CN103756397A - Zirconia composite nano-powder material and preparation method thereof - Google Patents
Zirconia composite nano-powder material and preparation method thereof Download PDFInfo
- Publication number
- CN103756397A CN103756397A CN201310740177.0A CN201310740177A CN103756397A CN 103756397 A CN103756397 A CN 103756397A CN 201310740177 A CN201310740177 A CN 201310740177A CN 103756397 A CN103756397 A CN 103756397A
- Authority
- CN
- China
- Prior art keywords
- preparation
- composite nano
- solution
- zirconia composite
- nano 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
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a zirconia composite nano-powder material and a preparation method thereof and belongs to the field of manufacturing for metal oxide ultra-microstructures. The zirconia composite nano-powder material is characterized by being composed of the following chemical constituents in percentage by mass: 70-90% of zirconium dioxide ZrO2 and 10-30% of titanium dioxide TiO. The preparation method comprises the following steps: continuously spraying atomized ammonium bicarbonate aqueous solution in the absolute ethyl alcohol solution of zirconium oxychloride ZrOCl2.8H2O and butyl titanate which are pre-prepared respectively and uniformly mixed, while stirring, to react to prepare a mixed sol, using butanol as an azeotropy agent for the mixed sol, and then calcining the dry material after butanol azeotropy and dehydration to prepare the zirconia composite nano-powder material; the zirconia composite nano-powder material has a particle size of 30-50 nm and a specific surface area of not less than 30 m<2>/g. A zirconia composite nano-powder material which is high in activity, and good in dispersity and stability is provided; the zirconia composite nano-powder material is suitable for heat-isolating coatings for building outer walls, transparent heat-isolating coatings for vehicle windows and building glass, and transparent heat-isolating conductive coatings, as well as also suitable for being used for preparing catalysts and catalyst carriers, and used as biological materials for dentistry and orthopaedics.
Description
Technical field
The present invention is a kind of Zirconia composite nano powder body material and preparation method thereof.Belong to the manufacture of metal oxide ultrastructure.
Background technology
Nanoparticle is the molecule less by number or the aggregate of atomic building, and it is between macroscopic material and microcosmic atom, molecule, and activity is quite high, in thermodynamic (al) unsteady state.
Nano-powder material refers to powder or the particle of particle diameter at 1～100nm.Because its particle diameter is little, specific surface area is large, interface is many, thereby shows the different special physicochemical property of many and conventional powder, i.e. surface effects, small-size effect, quantum size effect, macro quanta tunnel effect etc.Just because of these special character of nanoparticle, give the many macroscopic material of nanoparticle incomparable premium properties.For example: change the fusing point of metal, improve the chemical reactivity of material, improve catalyst activity, improve intensity, hardness, the toughness of organic synthesis material; Greatly improve coating hardness, toughness, resistance to wear, scrape resistant, heat-insulation and heat-preservation, corrosion-resistant, high temperature resistant, antibacterial etc. being on good terms; Change the sound of metal, optical, electrical, thermal and magnetic, mechanical property etc.Therefore nano material is in the concrete wide DEVELOPMENT PROSPECT of the numerous areas such as electronics, chemical industry, environmental protection, biology, medicine, pottery, catalysis, the energy.
Zirconium white has excellent physics, chemical property, is the best stupalith of current toughness intensity.Be desirable wear-resistant, high temperature resistant, corrosion-resistant, biologically inert is good, high-intensity structural ceramic material.
Nano zircite not only has all good characteristics of zirconium white, and has increased many excellent characteristics of nanoparticle.After nano zircite and other materials Surface Contact, be no longer only the absorption of common powder body material, but mutually combine and be integrated by part chemical bond, there is high stability.For the preparation of various coating, can significantly improve the water-fastness of coated material, wear-resistant, scrape resistant, the performance index such as corrosion-resistant, fire-resistant.
But nano zircite is separately for the manufacture of thermal insulating coating, desirable not enough at reflectivity and the infrared radiation rate aspect of performance of the desired high visible ray of activity, lagging material of nanoparticle, near infrared light.
In addition, dispersion, the stability of raising nano zirconium oxide powder material are problems anxious to be resolved.
It is to be solved that nano zircite product of the prior art exists following technical problem to have:
1. nano zirconium oxide powder material, is difficult to obtain desirable dispersion state, has caused great puzzlement to the application of material, and the normal performance that becomes nano zirconium oxide powder material excellent properties is provided with technology barrier.
2. nm-class powder of zirconium oxide is because particle diameter is little, and specific surface energy is high, in coating be very easy to reunite or by other fillers, pigment embedding.Be difficult to make high-performance nano zirconium white-titanium oxide coating, make it in coating, still can keep nano level state.
3. good dispersity, the zirconium white titanium oxide composite nano powder material product of excellent performance there is not yet.
Summary of the invention
The object of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of active high, the Zirconia composite nano powder body material of dispersion, good stability.
The present invention also aims to provide a kind of active high, disperse, good stability the preparation method of Zirconia composite nano powder body material.
Object of the present invention can reach by following measure:
Zirconia composite nano powder body material of the present invention, is characterized in that the chemical constitution being calculated in mass percent is as follows:
Zirconium dioxide ZrO
270～90
Titanium dioxide TiO
210～30
Preparation method is as follows:
The ammonium bicarbonate aqueous solution of atomization is sprayed into the preparation respectively in advance under stirring, the basic zirconium chloride ZrOCl then mixing continuously
2.8H
2in the ethanol solution of O and butyl (tetra) titanate, mixed sols is prepared in reaction, and it is entrainer that mixed sols adopts butanols, after butanols azeotropic dehydration, and the siccative obtaining, then calcining makes;
The Zirconia composite nano powder body material making, reaches following technical indicator:
Particle diameter nm 30～50
Specific surface area m
2/ g>=30.
Contriver finds, zirconium dioxide is mutually compound with titanium dioxide, particularly zirconium white-the titanium oxide composite material of nanometer, with independent Zirconium powder material to relatively, there is higher activity, there is reflectivity and the infrared radiation rate performance of the desired high visible ray of lagging material, near infrared light.
Nano titanium oxide has retained TiO
2intrinsic stable chemical nature, resistance to oxidation, fusing point is high, high temperature resistant, has very high specific refraction, thereby possesses very high visible ray and near infrared light reflection potential.Many special propertys such as nano titanium oxide also has safety non-toxic, long service life and distinctive specific surface area is large, photocatalysis performance good, magnetic is strong, surfactivity is large, good dispersity, thermal conduction are strong.Nano titanium oxide is under the condition of Guang Heshui, electronics in its valence band is excited to conduction band, in valence band, produce hole, unbound electron-hole is to making oxygen and water activation, generation has very active oxygen and the OH free radical of high reaction activity, and airborne obnoxious flavour (oxynitride, sulfurous gas, formaldehyde, benzene, ammonia, acetone etc.) and bacterium are had to very strong Degradation.Nano titanium oxide, under illumination condition, can form equally distributed hydrophilic microcell (nanoscale) on its surface, can, by isolated to oiliness pollutent and surface, be difficult for gathering on surface, very easily cleans, and when stopping illumination, again recovers hydrophobic structure.Nano titanium oxide is a kind of well ultraviolet screening agent, can increase substantially the ageing-resistant performance of coating.
The preparation method of Zirconia composite nano powder of the present invention adopts chemical liquid phase reaction to prepare composite nano-powder.Liquid phase method is prepared in nano-powder process in the aqueous solution, after primary particle precipitation forms, the mutual collision opportunity of primary sedimentation particle is very large, these particles mutually collide and are coalescent, form offspring, the offspring of formation equally also can collide and coalescent mutually, forms larger particle, precipitation particles is reunited and become large, affected final powder granularity.While there is hydrolysis or precipitin reaction in liquid phase method in alcohol-aqueous solution, because the surface tension of alcohol-aqueous solution is less than water, can reduce the reunion of precipitation particles, also be conducive to improve the dispersiveness of precipitation particles, especially adopt the mode of spray atomization to spray into the aqueous solution, originally in alcohol-water, the ratio of alcohol is very large, can farthest reduce the reunion of precipitation particles, dispersed raising.In addition, appropriate polyoxyethylene glycol dispersion agent adds the dispersiveness that is also conducive to reduce the reunion of precipitation particles and improves precipitation particles.
When reaction, ammonium bicarbonate aqueous solution adopts the mode of spray atomization to spray to basic zirconium chloride under whipped state and the dehydrated alcohol mixing solutions of butyl (tetra) titanate, by controlling temperature of reaction and final pH value, the main colloidal sol that generates three kinds of forms in reaction process, one is that partial hydrolysis generation Zr (OH) occurs basic zirconium chloride in alcohol-aqueous solution
4colloidal sol, another kind is that basic zirconium chloride and bicarbonate of ammonia reaction generate basic carbonate oxygen zirconium colloidal sol, the third is that hydrolysis generation Ti (OH) occurs butyl (tetra) titanate
4colloidal sol adopts butanols to carry out, after component distillation, at the temperature of 600～800 ℃, calcining after ageing, filtration, washing, obtains zirconium white-titanium oxide composite nano powder.
When preparing nano-powder calcining, wet chemistry method easily forms hard aggregation, the major cause forming is that presoma surface adsorption has a large amount of planar water, coordinated water ,-0H base etc., if convection drying dehydration, the kapillary stress producing in water evaporative process can cause in gel particle closely close, and produce hard aggregation by dehydrating condensation between particle surface hydroxyl (OH), thereby have a strong impact on the performance of precursor powder.Azeotropic distillation technology removes the water in gel, its action principle is: wet gel and a kind of organic solvent are mixed to rear distillation, when organic solvent and water vapor pressure sum equal normal atmosphere. biphasic mixture starts to form azeotropic, and along with the carrying out of distillation, in mixture, the content of water constantly reduces; Along with the variation of this component of mixture, the azeotropic point of mixture constantly raises, until the boiling point of organic solvent.By component distillation, can make the water molecules wrapping up in gel precipitation be removed to greatest extent with the form of azeotrope, thereby prevent the formation of hard aggregation, guarantee the high dispersion of powder body material presoma.
Contriver passes through the preferred design for composite nano powder material chemical composition, and adopts rational preparation method, has completed task of the present invention.
Object of the present invention can also reach by following measure:
Zirconia composite nano powder body material of the present invention, in described preparation method, contains dispersion agent polyoxyethylene glycol in the ethanol solution of basic zirconium chloride, its molecular weight is 2000～6000.It is preferred technical scheme.
Zirconia composite nano powder body material of the present invention, in described preparation method, contains trolamine in the ethanol solution of butyl (tetra) titanate.It is preferred technical scheme.The trolamine adding plays the effect of hydrolysis inhibitor, avoids basic zirconium chloride also there is no the too fast hydrolysis of butyl (tetra) titanate in abundant situation of reacting.
Zirconia composite nano powder body material of the present invention, is characterized in that in described preparation method, entrainer butanols is propyl carbinol or isopropylcarbinol.Be preferred technical scheme, adopting isopropylcarbinol is optimum technical scheme as entrainer.Because the boiling point of the binary azeotrope of isopropylcarbinol and water is lower than the boiling point of the binary azeotrope of propyl carbinol and water, the boiling point of isopropylcarbinol is closer to the boiling point of water, and in the binary azeotrope of isopropylcarbinol and water the content of water apparently higher than the content of moisture in the binary azeotrope of propyl carbinol and water.
Introduce a kind of preparation method of Zirconia composite nano powder body material of the present invention below, it is characterized in that comprising following operation steps:
1.. solution A is basic zirconium chloride ZrOCl
2.8H
2the preparation of O ethanol solution
The ethanol solution of the basic zirconium chloride that first compound concentration is 0.5～1.5mol/L, then, to 0.5～2.0% the polyoxyethylene glycol that adds solution total mass in prepared solution, stirs;
2.. solution B is the preparation of the ethanol solution of butyl (tetra) titanate
The ethanol solution of the butyl (tetra) titanate that first compound concentration is 0.3～1.0mol/L, then, to 0.5～1.0% the trolamine that adds solution total mass in prepared solution, stirs;
3.. the ammonium bicarbonate aqueous solution that preparation volumetric molar concentration is 1.0～3.0mol/L;
4.. the preparation of mixed sols
First, two kinds of solution of solution B that 2. solution A of under agitation condition, 1. step being prepared and step are prepared mix, and the two volume ratio is A:B=0.75～3.0;
Then, after the ammonium bicarbonate aqueous solution spray atomization that 3. step is prepared, spray to the AB mixing solutions under whipped state; Control temperature of reaction at 40～70 ℃, spraying, stirring reaction to pH value are 7～8 o'clock, stop adding ammonium bicarbonate aqueous solution, continue to stir 5～8h, ageing 12～15h, and filtration, washing, obtain mixed sols;
5.. dehydrate
The mixed sols that 4. step is prepared, employing butanols is entrainer, by component distillation, dewaters, and removes the moisture in mixed sols, steams butanols, obtains siccative;
6.. calcining
Siccative after 5. step dehydrates, at the temperature lower calcination of 600～800 ℃, calcination time is 3～5 hours, obtains Zirconia composite nano powder body material product.
The spraying feed rate of the ammonium bicarbonate aqueous solution of above-mentioned preparation method's step described in is 4. average every square centimeter of 1～3ml/min.It is preferred technical scheme.
The processing condition of the component distillation dehydration of above-mentioned preparation method's step described in are 5. that to adopt propyl carbinol be entrainer, azeotropic point is 93 ℃, dewater complete, the temperature of system is elevated to 118 ℃ of the boiling points of propyl carbinol, at this temperature, steam propyl carbinol, be then controlled at 115-120 ℃ and dry 1～2 hour, obtain loose shape white siccative.It is preferred technical scheme.
The processing condition of the component distillation dehydration of above-mentioned preparation method's step described in are 5. that to adopt isopropylcarbinol be entrainer, azeotropic point is 89.9 ℃, dewater complete, the temperature of system is elevated to 108.4 ℃ of the boiling points of isopropylcarbinol, at this temperature, steam isopropylcarbinol, be then controlled at 115-120 ℃ and dry 1～2 hour, obtain loose shape white siccative.It is most preferred technical scheme.
5. above-mentioned preparation method's step dehydrates technological process carries out under vacuum condition, and vacuum degree control is at-0.01～-0.1Mpa.Can shorten the time of dehydrating, save energy, reduces production costs.It is preferred technical scheme.
The application of Zirconia composite nano powder body material of the present invention, is characterized in that being applicable to external wall heat insulating coat, the transparent heat-insulated coating of vehicle window, building glass, heat-insulation transparent conductive coating; Also be applicable to the preparation of catalyzer, support of the catalyst and be used as gear division, orthopedics biological material.
Zirconia composite nano powder body material of the present invention and preparation method thereof, has following positively effect compared to existing technology:
1. provide a kind of activity high, the Zirconia composite nano powder body material of dispersion, good stability.
2. provide a kind of activity high, disperse, good stability the preparation method of Zirconia composite nano powder body material.
3. adopt liquid phase method, by reacting spraying to after ammonium bicarbonate aqueous solution spray atomization in basic zirconium chloride under whipped state and butyl (tetra) titanate dehydrated alcohol mixing solutions, three kinds of main colloidal sols that form in reaction mix by stirring mutually, by alcohol-aqueous systems and the polyoxyethylene glycol dispersion agent that adds, can farthest reduce the reunion between particle; For the product that makes good dispersity has been made contribution.
4. utilize azeotropic distillation technology, effectively remove moisture, in follow-up calcination process basically eliminate the hard aggregation phenomenon of nanoparticle, prepare zirconium white-titanium oxide composite nano powder with good distribution performance, diameter of particle is 30～50nm, specific surface area >=30m2/g.
5. take zirconium white-titanium oxide composite nano powder as active ingredient, the composite granule of preparation integrates the performance of nano zirconium dioxide and nano titanium oxide.Greatly improved the over-all properties of powder body material.
6. Zirconia composite nano powder body material of the present invention, has successfully solved the not good difficult problem of dispersiveness of powder body material, is specially adapted to external wall heat insulating coat, the transparent heat-insulated coating of vehicle window, building glass, heat-insulation transparent conductive coating; Also be applicable to the preparation of catalyzer, support of the catalyst and be used as gear division, orthopedics biological material.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the composite nano powder prepared of the present invention
Fig. 2 is the TEM figure of embodiment 1 composite nano powder
Fig. 3 is the TEM figure of embodiment 2 composite nano powders
Fig. 4 is the TEM figure of embodiment 3 composite nano powders
Fig. 5 is the TEM figure of embodiment 4 composite nano powders
Fig. 6 is the TEM figure of embodiment 5 composite nano powders
Fig. 7 is the TEM figure of embodiment 6 composite nano powders
Embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
According to following operation steps, prepare Zirconia composite nano powder body material of the present invention
1.. solution A is basic zirconium chloride ZrOCl
2.8H
2the preparation of O ethanol solution
2000 milliliters of the ethanol solutions of the basic zirconium chloride that first compound concentration is 0.5mol/L, are then 12 grams of 2000 polyoxyethylene glycol to adding molecular weight in prepared solution, stir;
2.. solution B is the preparation of the ethanol solution of butyl (tetra) titanate
2325 milliliters of the ethanol solutions of the butyl (tetra) titanate that first compound concentration is 0.3mol/L then add 13 grams of trolamines in prepared solution, stir;
3.. the ammonium bicarbonate aqueous solution that preparation volumetric molar concentration is 2.0mol/L;
4.. the preparation of mixed sols
First, two kinds of solution of solution B that 2. solution A of under agitation condition, 1. step being prepared and step are prepared mix;
Then, after the ammonium bicarbonate aqueous solution spray atomization that 3. step is prepared, spray to the AB mixing solutions under whipped state; Control temperature of reaction at 50 ℃, spraying, stirring reaction to pH value are 7～8 o'clock, stop adding ammonium bicarbonate aqueous solution, continue to stir 5h, ageing 12h, and filtration, washing, obtain mixed sols;
5.. dehydrate
The mixed sols that 4. step is prepared, employing propyl carbinol is entrainer, azeotropic point is 93 ℃, dewater complete, the temperature of system is elevated to 118 ℃ of the boiling points of propyl carbinol, at this temperature, steam propyl carbinol, be then controlled at 115-120 ℃ and dry 1 hour, obtain loose shape white siccative.
6.. calcining
Siccative after 5. step dehydrates, at the temperature lower calcination of 600 ℃, calcination time is 5 hours, obtains Zirconia composite nano powder body material product.Its median size is 30nm after testing, specific surface area 45m
2/ g, wherein zirconium white 71%, titanium oxide 29%.
Embodiment 2
According to the method for embodiment 1 and step, concrete formula, processing condition are as follows:
The ethanol solution of the basic zirconium chloride of preparation 2000ml1.5mol/L, and add 21g polyoxyethylene glycol, stir; With dehydrated alcohol, be that solvent is prepared 1265ml0.5mol/L butyl (tetra) titanate solution, and add 11g trolamine in solution, stir; The ammonium bicarbonate aqueous solution that preparation volumetric molar concentration is 1.0mol/L; Under the condition stirring, two kinds of solution of a preparing, b are mixed, ammonium bicarbonate aqueous solution is sprayed to a, the b mixing solutions under whipped state after by spray atomization, temperature of reaction is 70 ℃, being sprayed to final pH value and being 7～8 stops adding, continue to stir 7h, ageing 15h, filters, washs; Dehydrating operation employing isopropylcarbinol is entrainer, and azeotropic point is 89.9 ℃, dewaters complete, the temperature of system is elevated to 108.4 ℃ of the boiling points of isopropylcarbinol, at this temperature, steams isopropylcarbinol, then be controlled at 115-120 ℃ and dry 2 hours, obtain loose shape white siccative.
Above-mentioned siccative is calcined at the temperature of 800 ℃, and calcination time is 3 hours, obtains zirconium white-titanium oxide composite nano powder.
Zirconium white-titanium oxide composite nano powder of preparing after testing its median size is 39nm, specific surface area 31m2/g, wherein zirconium white 89%, titanium oxide 11%.
Embodiment 3
According to the method for embodiment 1 and step, concrete formula, processing condition are as follows:
The ethanol solution of the basic zirconium chloride of preparation 2000ml1.0mol/L, and add 35g polyoxyethylene glycol, stir; With dehydrated alcohol, be that solvent is prepared 1350ml0.8mol/L butyl (tetra) titanate solution, and add 8g trolamine in solution, stir; The ammonium bicarbonate aqueous solution that preparation volumetric molar concentration is 3.0mol/L, temperature of reaction is 40 ℃, under the condition stirring, a preparing, two kinds of solution of b are mixed, ammonium bicarbonate aqueous solution is sprayed to a, the b mixing solutions under whipped state after by spray atomization, temperature of reaction is 60 ℃, is sprayed to final pH value and is 7～8 and stop adding, and continues to stir 8h, ageing 13h, filters, washs; Dehydrating operation employing propyl carbinol is entrainer, and azeotropic point is 93 ℃, dewaters complete, the temperature of system is elevated to 118 ℃ of the boiling points of propyl carbinol, at this temperature, steams propyl carbinol, then be controlled at 115-120 ℃ and dry 1 hour, obtain loose shape white siccative.
Above-mentioned siccative is calcined at the temperature of 700 ℃, and calcination time is 4 hours, obtains zirconium white-titanium oxide composite nano powder.
Zirconium white-titanium oxide composite nano powder of preparing after testing its median size is 46nm, specific surface area 33m2/g, wherein zirconium white 80%, titanium oxide 20%.
Embodiment 4
According to the method for embodiment 1 and step, concrete formula, processing condition are as follows:
The ethanol solution of the basic zirconium chloride of preparation 2000ml0.8mol/L, and add 38g polyoxyethylene glycol, stir; With dehydrated alcohol, be that solvent is prepared 665ml1.0mol/L butyl (tetra) titanate solution, and add 7g trolamine in solution, stir; The ammonium bicarbonate aqueous solution that preparation volumetric molar concentration is 1.5mol/L; Under the condition stirring, two kinds of solution of a preparing, b are mixed, ammonium bicarbonate aqueous solution is sprayed to a, the b mixing solutions under whipped state after by spray atomization, temperature of reaction is 55 ℃, being sprayed to final pH value and being 7～8 stops adding, continue to stir 6h, ageing 13h, filters, washs; Dehydrating operation employing isopropylcarbinol is entrainer, and azeotropic point is 89.9 ℃, dewaters complete, the temperature of system is elevated to 108.4 ℃ of the boiling points of isopropylcarbinol, at this temperature, steam isopropylcarbinol, be then controlled at 115-120 ℃ and dry 1 hour, obtain loose shape white siccative.
Above-mentioned siccative is calcined at the temperature of 700 ℃, and calcination time is 5 hours, obtains zirconium white-titanium oxide composite nano powder.
Zirconium white-titanium oxide composite nano powder of preparing after testing its median size is 37nm, specific surface area 33m2/g, wherein zirconium white 84%, titanium oxide 16%.
Embodiment 5
The ethanol solution of the basic zirconium chloride of preparation 2000ml1.2mol/L, and add 42g polyoxyethylene glycol, stir; With dehydrated alcohol, be that solvent is prepared 2650ml0.5mol/L butyl (tetra) titanate solution, and add 15g trolamine in solution, stir; The ammonium bicarbonate aqueous solution that preparation volumetric molar concentration is 2.5mol/L; Under the condition stirring, two kinds of solution of a preparing, b are mixed, ammonium bicarbonate aqueous solution is sprayed to a, the b mixing solutions under whipped state after by spray atomization, temperature of reaction is 60 ℃, being sprayed to final pH value and being 7～8 stops adding, continue to stir 8h, ageing 15h, filters, washs; Dehydrating operation, to adopt propyl carbinol be entrainer, and azeotropic point is 93 ℃, dewaters complete, and the temperature of system is elevated to 118 ℃ of the boiling points of propyl carbinol, at this temperature, steams propyl carbinol, is then controlled at 115-120 ℃ and dries 2 hours, obtains loose shape white siccative.
Above-mentioned siccative is calcined at the temperature of 800 ℃, and calcination time is 3 hours, obtains zirconium white-titanium oxide composite nano powder.
Zirconium white-titanium oxide composite nano powder of preparing after testing its median size is 45nm, specific surface area 30m2/g, wherein zirconium white 74%, titanium oxide 26%.
Embodiment 6
The ethanol solution of the basic zirconium chloride of preparation 2000ml0.6mol/L, and add 16g polyoxyethylene glycol, stir; With dehydrated alcohol, be that solvent is prepared 865ml0.6mol/L butyl (tetra) titanate solution, and add 7g trolamine in solution, stir; The ammonium bicarbonate aqueous solution that preparation volumetric molar concentration is 1.8mol/L; Under the condition stirring, two kinds of solution of a preparing, b are mixed, ammonium bicarbonate aqueous solution is sprayed to a, the b mixing solutions under whipped state after by spray atomization, temperature of reaction is 50 ℃, being sprayed to final pH value and being 7～8 stops adding, continue to stir 6h, ageing 15h, filters, washs; Dehydrating operation employing isopropylcarbinol is entrainer, and azeotropic point is 89.9 ℃, dewaters complete, the temperature of system is elevated to 108.4 ℃ of the boiling points of isopropylcarbinol, at this temperature, steams isopropylcarbinol, then be controlled at 115-120 ℃ and dry 2 hours, obtain loose shape white siccative.
Above-mentioned siccative is calcined at the temperature of 700 ℃, and calcination time is 5 hours, obtains zirconium white-titanium oxide composite nano powder.
Zirconium white-titanium oxide composite nano powder of preparing after testing its median size is 42nm, specific surface area 31m2/g, wherein zirconium white 80%, titanium oxide 20%.
Claims (11)
1. a Zirconia composite nano powder body material, is characterized in that the chemical constitution being calculated in mass percent is as follows:
Zirconium dioxide ZrO
270～90
Titanium dioxide TiO
210～30
Preparation method is as follows:
The ammonium bicarbonate aqueous solution of atomization is sprayed into the preparation respectively in advance under stirring, the basic zirconium chloride ZrOCl then mixing continuously
2.8H
2in the ethanol solution of O and butyl (tetra) titanate, mixed sols is prepared in reaction, and it is entrainer that mixed sols adopts butanols, after butanols azeotropic dehydration, and the siccative obtaining, then calcining makes;
The Zirconia composite nano powder body material making, reaches following technical indicator:
Particle diameter nm 30～50
Specific surface area m
2/ g>=30.
2. according to the Zirconia composite nano powder body material of claim 1, it is characterized in that, in described preparation method, containing dispersion agent polyoxyethylene glycol in the ethanol solution of basic zirconium chloride, its molecular weight is 2000～6000.
3. according to the Zirconia composite nano powder body material of claim 1, it is characterized in that, in described preparation method, in the ethanol solution of butyl (tetra) titanate, containing trolamine.
4. according to the Zirconia composite nano powder body material of claim 1, it is characterized in that in described preparation method, entrainer butanols is propyl carbinol or isopropylcarbinol.
5. according to the Zirconia composite nano powder body material of claim 1, it is characterized in that, in described preparation method, entrainer butanols is isopropylcarbinol.
6. a preparation method for the Zirconia composite nano powder body material of claim 1, is characterized in that comprising following operation steps:
1.. solution A is basic zirconium chloride ZrOCl
2.8H
2the preparation of O ethanol solution
The ethanol solution of the basic zirconium chloride that first compound concentration is 0.5～1.5mol/L, then, to 0.5～2.0% the polyoxyethylene glycol that adds solution total mass in prepared solution, stirs;
2.. solution B is the preparation of the ethanol solution of butyl (tetra) titanate
The ethanol solution of the butyl (tetra) titanate that first compound concentration is 0.3～1.0mol/L, then, to 0.5～1.0% the trolamine that adds solution total mass in prepared solution, stirs;
3.. the ammonium bicarbonate aqueous solution that preparation volumetric molar concentration is 1.0～3.0mol/L;
4.. the preparation of mixed sols
First, two kinds of solution of solution B that 2. solution A of under agitation condition, 1. step being prepared and step are prepared mix, and the two volume ratio is A:B=0.75～3.0;
Then, after the ammonium bicarbonate aqueous solution spray atomization that 3. step is prepared, spray to the AB mixing solutions under whipped state; Control temperature of reaction at 40～70 ℃, spraying, stirring reaction to pH value are 7～8 o'clock, stop adding ammonium bicarbonate aqueous solution, continue to stir 5～8h, ageing 12～15h, and filtration, washing, obtain mixed sols;
5.. dehydrate
The mixed sols that 4. step is prepared, employing butanols is entrainer, by component distillation, dewaters, and removes the moisture in mixed sols, steams butanols, obtains siccative;
6.. calcining
Siccative after 5. step dehydrates, at the temperature lower calcination of 600～800 ℃, calcination time is 3～5 hours, obtains Zirconia composite nano powder body material product.
7. according to preparation method claimed in claim 6, the spraying feed rate that it is characterized in that the ammonium bicarbonate aqueous solution described in step is 4. average every square centimeter of 1～3ml/min.
8. according to preparation method claimed in claim 6, the processing condition that it is characterized in that the component distillation dehydration described in step are 5. that employing propyl carbinol is entrainer, azeotropic point is 93 ℃, dewater complete, the temperature of system is elevated to 118 ℃ of the boiling points of propyl carbinol, at this temperature, steams propyl carbinol, then be controlled at 115-120 ℃ and dry 1～2 hour, obtain loose shape white siccative.
9. according to preparation method claimed in claim 6, the processing condition that it is characterized in that the component distillation dehydration described in step are 5. that employing isopropylcarbinol is entrainer, azeotropic point is 89.9 ℃, dewater complete, the temperature of system is elevated to 108.4 ℃ of the boiling points of isopropylcarbinol, at this temperature, steams isopropylcarbinol, then be controlled at 115-120 ℃ and dry 1～2 hour, obtain loose shape white siccative.
10. according to preparation method claimed in claim 6, it is characterized in that 5. step dehydrates technological process and carry out under vacuum condition, vacuum degree control is at-0.01～-0.1Mpa.
The application of 11. Zirconia composite nano powder body materials claimed in claim 1, is characterized in that being applicable to external wall heat insulating coat, the transparent heat-insulated coating of vehicle window, building glass, heat-insulation transparent conductive coating; Also be applicable to the preparation of catalyzer, support of the catalyst and be used as gear division, orthopedics biological material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310740177.0A CN103756397B (en) | 2013-12-27 | 2013-12-27 | Zirconia composite nano-powder material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310740177.0A CN103756397B (en) | 2013-12-27 | 2013-12-27 | Zirconia composite nano-powder material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103756397A true CN103756397A (en) | 2014-04-30 |
| CN103756397B CN103756397B (en) | 2015-02-11 |
Family
ID=50523730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310740177.0A Active CN103756397B (en) | 2013-12-27 | 2013-12-27 | Zirconia composite nano-powder material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103756397B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815634A (en) * | 2015-04-02 | 2015-08-05 | 吴肖颜 | Preparation method of TiO2-ZrO2 composite nanometer powder |
| CN107758718A (en) * | 2017-11-17 | 2018-03-06 | 宁波普莱斯帝金属制品有限公司 | A kind of method that calcium carbonate superfine powder nano-powder is prepared with calcite |
| CN111704368A (en) * | 2020-07-14 | 2020-09-25 | 浙江水晶光电科技股份有限公司 | Anti-fog glass with anti-reflection function and preparation method thereof |
| CN114570344A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院理化技术研究所 | Transition metal monatomic catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5978928A (en) * | 1982-10-25 | 1984-05-08 | Agency Of Ind Science & Technol | Manufacture of zirconia powder |
| JPH03141156A (en) * | 1989-10-26 | 1991-06-17 | Kanebo Ltd | Production of zirconia ceramics |
| CN1590284A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Preparation method of nano grade zirconium oxide crude powder |
| CN1865190A (en) * | 2006-06-01 | 2006-11-22 | 上海新业喷涂机械有限公司 | Zirconia/silicon carbide composite nano powder for hot spraying and its production method |
| JP2007246371A (en) * | 2006-03-17 | 2007-09-27 | Ngk Spark Plug Co Ltd | Piezoelectric ceramic composition and piezoelectric element using the same |
| CN101654280A (en) * | 2009-08-25 | 2010-02-24 | 苏州大学 | Preparation method of titanium dioxide nano powder |
-
2013
- 2013-12-27 CN CN201310740177.0A patent/CN103756397B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5978928A (en) * | 1982-10-25 | 1984-05-08 | Agency Of Ind Science & Technol | Manufacture of zirconia powder |
| JPH03141156A (en) * | 1989-10-26 | 1991-06-17 | Kanebo Ltd | Production of zirconia ceramics |
| CN1590284A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Preparation method of nano grade zirconium oxide crude powder |
| JP2007246371A (en) * | 2006-03-17 | 2007-09-27 | Ngk Spark Plug Co Ltd | Piezoelectric ceramic composition and piezoelectric element using the same |
| CN1865190A (en) * | 2006-06-01 | 2006-11-22 | 上海新业喷涂机械有限公司 | Zirconia/silicon carbide composite nano powder for hot spraying and its production method |
| CN101654280A (en) * | 2009-08-25 | 2010-02-24 | 苏州大学 | Preparation method of titanium dioxide nano powder |
Non-Patent Citations (2)
| Title |
|---|
| 仇海波等: "纳米氧化锆粉体的共沸蒸馏法制备及研究", 《无机材料学报》, vol. 9, no. 3, 30 September 1994 (1994-09-30), pages 365 - 370 * |
| 齐亮等: "氧化锆纳米粉体的制备及其材料的掺杂研究新进展", 《材料导报》, vol. 20, no. 2, 30 November 2006 (2006-11-30), pages 141 - 144 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815634A (en) * | 2015-04-02 | 2015-08-05 | 吴肖颜 | Preparation method of TiO2-ZrO2 composite nanometer powder |
| CN107758718A (en) * | 2017-11-17 | 2018-03-06 | 宁波普莱斯帝金属制品有限公司 | A kind of method that calcium carbonate superfine powder nano-powder is prepared with calcite |
| CN107758718B (en) * | 2017-11-17 | 2020-08-28 | 池州市富华粉体科技有限公司 | Method for preparing superfine calcium carbonate nano powder from calcite |
| CN111704368A (en) * | 2020-07-14 | 2020-09-25 | 浙江水晶光电科技股份有限公司 | Anti-fog glass with anti-reflection function and preparation method thereof |
| CN114570344A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院理化技术研究所 | Transition metal monatomic catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103756397B (en) | 2015-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101378993B (en) | Method for the preparation of aqueous dispersions of TiO2 in the form of nanoparticles, and dispersions obtainable with this method | |
| Ghosh et al. | Mesoporous titanium dioxide nanofibers with a significantly enhanced photocatalytic activity | |
| Yin et al. | Synthesis and photocatalytic properties of fibrous titania prepared from protonic layered tetratitanate precursor in supercritical alcohols | |
| CN101293669B (en) | Method for preparing nano-titanium dioxide powder with controllable phase ratio of anatase and rutile | |
| CN103756397B (en) | Zirconia composite nano-powder material and preparation method thereof | |
| CN103740165B (en) | Special nano zirconium dioxide composite powder material for architectural outer wall insulation paint | |
| Pakdel et al. | Visible and UV functionality of TiO2 ternary nanocomposites on cotton | |
| JP4698981B2 (en) | Fibrous titanium oxide particles, method for producing the same, and uses of the particles | |
| US20060104894A1 (en) | Method for making single-phase anatase titanium oxide | |
| KR101813190B1 (en) | Process for the preparation of titanium dioxide having nanometric dimensions and controlled shape | |
| CN103691433A (en) | Ag-doped TiO2 material, and preparation method and application thereof | |
| CN104624211A (en) | Preparation method of complex photocatalyst responsive to visible light and application of complex photocatalyst | |
| KR101857831B1 (en) | Visible light active photocatalyst coating composition, method for preparing visible light active photocatalyst coating composition and method for preparing visible light active photocatalyst layer | |
| CN101857267B (en) | Preparation method of titanium dioxide nano material with core-shell structure | |
| JPH11188270A (en) | Coating solution for forming transparent coating film having photocatalytic activity and substrate with transparent coating film | |
| CN1124983C (en) | Process for preparing nm-class rutile-type TiO2 | |
| CN103740164B (en) | Special nano zirconium dioxide composite powder material for glass reflective insulation paint | |
| Sampurnam et al. | Synthesis, characterization and heterogeneous photocatalytic activity of H3PW12O40/TiO2/Ag composites | |
| KR100941738B1 (en) | Photoactive composition comprising scoria and preparation method thereof | |
| US20120058887A1 (en) | Method for making single-phase anatase titanium oxide | |
| JP6198170B2 (en) | Tantalum oxide particles and method for producing the same | |
| CN105107504A (en) | Preparing method for photocatalyst/copper oxide compound light photocatalytic material | |
| CN109126762A (en) | A kind of CeO2/TiO2The preparation method of nanometer tube composite materials | |
| CN105435828A (en) | Fe and N co-doped mesoporous TiO2 microsphere array visible light photocatalyst and preparation method | |
| CN106215960B (en) | A kind of efficient composite photo-catalyst Fe-TiO2/BiPO4And preparation method thereof |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210113 Address after: 255100 16 A, Guangtong Road, Longquan Town, Zichuan District, Zibo City, Shandong Province Patentee after: Shandong Guangtong New Material Co., Ltd Address before: 255144 West Shouhui, Longquan Town, Zichuan District, Zibo City, Shandong Province Patentee before: ZIBO GUANGTONG CHEMICAL Co.,Ltd. |