, pressure and the retrievable energy of each molecule.At specific ultrasound condition, particularly under " cavitation " condition, can provide local ultrahigh-temperature simultaneously, special reaction condition and " spike " of gradient falls in ultra-high voltage, ultra high temp and pressure, is used to control the crystalline growth conditions.Ultrasonication not only derives from intermolecular interaction in chemical reaction, and main is to derive from ultrasonic cavitation.Different frequency, the energy of the ultrasonic generation of power, localized hyperthermia, high pressure and cavatition can make precursor be converted into product zinc oxide, have saved the precursor high-temperature sintering process in the traditional method, be a kind of saving energy, environmental method, required time is short, and entire reaction course only needs 1～2 hour.
Prove that by X-ray diffraction (XRD) this material is a hexagonal system zinc oxide; (TEM) carries out Microstructure characterization to this Zinc oxide powder by transmission electron microscope, confirms that particle shape is a single whisker bunch shape; Recording average particle size by laser light scattering is 50nm, illustrate that particle is a nano level, and every kind of sample distributes in very narrow particle size range.
The parallel pencil whisker nano zine oxide of this method preparation has that particle diameter is even, and form is controlled, and preparation condition is simple and easy, and the time is short, the characteristics that efficient is high.
Embodiment:
The method of the parallel pencil whisker of preparation of the present invention nano zine oxide, the employing liquid crystalline cpd is a template, ultrasonic sol method is the means of preparation, is undertaken by following step:
Selection is by semi-rigid macromole (as oxyethane-styrene block copolymer PEO-b-PS block copolymer), or comb dress (brush shape) grafts, polypeptide, amino acid, tensio-active agent is (as N, the two alkyl of N ' are for morpholine 4,4 '-N, N '-alkanediylbismorpholine, nonyl morpholine hydrochloride dihydrochloride salt of nonanediyl bismorpholine, the inclined to one side fluorine ammonium caprylate of capric acid ammonium ammonium decanoate/ ammonium perfluoro octanoate, cetyl trimethylammonium bromide hexadecyltrimethylammonium bromide (C16TAB)/Hexaethyl ethylene glycol monododecyl ether hexaethyleneglycol monododecyl ether (C12E6), capric acid ammonium ammonium decanoate/ ammonium caprylate ammoniumdodecanoate, sucrose fatty ester, sorbitan fatty acid ester, compounds such as glycerol fatty acid ester), form separately or according to a certain ratio, as the template (microreactor) of preparation target product.
(1) reaction template and the buffering solution (pH8-13) press certain mass than (0.1%-4%) mixing after, the acetic acid zinc solution that adds weight proportion 0.3%-30%, appointment proportioning (0.1-1mol/L), ultrasonic dispersing 15 minutes-1 hour, zinc acetate is included in the liquid crystal spatia, obtained reactive admixture I;
(2) the 0.3%-30%NaOH solution of weight ratio joins in the reaction template and buffering solution mixing solutions of above-mentioned same proportioning, and at power 2KW～4KW, frequency is that ultra-sonic dispersion (15 minutes-1 hour) obtains reactive admixture II under the condition of 15～35KHz;
(3) under the sonic oscillation with I, II mixes, at 20～60 ℃, power 2KW～4KW, frequency is under the condition of 15～35KHz ultrasonic reaction 0.5-2 hour;
(4) crude product is removed the throw out that may exist through 1000-4000 rev/min of centrifugation, and with deionized water wash, vacuum-drying promptly gets product.
Embodiment:
Embodiment 1
After the mixture A of sucrose monostearate, sorbitan monostearate, Zerol and PH10 buffered soln pressed A0.5% and mix, add the acetic acid zinc solution of 3%0.5mol/l, ultrasonic dispersing (15 minutes) obtains reactive admixture I; The NaOH solution of same amount 1mol/l is joined in the surfactant A and buffering solution mixing solutions of same proportioning, at power 4KW, frequency is that ultra-sonic dispersion obtained reactive admixture II in 15 minutes under the condition of 35KHz; With I, II mixes under the sonic oscillation, at 30 ℃, and power 4KW, frequency is a ultrasonic reaction 1 hour under the condition of 35KHz; Crude product is removed the throw out that may exist through 2000 rev/mins of centrifugations, washing, and vacuum-drying promptly gets product.The gained Zinc oxide powder is a whisker bunch shape, median size 40nm.
Embodiment 2
After the mixture A of sucrose monostearate, sorbitan monostearate, Zerol and PH11 buffered soln pressed A1% and mix, add the acetic acid zinc solution of 3%0.5mol/l, ultrasonic dispersing (30 minutes) obtains reactive admixture I; The NaOH solution of same amount 1mol/l is joined in the surfactant A and buffering solution mixing solutions of same proportioning, at power 4KW, frequency is that ultra-sonic dispersion obtained reactive admixture II in 30 minutes under the condition of 35KHz; With I, II mixes under the sonic oscillation, at 25 ℃, and power 4KW, frequency is a ultrasonic reaction 1 hour under the condition of 35KHz; Crude product is removed the throw out that may exist through 3000 rev/mins of centrifugations, washing, and vacuum-drying promptly gets product.The gained Zinc oxide powder is a whisker bunch shape, median size 50nm.
Embodiment 3
After the mixture A of sucrose monostearate, sorbitan monostearate, Zerol and PH10 buffered soln pressed A2% and mix, the acetic acid zinc solution that adds 30%0.5mol/l, at power 4KW, frequency is under the condition of 28KHz and 35KHz mixing, and ultrasonic dispersing (30 minutes) obtains reactive admixture I; The NaOH solution of same amount 1mol/l is joined in the surfactant A and buffering solution mixing solutions of same proportioning, at power 4KW, frequency is that ultra-sonic dispersion obtained reactive admixture II in 30 minutes under the condition of 28KHz and 35KHz mixing; With I, II mixes under the sonic oscillation, at 40 ℃, and power 2KW, frequency is a ultrasonic reaction 1 hour under the condition of 35KHz; Crude product is removed the throw out that may exist through 3000 rev/mins of centrifugations, washing, and vacuum-drying promptly gets product.The gained Zinc oxide powder is a whisker bunch shape, median size 60nm.
Embodiment 4
After the mixture A of sucrose monostearate, sorbitan monostearate, Zerol and PH11 buffered soln pressed A2% and mix, add the acetic acid zinc solution of 0.3%0.5mol/l, ultrasonic dispersing (15 minutes) obtains reactive admixture I; The NaOH solution of same amount 1mol/l is joined in the surfactant A and buffering solution mixing solutions of same proportioning, at power 2KW, frequency is that ultra-sonic dispersion obtained reactive admixture II in 15 minutes under the condition of 35KHz; With I, II mixes under the sonic oscillation, at 50 ℃, and power 2KW, frequency is a ultrasonic reaction 1 hour under the condition of 35KHz; Crude product is removed the throw out that may exist through 2000 rev/mins of centrifugations, washing, and vacuum-drying promptly gets product.The gained Zinc oxide powder is a whisker bunch shape, median size 40nm.
Embodiment 5
After oxyethane-styrene block copolymer B and PH10 buffered soln pressed B1% and mix, add the acetic acid zinc solution of 0.3%0.5mol/l, ultrasonic dispersing (30 minutes) obtains reactive admixture I; The NaOH solution of same amount 1mol/l is joined among the multipolymer B and buffering solution mixing solutions of same proportioning, at power 2KW, frequency is that ultra-sonic dispersion obtained reactive admixture II in 30 minutes under the condition of 35KHz; With I, II mixes under the sonic oscillation, at 50 ℃, and power 2KW, frequency is a ultrasonic reaction 1 hour under the condition of 35KHz; Crude product is removed the throw out that may exist through 2000 rev/mins of centrifugations, washing, and vacuum-drying promptly gets product.The gained Zinc oxide powder is a whisker bunch shape, median size 60nm.
Embodiment 6
After nonyl morpholine hydrochloride (2%) and the mixing of PH10 buffered soln, add the acetic acid zinc solution of 3%0.5mol/l, ultrasonic dispersing (15 minutes) obtains reactive admixture I; The NaOH solution of same amount 1mol/l is joined in the surfactant A and buffering solution mixing solutions of same proportioning, at power 4KW, frequency is that ultra-sonic dispersion obtained reactive admixture II in 15 minutes under the condition of 35KHz; With I, II mixes under the sonic oscillation, at 30 ℃, and power 4KW, frequency is a ultrasonic reaction 1 hour under the condition of 35KHz; Crude product is removed the throw out that may exist through 2000 rev/mins of centrifugations, washing, and vacuum-drying promptly gets product.The gained Zinc oxide powder is a whisker bunch shape, median size 40nm.
Claims (5)
1, a kind of method for making of parallel pencil nano zinc oxide crystal whisker is characterized in that preparing the method for parallel pencil whisker nano zine oxide, and the employing liquid crystalline cpd is a template, and ultrasonic sol method comprises the steps: for the means of preparation
Selection is made up of separately or according to a certain ratio semi-rigid macromole or comb dress grafts, polypeptide, amino acid, tensio-active agent, as the template for preparing target product;
1) after reaction template and pH8-13 buffered soln mix, the acetic acid zinc solution of add weight ratio 0.3%-30%, specifying proportioning 0.1-1mol/L, ultrasonic dispersing 15 minutes-1 hour obtains reactive admixture I;
2) NaOH solution is joined in the reaction template and buffering solution mixing solutions of above-mentioned same proportioning, at power 2KW ~ 4KW, frequency is a ultra-sonic dispersion 15 minutes-1 hour under the condition of 15 ~ 35KHz, obtains reactive admixture II;
3) sonic oscillation is down with above-mentioned 1) and 2), in I, II gives and mixes the thing mixing, at 20 ~ 60 ℃, power 2KW ~ 4KW, frequency is under the condition of 15 ~ 35KHz, ultrasonic reaction 0.5-2 hour;
4) crude product is through 1000-4000 rev/min of centrifugation, and with deionized water wash, vacuum-drying promptly gets product.
2, according to the method for making of the parallel pencil nano zinc oxide crystal whisker described in the claim 1, it is characterized in that described promoting agent is N, the two alkyl of N ' are for morpholine, the nonyl morpholine hydrochloride, capric acid ammonium/inclined to one side fluorine ammonium caprylate, cetyl trimethylammonium bromide, Hexaethyl ethylene glycol monododecyl ether, capric acid ammonium ammonium caprylate sucrose fatty ester, sorbitan fatty acid ester, or glycerine fatty acid ester cpds.
3,, it is characterized in that described semi-rigid macromole is oxyethane-styrene block copolymer according to the method for making of the parallel pencil nano zinc oxide crystal whisker described in the claim 1.
4, according to the method for making of the parallel pencil nano zinc oxide crystal whisker described in the claim 1, it is characterized in that 1), described in reaction template and buffering solution mix, be to mix by mass ratio 0.1%-4%.
5, according to the method for making of the parallel pencil nano zinc oxide crystal whisker described in the claim 1, it is characterized in that 2), described in the sodium hydroxide solution that adds, add-on is for adding weight ratio 0.3%-30%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317192C (en) * | 2005-07-25 | 2007-05-23 | 大连交通大学 | Method for preparing superfine zinc oxide and crystal whisker of zinc oxide |
| CN100435965C (en) * | 2006-11-28 | 2008-11-26 | 厦门大学 | Method for separating micro Nano material |
| CN102337581A (en) * | 2011-09-20 | 2012-02-01 | 清华大学 | Method for preparing zinc oxide crystal whisker by using recyclable solvent in low-temperature hydrothermal way |
| CN103159252A (en) * | 2013-03-01 | 2013-06-19 | 中国科学院深圳先进技术研究院 | Aluminum-doped zinc oxide electric conduction powder and preparation method thereof |
| CN104014802A (en) * | 2014-03-14 | 2014-09-03 | 常州大学 | Method for preparing single-crystal nano-particles through assistance of aerosol |
| CN105565367A (en) * | 2016-01-25 | 2016-05-11 | 延安大学 | Preparation method of nanometer zinc oxide powder material |
| CN105603527A (en) * | 2016-02-01 | 2016-05-25 | 山东科技大学 | Preparation method of zinc oxide nano monocrystals |
| CN106564930A (en) * | 2016-11-04 | 2017-04-19 | 龙岩学院 | Controlled synthesis method for micro-nano ZnO through morpholine ionic liquids |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086211C (en) * | 1999-04-22 | 2002-06-12 | 中国科学院金属研究所 | Process for preparing four-leg crystal whisker of zinc oxide |
| CN1079080C (en) * | 1999-09-08 | 2002-02-13 | 中国科学院广州化学研究所 | Preparation method of zinc oxide microparticles with specific form |
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2004
- 2004-06-25 CN CNB2004100277839A patent/CN1295384C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317192C (en) * | 2005-07-25 | 2007-05-23 | 大连交通大学 | Method for preparing superfine zinc oxide and crystal whisker of zinc oxide |
| CN100435965C (en) * | 2006-11-28 | 2008-11-26 | 厦门大学 | Method for separating micro Nano material |
| CN102337581A (en) * | 2011-09-20 | 2012-02-01 | 清华大学 | Method for preparing zinc oxide crystal whisker by using recyclable solvent in low-temperature hydrothermal way |
| CN102337581B (en) * | 2011-09-20 | 2014-05-07 | 清华大学 | Method for preparing zinc oxide crystal whisker by using recyclable solvent in low-temperature hydrothermal way |
| CN103159252A (en) * | 2013-03-01 | 2013-06-19 | 中国科学院深圳先进技术研究院 | Aluminum-doped zinc oxide electric conduction powder and preparation method thereof |
| CN103159252B (en) * | 2013-03-01 | 2014-10-08 | 中国科学院深圳先进技术研究院 | Aluminum-doped zinc oxide electric conduction powder and preparation method thereof |
| CN104014802A (en) * | 2014-03-14 | 2014-09-03 | 常州大学 | Method for preparing single-crystal nano-particles through assistance of aerosol |
| CN105565367A (en) * | 2016-01-25 | 2016-05-11 | 延安大学 | Preparation method of nanometer zinc oxide powder material |
| CN105603527A (en) * | 2016-02-01 | 2016-05-25 | 山东科技大学 | Preparation method of zinc oxide nano monocrystals |
| CN105603527B (en) * | 2016-02-01 | 2018-05-04 | 山东科技大学 | A kind of preparation method of zinc-oxide nano monocrystalline |
| CN106564930A (en) * | 2016-11-04 | 2017-04-19 | 龙岩学院 | Controlled synthesis method for micro-nano ZnO through morpholine ionic liquids |
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