CN102095789B - Carbon nanotube film ionizing sensor and method for detecting concentration of bi-component gas - Google Patents
Carbon nanotube film ionizing sensor and method for detecting concentration of bi-component gas Download PDFInfo
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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 the bi-component gas, and constructing a measuring data base of the bi-component gas with an interpolated sample; 5) constructing a data fusion instrument, and establishing a concentration measuring model of the bi-component gas; and 6) inputting the measured value of the sensor into the measuring model so as to obtain the exact measured value of the concentration of the bi-component gas. The sensor array detecting bi-component mixed 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 do not separating the method that directly detects two component mixed gas concentrations under the two component mixed gas conditions.
Background technology
Along with the development of pressing for of detecting of all trades and professions gas and 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, Humidity Detection field.Carbon nano-tube film two electrode ionizing transducers in carbon nano-tube gas-sensitive, temperature sensitive, the moisture sensor with its detection sensitivity height, detect advantages such as gas wide ranges, response be fast, become the research focus in gas, temperature, Humidity Detection 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 wideer.As air-sensitive, temperature sensitive, moisture sensor that sensitive material constitutes, have the irreplaceable advantage of conventional sensors with carbon nano-tube: the one, the specific surface area of carbon nano-tube is big, under the less situation of sensor overall dimensions, can improve the area of electrode greatly; 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 having dwindled sensor greatly, dynamic response is fast.Therefore, it has development prospect widely 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 international vaccum microelectronics international conference of the 14th IVMC 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 (Fig. 2 Fig. 3), can't measure gas concentration to present multivalued relation between sensor voltage breakdown, breakdown current and the gas concentration.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 bigger 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 identification and the measurement of concetration problem of the mixed gas of CNTFA; This sensor sparking voltage and discharge current are all bigger; And can't realize the measurement of the pure gas of CNTFA 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 constitute 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 that mixed gas directly detects the method for 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 stream, set up the ion stream of three electrode sensor collectors collections of the present invention and the single-valued relationship of two component concentration of two component mixed gass, temperature and humidity, overcome the many-valued nonlinear problem of carbon nano-tube film two electrode sensor gas-sensitive properties and wet quick characteristic.This sensor construction is simple, and cost is low, and it is highly sensitive to detect two component mixed gass.
Another object of the present invention, provide a kind of method based on carbon nano-tube film ionizing transducer array detection two component mixed gas concentrations, form sensor array by different poles spacing carbon nano-tube film ionizing transducer, measure two component mixed gass to be measured two component concentration, gas temperature and humidity respectively; The hardware configuration that this two components mixed gas concentration measuring method requires is simple, adopts data anastomosing algorithm, detects two component mixed gas accuracy height.
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 first electrode, second electrode and third electrodes that distribute successively from top to bottom, the electrode that described 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 constitutes; 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 first electrode and second electrode pad are 0.01～170mm over against area
2, second electrode and third electrode pole plate are 0.01～190mm over against area
2
The bleeder vent of the electrode surface of described first electrode is 1～4, and metallic film base growth or the serigraphy of adhering at the electrode inner surface have carbon nano-tube film;
The described second electrode extraction pole center is provided with 1～4 fairlead;
Described third electrode collector blind hole is corresponding with the fairlead of 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 two component mixed gas concentrations, and this 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 two component mixed gass to be measured, place two component mixed gass to be measured as carbon nano-tube film ionization type gas concentration sensor two carbon nano-tube film ionizing transducers of having set the different poles spacing respectively, 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 carbon nano-tube film ionization type humidity sensor respectively, form sensor array by all the sensors;
(3) respectively to the first electrode on-load voltage 0V of two carbon nano-tube film ionization type gas concentration sensors of step (2), carbon nano-tube film ionization type temperature sensor, carbon nano-tube film ionization type humidity sensor, the second electrode on-load voltage, 2～200V, third electrode on-load voltage 1～180V;
(4) in two component mixed gass, two component concentration to be measured, temperature and humidity measurement range, corresponding different concentration, temperature and humidity calibration value, the gas discharge ion flow valuve of all the sensors output in the measuring process (2) respectively;
(5) with all the sensors output ion flow valuve that in concentration, temperature and humidity measurement range, records in the step (4), with corresponding two component mixed gass, two component concentration, scale of thermometer definite value and humidity demarcating value, form different experimental calibration samples, adopt the piecewise interpolation technology that the experimental calibration sample is carried out interpolation then, obtain interpolated data, obtain interpolated sample, and set up two component mixed gas concentration measured database according to all samples that comprised experimental calibration sample and interpolated sample;
(6) adopt the data fusion technology, make up the data fusion instrument, set up the measurement model of carbon nano-tube film ionization type mixed gas concentration 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 two component 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 accurate measurement model of two component mixed gas concentrations of data fusion instrument output transducer array;
The accurate measurement model of two component mixed gas concentrations that the ion flow valuve input step (6) of output obtains during (7) with carbon nano-tube film ionization type gas concentration sensor, carbon nano-tube film ionization type temperature sensor and the actual measurement of carbon nano-tube film ionization type humidity sensor, this model is exported the accurate measured value of two component concentration of two component mixed gass.
The inventive method feature also is:
Each sensor in the described carbon nano-tube film ionizing transducer array, second electrode potential is higher than first electrode potential, and the third electrode current potential is lower than second electrode potential and is higher than first electrode potential.
Described establishment two component mixed gas concentration measured database, be 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 two component concentration, temperature and humidity calibration value and interpolated datas thereof in the two component mixed gass as the desired output sample.
Method based on carbon nano-tube film ionizing transducer array detection two component mixed gas concentrations, form sensor array by different poles spacing carbon nano-tube film ionizing transducer, measure two component mixed gass to be measured two component concentration, temperature and humidity respectively; Powered by the sensor electrical potential source; Exported by pA level current measurement system detecting sensor; Adjust electrode separation, adjust electrode voltage, in two component mixed gass 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 are formed two component 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 two component mixed gass to be measured; According to the data in the two component mixed gas concentration measured database, based on the data fusion technology, eliminate the influence of temperature, humidity, set up the accurate measurement model of two component mixed gas concentrations of sensor array; Two component mixed gas concentration measurement models are imported in the output of sensor array in real time during with actual measurement, just can obtain the accurate measured result of two component concentration in the mixed gas.This two components mixed gas concentration measuring method has overcome the many-valued nonlinear problem of carbon nano-tube film two electrode sensor gas-sensitive properties and wet quick characteristic, the hardware configuration that requires is simple, and cost is low, detects gas sensitivity height, accuracy height, is suitable for promoting the use of.
Two component mixed gas concentration detection methods of the present invention, the sensor array technology of employing different poles spacing under the condition of not separating mixed gas, can realize that the concentration of two component mixed gass is accurately measured, accuracy is 1%.The concentration detection method of tradition three electrode probes that use in these novel two component mixed gas concentration detection methods 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 two components in the two component mixed gass, 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 chromatograph again need be at 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 two component mixed gas concentration measuring methods of the present invention integrate sensor array technology, pA level current measurement techniques, piecewise interpolation technology and the data fusion technology of different poles spacing, do not need to separate two component mixed gass, the influence of temperature, humidity can be eliminated, the accurate measurement of two component concentration in the two component mixed gass 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 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 respectively.
Fig. 7 is that the present invention sets 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 respectively.
Fig. 8 is that the present invention sets 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 respectively.
Among the figure: 1, first electrode; 2, 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.
As Fig. 4, shown in Figure 5, this carbon nano-tube film ionizing transducer, comprise by three successively from top to bottom the electrode of mutual superposition constitute, these three mutual superposition electrodes are respectively first electrode 1, second electrode 2 and third electrode 3, and described 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 is provided with bleeder vent constitutes; 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 carbon nano-tube film ionizing transducer array detection sulphuric dioxide shown in Figure 6 and the embodiment of nitrogen monoxide two component mixed gas concentrations, the bleeder vent of the electrode surface of used sensor first electrode 1 has 2, and bleeder vent is circular; Inner surface at this first electrode 1 is attached with metallic film base 5, the carbon nano-tube film 6 that distributing on it, and this carbon nano-tube mouth of pipe is downward.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 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 second electrode 2 of the carbon nano-tube film that distributing, between second electrode 2 and the third electrode 3, namely insulation column 7 is distributed in second electrode 2 over against the surperficial both sides of 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 or serigraphy carbon nano-tube film 6 in metallic film base 5 growths.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, second electrode 2 are equipped with metal film.
On the electrode in the present invention's 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 firm attachment is at first electrode, 1 inner surface; Through the fairlead of second electrode 2, third electrode 3 collectors can be collected the positive ion stream that gas ionization produces.Between first electrode 1 and second electrode 2, isolate mutually by insulation column 7 between 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 nitrogen monoxide of the present invention, sulphuric dioxide two component mixed gas concentrations is described further.
Adopt carbon nano-tube film ionization type temperature, the humidity sensor of two different poles spacing carbon nano-tube film ionization type gas 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 flow 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 carbon nano-tube film ionizing transducer array detection sulphuric dioxide shown in Figure 6 and the nitrogen monoxide two component mixed gas concentration embodiment, 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.First electrode 1 of nitric oxide sensor and second electrode 2, second electrode 2 are 100 μ m with third electrode 3 die openings, and SO 2 sensor first electrode 1 and second electrode 2, 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.First electrode 1 of above-mentioned carbon nano-tube film ionizing transducer and second electrode, 2 pole plates are 170mm over against area
2, second electrode 2 is 190mm with third electrode 3 pole plates over against area
2Two first electrode cathode voltages of measuring two component mixed gas concentration sensors are 0V, the equal on-load voltage 100V of the second electrode extraction pole, the equal on-load voltage 10V of third electrode collector; 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 stream that the collector of two measurement two component gases concentration sensors is collected all reduces, and ion stream presents the relation that monodrome descends with two component gases concentration increases; Temperature, humidity sensor sensing 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 two-dimentional curved section 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 1352 groups of interpolated datas altogether, and form database with 36 groups of experimental calibration data; Select for use 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) data 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 150 μ m, 180 μ m.
Adopt carbon nano-tube film ionization type temperature, the 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 flow data input data fusion of sensor output is set up have obtained accuracy less than 1% sulphuric dioxide and the accurate measured value of nitrogen monoxide two component mixed gas concentrations.
Among carbon nano-tube film ionizing transducer array detection sulphuric dioxide shown in Figure 7 and the nitrogen monoxide two component mixed gas concentration embodiment, 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.First electrode 1 of nitric oxide sensor and second electrode 2, second electrode 2 are 150 μ m with third electrode 3 die openings, and SO 2 sensor first electrode 1 and second electrode 2, 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.First electrode 1 of above-mentioned carbon nano-tube film ionizing transducer and second electrode, 2 pole plates are 170mm over against area
2, second electrode 2 is 190mm with third electrode 3 pole plates over against area
2Two first electrode cathode voltages of measuring two component mixed gas concentration sensors are 0V, the equal on-load voltage 100V of the second electrode extraction pole, the equal on-load voltage 10V of third electrode collector; 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 stream that the collector of two measurement two component gases concentration sensors is collected all reduces, and ion stream presents the relation that monodrome descends with two component gases concentration increases; Temperature, humidity sensor sensing 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 two-dimentional curved section 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 1381 groups of interpolated datas altogether, and form database with 36 groups of experimental calibration data; Select for use 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) data 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 100 μ m, 180 μ m.
Adopt carbon nano-tube film ionization type temperature, the 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 flow 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 carbon nano-tube film ionizing transducer array detection sulphuric dioxide shown in Figure 8 and the nitrogen monoxide two component mixed gas concentration embodiment, 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.First electrode 1 of nitric oxide sensor and second electrode 2, second electrode 2 are 100 μ m with third electrode 3 die openings, and SO 2 sensor first electrode 1 and second electrode 2, 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.First electrode 1 of above-mentioned carbon nano-tube film ionizing transducer and second electrode, 2 pole plates are 170mm over against area
2, second electrode 2 is 190mm with third electrode 3 pole plates over against area
2Two first electrode cathode voltages of measuring two component mixed gas concentration sensors are 0V, the equal on-load voltage 100V of the second electrode extraction pole, the equal on-load voltage 10V of third electrode collector; 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 stream that the collector of two measurement two component gases concentration sensors is collected all reduces, and ion stream presents the relation that monodrome descends with two component gases concentration increases; Temperature, humidity sensor sensing 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 two-dimentional curved section 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 1390 groups of interpolated datas altogether, and form database with 36 groups of experimental calibration data; Select for use 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) data 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 two different poles spacing carbon nano-tube film ionizing transducers to measure nitrogen dioxide NO
2, sulphuric dioxide SO
2Two component concentration of two component mixed gass, adjacent two interelectrode die openings are identical in three electrodes, and the die opening of two sensors is respectively 250 μ m, 30 μ m.First electrode 1 of above-mentioned carbon nano-tube film ionizing transducer and second electrode, 2 pole plates are 0.01mm over against area
2, 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 first electrode 1 has 1, and bleeder vent is quadrilateral, pentagon or hexagon; 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 two different poles spacing carbon nano-tube film ionizing transducers to measure nitrogen dioxide, sulphuric dioxide two component gases concentration, the first electrode cathode voltage of two sensors is 0V, the second electrode extraction pole on-load voltage 2V, third electrode collector on-load voltage 1V.Ion flow valuve input nitrogen dioxide, the accurate measurement model of sulphuric dioxide two component mixed gas concentrations of output during with two carbon nano-tube film ionization type gas concentration sensors, temperature sensor and humidity sensor actual measurement, the accurate measured value of this model output nitrogen dioxide, two component concentration of sulphuric dioxide two component mixed gass.
Present embodiment basic structure is with embodiment 1, and difference is: adopt two different poles spacing carbon nano-tube film ionizing transducers to measure hydrogen H
2, acetylene C
2H
2Two component gases concentration of two component mixed gass, adjacent two interelectrode die openings are identical in three electrodes, and the die opening of two sensors is respectively 250 μ m, 150 μ m.First electrode 1 of above-mentioned carbon nano-tube film ionizing transducer and second electrode, 2 pole plates are 100mm over against area
2, second electrode 2 is 120mm with third electrode 3 pole plates over against area
2
The bleeder vent of the electrode surface of sensor first electrode 1 has 4, and bleeder vent is quadrilateral, pentagon or hexagon; 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 two different poles spacing carbon nano-tube film ionization type gas concentration sensors to measure hydrogen, acetylene two component gases concentration, the first electrode cathode voltage of two sensors is 0V, the second electrode extraction pole on-load voltage 200V, third electrode collector on-load voltage 180V.Ion flow valuve input hydrogen, the accurate measurement model of acetylene two component mixed gas concentrations of output during with carbon nano-tube film ionization type gas concentration sensor array, temperature sensor and humidity sensor actual measurement, the accurate measured value of this model output hydrogen, two component concentration of acetylene two 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 two components and mix gas to be measured, antijamming capability and by force, do not need to separate two component mixed gass to be measured, two high component mixed gas concentration measuring methods of accuracy.The sensor of different poles spacing in the sensor array directly detects two component concentration in the two component mixed gass under not separating two component mixed gas conditions, and the disturbing effect of detected temperatures, humidity in real time; PA level current measurement system can detect the pA level electric current of each sensor output of corresponding two component gases concentration, temperature, humidity simultaneously; Piecewise interpolation and data fusion method can be eliminated temperature, humidity interference, two high component mixed gas concentration measured values of output accuracy.
Though the present invention has made detailed description with above-mentioned preferred embodiment to the present invention, above-described embodiment also is not used in restriction the present invention.Under 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 (4)
1. carbon nano-tube film ionizing transducer, it is characterized in that: comprise three first electrode, second electrode and third electrodes that distribute successively from top to bottom, the electrode that described 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 constitutes; 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 100～150 μ m in described three electrodes; Described first electrode and second electrode pad are 0.01～170mm over against area
2, second electrode and third electrode pole plate are 0.01～190mm over against area
2
The bleeder vent of the electrode surface of described first electrode is 1～4, and metallic film base growth or the serigraphy of adhering at the electrode inner surface have carbon nano-tube film;
The described second electrode extraction pole center is provided with 1～4 fairlead;
Described third electrode collector blind hole is corresponding with the fairlead of second electrode, and the quantity of blind hole is 1～4.
2. based on the method for the described carbon nano-tube film ionizing transducer of claim 1 array detection two component mixed gas concentrations, it is characterized in that this 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 two component mixed gass to be measured, place two component mixed gass to be measured as carbon nano-tube film ionization type gas concentration sensor two carbon nano-tube film ionizing transducers of having set the different poles spacing respectively, and simultaneously the carbon nano-tube film ionizing transducer of two different poles spacings is placed two component mixed gass to be measured as carbon nano-tube film ionization type temperature sensor and carbon nano-tube film ionization type humidity sensor respectively, form sensor array by all the sensors;
(3) respectively to the first electrode on-load voltage 0V of two carbon nano-tube film ionization type gas concentration sensors of step (2), carbon nano-tube film ionization type temperature sensor, carbon nano-tube film ionization type humidity sensor, the second electrode on-load voltage, 2～200V, third electrode on-load voltage 1～180V;
(4) in two component concentration of two component mixed gass to be measured, temperature and humidity measurement range, corresponding different concentration, temperature and humidity calibration value, the gas discharge ion flow valuve of all the sensors output in the measuring process (2) respectively;
(5) with all the sensors output ion flow valuve that in concentration, temperature and humidity measurement range, records in the step (4), with corresponding two component mixed gass, two component concentration, scale of thermometer definite value and humidity demarcating value, form different experimental calibration samples, adopt the piecewise interpolation technology that the experimental calibration sample is carried out interpolation then, obtain interpolated data, obtain interpolated sample, and set up two component mixed gas concentration measured database according to all samples that comprised experimental calibration sample and interpolated sample;
(6) adopt the data fusion technology, make up the data fusion instrument, set up the measurement model of carbon nano-tube film ionization type gas concentration 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 two component 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 accurate measurement model of two component mixed gas concentrations of data fusion instrument output carbon nano-tube film ionizing transducer array;
The accurate measurement model of two component mixed gas concentrations that the ion flow valuve input step (6) of output obtains during (7) with carbon nano-tube film ionization type gas concentration sensor, carbon nano-tube film ionization type temperature sensor and the actual measurement of carbon nano-tube film ionization type humidity sensor, this model is exported the accurate measured value of two component concentration of two component mixed gass.
3. the method based on carbon nano-tube film ionizing transducer array detection two component mixed gas concentrations according to claim 2, it is characterized in that: in the described carbon nano-tube film ionizing transducer, second electrode potential is higher than first electrode potential, and the third electrode current potential is lower than second electrode potential and is higher than first electrode potential.
4. the method based on carbon nano-tube film ionizing transducer array detection two component mixed gas concentrations according to claim 2, it is characterized in that: described establishment two component mixed gas concentration measured database, be 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 two component concentration, temperature and humidity calibration value and interpolated datas thereof in the two component mixed gass as the desired output sample.
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| CN102095790B (en) * | 2011-02-16 | 2013-04-17 | 西安交通大学 | Carbon nanotube film ionizing sensor array and method for detecting concentration of mixed gas |
| 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 |
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| CN102081072A (en) * | 2011-02-16 | 2011-06-01 | 西安交通大学 | Carbon nanotube (CNT) film based ionization nitric oxide (NO) sensor and method for measuring concentration by adopting same |
| CN102109492A (en) * | 2011-02-16 | 2011-06-29 | 西安交通大学 | Carbon nanometer tube film ionization type gas humidity sensor and humidity measurement method thereof |
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| CN102081072A (en) * | 2011-02-16 | 2011-06-01 | 西安交通大学 | Carbon nanotube (CNT) film based ionization nitric oxide (NO) sensor and method for measuring concentration by adopting same |
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