JP4266850B2 - Concentration measuring device for binary gas mixture - Google Patents

Description

  The present invention relates to an apparatus for measuring the concentration of a mixed gas composed of two kinds of gases. In particular, the present invention relates to a concentration measuring apparatus that does not require an absolute pressure gauge for measuring the pressure of a mixed gas and that can detect the concentration of the mixed gas using only a crystal resonator.

Conventionally, an ultraviolet absorbance measurement method is known as a method for obtaining the concentration of a mixed gas composed of two kinds of gases. In this method, for example, when the ozone concentration in the ozone-oxygen mixed gas is measured, the mixed gas is irradiated with a specific wavelength that absorbs ozone but absorbs little oxygen in the ultraviolet rays. And the density | concentration was calculated | required by measuring the absorption factor of an ultraviolet-ray.

  In order to solve the various problems of this UV absorbance measurement method, viscosity, thermal conductivity, density, molecular weight, and the physical properties of the mixed gas as a function of them are measured. A method for calculating the concentration of gas has been developed (Patent Document 1).

  For this purpose, two types of pressure gauges are used. One is a pressure gauge sensitive to the physical property value of the mixed gas, and the other is a pressure gauge not affected by the physical property value of the mixed gas. In Patent Document 1, a quartz friction vibrator is cited as the former pressure gauge, and a diaphragm vibrator is cited as the latter pressure gauge.

Furthermore, a crystal oscillator capable of temperature compensation has been proposed (Patent Document 2).
Japanese Patent No. 3336384 US Pat. No. 5,228,344 (Japanese Patent Publication No. 7-97060)

  The method of Patent Document 1 adopts a method that can always measure an accurate concentration even when the pressure of the mixed gas is other than atmospheric pressure or even when the pressure changes, and does not irradiate heat or light. Therefore, it is excellent in that it can be safely measured even in a mixed gas in which an explosion occurs due to stimulation by heat or light. Further, it is excellent in that it does not require an ultraviolet lamp having a specific wavelength, is easy to maintain, and can immediately measure the concentration in response to a change in gas concentration.

  However, the method of Patent Document 1 uses two different types of pressure gauges based on the principle of the invention, so that the configuration of the apparatus is complicated and the consistency of data from the two types of pressure gauges is improved. Considering this, new issues such as the need for calibration have arisen. A diaphragm type pressure gauge is suitable for the dynamic pressure gauge, but the dynamic range is inferior to that of the quartz friction vibrator type pressure gauge. Therefore, it was necessary to select a diaphragm type pressure gauge according to the measurement pressure range. As described above, a pressure gauge using a diaphragm is suitable as a pressure gauge that is not affected by the physical property value of the mixed gas. However, the diameter of the diaphragm is increased in order to increase the measurement accuracy, thereby reducing the size of the apparatus. There was also a limit.

  Accordingly, an object of the present invention is to provide a concentration measuring apparatus for a two-component gas mixture that can solve the problems of enlargement and complication of the apparatus by using a single crystal unit to determine the concentration of the gas mixture. There is.

  Another object of the present invention is that, even if the pressure of the mixed gas changes, the accurate concentration of the mixed gas can be measured, an ultraviolet lamp having a specific wavelength is not required, maintenance is easy, An object of the present invention is to provide an apparatus for measuring the concentration of a two-component gas mixture that does not have the risk of explosion ignition as in the method of measuring by applying heat or light.

  Yet another object of the present invention is that there is no decomposition of the gas to be measured, so there is no need to prepare a large amount of sampling gas or to discard it, and the concentration is measured immediately in response to changes in the gas concentration. An object of the present invention is to provide an apparatus for measuring the concentration of a binary gas mixture that can be used.

One aspect of the present invention is an apparatus for measuring a concentration of a binary gas mixture having a known constituent gas and an unknown concentration.
A concentration measuring crystal resonator in contact with the mixed gas;
A measurement unit for measuring a resonance resistance value and a resonance frequency of the crystal resonator in contact with the mixed gas;
Based on the measured resonance resistance value and the resonance frequency, a calculation unit that calculates the concentration of the mixed gas;
A temperature control unit for controlling the temperature of the concentration measuring crystal resonator so that the concentration measuring crystal resonator is in a specific temperature range;
It is characterized by having.

  Since the concentration measuring crystal resonator is in direct contact with the gas mixture to be measured, it is possible to measure the pressure that varies depending on its physical properties such as viscosity and molecular density. This pressure P is a function of the resonance frequency f of the crystal resonator and the resonance resistance value Z, that is, P = F (f), P = F (Z). Eventually, the pressure reflecting the physical property value that changes according to the change in the concentration of the gas to be measured can be obtained from the resonance frequency f and the resonance resistance value z. Therefore, by eliminating the pressure P from the above functions, the concentration of the gas to be measured can be uniquely determined from the resonance frequency f and the resonance resistance value Z. At this time, since the resonance frequency f and the resonance resistance value Z have temperature dependency, in one embodiment of the present invention, the temperature measuring unit holds the concentration measuring crystal resonator in a specific temperature range.

  1 aspect of this invention, It further has the channel | path through which the said mixed gas passes, the measurement chamber which is connected to the said channel | path, and in which the said crystal | crystallization resonator for density | concentration measurement is arrange | positioned, and the thermostat which temperature-controls the said measurement chamber be able to. In this way, the mixed gas in the measurement chamber and the concentration measuring crystal resonator can be maintained in a specific temperature range.

  In one embodiment of the present invention, the gas mixture is used for the concentration measurement so that a temperature difference between the gas mixture contacting the concentration measurement crystal resonator and the crystal resonator for concentration measurement is a predetermined value or less. A heat exchanger for guiding to the crystal unit can be further included. In this way, the mixed gas is heat-exchanged by the heat exchanger, and the temperature is adjusted to a specific temperature range before coming into contact with the concentration measuring crystal resonator.

  In one aspect of the present invention, the calculation unit includes a difference between a resonance resistance value and a natural resonance resistance value of the concentration measurement crystal resonator from the measurement unit, and the concentration measurement crystal resonator from the measurement unit. Based on the difference between the resonance frequency and the natural resonance frequency, the concentration of the mixed gas can be calculated. Here, the natural resonance resistance and the natural resonance frequency can be measured in advance. Since the natural resonance resistance value and the natural resonance frequency are unchanged as long as the temperature is constant, they can be omitted from the concentration calculation, but they can also be used as the basis of the calculation.

Another aspect of the present invention is a device for measuring a concentration of a two-component mixed gas whose constituent gas is known and whose concentration is unknown,
A concentration measuring crystal resonator in contact with the mixed gas;
A measurement unit for measuring a resonance resistance value and a resonance frequency of the crystal resonator in contact with the mixed gas;
A temperature probe disposed adjacent to the concentration measuring crystal unit;
Based on the measurement information from the temperature probe, the temperature dependency of the concentration measuring crystal resonator is corrected, and the concentration of the mixed gas is calculated based on the corrected resonance resistance value and the resonance frequency. An arithmetic unit to perform,
It is characterized by having.

  In one aspect of the present invention, a temperature control unit is provided to maintain the concentration measuring crystal resonator in a specific temperature range. However, in another aspect of the present invention, measurement from a temperature gauge is used instead of or in addition thereto. Based on the information, the temperature dependency of the quartz crystal resonator for concentration measurement was corrected.

  In another aspect of the present invention, the temperature gauge may be enclosed in a sealed container that is isolated from the mixed gas, or may be sealed with a known gas in the sealed container. Thus, the temperature measuring element can measure the temperature without being influenced by the physical properties of the mixed gas.

In another aspect of the present invention, the temperature measuring element is formed of a temperature measuring crystal resonator,
The measurement unit measures a resonance frequency of the temperature measurement crystal resonator, and the correction unit determines the concentration measurement crystal resonator based on the characteristics of the resonance frequency and temperature of the temperature measurement crystal resonator. The temperature dependence of can be corrected.

  In another aspect of the present invention, the calculation unit includes a difference between a resonance resistance value and a natural resonance resistance value of the concentration measurement crystal resonator from the measurement unit, and the concentration measurement crystal resonator from the measurement unit. The concentration of the mixed gas can be calculated based on the difference between the resonance frequency and the resonance frequency after the natural resonance frequency and the temperature compensation amount obtained from the resonance frequency of the crystal resonator for temperature measurement. Here, the natural resonance resistance and the natural resonance frequency can be measured in advance at a specific temperature, for example.

  In another aspect of the present invention, the temperature probe can be formed by a thermocouple. In this case, the calculation unit is configured such that the difference between the resonance resistance value and the natural resonance resistance value of the concentration measurement crystal resonator from the measurement unit, the resonance frequency and the specific frequency of the concentration measurement crystal resonator from the measurement unit. Based on the difference after the resonance frequency and the temperature compensation amount obtained from the temperature measured from the thermocouple, the concentration of the mixed gas can be calculated.

  In one embodiment and another embodiment of the present invention, the calculation unit may vary the resonance resistance value and the resonance frequency of the crystal resonator for concentration measurement at least two points with different gas pressures with known compositions, or with known compositions. A memory for storing calibration results for calibration at at least two points having different gas concentrations can be further provided. Thereby, even if the quartz crystal resonator for concentration measurement is replaced, it is possible to prevent the deterioration of the concentration measurement accuracy depending on the resonance resistance value and the resonance frequency variation of the quartz crystal resonator for concentration measurement.

  In one embodiment and another embodiment of the present invention, the concentration measuring crystal resonator can be formed of a tuning fork crystal resonator.

<First Embodiment>
FIG. 1 shows a concentration measuring apparatus according to the first embodiment of the present invention. In FIG. 1, a pipe 10 supplies a mixed gas, for example, a binary mixed gas of ozone / oxygen. A gas supply source is connected to one end of the pipe 10. The other end of the pipe 10 is connected to a semiconductor manufacturing apparatus that forms, for example, an oxide film on the substrate. For example, when a cylinder containing liquefied ozone is used as the gas supply source, vaporized high-concentration ozone can be supplied to the pipe 10 and the film formation speed can be increased. Not limited to this, low concentration ozone and high concentration oxygen may be supplied to the pipe 10. In addition, since the density | concentration of the mixed gas supplied to the piping 10 fluctuates, the density | concentration needs to be measured.

  A concentration measuring crystal resonator 20 for measuring the concentration of the two-component mixed gas is disposed in the measurement chamber 12 that communicates with the pipe 10. In the crystal resonator 20 for concentration measurement, the resonance frequency f and the resonance resistance value z change according to the concentration of the two-component mixed gas. As will be described later, the measurement chamber 12 may not be provided separately from the pipe 10 and the inside of the pipe 10 may be used as the measurement chamber.

  The measurement chamber 12 includes a temperature control unit that heats or cools the concentration measurement crystal resonator 20 so as to be within a specific temperature range, for example, 20 ° C. ± 0.2 ° C. In this embodiment, the temperature control unit is the thermostat 30. Is formed.

  The concentration measuring crystal resonator 20 is in contact with the mixed gas, and the resonance resistance value and the resonance frequency change according to the concentration change of the mixed gas. In the present embodiment, the crystal unit 20 is configured by a tuning fork type crystal unit. The quartz crystal resonator 20 operates at room temperature, and the contact surface with the gas is only gold, quartz, and stainless steel, and there is no factor for decomposing ozone.

  Here, since the crystal resonator 20 for concentration measurement is in direct contact with the gas mixture to be measured, it is possible to measure a pressure that varies depending on its physical properties such as viscosity and molecular density. The pressure P is a function of the resonance frequency f and the resonance resistance value Z of the crystal unit 20, that is, P = F (f), P = F (Z). Eventually, the pressure reflecting the physical property value that changes according to the change in the concentration of the gas to be measured can be obtained from the resonance frequency f and the resonance resistance value z. Therefore, by eliminating the pressure P from the above functions, the concentration of the gas to be measured can be uniquely obtained from the resonance frequency f and the resonance resistance value Z (see FIG. 3 described later). At this time, since the resonance frequency f and the resonance resistance value Z have temperature dependence, in the present embodiment, the crystal unit 20 is held in a constant temperature range by the thermostat 30.

  In FIG. 1, a measuring unit 40 connected to the concentration measuring crystal resonator 20 is provided, and the resonance frequency f and the resonance resistance value Z of the concentration measuring crystal resonator 20 are output from the measuring unit 40. A concentration calculation unit 50 connected to the measurement unit 40 is further provided, and the concentration of the two-component mixed gas is calculated based on the resonance frequency value f and the resonance resistance value Z of the concentration measuring crystal resonator 20.

  FIG. 2 shows an example of an oscillation circuit 60 arranged in the measurement unit 40 and connected to the concentration measuring crystal resonator 20. FIG. 2 has the same configuration as the oscillation circuit disclosed in US Pat. No. 5,228,344. The oscillator 60 shown in FIG. 2 includes a current-voltage converter 100, a first full-wave rectifier 102, an attenuator 104, a comparator 106, a voltage-controlled attenuator 108, and a second full-wave rectifier 110.

Here, the natural resonance resistance of the quartz oscillator 20 and Z _0. When the crystal resonator 20 vibrates via the oscillator 60 when the crystal resonator 20 is disposed in the mixed gas atmosphere, the reciprocal 1 of the measured resonance resistance value Z ₁ is obtained from the second full-wave rectifier 110. / Z ₁ is obtained. The reciprocal 1 / Z ₁ (analog value) of the resonance resistance value Z ₁ from the oscillator 60 is input to the concentration calculation unit 50 via the A / D converter 120 shown in FIG.

The difference ΔZ = Z ₀ −Z ₁ between the natural resonance resistance value Z ₀ and the measured resonance resistance value Z ₁ corresponds to the pressure of the mixed gas depending on the viscosity (concentration). Here, although the natural resonance resistance value Z ₀ has temperature dependence, in this embodiment, since the temperature is maintained in a certain range, the natural resonance resistance value Z ₀ can also be regarded as constant. Therefore, it is not always necessary to measure the specific resonance resistance value Z ₀ in the concentration calculation in the present embodiment.

On the other hand, the oscillator 60 is configured to output the resonance frequency f ₁ of the crystal resonator 20. This resonance frequency f ₁ also reflects the pressure of the mixed gas depending on the viscosity (concentration). B Here, let the natural resonance frequency of the crystal resonator 20 be f ₀ . The difference Δf = f ₀ −f ₁ between the natural resonance frequency f ₀ and the measured resonance frequency f ₁ reflects the pressure of the mixed gas depending on the viscosity (concentration). Here, the natural resonance frequency f ₀ has temperature dependence. However, in this embodiment, the temperature is maintained in a certain range, so that the natural resonance frequency f ₀ can also be regarded as constant. Therefore, the concentration operation in the present embodiment, it is not always necessary to measure the natural resonant frequency f _0.

The resonance frequency f ₁ from the oscillator 60 is counted by the frequency counter 130 shown in FIG. 2 and then input to the concentration calculation unit 50 as a digital value.

  Next, a density calculation method in the density calculation unit 50 will be described.

  The concentration calculation unit 50 has a memory 52. As shown in FIG. 3, the memory 52 shows not only pure oxygen but also many known concentrations (in FIG. 3, only 5 vol% ozone-95 vol% oxygen mixed gas). ), The calibration curves A and B of the resonance frequency f and the resonance resistance value Z of the crystal resonator 20 measured in advance are stored. FIG. 3 shows a part thereof. For example, the resonance frequency f and the resonance resistance value Z of the crystal resonator 20 are measured in advance using a two-component mixed gas having different concentrations every 1 vol%, and stored as a calibration curve. 52.

In the calibration curve shown in FIG. 3, the horizontal axis represents the difference ΔZ = Z ₀ −Z ₁ between the natural resonance resistance value Z ₀ and the measured resonance resistance value Z _1, and the vertical axis represents the natural resonance frequency f _0. The difference Δf = f ₀ −f ₁ with respect to the resonance frequency f ₁ can be obtained. However, as described above, as long as the temperature is constant, the natural resonance resistance value Z ₀ and the natural resonance frequency f ₀ can be regarded as constant, so the horizontal axis is the resonance resistance value Z ₁ and the vertical axis is the resonance frequency f _1. good.

Here, when a gas mixture having an unknown concentration passes through the pipe 10, the resonance frequency f ₁ depending on the viscosity (concentration) of the gas mixture based on information from the crystal resonator 20 (the vertical axis coordinates in FIG. 3 ) . Position). On the other hand, based on the information from the crystal unit 20, a resonance resistance value Z ₁ (horizontal axis coordinate position in FIG. 3 ) depending on the viscosity (concentration) of the mixed gas is obtained. From the vertical and horizontal coordinate positions, the coordinate position C in FIG. 3 of the unknown gas mixture is obtained. The concentration calculation unit 40 interpolates the ozone concentration in an unknown gas mixture based on the coordinate position C in FIG. 3, the characteristic A of pure oxygen, and the characteristic B of ozone-oxygen concentration of 5 vol%. Can be measured.

  As described above, according to this embodiment, the concentration of the two-component gas mixture having a known composition can be accurately measured by one crystal resonator 20.

<Second Embodiment>
FIG. 4 shows a modification in which the heat exchanger 210 is arranged in the connecting passage 200 connecting the passage 10 and the measurement chamber 12. The heat exchanger 210 is introduced into the measurement chamber 12 from the passage 10 so that the temperature difference between the mixed gas contacting the concentration measuring crystal resonator 20 and the concentration measuring crystal resonator 20 is a certain value or less. The gas mixture is guided to the crystal resonator 20 for concentration measurement. The heat exchanger 210 includes, for example, heat exchange fins 202 that protrude alternately from the opposing inner walls 200a and 200b of the connecting passage 200. Note that the structure of the heat exchanger 210 is not limited to that shown in FIG. And the thermostat 30 which is a temperature control part is arrange | positioned surrounding the measurement chamber 12 and the connection channel | path 200. FIG.

  The mixed gas introduced into the passage 10 is heat-exchanged by coming into contact with the connection passage 200 and the heat-exchange fins 202 that are temperature-controlled in the thermostat 30, and before reaching the concentration measuring crystal resonator 20, It is heated or cooled to the temperature control temperature of the thermostat 30. As a result, the resonance resistance value and the resonance frequency value of the concentration measurement propulsion vibrator 20 can be measured in a constant temperature range, and the accuracy of the detected mixed gas concentration is further increased.

<Third Embodiment>
FIG. 5 shows a modification in which the concentration measuring crystal resonator 20 is disposed in the passage 10. In order to control the temperature of the mixed gas in contact with the concentration measuring crystal resonator 20 disposed in the passage 10, the metal mesh 220 is disposed in a single, double or multiple manner so as to surround the concentration measuring crystal resonator 20. Has been.

  In FIG. 5, the temperature adjustment unit that adjusts the temperature of the concentration measuring crystal resonator 20 and the surrounding mixed gas adjusts the temperature of the metal mesh 220 to a specific temperature range, for example, 20 ° C. ± 0.2 ° C. Also good.

  In the embodiment shown in FIG. 5, the mixed gas contacting the concentration measuring crystal resonator 20 disposed in the passage 10 is further retained in the metal mesh 220 when passing through the metal mesh 220. Then, the temperature is controlled by the temperature control unit. Therefore, as in the embodiment of FIG. 4, the temperature difference between the gas mixture in contact with the concentration measuring crystal resonator 20 and the concentration measuring crystal resonator 20 becomes a certain value or less.

<Fourth embodiment>
FIG. 6 shows an embodiment in which a temperature measuring element 230 is disposed in the measurement chamber 12 so as to be adjacent to the concentration measuring crystal resonator 20 instead of surrounding the measurement chamber 12 with the thermostat 30. The temperature measuring element 230 shown in FIG. 6 is formed of a temperature measuring crystal resonator such as a tuning fork crystal resonator. The temperature measuring crystal unit 230 is disposed in a sealed container 240 for isolation from a mixed gas. The sealed container 240 is evacuated or filled with a gas having a known composition, preferably an inert gas such as nitrogen or argon.

  A temperature measurement unit 250 is connected to the temperature measurement crystal unit 230, and a temperature T detected by the temperature measurement unit 250 (or a resonance frequency f of the temperature measurement crystal unit 230 having a correlation with the temperature T) is detected. , And output to the concentration calculation unit 260.

  The measurement unit 40 and the temperature measurement unit 240 shown in FIG. 6 may be formed by the oscillation circuit 60 shown in FIG. 2, but may be configured as shown in FIG.

  As shown in FIG. 7, by providing a double switch 310 at the output ends of the concentration measuring crystal resonator 20 and the temperature measuring crystal resonator 230, one oscillator 300 is provided instead of two oscillators 60 in FIG. It consists of. The double switch 310 can be configured by a semiconductor switch or the like that can be switched at high speed.

  In this way, the oscillator 300 can be shared in addition to the frequency counter 130 and the A / D converter 120 for the crystal resonators 20 and 230 for concentration measurement and temperature measurement, and the measurement device can be used. Further downsizing.

  Next, an example of performing temperature compensation for concentration calculation based on the resonance frequency f of the temperature measuring crystal unit 230 will be described.

  FIG. 8 is a characteristic diagram showing the correlation between the resonance frequency f and the temperature of the crystal resonator 230 for temperature measurement. Since the temperature measuring crystal unit 230 is arranged in the sealed container 240, it is not affected by the pressure of the mixed gas, and has a resonance frequency f-temperature T characteristic having a substantially linear characteristic as shown in FIG. Based on this, the temperature T can be measured from the measured resonance frequency f. The resonance frequency f-temperature T characteristic of the crystal unit 230 for temperature measurement is stored in the memory in the temperature measurement unit 250 or the concentration calculation unit 260 shown in FIG. 6 and is measured based on the characteristic. For example, the temperature T (for example, 24 ° C.) can be obtained from 32.746 kHz.

  FIG. 9 is a characteristic diagram showing the temperature dependence of the resonance resistance value Zt (= z1 + ΔZt) and the resonance frequency ft (= f1 + Δft) measured by the crystal resonator 20 for concentration measurement.

Here, the resonance frequency f1 is the resonance frequency of the concentration measuring crystal resonator 20 at a specific temperature, for example, 20 ° C., and the concentration measuring crystal vibrations of the first to third embodiments using the thermostat 30. This is data that can be detected by the child 20. However, in the present embodiment that does not use the thermostatic chamber 30, for example, at a temperature T = 24 ° C., the resonance frequency ft = f ₁ + Δft of the concentration measuring crystal resonator 20 is obtained, and the temperature-dependent component Δft is displaced. Therefore, the concentration calculation unit 50 is provided with a correction unit, which corrects the resonance frequency ft of the concentration measuring crystal resonator 20 measured at an arbitrary temperature T by Δft by Δft to obtain 20 ° C. ± 0. The resonance frequency f1 of the crystal resonator 20 for concentration measurement at 2 ° C. is obtained by temperature compensation.

  As shown in FIG. 9, the resonance frequency ft of the concentration-measuring crystal resonator 20 at an arbitrary temperature t includes a temperature fluctuation component Δft in addition to the resonance frequency f1 at 20 ° C. The temperature measurement unit 250 or the concentration calculation unit 260 in FIG. 6 has a memory that stores the temperature variation component Δft in association with the temperature t. Therefore, when the temperature T is measured by the temperature measuring crystal resonator 240, the temperature variation component Δft corresponding to the temperature T is known. Therefore, the resonance frequency f1 of the concentration measuring crystal resonator 20 at a specific temperature, for example, 20 ° C. can be obtained by calculating f1 = ft−Δft. The temperature compensation of the resonance resistance value Zt having temperature dependency can be performed in the same manner.

  In this way, the resonance resistance value Zt and the resonance frequency ft of the concentration measuring crystal resonator 20 at the actual temperature T are temperature compensated, and the resonance resistance value Z1 and the resonance of the concentration measuring crystal resonator 20 at a specific temperature, for example, 20 ° C. The frequency f1 is obtained, and based on these, the concentration of the mixed gas can be calculated from the calibration curve of FIG.

  In addition, although the thermostat is not arrange | positioned around the measurement chamber 12 in FIG. 6, a thermostat can also be arrange | positioned in the measurement chamber 12. FIG. In this case, the temperature of the concentration measuring crystal resonator 20 and the surrounding mixed gas can be controlled, and the detected mixed gas is based on the temperature detected based on the measurement information from the temperature measuring crystal resonator 230. The concentration can be temperature compensated, and the concentration detection accuracy is further increased.

  The temperature measuring element 230 shown in FIG. 6 is not necessarily limited to a crystal resonator, and may be another temperature measuring element such as a thermocouple. In order to prevent the thermocouple from coming into contact with the mixed gas and being contaminated, the thermocouple is arranged in a sealed container 240 in which a gas having a known composition or a vacuum is enclosed.

  6 is the difference between the resonance resistance value and the natural resonance resistance value of the concentration measurement crystal resonator 20 from the measurement unit 40, and the resonance frequency of the concentration measurement crystal resonator from the measurement unit 40. Based on the difference after the natural resonance frequency and the temperature compensation amount obtained from the resonance frequency (or temperature obtained from the thermocouple) of the temperature measuring crystal resonator 230, the concentration of the mixed gas can be calculated. Here, the natural resonance resistance and the natural resonance frequency are measured in advance at a specific temperature, for example, 20 ° C., or measured at an arbitrary temperature, and the specific resonance resistance value and the natural resonance frequency at a specific temperature, for example, 20 ° C. It can be obtained by correcting.

  In addition, the calculation unit 260 changes the resonance resistance value and the resonance frequency of the crystal resonator 20 for concentration measurement at at least two points where the pressures of the gases with known compositions are different or at least two points with different concentrations of the gases with known compositions. A memory for storing a calibration result to be calibrated may be further included. As a result, even if the concentration measuring crystal resonator 20 is replaced, it is possible to prevent the deterioration of the concentration measuring accuracy depending on the variation in the resonance resistance value and the resonance frequency of the concentration measuring crystal resonator.

  The present invention is not limited to the embodiments described above, and various modifications can be made within the scope of the gist of the present invention.

It is a schematic explanatory drawing of the density | concentration measuring apparatus which concerns on 1st Embodiment of this invention. It is a circuit diagram which shows an example of the oscillator arrange | positioned at the measurement part in FIG. FIG. 2 is a characteristic diagram showing a correlation between a resonance resistance value and a resonance frequency of the concentration measuring crystal resonator in FIG. 1 and a concentration of a mixed gas. It is a schematic explanatory drawing which shows the modification which arrange | positioned the heat exchanger between the channel | path and the measurement chamber. It is a schematic explanatory drawing which shows the modification which has arrange | positioned the crystal oscillator for density | concentration in the metal mesh provided in the channel | path. It is a schematic explanatory drawing of the modification which added the temperature measuring element in addition to the crystal oscillator for density | concentration measurement. FIG. 7 is a schematic explanatory diagram of a concentration measuring apparatus having an oscillator shared by the concentration measuring and temperature measuring crystal resonators shown in FIG. 6. It is a characteristic view which shows the correlation of the resonant frequency-temperature of the crystal oscillator for temperature measurement. It is a characteristic view which shows the temperature dependence characteristic of the resonance resistance value and resonance frequency of the crystal resonator for density | concentration measurement.

Explanation of symbols

10 piping, 12 measuring chamber, 20 crystal resonator for concentration measurement, 30 temperature control unit (constant temperature chamber), 40 measuring unit, 50, 260 concentration calculating unit, 52 memory, 60 oscillator, 120 A / D converter, 130 frequency Counter, 210 heat exchanger, 220 metal mesh, 230 crystal resonator for temperature measurement, 240 airtight container, 250 temperature measurement unit

Claims (13)

In the concentration measurement device for a binary gas mixture with known constituent gas and unknown concentration,
A concentration measuring crystal resonator in which a resonance film and a resonance frequency change according to a change in the concentration of the mixed gas by contacting with the mixed gas, and a sensitive film is not formed ,
A measurement unit for measuring a resonance resistance value and a resonance frequency of the crystal resonator in contact with the mixed gas;
An arithmetic unit that has a first memory and calculates the concentration of the mixed gas based on the information stored in the first memory and the measured resonance resistance value and the resonance frequency;
A temperature control unit for controlling the temperature of the concentration measuring crystal resonator so that the concentration measuring crystal resonator is in a specific temperature range;
Have
The first memory stores a calibration curve prepared in advance based on a resonance resistance value and a resonance frequency of the crystal resonator when the gas mixture is brought into contact with the gas mixture having a known concentration. An apparatus for measuring the concentration of a two-component gas mixture. In claim 1,
A passage through which the mixed gas passes;
A measurement chamber that is in communication with the passage and in which the crystal resonator for concentration measurement is disposed;
A thermostatic chamber for controlling the temperature of the measurement chamber;
An apparatus for measuring a concentration of a two-component mixed gas, comprising: In claim 1 or 2,
Heat that guides the mixed gas to the concentration measuring crystal resonator so that a temperature difference between the mixed gas contacting the concentration measuring crystal resonator and the concentration measuring crystal resonator is a predetermined value or less. An apparatus for measuring a concentration of a two-component gas mixture, further comprising an exchanger. In any one of Claims 1 thru | or 3,
The first memory includes a difference between a resonance resistance value and a natural resonance resistance value of the concentration measurement crystal resonator from the measurement unit, and a resonance frequency and a specific property of the concentration measurement crystal resonator from the measurement unit. An apparatus for measuring a concentration of a two-component gas mixture, wherein the calibration curve at the specific temperature is stored based on a difference after a resonance frequency. In the concentration measurement device for a binary gas mixture with known constituent gas and unknown concentration,
A concentration measuring crystal resonator in which a resonance film and a resonance frequency change according to a change in the concentration of the mixed gas by contacting with the mixed gas, and a sensitive film is not formed ,
A measurement unit for measuring a resonance resistance value and a resonance frequency of the crystal resonator in contact with the mixed gas;
A temperature probe arranged adjacent to the concentration measuring crystal resonator;
A correction unit and a first memory, wherein the correction unit corrects the temperature dependence of the concentration-measuring crystal resonator based on measurement information from the temperature probe, and the resonance resistance value at the corrected specific temperature And a calculation unit that calculates the concentration of the mixed gas based on the resonance frequency and the information stored in the first memory ;
I have a,
The first memory stores a calibration curve prepared in advance based on a resonance resistance value and a resonance frequency of the crystal resonator at the specific temperature when the gas mixture is brought into contact with the gas mixture having a known concentration. An apparatus for measuring the concentration of a two-component gas mixture. In claim 5,
The temperature measuring element is enclosed in an airtight container that is isolated from the mixed gas. In claim 5,
The temperature measuring element is disposed in a sealed container that is isolated from the mixed gas, and a known gas is sealed in the sealed container, and the concentration measuring apparatus for a two-component mixed gas is characterized in that In any of claims 5 to 7,
The temperature measuring element is formed of a temperature measuring crystal resonator,
The measurement unit measures a resonance frequency of the temperature measuring crystal resonator,
The correction unit corrects the temperature dependence of the concentration measuring crystal resonator based on the characteristics of the resonance frequency and temperature of the temperature measuring crystal resonator, and measures the concentration of the two-component gas mixture apparatus. In any of claims 5 to 7,
The temperature measuring element is formed by a thermocouple. In any one of Claims 5 thru | or 9 ,
Wherein the first memory, the resonance resistance of the concentration determination quartz oscillator has been corrected by the correcting unit is output from the measuring unit and the difference between the natural resonance resistance, output from the measuring unit and the correction the concentration of 2-component gas mixture, characterized in that the calibration curve prepared in advance on the basis of the difference after the resonant frequency and the natural resonance frequency of the corrected the concentration determination quartz oscillator at parts are stored measuring device. In any one of Claims 1 thru | or 10.
  The concentration measurement apparatus for a two-component gas mixture, wherein the calibration curve stored in the first memory is non-linear. In any one of Claims 1 thru | or 11,
The arithmetic unit calibrates the variation in the resonance resistance value and resonance frequency of the concentration measuring crystal resonator at at least two points where the gas pressures with known compositions are different or at least two points where the gas concentrations with known compositions are different. A two-component gas concentration measuring device further comprising a second memory for storing a calibration result. In any one of Claims 1 to 12,
The concentration measuring apparatus for two-component gas mixture, wherein the concentration measuring crystal resonator is formed of a tuning fork type crystal resonator.

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