WO2017145889A1 - ガスセンサ、ガス検出装置、ガス検出方法及びガス検出装置を備えた装置 - Google Patents
ガスセンサ、ガス検出装置、ガス検出方法及びガス検出装置を備えた装置 Download PDFInfo
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- WO2017145889A1 WO2017145889A1 PCT/JP2017/005457 JP2017005457W WO2017145889A1 WO 2017145889 A1 WO2017145889 A1 WO 2017145889A1 JP 2017005457 W JP2017005457 W JP 2017005457W WO 2017145889 A1 WO2017145889 A1 WO 2017145889A1
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- Prior art keywords
- gas
- resistance element
- thermal resistance
- heating
- adsorbing material
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Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
- G01N25/4873—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a flowing, e.g. gas sample
- G01N25/4893—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a flowing, e.g. gas sample by using a differential method
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/14—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/14—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature
- G01N27/18—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature caused by changes in the thermal conductivity of a surrounding material to be tested
Definitions
- the present invention relates to a gas sensor capable of detecting gas molecules, a gas detection device, a gas detection method, and an apparatus including the gas detection device.
- a gas sensor has been proposed in which a filter made of zeolite, activated alumina, or the like is provided in a housing that houses the sensor body in order to allow the gas sensor to withstand siloxane gas for a long time and to improve gas selectivity (patent) Reference 3).
- the conventional humidity sensor described above is based on the principle of detecting humidity by detecting a change in electrical resistance value according to the water vapor content in the atmosphere.
- the humidity sensors disclosed in Patent Document 1 and Patent Document 2 are adjusted to a high temperature so that the temperature is in the range of 300 to 500 ° C. by energizing the metal resistance conductor. There is a problem that energy for heating is large, power consumption is large, and life is short.
- the gas sensor shown in Patent Document 3 is provided with a filter such as zeolite, activated alumina and activated carbon, and the humidity sensor shown in Patent Document 4 and Patent Document 5 is a low temperature sensor. There is a problem that gas detection sensitivity is low.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a gas sensor, a gas detection device, a gas detection method, and a device including the gas detection device that can improve gas detection performance.
- the gas sensor according to claim 1 comprises a thermal resistance element, and a porous gas molecule adsorption material that is thermally coupled to the thermal resistance element and from which specific gas molecules are desorbed by heating. It is characterized by.
- the gas sensor according to claim 2 is a thermosensitive resistance element, and a porous gas molecule adsorbing material that is thermally coupled to the thermal resistance element and from which specific gas molecules are desorbed and adsorbed by heating and cooling. It is characterized by comprising.
- the gas sensor according to claim 3 is the gas sensor according to claim 1 or 2, wherein the heat sensitive resistance element for compensation and the porous gas molecule adsorption thermally coupled to the heat sensitive resistance element for compensation are provided. And a material having an adsorptivity different from that of the material.
- the material having an adsorptivity different from the porous gas molecule adsorbing material for example, a material such as molecular sieve, alumina, or silica that has been inactivated by heat treatment is used.
- the molecular sieve 3A can be used as a material in which the porous gas molecule adsorbing material has different adsorptivity with respect to the molecular sieve 4A.
- the material having different adsorptivity is not limited to a specific material.
- the heat-sensitive resistance element for compensation is housed in a sealed space.
- the gas sensor according to claim 5 is the gas sensor according to any one of claims 1 to 4, wherein the heat-sensitive resistance element is capable of self-heating when energized.
- a gas sensor according to a sixth aspect is the gas sensor according to any one of the first to fifth aspects, wherein a heating element for heating the porous gas molecule adsorption material is provided separately from the thermal resistance element. It is characterized by being.
- the heating element may be a normal resistance heating element, an indirectly heated infrared lamp, an infrared laser, or the like. It is not limited to a particular one.
- the gas sensor according to claim 7 is the gas sensor according to any one of claims 1 to 6, wherein the porous gas molecule adsorbing material is zeolite or a porous metal complex.
- zeolite for example, a molecular sieve of A-type zeolite is preferably used.
- Porous metal complexes are new materials for coordination polymers or organic-metal frameworks by utilizing metal complexes.
- the gas sensor according to claim 8 is the gas sensor according to any one of claims 3 to 7, wherein the material having an adsorptivity different from the porous gas molecule adsorption material is porous gas molecule adsorption.
- the material is characterized in that the material is inactivated.
- the gas sensor according to claim 9 is the gas sensor according to any one of claims 3 to 8, wherein the porous gas molecule adsorbing material and the porous gas molecule adsorbing material have different adsorptivity.
- the possessed material is characterized by having the same thermal properties.
- the thermal property means, for example, thermal conductivity, specific heat, and the like.
- the gas detection device according to claim 10 includes the gas sensor according to claim 1 or 3, and And a power supply control unit that heats and controls power supply to the thermal resistance element.
- a gas detection device includes the gas sensor according to the second or third aspect, and a power supply control unit that supplies and controls power to the thermal resistance element to heat and cool the gas sensor. It is characterized by.
- the gas detection device is the gas detection device according to claim 10 or claim 11, wherein the gas sensor is connected by a bridge circuit and detects gas by a differential output thereof.
- a gas detector according to claim 13 is the gas detector according to claim 12, further comprising an AC amplifier to which the differential output is connected.
- the gas detection method according to claim 14 includes a thermal resistance element and a porous gas molecule adsorption material that is thermally coupled to the thermal resistance element and from which specific gas molecules are desorbed by heating.
- a gas detection method comprising: a heating step for heating the porous gas molecule adsorbing material; and a detection step for detecting a specific gas by a temperature change of the thermal resistance element due to the heating.
- the gas detection method according to claim 15 is a porous gas molecule adsorption which is thermally coupled to the thermal resistance element and specific gas molecules are desorbed and adsorbed by heating and cooling.
- a gas detection method comprising: a heating step for bringing the porous gas molecule adsorption material into a heated state; and a cooling for bringing the porous gas molecule adsorption material into a cooling state at a lower temperature than the heating step. And a detection step of detecting a specific gas by a temperature change of the thermal resistance element due to the heating and cooling.
- the cooling state only needs to be a state where the heating state is lower than the heating state, and includes, for example, a case where the applied voltage is lowered to lower the heating temperature, and a case where the applied voltage is 0 V (stopped).
- the gas detection method according to claim 16 is the gas detection method according to claim 15, wherein the heating step and the cooling step are repeatedly performed at regular intervals.
- An apparatus including the gas detection device according to claim 17 includes the gas detection device according to any one of claims 10 to 13.
- An apparatus equipped with a gas detection device can be provided and applied to various devices for detecting gas molecules and humidity in home appliances, OA equipment, food storage equipment, medical equipment, transportation equipment such as automobiles, and the like.
- the specially applied device is not limited.
- the present invention it is possible to provide a gas detection device, a gas detection method, and a device including the gas detection device that can improve gas detection performance.
- the gas sensor which concerns on the 1st Embodiment of this invention is shown, (a) is sectional drawing, (b) is sectional drawing which follows the XX line in (a).
- It is a connection diagram for characteristic detection of the gas detection device It is a block block diagram which shows the same gas detection apparatus.
- the gas sensor which concerns on the 4th Embodiment of this invention is shown, (a) is sectional drawing, (b) is sectional drawing of the thermosensitive resistance element corresponded to (b) in FIG. It is a graph which shows the change of the output voltage. It is a graph which shows the temperature change. It is a perspective view which shows another embodiment (Example 1) of the gas sensor of this invention. It is sectional drawing which shows the same (Example 2). It is sectional drawing which shows the same (Example 3). It is sectional drawing which shows the same (Example 4). It is sectional drawing which shows the same (Example 5). It is sectional drawing which shows the same (Example 6).
- connection diagram which shows another embodiment (Example 1) for the characteristic detection in the gas detection apparatus of this invention. It is a connection diagram which shows the same (Example 2). It is a connection diagram which shows the same (Example 3), (a) is a connection diagram, (b) is sectional drawing of the thermosensitive resistance element corresponded to (b) in FIG. It is a connection diagram which shows the same (Example 4).
- FIG. 1 is a cross-sectional view showing a gas sensor
- FIG. 2 is a connection diagram for detecting characteristics of the gas detection device
- FIG. 3 is a block configuration diagram showing the gas detection device.
- 4 and 5 are graphs showing changes in the output voltage and temperature changes of the thermal resistance element.
- the gas sensor 1 includes a thermal resistance element 2, a gas molecule adsorbing material 3, a base member 4, and an outer case 5.
- the gas sensor 1 is a humidity sensor that detects water vapor gas (water molecules) in the atmosphere.
- the scale of each member is appropriately changed.
- the thermal resistance element 2 is a thin film thermistor and is a thermal resistance element for detection.
- a substrate 21, a conductive layer 22 formed on the substrate 21, a thin film element layer 23, and a protective insulating layer 24 are provided.
- the substrate 21 has a substantially rectangular shape, and is formed using a material such as insulating ceramics such as alumina, aluminum nitride, zirconia, or semiconductor silicon, germanium. On one surface of the substrate 21, an insulating thin film is formed by sputtering.
- the conductive layer 22 constitutes a wiring pattern and is formed on the substrate 21.
- the conductive layer 22 is formed by depositing a metal thin film by a sputtering method.
- the metal material includes noble metals such as platinum (Pt), gold (Au), silver (Ag), palladium (Pd), and the like. These alloys such as an Ag—Pd alloy are applied.
- the thin film element layer 23 is a thermistor composition and is composed of an oxide semiconductor having a negative temperature coefficient.
- the thin film element layer 23 is formed on the conductive layer 22 by a sputtering method and is electrically connected to the conductive layer 22.
- electrode portions 22 a electrically connected to the conductive layer 22 are formed at both ends of the substrate 21.
- the thin film element layer 23 is made of, for example, two or more elements selected from transition metal elements such as manganese (Mn), nickel (Ni), cobalt (Co), and iron (Fe). .
- the protective insulating layer 24 is formed so as to cover the thin film element layer 23 and the conductive layer 22.
- a lead wire 22b is connected to the electrode portion 22a by soldering or the like.
- the thermal resistance element is not limited to a thin film thermistor, and may be a thin film platinum resistance element.
- the thermistor element comprised with semiconductors, such as metal wires, such as a platinum wire and its alloy wire, metal oxide, silicide, nitride, may be sufficient.
- it may be composed of a thermocouple or a thermocouple element such as a thermopile in which a plurality of thermocouples are connected in series, and the thermosensitive resistance element is not limited to a particular one.
- a gas molecule adsorbing material 3 is thermally coupled to the thermosensitive resistance element 2 configured as described above. Specifically, the gas molecule adsorbing material 3 is held on the other surface side (back surface side) of the substrate 21 via an adhesive layer 31 such as a silicone adhesive having a heat resistance of about 200 ° C. Therefore, the thermosensitive resistance element 2 and the gas molecule adsorbing material 3 are thermally coupled via the substrate 21. That is, heat is conducted between the thermosensitive resistance element 2 and the gas molecule adsorbing material 3. Note that an inorganic or organic adhesive is appropriately used for the adhesive layer 31.
- the gas molecule adsorbing material 3 is a porous adsorbing material. For example, A-type zeolite molecular sieve 3A (pore diameter 0.3 nm) is used.
- the finely pulverized powder is placed in an electric furnace and heat treated at about 650 ° C. for 1 hour to remove the adsorbed gas molecules. Formed.
- the powdery gas molecule adsorbing material 3 is uniformly applied to the adhesive layer 31.
- the powdery gas molecule adsorbing material 3 is preferably applied by electrostatic powder coating.
- the gas molecule adsorbing material 3 is applied to the adhesive layer 31, it is not heat-treated at a high temperature during the application. Therefore, when the lead wire 22b is connected by soldering or the like, the solder melts when heated to a high temperature of 200 ° C. or higher, but since it is not heat-treated at the time of application, melting of the solder can be avoided.
- the gas molecule adsorbing material 3 is directly applied to the substrate 21 by heat treatment without providing the adhesive layer 31, the thriller-like gas molecule adsorbing material 3 is used in the process before soldering the lead wires 22 b and the like. May be formed on the back side of the substrate 21.
- molecular sieves 4A, 5A, 13X, high silica type zeolite, silver zeolite substituted with metal ions, or a porous metal complex can be used according to the detection target gas.
- the base member 4 is a metal member formed in a substantially disk shape, and the conductive terminal portion 42 is inserted through the insulating member 41.
- a lead wire 22b led out from the thermal resistance element 2 is electrically connected to the conductive terminal portion 42 by welding, soldering or the like.
- the insulating member 41 is made of an insulating material such as glass or resin.
- the base member 4 is formed of an insulating material, the insulating member 41 can be omitted. Further, the conductive terminal portion 42 may be formed of a printed wiring board or the like.
- the outer case 5 is a metal member having a good thermal conductivity formed in a substantially cylindrical shape, and has a circular opening 52 in which one end side is opened and a ventilation part 51 is provided on the other end side. Has been.
- the outer case 5 is attached to the base member 4 at one end side and has a function of covering and protecting the thermal resistance element 2.
- the ventilation portion 51 is formed of a gas-permeable member that reduces the influence of outside wind and allows gas to flow in and out, and is preferably made of a material such as a wire mesh, a nonwoven fabric, and a porous sponge.
- the ventilation part 51 is provided by being press-fitted or adhered to the inner peripheral side of the outer case 5. Further, the ventilation part 51 is not limited to the case provided in the outer case 5. It may be provided on the base member 4, or a gap may be formed between the exterior case 5 and the base member 4 so as to be provided at this portion.
- the outer case 5 can be formed of ceramic or resin material. In this case, metal plating or the like may be performed so that the inner wall surface of the outer case 5 has a function of reflecting infrared rays.
- the gas detection apparatus 10 is configured by connecting a power source (voltage source) E to the gas sensor 1.
- a power source voltage source
- the resistor 11 and the gas sensor 1 are connected in series with the power source E, and the output terminal is connected between the resistor 11 and the thermal resistance element 2, and the resistor 11 Is detected as the output voltage Vout.
- the resistor 11 is a resistor for voltage detection and overcurrent protection.
- the gas detection apparatus 10 is configured such that a microcomputer (hereinafter referred to as a “microcomputer”) 12 serving as a control unit executes overall control.
- the microcomputer 12 generally includes a CPU 13 having a calculation unit and a control unit, a ROM 14 and a RAM 15 that are storage units, and an input / output control unit 16.
- a power supply circuit 17 is connected to the input / output control means 16. Further, the circuit shown in FIG. 2 is connected to the power supply circuit 17.
- the power supply circuit 17 includes the power supply E, and has a function of changing the voltage of the power supply E and controlling the supply of power to the thermal resistance element 2. Specifically, the supply power of the power supply E in the power supply circuit 17 is controlled by a program stored in the storage means of the microcomputer 12. Further, the output voltage Vout is input to the microcomputer 12, is subjected to arithmetic processing, and is output as a detection output.
- the control of the power supplied from the power supply E is executed by, for example, a means constituted by the microcomputer 12 and the power supply circuit 17, that is, a power supply control unit.
- the power supply control unit only needs to have a function of controlling the power supplied from the power source E, and is not limited to a particular member or part.
- the power supply E of the power supply circuit 17 is applied to the thermal resistance element 2 as a constant voltage of 7V in accordance with an output signal from the microcomputer 12 for 30 seconds.
- the power source E is applied to the thermal resistance element 2 as a constant voltage of 3 V for 30 seconds.
- This state is a state in which power supply is controlled so that the thermal resistance element 2 is cooled. That is, the thermal resistance element 2 is controlled to shift from the heating process to the cooling process.
- the thermosensitive resistance element 2 can be self-heated by energization.
- the applied voltage in the heating process and the cooling process can be selected as appropriate. For example, the applied voltage in the cooling process may be 0 V, and the heating state is changed to a cooling state lower than the heating temperature. That's fine.
- the porous gas molecule adsorbing material 3 is an A-type zeolite molecular sieve 3A (pore diameter 0.3 nm).
- This gas molecule adsorbing material 3 produces a molecular sieving effect and adsorbs only molecules whose molecular diameter is smaller than the diameter of the pores. Therefore, hydrogen (H 2 ), helium (He), water vapor (water molecule) (H 2 O) and ammonia (NH 3 ) in the atmosphere are adsorbed, but the amount other than water vapor (H 2 O) is extremely small. Little effect on adsorption reaction. For this reason, water vapor (H 2 O) can be selectively adsorbed, and the selectivity of the detection target gas is enhanced.
- the gas molecule adsorbing material 3 has a characteristic that an exothermic reaction occurs when molecules are adsorbed and an endothermic reaction occurs when the molecules are desorbed. Therefore, the gas molecule adsorbing material 3 acts to generate heat when adsorbing water vapor (H 2 O) and to absorb heat when desorbing water vapor (H 2 O). That is, when heating the gas molecules adsorbing material 3 to separated water vapor (H 2 O) de absorbs heat, and cooled to heating the adsorbing water vapor (H 2 O).
- FIG. 4 shows the result of the change in the output voltage Vout in the power supply control as described above.
- the horizontal axis represents time (seconds), and the vertical axis represents output voltage (V).
- the solid line indicates the change in the output voltage Vout when the humidity is 0% RH, and the broken line indicates the change in the output voltage Vout when the humidity is 70% RH.
- FIG. 5 shows the temperature change of the thermal resistance element 2, the horizontal axis shows time (second), and the vertical axis shows temperature (° C.).
- the solid line indicates the temperature change when the humidity is 0% RH, and the broken line indicates the temperature change when the humidity is 70% RH.
- a temperature difference occurs in the first half of the heating process and the cooling process.
- the gas molecule adsorbing material 3 has an endothermic reaction due to the desorption of water vapor (H 2 O), and therefore the temperature of the thermal resistance element 2 when the humidity is 70% RH is higher than that when the humidity is 0% RH. Lower.
- water vapor (H 2 O) is adsorbed and an exothermic reaction occurs, so the temperature of the thermal resistance element 2 when the humidity is 70% RH is higher than when the humidity is 0% RH.
- heating is started and becomes stable at a temperature of about 170 ° C.
- cooling is started and becomes stable at a temperature of about 55 ° C.
- a temperature change due to desorption and adsorption of water vapor gas (water molecules) to the gas molecule adsorbing material 3 can be captured in a cycle of heating process and cooling process for 30 seconds.
- the heating process and the cooling process may be repeated multiple times.
- the gas detection device 10 generally detects the humidity in the atmosphere as follows.
- the storage means of the microcomputer 12 stores and stores a change pattern of the output voltage Vout and / or a temperature change pattern when the humidity is 0% RH as shown in FIGS. Based on this pattern.
- the microcomputer 12 When detecting the humidity in the atmosphere, for example, 70% RH, water vapor (H 2 O) flows in and out through the vent 51 by the heating process and the cooling process, and is desorbed and adsorbed on the gas molecule adsorbing material 3. 4 and the pattern of the change of the output voltage Vout and / or the temperature change shown in FIG.
- the microcomputer 12 performs an operation of comparing and calculating this pattern and a reference pattern of humidity 0% RH stored in advance in the storage means. Next, the microcomputer 12 calculates and outputs the humidity 70% RH from the difference in the output voltage Vout and / or the temperature change.
- the present embodiment has a heating process (heating step) for heating the gas molecule adsorbing material 3 and a cooling process (cooling step) for cooling the gas molecule adsorbing material 3 at a temperature lower than the heating process.
- a specific gas concentration is detected by comparing a reference temperature change pattern with a temperature change pattern of a gas to be detected.
- the gas concentration may be detected from a temperature change in at least one of the heating process and the cooling process, that is, a change in the output voltage Vout and / or a difference in the temperature change.
- FIG. 6 is a cross-sectional view showing the gas sensor
- FIG. 7 is a connection diagram for detecting characteristics of the gas detection device
- FIG. 8 is a block configuration diagram showing the gas detection device.
- FIG. 9 shows the change in the output voltage
- FIGS. 10 and 11 are graphs showing the voltage difference and temperature difference between the detection thermal resistance element and the compensation thermal resistance element.
- FIG. 12 is a graph showing the correlation between absolute humidity and temperature difference in a low temperature environment.
- FIG. 13 is a graph showing changes in characteristics with respect to ethanol (C 2 H 6 O).
- symbol is attached
- the gas sensor 1 of the present embodiment is a humidity sensor that detects water vapor gas (water molecules) in the atmosphere, and includes a pair of thermal resistance elements. That is, the detection thermal resistance element 2 and the compensation thermal resistance element 2 a are provided so as to be covered with the outer case 5.
- the gas molecule adsorbing materials 3 and 3a are applied to the back side of the substrate 21 of the detection thermal resistance element 2 and the compensation thermal resistance element 2a.
- the detection thermal resistance element 2 and the compensation thermal resistance element 2a have basically the same configuration, but the configuration of the gas molecule adsorbing material 3a provided in the compensation thermal resistance element 2a is different.
- the gas molecule adsorbing material 3a is a material having an adsorptivity different from that of the porous gas molecule adsorbing material 3, and an inactivated molecular sieve 3A of zeolite A is used.
- the deactivated molecular sieve 3A has a crystal structure obtained by heat-treating a powdery body formed by removing adsorbed gas molecules at a temperature of about 850 ° C. for several hours. It is made by destroying.
- the deactivated molecular sieve 3A hardly adsorbs water vapor gas, but has the same physical properties as the molecular sieve 3A provided in the detection thermal resistance element 2, and therefore has the same thermal properties.
- the heat capacity is almost the same, and good temperature compensation can be expected.
- a power source (voltage source) E is connected to the gas sensor 1 to form a bridge circuit.
- a series circuit of the detection thermal resistance element 2 and the detection resistor 11 and a series circuit of the compensation thermal resistance element 2a and the compensation resistor 11a are connected in parallel to the power source E.
- an output terminal is connected in the middle of each series circuit so that the differential output can be detected as the output voltages Vout1 and Vout2. Therefore, a minute signal can be detected.
- the gas detection apparatus 10 includes a microcomputer 12 and a power supply circuit 17 as in the first embodiment, and the power supply circuit 17 is connected to the circuit shown in FIG.
- the power supply circuit 17 includes the power supply E, and controls the supply of power to the thermal resistor 2 by changing the voltage of the power supply E.
- the supply power of the power supply E in the power supply circuit 17 is controlled by a program stored in the storage means of the microcomputer 12.
- the output voltages Vout1 and Vout2 are input to the microcomputer 12, are subjected to arithmetic processing, and are output as detection outputs.
- control of the power supply of the power supply E is performed by the power supply control part comprised by the microcomputer 12 or the power supply circuit 17, for example.
- the power supply E of the power supply circuit 17 is set to a constant voltage of 7 V according to the output signal from the microcomputer 12, and the detection thermal resistance element 2 and the compensation thermal resistance element 30 seconds. Apply to 2a.
- power is supplied and controlled so that the detection thermal resistance element 2 and the compensation thermal resistance element 2a are heated.
- the power source E is applied as a constant voltage of 3V to the detection thermal resistance element 2 and the compensation thermal resistance element 2a for 30 seconds.
- power is supplied and controlled so that the detection thermal resistance element 2 and the compensation thermal resistance element 2a are cooled. That is, the detection thermal resistance element 2 and the compensation thermal resistance element 2a are controlled to shift from the heating process to the cooling process.
- the heating process and the cooling process may be repeated a plurality of times at regular intervals.
- FIG. 9 shows the results of changes in the output voltages Vout1 and Vout2 in the power supply control as described above.
- the horizontal axis represents time (seconds)
- the vertical axis represents output voltage (V)
- the voltage across the detection resistor 11 in series with the element 2 is shown.
- FIG. 9 it can be seen that there is a voltage difference between the compensating thermal resistance element 2a side and the sensing thermal resistance element 2 side in the first half of the heating and cooling processes.
- this voltage difference becomes large because water vapor (H 2 O) is desorbed from the gas molecule adsorbing material 3 in the heating process and an endothermic reaction occurs, and in the cooling process, the water vapor (H 2 O) is increased. Adsorbs and becomes exothermic, resulting in an increase.
- a temperature difference is generated between the compensation thermal resistance element 2a and the detection thermal resistance element 2 so as to correspond to this voltage difference.
- the gas detection device 10 generally detects the humidity in the atmosphere as follows.
- the output voltages Vout1 and Vout2 are input to the microcomputer 12 and are processed to detect humidity as a detection output.
- a voltage difference (temperature difference) is generated between the detection thermal resistance element 2 and the reference compensation thermal resistance element 2a. Based on this voltage difference (temperature difference), the microcomputer 12 calculates and outputs a humidity of 70% RH.
- FIG. 13 is a graph confirming the influence on a gas other than the detection target gas.
- FIG. 13 shows a change in characteristics with respect to ethanol (C 2 H 6 O).
- the horizontal axis indicates the concentration (%) of ethanol (C 2 H 6 O), and the vertical axis indicates the temperature difference (° C.) in the cooling process.
- Little change in the temperature difference with respect to the concentration of ethanol (C 2 H 6 O) is not also can be seen that no effect on the high concentration of ethanol near the explosion limit (C 2 H 6 O). Therefore, it is possible to obtain a gas detection device with high detection accuracy.
- the present embodiment has a heating process (heating step) for heating the gas molecule adsorbing material 3 and a cooling process (cooling step) for cooling at a lower temperature than this heating process, and the detection thermal resistance.
- the concentration of a specific gas is detected based on a temperature difference due to a temperature change (voltage change) between the element 2 and the compensating thermosensitive resistance element 2a.
- the temperature change in both the heating process and the cooling process that is, the gas concentration may be detected from the temperature difference, or at least in one of the heating process and the cooling process. You may make it detect the density
- FIG. 14 shows a change in the output voltage
- FIG. 15 is a graph showing a voltage difference between the detection thermal resistance element and the compensation thermal resistance element
- FIG. 16 is a graph showing a voltage difference between the sensing thermal resistance element and the compensating thermal resistance element when the heating process and the cooling process are repeated at regular intervals
- FIG. 17 shows a change in the heating temperature during the heating process. It is a graph which shows the voltage difference of the heat sensitive resistive element for a detection, and the heat sensitive resistive element for a compensation in the case of.
- the description which overlaps about the same or equivalent part as 1st Embodiment and 2nd Embodiment is abbreviate
- the detection target gas is hydrogen (H 2 ).
- the gas detection device is applied to a hydrogen station or a fuel cell vehicle in an environment where a predetermined amount of hydrogen (H 2 ) may exist.
- the gas detection device has the same configuration as that shown in FIGS. 6 to 8 described in the second embodiment. Accordingly, the detailed configuration and operation of the gas detection device have been described above and will not be described.
- the power supply E of the power supply circuit 17 is applied as a constant voltage of 7V to the detection thermal resistance element 2 and the compensation thermal resistance element 2a for 10 seconds.
- This state is a heating process.
- the power source E is applied as a constant voltage of 3V to the detection thermal resistance element 2 and the compensation thermal resistance element 2a for 10 seconds.
- This state is a cooling process. That is, the detection thermal resistance element 2 and the compensation thermal resistance element 2a are controlled to shift from the heating process to the cooling process.
- FIG. 14 (corresponding to FIG. 9) shows the results of changes in the output voltages Vout1 and Vout2 when hydrogen (H 2 ) is 1% in the power supply control as described above.
- FIG. 14 it can be seen that there is a voltage difference between the compensation thermal resistance element 2a side and the detection thermal resistance element 2 side in the first half of the heating process.
- FIG. 15 shows this voltage difference.
- the voltage of the sensing thermal resistance element 2 is lower than the voltage of the compensation thermal resistance element 2a in the heating process, and the compensation thermal resistance element in the cooling process.
- the voltage of the detection thermal resistance element 2 is slightly higher than the voltage 2a.
- the detection target gas is hydrogen (H 2 )
- the relationship is opposite to that of water vapor (H 2 O).
- Water vapor (H 2 O) is an endothermic reaction when the gas molecules are desorbed from the gas molecule adsorbing material 3 in the heating process, and an exothermic reaction occurs when the gas molecules are adsorbed on the gas molecule adsorbing material 3 in the cooling process.
- hydrogen (H 2 ) the desorption of gas molecules from the gas molecule adsorbing material 3 during the heating process is an exothermic reaction, and the adsorption of gas molecules to the gas molecule adsorbing material 3 during the cooling process is performed. A slight endothermic reaction occurs.
- the output voltages Vout1 and Vout2 are input to the microcomputer 12 and are subjected to arithmetic processing to detect hydrogen (H 2 ) as a detection output.
- a voltage difference occurs between the detection thermal resistance element 2 and the reference thermal resistance element 2a. Based on the voltage difference (temperature difference) in the heating process and the cooling process, the microcomputer 12 calculates and outputs a hydrogen (H 2 ) concentration.
- the detection target gas is hydrogen (H 2 )
- a voltage difference temperature difference
- the gas concentration can be detected based on at least the temperature change in the heating process, that is, the temperature difference.
- the heating process and the cooling process may be repeated multiple times at regular intervals. By detecting the voltage difference of this cycle, improvement in the accuracy of gas detection can be expected.
- FIG. 17 shows a voltage difference between the detection thermal resistance element 2 and the compensation thermal resistance element 2a when the heating voltage (temperature) in the heating process is changed.
- the cooling voltage (temperature) in the cooling process is kept constant at 3 V and applied for 30 seconds.
- the heating voltage was changed to 6V, 6.5V, and 7V and applied for 30 seconds each.
- the temperature of the detection thermal resistance element 2 is 138 ° C. when the heating voltage is 6V, 154 ° C. when the heating voltage is 6.5V, and 168 ° C. when the heating voltage is 7V.
- the heating temperature and the heating rate change. For example, when the heating voltage is 7V, it can be seen that the peak voltage of the voltage difference appears earlier. Furthermore, the output voltage tends to increase as the heating temperature increases. Therefore, in the case of hydrogen (H 2 ), it is suggested that the sensitivity can be easily increased by increasing the heating temperature.
- H 2 hydrogen
- This characteristic is thought to be because the moving speed of gas molecules differs depending on the molecule. Using this characteristic, it is possible to selectively detect a specific gas by setting the heating time and cooling time in the heating process and the cooling process, or by setting the heating temperature and the cooling temperature, The selectivity of the detection target gas can be increased.
- the information on the gas molecules to be detected can be selectively obtained by changing the time of one cycle of the heating process and the cooling process and the time of at least one of the heating process and the cooling process.
- the heating temperature in the heating process it has been confirmed that there is an optimum temperature for realizing high sensitivity.
- the preferred heating temperature is 150 ° C. to 170 ° C.
- the optimum temperature is 160 ° C. Beyond this, the sensitivity will decrease. This is because, in the case of water vapor (H 2 O), the adsorption capacity of zeolite decreases as the temperature increases. This suggests that the optimum temperature differs depending on the molecule.
- FIG. 18 is a cross-sectional view showing the gas sensor
- FIGS. 19 and 20 are graphs showing the output voltage and temperature change of the detection thermal resistance element.
- symbol is attached
- the gas sensor 1 of the present embodiment is a sensor that detects carbon dioxide (CO 2 ) in the atmosphere, and is a surface-mount type that includes a pair of thermal resistance elements.
- the gas sensor 1 includes a mounting board 6, a detection thermal resistance element 2 and a compensation thermal resistance element 2 a disposed on the mounting board 6, and an exterior covering the detection thermal resistance element 2 and the compensation thermal resistance element 2 a.
- a case 5 a ventilation portion 51, an insulating base member 4, and conductive terminal portions 42 provided on both sides of the base member 4 are provided.
- the mounting board 6 is, for example, a flexible wiring board (FPC) having flexibility.
- the conductive terminal portion 42 has a substantially U-shaped cross section, and electrically connects the terminal portion formed on the mounting substrate 6 and the terminal portion formed on the circuit substrate 7 to detect the thermal resistor for detection. This is a member for connecting the element 2 and the compensating thermosensitive resistance element 2 a to the wiring pattern formed on the circuit board 7.
- the detection thermal resistance element 2 and the compensation thermal resistance element 2a are substantially the same as those described in the first embodiment (see FIG. 1).
- the detection thermal resistance element 2 and the compensation thermal resistance element 2a are mounted on the mounting substrate 6 in a face-down manner. Further, gas molecule adsorbing materials 3 and 3a are thermally coupled to the detection thermal resistance element 2 and the compensation thermal resistance element 2a.
- the detection thermal resistance element 2 and the compensation thermal resistance element 2a have basically the same configuration, but the gas molecule adsorption materials 3, 3a provided in the detection thermal resistance element 2 and the compensation thermal resistance element 2a are the same.
- the configuration is different. That is, the porous gas molecule adsorbing material 3 provided in the detection heat-sensitive resistance element 2 and the gas molecule adsorbing material 3a provided in the compensation heat-sensitive resistance element 2a are formed of materials having different adsorptivity.
- the gas molecule adsorbing material 3 provided in the detection thermosensitive resistance element 2 is a molecular sieve 4A (pore diameter 0.4 nm), and the gas molecule adsorbing material 3 provided in the compensating thermosensitive resistance element 2a. Is molecular sieve 3A (pore diameter 0.3 nm).
- the molecular sieve 4A and the molecular sieve 3A have the property of similarly adsorbing hydrogen (H 2 ), helium (He), water vapor (H 2 O), and ammonia (NH 3 ) in the atmosphere. Therefore, this gas sensor 1 becomes insensitive to four types of gas molecules, hydrogen (H 2 ), helium (He), water vapor (H 2 O), and ammonia (NH 3 ). On the other hand, it has sensitivity to gas molecules that can be adsorbed by the molecular sieve 4A other than the above four types.
- the gas sensor 1 hydrogen sulfide (H 2 S), carbon dioxide (CO 2 ), ethane (C 2 H 6 ), ethanol (C 2 H 6 O), propylene (C 3 H 6 ), A sensor that can detect gas molecules such as butadiene (C 4 H 6 ) in a limited manner. Among these gas molecules, carbon dioxide (CO 2 ) is contained in the atmosphere. Therefore, the gas sensor 1 effectively functions as a gas sensor that detects carbon dioxide (CO 2 ) in the atmosphere.
- the gas sensor 1 is connected as shown in FIGS. 7 and 8 described in the second embodiment, and is similarly configured as the gas detection device 10. Therefore, the detailed operation has been already described and will be omitted.
- the power supply E of the power supply circuit 17 is applied to the detection thermal resistance element 2a and the compensation thermal resistance element 2a as a constant voltage of 6.5V for 30 seconds. Then, the heating process is performed, and then the power source E is applied to the detection thermal resistance element 2 and the compensation thermal resistance element 2a as a constant voltage of 3 V for 30 seconds to perform the cooling process.
- the heating process and the cooling process may be repeated a plurality of times at regular intervals.
- 19 and 20 show the output voltage Vout1 and the temperature change of the detection thermal resistance element 2, and the concentration of carbon dioxide (CO 2 ) is 0%, 4.4%, 12.9% and 26.6. The change in the case of% is shown.
- the voltage of the detection thermal resistance element 2 with respect to the voltage Vout2 of the compensation thermal resistance element 2a (corresponding to the voltage of the detection thermal resistance element 2 having a concentration of 0%).
- Vout1 is low, and in the cooling process, the voltage of the detection thermal resistance element 2 is slightly higher than the voltage of the compensation thermal resistance element 2a.
- the detection target gas is carbon dioxide (CO 2 )
- the relationship is opposite to that of water vapor (H 2 O), as is the case with hydrogen (H 2 ).
- CO 2 carbon dioxide
- the desorption of gas molecules from the gas molecule adsorption material 3 in the heating process is an exothermic reaction, and the adsorption of gas molecules to the gas molecule adsorption material 3 in the cooling process is extremely high. A slight endothermic reaction is considered to have occurred.
- a temperature change occurs in the detection thermal resistor 2 so as to correspond to the change in the output voltage Vout1.
- the gas detection apparatus 10 receives the output voltages Vout1 and Vout2 to the microcomputer 12, and performs arithmetic processing based on this temperature difference to detect the concentration of carbon dioxide (CO 2 ) as a detection output.
- the gas sensor 1 shown in FIG. 21 is a prototype gas sensor.
- the heat-sensitive resistance element 2 is formed by winding a metal wire such as platinum of 10 ⁇ m to 60 ⁇ m and its alloy wire in a coil shape.
- a gas molecule adsorbing material 3 is thermally coupled to the thermosensitive resistance element 2. Specifically, the gas molecule adsorbing material 3 is applied so as to surround at least a part of the thermosensitive resistance element 2 of a metal wire.
- the molecular sieve 3A is finely pulverized by a vibration mill, and then this finely pulverized powder is put in an electric furnace and heat-treated at about 650 ° C. for 1 hour to adsorb gas molecules. Remove. Aluminum hydroxide is added to 10% by weight of the adsorbed gas molecules removed, and the mixture is further pulverized and mixed by a vibration mill. Then, water and glycerin are added to form a slurry of the gas-phase adsorbing material 3 in paste form. Make it.
- both ends of the metal wire thermal resistance element 2 are fixed to the conductive terminal portion 42 by spot welding, and after applying the gas molecule adsorbing material 3 to the thermal resistance element 2 and drying, a voltage is applied to the thermal resistance element 2.
- the thermal resistance element 2 is heated and heat-treated at about 650 ° C. for 2 hours. In this way, the gas molecule adsorbing material 3 is provided on the thermosensitive resistance element 2.
- the gas sensor 1 shown in FIG. 22 has basically the same configuration as the gas sensor described in the first embodiment (see FIG. 1). The difference is that, in the present embodiment, as in the first embodiment, the thermal resistance element 2 is formed by winding a metal wire such as platinum of 10 ⁇ m to 60 ⁇ m and its alloy wire in a coil shape. A gas molecule adsorbing material 3 is provided on the metal wire. (Example 3)
- the gas sensor 1 shown in FIG. 23 has basically the same configuration as the gas sensor described in the second embodiment (see FIG. 6). The difference is that, in this example, as in Example 1, the thermosensitive resistance element 2 for detection was formed by winding a metal wire such as platinum of 10 ⁇ m to 60 ⁇ m and its alloy wire in a coil shape, A gas molecule adsorbing material 3 is provided on the metal wire.
- the thermosensitive resistance element 2 for detection was formed by winding a metal wire such as platinum of 10 ⁇ m to 60 ⁇ m and its alloy wire in a coil shape, A gas molecule adsorbing material 3 is provided on the metal wire.
- the compensation heat-sensitive resistance element 2a like the detection heat-sensitive resistance element 2, is formed by winding a metal wire in a coil shape, but the gas molecule adsorbing material 3a is inactivated.
- A-type zeolite molecular sieve 3A is used.
- the deactivated molecular sieve 3A is produced by further heat-treating the slurry of the paste-like gas molecule adsorbing material 3 described in Example 1 at a temperature of about 850 ° C. for several hours to destroy the crystal structure. .
- This inactivated molecular sieve 3A hardly adsorbs gas. Since it has the same physical properties as the molecular sieve 3A provided in the detection heat-sensitive resistance element 2, the thermal properties are the same, the heat capacity is substantially the same, and good temperature compensation can be expected. (Example 4)
- the gas sensor 1 shown in FIG. 24 is the same as the gas sensor shown in the third embodiment, in which the compensation thermal resistance element 2a side is hermetically sealed by the exterior case 5, and the compensation thermal resistance element 2a is accommodated in the sealed space S. .
- the detection thermal resistance element 2 side and the compensation thermal resistance element 2a side can have substantially the same configuration. That is, it has the same adsorptivity and physical properties as the gas molecule adsorbing material 3 provided in the sensing thermal resistance element 2 without inactivating the gas molecule adsorbing material 3a provided in the compensating thermosensitive resistance element 2a. can do.
- the detection thermal resistance element 2 side and the compensation thermal resistance element 2a side have substantially the same heat capacity, and good temperature compensation can be realized.
- the detection thermal resistance element 2 and the compensation thermal resistance element 2a may use thin film thermistors and are not limited to specific ones. (Example 5)
- the gas sensor 1 shown in FIG. 25 has basically the same configuration as the gas sensor described in the first embodiment (see FIG. 1).
- the configuration of the thermal resistance element 2 is different.
- the thermosensitive resistance element 2 of this example is a thermistor element having a thermistor composition 23 and a platinum wire lead 22 b embedded in the thermistor composition 23.
- the thermistor composition 23 is composed of an oxide thermistor material containing a composite metal oxide as a main component. Further, the gas molecule adsorbing material 3 is applied and provided so as to surround the thermistor composition 23.
- the gas molecule adsorbing material 3 is formed in the same process as the production of the gas molecule adsorbing material 3 described in the first embodiment.
- the thermistor composition 23 can be provided. Since this sensor can withstand heating at 800 ° C., when detecting hydrogen (H 2 ), it becomes a high-sensitivity sensor and can be detected even at a low concentration of about 1 ppm. (Example 6)
- the gas sensor 1 shown in FIG. 26 is a gas sensor having a MEMS structure.
- the MEMS chip constituting the thermosensitive resistance element 2 is configured by providing a thermopile 23 in which a self-heatable thermocouple is connected in series to an insulating film 21 b formed on a cavity 21 a of a silicon (Si) substrate 21. ing. Further, the gas molecule adsorbing material 3 is provided through the insulating film 21c.
- the gas sensor 1 having such a MEMS structure can realize a sensor with further reduced power consumption and good response. Ideal for use in battery-powered gas detectors.
- Example 1 Another embodiment of the characteristic detection connection diagram in the gas detection device will be described with reference to FIGS.
- symbol is attached
- Example 1 the same code
- a power source (voltage source) E is connected to the gas sensor 1 to form a bridge circuit.
- a differential output between the output voltages Vout1 and Vout2 can be detected, which is the same as the connection diagram shown in FIG. 7 of the second embodiment.
- the series circuit of the detection thermal resistance element 2 and the compensation thermal resistance element 2a and the series circuit of the resistor 11 and the variable resistor 11a are connected in parallel to the power source E via the overcurrent protection resistor 11b. .
- variable resistor 11a has a function of adjusting the bridge balance when the resistance values of the detection thermal resistance element 2 and the compensation thermal resistance element 2a vary.
- a power supply (voltage source) E is connected to the gas sensor 1 to form a full bridge circuit.
- a differential output between the output voltages Vout1 and Vout2 can be detected.
- the series circuit of the detection thermal resistance element 2-1 and the compensation thermal resistance element 2a-1 and the series circuit of the compensation thermal resistance element 2a-2 and the detection thermal resistance element 2-2 are overcurrent with respect to the power source E. They are connected in parallel via the protective resistor 11b. By configuring the full bridge circuit in this way, the output can be doubled, which is effective in detecting a very small amount of gas molecules. (Example 3)
- the gas detection device 10 is provided with a heating element 8 for heating the heat-sensitive resistance element 2 and the gas molecule adsorbing material 3.
- the heating element 8 is controlled by a heater control circuit 9 so that a heating pattern can be arbitrarily set.
- the heating control can function effectively.
- FIG. 29B is a cross-sectional view corresponding to FIG. 1B in the first embodiment.
- the gas molecule adsorbing material 3 is provided on the protective insulating layer 24, and the heating element 8 is provided on the back side of the substrate 21. (Example 4)
- an AC power source (voltage source) E is connected to the gas sensor 1 to form a bridge circuit.
- a differential output between the output voltages Vout1 and Vout2 can be detected.
- This differential output is connected to a differential amplifier Amp1, and further connected to an AC amplifier Amp2 via a capacitor C that cuts a DC component, and is output.
- the gas sensor 1 and the characteristic detection connection diagrams described in the above embodiments can be applied in any combination depending on the gas to be detected, the use of the gas detection device, and the like.
- porous metal complex can be used for the porous gas molecule adsorbing material.
- Porous metal complexes are a new group of substances that cross the boundary between organic and inorganic compounds by utilizing metal complexes. "Coordination polymers (especially porous coordination polymers with a nano-sized space, porous coordination polymer; PCP) or organic-metal framework (MOF)" are attracting attention as new materials. ing.
- each embodiment by having a heating process in which the porous gas molecule adsorbing material is at least in a heated state, gas molecules are desorbed and a specific gas is supplied based on the temperature change at that time. It can be detected. As a result, it is possible to improve the gas detection sensitivity at low temperatures and the gas selectivity of the gas to be detected, and to reduce power consumption. Therefore, it is possible to provide a gas sensor, a gas detection device, a gas detection method, and an apparatus including the gas detection device that have an effect of improving gas detection performance.
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Abstract
Description
このようなガス検出装置あっては、低温下でのガス検出感度や検出対象とするガスを選択するというガス選択性の向上が必要である。
請求項4に記載のガスセンサは、請求項3に記載のガスセンサにおいて、前記補償用感熱抵抗素子は、密閉空間に収容されていること特徴とする。
加熱素子は、通常の抵抗発熱体、間接的に加熱する赤外線ランプや赤外線レーザー等であってもよい。格別特定のものに限定されるものではない。
熱的性質は、例えば、熱伝導率や比熱等を意味している。
請求項10に記載のガス検出装置は、請求項1又は請求項3に記載のガスセンサと、
前記感熱抵抗素子に電力を供給制御して、加熱する電力供給制御部と、を具備することを特徴とする。
請求項13に記載のガス検出装置は、請求項12に記載のガス検出装置において、前記差動出力が接続される交流アンプを具備することを特徴とする。
請求項17に記載のガス検出装置を備えた装置は、請求項10乃至請求項13のいずれか一に記載されたガス検出装置が備えられていることを特徴とする。
ガス分子吸着材料3は、多孔性の吸着材料であり、例えば、A型ゼオライトのモレキュラーシーブ3A(細孔の直径0.3nm)が用いられている。
なお、電源Eの供給電力の制御は、例えば、マイコン12や電源回路17によって構成される電力供給制御部によって実行されるようになっている。
また、図11に示すように、この電圧差に対応するように補償用感熱抵抗素子2aと検知用感熱抵抗素子2との間に温度差が生じている。
ガス検出装置10は、マイコン12に出力電圧Vout1及びVout2が入力され、演算処理されて検出出力として水素(H2)を検出する。
このように加熱電圧を変えて、検出対象ガスに対して最適な加熱温度及び加熱速度(時間)を求めて設定値を決定することができる。
(実施例1)
(実施例2)
(実施例3)
(実施例4)
(実施例5)
このセンサは800℃の加熱に耐えられるので、水素(H2)を検知する場合には、高感度センサとなり、1ppm程度の低濃度でも検知可能となる。
(実施例6)
(実施例1)
(実施例2)
このようにフルブリッジ回路を構成することにより、出力を2倍にすることができ、微量のガス分子を検出する場合に有効である。
(実施例3)
(実施例4)
したがって、ガス検出性能を向上できる効果を有するガスセンサ、ガス検出装置、ガス検出方法及びガス検出装置を備えた装置を提供することができる。
2・・・検知用感熱抵抗素子
2a・・・補償用感熱抵抗素子
3・・・ガス分子吸着部材
3a・・・異なる吸着性を有する材料
4・・・ベース部材
5・・・外装ケース
8・・・加熱用素子
10・・・ガス検出装置
12・・・マイコン
17・・・電源回路
21・・・基板
22・・・導電層
23・・・薄膜素子層
31・・・接着層
42・・・導電端子部
51・・・通気部
S・・・密閉空間
Claims (17)
- 感熱抵抗素子と、
前記感熱抵抗素子と熱的に結合されるとともに、加熱により特定のガス分子が脱離される多孔性のガス分子吸着材料と、
を具備することを特徴とするガスセンサ。 - 感熱抵抗素子と、
前記感熱抵抗素子と熱的に結合されるとともに、加熱及び冷却により特定のガス分子が脱離及び吸着される多孔性のガス分子吸着材料と、
を具備することを特徴とするガスセンサ。 - 前記請求項1又は請求項2に記載のガスセンサにおいて、
補償用感熱抵抗素子と、
前記補償用感熱抵抗素子と熱的に結合された前記多孔性のガス分子吸着材料とは異なる吸着性を有する材料と、
を具備することを特徴とするガスセンサ。 - 前記補償用感熱抵抗素子は、密閉空間に収容されていること特徴とする請求項3に記載のガスセンサ。
- 前記感熱抵抗素子は、通電により自己加熱が可能であること特徴とする請求項1乃至請求項4のいずれか一に記載のガスセンサ。
- 前記感熱抵抗素子とは別に、前記多孔性のガス分子吸着材料を加熱する加熱素子が設けられていること特徴とする請求項1乃至請求項5のいずれか一に記載のガスセンサ。
- 前記多孔性のガス分子吸着材料は、ゼオライト又は多孔性金属錯体であることを特徴とする請求項1乃至請求項6のいずれか一に記載のガスセンサ。
- 前記多孔性のガス分子吸着材料とは異なる吸着性を有する材料は、多孔性のガス分子吸着材料を不活性化した材料であることを特徴とする請求項3乃至請求項7のいずれか一に記載のガスセンサ。
- 前記多孔性のガス分子吸着材料と、前記多孔性のガス分子吸着材料とは異なる吸着性を有する材料とは、熱的性質が同等であることを特徴とする請求項3乃至請求項8のいずれか一に記載のガスセンサ。
- 請求項1又は請求項3に記載のガスセンサと、
前記感熱抵抗素子に電力を供給制御して、加熱する電力供給制御部と、
を具備することを特徴とするガス検出装置。 - 請求項2又は請求項3に記載のガスセンサと、
前記感熱抵抗素子に電力を供給制御して、加熱及び冷却する電力供給制御部と、
を具備することを特徴とするガス検出装置。 - 前記ガスセンサは、ブリッジ回路によって接続されており、その差動出力によりガスを検出することを特徴とする請求項10又は請求項11に記載のガス検出装置。
- 前記差動出力が接続される交流アンプを具備することを特徴とする請求項12に記載のガス検出装置。
- 感熱抵抗素子と、この感熱抵抗素子と熱的に結合されるとともに、加熱により特定のガス分子が脱離される多孔性のガス分子吸着材料とを備えたガス検出方法であって、
前記多孔性のガス分子吸着材料を加熱状態とする加熱ステップと、
前記加熱による前記感熱抵抗素子の温度変化によって特定のガスを検出する検出ステップと、
を具備することを特徴とするガス検出方法。 - 感熱抵抗素子と、この感熱抵抗素子と熱的に結合されるとともに、加熱及び冷却により特定のガス分子が脱離及び吸着される多孔性のガス分子吸着材料とを備えたガス検出方法であって、
前記多孔性のガス分子吸着材料を加熱状態とする加熱ステップと、
前記多孔性のガス分子吸着材料を前記加熱ステップより低い温度の冷却状態とする冷却ステップと、
前記加熱及び冷却による前記感熱抵抗素子の温度変化によって特定のガスを検出する検出ステップと、
を具備することを特徴とするガス検出方法。 - 前記加熱ステップ及び冷却ステップは、一定間隔で繰り返し行われることを特徴とする請求項15に記載のガス検出方法。
- 請求項10乃至請求項13のいずれか一に記載されたガス検出装置が備えられていることを特徴とするガス検出装置を備えた装置。
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US20190049398A1 (en) | 2019-02-14 |
JPWO2017145889A1 (ja) | 2018-03-01 |
DE112017000920T5 (de) | 2018-11-29 |
CN108700534A (zh) | 2018-10-23 |
US11397160B2 (en) | 2022-07-26 |
JP6279818B2 (ja) | 2018-02-14 |
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