CN101407328A - Method for preparing zinc aluminum oxide nano-powder - Google Patents

Method for preparing zinc aluminum oxide nano-powder Download PDF

Info

Publication number
CN101407328A
CN101407328A CNA2008102334482A CN200810233448A CN101407328A CN 101407328 A CN101407328 A CN 101407328A CN A2008102334482 A CNA2008102334482 A CN A2008102334482A CN 200810233448 A CN200810233448 A CN 200810233448A CN 101407328 A CN101407328 A CN 101407328A
Authority
CN
China
Prior art keywords
zinc
zao
solution
powder
nanometer powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2008102334482A
Other languages
Chinese (zh)
Other versions
CN101407328B (en
Inventor
宋宁
戴永年
杨斌
马文会
陈为亮
杜景红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN2008102334482A priority Critical patent/CN101407328B/en
Publication of CN101407328A publication Critical patent/CN101407328A/en
Application granted granted Critical
Publication of CN101407328B publication Critical patent/CN101407328B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to a method for preparing zinc-aluminium oxide (ZAO) nanometer powder, which takes zinc sulfate and aluminium sulphate as materials, ammonia, sodium hydroxide and ammonium carbonate as precipitators, absolute ethyl alcohol as a stabilizing agent and a dehydrating agent, and deionized water as a solvent, and carries out ultrasonic chemistry coprecipitation reaction at the temperature of 30-60 DEG C, and then carries out temperature-preservation ageing, centrifuge separating, washing, microwave drying and sintering to prepare the ZAO nanometer powder. The method utilizes ultrasonic cavitation reaction environment for controlling the conglobation of the ZAO nanometer powder, thus leading the coprecipitation reaction temperature to be lowered down and shortening the preparation period of the ZAO nanometer powder. The prepared ZAO nanometer powder has particle size of 15-30nm, specific surface area of 40-75m<2>/g, spherical particles, high product purity, even distribution, and good dispersion and photoelectric properties.

Description

A kind of method for preparing zinc aluminum oxide nano-powder
One, technical field:
The present invention relates to a kind of method for preparing zinc aluminum oxide nano-powder, belong to powder metallurgical technology.
Two, background technology
(Zinc Aluminum Oxide is ZnAl to Zinc-aluminium 2O 4Be called for short ZAO) be a kind of n type transparent conductive oxide material, because of having big carrier concentration and optical energy gap, and show good photoelectric characteristic, it is the base mateiral of modern optical electronic industry, more because the used starting material zinc-aluminium of ZAO film aboundresources, with low cost, nontoxic, thermostability and good chemical stability, being considered to has one of transparent conductive material of development potentiality at present most, be applied to solar cell, liquid-crystal display is in anti-electrostatic specific function window coating and other photoelectric device fields.
At present, the method for preparing nano-powder both at home and abroad is a lot, mainly contains homogeneous coprecipitation method, aqueous solution coprecipitation method, electrolytic process, sol-gel method, spray heating decomposition and mechanical milling method etc.In these methods, liquid phase method is that industrial preparation ultrafine powder is most widely used, its basic skills is to select one or more soluble metallic salts, press composition metering wiring solution-forming, make each element be the lewis' acid attitude, use a kind of precipitation agent again, with the desired substance precipitation from homogeneous solution, crystallize out, make ultrafine powder through process such as dehydration or heating.And the chemistry of aqueous solution coprecipitation method is noticeable a kind of method, this method adopts and adds precipitation agent from the outside, its technology is simple, the cycle short, easy to operate, less demanding to equipment, less investment, production cost is low, be suitable for scale operation and be widely adopted, but this method exists outstanding agglomeration in concrete preparation process, promptly nanoparticle is agglomerated into bigger particle again.For the preparation of n type transparent conductive material zinc aluminum oxide nano-powder, present known main preparation methods has homogeneous coprecipitation method, aqueous solution coprecipitation method, solid reaction process and sol-gel method etc.(chemistry and biotechnology .2006,23 (9): such as Xu Li 15-17.) with Zn (Ac) 2.2H 2O, Al (NO 3) 39H 2O, citric acid and ethanol etc. are raw material, and adopting sol-gel method to prepare median size is the linen nanometer ZAO composite granule of 22nm.(Journalof University of Science and Technology Beijing, 2006,13 (4): such as Wei Shao 346-349.) with Al (NO 3) 39H 2O, Zn (NO 3) 26H 2O and NH 4HCO 3Be raw material, adopting chemical coprecipitation to prepare median size at 800 ℃ of calcining 1.5h is that 21.3nm, specific surface area are 3.62m 2The ZAO nano-powder of/g.(Xi'an Institute of Technology's journal such as Liu Xiulan.2006,26 (1): be raw material with zinc acetate, aluminum nitrate, lanthanum nitrate hexahydrate, polyoxyethylene glycol, ammoniacal liquor and ethanol etc. 60-63.), the median size that adopts co-precipitation-supercritical fluid drying preparation to mix lanthanum is the ZAO nano-powder of 20nm.There is the Heating temperature height in these methods, and soaking time is long, and technological process is amplified difficult, and the energy consumption height needs to add practical problemss such as organic reagent.
Three, summary of the invention
The object of the present invention is to provide a kind of method for preparing zinc aluminum oxide nano-powder.With zinc sulfate (ZnSO 47H 2O), Tai-Ace S 150 (Al 2(SO 4) 318H 2O) be raw material, with ammoniacal liquor, sodium hydroxide (NaOH), volatile salt (NH 4) 2CO 3Be precipitation agent, with dehydrated alcohol (CH 3CH 2OH) be stablizer and dewatering agent, deionized water is a solvent, carries out the sonochemistry coprecipitation reaction under 30-60 ℃ temperature, the insulation ageing, and centrifugation, again through washing, microwave drying and calcining, the preparation zinc aluminum oxide nano-powder.Prepared zinc aluminum oxide nano-powder particle diameter is 15-30nm, and specific surface area is 40-75m 2/ g, powder granule are spherical, and the product purity height is evenly distributed, and dispersiveness and photoelectric properties are good.
The present invention finishes according to the following steps.
1) gets zinc sulfate and Tai-Ace S 150 and add deionized water respectively, be warming up to 30-55 ℃, continue stirring until zinc sulfate and Tai-Ace S 150 dissolves fully, make zinc sulfate and aluminum sulfate aqueous solution;
2) aqueous solution of gained is diluted to contains Zn 2+0.5-2.0mol/L solution of zinc sulfate and concentration be the alum liquor of 0.1-1.0mol/L, again two kinds of solution are pressed ZnO: Al 2O 3=95-97: the preparation of 3-5 weight percent mixes, the two stirring and evenly mixing 3-5min is placed in the ultrasonic water bath with thermostatic control and stirs, controlled temperature 30-60 ℃, simultaneously, successively dripping the NaOH solution of concentration 0.5-2.0mol/L and ammonia soln or concentration that concentration is 2.0-6.0mol/L is the (NH of 0.5-2.0mol/L 4) 2CO 3Solution to pH value is 8-11, and reaction aging 30-60min is then with centrifugation of 3000-4000r/min speed and repetitive scrubbing precipitation, up to the BaCl with 0.2mol/L 2There is not SO in the solution check washings 4 2-Till, will precipitate and use absolute ethanol washing 2-3 time, the precipitation that obtains is the Zinc-aluminium presoma;
3) the Zinc-aluminium presoma is put into the microwave oven drying, controlled temperature is 80-100 ℃, time 3-5min, and taking-up is finely ground to below the 30nm, places microwave oven to calcine again, and controlled temperature is 250-900 ℃, time 5-15min.Make zinc aluminum oxide nano-powder.
Compare advantage and positively effect that the present invention has with known technology
1) adopt sonochemistry co-precipitation-microwave drying calcining integrated process to prepare the ZAO nano-powder, strengthen co-precipitation chemical reaction or transmittance process by the effective integration of technology such as ultrasonic wave, microwave, one Technology is organically combined, the good product quality that makes is easy to realize suitability for industrialized production;
2) need not to add organic reagent and dispersion agent, utilize ultrasonic wave to have the reaction environment that ultrasonic cavitation produces, control the reunion of ZAO nano-powder, the coprecipitation reaction temperature is reduced, the reaction times shortens.Shortened the preparation cycle of ZAO nano-powder;
3) loose, the easy mill of powder structure is calcined in microwave drying, particle is little, rate of heating is fast.
Four, description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Five, embodiment
Embodiment 1: get zinc sulfate and Tai-Ace S 150 and add deionized water respectively, be warming up to 45 ℃, continue stirring until zinc sulfate and Tai-Ace S 150 dissolves fully, make the zinc-aluminium sulfate solution; Zinc sulfate solution is diluted to contains Zn 2+2.0mol/L solution to get 600ml and concentration be that the alum liquor 59ml of 0.5mol/L mixes, the two stirring and evenly mixing 3min is placed on 50kHz, stir in the ultrasonic water bath with thermostatic control of 100W, 50 ℃ of controlled temperature, NaOH solution to the pH value that drips concentration simultaneously and be 2.0mol/L is 9, is cooled to 35 ℃ and then drips (the NH that concentration is 2.0mol/L again 4) 2CO 3Solution to pH value is 10 to end, and ageing 30min is then with centrifugation of 4000r/min speed and repetitive scrubbing precipitation, up to the BaCl with 0.2mol/L 2There is not SO in the solution check washings 4 2-Till, to precipitate with absolute ethanol washing and precipitate 3 times, obtain basic carbonate zinc-aluminium presoma, presoma is put into the dry 5min of microwave oven (microwave power 750W, frequency 2450MHz), controlled temperature is 85 ℃, take out fine grinding, place microwave oven to calcine again, microwave power is 700W, and temperature is 500 ℃, time 13min makes product ZAO nano-powder.Its median size is 20nm, specific surface area 56.76m 2It is spherical that/g, powder granule all are, and is evenly distributed not have to reunite good dispersity.Its optical property shows as ultraviolet region (100-400nm) and has the intensive absorptivity, and visible region (400-800nm) has high perviousness, and infrared region (800-3500nm) has high reflectivity, and electric property shows as has low resistivity.
Embodiment 2: get zinc sulfate (ZnSO 47H 2O) and Tai-Ace S 150 (Al 2(SO 4) 318H 2O) add deionized water respectively, be warming up to 45 ℃, continue stirring until zinc sulfate and Tai-Ace S 150 dissolves fully, make the zinc-aluminium sulfate solution; Zinc sulfate solution is diluted to contains Zn 2+1.0mol/L dilute solution to get 1200ml and concentration be that the alum liquor 59ml of 0.5mol/L mixes, the two stirring and evenly mixing 3min is placed on 50kHz, stir in the ultrasonic water bath with thermostatic control of 100W, 55 ℃ of controlled temperature, NaOH solution to the pH value that drips concentration simultaneously and be 2.0mol/L is 9.5, and ammonia soln to the pH value that then drips concentration again and be 5.0mol/L is 10.5 to end ageing 50min, then with centrifugation of 3000r/min speed and repetitive scrubbing precipitation, up to BaCl with 0.2mol/L 2There is not SO in the solution check washings 4 2-Till, to precipitate with absolute ethanol washing and precipitate 3 times, obtain zinc-aluminium oxyhydroxide presoma, presoma is put into the dry 3min of microwave oven (microwave power 750W, frequency 2450MHz), controlled temperature is 100 ℃, take out fine grinding, place microwave oven to calcine again, microwave power is 700W, and temperature is 550 ℃, time 10min makes product ZAO nano-powder.Its median size is 15nm, specific surface area 74.37m 2It is spherical that/g, powder granule all are, and is evenly distributed not have to reunite good dispersity.Its optical property shows as ultraviolet region (100-400nm) and has the intensive absorptivity, and visible region (400-800nm) has high perviousness, and infrared region (800-3500nm) has high reflectivity, and electric property shows as has low resistivity.

Claims (1)

1, a kind of method for preparing zinc aluminum oxide nano-powder is characterized in that:
It is finished according to the following steps,
1) gets zinc sulfate and Tai-Ace S 150 and add deionized water respectively, be warming up to 30-55 ℃, continue stirring until zinc sulfate and Tai-Ace S 150 dissolves fully, make zinc sulfate and aluminum sulfate aqueous solution respectively;
2) aqueous solution of gained is diluted to contains Zn 2+0.5-2.0mol/L solution of zinc sulfate and concentration be the alum liquor of 0.1-1.0mol/L, again two kinds of solution are pressed ZnO: Al 2O 3The weight percent preparation of=95-97: 3-5 mixes, the two stirring and evenly mixing 3-5min is placed in the ultrasonic water bath with thermostatic control and stirs, controlled temperature 30-60 ℃, simultaneously, successively dripping the NaOH solution of concentration 0.5-2.0mol/L and ammonia soln or concentration that concentration is 2.0-6.0mol/L is the (NH of 0.5-2.0mol/L 4) 2CO 3Solution to pH value is 8-11, and reaction aging 30-60min is then with centrifugation of 3000-4000r/min speed and repetitive scrubbing precipitation, up to the BaCl with 0.2mol/L 2There is not SO in the solution check washings 4 2-Till, will precipitate and use absolute ethanol washing 2-3 time, the precipitation that obtains is the Zinc-aluminium presoma;
3) the Zinc-aluminium presoma is put into the microwave oven drying, controlled temperature is 80-100 ℃, time 3-5min, and taking-up is finely ground to below the 30nm, places microwave oven to calcine again, and controlled temperature is 250-900 ℃, time 5-15min.Make zinc aluminum oxide nano-powder.
CN2008102334482A 2008-10-16 2008-10-16 Method for preparing zinc aluminum oxide nano-powder Expired - Fee Related CN101407328B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008102334482A CN101407328B (en) 2008-10-16 2008-10-16 Method for preparing zinc aluminum oxide nano-powder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008102334482A CN101407328B (en) 2008-10-16 2008-10-16 Method for preparing zinc aluminum oxide nano-powder

Publications (2)

Publication Number Publication Date
CN101407328A true CN101407328A (en) 2009-04-15
CN101407328B CN101407328B (en) 2011-11-16

Family

ID=40570575

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008102334482A Expired - Fee Related CN101407328B (en) 2008-10-16 2008-10-16 Method for preparing zinc aluminum oxide nano-powder

Country Status (1)

Country Link
CN (1) CN101407328B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101560059B (en) * 2009-05-27 2012-09-12 中南大学 Aluminum-doped zinc oxide film coating and nano-rod array material as well as preparation method thereof
CN103482679A (en) * 2013-07-17 2014-01-01 南开大学 Aluminum zinc oxide (AZO) nano powder and preparation method of AZO sintered bodies
CN106315639A (en) * 2016-08-02 2017-01-11 上海理工大学 Ultrasonic preparation method of high-purity ZnAl2O4 nano particles
CN107170583A (en) * 2017-05-15 2017-09-15 北京化工大学 A kind of method and its application that the aluminium-doped zinc oxide for dye-sensitized solar cell anode is prepared based on hydrotalcite
CN110482592A (en) * 2019-08-19 2019-11-22 西北矿冶研究院 A kind of technique with steel-making cigarette ash preparing nano zinc oxide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101560059B (en) * 2009-05-27 2012-09-12 中南大学 Aluminum-doped zinc oxide film coating and nano-rod array material as well as preparation method thereof
CN103482679A (en) * 2013-07-17 2014-01-01 南开大学 Aluminum zinc oxide (AZO) nano powder and preparation method of AZO sintered bodies
CN106315639A (en) * 2016-08-02 2017-01-11 上海理工大学 Ultrasonic preparation method of high-purity ZnAl2O4 nano particles
CN107170583A (en) * 2017-05-15 2017-09-15 北京化工大学 A kind of method and its application that the aluminium-doped zinc oxide for dye-sensitized solar cell anode is prepared based on hydrotalcite
CN110482592A (en) * 2019-08-19 2019-11-22 西北矿冶研究院 A kind of technique with steel-making cigarette ash preparing nano zinc oxide

Also Published As

Publication number Publication date
CN101407328B (en) 2011-11-16

Similar Documents

Publication Publication Date Title
CN102616849B (en) Method for directly synthesizing M-phase vanadium dioxide nano particles by liquid phase method
CN101407328B (en) Method for preparing zinc aluminum oxide nano-powder
CN100593019C (en) Tin dioxide powder body doped with antimony and preparing method thereof
CN103318950B (en) Preparation method of indium tin oxide nano powder
CN103474245B (en) A kind of used by dye sensitization solar battery SnO 2 thin film electrode materials and its preparation method
CN102745737B (en) Synthesis method of basic zinc chloride monocrystal nanorods
CN103240073B (en) Zn&lt;2+&gt;-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof
CN105129861B (en) Preparation method for bismuth ferrite BiFeO3 nanosheet
CN102963930A (en) Method for preparing BiVO4 with photocatalytic performance under visible lights
CN104387807A (en) Preparation method of composite titanium dioxide
CN103588175A (en) Method for making nano-powder through ultrasonic atomization-microwave pyrolysis
CN105439555A (en) High-specific-surface-area nano barium stannate preparation method
CN104528799A (en) Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder
CN103435097B (en) Preparation method and application of nano zirconia
CN101665237B (en) Preparation method of spherical aluminum-doped zinc oxide nanometer powder
CN106082306A (en) A kind of aluminum-doped zinc oxide nanometer powder and microwave-assisted preparation method thereof and application
CN107803170A (en) A kind of preparation method of titanium dioxide/nickel oxide bivalve hollow ball
CN103531762B (en) A kind of preparation method of titania nanotube of aliovalent slaine doping
CN105731518B (en) Normal-temperature crystallization preparation method of octahedron cuprous oxide crystal
CN101850247A (en) Preparation method of composite oxide of cerium oxide and tin oxide
CN101214994B (en) Process for preparing nano powder of copper indium oxide
CN103523819A (en) Method for preparing monodisperse antimony-doped tin oxide nano-powder
CN102328094B (en) Method for preparing ultrafine silver powder with uniform particle size
CN102951685A (en) Preparation method of rod-like manganese tungstate microcrystal
CN104001493A (en) Preparation method of octahedral PbTiO3-TiO2 composite nanometer photocatalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20111116

Termination date: 20141016

EXPY Termination of patent right or utility model