CN102616828A - Nano zinc oxide-doped powder and preparation method thereof - Google Patents
Nano zinc oxide-doped powder and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano zinc oxide-doped powder and a preparation method thereof. Silicon-aluminum co-doped nano zinc oxide powder is synthesized by using a co-precipitation and calcining one-step method; and the mol ratio of aluminum as a doping element to zinc oxide and the mol ratio of silicon as a doping element to the zinc oxide are (0.03:1)-(0.18:1) respectively. The nano zinc oxide-doped powder disclosed by the invention has the advantages that the whiteness of nano zinc oxide and the light transmittance in a visible light band are improved; the photocatalytic activity of the nano zinc oxide, the dissolving of zinc ions and the particle size increase of the zinc oxide particles in the roasting process are inhibited; and the dispersibility of the nano zinc oxide in water is improved; and the preparation method has the advantages of convenience in operation, simple requirement on equipment, short process flow, low cost and suitability for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of nanometer Zinc oxide powder and preparation method thereof, particularly a kind of nanometer doped zinc oxide powder and preparation method thereof.
Background technology
Nano zine oxide is meant the zinc oxide material of particle diameter between 1～100nm; Have the performance better than common zinc oxide material; Like non-migrating property, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability etc.; At aspects such as magnetic, light, electricity, sensitivity, antibiotic and sterilizing, ultraviolet screeners, be a kind of new function material that has a extensive future.Huang, bad dispersibility, zine ion are prone to shortcomings such as stripping, thereby have limited its industrialized application partially yet nano zine oxide exists color in actual use.At present, preparation doping zinc-oxide powder receives much concern, and the doping zinc-oxide powder has good dispersion property, nontoxic, advantage such as whiteness is higher, physical and chemical stability is better and production cost is lower.
The preparation method of spherical aluminum-doped zinc oxide nanometer powder (country origin: China; Publication number: 101665237; The open date: 2010-3-10) disclose elder generation soluble zinc salt and aluminium salt are mixed with mixing salt solution by a certain percentage; Add ammoniacal liquor or ammonium salt then and generate precursor, precursor is moved into carry out hydro-thermal reaction in the reaction kettle again, can obtain spherical aluminum-doped zinc oxide nanometer powder 100 ℃ of oven dry at last.This method is used the hydro-thermal reaction method, and is higher to equipment requirements, be difficult for large-scale industrial production, and the spherical aluminum-doped zinc oxide powder whiteness that obtains is not very high.
A kind of multi-doping zinc-oxide-base wide-bandgap conducting material and preparation method thereof (country origin: China; Publication number: 101661808; Date is disclosed: 2010-3-3) disclose dopant source and zinc source are prepared burden according to the mole proportioning of each alloying element and zinc element; Obtain forerunner's adulterated powder through mix, oven dry and grinding then; Again with forerunner's adulterated powder 500 ℃～1000 ℃ pre-burnings 2～24 hours, with the adulterated powder moulded section after the pre-burning and 1100 ℃～1450 ℃ sintering 1～16 hour, promptly make multi-doping zinc-oxide-base wide-bandgap conducting material at last.The weak point of this method mainly is: 1. the mode through ball mill mixing is difficult to obtain uniform doping, and then influences the homogeneity of Zinc oxide-base electro-conductive material; 2. in the ball mill mixing process, introduce a large amount of impurity easily, cause Zinc oxide-base electro-conductive material purity drop; 3. the forerunner's adulterated powder that obtains behind the ball milling need carry out sintering under comparatively high temps, and hotchpotch and zinc oxide are prone to react and generate segregation mutually and the reunion of growing up easily of zinc oxide particle under the high temperature, thereby influences its electroconductibility and dispersiveness.
Summary of the invention
Goal of the invention: to the problems referred to above, the purpose of this invention is to provide a kind of nanometer doped zinc oxide powder and preparation method thereof, improve the performance of nanometer Zinc oxide powder, and be suitable for suitability for industrialized production.
Technical scheme: a kind of nanometer doped zinc oxide powder, alloying element are aluminium and silicon, said alloying element aluminium, said alloying element silicon is 0.03: 1 with the mol ratio of zinc oxide separately～and 0.18: 1.
The preparation method of above-mentioned a kind of nanometer doped zinc oxide powder, this method may further comprise the steps:
(1) aluminium salt and zinc salt are dissolved into the mixing salt solution that forms 0.2～2 mol in the deionized water jointly;
(2) temperature of the above-mentioned mixing salt solution of adjusting is 30 ℃～60 ℃, adds the precipitant solution of 0.2～3 mol while stirring, when the pH value of system reaches 3.5～4.0; Suspend the adding precipitant solution, in coprecipitated product, add the aqueous silicate solution of 0.1～1 mol, after aqueous silicate solution adds; Continue to add the precipitant solution of 0.2～3 mol; The regulation system pH value is 6.5～8.5, is warming up to 70 ℃～90 ℃, continues to stir slaking 0.5～4h;
(3) above-mentioned coprecipitated product is filtered; Remove soluble salt with the deionized water repetitive scrubbing; When the specific conductivity≤260 μ S/cm of filtrating, finish washing, drying obtains white product; White product is calcined 1～5h down at 700 ℃～900 ℃, obtain the nanometer Zinc oxide powder of sial codoped after the pulverizing.
Aluminium salt described in the step (1) be Tai-Ace S 150, aluminum nitrate, aluminum chloride one of them, said zinc salt be zinc sulfate, zinc nitrate, zinc chloride, zinc acetate one of them.
The aluminum ion described in the step (1) in the aluminium salt and the mol ratio of the zine ion in the said zinc salt are 0.03: 1～0.18: 1.
Precipitant solution described in the step (2) is one of them the aqueous solution of bicarbonate of ammonia, volatile salt, yellow soda ash, sodium hydrogencarbonate, ammoniacal liquor.
Silicate is water glass or potassium silicate described in the step (2).
The silicon ion described in the step (2) in the silicate and the mol ratio of zinc oxide are 0.03: 1～0.18: 1.
Beneficial effect: compared with prior art, advantage of the present invention is:
1, utilizes the nanometer Zinc oxide powder of co-precipitation-calcining single stage method synthesizing Si-Al codoped; The adulterated al element has improved the nano zine oxide whiteness on the one hand; Improved the light transmission of nano zine oxide on the other hand, precondition is provided for adapting to the different application field at visible light wave range;
2, silicate has reduced the pollution to environment simultaneously as silicon source and precipitation agent when having practiced thrift cost; The doped silicon element has suppressed the stripping of zine ion again when having suppressed the photocatalytic activity of nano zine oxide; Improved the dispersiveness of nano zine oxide in water; Having suppressed in the roasting process zinc oxide particle diameter simultaneously grows up; Alleviated between particle to a certain extent and reunited, made the powder dispersity that finally makes good and stable;
3, the nanometer Zinc oxide powder prepared of the inventive method has light stability and the transparency is excellent, the zine ion stripping quantity is little, particle diameter is little and advantages such as homogeneous, good dispersivity;
4, the inventive method is easy to operate, equipment requirements is simple, technical process is short, cost is low, is fit to large-scale industrial production.
Embodiment
Below in conjunction with specific embodiment; Further illustrate the present invention; Should understand these embodiment only be used to the present invention is described and be not used in the restriction scope of the present invention; After having read the present invention, those skilled in the art all fall within the application's accompanying claims institute restricted portion to the modification of the various equivalent form of values of the present invention.
Embodiment 1: with the ZnSO of 28.76g
47H
20 with the Al of 6.66g
2(SO4)
318H
2Forming total concn in the 0 adding deionized water is the mixing salt solution of 1.0 mol.The temperature of control mixing salt solution is 50 ℃, while stir the ammonium bicarbonate soln that in mixing salt solution, adds 1.5 mol, when the pH value of system reaches 3.8; Suspend to add ammonium bicarbonate soln, in coprecipitated product, add 24 milliliters of the sodium silicate aqueous solutions of 0.5 mol, after sodium silicate aqueous solution adds; Continue to add the ammonium bicarbonate soln of 1.5 mol; The pH value of regulation system is 7.5, is warming up to 75 ℃, stirs slaking 2h.The coprecipitated product of gained is filtered, remove soluble salt, when the specific conductivity of filtrating is 200 μ S/cm with the deionized water repetitive scrubbing; Finish washing; Drying obtains white product, and white product is calcined 2h down at 800 ℃, obtains the nanometer Zinc oxide powder of sial codoped after the pulverizing.The mol ratio of alloying element aluminium and zinc oxide is 0.1: 1 in the product, and the mol ratio of alloying element silicon and zinc oxide is 0.12: 1, and the whiteness that records product is 91, and median size is 23nm.
Embodiment 2: with the ZnSO of 28.76g
47H
20 with the Al of 1.998g
2(SO4)
318H
2Forming total concn in the 0 adding deionized water is the mixing salt solution of 0.2 mol.The temperature of control mixing salt solution is 30 ℃, while stir the sal volatile that in mixing salt solution, adds 3 mol, when the pH value of system reaches 3.5; Suspend to add sal volatile, in coprecipitated product, add 18 milliliters of the potassium silicate aqueous solutions of 1.0 mol, after potassium silicate aqueous solution adds; Continue to add the sal volatile of 3.0 mol; The pH value of regulation system is 7.0, is warming up to 90 ℃, stirs slaking 0.5h.The coprecipitated product of gained is filtered, remove soluble salt, when the specific conductivity of filtrating is 260 μ S/cm with the deionized water repetitive scrubbing; Finish washing; Drying obtains white product, and white product is calcined 5h down at 700 ℃, obtains the nanometer Zinc oxide powder of sial codoped after the pulverizing.The mol ratio of alloying element aluminium and zinc oxide is 0.03: 1 in the product, and the mol ratio of alloying element silicon and zinc oxide is 0.18: 1, and the whiteness that records product is 90, and median size is 17nm.
Embodiment 3: with the Zn (NO of 29.75g
3)
26H
2Al (the NO of O and 6.75g
3)
39H
2Forming total concn in the 0 adding deionized water is the mixing salt solution of 2.0 mol.The temperature of control mixing salt solution is 60 ℃, while stir the sodium carbonate solution that in mixing salt solution, adds 0.2 mol, when the pH value of system reaches 4.0; Suspend to add sodium carbonate solution, in coprecipitated product, add 30 milliliters of the sodium silicate aqueous solutions of 0.1 mol, after sodium silicate aqueous solution adds; Continue to add the sodium carbonate solution of 0.2 mol; The pH value of regulation system is 8.0, is warming up to 70 ℃, stirs slaking 4h.The coprecipitated product of gained is filtered, remove soluble salt, when the specific conductivity of filtrating is 150 μ S/cm with the deionized water repetitive scrubbing; Finish washing; Drying obtains white product, and white product is calcined 1h down at 900 ℃, obtains the nanometer Zinc oxide powder of sial codoped after the pulverizing.The mol ratio of alloying element aluminium and zinc oxide is 0.18: 1 in the product, and the mol ratio of alloying element silicon and zinc oxide is 0.03: 1, and the whiteness that records product is 94, and median size is 29nm.
Embodiment 4: with the ZnCl of 13.6g
2AlCl with 1.064g
3Forming total concn in the adding deionized water is the mixing salt solution of 0.8 mol.The temperature of control mixing salt solution is 38 ℃, while stir the sodium hydrogen carbonate solution that in mixing salt solution, adds 2.0 mol, when the pH value of system reaches 3.6; Suspend to add sodium hydrogen carbonate solution, in coprecipitated product, add 50 milliliters of the potassium silicate aqueous solutions of 0.3 mol, after potassium silicate aqueous solution adds; Continue to add the sodium hydrogen carbonate solution of 2.0 mol; The pH value of regulation system is 8.5, is warming up to 80 ℃, stirs slaking 1h.The coprecipitated product of gained is filtered, remove soluble salt, when the specific conductivity of filtrating is 180 μ S/cm with the deionized water repetitive scrubbing; Finish washing; Drying obtains white product, and white product is calcined 4h down at 750 ℃, obtains the nanometer Zinc oxide powder of sial codoped after the pulverizing.The mol ratio of alloying element aluminium and zinc oxide is 0.08: 1 in the product, and the mol ratio of alloying element silicon and zinc oxide is 0.15: 1, and the whiteness that records product is 92, and median size is 20nm.
Embodiment 5: with (the CH of 21.95g
3COO)
2Zn2H
20 with the Al of 9.324g
2(SO
4)
318H
2Forming total concn in the 0 adding deionized water is the mixing salt solution of 1.5 mol.The temperature of control mixing salt solution is 55 ℃, while stir the ammoniacal liquor that in mixing salt solution, adds 1.0 mol, when the pH value of system reaches 3.9; Suspend to add ammoniacal liquor, in coprecipitated product, add 8.75 milliliters of the sodium silicate aqueous solutions of 0.8 mol, after sodium silicate aqueous solution adds; Continue to add the ammoniacal liquor of 1.0 mol; The pH value of regulation system is 6.5, is warming up to 85 ℃, stirs slaking 3h.The coprecipitated product of gained is filtered, remove soluble salt, when the specific conductivity of filtrating is 220 μ S/cm with the deionized water repetitive scrubbing; Finish washing; Drying obtains white product, and white product is calcined 3h down at 850 ℃, obtains the nanometer Zinc oxide powder of sial codoped after the pulverizing.The mol ratio of alloying element aluminium and zinc oxide is 0.14: 1 in the product, and the mol ratio of alloying element silicon and zinc oxide is 0.07: 1, and the whiteness that records product is 93, and median size is 26nm.
To following 3 comparative examples and above-mentioned 5 embodiment, mixed the nanometer Zinc oxide powder of silicon and aluminium simultaneously in the advantage of photocatalytic activity, zine ion stripping, dispersiveness through experimental analysis contrast the present invention.
Comparative example 1: with the ZnSO of 28.76g
47H
2Forming concentration in the 0 adding deionized water is the zinc solution of 1.0 mol; The temperature of control zinc solution is 50 ℃, while stir the ammonium bicarbonate soln that in zinc solution, adds 1.5 mol, the pH value of regulation system is 7.5; Be warming up to 75 ℃, stir slaking 2h.The coprecipitated product of gained is filtered, remove soluble salt, when the specific conductivity of filtrating is 200 μ S/cm with the deionized water repetitive scrubbing; Finish washing; Drying obtains white product, and white product is calcined 2h down at 800 ℃, obtains pure micron Zinc oxide powder after the pulverizing.The whiteness that records pure micron Zinc oxide powder is 80, and median size is 210nm.
Comparative example 2: with the ZnSO of 28.76g
47H
20 with the Al of 6.66g
2(SO4)
318H
2Forming total concn in the 0 adding deionized water is the mixing salt solution of 1.0 mol.The temperature of control mixing salt solution is 50 ℃, while stir the ammonium bicarbonate soln that in mixing salt solution, adds 1.5 mol, the pH value of regulation system is 7.5, is warming up to 75 ℃, stirs slaking 2h.The coprecipitated product of gained is filtered, remove soluble salt, when the specific conductivity of filtrating is 200 μ S/cm with the deionized water repetitive scrubbing; Finish washing; Drying obtains white product, and white product is calcined 2h down at 800 ℃, obtains the adulterated micron of aluminium Zinc oxide powder after the pulverizing.The mol ratio of alloying element aluminium and zinc oxide is 0.1: 1 in the adulterated micron of the aluminium Zinc oxide powder, and the whiteness that records the adulterated micron of aluminium Zinc oxide powder is 88, and median size is 145nm.
Comparative example 3: with the ZnSO of 28.76g
47H
2Forming concentration in the 0 adding deionized water is the zinc solution of 1.0 mol; The temperature of control zinc solution is 50 ℃, stirs in zinc solution 24 milliliters of the sodium silicate aqueous solutions of adding 0.5 mol on one side, after sodium silicate aqueous solution adds; The ammonium bicarbonate soln that adds 1.5 mol; The pH value of regulation system is 7.5, is warming up to 75 ℃, stirs slaking 2h.The coprecipitated product of gained is filtered, remove soluble salt, when the specific conductivity of filtrating is 200 μ S/cm with the deionized water repetitive scrubbing; Finish washing; Drying obtains white product, and white product is calcined 2h down at 800 ℃, obtains the micron Zinc oxide powder of silicon doping after the pulverizing.The mol ratio of alloying element silicon and zinc oxide is 0.12: 1 in the micron Zinc oxide powder of silicon doping, and the whiteness that records the micron Zinc oxide powder of silicon doping is 85, and median size is 121nm.
The determination experiment of Zinc oxide powder photocatalytic activity: in XPA photochemical reaction appearance, add 1.0 and restrain the Zinc oxide powder that is equipped with; The methyl orange solution that to add 500 milliliters of mass concentrations again be 20 mg/litre is opened the air that stirs and feed from the bottom 0.02 liter/minute of flow, opens uv lamp; Power 20W, wavelength 254nm; Whenever after one period reaction times, sample 15 milliliters, spinning is got supernatant liquid and is tested.Under its maximum absorption wavelength, measure solution absorbency through spectrophotometer, degradation rate is calculated as follows:
η is degradation rate (%) in the formula; A
0, A
tBe respectively degrade preceding, the solution absorbance of t after the time; C
0, C
tBe respectively degrade preceding, the strength of solution of t after the time.
After 120 minutes, the different Zinc oxide powders of embodiment 1～embodiment 5, comparative example 1～comparative example 3 are as shown in the table to the degradation rate of tropeolin-D in light-catalyzed reaction:
This shows that embodiment 1～embodiment 5 is that mixed the simultaneously photocatalytic activity of nanometer Zinc oxide powder of silicon and aluminium of the present invention is effectively suppressed.
The determination experiment of Zinc oxide powder zine ion stripping: it is that 1% ammoniacal liquor, quality percentage composition are in 0.01% the salpeter solution that Zinc oxide powder is added deionized water, quality percentage composition respectively; Be mixed with solid content and be 5% suspension-s; Stirred 240 minutes down at 30 ℃; High speed centrifugation separates, and is as shown in the table with the zinc ion concentration that Vista-AX type plasma emission spectrum was measured in the stillness of night:
This shows that embodiment 1～embodiment 5 is that mixed the simultaneously zine ion stripping concentration of nanometer Zinc oxide powder of silicon and aluminium of the present invention obviously reduces.
The determination experiment that Zinc oxide powder is dispersed: get 10g Zinc oxide powder and 0.3g Sodium hexametaphosphate 99 and add in the deionized water; Pulverized ultra-sonic dispersion 0.5 hour with the intelligent supersonic cell of JYD650; Be mixed with the quality percentage composition and be 5% slurry, the graduated test tube of pack into diameter 1.5cm, total length 15cm vertically is placed on the test-tube stand; Left standstill at normal temperatures 2 days, the settling height of observing zinc oxide is as shown in the table:
This shows that embodiment 1～embodiment 5 is that mixed simultaneously the dispersed of nanometer Zinc oxide powder of silicon and aluminium of the present invention obviously improves.
Claims (7)
1. nanometer doped zinc oxide powder, it is characterized in that: alloying element is aluminium and silicon, said alloying element aluminium, said alloying element silicon is 0.03: 1 with the mol ratio of zinc oxide separately～and 0.18: 1.
2. the preparation method of a kind of nanometer doped zinc oxide powder according to claim 1 is characterized in that this method may further comprise the steps:
(1) aluminium salt and zinc salt are dissolved into the mixing salt solution that forms 0.2～2 mol in the deionized water jointly;
(2) temperature of the above-mentioned mixing salt solution of adjusting is 30 ℃～60 ℃, adds the precipitant solution of 0.2～3 mol while stirring, when the pH value of system reaches 3.5～4.0; Suspend the adding precipitant solution, in coprecipitated product, add the aqueous silicate solution of 0.1～1 mol, after aqueous silicate solution adds; Continue to add the precipitant solution of 0.2～3 mol; The regulation system pH value is 6.5～8.5, is warming up to 70 ℃～90 ℃, continues to stir slaking 0.5～4h;
(3) above-mentioned coprecipitated product is filtered; Remove soluble salt with the deionized water repetitive scrubbing; When the specific conductivity≤260 μ S/cm of filtrating, finish washing, drying obtains white product; White product is calcined 1～5h down at 700 ℃～900 ℃, obtain the nanometer Zinc oxide powder of sial codoped after the pulverizing.
3. the preparation method of a kind of nanometer doped zinc oxide powder according to claim 2; It is characterized in that: aluminium salt described in the step (1) be Tai-Ace S 150, aluminum nitrate, aluminum chloride one of them, said zinc salt be zinc sulfate, zinc nitrate, zinc chloride, zinc acetate one of them.
4. the preparation method of a kind of nanometer doped zinc oxide powder according to claim 2 is characterized in that: the aluminum ion described in the step (1) in the aluminium salt and the mol ratio of the zine ion in the said zinc salt are 0.03: 1～0.18: 1.
5. the preparation method of a kind of nanometer doped zinc oxide powder according to claim 2 is characterized in that: precipitant solution described in the step (2) is one of them the aqueous solution of bicarbonate of ammonia, volatile salt, yellow soda ash, sodium hydrogencarbonate, ammoniacal liquor.
6. the preparation method of a kind of nanometer doped zinc oxide powder according to claim 2 is characterized in that: silicate is water glass or potassium silicate described in the step (2).
7. the preparation method of a kind of nanometer doped zinc oxide powder according to claim 2 is characterized in that: the silicon ion described in the step (2) in the silicate and the mol ratio of zinc oxide are 0.03: 1～0.18: 1.
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Cited By (10)
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| CN102923758A (en) * | 2012-11-27 | 2013-02-13 | 中国科学院广州能源研究所 | Preparation method of highly-aluminium-doped zinc oxide nano-powder |
| CN103570056A (en) * | 2013-11-22 | 2014-02-12 | 江苏省东泰精细化工有限责任公司 | Method for preparing conductive powder by recoating aluminum-doped nano zinc oxide with aluminum |
| CN104445372A (en) * | 2014-11-26 | 2015-03-25 | 燕山大学 | Method for preparing carbon doped zinc oxide nanoparticles |
| CN105197980A (en) * | 2015-07-16 | 2015-12-30 | 南京工业大学 | Preparation method of silicon and zirconium co-doped zinc oxide nano powder |
| CN106430284A (en) * | 2016-09-13 | 2017-02-22 | 苏州市泽镁新材料科技有限公司 | Preparation method of sulfur-doped zinc oxide nano material |
| CN107892323A (en) * | 2017-11-02 | 2018-04-10 | 畅的新材料科技（上海）有限公司 | A kind of preparation method of Al doping ZnO low-resistivity nano-powders |
| CN109235056A (en) * | 2018-10-30 | 2019-01-18 | 广东菲安妮皮具股份有限公司 | A kind of preparation method for PVC artificial leather mould inhibitor |
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| CN114621681A (en) * | 2016-06-02 | 2022-06-14 | M技术株式会社 | Ultraviolet and/or near infrared ray blocking agent composition for transparent material |
| GB2619395A (en) * | 2022-04-29 | 2023-12-06 | Johnson Matthey Plc | Stabilised zinc oxide materials |
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| CN102923758A (en) * | 2012-11-27 | 2013-02-13 | 中国科学院广州能源研究所 | Preparation method of highly-aluminium-doped zinc oxide nano-powder |
| CN102923758B (en) * | 2012-11-27 | 2015-03-18 | 中国科学院广州能源研究所 | Preparation method of highly-aluminium-doped zinc oxide nano-powder |
| CN103570056A (en) * | 2013-11-22 | 2014-02-12 | 江苏省东泰精细化工有限责任公司 | Method for preparing conductive powder by recoating aluminum-doped nano zinc oxide with aluminum |
| CN103570056B (en) * | 2013-11-22 | 2015-01-07 | 江苏省东泰精细化工有限责任公司 | Method for preparing conductive powder by recoating aluminum-doped nano zinc oxide with aluminum |
| CN104445372B (en) * | 2014-11-26 | 2016-03-02 | 燕山大学 | A kind of method preparing carbon doping Zinc oxide nanoparticle |
| CN104445372A (en) * | 2014-11-26 | 2015-03-25 | 燕山大学 | Method for preparing carbon doped zinc oxide nanoparticles |
| CN105197980A (en) * | 2015-07-16 | 2015-12-30 | 南京工业大学 | Preparation method of silicon and zirconium co-doped zinc oxide nano powder |
| CN114621681A (en) * | 2016-06-02 | 2022-06-14 | M技术株式会社 | Ultraviolet and/or near infrared ray blocking agent composition for transparent material |
| CN106430284A (en) * | 2016-09-13 | 2017-02-22 | 苏州市泽镁新材料科技有限公司 | Preparation method of sulfur-doped zinc oxide nano material |
| CN107892323A (en) * | 2017-11-02 | 2018-04-10 | 畅的新材料科技（上海）有限公司 | A kind of preparation method of Al doping ZnO low-resistivity nano-powders |
| CN109235056A (en) * | 2018-10-30 | 2019-01-18 | 广东菲安妮皮具股份有限公司 | A kind of preparation method for PVC artificial leather mould inhibitor |
| CN111393889A (en) * | 2020-04-17 | 2020-07-10 | 肇庆市盛浩新材料科技有限公司 | Anticorrosive and mildewproof material for paint and preparation method and application thereof |
| CN111393889B (en) * | 2020-04-17 | 2021-11-30 | 肇庆市盛浩新材料科技有限公司 | Anticorrosive and mildewproof material for paint and preparation method and application thereof |
| GB2619395A (en) * | 2022-04-29 | 2023-12-06 | Johnson Matthey Plc | Stabilised zinc oxide materials |
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