CN100417753C - Technology for preparing tetrapod-like zinc oxide whisker by normal pressure zinc vapour oxidation method - Google Patents
Technology for preparing tetrapod-like zinc oxide whisker by normal pressure zinc vapour oxidation method Download PDFInfo
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- CN100417753C CN100417753C CNB2006100974108A CN200610097410A CN100417753C CN 100417753 C CN100417753 C CN 100417753C CN B2006100974108 A CNB2006100974108 A CN B2006100974108A CN 200610097410 A CN200610097410 A CN 200610097410A CN 100417753 C CN100417753 C CN 100417753C
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Abstract
The invention relates to a technology for preparing tetrapod-like zinc oxide whiskers by a normal-pressure zinc vapor oxidation method. Under normal pressure, metal zinc ingot, industrial crude zinc, zinc alloy (except copper-zinc alloy), zinc-containing metal waste, zinc powder and zinc particles are used as raw materials, specially-made zinc powder or zinc particles coated with oxide films are not needed, the raw materials are directly heated to generate zinc vapor, or the zinc vapor in the metal smelting and zinc powder preparation processes is directly used as the raw materials, and the overflowed zinc vapor is contacted with air or oxygen and is oxidized to be converted into the tetrapod-like zinc oxide whiskers. The production process can realize the serialization, simplifies the preparation process, and directly obtains the high-quality tetrapod-like zinc oxide crystal whisker with single appearance. The product can be used for high polymer materials, antistatic materials, wear-resistant and anti-skid materials, semiconductors, piezoelectricity, microwave absorption materials, vibration and noise reduction materials, ceramic toughening and anti-fragmentation materials, reinforcing materials, antibacterial composite materials, photocatalytic materials and the like.
Description
Technical field
The present invention relates to the technology that a kind of normal pressure zinc fume oxidation style prepares four acicular type zinc oxide crystal whisker, belong to inorganic materials technology and Non-ferrous Metallurgy field.Especially relate to utilizing the zinc fume that the heating material containing zinc produces or smelting zinc fume and be raw material, directly contact also oxidizedly, prepare the technological method of four acicular type zinc oxide crystal whisker with air.
Background technology
Four acicular type zinc oxide crystal whisker (Tetrapod-like Zinc Oxide Whisker is called for short T-ZnOw) is a kind of three-dimensional four acicular single crystal fibres that grow into.This unique texture of four acicular type zinc oxide crystal whisker makes it become strongthener, and simultaneously T-ZnOw also has outstanding multi-functional characteristic, as wear-resisting, anti-skidding, the noise reduction of excellence, suction ripple, anti-aging, shock resistance, antistatic, anti-algae, antibiotic etc.Compare with common zinc oxide, four acicular type zinc oxide crystal whisker T-ZnOw has many advantages, and its main application at present comprises: macromolecular material antistatic material, wear-resisting anti-slip material, semi-conductor, piezoelectricity, microwave absorbing material, vibration and noise reducing material, ceramic toughening shatter-resistant material, strongthener, antimicrobial composite material, photocatalyst material etc.
The technology of preparing of T-ZnOw ZnOw is mainly divided zinc powder preoxidation and zinc powder direct oxidation method at present.Method one is in advance with the zinc powder surface oxidation in the zinc powder preoxidation, be about to high-purity zinc powder and place deionized water for stirring, ageing, drying, make its surface generate certain thickness oxide film, more this zinc powder is prepared four needle-like whiskers in about 1000 ℃ heating of high temperature gasification in about 1 hour oxidation.Oxide film can suppress melt metal zinc from the very fast loss of granule interior in the heat-processed, also controls the rate of migration of oxygen to zinc granule inside, needed time of bonding crystal growth simultaneously.Method two is that the zinc powder that will have oxide film under the inert gas protection is heated to more than the boiling point; be carrier gas then with the rare gas element; zinc fume is introduced oxygen-containing gas or oxygen-containing gas is blown in the zinc fume, zinc is contacted in gas phase with oxygen, generate zinc oxide four needle-like whiskers.Method three is with zinc powder and NH
4 +, CO
3 2-(or HCO
3 -) and H
2O mixes by a certain percentage, generates ZnCO under prescribed condition
3, be heated to specified temp then, ZnCO
3Then slowly be decomposed to form zinc oxide four needle-like whiskers.Method four is to use the zinc powder through surface oxidation to mix with white carbon black (or clay), and bubbling air carries out oxidation when being heated to 900～1000 ℃, has prepared T-ZnOw.Method five is that zinc powder and activated carbon through surface oxidation are placed in the electric furnace N by the suitable proportion mixing
2And O
2Feed by a certain percentage in the reaction chamber, controlled temperature is at 1050～1150 ℃, and reaction 5h can make long 20～25mm, the needle-like whisker of the about 0.1mm of diameter.
The T-ZnOw size of preoxidation preparation is big, regularity is better.But to the purity (Zn＞99.99%) and the granularity requirements strictness of zinc powder, the pre-oxidation treatment technology of zinc powder is very numerous and diverse.Preparation during raw material the own part of zinc oxidized, the recovery rate of whisker lower (be about 40% of zinc powder quality, in the time of better 80～86%) has increased the preparation cost of T-ZnOw.
The zinc powder direct oxidation method is promptly directly produced T-ZnOw with the zinc powder oxidation.Method one is the metal zinc ingot fusion to be sprayed into make zinc powder in the water, is 5: 1 batchings by zinc powder and coke ratio, is heated to 950～1050 ℃ in the container of packing into after the mixing in atmosphere, and insulation 10～20min makes zinc oxide four needle-like whiskers.Method two is a reaction tubes of zinc powder being put into an end opening, and 500～850 ℃ of temperature of reaction are incubated 0.5～2h, make the whisker of two kinds of forms.There is the incomplete problem of part zinc powder oxidation in direct oxidation method, and productivity is lower.Compare with preoxidation, improved if take appropriate measures, direct oxidation method will be the Technology of more promising realization T-ZnOw industrialization.At the different characteristics of aforesaid method, more domestic contrivers have proposed new preparation method and technology.
Contriver Zhou Zuowan, Qiu Binwu, Xie Ning etc. have applied for a kind of process for preparing zinc oxide crystal whisker; this method is a raw material with zinc granule or zinc metal sheet; utilize the principle of air expanded by heating; make in encloses container that when gases are heated, they expand in the furnace chamber; air capacity reduces, thereby amount of oxygen is wherein reduced thereupon, when resistance furnace is heated to 700～1100 ℃; put into raw material zinc, heating promptly generated the ZnOw that outward appearance is the white loose shape in 3～12 minutes.Its application content is referring to " a kind of process for preparing zinc oxide crystal whisker ", and publication number is CN1206756A, and application number is CN97107607.3.
Contriver Wu Run, the sea of following what is right, Liu Hongfang, Liu Jing, thank long-living, Wang Aihua, Cai Wei's equality and applied for a kind ofly containing the method for producing the ZnO nano whisker the zinc waste from metallurgy with vapor phase process, its method is that to contain the zinc waste with metallurgy be raw material, put into the heating of vacuum-evaporation chamber after the enrichment again, when the zinc fume flame sprays, rare gas element with the high speed thread imports reaction chamber with this bluster, carries out the synthetic of nano zine oxide.Its application content is referring to " a kind of ZnO nano crystal whisker material and preparation method thereof ", and publication number is CN1458305A, and application number is CN02115818.5.
Contriver Tang becomes spring, Cheng Chun, Ding Xiaoxia, Qi Shouren etc. to apply for the method for a kind of alloy gas controlled evaporation method synthesizing zinc oxide micron, nanofiber, the brass ingot that this method is utilized copper zinc mixed powder or directly used commercial purity is as reactant, the metallic zinc steam that direct oxidation frit reaction thing discharges under the high temperature in air.Its principle is after zinc and copper form alloy, and under identical temperature, the vapor pressure lowering of zinc reaches the purpose that oxidation forms zinc oxide fiber by the vapour pressure of regulating and control zinc.Its application content is referring to " synthetic micron of alloy gas controlled evaporation method and nano zine oxide fiber ", and publication number is CN1594098A, and application number is CN200410013391.7.
Contriver Yang Dajin, Chen Jiaxi, Xu Yafei, Yan Jiangfeng etc. have applied for a kind of production technique and equipment patent of four acicular type zinc oxide crystal whisker, are raw material with industrial zinc ingot metal, and the zinc fume that volatilizes is by high temperature N
2Bring in the whisker reactor, and send into N outward
2Form zinc oxide with the high temperature oxidation stability gas reaction of air mixed, controls reaction speed makes the zinc oxide crystallization, grows up, and forms four acicular type zinc oxide crystal whisker at last, and ZnOw is by N
2Take out of, cool and isolate four acicular type zinc oxide crystal whisker, separate the N of whisker
2Return or as zinc fume bring gas into or as the gas of bringing into of oxidizing gas, whisker transformation efficiency height is four acicular type zinc oxide crystal whisker more than 95% in the product, the direct yield 80～90% of crystal whisker products simultaneously, zinc recovery＞95%.The application content is referring to " production technique of four acicular type zinc oxide crystal whisker and equipment ", and publication number CN1384056A, application number are CN02113881.8.
Contriver Chen Yi peak, Tang Motang, Yang Shenghai, the ripple Tang Dynasty, Yao Weiyi, how to wait having applied for a kind of method of producing ZnOw quietly, this method profit is raw material with the hot galvanizing residue, be increased to 850～1000 ℃ in furnace temperature, the reactor that cadmia is housed is placed in the special electric furnace, aerating oxygen and nitrogen, in certain atmosphere, reacted 15～25 minutes, generate outward appearance and be white loose ZnOw.Its application content is referring to " a kind of method of producing ZnOw ", and publication number is CN1566417A, and application number is CN03124553.6.
The method that one of inventor Li Dun francium and other co-workers once applied for preparing different shape zinc oxide by vacuum limit oxygen method, in vacuum environment, under certain temperature, regulate and control the content and the dividing potential drop of the vapor pressure and the restriction oxygen of metallic zinc with certain vacuum degree, thereby the metallic zinc steam is reacted under different physical and chemical conditions with oxygen, preparation comprises the different shape zinc oxide of four acicular type zinc oxide crystal whisker, and application number is 200510039156.1.But this method needs more utility appliance.
The preparation method of above-mentioned four acicular type zinc oxide crystal whisker and invention have relative merits separately.Some nearest research reports show that the growth mechanism of four needle-like oxidation whiskers can be explained with gas-solid reaction model (VS).The inventor is by discovering, different with foregoing invention is, adopting metal zinc ingot, industrial crude zinc, zinc alloy (except the copper zinc alloy), zinc-containing metal waste material, zinc powder, zinc granule, smelting zinc fume under normal pressure is raw material, does not need special zinc powder, nitrogen N
2(or rare gas element) is as carrier gas and airtight or vacuum reaction environment, directly raw material is added the thermogenesis zinc fume, the zinc fume that overflows contacts with air and can produce four acicular type zinc oxide crystal whisker equally after oxidized, and needn't control the concentration of zinc fume specially, production process can realize serialization, simplify preparation process greatly, directly obtained the single four acicular type zinc oxide crystal whisker of high-quality pattern.As producing the smelting zinc fume that produces in the metal zinc process with metal smelting zinc and indirect method is raw material, and then preparation technology also can simplify, and obtains identical product.
Yet there are no report with identical summary of the invention of the present invention and claim.
The present invention adopts new technological method to prepare T-ZnOw, except that adopting metal zinc ingot, industrial crude zinc, zinc alloy (except the copper zinc alloy), zinc-containing metal waste material, zinc powder, zinc granule is the raw material, also can directly adopt in the zinc metallurgical process in the crude zinc refining rectifying tower or produces the zinc fume that produces in the zinc powder production process as feedstock production T-ZnOw.Present domestic the have enterprise of many employing zinc rectifying tower refining crude zincs or the enterprise that the zinc distillation method is produced zinc powder, zinc fume production particulate state high grade zinc oxide or metal zinc that they utilize the zinc rectifying tower to produce aborning.If adopt method of the present invention, utilize their part production capacity to realize the large-scale continuous production of T-ZnOw, will reduce the production cost of T-ZnOw greatly.Utilize the existing technological process of production and equipment, increase value-added content of product, improve the deep processing ability of enterprise product.
Summary of the invention
The objective of the invention is: propose the method that a kind of normal pressure zinc fume oxidation style prepares four acicular type zinc oxide crystal whisker, can or under normal pressure, regulate and control the vapor pressure of metallic zinc and the dividing potential drop of oxidizing gas at air, not needing the zinc powder or the zinc granule of special outsourcing oxide film is raw material, is the feedstock production four acicular type zinc oxide crystal whisker and produce the smelting zinc fume that produces in the metal zinc process with metal zinc ingot, industrial crude zinc, zinc alloy (except the copper zinc alloy), zinc-containing metal waste material, zinc powder, zinc granule, metal smelting zinc and indirect method.
Main process of the present invention is: normal pressure zinc fume oxidation style prepares the method for four acicular type zinc oxide crystal whisker, under normal pressure, the material of metallic zinc or containing metal zinc is put into process furnace, heating makes the metallic zinc evaporation, when temperature reaches 650～1300 ℃ of Heating temperatures, zinc fume overflows, do not need of the carrier gas of gas such as nitrogen, directly, generate four acicular type zinc oxide crystal whisker by extraneous air or the air or oxygen oxidation that is blown into as zinc fume; Or metal smelting zinc and indirect method are produced the zinc fume that produces in the metal zinc process contact the acquisition four acicular type zinc oxide crystal whisker with being blown into air or oxygen.
Especially the material of metallic zinc or containing metal zinc is put into process furnace, and the zinc fume air outlet temporary close that will communicate with air, air can not be entered in the process furnace.When material is heated to certain temperature, has higher zinc fume pressure in the process furnace, at this moment open the zinc fume air outlet, zinc fume is by the oxidation of air or oxygen institute in oxidation reactor, constantly generate four acicular type zinc oxide crystal whisker, be gathered into the fluffy floss of white, be the finished product after the cooling.
The material of containing metal zinc is that metal zinc ingot, industrial crude zinc, zinc alloy (except the copper zinc alloy), zinc-containing metal waste material, zinc powder, zinc granule, smelting zinc fume are raw material, carries out in a unlimited system that communicates with air, and production process can be carried out continuously.
Particular content of the present invention is as follows:
1, the material with metallic zinc or containing metal zinc is a raw material, in process furnace He under the normal pressure, carry out heating evaporation, close the zinc fume outlet, along with the rising of temperature, the vapour pressure of zinc constantly increases, when zinc fume reaches certain pressure, open the zinc fume outlet, in the oxidation reactor that zinc fume is introduced with air communicates, zinc fume and airborne oxygen reaction, generate four acicular type zinc oxide crystal whisker, constantly accumulate in the reactor, from material taking mouth, regularly take out.According to the character of different material, control different heating evaporation temperature, obtain four acicular type zinc oxide crystal whisker.The zinc raw material can disposablely add, also graded or adding continuously.
2, with above-mentioned summary of the invention 1 described content and method, can adopt metal zinc ingot, industrial crude zinc, zinc alloy (except the copper zinc alloy), zinc-containing metal waste material, zinc powder, zinc granule is raw material, or is raw material to smelt zinc fume directly.
3, with above-mentioned summary of the invention 1 described content and method, can in air, suitably feed a certain amount of rare gas element, CO
2, CO, SO
2Gas forms different oxidizing atmosphere as assist gas, can obtain the four acicular type zinc oxide crystal whisker of size and different-shape.
4, with above-mentioned summary of the invention 1,2,3 described content and methods, can be in the zinc fume that overflows the nano level auxiliary agent, as ZrO
2, SiO
2, Al
2O
3, TiO
2, ZnO, ZnS, CaO, ZnCO
3, MgO, CaCO
3, mica, zeolite, glass, gac, clay powders, composite oxides etc. are as auxiliary agent, or zinc fume are contacted with various coatingsurfaces, improve the speed of growth of four acicular type zinc oxide crystal whisker, the pattern of control four acicular type zinc oxide crystal whisker.
The present invention heats up at the process furnace internal heating, and when rising to certain temperature, the zinc fume of generation overflows, enter with oxidation reactor that air communicates in, by the oxidation of airborne oxygen institute, or, obtain four acicular type zinc oxide crystal whisker after the oxidation to smelt zinc fume as the zinc fume raw material.Can realize simultaneously effectively separating of four acicular type zinc oxide crystal whisker and zinc residue on evaporation, improve quality product.Raw material sources are wide, simplified the technological process of production, reduced production cost significantly, and the production process serialization is for the broad practice of four needle-like oxidation whiskers provides condition.
Characteristics of the present invention are: adopting material and smelting zinc fume with containing metal zinc is raw material, utilizes the method for atmospheric oxidation zinc fume to prepare four acicular type zinc oxide crystal whisker under non-pressurized condition.The technology of the present invention method raw material sources are wide, do not need special raw material and equipment, and the technological process of production is short, and operational condition is simple, and production process is easy to control, the production process serialization, and production cost is low.
Description of drawings
Fig. 1 is the scanning electronic microscope SEM photo of the pattern of the prepared four acicular type zinc oxide crystal whisker of employing the present invention.
Embodiment
Embodiment 1
With the metal zinc ingot is raw material, and the zinc vapourizing furnace is a bubble-tight inner lining with silicon carbide material heating stove, and 3kg metal spelter is added in the stove, seals, and goes out programmed temperature control instrument and realizes zinc vapourizing furnace temperature auto control.Control the Heating temperature of zinc vapourizing furnace, can obtain the zinc fume of different pressures, the zinc fume that the zinc vapourizing furnace produces is imported in the horizontal horizontal type oxidizing reaction electric furnace by alumina tube or silica tube.
After treating the metallic zinc fusing, the temperature of the zinc vapourizing furnace that raises fast.When the temperature of zinc vapourizing furnace was increased to design temperature, control reaction temperature was about 650～1300 ℃; Keep the temperature in the oxidizing reaction electric furnace, can accurately control the air or oxygen amount of feeding, and keep the pressure in the reactor certain, the fluffy oxidized zinc products of white constantly generates, and is deposited on a container of putting in advance.To the regular hour, accumulated the zinc oxide of some amount, take out cooling.With the pattern and the crystalline structure of scanning electronic microscope (SEM) and X-ray diffractometer (XRD) assay products, illustrate that product is uniform four acicular type zinc oxide crystal whisker.
Adopting other material containing zinc, is raw material as industrial crude zinc, zinc alloy, zinc-containing metal waste material, zinc powder, zinc granule etc., with above-mentioned method and apparatus, can obtain four acicular type zinc oxide crystal whisker equally, but the length-to-diameter ratio difference of whisker.When being raw material to smelt zinc fume, can economize dezincify evaporation heating installation, it is indoor only zinc fume need to be fed oxidizing reaction, and keeps certain temperature, can obtain four acicular type zinc oxide crystal whisker.
Embodiment 2
With the zinc granule is raw material, adds in the zinc vapourizing furnace, and isolates with the ambient atmosphere environmental facies.The temperature of rising zinc vapourizing furnace when the pressure of zinc fume reaches one regularly, imports zinc fume in the reaction zone, and control reaction temperature is about 650～1300 ℃.Open inlet mouth, and be blown into the Zinc oxide powder that granularity is 10～50 nanometers with air, zinc fume is constantly oxidized, generates white floss, has generated about 230 gram products in 15 minutes.Determine that through scanning electronic microscope (SEM) product is a four acicular type zinc oxide crystal whisker.
Be blown into different nano level auxiliary agents in zinc fume, with air as ZrO
2, SiO
2, Al
2O
3, TiO
2, ZnS, CaO, ZnCO
3, MgO, CaCO
3, mica, zeolite, glass, gac, clay powders, composite oxides etc. be as auxiliary agent, or in air zinc fume contacted with various coatingsurfaces, can control the size and the pattern of four acicular type zinc oxide crystal whisker.
Embodiment 3
Earlier the 2kg metal zinc is added in the zinc vapourizing furnace, the Heating Zn vapourizing furnace when temperature reaches 900 ℃, imports the zinc fume that produces in the oxidizing reaction electric furnace.In air, allocate a certain amount of CO into
2Gas forms different oxidizing atmosphere as assist gas, can obtain the four acicular type zinc oxide crystal whisker of different sizes and different whisker length-to-diameter ratios.Under 650～1300 ℃ of temperature, pass through the different temperature of reaction of control, the reaction generating rate difference of four acicular type zinc oxide crystal whisker.Metal zinc can regularly replenish adding.
In air, suitably feed a certain amount of rare gas element, CO, SO
2Gas forms different oxidizing atmosphere as assist gas, also can play and CO
2The effect that gas is identical obtains the four acicular type zinc oxide crystal whisker product.
Claims (4)
1. normal pressure zinc fume oxidation style prepares the method for four acicular type zinc oxide crystal whisker, it is characterized in that under normal pressure, the material of metallic zinc or containing metal zinc being put into process furnace, heating makes the metallic zinc evaporation, when temperature reaches 650～1300 ℃, zinc fume overflows, directly, generate four acicular type zinc oxide crystal whisker by extraneous air or the air or oxygen oxidation that is blown into; Or metal smelting zinc and indirect method are produced the zinc fume that produces in the metal zinc process contact the acquisition four acicular type zinc oxide crystal whisker with the air or oxygen that is blown into; And be blown into nano level auxiliary agent: ZrO at zinc fume oxidising process air
2, SiO
2, Al
2O
3, TiO
2, ZnO, ZnS, CaO, ZnCO
3, MgO, CaCO
3, mica, zeolite, glass, gac or clay powders, be used to control the size and the pattern of four acicular type zinc oxide crystal whisker.
2. the method for preparing four acicular type zinc oxide crystal whisker by the described normal pressure zinc fume of claim 1 oxidation style, it is characterized in that adopting zinc alloy, zinc-containing metal waste material, zinc powder, zinc granule, smelting zinc fume except metal zinc ingot, industrial crude zinc, the copper zinc is raw material, carry out in a unlimited system that communicates with air, preparation process is carried out continuously.
3. the method that is prepared four acicular type zinc oxide crystal whisker by claim 1 or 2 described normal pressure zinc fume oxidation style is characterized in that feeding a certain amount of rare gas element, CO in air
2, CO or SO
2Gas forms different oxidizing atmosphere as assist gas, can obtain the four acicular type zinc oxide crystal whisker of size and different-shape.
4. the method for preparing four acicular type zinc oxide crystal whisker by claim 1 or 2 described normal pressure zinc fume oxidation style, it is characterized in that the material of metallic zinc or containing metal zinc is put into process furnace, and the zinc fume air outlet temporary close that will communicate with air, make air can not enter in the process furnace; When material is heated to 650～1300 ℃, open the zinc fume air outlet and enter oxidation reactor, zinc fume is oxidized by the air in oxidation reactor, generates four acicular type zinc oxide crystal whisker, is gathered into the fluffy floss of white, is the finished product after the cooling.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967679B (en) * | 2010-10-29 | 2012-04-25 | 北京矿冶研究总院 | Method for regulating and controlling morphology of zinc oxide whisker |
| CN102426867B (en) * | 2011-08-25 | 2013-03-13 | 哈尔滨东大高新材料股份有限公司 | Whisker reinforced copper-based electrical contact material and preparation method thereof |
| CN102874862B (en) * | 2012-10-17 | 2015-05-06 | 栾川县锌源矿冶有限公司 | Production and calcination process and equipment of spontaneous-combustion environmental-protection zinc oxide |
| CN105668609B (en) * | 2016-01-11 | 2017-07-28 | 合肥师范学院 | A kind of plane hierarchy nano zine oxide and preparation method thereof |
| CN106115770A (en) * | 2016-06-30 | 2016-11-16 | 安徽省含山县锦华氧化锌厂 | A kind of environment-friendly type zinc oxide preparation method |
| CN107059124B (en) * | 2017-03-31 | 2020-01-17 | 中原工学院 | Method for synthesizing large-size zinc oxide crystal by using microwaves |
| CN108796607A (en) * | 2018-06-07 | 2018-11-13 | 邯郸钢铁集团有限责任公司 | Utilize the method for secondary cadmia continuous production nano four-needle-shape zinc oxide |
| CN108866634B (en) * | 2018-07-27 | 2019-11-05 | 辽宁科技大学 | A method of magnesia crystal whisker is prepared using waste magnesia carbon brick substrate material as raw material |
| CN111285395A (en) * | 2020-02-25 | 2020-06-16 | 兴化市庆丰锌品有限公司 | Production process of high-purity zinc oxide indirect method |
| CN111610305B (en) * | 2020-04-28 | 2021-11-09 | 北京科技大学 | Method for quantitatively evaluating crushing resistance and wear resistance of iron alloy for steelmaking by using rotary drum |
| CN115872438B (en) * | 2022-12-07 | 2024-03-19 | 河南城建学院 | Tetrapod-like zinc oxide gas-sensitive material with brush-like structure, and preparation method and application thereof |
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