CN102095781B - Carbon nano tube film ionizing sensor and method for detecting concentration of single gas based on same - Google Patents
Carbon nano tube film ionizing sensor and method for detecting concentration of single gas based on same Download PDFInfo
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- CN102095781B CN102095781B CN201110038489A CN201110038489A CN102095781B CN 102095781 B CN102095781 B CN 102095781B CN 201110038489 A CN201110038489 A CN 201110038489A CN 201110038489 A CN201110038489 A CN 201110038489A CN 102095781 B CN102095781 B CN 102095781B
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Abstract
The invention discloses a carbon nano tube film ionizing sensor and a method for detecting the concentration of a single gas based on the same. The sensor comprises a first electrode, a second electrode and a third electrode which are distributed sequentially; a ventilating hole is formed on the first electrode; a metal film substrate on which a carbon nano tube film is distributed is attached to the inner surface of the ventilating hole; an lead-out hole is formed in the centre of the second electrode; a blind hole is formed on the board of the third electrode; and the three electrodes are isolated mutually. The method comprises the following steps of: 1) placing three sensors with different interelectrode distances; 2) exerting voltage on the electrodes; 3) measuring ion current values of the sensors; 4) forming a sample by combining the measured values and the calibration values of the concentration, the temperature and the humidity of the single gas, and constructing a gas concentration measurement database by the sample and an interpolation sample; 5) constructing a data fusion device and building a single gas concentration accurate measurement model; and 6) inputting the actually measured values of the sensors into the measurement model to obtain an accurate measured value of the concentration of the single gas. The sensor is high in gas detection sensitivity, high in linearity and high in accuracy.
Description
Technical field
The present invention relates to the gas sensing field, particularly a kind of based on the ionizing transducer of carbon nano-tube film and gas discharge principle and the method for detection pure gas concentration thereof.
Background technology
Along with pressing for and the development of nanometer technology of all trades and professions gas detection, nano-sensor has obtained considerable progress.Especially along with the discovery of CNT in latter stage in 20th century, CNT 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 advantages such as its detection sensitivity height, detected gas wide ranges, response are fast, become gas, temperature, Humidity Detection hot research fields.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 CNT: the one, the specific surface area of CNT 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 near the CNT tip, obtain extremely strong electric field intensity, under low-voltage, make tested gas ionization; The 3rd, the size of having dwindled sensor greatly, dynamic response is fast.Therefore, it has result of extraction at aspects such as biology, chemistry, machinery, aviation, military affairs, anti-terrorisms.
Existing carbon nano-tube film two electrode ionization type sensors comprise by people such as the Liu Junhua of Xi'an Communications University, Zhang Yong, 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 Nikhil Koratkar of U.S. Rensselaer Polytech Inst (Rensselaer Polytechnic Institute) and Pulickel M professor Ajayan have developed carbon nano-tube 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; Sparking voltage and discharge current are bigger; Can't realize of the measurement of carbon nano-tube film anode to pure gas.The Hui Guohua of Zhejiang University's biomedical engineering and instrumental science institute, Chen Yuquan professor develop 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 of all kinds of pure gases of sensitivity and detect the research of the method for pure gas concentration, become the technical matters that needs to be resolved hurrily.
Summary of the invention
One of the object of the 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 flow; Set up the single-valued relationship of ion flow that ionizing transducer collector of the present invention collects and pure gas concentration, temperature, humidity, overcome carbon nano-tube film two electrode sensor gas-sensitive properties and the many-valued nonlinear problem of the quick characteristic that wets.This sensor construction is simple, and cost is low, and detected gas is highly sensitive.
Another object of the present invention provides a kind of method that detects pure gas concentration based on the carbon nano-tube film ionizing transducer; Form sensor array by different poles spacing carbon nano-tube film ionizing transducer, measure pure gas concentration to be measured, gas temperature and humidity respectively; The hardware configuration that this concentration measuring method requires is simple, and any pure gas of energy measurement adopts data anastomosing algorithm, and the detected gas accuracy is high.
The objective of the invention is to realize through 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 said 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 up of the extraction pole pole plate that the center is provided with fairlead; Third electrode is made up of the collector that the plate face is provided with blind hole; These three electrodes are isolated through insulation column respectively each other.
Architectural feature of the present invention also is:
The die opening of adjacent two electrodes is 30～250 μ m in said three electrodes;
Said 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 said first electrode is 1～4, and growth or serigraphy have carbon nano-tube film on the metallic film base that the electrode inner surface adheres to;
The said second electrode extraction pole center is provided with 1～4 bleeder vent;
Said 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 detection pure gas concentration, and this method comprises the steps:
(1) select the die opening of adjacent two electrodes in three electrodes to be set at the carbon nano-tube film ionizing transducer of 30～250 μ m;
The carbon nano-tube film ionizing transducer of three different poles spacings (2) will setting respectively is placed in the atmosphere that contains pure gas to be measured as carbon nano-tube film ionization type pure gas sensor, carbon nano-tube film ionization type temperature sensor, carbon nano-tube film ionization type humidity sensor respectively;
(3) respectively to the first electrode on-load voltage 0V of said carbon nano-tube film ionization type pure gas 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;
(4) in pure gas 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 pure gas concentration, temperature and humidity calibration 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 pure gas concentration measurement data storehouse according to all samples that comprised experimental calibration sample and interpolated sample;
(6) adopt the data fusion technology, make up the data fusion appearance, set up the measurement model of pure gas sensor, temperature sensor and humidity sensor; With input sample and the desired output sample of the data in the pure gas concentration measurement data storehouse as the data fusion appearance; And train and check as the training sample and the test samples of data fusion appearance respectively with data different in the range ability; When assay satisfies the measurement error requirement, the accurate measurement model of concentration of data fusion appearance output pure gas sensor;
The accurate measurement model of pure gas concentration that the ion flow valuve input step (6) of output obtains during (7) with carbon nano-tube film ionization type pure gas sensor, temperature sensor and humidity sensor actual measurement, the accurate measured value of this model output pure gas concentration.
The inventive method characteristic also is:
In the said 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.
The said pure gas concentration measurement data storehouse of setting up; Be that experimental calibration data and interpolated data are formed database; With each sensor output ion flow valuve and interpolated data thereof as the input sample, with pure gas concentration, temperature and humidity calibration value and interpolated data thereof as the desired output sample.
Based on the measuring method of carbon nano-tube film ionizing transducer detection pure gas concentration, form sensor array by different poles spacing carbon nano-tube film ionizing transducer, measure pure gas concentration to be measured, temperature and humidity respectively; Supply power by the sensor electrical potential source; Export by pA level current measurement system detecting sensor; The adjustment electrode separation, the adjustment electrode voltage in pure gas to be measured, carries out the calibration experiment of sensor in temperature, humidity environment; 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 pure gas concentration measurement data storehouse, obtain monodrome gas-sensitive property, monodrome responsive to temperature characteristic, the monodrome humidity sensitive characteristic of pure gas to be measured; According to the data in the pure gas concentration measurement data storehouse, based on piecewise interpolation technology and data fusion technology, eliminate the influence of temperature, humidity, set up the accurate measurement model of concentration of pure gas sensor; Pure gas measurement of concetration model is imported in the output of sensor array in real time during with actual measurement, just can obtain the measured result of pure gas concentration.This pure 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; Any pure gas of energy measurement adopts data anastomosing algorithm, and cost is low; Detected gas is highly sensitive, accuracy is high, is suitable for promoting the use of.
Pure gas concentration detection method of the present invention can be realized the measurement of concetration of pure gas, and accuracy is 1%.The gas concentration detection method of tradition three electrode probes that use in this new gas concentration detection method and the existing ionization detector chromatograph is compared; Do electrode owing to adopt carbon nano-tube film; Sensor comprises that to all pure gases inflammable and explosive and toxic gas all has the measurement of concetration accuracy of high sensitivity and 1%, so overcome the difficult problem that chromatograph need be changed the variety classes detector to gas with various in the measuring process.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 pure gas concentration measuring method of the present invention integrates sensor array technology, pA level current measurement techniques, piecewise interpolation technology and the data fusion technology of different poles spacing; The influence of temperature, humidity can be eliminated, the accurate measurement of pure gas concentration 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 a carbon nano-tube film ionizing transducer structural representation of the present invention.
Fig. 5 is a carbon nano-tube film ionizing transducer spatial structure side view of the present invention.
Fig. 6 is the gas discharge ion flow in pure gas sulphuric dioxide, exported of carbon nano-tube film ionizing transducer of the present invention and the single valued relation of gas concentration.
Fig. 7 is the gas discharge ion flow in pure gas nitrogen dioxide, exported of carbon nano-tube film ionizing transducer of the present invention and the single valued relation of gas concentration.
Fig. 8 is the gas discharge ion flow in the pure gas nitrogen monoxide, exported of carbon nano-tube film ionizing transducer of the present invention and the single valued relation of gas concentration.
Among the figure: 1, first electrode; 2, second electrode; 3, third electrode; 4, be provided with the electrode of bleeder vent; 5, metallic film base; 6, carbon nano-tube film; 7, insulation column.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is further specified.
Like 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 said 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 up of the extraction pole pole plate that the center is provided with fairlead; Third electrode 3 is made up of the collector that the battery lead plate face is provided with blind hole; These three electrodes are isolated through insulation column 7 respectively each other.
Among the carbon nano-tube film ionizing transducer embodiment shown in Figure 4, the bleeder vent of the electrode surface of first electrode 1 has 2, and bleeder vent is circular; Side surface at this electrode is attached with metallic film base 5, is distributed with carbon nano-tube film 6 on it, and this CNT mouth of pipe is downward.Second electrode, 2 centers are provided with 1～4 fairlead, have provided among Fig. 4, Fig. 5 a fairlead and fairlead are set are circular embodiment.Third electrode 3 collector blind holes are corresponding with the fairlead of second electrode, and the quantity of blind hole is 1～4, 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, promptly insulation column 7 be distributed in second electrode 2 over against the both sides on the inboard golden film surface of first electrode 1 and second electrode 2 over against the both sides 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; Said carbon nano-tube film 6 can adopt FePC as catalyzer, and adopts carbon source, and carbon nano-tube film 6 is made in growth on metallic film base 5, and perhaps the serigraphy carbon nano-tube film 6.Second electrode 2 all adopts silicon wafer to manufacture with third electrode 3.The two sides of first electrode 1 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 get into electrode gap; Metallic film base has conductive capability, and firm attachment is at first electrode, 1 one side surfaces; Second electrode 2 is provided with positive ion stream fairlead; Third electrode 3 collectors can be collected the positive ion stream that gas ionization produces through the fairlead of second electrode 2.Between first electrode 1 and second electrode 2, isolate each other through insulation column 7 between second electrode 2 and the third electrode 3; Tested gas gets in the gap of adjacent two electrodes of sensor through the gap between the sensor peripheral electrode.
The present invention takes the thin ionizing transducer of the CNT of said structure when measuring pure gas concentration, and 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.Second electrode and first electrode form the electron stream loop, and the third electrode and first electrode form the ion flow loop, realize electron stream is separated with ion flow.Between the ion flow of carbon nano-tube film ionizing transducer output and pure gas concentration, gas temperature, the humidity; Apply at second electrode on the basis of certain voltage, present monodrome gas concentration sensitive relations (Fig. 6～Fig. 8), monodrome responsive to temperature relation, monodrome humidity sensitive relation.Through piecewise interpolation and data fusion, realized the accuracy of measurement of pure gas concentration 1%.The carbon nano-tube film ionizing transducer array technique of different poles spacing, pA level current measurement techniques, piecewise interpolation technology and data fusion technology are the characteristics of concentration measuring method of the present invention.
Through an instantiation, the method that carbon nano-tube film ionizing transducer of the present invention is detected pure gas concentration further specifies below.
Adopt the fixing carbon nano-tube film ionizing transducer of die opening; Experiment has obtained the monodrome gas-sensitive property (shown in Figure 6) of pure gas sulphuric dioxide; Pure gas measurement of concetration model that the ion flow data input data fusion of sensor output is set up has obtained accuracy less than 1% pure gas sulfur dioxide concentration measured value.
Carbon nano-tube film ionizing transducer shown in Figure 6 detects among the embodiment of pure gas sulfur dioxide concentration, and the experimental situation condition is 20.5 ℃ of temperature, relative humidity 25.8%RH, atmospheric pressure 93.4KPa.Carbon nano-tube film ionization type SO 2 sensor first electrode 1 and second electrode, 2 die openings are that 200 μ m, second electrode 2 are 220 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 three carbon nano-tube film ionizing transducers 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
2 Pure gas SO 2 sensor first electrode 1 cathode voltage is 0V, second electrode, 2 extraction pole on-load voltage 100V, third electrode 3 collector on-load voltage 10V; 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 the increase of sulfur dioxide concentration, the ion flow that pure gas SO 2 sensor collector is collected reduces, and presents monodrome decline relation between ion flow and the sulfur dioxide concentration; Temperature, humidity sensor sensing characteristic and pure gas SO 2 sensor are similar.In 0～739ppm concentration of SO 2 gas scope, 10 groups of experimental calibration data have been obtained.Three sensor ion flow valuves are as the input sample, and the concentration of SO 2 gas calibration value is as the desired output sample data.Adopt linear interpolation to 10 groups of experimental calibration sample data interpolation; In 0～739ppm concentration of SO 2 gas scope, be that spacing is carried out equidistant interpolation with 20ppm; And near concentration demand value (being the gas concentration critical value), carry out intensive interpolation; Obtain 67 groups of interpolated datas altogether, and form database with 10 groups of experimental calibration data; Select for use 67 groups of interpolated datas and 2 groups of experimental calibration data totally 69 groups of data as training sample; Remaining 8 groups of experimental calibration data that are different from training sample are as test samples; Input data fusion appearance through the training check, obtains pure gas sulfur dioxide concentration measurement model.The linearity of sulfur dioxide concentration measurement model is that the assay fiducial error maximal value of 0.31%, 8 group of test samples is 0.32%, has reached 1% measurement of concetration accuracy.
Present embodiment sensor basic structure is with embodiment 1, and different is:
The die opening of adjacent two electrodes is fixed as 200 μ m in three electrodes of the carbon nano-tube film ionizing transducer of measurement pure gas content of nitrogen dioxide; The bleeder vent of first electrode 1 is that 2, the fairlead of second electrode 2 are 1, and the blind hole of third electrode 3 is 1.
Adopt the fixing carbon nano-tube film ionizing transducer of above-mentioned die opening; Experiment has obtained the monodrome gas-sensitive property (shown in Figure 7) of pure gas nitrogen dioxide; Content of nitrogen dioxide measurement model that the ion flow data input data fusion of sensor output is set up has obtained accuracy less than 1% pure gas content of nitrogen dioxide measured value.
Carbon nano-tube film ionizing transducer shown in Figure 7 detects among the embodiment of pure gas content of nitrogen dioxide, and the experimental situation condition is 40.7 ℃ of temperature, relative humidity 18.5%RH, atmospheric pressure 93.5KPa.Pure gas carbon nano-tube film ionizing transducer first electrode 1 and second electrode, 2 die openings are that 200 μ m, second electrode 2 are 200 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 three carbon nano-tube film ionizing transducers 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
2The pure gas nitrogen dioxide sensor first electrode cathode voltage is 0V, the second electrode extraction pole on-load voltage 100V, third electrode collector on-load voltage 10V; 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 the increase of content of nitrogen dioxide, the ion flow that pure gas nitrogen dioxide sensor collector is collected reduces, and presents monodrome decline relation between ion flow and the content of nitrogen dioxide; Temperature, humidity sensor sensing characteristic and pure gas nitrogen dioxide sensor are similar.In 0～734.795ppm content of nitrogen dioxide scope, 10 groups of experimental calibration data have been obtained.Three sensor ion flow valuves are as the input sample, and pure gas content of nitrogen dioxide calibration value is as the desired output sample data.Adopt piecewise linear interpolation to 10 groups of experimental calibration sample data interpolation; In 0～734.795ppm content of nitrogen dioxide scope, be that spacing is carried out equidistant interpolation with 5ppm; And near concentration demand value (being the gas concentration critical value), carry out intensive interpolation; Obtain 266 groups of interpolated datas altogether, and form database with 10 groups of experimental datas; Select for use 266 groups of interpolated datas and 1 group of experimental calibration data totally 267 groups of data as training sample; 9 groups of experimental calibration data are as test samples; Input SVMs training model machine through the training check, obtains pure gas nitrogen dioxide gas concentration measurement model.The linearity of content of nitrogen dioxide measurement model is that the assay fiducial error maximal value of 0.185%, 9 group of test samples is 0.187%, has reached 1% measurement of concetration accuracy.
Present embodiment sensor basic structure is with embodiment 1, and different is:
The die opening of adjacent two electrodes is respectively 200 μ m, 220 μ m in three electrodes of the carbon nano-tube film ionizing transducer of measurement pure gas nitric oxide concentration; The bleeder vent of first electrode 1 is that 2, the fairlead of second electrode 2 are 1, and the blind hole of third electrode 3 is 1.
Adopt the fixing carbon nano-tube film ionizing transducer of above-mentioned die opening; Experiment has obtained the nitric oxide production monodrome gas-sensitive property of pure gas (shown in Figure 8); Nitric oxide concentration measurement model that the ion flow data input data fusion of sensor output is set up has obtained accuracy less than 1% pure gas nitric oxide concentration measured value.
Carbon nano-tube film ionizing transducer shown in Figure 8 detects among the embodiment of pure gas nitric oxide concentration, and the experimental situation condition is 22.4 ℃ of temperature, relative humidity 24.5%RH, atmospheric pressure 93.4KPa.Carbon nano-tube film ionization type nitric oxide sensor first electrode 1 and second electrode, 2 die openings are that 200 μ m, second electrode 2 are 220 μ m with third electrode 3 die openings, and 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 three carbon nano-tube film ionizing transducers 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
2The pure gas nitric oxide sensor first electrode cathode voltage is 0V, the second electrode extraction pole on-load voltage 100V, third electrode collector on-load voltage 10V; 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 the increase of nitric oxide concentration, the ion flow that pure gas nitric oxide sensor collector is collected reduces, and presents monodrome decline relation between ion flow and the nitric oxide concentration; Temperature, humidity sensor sensing characteristic and pure gas nitric oxide sensor are similar.In 0～1120ppm nitric oxide gas concentration range, 10 groups of experimental calibration data have been obtained.Three sensor ion flow valuves are as the input sample, and pure gas nitric oxide concentration calibration value is as the desired output sample data.Adopt linear interpolation to 10 groups of experimental calibration sample data interpolation; In 0～1120ppm concentration range, be that spacing is carried out equidistant interpolation with 30ppm; Obtain 38 groups of interpolated datas, near concentration demand value (being the gas concentration critical value), carry out intensive interpolation, the 55 groups of interpolated datas of reentrying; Totally 93 groups of interpolated datas, and form databases with 10 groups of experimental datas; Select for use 93 groups of interpolated datas as training sample, 10 groups of experimental calibration data are as test samples, and input data fusion model machine through the training check, obtains pure gas nitric oxide concentration measurement model.The linearity of nitric oxide concentration measurement model is that the assay fiducial error maximal value of 0.19%, 10 group of test samples is 0.211%, has reached 1% measurement of concetration accuracy.
Present embodiment basic structure is with embodiment 1; Different is: adjacent two interelectrode die openings are respectively 250 μ m, 30 μ m in three electrodes of carbon nano-tube film ionization type pure gas sensor, and first electrode 1 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 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 and embodiment 1 are basic identical, and different is:
The first electrode cathode voltage of carbon nano-tube film ionization type pure gas sensor is 0V, the second electrode extraction pole on-load voltage 2V, third electrode collector on-load voltage 1V.
Present embodiment basic structure is with embodiment 1; Different is: adjacent two interelectrode die openings are respectively 250 μ m, 30 μ m in three electrodes of carbon nano-tube film ionization type pure gas sensor, and first electrode 1 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 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 and embodiment 1 are basic identical, and different is:
The first electrode cathode voltage of carbon nano-tube film ionization type pure gas sensor is 0V, the second electrode extraction pole on-load voltage 200V, third electrode collector on-load voltage 180V.
The present invention forms sensor array, the output of pA level current measurement system survey sensor, piecewise interpolation and data fusion method through different poles spacing carbon nano-tube film ionizing transducer, form a kind of novel, can measure any pure gas, antijamming capability is strong, accuracy is high pure gas concentration measuring method.The sensor of different poles spacing in the sensor array is measured the disturbing effect of temperature, humidity in real time, directly measures pure gas concentration; PA level current measurement system can be measured the pA level electric current of each sensor output of corresponding pure gas concentration, temperature and humidity simultaneously; Piecewise interpolation and data fusion method can be eliminated temperature, humidity interference, the high pure gas concentration measurement of output accuracy.
Though the present invention has made detailed description with above-mentioned preferred embodiment to the present invention, the foregoing description also is not used in qualification the present invention.Under the situation that does not break away from given technical characterictic of technical scheme 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 (6)
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 said 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 up of the extraction pole pole plate that the center is provided with fairlead; Third electrode is made up of the collector that the plate face is provided with blind hole; These three electrodes are isolated through insulation column respectively each other.
2. carbon nano-tube film ionizing transducer according to claim 1 is characterized in that: adjacent two interelectrode die openings are 30～250 μ m in said three electrodes; Said 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
3. carbon nano-tube film ionizing transducer according to claim 1; It is characterized in that: the bleeder vent of the electrode surface of said first electrode is 1～4, and growth or serigraphy have carbon nano-tube film on the metallic film base that the electrode inner surface adheres to;
The said second electrode extraction pole center is provided with 1～4 fairlead;
Said third electrode collector blind hole is corresponding with the fairlead of second electrode, and the quantity of blind hole is 1～4.
4. a method of utilizing the described carbon nano-tube film ionizing transducer of claim 1 to detect pure gas concentration is characterized in that this method comprises the steps:
(1) select the die opening of adjacent two electrodes in three electrodes to be set at the carbon nano-tube film ionizing transducer of 30～250 μ m;
The carbon nano-tube film ionizing transducer of three different poles spacings (2) will setting respectively is placed in the atmosphere that contains pure gas to be measured as carbon nano-tube film ionization type pure gas sensor, carbon nano-tube film ionization type temperature sensor and carbon nano-tube film ionization type humidity sensor respectively;
(3) respectively to the first electrode on-load voltage 0V of said carbon nano-tube film ionization type pure gas 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;
(4) in pure gas 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 pure gas concentration, temperature and humidity calibration 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 pure gas concentration measurement data storehouse according to all samples that comprised experimental calibration sample and interpolated sample;
(6) adopt the data fusion technology, make up the data fusion appearance, set up the measurement model of pure gas sensor, temperature sensor and humidity sensor; With input sample and the desired output sample of the data in the pure gas concentration measurement data storehouse as the data fusion appearance; And train and check as the training sample and the test samples of data fusion appearance respectively with data different in the range ability; When assay satisfies the measurement error requirement, the accurate measurement model of concentration of data fusion appearance output pure gas sensor;
The accurate measurement model of pure gas concentration that the ion flow valuve input step (6) of output obtains during (7) with carbon nano-tube film ionization type pure gas sensor, temperature sensor and humidity sensor actual measurement, the accurate measured value of this model output pure gas concentration.
5. the method for detection pure gas concentration according to claim 4; 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.
6. the method for detection pure gas concentration according to claim 4; It is characterized in that: the said pure gas concentration measurement data storehouse of setting up; Be that experimental calibration data and interpolated data are formed database; With each sensor output ion flow valuve and interpolated data thereof as the input sample, with pure gas concentration, temperature and humidity calibration value and interpolated data thereof as the desired output sample.
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| CN102081072B (en) * | 2011-02-16 | 2013-05-22 | 西安交通大学 | Carbon nanotube (CNT) film based ionization nitric oxide (NO) sensor and method for measuring concentration by adopting same |
| 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 |
| CN102095789B (en) * | 2011-02-16 | 2013-07-10 | 西安交通大学 | Carbon nanotube film ionizing sensor and method for detecting concentration of bi-component gas |
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