System, method and computer program product for gas analysis
11313836 · 2022-04-26
Assignee
Inventors
- Kazushi Yamanaka (Sendai, JP)
- Nobuo Takeda (Sendai, JP)
- Shingo Akao (Sendai, JP)
- Toshihiro Tsuji (Sendai, JP)
- Toru Oizumi (Sendai, JP)
- Hideyuki Fukushi (Sendai, JP)
- Tatsuhiro Okano (Sendai, JP)
- Nagisa Sato (Sendai, JP)
- Yusuke Tsukahara (Sendai, JP)
Cpc classification
G01N29/221
PHYSICS
G01N29/022
PHYSICS
G01N29/348
PHYSICS
International classification
G01N29/22
PHYSICS
G01N33/00
PHYSICS
Abstract
A collimated beam (23) of a surface acoustic wave propagates on a piezoelectric substrate (22) while passing through sensitive film (25) to adsorb a sensing gas. Signal processing unit (40) transmits an exciting burst signal to sensor electrode (24) to excite the collimated beam (23), receives first and second returned burst signals after the collimated beam (23) has propagated, and calculates a target gas parameter by a target leakage factor of the background gas and a relation between reference gas parameters and reference leakage factors of reference gases, the leakage factor is provided by first and second attenuations of the first and second returned burst signals, respectively, using waveform data of the first and second returned burst signals.
Claims
1. A system for gas analysis, comprising: a sensor having: a piezoelectric substrate, a sensor electrode configured to generate a collimated beam of a surface acoustic wave of first and second frequencies, which propagates on the piezoelectric substrate, and a sensitive film configured to adsorb a sensing gas contained in a background gas, the sensitive film is deposited in a position where the collimated beam passes through; and a signal processing unit having: a signal generator configured to transmit an exciting burst signal to the sensor electrode so as to excite the collimated beam, a signal receiver configured to receive first and second returned burst signals of the collimated beam through the sensor electrode after the collimated beam has propagated on the piezoelectric substrate, the first returned burst signal having the first frequency and the second returned burst signal having the second frequency, and a data processor configured to calculate a target gas parameter both by a target leakage factor of the background gas and by a relation between reference gas parameters and reference leakage factors of reference gases, the target leakage factor is calculated by a first attenuation of the first returned burst signal and a second attenuation of the second returned burst signal using waveform data of the first and second returned burst signals, wherein the target leakage factor and the target gas parameter are given by,
Δα.sub.L≡[(f.sub.2/f.sub.1).sup.uα.sub.1−α.sub.2]/l, and
G=A(T.sup.1/2/P)(Δα.sub.L−d) where, Δα.sub.L is the target leakage factor and G is the target gas parameter, respectively, f.sub.1 and f.sub.2 are the first and second frequencies, respectively, α.sub.1 and α.sub.2 are the first and second attenuations, respectively, u is a real number satisfying 1.8≤u≤2.3, and l is a propagation length of the surface acoustic wave, T and P are temperature and pressure of the background gas, respectively, and A and d are a coefficient and a term caused by a loss of the sensor, respectively.
2. The system of claim 1, wherein each of the reference gas parameters is provided as a square root of a product of molecular weight of each of the reference gases and a ratio of specific heat at constant pressure to specific heat at constant volume of said each of the reference gases, and each of the reference leakage factors is provided by a first reference attenuation of a first reference burst signal and a second reference attenuation of a second reference burst signal using waveform data of a reference burst signals.
3. The system of claim 1, wherein the data processor compares the target gas parameter with the reference gas parameters so as to estimate a gas species of the background gas.
4. The system of any one of claim 1, wherein the data processor measures a viscoelastic factor of the background gas so as to calculate a concentration of the sensing gas, the viscoelastic factor is provided by the first attenuation and the second attenuation.
5. The system of claim 4, wherein, the viscoelastic factor is given by,
Δα.sub.V≡[α.sub.2−(f.sub.2/f.sub.1).sup.zα.sub.1]/l, where, Δα.sub.V is the viscoelastic factor, f.sub.1 and f.sub.2 are the first and second frequencies, respectively, α.sub.1 and α.sub.2 are the first and second attenuations, respectively, z is a real number satisfying 0.8≤z≤1.3, and l is a propagation length of the surface acoustic wave.
6. The system of claim 1, wherein, the background gas includes a plurality of component gases, and each of the reference gas parameters is defined as a square root of a product of an average molecular weight and a ratio of an average specific heat at constant pressure to an average specific heat at constant volume of each of the component gases.
7. The system of claim 6, wherein the background gas is a mixture of two component gases and the data processor calculates a concentration of anyone of the component gases by the reference gas parameters.
8. The system of claim 7, wherein the background gas is a mixture of a natural gas and hydrogen injected in the natural gas.
9. The system of claim 6, further comprising a velocity measurement unit configured to measure a sound velocity of the background gas, wherein the data processor calculates an average leaky attenuation coefficient by the target leakage factor and an average sound velocity of the background gas measured using the velocity measurement unit, and the data processor calculates an average compressibility of the background gas and an average density of the background gas by the average leaky attenuation coefficient and the average sound velocity.
10. The system of claim 9, wherein the data processor further calculates an average molecular weight and an average ratio of specific heat by the average gas parameter and the average sound velocity.
11. A method for gas analysis using a surface acoustic wave sensor having a sensor electrode generating a surface acoustic wave and a sensitive film adsorbing a sensing gas, on a piezoelectric substrate, comprising: flowing a background gas containing the sensing gas into a sensor cell having the surface acoustic wave sensor in place; transmitting an exciting burst signal to the sensor electrode so as to excite a collimated beam of the surface acoustic wave of first and second frequencies, which propagates on the piezoelectric substrate while passing through the sensitive film deposited in a position where the collimated beam passes through; receiving first and second returned burst signals of the collimated beam through the sensor electrode after the collimated beam has propagated on the piezoelectric substrate, the first returned burst signal having the first frequency and the second returned burst signal having the second frequency; and calculating a target gas parameter by a target leakage factor of the background gas and a relation between reference gas parameters and reference leakage factors of reference gases, the leakage factor is provided by a first attenuation of the first returned burst signal and a second attenuation of the second returned burst signal using waveform data of the first and second returned burst signals, wherein the target leakage factor and the target gas parameter are given by,
Δα.sub.L≡[(f.sub.2/f.sub.1).sup.uα.sub.1−α.sub.2]/l, and
G=A(T.sup.1/2/P)(Δα.sub.L−d) where, Δα.sub.L is the target leakage factor and G is the target gas parameter, respectively, f.sub.1 and f.sub.2 are the first and second frequencies, respectively, α.sub.1 and α.sub.2 are the first and second attenuations, respectively, u is a real number satisfying 1.8≤u≤2.3, and l is a propagation length of the surface acoustic wave, T and P are temperature and pressure of the background gas, respectively, and A and d are a coefficient and a term caused by a loss of the sensor, respectively.
12. The method of claim 11, wherein each of the reference gas parameters is provided as a square root of a product of molecular weight of each of the reference gases and a ratio of specific heat at constant pressure to specific heat at constant volume of said each of the reference gases, and each of the reference leakage factors is provided by a first reference attenuation of a first reference burst signal and a second reference attenuation of a second reference burst signal using waveform data of a reference burst signals.
13. The method of claim 11, further comprising comparing the target gas parameter with the reference gas parameters so as to estimate a gas species of the background gas.
14. The method of any one of claim 12, further comprising measuring a viscoelastic factor of the background gas so as to calculate a concentration of the sensing gas, the viscoelastic factor is provided by the first attenuation and the second attenuation.
15. The method of claim 11, wherein the background gas includes a plurality of component gases, and each of the reference gas parameters is defined as a square root of a product of an average molecular weight and a ratio of an average specific heat at constant pressure to an average specific heat at constant volume of each of the component gases.
16. The method of claim 15, wherein the background gas is a mixture of two component gases and further comprising: calculating a concentration of anyone of the component gases by the reference gas parameters.
17. The method of claim 11, further comprising: measuring an average sound velocity of the background gas using a velocity measurement unit; and calculating an average compressibility of the background gas and an average density of the background gas by the average leaky attenuation coefficient and the average sound velocity.
18. The method of claim 17, further comprising calculating an average molecular weight and an average ratio of specific heat by the average gas parameter and the average sound velocity.
19. A computer-readable recording medium having recorded thereon a computer program for gas analysis using a surface-acoustic-wave sensor having a sensor electrode generating a surface-acoustic-wave and a sensitive film adsorbing a sensing gas, on a piezoelectric substrate, the computer program comprising: instructions to flow a background gas containing the sensing gas into a sensor cell having the surface-acoustic-wave sensor in place; instructions to transmit an exciting burst signal to the sensor electrode so as to excite a collimated beam of the surface-acoustic-wave of first and second frequencies, which propagates on the piezoelectric substrate while passing through the sensitive film deposited in a position where the collimated beam passes through; instructions to receive first and second returned burst signals of the collimated beam through the sensor electrode after the collimated beam has propagated on the piezoelectric substrate, the first returned burst signal having the first frequency and the second returned burst signal having the second frequency; and instructions to calculate a target gas parameter by a target leakage factor of the background gas and by a relation between reference gas parameters and reference leakage factors of reference gases, the target leakage factor is provided by a first attenuation of the first returned burst signal and a second attenuation of the second returned burst signal using waveform data of the first and second returned burst signals; wherein the target leakage factor and the target gas parameter are given by,
Δα.sub.L≡[(f.sub.2/f.sub.1).sup.uα.sub.1−α.sub.2]/l, and
G=A(T.sup.1/2/P)(Δα.sub.L−d) where, Δα.sub.L is the target leakage factor and G is the target gas parameter, respectively, f.sub.1 and f.sub.2 are the first and second frequencies, respectively, α.sub.1 and α.sub.2 are the first and second attenuations, respectively, u is a real number satisfying 1.8≤u≤2.3, and l is a propagation length of the surface acoustic wave, T and P are temperature and pressure of the background gas, respectively, and A and d are a coefficient and a term caused by a loss of the sensor, respectively.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
(25) Embodiments of the present invention will be described below with reference to the drawings. In the descriptions of the following drawings, the same or similar reference numerals are assigned to the same or similar portions. However, the drawings are diagrammatic, and attention should be paid to a fact that the relations between thicknesses and plan view dimensions, the configuration of the apparatus and the like differ from the actual data. Thus, the specific thicknesses and dimensions should be judged by considering the following descriptions. Also, even between the mutual drawings, the portions in which the relations and rates between the mutual dimensions are different are naturally included. Also, the first and second embodiments as described below exemplify the apparatuses and methods for embodying the technical ideas of the present invention, and in the technical ideas of the present invention, the materials, shapes, structures, arrangements and the like of configuration parts are not limited to the followings.
(26) In the following description, α, β, γ, Δ and ρ represent Greek alphabet characters, respectively. And, the “horizontal” direction or the “vertical” direction is simply assigned for convenience of explanation and does not limit the technical spirit of the present invention. Therefore, for example, when the plane of paper is rotated 90 degrees, the “horizontal” direction is changed to the “vertical” direction and the “vertical” direction is changed to the “horizontal” direction. When the plane of paper is rotated 180 degrees, the “left” side is changed to the “right” side and the “right” side is changed to the “left” side. Therefore, various changes can be added to the technical ideas of the present invention, within the technical scope prescribed by claims.
(27) (Construction of Gas Analyzer)
(28) As illustrated in
(29) The SAW sensor 2 is connected to a rod-shaped external electrode 35 through a contact pin 35a along a vertical direction via the canal at the bottom of the electrode-holder base 32. The external electrode 35 is held in a hollow space of a vertically aligned cylindrical electrode holder 34, the bottom of which is inserted in an inner portion of the sensor-cell cap 33. A sensing gas containing in a background gas, for example, a humid gas, is introduced into the sensor cell 31 through a horizontally aligned tubing 36 with a gas flow rate v, so that the humid gas can touch the surface of the SAW sensor 2. The gas flow rate v is typically 0.1 L/min to 1 L/min.
(30) As illustrated in
(31) For the piezoelectric ball 20, a crystal sphere, such as quartz, langasite (La.sub.3Ga.sub.5SiO.sub.14), lithium niobate (LiNbO.sub.3), lithium tantalate (LiTaO.sub.3), piezoelectric ceramics (PZT), bismuth germanium oxide (Bi.sub.12GeO.sub.20) and the like, may be used. For the sensitive film 23, a silica (SiO.sub.x) film and the like may be used. The sensor electrode 22 may be deposited in an opening of the sensitive film 23, the opening exposes a part of the surface of the piezoelectric ball 20, in a configuration such that the opening is formed on a part of the equator of the homogeneous piezoelectric ball 20. For the sensor electrode 22, an interdigital electrode (IDT) using a chromium (Cr) film and the like may be used as an electroacoustic transducer. In the case of a sphere of single crystal such as the homogeneous piezoelectric ball 20, a SAW orbiting route is limited to a specific orbital band having a constant width, depending on type of crystal material. The width of the orbital band may be increased or decreased depending on anisotropy of the crystal.
(32) There are no diffraction losses during roundtrips around the piezoelectric ball 20, and only propagation loss due to material attenuation. The collimated beam 21 is scheduled to propagate many turns passing through the sensitive film 23, which is configured to adsorb water molecules. Because the adsorbed water molecules change the propagation characteristic of the SAW, the changes due to adsorbed water molecules in the humid gas on the sensitive film 23 can be integrated every turn through the multiple roundtrips. Thus, even though the sensitive film 23 may be so thin as to adsorb the small amount of the water vapor, measurement accuracy of gas analysis may be increased.
(33) The suitable relationship between the first frequency f.sub.1 of the fundamental wave and the second frequency f.sub.2 of the harmonic wave shall be represented by f.sub.2=nf.sub.1, where n=3 or 5. That is, in the system for gas analysis pertaining to the embodiment of the present invention, the harmonic wave is the third-order harmonic wave or the fifth-order harmonic wave. Thus, when the first frequency f.sub.1 is 80 MHz, the second frequency f.sub.2 is 240 MHz for the third-order harmonic wave or 400 MHz for the fifth-order harmonic wave. Appropriate range of the first frequency f.sub.1 for the piezoelectric ball 20 of 3.3 millimeters diameter may be from 60 MHz to 100 MHz, and the most suitable first frequency f.sub.1 may be 80 MHz. The first frequency f.sub.1 is inversely proportional to the diameter of the piezoelectric ball 20.
(34) For example, the SAW sensor 2 may be fabricated as described below. A pattern of an IDT of about 150 nanometers thick Cr film is deposited on a surface of a quartz ball having a diameter of 3.3 millimeters. The IDT has a pair of bus bars, and a plurality of electrode fingers extending from the bus bars, respectively. The electrode fingers overlap each other with a cross width Wc, and each electrode finger has a width Wf and a periodicity P. The cross width Wc, the width Wf and the periodicity P are designed as 364 micrometers, 6.51 micrometers and 10.0 micrometers, respectively, for the natural collimation of 80 MHz SAW (refer to NPL 1).
(35) The IDT on the quartz ball having 3.3 millimeters diameter can generate 80 MHz SAW as a fundamental wave and 240 MHz SAW as a third-order harmonic wave. Then a silica film is synthesized by using a sol-gel method and coated on the surface of the quartz ball as follows: 3.47 grams of tetraethoxysilane (TEOS), 0.75 grams of isopropanol (IPA), and 1.50 grams of 0.1N hydrochloric acid (HCl) are mixed and stirred by sonication (27, 45, 100 kHz, 60 minutes). TEOS is polymerized by hydrolysis and resulted in SiO.sub.x. After sonication, the mixture is diluted with IPA and 0.5 mass % SiO.sub.x solution is obtained. The surface of propagation route of SAW is coated with the SiO.sub.x solution using a spin coating. Condition of the spin coating is 3000 rpm for 20 seconds. The thickness of SiO.sub.x film is confirmed as 1029 nanometers from measurement using interference microscope.
(36) An RF voltage is applied to the sensor electrode 22 via an electrode pad (not illustrated) arranged around the north-pole, which is a top of the piezoelectric ball 20 in
(37) In the above description, a ball SAW sensor is used as the SAW sensor 2, but a planar SAW sensor 2a illustrated in
(38) As illustrated in
(39) The signal processing unit 40, as illustrated in
(40) Moreover, the communication module 45 sends instructions to the signal generator/receiver 42 so that the signal generator 42a illustrated in
(41) The calculation module 46 of the waveform data processor 44 calculates a gas parameter by using first and second attenuations in amplitudes of the SAWs of the first and second frequencies, respectively, using the waveform data of the returned burst signals. The comparison module 47 of the waveform data processor 44 compares the calculated gas parameter with data of gas parameters for various gases in order to determine gas species. The memory unit 48 of the waveform data processor 44 stores a program for driving the waveform data processor 44 to implement processing of the waveform data for calculating the gas parameter. Also, the memory unit 48 stores the data of gas parameters for various gases, and data obtained during the calculation and analysis of the gas during the operation of the waveform data processor 44.
(42) The waveform data processor 44 may be a part of central processing unit (CPU) of a general purpose computer system, such as a personal computer (PC) and the like. The waveform data processor 44 may include an arithmetic logic unit (ALU) that performs arithmetic and logic operations, a plurality of registers that supply operands to the ALU and store the results of ALU operations, and a control unit that orchestrates the fetching (from memory) and execution of instructions by directing the coordinated operations of the ALU. The communication module 45, the calculation module 46, and the comparison module 47 implementing the ALU may be discrete hardware resources such as logical circuit blocks or the electronic circuitry contained on a single integrated circuit (IC) chip, or alternatively, may be provided by virtually equivalent logical functions achieved by software, using the CPU of the general purpose computer system.
(43) In addition, the program for the waveform data processor 44 for the gas analysis is not limited to being stored in the memory unit 48 installed in the waveform data processor 44. For example, the program may be stored in an external memory. Moreover, the program may be stored in a computer readable medium. By reading the computer readable medium in the memory unit 48 of the computer system, which includes the waveform data processor 44, the waveform data processor 44 implements coordinated operations for the gas analysis, in accordance with a sequence of instructions recited in the program. Here, the “computer readable medium” refers to a recording medium or a storage medium, such as an external memory unit of a computer, a semiconductor memory, a magnetic disk, an optical disk, a magneto optical disk, and a magnetic tape, on which the program can be recorded.
(44) (Basis of Analysis)
(45) In NPL 2, leaky attenuation coefficient α.sub.L of SAW is given by
(46)
where f is a frequency, ρ.sub.s is a density of the piezoelectric ball 20, V.sub.s is a SAW velocity of the piezoelectric ball 20, ρ is a density of the gas and K.sub.G is a compressibility of the gas. Substituting known relations
ρ=MP/RT and K.sub.G=1/(γP) (2)
into Eq. (1), it becomes
(47)
where M is a molecular weight of the gas, P is a pressure of the gas, R is a gas constant, T is a temperature and γ is the heat capacity ratio which is ratio of the specific heat at constant pressure to the specific heat at constant volume of the gas.
(48) In a SAW sensor shown in
Δα.sub.L[(f.sub.2/f.sub.1).sup.xα.sub.1−α.sub.2]/l (4)
where the superscript “u” is an index to describe the frequency dependence of the attenuation by the sensing gas, which is 1.8 or more and 2.3 or less, and l is the SAW propagation length.
(49) A model is constructed for the calculation purpose with
α.sub.1=a.sub.0F.sub.1.sup.z+a.sub.1(w)F.sub.1.sup.u+a.sub.2F.sub.1.sup.y, and (5)
α.sub.2=a.sub.0F.sub.2.sup.z+a.sub.1(w)F.sub.2.sup.u+a.sub.2F.sub.2.sup.y, (6)
where F.sub.1=f.sub.1/f.sub.0, F.sub.2=f.sub.2/f.sub.0, f.sub.0 is a reference frequency, and with the propagation length l of the SAW,
a.sub.0=α.sub.L′l=[f.sub.0PI/(Rho [Greek].sub.sV.sub.s.sup.2)][Gamma [Greek]M/(RT)].sup.1/2 (7)
is an attenuation caused by a leakage to the background gas at frequency f.sub.0, the superscript “z” is a frequency dependence index of leaky attenuation α.sub.L′, a.sub.1(w) is a loss by the sensing gas, w is a concentration of the sensing gas, a.sub.2 is a device loss due to scattering at the sensor electrode 22, etc., the superscript “y” is a frequency dependence index of the device loss. The index z is normally equal to 1.0 according to NPL2, as in Eq. (1) and Eq. (3), and α.sub.L′=α.sub.L is assumed as described later. However, the index z may be 0.8 or more and 1.3 or less. It is noted that the concept and process of modifications to Eq. (8) and following equations of Eq. (8) in the case of using z other than z=1 is obvious to a person having skills in the technical field.
(50) It is noted that [γM].sup.1/2 in Eq. (7) is an important parameter describing property of the background gas, and thus it is defined as a gas parameter, here. Examples of gas parameters G, or “reference gas parameters”, for typical light gasses, each of which is calculated by molecular weight M and heat capacity ratio γ of each gas, are listed in a table of
(51) Subtracting Eq. (6) from Eq. (5) multiplied by (F.sub.2/F.sub.1).sup.u, the leakage factor Δα.sub.L is related to the losses by
Δα.sub.L=α.sub.L(F.sub.1.sup.1-xF.sub.2.sup.x−F.sub.2)+(a.sub.2/l)(F.sub.1.sup.y-xF.sub.2.sup.x−F.sub.2.sup.y) (8)
As a special case, we define F.sub.2=3F.sub.1, F.sub.1=1 and the loss to be a viscoelastic loss with u=2 (refer to NPL 3). Then,
Δα.sub.L=α.sub.L(3.sup.x−3)+(a.sub.2/l)(3.sup.x−3.sup.y)=6α.sub.L+(a.sub.2/l)(9−3.sup.y). (9)
From Eq. (9),
(52)
Using second equation of Eq. (7) and Eq. (10), the gas parameter is given by
G=√{square root over (γM)}=B[Δα.sub.L−(a.sub.2/l)(9−3.sup.y)] (11)
(53) Coefficient A and term d caused by device loss can be determined by calibration. To determine A and d, the leakage factor Δα.sub.L is first measured at T.sub.1 and P.sub.1 for a gas having a gas parameter G.sub.1 and secondly at T.sub.2 and P.sub.2 for a gas having a gas parameter G.sub.2. Thus, G.sub.1=A(T.sub.1.sup.1/2/P.sub.1)(Δα.sub.L,1−d) and G.sub.2=A(T.sub.2.sup.1/2/P.sub.2)(Δα.sub.L,2−d) giving
A=(P.sub.2G.sub.2/T.sub.2.sup.1/2−P.sub.1G.sub.1/T.sub.1.sup.1/2)/(Δα.sub.L,2−Δα.sub.L,1) and
d=Δα.sub.L,1−P.sub.1G.sub.1/(AT.sub.1.sup.1/2) (12)
In the second measurement, all parameters (T.sub.2, P.sub.2, G.sub.2) do not have to be changed from (T.sub.1, P.sub.1, G.sub.1). Different gas species can be measured at the same temperature and the same pressure, that is, calibration-condition (T.sub.2=T.sub.1, P.sub.2=P.sub.1, G.sub.2≠G.sub.1) or only the pressure is changed, that is, calibration-condition (T.sub.2=T.sub.1, P.sub.2≠P.sub.1, G.sub.2=G.sub.1). In an environment with constant temperature T or pressure P, calibration can be made by
G=B(Δα.sub.L−d), (13)
with
B=A(T.sup.1/2/P). (14)
(54) Since the leaky attenuation is proportional to the first frequency F.sub.1 and the second frequency F.sub.2 when z is equal to 1 in Eqs. (5) and (6), it will be cancelled in a viscoelastic factor Δα.sub.V defined and given by
(55)
In a special case of F.sub.2=3F.sub.1, F.sub.1=1,
Δα.sub.V=6[a.sub.1(w)/l]+(a.sub.2/l)(3.sup.y−3). (16)
First Example
(56) <Measurement of Background Gas>
(57) Test measurements for gas analysis of background gases have been executed using a humid gas in which trace moisture as a sensing gas has been mixed in various background gases. The gas supply unit 17 used for the test measurement, as illustrated in
(58) In the test measurement, the fundamental wave and the third-order harmonic wave of the SAW, that is, f.sub.2=3f.sub.1, has been used. Each procedure of the test measurements will be described with reference to the flowchart illustrated in
(59) In step S100, the gas supply unit 17 supplies the humid gas with the background gas, which is selected from the gas sources 52a to 52d, into the sensor unit 1. In step S101, the signal generator 42a of the signal generator/receiver 42 transmits the burst signal to the SAW sensor 2, so as to excite the collimated beam 21 of the SAW as illustrated in
(60) In step S103, the waveform data processor 44 measures a first attenuation α.sub.1 of a first burst signal having the first frequency f.sub.1 and a second attenuation α.sub.2 of a second burst signal having the second frequency f.sub.2. In step S104, the waveform data processor 44 calculates the target gas parameter G of the target gas using the leaky attenuation coefficient α.sub.L and the leakage factor Δα.sub.L, which is derived by the first and second attenuations α.sub.1 and α.sub.2 using Eqs. (4) and (11). Then, in Step S105, the waveform data processor 44 estimates a gas species of the target gas by comparing the measured gas parameter with the true gas parameters, or the reference gas parameters, which are calculated by the physical-property data of gases. In addition, the waveform data processor 44 measures the viscoelastic factor Δα.sub.V of the target gas using Eq. (15) so as to calculate a concentration of the sensing gas.
(61) <Calibration>
(62) An example of calibration for the coefficient B and the term d in Eqs. (13) and (14) will be described below. In the calibration procedure, a humid gas having frost point of −60° C. or water concentration of 10.7 ppmv has been used with background gases of Air, N.sub.2, Ar and CH.sub.4 which have been supplied from the gas source 52a to 52d of the gas supply unit 17 illustrated in
(63) <Estimation of Background Gas-1>
(64) Assuming that the first background gas and the fourth background gas in
(65) Using Eq. (11) with the calibrated parameter B, measured gas parameters G*, or target gas parameters G*, of the target gases X1 and X2 have been measured, as 4.43 and 6.36 as listed in a table of
(66) <Estimation of Background Gas-2>
(67) In a humid gas having another humidity of frost point of −50° C. and water concentration of 38.8 ppmv, the background gases X3, X4, X5, X6 have been used as target gases. The background gas has been changed in order of X6, X3, X5 and X4, as illustrated in
(68) The measured gas parameters G* and the true gas parameters G are summarized in a graph illustrated in
(69) <Measurement of Sensing Gas>
(70) In the gas analyzer according to the embodiment of the present invention, it is also possible to measure a concentration of the sensing gas in the background gas with high precision using the viscoelastic factor Δα.sub.V, even when composition of the background gas is changed. To verify that the viscoelastic factor Δα.sub.V does not depend on the background composition but only on the moisture content, the leakage factor Δα.sub.L evaluated using Eq. (4) and the viscoelastic factor Δα.sub.V evaluated using Eq. (15) have been compared in a wide time range of about 65 hours using humid gases having the frost points of −60° C., −50° C. and −40° C., which correspond to 10.7 ppmv, 38.8 ppmv and −127 ppmv, as illustrated in
Second Example
(71) In the following explanation of the second example, each of M(bar), G(bar), γ(bar), C.sub.p(bar) and C.sub.V(bar), etc. represents a symbol labeled with an horizontal over line, or an over bar on the top of the characters of M, γ, C.sub.p and C.sub.v, etc.
(72) <Application to Mixed Gas>
(73) In a mix gas having a plurality of component gases, an average gas parameter G(bar) is given by
G(bar)={γ(bar)M(bar)}.sup.1/2=[C.sub.P(bar)/C.sub.V(bar)].sup.1/2M(bar) (17)
where M(bar) is average molecular weight and γ(bar) is average ratio of average specific heat C.sub.p(bar) at constant pressure to average specific heat C.sub.V(bar) at constant volume. M(bar), C.sub.p(bar) and C.sub.v(bar) are given by
M(bar)=Σ.sub.i=1.sup.Nx.sub.iM.sub.i,C.sub.P(bar)=Σ.sub.i=1.sup.Nx.sub.iC.sub.Pi,C.sub.V(bar)=Σ.sub.i=1.sup.Nx.sub.iC.sub.Vi,Σ.sub.i=1.sup.Nx.sub.i=1 (18)
where M.sub.i, C.sub.Pi, C.sub.Vi, x.sub.i and N are molecular weight, specific heat at constant pressure, specific heat at constant volume, molar fraction of each component gas i and number digit of component gases, respectively.
(74) In the case of two background gases of XA and XB, G(bar) is derived as
G(bar)={[(C.sub.PA−C.sub.PB)x+C.sub.PB][(M.sub.A−M.sub.B)x+M.sub.B]/[(C.sub.VA−C.sub.VB)x+C.sub.VB]}.sup.1/2 (19)
where x is the concentration by mole percentage, or mol %, of gas XA, M.sub.A, C.sub.PA and C.sub.VA are molecular weight, specific heat at a constant pressure and specific heat at constant volume of the gas XA, and M.sub.B, C.sub.PB, C.sub.VB are molecular weight, specific heat at a constant pressure and specific heat at constant volume of the gas XB, respectively.
(75) To verify Eq. (19), helium (He) as the gas XA has been mixed with N.sub.2 as gas XB, where molecular weight, specific heat at a constant pressure, specific heat at constant volume, ratio of specific heats and gas parameter of He and N.sub.2 are listed in
(76) The measured leakage factor α.sub.L in the measurement sequence is plotted against time in
G.sub.S(bar)={γM}.sup.1/2(bar) (20)
of He and N.sub.2, illustrated by dashed line in
(77) The concentration of He can be measured by the average gas parameter G(bar) with using a calibration curve. The calibration curve may be calculated by replacing C.sub.PB with βC.sub.PB and C.sub.VB with βC.sub.VB in Eq. (19) where the β is an adjustable parameter. The replacement does not change the average gas parameter G(bar) at the molar fraction x=0 or at the molar fraction x=1 but changes the average gas parameter G(bar) in the intermediate range of the molar fraction x from 0.1 to 0.9, that is, 10 mol % to 90 mol %. Though the adjustable parameter β has no physical meaning, the adjustable parameter β helps to improve the agreement between the experimental data and the calibration curve when the adjustable parameter β is set to 3.0, as illustrated by dotted curve in
(78) Using the calibration curve, He concentration has been measured as illustrated in
(79) <Application to Glove Box>
(80) Further, it is also possible to apply the gas analyzer according to the embodiment of the present invention for checking whether an interior of a glove box has been replaced with a purge-gas. For example, the glove box used for Li-ion batteries or for 3D printers of metal objects, it is required to replace air and moisture in the glove box with the purge-gas. For the purge-gas, an inert gas, such as argon, helium, N.sub.2 and the like, or a mixture of inert gases may be preferably used to avoid unwanted chemical reactions with oxygen (O.sub.2) in the air and the moisture. While purging the air and the moisture by introducing the purge-gas into the glove box, the purge-gas and the air may be implemented by the mix gas and concentration of the purge-gas may increase with time. Thus, it is possible to measure the concentration of the purge-gas as a component gas, which is mixed with the air in the glove box, using the gas parameter G(bar) of Eq. (19). Also, it is expected to be precise enough for the measurement of the spatial distribution of the purge-gas in the glove box. In addition, concentration of the moisture in the glove box may be also measured as the sensing gas using the viscoelastic factor Δα.sub.V of Eq. (15).
(81) <Measurement of Average Molecular Weight and Average Specific Heat Ratio>
(82) With Mayer's relationship, C.sub.pi=C.sub.Vi+R, Eq. (19) is replaced by
M(bar)=Σ.sub.i=1.sup.Nx.sub.iM.sub.i,C.sub.P(bar)=Σ.sub.i=1.sup.Nx.sub.i(C.sub.Vi+R),C.sub.V(bar)=Σ.sub.i=1.sup.Nx.sub.iC.sub.Vi,Σ.sub.i=1.sup.Nx.sub.i=1. (21)
The average sound velocity V(bar) is usually measured in gas analysis as,
V(bar)=[γ(bar)RT/M(bar)].sup.1/2={[1+R/(C.sub.V(bar))]RT/M(bar)}.sup.1/2 (22)
In Eq. (22), independent quantity of molecular weight nor ratio of specific heat is not available. However, when the gas analyzer gives a gas parameter G(bar) in Eq. (17), the average molecular weight M(bar) and the average specific heat ratio γ(bar) are independently solved from Eq. (17) and Eq. (22) as
M(bar)=Σ.sub.i=1.sup.Nx.sub.iM.sub.i=G(bar)(RT).sup.1/2/V(bar) and
γ(bar)=Σ.sub.i=1.sup.Nx.sub.i(C.sub.Vi+R)/Σ.sub.i=1.sup.Nx.sub.iC.sub.Vi=G(bar)V(bar)/(RT).sup.1/2. (23)
The average molecular weight M(bar) and the average specific heat ratio γ(bar) are useful for calculation of many physical/chemical property of the mix gas.
(83) To obtain molar fraction x.sub.i (i=1, N) of each component gas, N independent equations are required.
(84) In a special case of N=3, measurements for the average gas parameter G(bar) and the average sound velocity V(bar) results in,
x.sub.1M.sub.1+x.sub.2M.sub.2+x.sub.3M.sub.3=G(bar)(RT).sup.1/2/V(bar) (24)
[x.sub.1(C.sub.V1+R)+x.sub.2(C.sub.V2+R)+x.sub.3(C.sub.V3+R)]/(x.sub.1C.sub.V1+x.sub.2C.sub.V2+x.sub.3C.sub.V3)=G(bar)V(bar)/(RT).sup.1/2, and (25)
x.sub.1+x.sub.2+x.sub.3=1. (26)
Linear simultaneous Eqs. (24), (25) and (26) can be solved for molar fraction (x.sub.1, x.sub.2, x.sub.3).
(Case A)
(85) When hydrogen is injected to a mix gas of natural gases, for example, methane and ethane, and x.sub.1=[H.sub.2], x.sub.2=[CH.sub.4], x.sub.3=[C.sub.2H.sub.6], mole fraction (x.sub.1, x.sub.2, x.sub.3) is solved by Eqs. (24) to (26).
(86) (Case B)
(87) When hydrogen is injected to methane, and x.sub.1=[H.sub.2], x.sub.2=[CH.sub.4],
G(bar)={[x.sub.1(C.sub.V1+R)+x.sub.2(C.sub.V2+R)](x.sub.1M.sub.1+x.sub.2M.sub.2)/(x.sub.1C.sub.V1+x.sub.2C.sub.V2)}.sup.1/2 (27)
x.sub.1+x.sub.2=1. (28)
Then, molar fraction (x.sub.1, x.sub.2) is solved by Eqs. (27) and (28).
(Measurement of Density and Compressibility)
(88) As illustrated in
V(bar)={1/[ρ(bar)K.sub.G(bar)]}.sup.1/2 (29)
In such case, it is useful to express the average leaky attenuation coefficient α.sub.L(bar) as
α.sub.L(bar)=f[ρ(bar)/K.sub.G(bar)].sup.1/2/[ρ.sub.SV.sub.S.sup.2] (30)
similarly to Eq. (1). Then, from Eqs. (29) and (30), the average compressibility and the average density are solved as
K.sub.G(bar)={f/[ρ.sub.SV.sub.S.sup.2]}{1/[V(bar)α(bar)]} (31)
ρ(bar)={[ρ.sub.SV.sub.S.sup.2]/f}{α.sub.L(bar)/V(bar)}. (32)
The average leaky attenuation coefficient α.sub.L(bar) is calculated by,
α.sub.L(bar)={Δα.sub.L−(a.sub.2/l)(9−3.sup.y)}/6. (33)
similarly to Eq. (10).
(89) The average molecular weight and the average specific heat ratio can not be separated by merely measuring the average gas parameter. However, by adding measurement of the average sound velocity of the mix gas, it is possible to independently measure the average molecular weight and the average specific heat ratio. Thus, there is an advantage that other thermodynamic quantities can be calculated by independently measuring the average molecular weight and the average specific heat ratio.
Other Embodiments
(90) While the present invention has been described above by reference to the embodiment, it should be understood that the present invention is not intended to be limited to the descriptions of the specification and the drawings implementing part of this disclosure. Various alternative embodiments, examples, and technical applications will be apparent to those skilled in the art according to this disclosure. It should be noted that the present invention includes various embodiments which are not disclosed herein. Therefore, the scope of the present invention is defined only by the present invention specifying matters according to the claims reasonably derived from the description heretofore.
REFERENCE SIGNS LIST
(91) 1 sensor unit 2 SAW sensor (ball SAW sensor) 2a planar SAW sensor 10 temperature control unit 11 holder 12 Peltier element 13 thermistor 14 adapter 16 temperature controller 17 gas supply unit 18 velocity measurement unit 20 piezoelectric ball 20a piezoelectric substrate 21 collimated beam 22 sensor electrode 22a input electrode 22b output electrode 23, 23a sensitive film 31 sensor cell 32 electrode-holder base 33 sensor-cell cap 34 electrode holder 35 external electrode 36 tubing 40 signal processing unit 42 signal generator/receiver 42a signal generator 42b signal receiver 44 waveform data processor 45 communication module 46 calculation module 47 comparison module 48 memory unit 50 gas-switching valve 52a, 52b, 52c, 52d gas source 54 moisture generator