Method and polymer-based sensor for measuring the concentration of non-polar gases such as carbon dioxide

Abstract: The disclosure relates to a method and sensor structure for measuring the concentration of nonpolar gases such as carbon dioxide. According to the method, the concentration of the nonpolar gas adsorbed/absorbed in a polymer film (2) is determined by detecting the weight of the polymer film (2). According to the application, the dielectric coefficient of the polymer film (2) is measured, and on the basis of this, a correction is made in the concentration measurement result obtained from the weight measurement.

Description: The invention relates to a concentration sensor structure according to the preamble of claim 1 and a method according to the preamble of claim 2 for measuring the concentration of nonpolar gases such as carbon dioxide by a means of a polymer-based sensor. Water is generally absorbed in significant amounts in all polymers. When besides water, also concentrations of other gases are desired to be measured using methods based on weighing a polymer film utilizing, e.g., a film-coated quartz crystal or a surface acoustic wave component, the presence of water forms a strongly disturbing factor. With variations in the relative humidity of air, also the amount of absorbed/adsorbed water, and resultingly, the weight of the polymer film, changes. The publication in Sensors and Actuators B. Chemical by R. Zhou et al entitled "Reliable CO 2 sensors with silicon-based polymers on quartz microbalance transducers" vol. B19 (1994) April Nos. 1/3, Lausanne, CH pages 415 to 420 discloses the use of microbalance oscillators to monitor changes in mass by means of frequency changes in polymer coatings on sensor electrodes. It is an object of the present invention to overcome the drawbacks of the above-described techniques and to achieve an entirely novel type of method and sensor structure for measuring the concentration of nonpolar gases such as carbon dioxide by means of a polymer-based sensor. The goal of the invention is achieved by detecting the amount of humidity (that is, water) absorbed/adsorbed in a polymer film through measuring the dielectric coefficient ε of the film, in practice, through measuring the capacitance of the sensor structure. Thus, the effect of humidity can be eliminated in the measurement of another nonpolar gas (such as CO 2 ) based on the weighing of the polymer film. More specifically, the method according to the invention comprises a method as defined in the opening paragraph characterized by what is stated in the characterizing part of claim 2. Claims 3 and 4 recite preferred features of the method of the invention. Furthermore, the sensor structure according to the invention comprises a structure as defined in the opening paragraph characterized by what is stated in the characterizing part of claim 1. The invention offers significant benefits. As the effect of relative humidity variations can be eliminated almost completely, the accuracy of the concentration measurement of a nonpolar gas can be essentially increased. In the following, the invention will be examined in more detail by means of exemplifying embodiments with reference to the attached drawings, in which: Figure 1a is a longitudinally sectional side view of a sensor structure according to the invention; Figure 1b is a top view of the sensor structure illustrated in Fig. 1a with the upper electrode, the polymer film and the crystal shown transparent; Figure 2 is a graph showing the effect of relative humidity on the sensor capacitance; and Figure 3 is a graph showing the change of the crystal oscillating frequency as a function of relative humidity at two different CO 2 concentrations. Next, an example is given of the measurement algorithm according to the invention. 1. A response function of the film mass is defined for the gas to be measured: p k = f 1 (S 1 ), where p k = partial pressure of the gas to be measured, and S 1 = film-mass-related output variable of the sensor (e.g., oscillating frequency). Typically, the function f 1 may be a polynomial: where a i is a constant. 2. The relationship of the polymer film capacitance with the mass of the polymer film is determined over the entire range of relative humidity at zero concentration of the gas to be measured: S 1rh = f 2 (C), where C is the capacitance of the sensor structure. Typically, the function f 2 may be a polynomial: where b i is a constant. 3. At low concentrations of the gas to be measured as is typical in environmental measurements, the amount of adsorbed/absorbed water has an insignificant effect on the sorption of the gas to be measured. Then, the partial pressure of the gas to be measured can be computed when the total mass S tot and the capacitance C of the polymer film are known: p k = f 1 (S tot -f 2 (C)) At high partial pressures of the gas to be measured, the amount of adsorbed/absorbed water affects the sorption of the gas to be measured. Then, the foregoing method must be generalized: p k = f 3 (S tot , C) An exemplary form of function f 3 could be written as: In the following a practical example is described with reference to the sensor structure illustrated in Figs. 1a and 1b. Referring to Fig. 1, a quartz crystal 1 is coated with a polymer film 2. Prior to coating, the resonant frequency of the crystal 1 was approx. 11 MHz. After coating the crystal 1 with the film 2, the resonant frequency dropped by about 60 kHz. The thickness of the film 2 may be varied in the range 0.1 - 10 µm, and typically, the thickness of the film is approx. 1 µm. On top of the crystal 1 are formed a first electrode structure 3 for generating the oscillations and a second electrode structure 4 for measuring the capacitance. The upper surface electrode 5 of the second electrode structure 4 formed on the polymer film 2 is made permeable to the gas to be measured. The electrodes are connected at the contact areas 6 to measurement and control circuits (not shown). The capacitance of the second electrode structure 4 in the sensor was measured at 100 kHz measurement frequency, and the resonant frequency change of the crystal 1 as a function of relative humidity is given in the following table: RH [%] C [pF] df [kHz] 0 51.76 0.0 30 51.97 -22.7 50 52.11 -38.5 75 52.28 -58.8 95 52.42 -75.0 In can be seen from the table that the change of resonant frequency is linearly proportional to sensor capacitance with a slope df/dC = -144.4. The graph corresponding to the table is plotted in Fig. 2. The next table gives the measurement results as a function of ambient relative humidity at two different concentrations of CO 2 . RH [%] C [pF] df [at 0 ppm] df [at 500 ppm] df [at 1000 ppm] 0 51.76 0.0 -29.5 -57.5 30 51.97 -22.7 -51.5 -80.4 50 52.11 -38.5 -66.7 -95.2 75 52.28 -58.8 -85.5 -114.5 95 52.42 -75.0 -101.3 -129.1 Not even a 1000 ppm concentration of CO 2 could be detected unless the sensor capacitance is known. The graphs corresponding to the results given in the table are plotted in Fig. 3. The algorithm described above is now applied in the simplest possible form: Frequency change df is chosen as the measurement variable indicating the weight of the polymer film. By fitting a line between the measurement results of 0 ppm and 1000 ppm at 0 %RH, we obtain: PPM CO2 = -17.4·df CO2 The simplest formula describing the effect of humidity as a change of crystal resonant frequency is df rh , = 5921.34 - 114.4·C. Now, the CO 2 concentration may be computed as: PPM CO2 (df,C) = 17.4·(df - (5921.34 - 114.4·C)) Applying this formula to the above-listed measurement results gives the following table of humidity corrected values: RH [%] 0 ppm 500 ppm 1000 ppm 0 0 512 1001 30 -17 484 986 50 -16 474 970 75 -7 458 961 95 0 458 941 As seen, the greatest error of -59 ppm occurs in the measurement of the maximum concentration at the maximum ambient humidity. The accuracy of measurements is improved very substantially with respect to the prior art.

Claims: A sensor structure for measuring the concentration of nonpolar gases such as carbon dioxide in an atmosphere, said sensor structure comprising a quartz crystal (1), a first pair (3) of electrodes formed on opposite surfaces of the quartz crystal (1) for generating oscillations in the crystal (1), and a polymer film (2) formed on one of the said opposite surfaces of the quartz crystal, characterised by a second pair (4) of electrodes formed on opposite surfaces of said polymer film (2), whereby one of the second pair of electrodes is exposed to said atmosphere and is permeable to the gas to be measured. A method of measuring the partial pressure of nonpolar gases, such as carbon dioxide, by means of the sensor structure of claim 1, in which method the partial pressure of the nonpolar gas adsorbed and/or absorbed in the polymer film (2) is determined by detecting the mass of the polymer film (2), characterised in that the additional steps are performed, the dielectric coefficient (ε) of the polymer film (2) is measured, and on the basis of the measured dielectric coefficient, a correction is made in the partial pressure measurement result obtained from the mass determination. A method as defined in claim 2 of measuring low partial pressures of gas typical in environmental measurements, in which method a polymer film (2) is formed on the surface of an oscillating quartz crystal (1) and the mass of the film (2) is detected from the change of the resonant frequency, characterised in that in a first step the effect of the partial pressure of the gas to be measured on the mass of the polymer film (2) is determined under known partial pressure of the gas to be measured, in a second step the relationship of the capacitance of the polymer film (2) with the mass of the polymer film (2) is determined over the entire ambient humidity range at zero partial pressure of the gas to be measured, and finally, in a third step the partial pressure of the gas to be measured, is determined by correcting the result obtained from the measurement of the film mass by means of a humidity correction function obtained from the capacitance measurement step. A method as defined in claim 2 of measuring high partial pressures of gas where the amount of adsorbed/absorbed water affects the adsorption/absorption of the gas to be measured, in which method a polymer film (2) is formed on the surface of an oscillating quartz crystal (1) and the mass of the film (2) is detected from the change of the resonant frequency, characterised in that in a first step the effect of the partial pressure of the gas to be measured on the mass of the polymer film (2) is determined under known partial pressure of the gas to be measured, in a second step the relationship of the capacitance of the polymer film (2) with the mass of the polymer film (2) is determined over the entire ambient humidity range at zero partial pressure of the gas to be measured, the partial pressure of the gas to be measured is determined by correcting the result obtained from the measurement of the film mass by means of a humidity correction function obtained from the capacitance measurement step, and finally, the resulted is corrected by a term which takes into account the disturbing effect of relative humidity on the sorption of the gas to be measured.

Inventors: STORMBOM LARS, STORMBOM, LARS
Applicants: VAISALA OYJ
Application year: 1995
Main classification: G01N27
IPC codes: G01N27, G01N5, G01N29