CN102095790B - Carbon nanotube film ionizing sensor array and method for detecting concentration of mixed gas - Google Patents
Carbon nanotube film ionizing sensor array and method for detecting concentration of mixed gas Download PDFInfo
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- CN102095790B CN102095790B CN 201110039976 CN201110039976A CN102095790B CN 102095790 B CN102095790 B CN 102095790B CN 201110039976 CN201110039976 CN 201110039976 CN 201110039976 A CN201110039976 A CN 201110039976A CN 102095790 B CN102095790 B CN 102095790B
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Abstract
The invention discloses a carbon nanotube film ionizing sensor and a method for detecting concentration of bi-component gas, wherein the sensor comprises a first electrode, a second electrode and a third electrode, wherein the first electrode, the second electrode and the third electrode are orderly distributed; the first electrode is provided with ventilation holes, and the internal surface of the first electrode is adhered with a metal film substrate which is distributed with the carbon nanotube film; guiding-out holes are arranged at the center of the second electrode; blind holes are arranged at a panel surface of the third electrode; and the three electrodes are separated with each other. The method comprises the following steps of: 1) placing a plurality of sensors with different interpolar spaces; 2) applying voltage on the electrode; 3) measuring an ion stream value of each sensor; 4) composing a sample by the measured value and concentration, temperature and humidity calibration values of each component of the mixed gas, and constructing a measuring data base of the mixed gas with an interpolated sample; 5) constructing a data fusion instrument, and establishing a concentration measuring model of the mixed gas; and 6) inputting the measured value of each sensor in the sensor array into the measuring model so as to obtain the exact measured value of the concentration of each component of the mixed gas. The sensor array detecting gas is high in sensitivity, excellent in linearity and high in accuracy.
Description
Technical field
The present invention relates to the gas sensing field, particularly a kind of ionizing transducer and array thereof based on carbon nano-tube and gas discharge principle, and in the method for not separating direct-detection mixed gas concentration under the mixed gas condition.
Background technology
Along with all trades and professions gas detect in the urgent need to and the development of nanometer technology, nano-sensor has obtained considerable progress.Especially along with the discovery of carbon nano-tube in latter stage in 20th century, carbon nano-tube shows tempting application prospect in gas, temperature and humidity measure field.Carbon nano-tube film two electrode ionizing transducers in carbon nano-tube gas-sensitive, temperature sensitive, the moisture sensor, high with its detection sensitivity, detect the advantages such as gas wide ranges, response be fast, become the study hotspot in gas, temperature and humidity measure field.Carbon nano-tube film two electrode Gas-Sensitive Sensor of Ionized Type have overcome the shortcoming of carbon nano-tube gas-sensitive sensors saturated poisoning in tested gas of other type based on gas discharge principle, and gas concentration measurement scope and tested gaseous species scope are wider.As air-sensitive, temperature sensitive, moisture sensor that sensitive material consists of, have the irreplaceable advantage of conventional sensors with carbon nano-tube: the one, the specific surface area of carbon nano-tube is large, in the less situation of sensor overall dimensions, can greatly improve the area of electrode; Two are based on the tip curvature radius of carbon nanotube level, and working sensor voltage is greatly reduced, and obtain extremely strong electric field intensity near the carbon nano-tube tip, make tested gas ionization under low-voltage; The 3rd, the size of greatly having dwindled sensor, dynamic response is fast.Therefore, it has widely development prospect at aspects such as biology, chemistry, machinery, aviation, military affairs, anti-terrorisms.
Existing carbon nano-tube film two electrode ionizing transducers comprise by people such as Liu Junhua, the Zhang Yong of Xi'an Communications University, Li Xin, professors Zhu Changchun at the disclosed carbon nano-tube film two electrode ionization type gas sensors (shown in Figure 1) of the 14th the IVMC international vacuum microelectronics international conference of calendar year 2001.This working sensor is afterwards because interpolar discharge rear space electric charge is difficult to diffusion, sensor is difficult to return to original state, and present multivalued relation (Fig. 2, Fig. 3) between sensor voltage breakdown, breakdown current and the gas concentration, can't measure gas concentration.The people such as the Nikhil Koratkar of U.S. Rensselaer Polytech Inst (Rensselaer Polytechnic Institute) and Pulickel M professor Ajayan have developed carbon nano-tube film positive C NTFA (carbon nanotube film anode) two-electrode gas sensor.Present nonlinear relationship between this sensor voltage breakdown and the gas concentration, linear error is larger between disruptive discharge electric current and the gas concentration; Simultaneously this sensor must with the chromatograph coupling, substitute gas detector in traditional chromatograph with CNTFA, adopt the chromatographic column isolation technics, solve CNTFA to identification and the measurement of concetration problem of mixed gas; This sensor sparking voltage and discharge current are all larger; And can't realize that CNTFA is to the measurement of pure gas and mixed gas.The Hui Guohua of Zhejiang University's biomedical engineering and instrumental science institute, Chen Yuquan professor develops carbon nano-tube thin film cathode two-electrode gas sensor under the condition of 120 microns die openings, studied the flash-over characteristic of sensor in three kinds of pure gases, because sensitivity is lower, do not consist of the gas sensor of measuring concentration.
Therefore, at present to the carbon nano-tube film ionizing transducer array of responsive mixed gas each component and do not separate the research of the method for mixed gas direct-detection mixed gas each component concentration, become the technical matters that needs to be resolved hurrily.
Summary of the invention
One of purpose of the present invention, provide a kind of carbon nano-tube film ionizing transducer, the output current of conventional carbon nano-tube film two electrode sensors is divided into electron stream and ion current, set up the single-valued relationship of ion current that carbon nano-tube film ionizing transducer collector of the present invention collects and mixed gas each component concentration, temperature and humidity, overcome the many-valued nonlinear problem of carbon nano-tube film two electrode sensor gas-sensitive properties and wet sensitive characteristic.This sensor construction is simple, and cost is low, and it is high to detect gas sensitivity.
Another object of the present invention, provide a kind of method based on carbon nano-tube film ionizing transducer array detection mixed gas concentration, form sensor array by different poles spacing carbon nano-tube film ionizing transducer and measure respectively mixed gas each component concentration to be measured, gas temperature and humidity; The hardware configuration that this mixed gas concentration measuring method requires is simple, can measure any mixed gas, adopts data anastomosing algorithm, and it is high to detect the mixed gas accuracy.
The objective of the invention is to realize by following technical proposals.
The carbon nano-tube film ionizing transducer, it is characterized in that: comprise three the first electrode, the second electrode and third electrodes that distribute successively from top to bottom, the electrode that described the first electrode adheres to the metallic film base that the carbon nano-tube film that distributing is arranged by inside surface and is provided with bleeder vent consists of; The second electrode is made of the extraction pole pole plate that the center is provided with fairlead; Third electrode is made of the collector that the plate face is provided with blind hole; These three electrodes are isolated mutually by insulation column respectively.
Architectural feature of the present invention also is:
The die opening of adjacent two electrodes is 30～250 μ m in described three electrodes; Described the first electrode and the second electrode pad are 0.01～170mm over against area
2, the second electrode and third electrode pole plate are 0.01～190mm over against area
2
The bleeder vent of the electrode surface of described the first electrode is 1～4, and the metallic film base growth or the screen printing that adhere at the electrode inner surface are brushed with carbon nano-tube film;
Described the second electrode extraction pole center is provided with 1～4 fairlead;
Described third electrode collector blind hole is corresponding with the fairlead of the second electrode, and the quantity of blind hole is 1～4.
The present invention gives a kind of method based on carbon nano-tube film ionizing transducer array detection mixed gas concentration, and the method comprises the steps:
(1) selecting the die opening of adjacent two electrodes in three electrodes is the carbon nano-tube film ionizing transducer of 30～250 μ m;
(2) according to the component gases quantity in the mixed gas to be measured, the carbon nano-tube film ionizing transducer that to set respectively the different poles spacing places mixed gas to be measured as carbon nano-tube film ionization type gas each component sensor, and simultaneously the carbon nano-tube film ionizing transducer of two different poles spacings is placed gas to be measured as carbon nano-tube film ionization type temperature sensor and humidity sensor respectively;
(3) respectively to the first electrode on-load voltage 0V of step (2) carbon nano-tube film ionization type mixed gas each component sensor, carbon nano-tube film ionization type temperature sensor and carbon nano-tube film ionization type humidity sensor, the second electrode on-load voltage 2～200V, third electrode on-load voltage 1～180V;
In the described carbon nano-tube film ionizing transducer, the second electrode potential is higher than the first electrode potential, and the third electrode current potential is lower than the second electrode potential and is higher than the first electrode potential;
(4) in mixed gas each component concentration to be measured, temperature and humidity measurement range, corresponding different concentration, temperature and humidity calibration value, respectively the gas discharge ion flow valuve of all the sensors output in the measuring process (2);
(5) with all the sensors output ion flow valuve that in concentration, temperature and humidity measurement range, records in the step (4), with corresponding mixed gas each component concentration, the scale of thermometer and humidity demarcating value, form different experimental calibration samples, then adopt the piecewise interpolation technology that the experimental calibration sample is carried out interpolation, obtain interpolated data, obtain interpolated sample, and set up the mixed gas concentration measured database according to all samples that comprised experimental calibration sample and interpolated sample;
(6) adopt Data fusion technique, make up the data fusion instrument, set up the measurement model of carbon nano-tube film ionization type hybrid gas sensor, carbon nano-tube film ionization type temperature sensor and carbon nano-tube film ionization type humidity sensor; With input sample and the desired output sample of the data in the mixed gas concentration measured database as the data fusion instrument, and train and check as training sample and the test samples of data fusion instrument respectively with data different in the range ability, when assay satisfies the measurement error requirement, the mixed gas concentration Measurement accuracy model of data fusion instrument output transducer array;
The mixed gas concentration Measurement accuracy model that the ion flow valuve input step (6) of output obtains during (7) with carbon nano-tube film ionizing transducer array, temperature sensor and humidity sensor actual measurement, the Measurement accuracy value of this model output mixed gas each component concentration.
The inventive method feature also is:
Described establishment mixed gas concentration measured database, that experimental calibration data and interpolated data are formed database, with the ion flow valuve of each sensor output in the sensor array and interpolated data thereof as the input sample, with each component concentration, temperature, humidity demarcating value and interpolated data thereof in the mixed gas as the desired output sample.
Based on the method for carbon nano-tube film ionizing transducer array detection mixed gas concentration, form sensor array by different poles spacing carbon nano-tube film ionizing transducer, measure respectively mixed gas each component concentration to be measured, temperature and humidity; Powered by the sensor electrical potential source; Exported by pA level current measurement system detecting sensor; Adjust electrode separation, adjust electrode voltage, in mixed gas to be measured, in temperature, humidity environment, carry out the calibration experiment of sensor; Based on the piecewise interpolation technology experimental calibration data are carried out interpolation, obtain interpolated data; All data that will comprise experimental calibration data and interpolated data form the mixed gas concentration measured database, and the acquisition sensor array is listed in monodrome gas-sensitive property, monodrome responsive to temperature characteristic, the monodrome humidity sensitive characteristic in the mixed gas to be measured; According to the data in the mixed gas concentration measured database, the based on data integration technology is eliminated the impact of temperature, humidity, sets up the mixed gas concentration Measurement accuracy model of sensor array; The mixed gas concentration measurement model is inputted in the output of sensor array in real time during with actual measurement, just can obtain the measured result of mixed gas each component concentration.This mixed gas concentration measuring method has overcome the many-valued nonlinear problem of carbon nano-tube film two electrode ionizing transducer gas-sensitive properties and wet sensitive characteristic, the hardware configuration that requires is simple, can measure any mixed gas, and cost is low, the detection gas sensitivity is high, accuracy is high, is suitable for promoting the use of.
Method for detecting concentration of mixed gas of the present invention, the sensor array technology of employing different poles spacing under the condition of not separating mixed gas, can realize the concentration Measurement accuracy of mixed gas, accuracy is 1%.The concentration detection method of tradition three electrode probes that use in this novel method for detecting concentration of mixed gas and the existing ionization detector chromatograph is compared, because the employing carbon nano-tube film is done electrode and adopt the sensor of different poles spacing to form array, respective sensor in the array all has the measurement of concetration accuracy of high sensitivity and 1% to the each component in the mixed gas, therefore both avoided in the measuring process adopting for example process of chromatographic column separating mixed gas of equipment for separation of gases, having overcome again chromatograph need to be for the difficult problem of gas with various component replacing variety classes detector.And the carbon nano-tube film ionizing transducer can be realized working sensor voltage with the tip curvature radius of carbon nanotube level, from the safe and practical scope below 600 volts of high pressure drop to 200 volts of ionization detector.Novel mixed gas concentration measuring method of the present invention integrates sensor array technology, pA level current measurement techniques, piecewise interpolation technology and the Data fusion technique of different poles spacing, do not need separating mixed gas, the impact of temperature, humidity can be eliminated, the Measurement accuracy of each component concentration in the mixed gas can be realized.
Description of drawings
Fig. 1 is carbon nano-tube thin film cathode two electrode sensor structural representations.
Fig. 2 is the voltage breakdown of prior art carbon nano-tube film two-electrode gas sensor and the many-valued non-linear gas-sensitive property of gas concentration.
Fig. 3 is the breakdown current of prior art carbon nano-tube film two-electrode gas sensor and the non-linear many-valued gas-sensitive property of gas concentration.
Fig. 4 is carbon nano-tube film ionizing transducer structural representation of the present invention.
Fig. 5 is carbon nano-tube film ionizing transducer spatial structure side view of the present invention.
Fig. 6 is that the present invention sets respectively the single valued relation that die opening is 150 μ m and 100 μ m carbon nano-tube film ionizing transducer array detection sulphuric dioxide and nitrogen monoxide two component mixed gas concentrations.
Fig. 7 is that the present invention sets respectively the single valued relation that die opening is 180 μ m and 150 μ m carbon nano-tube film ionizing transducer array detection sulphuric dioxide and nitrogen monoxide two component mixed gas concentrations.
Fig. 8 is that the present invention sets respectively the single valued relation that die opening is 180 μ m and 100 μ m carbon nano-tube film ionizing transducer array detection sulphuric dioxide and nitrogen monoxide two component mixed gas concentrations.
Among the figure: 1, the first electrode; 2, the second electrode; 3, third electrode; The electrode that 4, bleeder vent is arranged; 5, metallic film base; 6, carbon nano-tube film; 7, insulation column.
Embodiment
The present invention will be further described below in conjunction with drawings and the specific embodiments.
Such as Fig. 4, shown in Figure 5, this carbon nano-tube film ionizing transducer, comprise by three electrodes that mutually superpose from top to bottom successively and consisting of, these three mutual overlay electrodes are respectively equipped with the first electrode 1, the second electrode 2 and third electrode 3, and described the first electrode adheres to the metallic film base 5 that the carbon nano-tube film that distributing is arranged by inside surface and the electrode 4 that bleeder vent is arranged consists of; The second electrode 2 is made of the extraction pole pole plate that the center is provided with fairlead; Third electrode 3 is made of the collector that the battery lead plate face is provided with blind hole; These three electrodes are isolated mutually by insulation column 7 respectively.
Among the embodiment of carbon nano-tube film ionizing transducer array detection two component mixed gas concentrations shown in Figure 6, the bleeder vent of the electrode surface of used sensor the first electrode 1 has 2, and bleeder vent is circular; Side surface at this bleeder vent is attached with metallic film base 5, is distributed with carbon nano-tube film 6 on it, and this carbon nano-tube mouth of pipe is downward.The second electrode 2 centers are provided with 1 fairlead and fairlead is circular embodiment.Third electrode 3 collector blind holes are corresponding with the fairlead of the second electrode, provided among Fig. 4, Fig. 5 a blind hole to be set and blind hole is the embodiment of cylindrical structure.Insulation column 7 is separately positioned between the metallic film base 5 and the second electrode 2 of the carbon nano-tube film that distributing, between the second electrode 2 and the third electrode 3, namely insulation column 7 is distributed in the second electrode 2 over against the surperficial both sides of the first electrode 1 and the both sides on the inboard golden film surface of third electrode 3.
The electrode 4 plate faces that the present invention is provided with bleeder vent adopt silicon sheet material to make; Metallic film base 5 adopts titanium, nickel, three kinds of metal materials of gold to make; Described carbon nano-tube film 6 can adopt FePC as catalyzer, and adopts carbon source, makes carbon nano-tube film 6 in metallic film base 5 growths, and perhaps the serigraphy carbon nano-tube film 6.The second electrode 2 and third electrode 3 all adopt silicon wafer to manufacture.The two sides that are provided with the electrode 4 of bleeder vent and third electrode 3 medial surfaces, the second electrode 2 are equipped with metal film.
On the electrode in the present invention's the first electrode 12 bleeder vents are arranged, be convenient to gas to be detected and enter electrode gap; Metallic film base has conductive capability, and strong bond is at the first electrode 1 inner surface; Through the fairlead of the second electrode 2, third electrode 3 collectors can be collected the positive ion stream that gas ionization produces.Between the first electrode 1 and the second electrode 2, mutually isolate by insulation column 7 between the second electrode 2 and the third electrode 3; Tested gas enters in the gap of adjacent two electrodes of sensor by the gap between the sensor peripheral electrode.
Below by an instantiation, the method for carbon nano-tube film ionizing transducer array detection mixed gas concentration of the present invention is described further.
Adopt the carbon nano-tube film ionization type temperature-humidity sensor of two different poles spacing carbon nano-tube film ionization type component gases concentration sensors, two different poles spacings to form sensor array, experiment has obtained sulphuric dioxide SO
2Monodrome gas-sensitive property (shown in Figure 6) with nitrogen monoxide NO two component mixed gass, sulphuric dioxide and nitrogen monoxide two component mixed gas concentration measurement models that the ion current data input data fusion of sensor output is set up have obtained accuracy less than 1% sulphuric dioxide and nitrogen monoxide two component mixed gas concentration measured values.
Among the gas discharge ion current that SO 2 sensor and nitric oxide sensor are exported in two component mixed gass in the carbon nano-tube film ionizing transducer array shown in Figure 6 and the embodiment of two component gases concentration, the experimental situation condition is 20.5 ℃ of temperature, relative humidity 25.2%RH, atmospheric pressure 93.7KPa.Top-surface camber is the monodrome characteristic of nitric oxide sensor among Fig. 6, and lower surface camber is the monodrome characteristic of SO 2 sensor.The first electrode 1 of nitric oxide sensor and the second electrode 2, the second electrode 2 are 100 μ m with third electrode 3 die openings, and SO 2 sensor the first electrode 1 and the second electrode 2, the second electrode 2 are 150 μ m with third electrode 3 die openings; The die opening of the carbon nano-tube film ionizing transducer adjacent electrode that monitor temperature is used is 170 μ m; The die opening of the carbon nano-tube film ionizing transducer adjacent electrode that monitoring humidity is used is respectively 200 μ m, 100 μ m.The first electrode 1 of above-mentioned carbon nano-tube film ionizing transducer and the second electrode 2 pole plates are 170mm over against area
2, the second electrode 2 is 190mm with third electrode 3 pole plates over against area
2Two the first electrode 1 cathode voltages of measuring two component mixed gas concentration sensors are 0V, the equal on-load voltage 100V of the second electrode 2 extraction poles, the equal on-load voltage 10V of third electrode 3 collectors; Temperature sensor first, second, third electrode voltage is respectively 0V, 70V, 10V; Humidity sensor first, second, third electrode voltage is respectively 0V, 90V, 10V.Along with SO
2With the rising of NO gas concentration, the ion current that the collector of two measurement two component gases concentration sensors is collected all reduces, and ion current presents the relation that monodrome descends with two component gases concentration increases; Temperature-humidity sensor sensitivity characteristic and gas sensor are similar.At SO
2In gas 0～737.884ppm concentration range and in the concentration range of NO gas 0～1127.976ppm, 36 groups of experimental calibration data have been obtained.Four sensor ion flow valuves are as the input sample, and two component gases concentration calibration values are as the desired output sample data.Adopt the Two-dimensional Surfaces piecewise linear interpolation, at SO
2In gas 0～737.884ppm concentration range and in the concentration range of NO gas 0～1127.976ppm, 36 groups of experimental calibration sample datas are carried out interpolation, obtain altogether 1352 groups of interpolated datas, and form database with 36 groups of experimental calibration data; Select 1332 groups of interpolated datas as training sample, remain 20 groups of interpolated datas that are different from training sample and 30 groups of experimental calibration data totally 50 groups of concentration demand values (being the gas concentration critical value) as test samples, input data fusion instrument by the training check, obtains SO
2, NO two component mixed gas concentration measurement models.This model SO
2Component measurement of concetration result's the linearity is that the assay fiducial error maximal value of 0.49%, 50 group of test samples is 0.49%; NO component measurement of concetration result's the linearity is that the assay fiducial error maximal value of 0.23%, 50 group of test samples is 0.24%, has reached 1% measurement of concetration accuracy.
Present embodiment basic structure is with embodiment 1, difference is: adopt two different poles spacing carbon nano-tube film ionizing transducers to measure sulphuric dioxide and nitrogen monoxide two component gases concentration, adjacent two interelectrode die openings are identical in three electrodes, and the die opening of two sensors is respectively 180 μ m, 150 μ m.
Adopt the carbon nano-tube film ionization type temperature-humidity sensor of above-mentioned two different poles spacing carbon nano-tube film ionization type gas concentration sensors, two different poles spacings to form sensor array, experiment has obtained the monodrome gas-sensitive property (shown in Figure 7) of sulphuric dioxide and nitrogen monoxide two component mixed gass, sulphuric dioxide and nitrogen monoxide two component mixed gas concentration measurement models that the ion current data input data fusion of sensor output is set up have obtained accuracy less than 1% sulphuric dioxide and nitrogen monoxide two component mixed gas concentration Measurement accuracy values.
Among the gas discharge ion current that SO 2 sensor and nitric oxide sensor are exported in two component mixed gass in the carbon nano-tube film ionizing transducer array shown in Figure 7 and the embodiment of two component gases concentration, the experimental situation condition is 20.5 ℃ of temperature, relative humidity 25.2%RH, atmospheric pressure 93.7KPa.Top-surface camber is the monodrome characteristic of nitric oxide sensor among Fig. 7, and lower surface camber is the monodrome characteristic of SO 2 sensor.The first electrode 1 of nitric oxide sensor and the second electrode 2, the second electrode 2 are 150 μ m with third electrode 3 die openings, and SO 2 sensor the first electrode 1 and the second electrode 2, the second electrode 2 are 180 μ m with third electrode 3 die openings; The die opening of the carbon nano-tube film ionizing transducer adjacent electrode that monitor temperature is used is 170 μ m; The die opening of the carbon nano-tube film ionizing transducer adjacent electrode that monitoring humidity is used is respectively 200 μ m, 100 μ m.The first electrode 1 of above-mentioned carbon nano-tube film ionizing transducer and the second electrode 2 pole plates are 170mm over against area
2, the second electrode 2 is 190mm with third electrode 3 pole plates over against area
2Two the first electrode 1 cathode voltages of measuring two component mixed gas component concentration sensors are 0V, the equal on-load voltage 100V of the second electrode 2 extraction poles, the equal on-load voltage 10V of third electrode 3 collectors; Temperature sensor first, second, third electrode voltage is respectively 0V, 70V, 10V; Humidity sensor first, second, third electrode voltage is respectively 0V, 90V, 10V.Along with SO
2With the rising of NO gas concentration, the ion current that the collector of two measurement two component gases concentration sensors is collected all reduces, and ion current presents the relation that monodrome descends with two component gases concentration increases; Temperature-humidity sensor sensitivity characteristic and gas sensor are similar.At SO
2In gas 0～737.884ppm concentration range and in the concentration range of NO gas 0～1127.976ppm, 36 groups of experimental calibration data have been obtained.Four sensor ion flow valuves are as the input sample, and two component gases concentration calibration values are as the desired output sample data.Adopt the Two-dimensional Surfaces piecewise linear interpolation, at SO
2Carry out interpolation in gas 0～737.884ppm concentration range and in the concentration range of NO gas 0～1127.976ppm, obtain altogether 1381 groups of interpolated datas, and form database with 36 groups of experimental calibration data; Select 1356 groups of interpolated datas and 11 groups of experimental calibration data totally 1367 groups of data as training sample, in the interpolated data in remaining 25 groups of data that are different from training sample and the experimental calibration data remaining 25 groups of data that are different from training sample totally 50 groups of concentration demand values (being the gas concentration critical value) as test samples, input data fusion instrument, by the training check, obtain SO
2, NO two component mixed gas concentration measurement models.This model SO
2Component measurement of concetration result's the linearity is that the assay fiducial error maximal value of 0.43%, 50 group of test samples is 0.49%; NO component measurement of concetration result's the linearity is that the assay fiducial error maximal value of 0.24%, 50 group of test samples is 0.29%, has reached 1% measurement of concetration accuracy.
Present embodiment basic structure is with embodiment 1, difference is: adopt two different poles spacing carbon nano-tube film ionizing transducers to measure sulphuric dioxide and nitrogen monoxide two component gases concentration, adjacent two interelectrode die openings are identical in three electrodes, and the die opening of two sensors is respectively 180 μ m, 100 μ m.
Adopt the carbon nano-tube film ionization type temperature-humidity sensor of above-mentioned two different poles spacing carbon nano-tube film ionization type gas concentration sensors, two different poles spacings to form sensor array, experiment has obtained the monodrome gas-sensitive property (shown in Figure 8) of sulphuric dioxide and nitrogen monoxide two component mixed gass, sulphuric dioxide and nitrogen monoxide two component mixed gas concentration measurement models that the ion current data input data fusion of sensor output is set up have obtained accuracy less than 1% sulphuric dioxide and nitrogen monoxide two component mixed gas concentration measured values.
Among the gas discharge ion current that SO 2 sensor and nitric oxide sensor are exported in two component mixed gass in the carbon nano-tube film ionizing transducer array shown in Figure 8 and the embodiment of two component gases concentration, the experimental situation condition is 20.5 ℃ of temperature, relative humidity 25.2%RH, atmospheric pressure 93.7KPa.Top-surface camber is the monodrome characteristic of nitric oxide sensor among Fig. 8, and lower surface camber is the monodrome characteristic of SO 2 sensor.The first electrode 1 of nitric oxide sensor and the second electrode 2, the second electrode 2 are 100 μ m with third electrode 3 die openings, and SO 2 sensor the first electrode 1 and the second electrode 2, the second electrode 2 are 180 μ m with third electrode 3 die openings; The die opening of the carbon nano-tube film ionizing transducer adjacent electrode that monitor temperature is used is 170 μ m; The die opening of the carbon nano-tube film ionizing transducer adjacent electrode that monitoring humidity is used is respectively 200 μ m, 100 μ m.The first electrode 1 of above-mentioned carbon nano-tube film ionizing transducer and the second electrode 2 pole plates are 170mm over against area
2, the second electrode 2 is 190mm with third electrode 3 pole plates over against area
2Two the first electrode 1 cathode voltages of measuring two component mixed gas concentration sensors are 0V, the equal on-load voltage 100V of the second electrode 2 extraction poles, the equal on-load voltage 10V of third electrode 3 collectors; Temperature sensor first, second, third electrode voltage is respectively 0V, 70V, 10V; Humidity sensor first, second, third electrode voltage is respectively 0V, 90V, 10V.Along with SO
2With the rising of NO gas concentration, the ion current that the collector of two measurement two component gases concentration sensors is collected all reduces, and ion current presents the relation that monodrome descends with two component gases concentration increases; Temperature-humidity sensor sensitivity characteristic and gas sensor are similar.At SO
2In gas 0～737.884ppm concentration range and in the concentration range of NO gas 0～1127.976ppm, 36 groups of experimental calibration data have been obtained.Four sensor ion flow valuves are as the input sample, and two component gases concentration calibration values are as the desired output sample data.Adopt the Two-dimensional Surfaces piecewise linear interpolation, at SO
2Carry out interpolation in gas 0～737.884ppm concentration range and in the concentration range of NO gas 0～1127.976ppm, obtain altogether 1390 groups of interpolated datas, and form database with 36 groups of experimental calibration data; Select 1365 groups of interpolated datas and 11 groups of experimental calibration data totally 1376 groups of data as training sample, in the interpolated data in remaining 25 groups of data that are different from training sample and the experimental calibration data remaining 25 groups of data that are different from training sample totally 50 groups of concentration demand values (being the gas concentration critical value) as test samples, input data fusion instrument, by the training check, obtain SO
2, NO mixed gas concentration measurement model.This model SO
2Component measurement of concetration result's the linearity is that the assay fiducial error maximal value of 0.42%, 50 group of test samples is 0.49%; NO component measurement of concetration result's the linearity is that the assay fiducial error maximal value of 0.14%, 50 group of test samples is 0.18%, has reached 1% measurement of concetration accuracy.
Present embodiment basic structure is with embodiment 1, and difference is: adopt three different poles spacing carbon nano-tube film ionizing transducers to measure nitrogen dioxide NO
2, nitrogen monoxide NO and sulphuric dioxide SO
2Three component concentration of three component mixed gass, adjacent two the interelectrode die openings of three electrodes of each sensor are identical, the die opening of three sensors is respectively 250 μ m, 150 μ m, 30 μ m, and the first electrode 1 and the second electrode 2 pole plates are 0.01mm over against area
2, the second electrode 2 is 0.01mm with third electrode 3 pole plates over against area
2
The bleeder vent of the electrode surface of sensor the first electrode 1 has 1, and bleeder vent is quadrilateral, pentagon or hexagon; The second electrode 2 center fairleads are 4, and fairlead is quadrilateral, pentagon or hexagon; The quantity of third electrode 3 blind holes is 4, and blind hole is 3～6 prisms or pyramid.
The detection method of present embodiment is substantially the same manner as Example 1, and difference is:
Adopt three different poles spacing carbon nano-tube film ionizing transducers to measure nitrogen dioxide, nitrogen monoxide and sulphuric dioxide two component gases concentration, the first electrode cathode voltage of three sensors is 0V, the second electrode extraction pole on-load voltage 2V, third electrode collector on-load voltage 1V.The input of ion flow valuve nitrogen dioxide, nitrogen monoxide and the sulphuric dioxide three component mixed gas concentration Measurement accuracy models of output during with three carbon nano-tube film ionization type gas concentration sensors, temperature sensor and humidity sensor actual measurement, the Measurement accuracy value of these model output nitrogen dioxide, nitrogen monoxide and three component concentration of sulphuric dioxide three component mixed gass.
Present embodiment basic structure is with embodiment 1, and difference is: adopt four different poles spacing carbon nano-tube film ionizing transducers to measure nitrogen dioxide NO
2, nitrogen monoxide NO, sulphuric dioxide SO
2Four component concentration with carbon monoxide CO four component mixed gass, three adjacent two interelectrode die openings of electrode are identical in each sensor, the die opening of four sensors is respectively 250 μ m, 150 μ m, 100 μ m, 30 μ m, and the first electrode 1 and the second electrode 2 pole plates are 100mm over against area
2, the second electrode 2 is 120mm with third electrode 3 pole plates over against area
2
The bleeder vent of the electrode surface of sensor the first electrode 1 has 4, and bleeder vent is quadrilateral, pentagon or hexagon; The second electrode 2 center fairleads are 2, and fairlead is quadrilateral, pentagon or hexagon; The quantity of third electrode 3 blind holes is 2, and blind hole is 3～6 prisms or pyramid.
The detection method of present embodiment is substantially the same manner as Example 1, and difference is:
Adopt four different poles spacing carbon nano-tube film ionization type gas concentration sensors to measure nitrogen dioxide, nitrogen monoxide, sulphuric dioxide and carbon monoxide four component gases concentration, the first electrode cathode voltage of four sensors is 0V, the second electrode extraction pole on-load voltage 200V, third electrode collector on-load voltage 180V.Ion flow valuve input nitrogen dioxide, nitrogen monoxide, sulphuric dioxide and the carbon monoxide four component mixed gas concentration Measurement accuracy models of output during with carbon nano-tube film ionization type gas concentration sensor array, temperature sensor and humidity sensor actual measurement, the Measurement accuracy value of this model output nitrogen dioxide, nitrogen monoxide, sulphuric dioxide and four component concentration of carbon monoxide four component mixed gass.
The present invention forms sensor array, the output of pA level current measurement system detecting sensor, piecewise interpolation and data fusion method by different poles spacing carbon nano-tube film ionizing transducer, form a kind of novel, can measure various mixing gas to be measured, antijamming capability by force, does not need to separate mixed gas to be measured, the high mixed gas concentration measuring method of accuracy.The sensor of different poles spacing in the sensor array, the each component concentration under not separating the mixed gas condition in the direct-detection mixed gas, and the real-time disturbing effect of detected temperatures, humidity; PA level current measurement system can detect the pA level electric current of each sensor output of corresponding each component gas concentration, temperature, humidity simultaneously; Piecewise interpolation and data fusion method can be eliminated temperature, humidity interference, the high mixed gas concentration measured value of output accuracy.
Although the present invention has made detailed description with above-mentioned preferred embodiment to the present invention, above-described embodiment is not intended to limit the present invention.In the situation that does not break away from the given technical characterictic of technical solution of the present invention and range of structures, the increase that technical characterictic is done, distortion or with the replacement of the same content in this area all should belong to protection scope of the present invention.
Claims (3)
1. carbon nano-tube film ionizing transducer, it is characterized in that: comprise three the first electrode, the second electrode and third electrodes that distribute successively from top to bottom, the electrode that described the first electrode adheres to the metallic film base that the carbon nano-tube film that distributing is arranged by inside surface and is provided with bleeder vent consists of; The second electrode is made of the extraction pole pole plate that the center is provided with fairlead; Third electrode is made of the collector that the plate face is provided with blind hole; These three electrodes are isolated mutually by insulation column respectively;
The die opening of adjacent two electrodes is respectively 180 μ m, 150 μ m in described three electrodes; Described the first electrode and the second electrode pad are 0.01～170mm over against area
2, the second electrode and third electrode pole plate are 0.01～190mm over against area
2
The bleeder vent of the electrode surface of described the first electrode is 1～4, and the metallic film base growth or the screen printing that adhere at the electrode inner surface are brushed with carbon nano-tube film;
Described the second electrode extraction pole center is provided with 1～4 fairlead;
Described third electrode collector blind hole is corresponding with the fairlead of the second electrode, and the quantity of blind hole is 1～4.
2. based on the method for carbon nano-tube film ionizing transducer array detection mixed gas concentration claimed in claim 1, it is characterized in that the method comprises the steps:
(1) die opening of adjacent two electrodes in three electrodes of selection is respectively the carbon nano-tube film ionizing transducer of 180 μ m, 150 μ m;
(2) according to the component gases quantity in the mixed gas to be measured, the carbon nano-tube film ionizing transducer that to set respectively the different poles spacing places mixed gas to be measured as carbon nano-tube film ionization type gas each component sensor, and simultaneously the carbon nano-tube film ionizing transducer of two different poles spacings is placed gas to be measured as carbon nano-tube film ionization type temperature sensor and humidity sensor respectively;
(3) respectively to the first electrode on-load voltage 0V of step (2) carbon nano-tube film ionization type mixed gas each component sensor, carbon nano-tube film ionization type temperature sensor and carbon nano-tube film ionization type humidity sensor, the second electrode on-load voltage 2～200V, third electrode on-load voltage 1～180V;
In the described carbon nano-tube film ionizing transducer, the second electrode potential is higher than the first electrode potential, and the third electrode current potential is lower than the second electrode potential and is higher than the first electrode potential;
(4) in mixed gas each component concentration to be measured, temperature and humidity measurement range, corresponding different concentration, temperature and humidity calibration value, respectively the gas discharge ion flow valuve of all the sensors output in the measuring process (2);
(5) with all the sensors output ion flow valuve that in concentration, temperature and humidity measurement range, records in the step (4), with corresponding mixed gas each component concentration, the scale of thermometer and humidity demarcating value, form different experimental calibration samples, then adopt the piecewise interpolation technology that the experimental calibration sample is carried out interpolation, obtain interpolated data, obtain interpolated sample, and set up the mixed gas concentration measured database according to all samples that comprised experimental calibration sample and interpolated sample;
(6) adopt Data fusion technique, make up the data fusion instrument, set up the measurement model of carbon nano-tube film ionization type hybrid gas sensor, carbon nano-tube film ionization type temperature sensor and carbon nano-tube film ionization type humidity sensor; With input sample and the desired output sample of the data in the mixed gas concentration measured database as the data fusion instrument, and train and check as training sample and the test samples of data fusion instrument respectively with data different in the range ability, when assay satisfies the measurement error requirement, the mixed gas concentration Measurement accuracy model of data fusion instrument output transducer array;
The mixed gas concentration Measurement accuracy model that the ion flow valuve input step (6) of output obtains during (7) with carbon nano-tube film ionizing transducer array, temperature sensor and humidity sensor actual measurement, the Measurement accuracy value of this model output mixed gas each component concentration.
3. the method based on carbon nano-tube film ionizing transducer array detection mixed gas concentration according to claim 2, it is characterized in that: described establishment mixed gas concentration measured database, that experimental calibration data and interpolated data are formed database, with the ion flow valuve of each sensor output in the sensor array and interpolated data thereof as the input sample, with each component concentration, temperature and humidity calibration value and interpolated data thereof in the mixed gas as the desired output sample.
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| CN102081067B (en) * | 2011-02-16 | 2013-01-02 | 西安交通大学 | Carbon nanotube (CNT) film based ionization nitrogen dioxide sensor and method for measuring concentration by adopting same |
| CN103217471A (en) * | 2013-03-27 | 2013-07-24 | 浙江工商大学 | Electronic nose system based on carbon nanotube micro-nano gas sensor array |
| CN106248779B (en) * | 2016-08-03 | 2019-03-01 | 西安交通大学 | Three electrode ionizing transducer array of Jenner's metre hole film with temperature compensation function |
| CN106248776B (en) * | 2016-08-03 | 2019-03-01 | 西安交通大学 | A kind of sensor array of detectable multiple groups part mixed gas |
| CN106970182A (en) * | 2017-04-21 | 2017-07-21 | 上海纳晶科技有限公司 | A kind of apparatus and method of on-line checking mixed gas concentration |
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