CN1962447A - Method for preparing nanometer alumina powder - Google Patents
Method for preparing nanometer alumina powder Download PDFInfo
- Publication number
- CN1962447A CN1962447A CN 200510086825 CN200510086825A CN1962447A CN 1962447 A CN1962447 A CN 1962447A CN 200510086825 CN200510086825 CN 200510086825 CN 200510086825 A CN200510086825 A CN 200510086825A CN 1962447 A CN1962447 A CN 1962447A
- Authority
- CN
- China
- Prior art keywords
- solution
- ratio
- deionized water
- reaction
- alumina 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
Links
Abstract
The invention discloses a preparing method of alumina nanometer powder, which comprises the following steps: adding organic dispersant solution in the initial reacting solution; forming even aluminium dispersing reacting solution and alkaline dispersing reacting solution; adding aluminium dispersing reacting solution in the alkaline dispersing reacting solution; proceeding ultrasonic chemical reaction; obtaining slurry suspension; washing slurry suspension through ultrasound; drying; proceeding heat disposal to obtain the alumina nanometer powder.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer alumina powder.
Technical background
Nano alumina powder jointed is the particulate of a kind of grain size in 1nm～100nm scope.Aluminum oxide has high rigidity, high strength, advantage such as high temperature resistant, corrosion-resistant, and nano aluminium oxide has more excellent physicochemical property, thereby all be widely used in fields such as fine ceramics, matrix material, electronic industry, chemical metallurgies [119].Along with the continuous development of new and high technology, more and more higher to the requirement of material, as granularity super-refinement, uniform particlesization, the high purifying of component, preparation process low-temperature environment-friendlyization or the like.Nano material makes the material field enter a brand-new developmental stage with characteristics such as its surface effects, quantum size effect and volume effects.It is a lot of to prepare nano alumina powder jointed method, as using vaporization condensation process, chemical precipitation method, hydrothermal synthesis method, pyrolysis method, solid reaction process, the ultrasonic atomizatio method, the hypergravity carbon method, chemical Vapor deposition process, sol-gel method etc., wherein the sol-gel fado utilizes organic alkoxide of aluminium as raw material, add the paucidisperse agent under certain condition, make its hydrolysis, gelation, again through vacuum-drying, the control pyrolysis temperature, finally make nano alumina powder jointed, though this method can make nano-powder, but cost of material height and technical process are long, have environmental pollution in the binder removal process; Often there is the technological factor complexity in method and using vaporization condensation process, chemical Vapor deposition process and hydro-thermal be synthetic etc., the big and apparatus expensive of operation easier and be difficult for problems such as realization suitability for industrialized production; Chemical precipitation method often adopts ammonium salt as precipitation agent, obtains nano-powder through thermal treatment then, and material cost is lower, and required equipment is simple, and the preparation process processing parameter is easy to control, but has shortcomings such as the product size-grade distribution is wide.
Sonochemistry is a new subdiscipline of the synthetic and field of new material preparation of material organic chemistry in recent years.Its mainly be utilize ultrasonic wave by liquid medium to around propagate, when its energy is enough big, can produce the excusing from death cavitation phenomenon in the liquid medium, and generation speed is about the microjet with intense impact power of 110ms-1, while liquid is in the HF oscillation state.The ultrasonic cavitation effect can increase the surface-area of inhomogeneous reaction, upgrade reaction interface, improve the rate of mass transfer between the interface and promote the generation of cenotype, therefore ultrasonic wave is combined with chemical reaction and formed a new direction of high energy chemisty, and the application in the novel material technology of preparing is increasingly extensive.
The method that a kind of sol-gel method prepares superfine alumina powder is disclosed among the Chinese patent CN03147969.3.Mainly utilize aluminum chloride to make various crystal formation aluminum oxide through not exclusively pyrolysis, dissolving, secondary filter, colloidal sol, gel, drying, the superfine grinding of calcining phase inversion.Gained powder specific surface area is big, active high.Mainly the main alkali lye that adopts sprays in the aluminium colloidal sol fast in technological process, and gel is carried out spraying drying or condensation drying, calcines and obtains aluminum oxide, and whole technique process complexity, process cycle are long.
A kind of high-purity ultra-fine active alumina preparation method who is used for the support of the catalyst coated material is disclosed among the Chinese patent CN200410102804.9, it mainly is raw material with the industrial aluminium hydroxide, form Tai-Ace S 150 with sulfuric acid dissolution, add then and contain the bicarbonate of ammonia of template direction agent hydration carbon containing alumina precursor as neutralizing agent, by control synthesis temperature and pH value, obtain intermediate hydration carbon containing aluminum oxide, add composite thermal stabilizer La again, Ce, Mg salt, high-temperature calcination obtains the ultrafine high activity aluminum oxide, grain size is 0.1 μ m～0.2 μ m, gained powder crystal grain is bigger, and can think that from another angle the composite thermal stabilizer of introducing will be present in the finished product as impurity.
A kind of preparation method who prepares the nano aluminium oxide of hard aggregation-free is disclosed among the Chinese patent CN200410013256.2, the main nano alumina powder jointed granularity local distribution of concentration control that adopts reactant and additive, and dry gained powder is added in the solution of propyl carbinol and water, adopt azeotropic distn to remove propyl carbinol and the hard aggregation phenomenon of moisture behind the ultra-sonic dispersion, obtain nano alumina powder jointed through calcining with the elimination nanoparticle.Though this method can reduce the dispersiveness that hard aggregation improves powder to a certain extent, but owing to after dry link is finished, add propyl carbinol, at this moment synthetic chemistry reaction is finished substantially, carrying out ultra-sonic dispersion and component distillation again can only play a role in the part, therefore can not fundamentally solve the hard aggregation problem, have certain limitation.
Disclose a kind of production method of alumina in the U.S. Pat 2005238571, mainly adopting aluminum trihydrate is raw material, through different calcinating systems, gets rid of water of constitution and produces Calcined polishing aluminum oxide.A kind of method for preparing ball-aluminium oxide is disclosed among the Japanese Patent JP2001019425, employing aluminium hydroxide is raw material, make the water paste that concentration is 20mass%, it is alumina powder jointed that flame atomizing decomposes generation under the 773K condition, the alumina powder jointed good sphericity of this method gained, but granularity at several microns, is difficult to make nano-alumina powder usually.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of nanometer alumina powder,, carry out the sonochemistry prepared in reaction and go out dispersed better, active high nanometer alumina powder by in initial reactant, introducing organic dispersing agent; This method technology is simple, with short production cycle, and production cost is low, is easy to suitability for industrialized production.
The present invention comprises that at initial reaction liquid containing aluminium disperses reaction solution and alkalescence to disperse to add organic dispersing agent respectively in the reaction solution, and the surface that is coated on the nanoparticle of generation in reaction process stops further growing up of nanoparticle and reunites; Utilize the sonochemistry reaction synthetic simultaneously, the ultrasonic wave of on the one hand certain intensity can provide energy needed in the reaction process, the reaction particle disordered motion that causes of ultrasonic wave can be so that reaction system be more even on the other hand, thereby can prepare the tiny high-activity nano powder of epigranular.Simultaneously can adopt different thermal treatment temps to carry out calcination according to actual needs, just can obtain the globule size and the different nano-alumina powder that distributes.
The method that the present invention proposes to prepare nanometer alumina powder comprises following processing step:
(1) with poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) with 1～10: 1～10: 1～10 mol ratio is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.001mol/L～1mol/L;
(2) with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 0.1mol/L～10.0mol/L contain reactive aluminum solution;
(3) ratio according to volume ratio 1: 10～50 contains the dispersion liquid adding in the reactive aluminum solution, and powerful stirring forms and contains aluminium dispersing and mixing solution uniformly;
(4) with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) with 0.1～3.0: 10 mol ratio is dissolved in the deionized water dilution, and making volumetric molar concentration is the alkali reaction solution of 0.1～6.0mol/L;
(5) ratio according to volume ratio 1: 10～50 adds dispersion liquid in the alkali reaction solution, and powerful the stirring forms uniform alkaline dispersing and mixing solution;
(6) will be according to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 3～6 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 7～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 313K～373K, carry out sonochemistry reaction 30 minutes～180 minutes, obtain translucent pulpous state suspensoid;
(7) then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma;
(8) this presoma is put into loft drier, under the temperature condition of 333K～383K, dry, after grinding, sieving, obtain xerogel again;
(9) xerogel is put into the thermal treatment 3 hours under 773K～923K condition of globars High Temperature Furnaces Heating Apparatus, it is nano alumina powder jointed promptly to obtain target;
(10) chemical ingredients of usefulness XRF-1700 type Xray fluorescence spectrometer analysis of material;
(11) carry out phase composite of material thing and grain size analysis with Dutch PANalytical X ' the Pert Pro MPD of company type multi-functional X-ray diffractometer (CuK α line);
(12) with the microscopic appearance and the globule size of Japanese H-800 type transmission electron microscope observation powder.
Above-mentioned aluminum nitrate can be Tai-Ace S 150 or aluminum chloride replaces; Organic dispersing agent can be one or more in Terpineol 350, ammonium citrate, the soil temperature 80 etc.; Ammoniacal liquor in the alkali lye can be in sodium hydroxide, potassium hydroxide, salt of wormwood, the bicarbonate of ammonia one or more.
Alumina powder jointed for gained of the present invention, with the sample after the transmission electron microscope observing treatment of different temperature, find the appearance of the electron diffraction ring of powder after drying, show that the aluminum oxide nucleus just forms in sonochemistry reaction back, raise with thermal treatment temp, nucleus is grown up gradually and is become complete, and all powder granularities are even, and form is subsphaeroidal.
The present invention compared with prior art outstanding feature is:
(1) introduce organic dispersing agent in the initial reaction raw material, adopt sonochemical method synthetic simultaneously, disperse to be accompanied by entire reaction course, reaction system is even, and reaction process is easy to control; Reaction conditions is alkaline environment (pH=7～10), does not need strict control;
(2) the powder synthesis temperature is low, just forms through sonochemistry reaction nucleus; Can adjust the globule size and the distribution of powder by control thermal treatment temp and time;
(3) the inventive method has that technology is simple, with short production cycle, cost is low and be easy to advantages such as suitability for industrialized production.
Because the introducing of organic additive; in initial reaction stage; organism just can form the organism protective membrane on the surface of reaction product; hindered the gathering of reaction product; therefore organism follows preparation process all the time in the absorption on reaction product surface; thereby in dry and heat treatment process, hinder the reunion of nano-powder, finally obtain the high quality aluminum oxide nano-powder of good dispersity.Owing to adopt the synthetic existence of organic additive simultaneously of sonochemistry, make reaction be in a kind of state of comparatively homogeneous, so the gained powder granularity is even, it is subsphaeroidal that particle is.
According to method proposed by the invention, under organic dispersing agent and sonochemistry acting in conjunction condition, can obtain the good nanometer alumina powder of purity polymolecularity; The processing parameter variable range is wide; With short production cycle; The environmental pollution minor benefit is in environmental protection; Gained powder purity height, granularity are little, epigranular, be convenient to industrial amplification production.
Embodiment
Further specify the present invention with specific embodiment below.Raw materials used purity is chemical pure or more than the analytical pure in following examples.
Embodiment 1
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 1: 1: 1 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.1mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 1mol/L contain reactive aluminum solution; According to 1: 10 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 0.1: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 1mol/L; According to 1: 10 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 3 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 7～8, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 353K, carry out sonochemistry reaction 100 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 383K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 773K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows, powder purity height, and impurity does not detect; The powder thing is γ-Al mutually
2O
3The about 7nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result; Xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Embodiment 2
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 10: 1: 1 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.001mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 0.1mol/L contain reactive aluminum solution; According to 1: 50 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea (NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 3: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 0.1mol/L; According to 1: 50 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 6 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 9～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 313K, carry out sonochemistry reaction 30 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 333K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 773K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows, powder purity height, and impurity does not detect; Thing is γ-Al mutually
2O
3The about 6.7nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result; Xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Embodiment 3
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 10: 10: 1 is dissolved in the deionized water, makes the dispersion liquid that concentration is 1mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 10.0mol/L contain reactive aluminum solution; According to 1: 50 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 0.1: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 6.0mol/L; According to 1: 50 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 3 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 8～9, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 313K, carry out sonochemistry reaction 30 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 333K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 923K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows, powder purity height, and impurity does not detect; Thing is γ-Al mutually
2O
3The about 26nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result; Xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Embodiment 4
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 10: 1: 1 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.1mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 5.0mol/L contain reactive aluminum solution; According to 1: 50 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 2.5: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 5.0mol/L; According to 1: 50 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 5 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 8～9, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 373K, carry out sonochemistry reaction 120 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 363K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 823K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.To powder carry out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, the result shows, powder purity height, impurity does not detect; Thing is γ-Al mutually
2O
3The about 5.3nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result, and presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Embodiment 5
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 5: 2: 5 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.05mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 1.0mol/L contain reactive aluminum solution; According to 1: 30 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 3.0: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 3.0mol/L; According to 1: 10 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 3 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 9～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 313K, carry out sonochemistry reaction 30 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 363K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 773K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.To powder carry out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, the result shows, powder purity height, impurity does not detect; Thing is γ-Al mutually
2O
3The about 4.7nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result, and presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Embodiment 6
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 10: 1: 10 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.001mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 5mol/L contain reactive aluminum solution; According to 1: 30 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 1.5: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 5.0mol/L; According to 1: 20 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 4 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 9～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 353K, carry out sonochemistry reaction 90 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 383K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 823K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows, powder purity height, and impurity does not detect; Thing is γ-Al mutually
2O
3The about 17nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result; Xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Embodiment 7
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 7: 3: 5 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.5mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 3mol/L contain reactive aluminum solution; According to 1: 10 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 3: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 3mol/L; According to 1: 50 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 3 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 9～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 313K, carry out sonochemistry reaction 180 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 333K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 773K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows that xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature; Powder purity height, impurity does not detect; Thing is γ-Al mutually
2O
3The about 4.2nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result.
Embodiment 8
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 8: 2: 1 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.1mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 10.0mol/L contain reactive aluminum solution; According to 1: 50 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 3: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 6.0mol/L; According to 1: 50 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 6 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 9～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 373K, carry out sonochemistry reaction 30 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 383K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 773K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows that xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature; Powder purity height, impurity does not detect; Thing is γ-Al mutually
2O
3The about 9.7nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result.
Embodiment 9
At first ammonium citrate (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 10: 1: 5 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.1mol/L; Then with aluminum chloride (AlCl
3) be dissolved in make in the deionized water be prepared into concentration be 3mol/L contain reactive aluminum solution; According to 1: 50 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea (NH
2)
2CO) and sodium hydroxide (NaOH) be dissolved in the deionized water dilution with 0.1: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 3.0mol/L; According to 1: 50 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 6 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 9～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 373K, carry out sonochemistry reaction 30 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 333K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 873K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows that xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature; Powder purity height, impurity does not detect; Thing is γ-Al mutually
2O
3The about 7.1nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result.
Embodiment 10
At first ammonium citrate (C.R.), ammonium polyacrylate (C.R.) and polyoxyethylene glycol (C.R.) mol ratio with 10: 1: 5 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.1mol/L; Then with aluminum chloride (AlCl
3) be dissolved in make in the deionized water be prepared into concentration be 3mol/L contain reactive aluminum solution; According to 1: 30 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and sodium hydroxide (NaOH) be dissolved in the deionized water dilution with 3: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 3.0mol/L; According to 1: 30 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 5 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 9～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 373K, carry out sonochemistry reaction 120 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 333K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 873K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows that xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature; Powder purity height, impurity does not detect; Thing is γ-Al mutually
2O
3The about 8.5nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result.
Embodiment 11
At first poly amic acid (C.R.), tween 80 (C.R.) and polyvinyl alcohol (C.R.) mol ratio with 10: 1: 10 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.01mol/L; Then with aluminum nitrate (Al
2(SO
4)
3) be dissolved in make in the deionized water be prepared into concentration be 5mol/L contain reactive aluminum solution; According to 1: 30 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and bicarbonate of ammonia (NH
4HCO
3) be dissolved in the deionized water dilution with 1.5: 10 mol ratios, making volumetric molar concentration is the alkali reaction solution of 6.0mol/L; According to 1: 20 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 4 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 9～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 353K, carry out sonochemistry reaction 90 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 383K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 923K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows, powder purity height, and impurity does not detect; Thing is γ-Al mutually
2O
3The about 15nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result; Xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Embodiment 12
At first poly amic acid (C.R.), polyvinyl alcohol (C.R.) and Terpineol 350 (C.R.) mol ratio with 1: 1: 1 is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.1mol/L; Then with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 1mol/L contain reactive aluminum solution; According to 1: 10 ratio of volume ratio the dispersion liquid adding is contained in the reactive aluminum solution, powerful stirring forms and contains aluminium dispersing and mixing solution uniformly; Again with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) be dissolved in the deionized water dilution with 0.1: 10 mol ratio, making volumetric molar concentration is the alkali reaction solution of 1mol/L; According to 1: 50 ratio of volume ratio dispersion liquid is added in the alkali reaction solution then, the powerful stirring forms uniform alkaline dispersing and mixing solution; According to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 3 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 7～8, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 353K, carry out sonochemistry reaction 100 minutes, obtain translucent pulpous state suspensoid; Then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma; Presoma is put into loft drier, under the temperature condition of 383K, dry, after grinding, sieving, obtain xerogel again; Xerogel is put into the thermal treatment 3 hours under the 773K condition of globars High Temperature Furnaces Heating Apparatus, and it is nano alumina powder jointed promptly to obtain target.Xerogel and powder are carried out X-ray fluorescence spectra analysis, X-ray diffraction analysis and transmission electron microscope observing, and the result shows, powder purity height, and impurity does not detect; The powder thing is γ-Al mutually
2O
3The about 6.7nm of mean particle size; The microscopic appearance of powder is subsphaeroidal, epigranular, and globule size is consistent with the X-ray diffraction analysis result; Xerogel presents the electron diffraction ring, and this shows that the aluminum oxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Claims (2)
1, a kind of preparation method of nanometer alumina powder is characterized in that this method processing step is as follows:
(1) with poly amic acid (C.R.), polyvinyl alcohol (C.R.) and polyoxyethylene glycol (C.R.) with 1～10: 1～10: 1～10 mol ratio is dissolved in the deionized water, makes the dispersion liquid that concentration is 0.001mol/L～1mol/L;
(2) with aluminum nitrate (Al (NO
3)
36H
2O) be dissolved in make in the deionized water be prepared into concentration be 0.1mol/L～10.0mol/L contain reactive aluminum solution;
(3) ratio according to volume ratio 1: 10～50 contains the dispersion liquid adding in the reactive aluminum solution, and powerful stirring forms and contains aluminium dispersing and mixing solution uniformly;
(4) with urea ((NH
2)
2CO) and ammoniacal liquor (NH
3H
2O) with 0.1～3.0: 10 mol ratio is dissolved in the deionized water dilution, and making volumetric molar concentration is the alkali reaction solution of 0.1～6.0mol/L;
(5) ratio according to volume ratio 1: 10～50 adds dispersion liquid in the alkali reaction solution, and powerful the stirring forms uniform alkaline dispersing and mixing solution;
(6) will be according to [Al
3+] ion and [OH
-] the ionic mol ratio is 1: 3～6 ratio, to contain aluminium dispersing and mixing solution slowly adds in the alkaline dispersion soln, place reactor, add ammoniacal liquor conditioned reaction pH value of solution value simultaneously between 7～10, and this reaction vessel is placed on the ultrasonic generator, in the temperature range of 313K～373K, carry out sonochemistry reaction 30 minutes～180 minutes, obtain translucent pulpous state suspensoid;
(7) then the pulpous state suspensoid is added in the deionized water, continued ultra-sonic dispersion 10 minutes, repeat 3 times, add dehydrated alcohol ultrasonic cleaning 3 times afterwards again, obtain nano alumina powder jointed presoma;
(8) this presoma is put into loft drier, under the temperature condition of 333K～383K, dry, after grinding, sieving, obtain xerogel again;
(9) xerogel is put into the thermal treatment 3 hours under 773K～923K condition of globars High Temperature Furnaces Heating Apparatus, it is nano alumina powder jointed promptly to obtain target.
2, the preparation method of a kind of nanometer alumina powder according to claim 1 is characterized in that: aluminum nitrate can be Tai-Ace S 150 or aluminum chloride replaces; Organic additive can be one or more in Terpineol 350, ammonium citrate, the soil temperature 80 etc.; Ammoniacal liquor in the alkali lye can be in sodium hydroxide, potassium hydroxide, salt of wormwood, the bicarbonate of ammonia one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510086825A CN100577571C (en) | 2005-11-10 | 2005-11-10 | Method for preparing nanometer alumina powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510086825A CN100577571C (en) | 2005-11-10 | 2005-11-10 | Method for preparing nanometer alumina powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962447A true CN1962447A (en) | 2007-05-16 |
| CN100577571C CN100577571C (en) | 2010-01-06 |
Family
ID=38081702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510086825A Expired - Fee Related CN100577571C (en) | 2005-11-10 | 2005-11-10 | Method for preparing nanometer alumina powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100577571C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456568B (en) * | 2008-12-25 | 2010-12-15 | 中国计量学院 | Method for synthesizing nano alumina powder |
| CN101486479B (en) * | 2009-02-24 | 2011-04-27 | 中国石油化工集团公司 | Method for simply synthesizing gamma-Al2O3 and use thereof in ethanol dehydration |
| CN103204526A (en) * | 2012-01-15 | 2013-07-17 | 湖南晟通科技集团有限公司 | A method for preparing an alumina sol |
| CN109534379A (en) * | 2019-01-09 | 2019-03-29 | 上海大学(浙江·嘉兴)新兴产业研究院 | A kind of nano-level sphere γ-Al2O3The low cost preparation method of powder |
| CN111960809A (en) * | 2020-08-26 | 2020-11-20 | 武汉理工大学 | Spherical Al for photocuring 3D printing2O3Method for preparing powder |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW579372B (en) * | 1998-07-29 | 2004-03-11 | Sumitomo Chemical Co | Process for producing alumina sintered body |
| CN1348836A (en) * | 2001-08-04 | 2002-05-15 | 连加松 | Nano level alumina as catalyst carrier and its prepn |
| US20050238571A1 (en) * | 2004-04-26 | 2005-10-27 | Raahauge Benny E | Process and apparatus for the production of alumina |
| CN1273384C (en) * | 2004-06-02 | 2006-09-06 | 武汉大学 | Preparation of nano aluminum oxide without hard coacervation |
-
2005
- 2005-11-10 CN CN200510086825A patent/CN100577571C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456568B (en) * | 2008-12-25 | 2010-12-15 | 中国计量学院 | Method for synthesizing nano alumina powder |
| CN101486479B (en) * | 2009-02-24 | 2011-04-27 | 中国石油化工集团公司 | Method for simply synthesizing gamma-Al2O3 and use thereof in ethanol dehydration |
| CN103204526A (en) * | 2012-01-15 | 2013-07-17 | 湖南晟通科技集团有限公司 | A method for preparing an alumina sol |
| CN103204526B (en) * | 2012-01-15 | 2016-02-17 | 晟通科技集团有限公司 | A kind of method preparing alumina sol |
| CN109534379A (en) * | 2019-01-09 | 2019-03-29 | 上海大学(浙江·嘉兴)新兴产业研究院 | A kind of nano-level sphere γ-Al2O3The low cost preparation method of powder |
| CN111960809A (en) * | 2020-08-26 | 2020-11-20 | 武汉理工大学 | Spherical Al for photocuring 3D printing2O3Method for preparing powder |
| CN111960809B (en) * | 2020-08-26 | 2022-07-19 | 武汉理工大学 | Spherical Al for photocuring 3D printing2O3Method for preparing powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100577571C (en) | 2010-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Saedy et al. | Hydrothermal synthesis and physicochemical characterization of CuO/ZnO/Al2O3 nanopowder. Part I: Effect of crystallization time | |
| CN101318700B (en) | Bismuth vanadate powder and preparation method thereof | |
| CN100494066C (en) | Method for preparing ordered mesoporous aluminium oxide | |
| CN101234750B (en) | Method of preparing superfine micro-particle and nano granule | |
| CN104525245B (en) | Nanocrystalline accumulation meso-microporous ZSM-5 catalyst and preparation and application | |
| CN100577571C (en) | Method for preparing nanometer alumina powder | |
| CN104556176B (en) | A kind of preparation method of aluminum oxide nanoparticle | |
| CN102659149A (en) | Preparation method for monodisperse high-purity alpha-Al2O3 powder | |
| Pan et al. | Different copper oxide nanostructures: Synthesis, characterization, and application for C‐N cross‐coupling catalysis | |
| CN101293674A (en) | Method for preparing spindle shaped alpha-Fe2O3 powder | |
| CN102698785A (en) | Preparation method of diatomite-loaded nitrogen-doped nanometer TiO2 photocatalysis material | |
| CN104891542A (en) | Preparation method of ultrafine alpha-Al2O3 powder | |
| CN101704538A (en) | Hydrothermal method for preparing series of special-shaped graded pseudo-boehmite | |
| CN102531015A (en) | Method for preparing porous aluminum oxide superfine powder | |
| CN103950985B (en) | Nanometer bismuth tungstate of a kind of middle short side spherical structure and preparation method thereof | |
| Ray et al. | Non-isothermal decomposition kinetics of nano-scale CaCO3 as a function of particle size variation | |
| CN108217702A (en) | A kind of method that the synthesis and its pyrolysis of ultramicropore aluminum carbonate basic ammonium prepare aluminium oxide | |
| CN100368296C (en) | Method for preparing Nano alpht-A12O3 through catalyzing calcinations in low tempeature | |
| CN112403474B (en) | Load type CO2Hydrogenation catalyst and preparation method thereof | |
| CN111054425A (en) | hydrotalcite/MCM-41 mesoporous silicon composite solid base catalyst and in-situ preparation method and application thereof | |
| CN105727922B (en) | A kind of Li adulterates SrTiO3The preparation method and product of ten octahedron nanometer particles | |
| CN101376517A (en) | Method for preparing ordered mesoporous aluminum oxide in batch | |
| CN103449537A (en) | Preparation method of nickel molybdate powder material | |
| CN103449511A (en) | Strontium titanate submicron crystal and preparation method thereof | |
| RU2506228C1 (en) | Method of obtaining mesoporous nanosized cerium dioxide powder (versions) |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100106 Termination date: 20131110 |