CN1246443A - Powdered nm-class zinc oxide particles cladded by metallic compound on surface and preparation method - Google Patents
Powdered nm-class zinc oxide particles cladded by metallic compound on surface and preparation method Download PDFInfo
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- CN1246443A CN1246443A CN 98117464 CN98117464A CN1246443A CN 1246443 A CN1246443 A CN 1246443A CN 98117464 CN98117464 CN 98117464 CN 98117464 A CN98117464 A CN 98117464A CN 1246443 A CN1246443 A CN 1246443A
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Abstract
A process for preparing nm-class zinc oxide particles coated by metallic compound includes such steps as adding soluble zinc salt solution to the solution of soluble carbonate to obtain white deposit, adding 3-10% solution of sodium benzosulfonate (0-20 ml) to the white deposit, adding solution of titanium sulfate or aluminium sulfate, stirring and slowly adding the solution of ammonium hydrogen carbonate to obtain white zinc oxide particles coated by Ti or Al compound. The particle diameter is 50-90 nm and the thickness of coated layer is 2-10 nm. The particles have excellent ultraviolet absorption and high reflectivity of visual light.
Description
The invention belongs to field of inorganic nano material, particularly the nanometer Zinc oxide powder of particles cladded by metallic compound on surface and preparation method.
Nanoparticle is because its size is little, and, quantum size effect, surface effects and small-size effect etc. differ from the not available characteristic of conventional body material because having it, as in characteristic that is had aspect optics, electricity, the biological and chemical etc., and it is unusual active in the investigation of materials field, comprising new preparation method, new performance and new application.Nano zine oxide is one to have the important inorganic materials of optics, electricity and biological effect, and its preparation and performance study have obtained paying attention to widely.
For the performances such as magnetic, chemistry and optics of improving powder, often the powder granule surface is modified, mainly adopt surface coating technology to realize, this surface coating technology has obtained widespread use.The elementary operation of this technology is earlier the blapharoplast that coats to be dispersed in gas phase or the liquid phase, in order to be disperseed preferably, often add certain amount of dispersant, adopt methods such as vapour deposition or liquid-phase precipitation to form a skim then on dispersive blapharoplast surface.Last drying, roasting form needed surface-coated powder.Technical process as shown in Figure 1.
(Ou Kele etc. such as Ou Kele, the colloidal solid preparation and the performance 6 titanium oxide coating zinc oxides that evenly coat, Lang Gemiuer, 1991,12 (7): 2911-16[M.Ocana, Wan Peter Hsu and EgonMatijevic " Preparation and Properties of Uniform-Coated Collidal Particles.6.Titaniaon Zinc Oxide " Langmuir, 1991,12 (7): 2911-16] be that the Zinc oxide particles outside of 0.4 μ m has coated one deck titanium compound) in median size, they the zinc oxide ultra-sonic dispersion in the mixing solutions of second alcohol and water, utilize the hydrolysis of titanium alkoxide to prepare the titanium compound coating layer, obtained the Zinc oxide powder of coated titanium at last at 200-900 ℃ of calcination.Their main purpose is to want to make the cheap Zinc oxide powder with titanium white performance.Can only carry out the surface to the thicker submicron order Zinc oxide powder of particle in this way and coat, then be difficult to obtain surface coated nanometer Zinc oxide powder with this method for nano granular of zinc oxide.
Unit dyes etc. in the river that (dye etc. in first river, the Zinc oxide powder light reflective of adulterated al, Applied Physics, 1991,69 (2): 959-964.[H.Rafla-Yuan and J.F.Cordaro " Optical Reflctance of Aluminum-dopedZinc Oxide Powders " J.Appl.Phys., 1991,69 (2): 959-964]) utilize the aluminium acetylacetonate hydrolysis to form gel, then Zinc oxide particles is dispersed in the above-mentioned gel, after drying, the grinding, 900 ℃ of roastings 10 hours, obtain the Zinc oxide powder of metallized aluminum, particle grain size is approximately 0.55 μ m.Their main purpose is to want to study surface coated aluminium for improving the influence of Zinc oxide powder xanchromatic.They also only are suitable for the submicron order Zinc oxide powder by this method for coating.
Because nano granular of zinc oxide is very thin, it disperses relatively difficulty, and very easily forms reunion.If adopting above-mentioned method that it is carried out the surface coats; then owing to be subjected to the influence of Zinc oxide particles shape, size and aggregating state; it is thicker that particle after the coating can become; the scope that exceeds nano particle; also many performances that nano-powder had will have been lost; as the light transmission of nano zine oxide, photocatalytic activity etc.
Nanometer Zinc oxide powder is one to have the important inorganic materials of optics, electricity and biological effect.It has not only strengthened the existing function of Zinc oxide powder, and has shown many new optics and chemical property.But utilize the nanometer Zinc oxide powder of wet chemistry method preparation, owing to there is " F colour center " defective, often the powder outward appearance is yellow, has brought many inconvenience to use.
One of purpose of the present invention just provides a kind of new method for coating, prepares the nanometer Zinc oxide powder of coating.
Another object of the present invention is exactly to provide a kind of cladding process to prepare that white is transparent effectively to absorb ultraviolet nanometer Zinc oxide powder again.
Technical scheme of the present invention is achieved in that it is to have proposed a kind of new surperficial clad nano zinc oxide preparation method.This method is in the preparation process of nano-powder, place surface coating process the precursor that obtains oxide compound to carry out, just place the surface coating process of titanium or aluminum compound precursor one zinc carbonate or the zinc subcarbonate of zinc oxide to carry out, so just can avoid repeated drying and calcination and the particle agglomeration that causes and growing up.Particularly, at first the soluble salt solution of zinc is joined in the soluble carbon acid salt solution, be heated to 30-60 ℃, and constantly stirred 10-30 minute, obtain white precipitate.The concentration that adds 0-20ml in this white precipitate is the benzene sodium sulfonate solution of 3-10%, dispersed with stirring 5-20 minute.Add titanium sulfate solution or alum liquor then respectively, wherein the add-on of titanium sulfate or Tai-Ace S 150 is by titanium content, and be the 0.5-20% of zinc content in the zinc sulfate, stir, slowly add ammonium bicarbonate soln again, conventional heated and stirred 20-40 minute, at last throw out is filtered, washs, dries, pulverize the back at 450-650 ℃ of calcination 1-3 hour, obtain the coated titanium of white 50-90nm or the Zinc oxide powder of aluminum compound respectively.
The soluble salt of described zinc is zinc sulfate or zinc chloride; The soluble carbon hydrochlorate is bicarbonate of ammonia or yellow soda ash.
In order to realize another object of the present invention, adopt aforesaid method for coating, the spherical particle diameter of the nanometer Zinc oxide powder of the particles cladded by metallic compound on surface of preparing is 50-90nm, the thickness of coating layer is 2-10 nm; The nanometer Zinc oxide powder particle diameter 50-80nm of coated titanium particularly, the nanometer Zinc oxide powder particle diameter 50-90nm of metallized aluminum, and their coating thicknesses are 2-10nm, the thickness of coating layer is relevant with the coating addition.Utilize ultraviolet-visible spectrophotometer (UV-2100S) to measure their reflection characteristic.
The clad nano oxide powder and zinc preparation that the present invention proposes, the Zinc oxide powder particle diameter of compounds such as prepared coated titanium that goes out or metallized aluminum is 50-90nm, and coating layer is even.The clad nano Zinc oxide powder that adopts method of the present invention to prepare, the powder outward appearance is white in color.It can absorb ultraviolet ray effectively, has very high visible light reflection characteristic.The nanometer Zinc oxide powder ultraviolet-visible light reflectivity curve of coated titanium and metallized aluminum is seen accompanying drawing 2 and 3 respectively.
Below in conjunction with accompanying drawing technical scheme of the present invention is further described.
Accompanying drawing 1 is the technical process that conventional bag whiting system is equipped with.
Accompanying drawing 2 is nanometer Zinc oxide powder ultraviolet-visible light reflectivity curves of surperficial coated titanium.
Accompanying drawing 3 is nanometer Zinc oxide powder ultraviolet-visible light reflectivity curves of surperficial metallized aluminum.
Among the figure, ZnO is meant the nanometer Zinc oxide powder that does not coat, and (ZnO) Ti is meant the nanometer Zinc oxide powder of coated titanium, and (ZnO) Al is meant the nanometer Zinc oxide powder of clad ratio.
Embodiment 1. 311.98ml (125.7g/l) solution of zinc sulfate, 100ml (100g/l) titanium sulfate solution, 158.1ml (600g/l) ammonium bicarbonate soln.Earlier solution of zinc sulfate is joined in the ammonium bicarbonate soln, be heated to 50 ℃, and constantly stirred 20 minutes, obtain white precipitate.The concentration that adds 10ml in this white precipitate is 5% benzene sodium sulfonate solution, dispersed with stirring 5 minutes.Add titanium sulfate solution then, stir, slowly add 21.9ml (600g/l) ammonium bicarbonate soln again, conventional heated and stirred 30 minutes, at last throw out is filtered, washs, dries, pulverize the back, obtain the Zinc oxide powder that coats about the 50nm of white 450 ℃ of calcinations 1 hour.
Embodiment 2. 200ml (123.3g/l) liquor zinci chloridi, 100ml (100g/l) titanium sulfate solution, 158.1ml (600g/l) ammonium bicarbonate soln.Earlier solution of zinc sulfate is joined in the ammonium bicarbonate soln, be heated to 50 ℃, and constantly stirred 20 minutes, obtain white precipitate.The concentration that adds 10ml in this white precipitate is 5% benzene sodium sulfonate solution, dispersed with stirring 5 minutes.Add titanium sulfate solution then, stir, slowly add 21.9ml (600g/l) ammonium bicarbonate soln again, conventional heated and stirred 30 minutes, at last throw out is filtered, washs, dries, pulverize the back, obtain the Zinc oxide powder that coats about the 50nm of white 450 ℃ of calcinations 1 hour.
Embodiment 3. changes the calcination temperature, and all the other steps obtain the Zinc oxide powder of different calcination temperature with embodiment 1.When the calcination temperature is 500 ℃, obtain the coating zinc oxide powder about white 60nm; Obtain the white coating zinc oxide powder about 80nm in the time of 650 ℃.
Embodiment 4. changes titanium sulfate solution and corresponding bicarbonate of ammonia addition, and all the other steps obtain the coating system of different Zn/Ti mol ratios with embodiment 1.Table 1 obtains the granular size that powder is cut out during for different Zn/Ti mol ratio.
Obtain during the different Zn/Ti mol ratio of table 1. granular size that powder cuts out (450 ℃ * 1h)
| Zn/Ti(mol) | 20/1 | ?15/1 | ??10/1 | ??5/1 |
| Particle size range (nm) | 60-80 | ?40-60 | ??30-50 | ??30-60 |
Embodiment 5. precipitation agents change yellow soda ash into, and all the other steps are with embodiment 1, basically identical when the clad nano Zinc oxide powder effect that obtains is done precipitation agent with bicarbonate of ammonia basically.
Embodiment 6. does not add benzene sodium sulfonate solution, and all the other steps obtain the Zinc oxide powder that coats about the 80nm of white with embodiment 1.
Embodiment 7. 400ml (100g/l) solution of zinc sulfate, 120ml (136.3g/l) alum liquor, 161ml (600g/l) ammonium bicarbonate soln.Earlier solution of zinc sulfate is joined in the ammonium bicarbonate soln, be heated to 50 ℃, and constantly stirred 20 minutes, obtain white precipitate.The concentration that adds 10ml in this white precipitate is 5% benzene sodium sulfonate solution, dispersed with stirring 5 minutes.Add alum liquor then, stir, slowly add 19.4ml (600g/l) ammonium bicarbonate soln again, heated and stirred 30 minutes, at last throw out is filtered, washs, dries, pulverize the back, obtain the Zinc oxide powder of the 60nm left and right sides metallized aluminum of white 450 ℃ of calcinations 1 hour.
Embodiment 9. changes titanium sulfate solution and corresponding bicarbonate of ammonia addition, and all the other steps obtain the coating system of different Zn/Al mol ratios with embodiment 5.Table 2 obtains the granular size of coating zinc oxide powder during for different Zn/Al mol ratio.
Obtain during the different Zn/Al mol ratio of table 2. granular size that powder cuts out (450 ℃ * 1h)
| Zn/Al(mol) | 25/1 | ?20/1 | ?10/1 | ?5/1 |
| Particle size range (nm) | 50-70 | ?40-60 | ?30-60 | ?30-70 |
Embodiment 10. precipitation agents change yellow soda ash into, and all the other steps are with embodiment 5, basically identical when the nanometer Zinc oxide powder effect that obtains is done precipitation agent with bicarbonate of ammonia basically.
Claims (3)
- The nanometer Zinc oxide powder of 1 one kinds of particles cladded by metallic compound on surface, the spherical particle diameter that it is characterized in that the nanometer Zinc oxide powder of particles cladded by metallic compound is 50-90 nm, the thickness of coating layer is 2-10 nm.
- The preparation method of the nanometer Zinc oxide powder of 2 one kinds of particles cladded by metallic compound on surface is characterized in that at first the soluble salt solution of zinc being joined in the soluble carbon acid salt solution, is heated to 30-60 ℃, and constantly stirs 10-30 minute, obtains white precipitate; The concentration that adds 0-20 ml in this white precipitate is the benzene sodium sulfonate solution of 3-10%, dispersed with stirring 5-20 minute; Add titanium sulfate solution or alum liquor then respectively, wherein the add-on of titanium sulfate or Tai-Ace S 150 is by titanium content, and be the 0.5-20% of zinc content in the zinc sulfate, stir, slowly add ammonium bicarbonate soln again, conventional heated and stirred 20-40 minute, at last throw out is filtered, washs, dries, pulverize the back at 450-650 ℃ of calcination 1-3 hour, obtain the coated titanium of white 50-90nm or the Zinc oxide powder of aluminum compound respectively.
- 3 methods as claimed in claim 2, the soluble salt that it is characterized in that described zinc are zinc sulfate or zinc chloride; The soluble carbon hydrochlorate is bicarbonate of ammonia or yellow soda ash.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100436375C (en) * | 2006-02-09 | 2008-11-26 | 武汉理工大学 | Process for preparing coated ZrB2 composite powder |
| CN104609459A (en) * | 2015-01-27 | 2015-05-13 | 扬州大学 | Preparation method for gold-coated zinc oxide flower-like microspheres |
| CN105418302A (en) * | 2016-01-18 | 2016-03-23 | 河北麦森钛白粉有限公司 | Method using nano titanium dioxide to prepare wide leaf plant leaf fertilizer |
| CN105482003A (en) * | 2014-10-10 | 2016-04-13 | 中国石油化工股份有限公司 | Carrier for ethylene polymerization catalyst and catalyst of carrier |
| CN105552334A (en) * | 2016-01-11 | 2016-05-04 | 杭州电子科技大学 | Preparation method for carbon-film-coated zinc oxide hollow sphere |
| CN107829304A (en) * | 2017-11-23 | 2018-03-23 | 苏州经贸职业技术学院 | A kind of waterproof uvioresistant material treatment agent and preparation method thereof |
| CN110382440A (en) * | 2016-11-07 | 2019-10-25 | 科罗拉多大学董事会 | The performance of improved technology grade ceramics |
| CN114698647A (en) * | 2022-03-23 | 2022-07-05 | 中氪新能源科技(上海)有限公司 | Zinc oxide/metal antibacterial powder and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053412A (en) * | 1990-01-19 | 1991-07-31 | 辛集市化工二厂 | The bicarbonate of ammonia neutralisation is produced zinc oxide |
| GB9121143D0 (en) * | 1991-10-04 | 1991-11-13 | Tioxide Chemicals Limited | Dispersions |
| CN1184079A (en) * | 1996-12-05 | 1998-06-10 | 云南大学 | Supersonic emulsifying co-precipitation process preparing compound zinc oxide voltage-sensitive resistor powder |
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1998
- 1998-09-02 CN CN98117464A patent/CN1091748C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436375C (en) * | 2006-02-09 | 2008-11-26 | 武汉理工大学 | Process for preparing coated ZrB2 composite powder |
| CN105482003B (en) * | 2014-10-10 | 2018-01-23 | 中国石油化工股份有限公司 | Carrier and its catalyst used in a kind of ethylene rolymerization catalyst |
| CN105482003A (en) * | 2014-10-10 | 2016-04-13 | 中国石油化工股份有限公司 | Carrier for ethylene polymerization catalyst and catalyst of carrier |
| CN104609459B (en) * | 2015-01-27 | 2016-04-06 | 扬州大学 | The preparation method of the flower-shaped micron ball of a kind of gold parcel zinc oxide |
| CN104609459A (en) * | 2015-01-27 | 2015-05-13 | 扬州大学 | Preparation method for gold-coated zinc oxide flower-like microspheres |
| CN105552334A (en) * | 2016-01-11 | 2016-05-04 | 杭州电子科技大学 | Preparation method for carbon-film-coated zinc oxide hollow sphere |
| CN105552334B (en) * | 2016-01-11 | 2018-04-17 | 杭州电子科技大学 | A kind of preparation method of carbon film coated zinc oxide hollow ball |
| CN105418302A (en) * | 2016-01-18 | 2016-03-23 | 河北麦森钛白粉有限公司 | Method using nano titanium dioxide to prepare wide leaf plant leaf fertilizer |
| CN105418302B (en) * | 2016-01-18 | 2018-12-14 | 河北麦森钛白粉有限公司 | The method for preparing wide leaf Plant leaf fertilizer using nanometer titanium dioxide |
| CN110382440A (en) * | 2016-11-07 | 2019-10-25 | 科罗拉多大学董事会 | The performance of improved technology grade ceramics |
| US11613502B2 (en) | 2016-11-07 | 2023-03-28 | The Regents Of The University Of Colorado | Core-shell ceramic particle colloidal gel and solid oxide fuel cell electrolyte |
| CN107829304A (en) * | 2017-11-23 | 2018-03-23 | 苏州经贸职业技术学院 | A kind of waterproof uvioresistant material treatment agent and preparation method thereof |
| CN114698647A (en) * | 2022-03-23 | 2022-07-05 | 中氪新能源科技(上海)有限公司 | Zinc oxide/metal antibacterial powder and preparation method thereof |
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