CN2807255Y - Nitrogen oxide sensor - Google Patents
Nitrogen oxide sensor Download PDFInfo
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- CN2807255Y CN2807255Y CN 200420069137 CN200420069137U CN2807255Y CN 2807255 Y CN2807255 Y CN 2807255Y CN 200420069137 CN200420069137 CN 200420069137 CN 200420069137 U CN200420069137 U CN 200420069137U CN 2807255 Y CN2807255 Y CN 2807255Y
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- CN
- China
- Prior art keywords
- nox sensor
- gas
- sensor
- nitrogen oxide
- sensitivity
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title abstract 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 239000010409 thin film Substances 0.000 claims abstract 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 13
- 239000010408 film Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 29
- 230000035945 sensitivity Effects 0.000 abstract description 21
- 238000011084 recovery Methods 0.000 abstract description 8
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract 2
- 229910002089 NOx Inorganic materials 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
The utility model discloses a nitrogen oxide sensor. The surface of a nitrogen oxide sensor body (1) is coated with a thin film (2). The utility model has the thin-film formula, according to weight ratio, that tungsten trioxide: silicon dioxide = (100-90): (0-10). The utility model relates to a nitrogen oxide sensor which has the advantages of good responsive property, high selectivity, high detection sensitivity, low detection lower-limit, rapid response-recovery, high stability and low working temperature on nitrogen dioxide gas, and has simple fabrication processes.
Description
Technical field
The utility model relates to a kind of gas sensor, particularly relates to a kind of NOx sensor.
Background technology
Oxides of nitrogen (NOx) is typical atmosphere pollution, can cause acid rain, photochemical fog etc.Use reasons such as mineral fuel, vehicle exhaust all can cause airborne nitrogen dioxide to increase.The too high meeting of content of nitrogen dioxide causes diseases such as respiratory system, injury of lungs in the air, and the ozonosphere in the atmospheric envelope is also had certain destruction, and the serious harm people are healthy.NO can autoxidation become NO in air
2, therefore, airborne oxides of nitrogen mainly is meant NO
2, detect NO in the air at present
2The main method of gas is the Saltzman method, and the method need be not suitable for being used for outdoor monitoring with special large-scale instrument, and difficulty is promoted the use of.In how on a large scale to oxides of nitrogen carry out original position, Study of Monitoring is very significant work in the environmental protection in real time, Fa Zhan semiconductor gas sensor was expected to address that need in the last few years.Since T.Seiyama in 1962 proposed conductor oxidate first and has gas sensing property, the research of solid state gas sensors had obtained development faster, develops to microminiaturized and integrated direction at present, and is used to develop the microsensor array.Shaver takes the lead in to WO
3Gas sensing property study, point out WO with Pt activation
3To H
2Has response.Further studies show that WO
3Be good NO
2Gas sensitive.
Based on WO
3The semiconductor N O of material
2Gas sensor has many reported in literature.Take a broad view of these documents and can learn WO
3The preparation method and the manufacturing technology of sensitive membrane directly influence its air-sensitive performance.Complicated physical method is adopted in the making of sensitive membrane mostly, since the sensitive membrane less stable that adopts physical method to make, more difficult so far Application and Development.Therefore, research cost is lower, make simply, and stable practical NO
2Gas sensor is a problem that is worth exploration.
The utility model content
Technical problem to be solved in the utility model provide a kind of to nitrogen dioxide gas have good response, selectivity, detection sensitivity height, detect that lower limit is low, response-recovery fast, good stability, NOx sensor that working temperature is low.
In order to solve the problems of the technologies described above, the NOx sensor that the utility model provides is to be coated with film on its body surface, and the prescription of its film is by weight: tungstic acid: silicon dioxide=(100-90): (0-10);
The prescription of its film is haggled over excellent value by weight:
Tungstic acid: silicon dioxide=100: 0; Or
Tungstic acid: silicon dioxide=99: 1; Or
Tungstic acid: silicon dioxide=97: 3; Or
Tungstic acid: silicon dioxide=95: 5; Or
Tungstic acid: silicon dioxide=90: 10.
NOx sensor of the present utility model has film in its surface-coated, utilizes SiO
2The space reticulate texture, increase oxides of nitrogen and WO
3Contact area, thereby improve the sensitivity of NOx sensor to oxides of nitrogen, be coated with WO
3And SiO
2The NOx sensor of powder film, it is low to measure the oxides of nitrogen cost, the measuring accuracy height, manufacture craft is simple, and is easy to utilize.
In sum, the utility model is a kind of nitrogen dioxide gas to be had good response, selectivity, detection sensitivity height, and it is low to detect lower limit, and response-recovery is fast, good stability, the NOx sensor that working temperature is low.
Description of drawings
Fig. 1 is SiO
2Doping is 1% WO
3The x-ray diffraction pattern of powder;
Fig. 2 be working temperature 160 ℃ down the resistance of each sensor with NO
2The changing value of gas concentration;
Fig. 3 is sensitivity and the NO of each sensor when working temperature is 160 ℃
2The relation of gas concentration;
Fig. 4 working temperature is to the influence of sensitivity;
Fig. 5 is NO
2Concentration is 10ppm, the response-recovery curve of 3% sensor when working temperature is 200 ℃;
Fig. 6 be 3% the sensor all gases that concentration is 30ppm remolding sensitivity;
Fig. 7 is this NOx sensor structural representation.
Embodiment
Embodiment 1:
Referring to Fig. 7, in NOx sensor body 1 surface-coated film 2 is arranged, the tungstic acid in its film 2: silicon dioxide is 100: 0 powders by weight.
Embodiment 2:
Referring to Fig. 7, in NOx sensor body 1 surface-coated film 2 is arranged, the tungstic acid in the film 2 in its film: silicon dioxide is 99: 1 by weight.
Embodiment 3:
Referring to Fig. 7, in NOx sensor body 1 surface-coated film 2 is arranged, the tungstic acid in its film 2: silicon dioxide is 97: 3 by weight.
Embodiment 4:
Referring to Fig. 7, in NOx sensor body 1 surface-coated film 2 is arranged, the tungstic acid in its film 2: silicon dioxide is 95: 5 by weight.
Embodiment 5:
Referring to Fig. 7, in NOx sensor body 1 surface-coated film 2 is arranged, the tungstic acid in its film 2: silicon dioxide is 90: 10 by weight.
Below in conjunction with experimental data the utility model is elaborated.
A, air-sensitive performance test
Test job is finished on HWC-30A air-sensitive test macro, and native system adopts the current/voltage method of testing.The sensitivity of definition sensor is S=R
g/ R
a(to oxidizing gas) or S=R
a/ R
g(to reducibility gas), R
gThe resistance value of expression sensor in tested gas, R
aThe aerial resistance value of expression sensor.
B, result and discussion
B.1 WO
3Powder characteristics
Fig. 1 is SiO
2Doping is 1% WO
3The x-ray diffraction pattern of powder.The analysis showed that this WO
3Powder belongs to orthorhombic system, SiO
2Doping do not influence WO
3The formation of crystalline phase.Calculate WO by the Scherrer formula
3The mean grain size of powder is 62nm..
B.2 the air-sensitive performance of senser element
The response theory of semiconductor NOx sensor is based on changes in resistance, when the semiconductor sensitive membrane is exposed in the tested atmosphere, tested gas molecule will with the O that is adsorbed on semiconductor surface
-, O
2-Or O
2 -Chemical reaction takes place, thereby causes semi-conductive resistance to increase or reduce.SiO
2The WO that mixes
3Be the N-N-type semiconductor N, with the sensor and the oxidizing gas NO of this material
2Do the time spent, cause that resistance increases its increase value and NO
2Concentration is relevant.Fig. 2 has provided the resistance of working temperature each NOx sensor under 160 ℃ with NO
2The changing value of gas concentration.The result shows that the resistance of each NOx sensor is with NO
2The increase of concentration and increasing, and to NO
2Gas has the better linearity response.
Sensitivity is the important parameter of NOx sensor.Sensitivity and the NO of each NOx sensor when working temperature is 160 ℃
2The relation of gas concentration as shown in Figure 3.As seen from the figure, along with NO
2The increase of volume fraction, sensitivity increases.In addition, for the NOx sensor of different dopings, its sensitivity difference, SiO suitably mixes
2Help improving sensitivity.But, work as SiO
2Doping 〉=10% o'clock cause sensitivity to descend on the contrary, more suitable with doping 1% to 5%.Sensitivity is also relevant with working temperature, and Fig. 4 has provided and worked as NO
2When gas concentration is 10ppm, the sensitivity of each NOx sensor under the different operating temperature.As can be seen, increase from the sensitivity of 120 ℃ of-200 ℃ of each NOx sensor rising with working temperature, reach maximal value during to 200 ℃, sensitivity descends then.The optimum working temperature that shows NOx sensor is 200 ℃.
The response-recovery time can directly read from the response-recovery curve.Fig. 5 has provided NO
2Concentration is 10ppm, the response-return curve of 3% NOx sensor when working temperature is 200 ℃.Response time is about 11s, is about 50s release time.Show that the NOx sensor response-recovery is very fast.Experiment shows that also when concentration was 2.5ppm, response performance was still fine, so this sensor can be realized low concentration of NO
2The detection of gas.
Each NOx sensor is to NO
2Gas has good selectivity, and Fig. 6 is 3% NOx sensor is all gases of 30ppm to concentration response.When working temperature is 165 ℃, remove C
2H
5OH and NH
3Have outside the more weak response, to CO, CH
4And C
4H
10Basically not response.This shows that NOx sensor is to NO
2Good selectivity is arranged.This group NOx sensor also has goodish stability, and table 1 is 200 ℃ for the 110d front and back in working temperature, NO
2Gas concentration is the sensitivity of each NOx sensor under the same terms of 10ppm.The result shows that each NOx sensor is very stable in 110d.But SiO does not mix
2, directly use WO
3The NOx sensor stability that powder makes is relatively poor relatively.
The sensitivity that table 1 different time records
| Sensor |
| 0 | 1％ | 3％ | 5％ | 10％ | |
| Before 110 days | 37.4 | 87.4 | 64.2 | 60.6 | 39.3 |
| After 110 days | 28.2 | 82.4 | 62.9 | 57.9 | 36.7 |
C, conclusion
Prepared SiO by white tungstic acid and silester
2The WO that mixes
3The nanometer particle film NOx sensor, prepared nano particle mean grain size is 62nm.By doping SiO
2Can improve the sensitivity and the stability of sensor.Test result shows that this class NOx sensor is highly sensitive, and it is low to detect lower limit, and response-recovery is fast, and good stable and selectivity are arranged, and working temperature is low.Therefore, be expected to be used for to airborne NO
2Gas carries out original position, monitoring in real time.
Claims (2)
1, a kind of NOx sensor comprises the NOx sensor body, it is characterized in that: in described NOx sensor body (1) surface-coated thin film (2) is arranged.
2, a kind of NOx sensor according to claim 1 is characterized in that: described film (2) is counted (100-90) by weight by tungstic acid and silicon dioxide: (0-10) form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200420069137 CN2807255Y (en) | 2004-11-10 | 2004-11-10 | Nitrogen oxide sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200420069137 CN2807255Y (en) | 2004-11-10 | 2004-11-10 | Nitrogen oxide sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN2807255Y true CN2807255Y (en) | 2006-08-16 |
Family
ID=36921555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200420069137 Expired - Fee Related CN2807255Y (en) | 2004-11-10 | 2004-11-10 | Nitrogen oxide sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN2807255Y (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344966C (en) * | 2004-11-10 | 2007-10-24 | 浣石 | Nitrogen oxide sensor and producing technology thereof |
| CN100427939C (en) * | 2006-12-21 | 2008-10-22 | 天津大学 | Tungstic acid thin film air-sensitive sensor surface modifying method |
| CN101842699A (en) * | 2007-10-31 | 2010-09-22 | 卡特彼勒公司 | Multilayer gas sensor with dual heating zones |
| CN102243195A (en) * | 2011-04-13 | 2011-11-16 | 刘震国 | A resistance-type nitrogen dioxide gas sensor, and an apparatus manufactured with the sensor |
-
2004
- 2004-11-10 CN CN 200420069137 patent/CN2807255Y/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344966C (en) * | 2004-11-10 | 2007-10-24 | 浣石 | Nitrogen oxide sensor and producing technology thereof |
| CN100427939C (en) * | 2006-12-21 | 2008-10-22 | 天津大学 | Tungstic acid thin film air-sensitive sensor surface modifying method |
| CN101842699A (en) * | 2007-10-31 | 2010-09-22 | 卡特彼勒公司 | Multilayer gas sensor with dual heating zones |
| CN102243195A (en) * | 2011-04-13 | 2011-11-16 | 刘震国 | A resistance-type nitrogen dioxide gas sensor, and an apparatus manufactured with the sensor |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: GUANGZHOU CHUANGFU DECTION ELECTRONIC EQUIPMENT CO Free format text: FORMER OWNER: HUAN SHI Effective date: 20101115 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 510405 EARTHQUAKE ENGINEERING CENTER OF GUANGZHOU UNIVERSITY, NO.248, GUANGYUAN MIDDLE ROAD, GUANGZHOU CITY, GUANGDONG PROVINCE TO: 510663 UNIT 407-409, 4/F, ZONE D, SCIENCE AND TECHNOLOGY INNOVATION BASE, NO.80, LANYUE ROAD, SCIENCE CITY, NEW AND HIGH TECHNOLOGY INDUSTRIAL DEVELOPMENT AREA, GUANGZHOU, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20101115 Address after: 510663 Guangdong province high tech Industrial Development Zone of Guangzhou city science and technology innovation base on Road No. 80 D District fourth floor unit 407-409 Patentee after: Guangzhou Chuangfu Testing Electronic Equipment Co., Ltd. Address before: Guangzhou City, Guangdong Province, Guangyuan Road 510405 No. 248 Earthquake Engineering Center of Guangzhou University Patentee before: Huan Shi |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060816 Termination date: 20091210 |