CN114184652B - Preparation method of Freon gas-sensitive material, prepared gas-sensitive material and application thereof - Google Patents
Preparation method of Freon gas-sensitive material, prepared gas-sensitive material and application thereof Download PDFInfo
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- CN114184652B CN114184652B CN202111313659.9A CN202111313659A CN114184652B CN 114184652 B CN114184652 B CN 114184652B CN 202111313659 A CN202111313659 A CN 202111313659A CN 114184652 B CN114184652 B CN 114184652B
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- 239000000463 material Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000001462 antimony Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 150000002940 palladium Chemical class 0.000 claims abstract 2
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000379 antimony sulfate Inorganic materials 0.000 claims description 2
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 claims description 2
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 23
- 230000007774 longterm Effects 0.000 abstract description 21
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 95
- 239000002086 nanomaterial Substances 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000004044 response Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 101150003085 Pdcl gene Proteins 0.000 description 8
- 229910006404 SnO 2 Inorganic materials 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002077 nanosphere Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a preparation method of a Freon gas-sensitive material, which relates to the technical field of gas-sensitive materials and comprises the following steps: (1) Dissolving tin salt in a reaction solvent, adding antimony salt and a surfactant, heating and stirring in a water bath after dissolving, then adding alkali liquor until the pH value of the mixed liquor reaches 9.5-10.5, cooling, centrifuging, freeze-drying after the reaction is finished, sintering the dried powder, and preparing the sintered material into powder to obtain a sensitive material main body; (2) Mixing the sensitive material main body with PMMA dispersion liquid, organic alcohol, volatile solvent, palladium salt and tetraethyl silicate, ball milling and drying. The invention also provides the gas-sensitive material prepared by the method and application thereof. The invention has the advantages that: the gas-sensitive material has high sensitivity to Freon gas, strong stability, small interference from external environment in air, stable long-term resistance value, stable long-term sensitivity and excellent capability of resisting environmental temperature and humidity changes.
Description
Technical Field
The invention relates to the technical field of gas-sensitive materials, in particular to a preparation method of a Freon gas-sensitive material, the prepared gas-sensitive material and application thereof.
Background
With the increasing demands of people for living things, the demands of refrigerators, air conditioners, automobiles and the like are also increasing in recent years. In the process of using the product, the refrigerant is needed, and the refrigerant commonly used at present is Freon. Freon is a very wide variety, is generally gaseous at normal temperature and pressure, has slightly aromatic flavor, and is transparent liquid under low temperature and pressure. Can be mixed and dissolved with halohydrocarbon, monohydric alcohol or other organic solvents in any proportion, and fluorine refrigerants can be mutually dissolved, so that the fluorine refrigerant can be widely applied to industries such as foaming, solvents, spray, cleaning of electronic elements and the like. Freon is currently broadly divided into three categories, including chlorofluorocarbons, hydrochlorofluorocarbons, and hydrofluorocarbons. Currently, chlorofluorocarbons are prohibited or limited in use due to environmental pollution, ozone depletion, etc., and hydrofluorocarbons will be the mainstream in the future market. However, even if they can be safely used under certain conditions, these hydrofluorocarbon gases are important greenhouse gases and need to be treated with care. Common freons such as R22, R134a, R32, etc. are flammable, burn and even explode when exposed to an open flame, and produce toxic gases.
At present, domestic freon for household appliances and automobiles is not detected, so that explosion events caused by freon leakage frequently occur, death of multiple people is seriously caused, and the requirements for freon leakage detection are more and more urgent. Traditional gas sensors are only sensitive to fluorochlorohydrocarbons, but not to hydrofluorocarbon environment-friendly refrigerants. However, there is still a considerable amount of use in the hydrochlorofluorocarbon market today, so it is necessary to develop gas sensors that are sensitive to both types of gases.
In addition, the resistance stability and the temperature and humidity resistance performance of the currently reported Freon sensor are not mentioned in the use process of the sensor, but most of efforts are put on the sensitivity of the gas-sensitive material to target gas, such as a preparation method of a gas-sensitive element of a refrigerant gas sensor of patent publication No. CN102064277, for example.
The resistance should be stable in a clean atmosphere. The resistance and sensitivity should be stable under different temperature and humidity conditions. This can reduce the complexity of the software associated with the sensor when in use, reducing the cost of subsequent development. Therefore, the improvement of the stability of the sensor sensitive material is of great importance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a Freon gas-sensitive material with strong stability, small interference from external environment in air, stable long-term resistance and stable long-term sensitivity, the prepared Freon gas-sensitive material and application thereof.
The invention solves the technical problems by the following technical means:
a preparation method of a Freon gas-sensitive material comprises the following steps:
(1) Dissolving tin salt in a reaction solvent, adding antimony salt and a surfactant, heating and stirring the mixed solution in a water bath at 80-100 ℃, adding alkali liquor with the dropping speed of 1-5mL/min until the pH value of the mixed solution reaches 9-11, cooling, centrifuging and freeze-drying after the reaction is finished, sintering the dried powder, and preparing the sintered material into powder to obtain a sensitive material main body; the ratio of the mass of the surfactant to the mass of the tin salt is 2-6:5;
(2) Mixing sensitive material main body with PMMA dispersion liquid, organic alcohol, volatile solvent and PdCl 2 Mixing with tetraethyl silicate, and ball milling to obtain the freon gas-sensitive material.
The beneficial effects are that: the gas-sensitive material has high sensitivity and strong stability to freon gas, especially freon and hydrofluorocarbon freon gas, is little disturbed by external environment in air, has stable long-term resistance value and long-term sensitivity, and has excellent capability of resisting environmental temperature and humidity changes.
The invention uses the gas-sensitive material SnO 2 The synthesis and the functional modification of the material are completed separately, the performance of each step can be regulated effectively, the method is simple and efficient, the mass production of sensitive materials is easy to carry out, and the preparation method is green and has low energy consumption.
The invention prepares SnO by a solution gel method 2 The nanospheres can be used for preparing main components of materials sensitive to freon gas in a large scale, and the nanospheres with uniform morphology and large specific surface area can be prepared by controlling the surfactant in the reaction, so that the response of the gas-sensitive material can be effectively improved; and secondly, the nanospheres are doped and modified, so that the stability and the temperature and humidity resistance of the sensor can be effectively improved.
According to the invention, the nucleation and growth of the nano material in the reaction are controlled by adjusting the pH value of the mixed solution, the adding speed of the alkali solution, the reaction time and the reaction temperature and the adding amount of the surfactant, so that the prepared tin dioxide nano material has uniform sphericity, smaller particle size, large specific surface area, higher response speed of the gas sensitive material and higher sensitivity.
Too low a pH reaction cannot be performed, too high a pH material nucleates too quickly, the size of the nanomaterial can be large, and the morphology of the sensitive material host material is poor, so that the performance of the gas sensitive material is affected. The addition amount of the surfactant is too small, the size of the sensitive material main body nano material can be enlarged, the appearance is poor, the specific surface area is low, and the main body reaction can be influenced due to the too large addition amount.
The antimony salt is added into the main body material of the sensitive material, so that the material resistance can be reduced, and if the antimony salt is not added, the overall resistance of the gas sensitive material is overlarge, so that the development and the use of a later-stage sensor are not facilitated.
According to the invention, the nano material is dried into powder through freeze drying, so that the agglomeration of the nano material in the sintering process is effectively avoided, and the sensitivity is reduced.
The invention uses ball milling to make the modifier element Pd and the sensitive material main material SnO 2 The mixing method is simple and easy to batch. The PMMA dispersion assists the dispersion of the nano material, and simultaneously reduces the resistance of the gas sensitive material. A gas-sensitive material slurry in a uniform state is obtained by an organic alcohol. The long-term resistance stability of the gas-sensitive material in the environment is regulated by palladium element, and the tetraethyl silicate forms SiO 2 The bonding force between the gas-sensitive material and the substrate is improved, and meanwhile, the stability and the temperature and humidity resistance of the sensor are enhanced due to the combined action of the palladium element and the tetraethyl silicate.
Preferably, the ratio of the adding amount of the tin salt to the volume of the reaction solvent is 5g:150mL-300 mL, and the adding amount of the antimony salt is 1-10% of the mass of the tin salt.
The beneficial effects are that: and if the addition amount of the antimony salt is lower than the range value, the resistance of the gas sensitive material is relatively excessive, and if the addition amount of the antimony salt is higher than the range value, the resistance of the gas sensitive material is excessively small, so that the power consumption of a sensor circuit is increased.
Preferably, the step (1) is carried out for 1 hour after the pH of the mixed solution is adjusted to 10.
Preferably, the ultrasonic dispersion is carried out in the water bath heating process in the step (1).
The beneficial effects are that: the ultrasonic dispersion ensures that the raw materials are mixed more uniformly, and the growth of the tin dioxide nano material is controlled to a certain extent, so that the nano material has smaller size, large specific surface area and increased reactive sites.
Preferably, the supernatant is removed after centrifugation in the step (1), ultrasonic washing is performed with ethanol, deionized water is added to the obtained solid, and freeze drying is performed after freezing.
Preferably, the tin salt in step (1) is selected from SnCl 4 ·5H 2 O、SnCl 2 ·2H 2 O、SnSO 4 One of the following;
the reaction solvent is one of methanol, ethanol, water and 90% ethanol-water mixed solution; the antimony salt is one of antimony nitrate, antimony sulfate, antimony trichloride and antimony pentachloride;
the surfactant is one of cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, polyacetylimine and sodium dodecyl sulfonate;
the alkali liquor is one of tetramethylammonium hydroxide solution, tetraethylammonium hydroxide solution, tetrapropylammonium hydroxide solution, butylammonium hydroxide solution, trimethylamine, triethylamine, ethanolamine and triethanolamine.
Preferably, the sintering temperature in the step (1) is 300-700 ℃.
Preferably, the PMMA dispersion in the step (2) has a mass concentration of 1% -20%.
Preferably, the organic alcohol in the step (2) is one of ethylene glycol, glycerol and terpineol.
Preferably, pdCl in the step (2) 2 Is PdCl 2 Aqueous solution of PdCl 2 The mass concentration of the aqueous solution is 1-5%.
Preferably, the volume ratio of PMMA dispersion liquid to tetraethyl silicate in the step (2) is 5:0.1-1.
Preferably, the volatile solution is ethanol and water, and the volume ratio of the ethanol to the water is 1:1.
The Freon gas-sensitive material prepared by the method.
The beneficial effects are that: the gas-sensitive material has high sensitivity and strong stability to freon gas, especially freon and hydrofluorocarbon freon gas, is little disturbed by external environment in air, has stable long-term resistance value and long-term sensitivity, and has excellent capability of resisting environmental temperature and humidity changes.
And the MEMS sensitive chip comprises the freon gas-sensitive material.
Preferably, the preparation method of the MEMS sensitive chip comprises the following steps: and coating the Freon gas-sensitive material on the MEMS heater, and then performing heat treatment to obtain the MEMS sensitive chip.
The beneficial effects are that: the MEMS sensitive chip has high sensitivity and strong stability to freon gas, especially freon and hydrofluorocarbon freon gas, is little interfered by external environment in air, has stable long-term resistance value and long-term sensitivity, and has excellent capability of resisting environmental temperature and humidity changes.
Preferably, the heat treatment is performed at a high temperature of 500 ℃ for 2 hours.
The beneficial effects are that: the annealing can increase the binding force between the material and the chip, and burn off organic matters in the material, so that the material can quickly enter a stable state.
And the MEMS gas sensor comprises the freon gas-sensitive material.
The beneficial effects are that: the MEMS gas sensor has high sensitivity and strong stability to freon gas, especially freon and hydrofluorocarbon freon gas, is little disturbed by external environment in air, has stable long-term resistance value and long-term sensitivity, and has excellent capability of resisting environmental temperature and humidity changes.
Preferably, the preparation method of the MEMS gas sensor comprises the following steps: and coating a freon gas-sensitive material on the MEMS heater, then performing heat treatment to obtain an MEMS sensitive chip, and then packaging the MEMS sensitive chip to obtain the MEMS gas sensor.
The invention has the advantages that: the gas-sensitive material has high sensitivity and strong stability to freon gas, especially freon and hydrofluorocarbon freon gas, is little disturbed by external environment in air, has stable long-term resistance value and long-term sensitivity, and has excellent capability of resisting environmental temperature and humidity changes.
The invention uses the gas-sensitive material SnO 2 The synthesis and the functional modification of the material are completed separately, the performance of each step can be regulated effectively, the method is simple and efficient, the mass production of sensitive materials is easy to carry out, and the preparation method is green and has low energy consumption.
The invention prepares SnO by a solution gel method 2 The nanospheres can be used for preparing main components of materials sensitive to freon gas in a large scale, and the nanospheres with uniform morphology and large specific surface area can be prepared by controlling the surfactant in the reaction, so that the response of the gas-sensitive material can be effectively improved; and secondly, the nanospheres are doped and modified, so that the stability and the temperature and humidity resistance of the sensor can be effectively improved.
According to the invention, the nucleation and growth of the nano material in the reaction are controlled by adjusting the pH value of the mixed solution, the adding speed of the alkali solution, the reaction time and the reaction temperature and the adding amount of the surfactant, so that the prepared tin dioxide nano material has uniform sphericity, smaller particle size, large specific surface area, higher response speed of the gas sensitive material and higher sensitivity.
Too low a pH reaction cannot be performed, too high a pH material nucleates too quickly, the size of the nanomaterial can be large, and the morphology of the sensitive material host material is poor, so that the performance of the gas sensitive material is affected. The addition amount of the surfactant is too small, the size of the sensitive material main body nano material can be enlarged, the appearance is poor, the specific surface area is low, and the main body reaction can be influenced due to the too large addition amount.
The antimony salt is added into the main body material of the sensitive material, so that the material resistance can be reduced, and if the antimony salt is not added, the overall resistance of the gas sensitive material is overlarge, so that the development and the use of a later-stage sensor are not facilitated.
According to the invention, the nano material is dried into powder through freeze drying, so that the agglomeration of the nano material in the sintering process is effectively avoided, and the sensitivity is reduced.
The invention uses ball milling to make the modifier element Pd and the sensitive material main material SnO 2 The mixing method is simple and easy to batch. The PMMA dispersion assists the dispersion of the nano material, and simultaneously reduces the resistance of the gas sensitive material. A gas-sensitive material slurry in a uniform state is obtained by an organic alcohol. The long-term resistance stability of the gas-sensitive material in the environment is regulated by palladium element, and the tetraethyl silicate forms SiO 2 The bonding force between the gas-sensitive material and the substrate is improved, and meanwhile, the stability and the temperature and humidity resistance of the sensor are enhanced due to the combined action of the palladium element and the tetraethyl silicate.
The invention uses the gas-sensitive material SnO 2 The synthesis and the functional modification of the material are completed separately, the performance of each step can be regulated effectively, the method is simple and efficient, and the mass production of sensitive materials is easy to carry out.
The antimony salt is added into the main body material of the sensitive material, so that the material resistance can be reduced, and if the antimony salt is not added, the overall resistance of the gas sensitive material is overlarge, so that the development and the use of a later-stage sensor are not facilitated.
According to the invention, the nano material is dried into powder through freeze drying, so that the agglomeration of the nano material in the sintering process is effectively avoided, and the sensitivity is reduced.
The MEMS sensitive chip and the gas sensor have high sensitivity and strong stability to freon gas, especially freon gas such as chlorofluorocarbon and hydrofluorocarbon, are little disturbed by the external environment in the air, have stable long-term resistance value and long-term sensitivity, and have excellent capability of resisting environmental temperature and humidity changes.
And if the addition amount of the antimony salt is lower than the range value, the resistance of the gas sensitive material is relatively excessive, and if the addition amount of the antimony salt is higher than the range value, the resistance of the gas sensitive material is excessively small, so that the power consumption of a sensor circuit is increased.
The ultrasonic dispersion ensures that the raw materials are mixed more uniformly, and the growth of the tin dioxide nano material is controlled to a certain extent, so that the nano material has smaller size, large specific surface area and increased reactive sites.
The annealing can increase the binding force between the material and the chip, and burn off organic matters in the material, so that the material can quickly enter a stable state.
Drawings
FIG. 1 shows SnO obtained in the step (1) of example 1 of the present invention 2 Scanning electron microscope image of a body of sensitive material.
FIG. 2 shows SnO obtained in the step (1) of example 1 of the present invention 2 Scanning electron microscope image of a body of sensitive material at another magnification.
FIG. 3 shows SnO obtained in the step (1) of example 1 of the present invention 2 XRD pattern of the body of sensitive material.
FIG. 4 is a graph showing the response of a gas sensor to Freon in example 1 of the present invention.
Fig. 5 is a diagram showing the long-term stability of the gas sensor in air in example 1 of the present invention.
Fig. 6 is a graph showing temperature and humidity resistance of the gas sensor according to example 1 of the present invention.
FIG. 7 is a graph showing the comparison of resistance values of a gas sensitive material with and without the addition of an antimony salt (comparative example 1).
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
The preparation method of the Freon gas-sensitive material, the MEMS sensitive chip and the MEMS gas sensor specifically comprises the following steps:
(1) Preparation of a Freon gas-sensitive material main body: 5g of stannous sulfate was weighed into a 250mL beaker and 150mL of ethanol was added. The salt was completely dissolved by stirring with a glass rod, 0.5g of antimony trichloride was weighed into it, and completely dissolved by stirring. Then, 5g of cetyltrimethylammonium bromide was weighed and added thereto, and the surfactant was completely dissolved by stirring to obtain a mixed solution.
Placing the mixed solution into a constant-temperature water bath kettle, controlling the temperature of the water area to be 90 ℃, assembling an ultrasonic dispersing instrument with the power of 100W in the water bath kettle, slowly adding ethanolamine into the mixed solution, controlling the dripping speed of the ethanolamine to be 1mL/min, and stopping adding alkali liquor until the pH value of the solution reaches 10. After the reaction was continued for 1 hour, the reaction was stopped.
And standing and cooling the reactant, centrifuging the reacted substance to remove supernatant, ultrasonically cleaning the supernatant with ethanol for three times, adding 5mL of deionized water into the obtained solid, putting the solid into a refrigerator for freezing, and then putting the solid into a freeze dryer for drying. Then placing the dried powder into a quartz vessel, placing the quartz vessel into a sintering furnace for sintering at 600 ℃, keeping the temperature for 2 hours at a heating rate of 1 ℃/min, and then naturally cooling. The sintered material is ground into powder by an agate grinding bowl for standby.
(2) Modification of sensitive materials: weighing 0.5g of sintered powder, adding into a 50mL agate ball milling tank, adding 5mL of 10% PMMA aqueous solution, 0.5g of ethylene glycol, 5mL ethanol, 5mL of water and 0.5mL of 2% PdCl 2 Ball-milling the aqueous solution and 0.5mL of tetraethyl silicate at the speed of 800r/min for 6 hours, transferring the ball-milled mixed solution into a beaker, and putting the beaker into a baking oven at 70 ℃ to remove water and ethanol, thereby obtaining relatively viscous slurry.
(3) And (3) coating a freon gas-sensitive material on a heater of the MEMS micro-heating chip, then placing the chip into a high temperature of 500 ℃ for annealing for 2 hours to obtain the MEMS sensitive chip, and packaging the MEMS sensitive chip to obtain the MEMS gas sensor.
Example 2
The preparation method of the Freon gas-sensitive material, the MEMS sensitive chip and the MEMS gas sensor specifically comprises the following steps:
(1) Preparation of a Freon gas-sensitive material main body: 5g of stannous sulfate was weighed into a 250mL beaker and 150mL of ethanol was added. The salt was completely dissolved by stirring with a glass rod, 0.5g of antimony trichloride was weighed into it, and completely dissolved by stirring. Then, 5g of polyvinylpyrrolidone was weighed and added thereto, and stirring was performed to completely dissolve polyvinylpyrrolidone, thereby obtaining a mixed solution.
Placing the mixed solution into a constant-temperature water bath kettle, controlling the temperature of the water area to be 80 ℃, assembling an ultrasonic dispersing instrument with the power of 100W, slowly adding tetrapropylammonium hydroxide into the mixed solution, controlling the dropping speed of the tetrapropylammonium hydroxide to be 2mL/min, and stopping adding alkali liquor until the pH value of the solution reaches 10. After the reaction was continued for 1 hour, the reaction was stopped.
And standing and cooling the reactant, centrifuging the reacted substance to remove supernatant, ultrasonically cleaning the supernatant with ethanol for three times, adding 5mL of deionized water into the obtained solid, putting the solid into a refrigerator for freezing, and then putting the solid into a freeze dryer for drying. Then placing the dried powder into a quartz vessel, placing the quartz vessel into a sintering furnace for sintering at 500 ℃, keeping the temperature for 2 hours at a heating rate of 1 ℃/min, and then naturally cooling. The sintered material is ground into powder by an agate grinding bowl for standby.
(2) Modification of sensitive materials: weighing 0.5g of sintered powder, adding into a 50mL agate ball milling tank, adding 5mL of 10% PMMA aqueous solution, 0.5g of ethylene glycol, 5mL ethanol, 5mL of water and 0.5mL of 5% PdCl 2 Ball-milling the aqueous solution and 0.5mL of tetraethyl silicate at the speed of 800r/min for 6h, transferring the ball-milled mixed solution into a beaker, and putting the beaker into a baking oven at 70 ℃ to remove water and ethanol, thereby obtaining a relatively viscous slurry and obtaining the freon gas-sensitive material.
(3) And (3) coating a freon gas-sensitive material on a heater of the MEMS micro-heating chip, then placing the chip into a high temperature of 500 ℃ for annealing for 2 hours to obtain the MEMS sensitive chip, and packaging the MEMS sensitive chip to obtain the MEMS gas sensor.
Example 3
The preparation method of the Freon gas-sensitive material, the MEMS sensitive chip and the MEMS gas sensor specifically comprises the following steps:
(1) Preparation of a Freon gas-sensitive material main body: 5g of tin tetrachloride was weighed into a 250mL beaker and 150mL of ethanol was added. The salt was completely dissolved by stirring with a glass rod, 0.5g of antimony trichloride was weighed into it, and completely dissolved by stirring. Then, 5g of cetyltrimethylammonium bromide was weighed and added thereto, and the surfactant was completely dissolved by stirring to obtain a mixed solution.
Placing the mixed solution into a constant-temperature water bath kettle, controlling the temperature of the water area to be 90 ℃, assembling an ultrasonic dispersing instrument with the power of 100W in the water bath kettle, slowly adding ethanolamine into the mixed solution, controlling the dripping speed of the ethanolamine to be 5mL/min, and stopping adding alkali liquor until the pH value of the solution reaches 10. After the reaction was continued for 1 hour, the reaction was stopped.
And standing and cooling the reactant, centrifuging the reacted substance to remove supernatant, ultrasonically cleaning the supernatant with ethanol for three times, adding 5mL of deionized water into the obtained solid, putting the solid into a refrigerator for freezing, and then putting the solid into a freeze dryer for drying. And then placing the dried powder into a quartz vessel, placing the quartz vessel into a sintering furnace for sintering at 700 ℃, keeping the temperature for 2 hours at a heating rate of 1 ℃/min, and then naturally cooling. The sintered material is ground into powder by an agate grinding bowl for standby.
(2) Modification of sensitive materials: weighing 0.5g of sintered powder, adding into a 50mL agate ball milling tank, adding 5mL of 10% PMMA aqueous solution, 0.5g of ethylene glycol, 5mL ethanol, 5mL of water and 0.5mL of 4% PdCl 2 Ball-milling the aqueous solution and 0.1mL of tetraethyl silicate at the speed of 800r/min for 6 hours, transferring the ball-milled mixed solution into a beaker, and putting the beaker into a baking oven at 70 ℃ to remove water and ethanol, thereby obtaining relatively viscous slurry.
(3) And (3) coating a freon gas-sensitive material on a heater of the MEMS micro-heating chip, then placing the chip into a high temperature of 500 ℃ for annealing for 2 hours to obtain the MEMS sensitive chip, and packaging the MEMS sensitive chip to obtain the MEMS gas sensor.
Example 4
This embodiment differs from embodiment 1 in that: the addition amount of cetyl trimethylammonium bromide was 2g.
Example 5
This embodiment differs from embodiment 2 in that: the amount of polyvinylpyrrolidone added was 6g.
Example 6
This embodiment differs from embodiment 1 in that: the heating temperature in the water bath is 100 ℃.
Example 7
This embodiment differs from embodiment 1 in that: the mass concentration of the PMMA dispersion was 1%.
Example 8
This embodiment differs from embodiment 1 in that: the mass concentration of the PMMA dispersion was 20%.
Example 9
This embodiment differs from embodiment 1 in that: pdCl 2 The mass concentration of the aqueous solution was 1%.
Example 10
This embodiment differs from embodiment 1 in that: the amount of tetraethyl silicate added was 1mL.
Example 11
This embodiment differs from embodiment 1 in that: the organic alcohol is glycerol
Example 12
This embodiment differs from embodiment 1 in that: the organic alcohol is terpineol.
Comparative example 1
This comparative example differs from example 1 in that: antimony trichloride is not added in the step (1).
Experimental data and analysis:
FIGS. 1 and 2 show SnO prepared in example 1 of the present invention 2 Scanning electron microscope image of a body of sensitive material. It can be seen that the synthesized spherical SnO 2 The size is uniform, the diameter is about 300nm, and the rough nano material surface enables the nano material surface to have larger specific surface area.
FIG. 3 shows SnO prepared in example 1 of the present invention 2 XRD pattern of the body of sensitive material. SnO in the figure 2 The peak was found to be similar to JCPDS:46-1088 are completely matched, which shows that the synthesized material is SnO 2 . The synthetic material in other examples also proved to be SnO 2 。
FIG. 4 is a graph showing the response of the gas sensor to Freon in example 1 of the present invention, and it can be seen that the sensor has good responses to chlorofluorocarbon (R22) and hydrofluorocarbon gases R32, R134a, R454b, and the responses of R22, R410a, R454b can be 20 times or more for 1000ppm, and the responses of R32 can be 5 times or more, and the responses of R134a can be 2 times or more, all of which satisfy the practical requirements.
Fig. 5 is a graph of the long-term stability in air of a gas sensor prepared according to the present invention. The measurement result is obtained by adopting a HIS9010 gas-sensitive performance test system of micro-nano sensing (fertilizer combination) technology, but the specific measurement is not limited to the test method. It can be seen that the resistance and the sensitivity do not drift in the environment of the gas sensor in the long-term power supply state.
By adjusting the temperature and humidity change in the temperature and humidity box, the resistance change of the sensor is monitored, and fig. 6 is a graph of the temperature and humidity resistance change of the gas sensor prepared by the invention. It can be seen that the resistance value of the sensor is not changed obviously under different temperature and humidity conditions, which indicates that the temperature and humidity resistance of the sensor is excellent.
FIG. 7 is a graph showing the resistance of a gas sensitive material with and without the addition of antimony salt (comparative example 1), and it can be seen that the addition of antimony salt can greatly reduce the sensor resistance.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of a Freon gas-sensitive material is characterized in that: the method comprises the following steps:
(1) Dissolving tin salt in a reaction solvent, adding antimony salt and a surfactant, heating and stirring the mixed solution in a water bath at 80-100 ℃, adding alkali liquor with the dropping speed of 1-5mL/min, adjusting the pH value of the mixed solution to 10, and continuously reacting for 1h; cooling, centrifuging and freeze-drying after the reaction is finished, sintering the dried powder, and preparing the sintered material into powder to obtain a sensitive material main body; the ratio of the mass of the surfactant to the mass of the tin salt is 2-6:5; the ratio of the adding amount of the tin salt to the volume of the reaction solvent is 5g:150-300mL, and the adding amount of the antimony salt is 1-10% of the mass of the tin salt; the surfactant is one of cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, polyacetylimine and sodium dodecyl sulfonate; ultrasonic dispersion is carried out in the water bath heating process;
(2) Mixing the sensitive material main body with PMMA dispersion liquid, organic alcohol, volatile solvent, palladium salt and tetraethyl silicate, and performing ball milling to obtain the freon gas-sensitive material.
2. The method for producing a freon gas-sensitive material according to claim 1, wherein: and (3) removing the supernatant after centrifugation in the step (1), ultrasonically cleaning with ethanol, adding deionized water into the obtained solid, freezing, and freeze-drying.
3. The method for producing a freon gas-sensitive material according to claim 1, wherein: the tin salt in the step (1) is selected from SnCl 4 ·5H 2 O、SnCl 2 ·2H 2 O、SnSO 4 One of the following;
the reaction solvent is one of methanol, ethanol, water and 90% ethanol-water mixed solution;
the antimony salt is one of antimony nitrate, antimony sulfate, antimony trichloride and antimony pentachloride;
the alkali liquor is one of tetramethylammonium hydroxide solution, tetraethylammonium hydroxide solution, tetrapropylammonium hydroxide solution, butylammonium hydroxide solution, trimethylamine, triethylamine, ethanolamine and triethanolamine.
4. The method for producing a freon gas-sensitive material according to claim 1, wherein: the mass concentration of the PMMA dispersion liquid in the step (2) is 1-20%.
5. The freon gas sensitive material produced by the production process according to any one of claims 1 to 4.
MEMS sensitive chip, its characterized in that: the MEMS sensitive chip comprises the Freon gas sensitive material prepared by the preparation method of any one of claims 1-4.
MEMS gas sensor, its characterized in that: the MEMS gas sensor comprising the freon gas sensitive material produced by the production method of any one of claims 1 to 4.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0147213A2 (en) * | 1983-12-30 | 1985-07-03 | Westinghouse Electric Corporation | An antimony-doped stannic oxide thick film gas sensor |
| JP2011095153A (en) * | 2009-10-30 | 2011-05-12 | Sumitomo Osaka Cement Co Ltd | Method for manufacturing gas sensing body, the gas sensing body and gas sensor |
| CN105158297A (en) * | 2015-09-24 | 2015-12-16 | 雷鸣 | MEMS metal-oxide semiconductor gas sensor and manufacturing method thereof |
| CN105572170A (en) * | 2015-12-10 | 2016-05-11 | 郑州大学 | SnO2-based hotwire type semiconductor gas sensor with environment temperature and humidity self-compensation ability |
| CN105823800A (en) * | 2016-03-23 | 2016-08-03 | 云南大学 | Sensitive material for detecting methyl alcohol gas |
| CN107188225A (en) * | 2017-07-14 | 2017-09-22 | 广东拓扑中润科技发展有限公司 | A kind of indium-doped antimony oxidation tin nano-powder and preparation method thereof |
| CN107758741A (en) * | 2017-11-29 | 2018-03-06 | 广西生富锑业科技股份有限公司 | A kind of Sb-doped nano tin oxide raw powder's production technology |
| CN108120747A (en) * | 2017-11-30 | 2018-06-05 | 苏州慧闻纳米科技有限公司 | The preparation method of tin dioxide gas sensor and CO gas sensor system |
| CN111982981A (en) * | 2020-08-17 | 2020-11-24 | 合肥微纳传感技术有限公司 | SnO (stannic oxide)2Gas-sensitive material, preparation method and application thereof |
-
2021
- 2021-11-08 CN CN202111313659.9A patent/CN114184652B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0147213A2 (en) * | 1983-12-30 | 1985-07-03 | Westinghouse Electric Corporation | An antimony-doped stannic oxide thick film gas sensor |
| JP2011095153A (en) * | 2009-10-30 | 2011-05-12 | Sumitomo Osaka Cement Co Ltd | Method for manufacturing gas sensing body, the gas sensing body and gas sensor |
| CN105158297A (en) * | 2015-09-24 | 2015-12-16 | 雷鸣 | MEMS metal-oxide semiconductor gas sensor and manufacturing method thereof |
| CN105572170A (en) * | 2015-12-10 | 2016-05-11 | 郑州大学 | SnO2-based hotwire type semiconductor gas sensor with environment temperature and humidity self-compensation ability |
| CN105823800A (en) * | 2016-03-23 | 2016-08-03 | 云南大学 | Sensitive material for detecting methyl alcohol gas |
| CN107188225A (en) * | 2017-07-14 | 2017-09-22 | 广东拓扑中润科技发展有限公司 | A kind of indium-doped antimony oxidation tin nano-powder and preparation method thereof |
| CN107758741A (en) * | 2017-11-29 | 2018-03-06 | 广西生富锑业科技股份有限公司 | A kind of Sb-doped nano tin oxide raw powder's production technology |
| CN108120747A (en) * | 2017-11-30 | 2018-06-05 | 苏州慧闻纳米科技有限公司 | The preparation method of tin dioxide gas sensor and CO gas sensor system |
| CN111982981A (en) * | 2020-08-17 | 2020-11-24 | 合肥微纳传感技术有限公司 | SnO (stannic oxide)2Gas-sensitive material, preparation method and application thereof |
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