WO2005098405A1 - ガスセンサ用ヒータコイル、ガスセンサ用検知素子、接触燃焼式ガスセンサおよび接触燃焼式ガスセンサの製造方法 - Google Patents
ガスセンサ用ヒータコイル、ガスセンサ用検知素子、接触燃焼式ガスセンサおよび接触燃焼式ガスセンサの製造方法 Download PDFInfo
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- WO2005098405A1 WO2005098405A1 PCT/JP2005/005407 JP2005005407W WO2005098405A1 WO 2005098405 A1 WO2005098405 A1 WO 2005098405A1 JP 2005005407 W JP2005005407 W JP 2005005407W WO 2005098405 A1 WO2005098405 A1 WO 2005098405A1
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- Prior art keywords
- coil
- heater coil
- gas sensor
- wire
- wound
- Prior art date
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- 238000001514 detection method Methods 0.000 title claims abstract description 72
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- 230000000052 comparative effect Effects 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- OGSYQYXYGXIQFH-UHFFFAOYSA-N chromium molybdenum nickel Chemical compound [Cr].[Ni].[Mo] OGSYQYXYGXIQFH-UHFFFAOYSA-N 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/18—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor the conductor being embedded in an insulating material
-
- 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
- G01N27/16—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 burning or catalytic oxidation of surrounding material to be tested, e.g. of gas
-
- 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
Definitions
- Heater coil for gas sensor sensing element for gas sensor, contact combustion type gas sensor, and method of manufacturing contact combustion type gas sensor
- the present invention relates to a heater coil for a gas sensor, a sensing element for a gas sensor, a contact combustion type gas sensor, and a method for manufacturing a contact combustion type gas sensor.
- a catalytic combustion type gas sensor has been known as a sensor for detecting a combustible gas such as hydrogen gas or methane gas.
- the contact combustion type gas sensor heats a sensing element, in which a catalyst layer is carried on a heat conduction layer covering a heater coil, to a predetermined temperature, contacts a combustible gas to the catalyst layer and burns it.
- a sensing element in which a catalyst layer is carried on a heat conduction layer covering a heater coil, to a predetermined temperature, contacts a combustible gas to the catalyst layer and burns it.
- FIG. 18 is a cross-sectional view showing a configuration of a conventional sensing element
- FIG. 19 is a front view showing a configuration of a conventional heater coil.
- the conventional sensing element 1 has a configuration in which a heater coil 12 is embedded in a heat conductive layer 11 and a catalyst layer 13 is attached to the surface of the heat conductive layer 11.
- a portion embedded in the heat conductive layer 11 (hereinafter, referred to as a bead portion) is a single-turn coil in which a wire is wound in a coil shape (for example, See Patent Document 1.)
- the lead portion 15 which also increases both end forces of the bead portion 14, is not coiled.
- a portion of the sensing element where the bead portion of the heater coil is covered by the heat conduction layer and the catalyst layer is referred to as a combustion portion.
- a resistance wire is wound around a core wire, and an insulating agent is charged in that state.
- an insulating agent is charged in that state.
- a method of welding the electrode pins are known (e.g., see Patent Document 3.) 0 According to this method, it is possible to prevent the shape of the winding portion of the resistance wire from being broken when manufacturing the sensing element.
- Patent Document 1 Japanese Patent Application Laid-Open No. 3-162658 (FIG. 1)
- Patent Document 2 Japanese Patent Publication No. 2-59949 (Fig. 1)
- Patent Document 3 JP-A-52-116289
- the voltage output from the Wheatstone bridge circuit be stabilized in a short time as long as the gas concentration is the same.
- the shorter the time required to stabilize the output voltage the faster the response speed.
- embed the heater coil wire in the combustion part as long as possible so that the heater coil receives the combustion heat efficiently and the resistance change of the heater coil occurs efficiently.
- the bead portion of the heater coil becomes large, and accordingly, the amount of the heat conductive layer and the amount of the catalyst layer covering the bead portion also increase, so that the combustion portion becomes heavy.
- the sensing element is mounted inside the sensor by supporting the leads at both ends of the heater coil with electrode pins for external connection, so if the combustion part becomes heavy, the sensing element cannot be supported by the lead, Failures such as breakage of the lead portion are likely to occur.
- the gas sensitivity is improved and the response speed is increased without sacrificing the ability to support the sensing element at the lead portion of the heater coil. It is extremely difficult. Further, in the conventional contact combustion type gas sensor, since the lead portion of the heater coil has no shock absorbing ability, when an external force is applied, the impact is hardly alleviated and concentrates on the combustion portion. Therefore, there is a disadvantage that the catalyst layer is likely to be missing, and the adjusted zero point fluctuates greatly.
- the present inventors have replaced a conventional heater coil in which only the portion embedded in the combustion section is formed in a coil shape, and further wound a part of a coil wire in which a wire is wound in a coil shape. It is proposed to use a coiled coil as a heater coil. According to this proposal, the actual length of the wire constituting the heater coil becomes longer than before even if the dimensions of the appearance are the same as the conventional heater coil, so that the resistance of the heater coil increases and the gas sensitivity becomes lower. Get higher. Further, since the coiled coil portion of the heater coil is embedded in the combustion section, the length of the wire in the combustion section becomes longer than before, so that the resistance change of the heater coil occurs efficiently and the response speed increases.
- the present invention has been made in view of the above, and has a heater coil for a gas sensor capable of improving gas sensitivity without sacrificing the ability to support a detection element at a lead portion of the heater coil.
- a gas sensor heater coil capable of providing a gas sensor detection element and a contact combustion type gas sensor, or capable of achieving a high response speed without sacrificing the ability to support the detection element at a lead portion of the heater coil.
- An object of the present invention is to provide a detection element for a gas sensor and a contact combustion type gas sensor. Further, the present invention provides a gas sensor heater coil capable of reducing the amount of change of the zero point when an impact is applied, An object of the present invention is to provide a detection element for a gas sensor and a contact combustion type gas sensor.
- the present invention also provides a method for manufacturing a contact combustion type gas sensor that can easily handle a heater coil without breaking the shape of a winding portion of a heater coil having at least both ends wound in a coil shape.
- the purpose is to:
- Another object of the present invention is to provide a method for manufacturing a contact combustion type gas sensor capable of reducing variation in resistance value of a heater coil having at least both ends wound in a coil shape.
- Still another object of the present invention is to provide a method for manufacturing a contact combustion type gas sensor that can increase the bonding strength between a heater coil having at least both ends wound in a coil shape and an electrode pin.
- a heater coil for a gas sensor according to the invention of claim 1 is a heater coil used for a contact combustion type gas sensor, and a combustion heat generated at the time of gas combustion.
- the bead portion has a bead portion whose electrical characteristic value changes, and a lead portion in which both end forces of the bead portion also extend, and the bead portion is wound in a coil shape for an integer n of 2 or more (n — 1) It is characterized by comprising an n-fold wound coil in which a wire consisting of a double-turn coil is further wound in a coil shape.
- the sensing element using the heater coil by manufacturing the sensing element using the heater coil, even if the size of the burning portion of the sensing element is almost the same as that of the conventional device, the inside of the burning portion is formed.
- the effective length of the bead portion to be embedded is longer than when the bead portion is formed by a conventional single-turn coil. Therefore, since the resistance of the heater coil increases, the gas sensitivity of the contact combustion type gas sensor using the heater coil increases.
- the heater coil receives more combustion heat and causes a change in resistance efficiently, the contact combustion type gas sensor using the heater coil has a higher response speed. Further, since the size of the combustion part may be almost the same as the conventional one, the weight of the combustion part becomes almost the same as the conventional one. Therefore, by using this heater coil, it is possible to improve the gas sensitivity of the contact combustion type gas sensor and to increase the response speed without sacrificing the ability to support the sensing element at the lead portion.
- a gas sensor heater coil according to claim 2 is characterized in that, in the invention according to claim 1, the lead portion is configured by a (n-1) double-wound coil.
- the lead portion has the same configuration as that of the coil spring.
- the shock applied from the outside is absorbed by the spring elasticity of the lead portion. Therefore, since the impact transmitted to the combustion part is reduced, the catalyst layer is less likely to be lost, and the zero point of the contact combustion type gas sensor can be prevented from greatly fluctuating due to the impact.
- the heater coil for a gas sensor according to the invention of claim 3 is the invention according to claim 1 or 2, wherein the wire diameter of the non-coiled raw wire as a starting material is 1111 or more and 100111 or less. It is characterized by being.
- the wire diameter of the original wire is 1 ⁇ m or more, it is easy to manufacture a heater coil having a bead portion formed of a multi-turn coil.
- the diameter of the original wire is 100 m or less, the use of this heater coil provides a sensing element having a size suitable for use in a contact combustion type gas sensor.
- the heater coil for a gas sensor according to the invention of claim 4 is the invention according to claim 1 or 2, wherein the diameter of the non-coiled raw wire as a starting material is 10 111 or more and 50 111 or less. It is characterized by being.
- a power supply circuit having an appropriate voltage and current value can be used as a power supply circuit for driving a control circuit of the contact combustion type gas sensor.
- the use of an appropriate power supply circuit is important because the catalytic layer can be brought to an appropriate operating temperature when operating a catalytic combustion gas sensor.
- the heater coil for a gas sensor according to the invention of claim 5 is the invention according to claim 1 or 2, wherein the diameter of the non-coiled raw wire as a starting material is 20 111 or more and 30 111 or less. It is characterized by being.
- this heater coil by using this heater coil, a sensing element having a weight of about 1 mg in the combustion part can be obtained, so that the sensing element can be sufficiently supported by the lead portion of the heater coil. . Further, in the contact combustion type gas sensor using the heater coil, the impact strength is improved. Further, by using the heater coil, the bead portion of the heater coil is embedded at a higher density in the combustion portion of the detection element, so that the heater coil can receive more combustion heat. Thereby, the resistance change of the heater coil occurs more efficiently. Therefore, in the contact combustion type gas sensor using the heater coil, The response speed becomes faster. In addition, since the resistance of the heater coil is further increased, the power supply voltage can be further increased. Therefore, in the contact combustion type gas sensor using the heater coil, the gas sensitivity is further increased.
- the wire diameter of the base wire is smaller than 20 ⁇ m, the yield decreases when manufacturing the heater coil. Since the wire diameter of the base wire is 20 m or more, the heater coil can be easily manufactured. can do. That is, it is possible to manufacture a heater coil without lowering the yield, and by using the heater coil, it is possible to further improve the gas sensitivity and the response characteristics of the contact combustion type gas sensor. From the above, considering the gas sensitivity and response characteristics of the contact combustion type gas sensor and the easiness of manufacturing the heater coil, the wire diameter of the raw wire is optimally between 20 ⁇ m and 30 ⁇ m. .
- the heater coil for a gas sensor according to the invention of claim 6 is the invention according to any one of claims 115, wherein the m-fold wound coil corresponds to an integer m of 1 or more and n or less.
- the winding diameter is not less than 0.5 times and not more than 20 times the diameter of the core used for winding the coil when forming the m-fold wound coil.
- the combustion portion of the detection element does not become heavy, so that the detection element can be sufficiently supported by the lead portion of the heater coil.
- the amount of the heat conductive layer filled in the inner space of the bead coil increases.
- the support performance of the sensing element by the lead part is reduced, and the impact resistance of the contact combustion type gas sensor may be reduced to a range that is practically allowable.
- the heater coil for a gas sensor according to the invention of claim 7 is the invention according to any one of claims 115, wherein the m-fold wound coil is provided for an integer m of 1 or more and n or less.
- the winding diameter is 1 to 10 times the diameter of the core used to wind the coil when forming an m-fold wound coil.
- the heater coil can be obtained with a high yield.
- the support performance of the sensing element by the lead portion can be obtained stably. Even if the winding diameter of the m-fold wound coil is 20 times or less the diameter of the core metal, If it exceeds 10 times, the shape stability of the m-fold wound coil after winding processing will be slightly lower.
- the number of turns of the n-fold wound coil is 1 or more and 30 or less. It is characterized by the following.
- the combustion portion of the detection element does not become heavy, so that the detection element can be sufficiently supported by the lead portion of the heater coil. If a heater coil with more than 30 turns is used, the combustion part becomes heavy and the lead of the heater coil cannot stably support the sensing element.
- the gas sensor heater coil according to the ninth aspect of the present invention is the gas sensor heater coil according to any one of the eighteenth to eighteenth aspects, wherein, for an integer k of 1 or more, k in the n-fold wound coil
- the length of the gap between the winding part of the winding and the winding part of the (k + 1) winding is 0.5 times or more of the diameter of the wire composed of the (n-1) double winding coil. It is characterized by being less than twice.
- the contact combustion type gas sensor using the heater coil in the contact combustion type gas sensor using the heater coil, a sufficiently high-speed response characteristic can be obtained. Also, when a sensing element is manufactured using this heater coil, it is possible to prevent short-circuiting between the winding part of the k-th winding and the winding part of the (k + 1) -th winding in the n-fold winding coil.
- the catalyst layer can be formed by filling the space inside the coil of the bead portion with the heat conductive layer.
- the adjacent windings may come into contact with each other to cause a short circuit.
- the gap exceeds 10 times the diameter of the wire, the gap between the windings is too large, so that the space inside the coil of the bead can be sufficiently filled with the heat conductive layer. Therefore, a catalyst layer cannot be formed.
- the gas sensor heater coil according to the tenth aspect of the present invention is characterized in that, in the invention according to any one of the first to nineteenth aspects, it is made of a platinum wire.
- the heater coil for a gas sensor according to the invention of claim 11 is characterized in that, in the invention according to any one of claims 11 to 19, it is made of a platinum-based alloy wire.
- the heater coil for a gas sensor according to the invention of claim 12 is a heater coil used for a contact combustion type gas sensor, and has an electric characteristic due to combustion heat generated at the time of gas combustion. It has a bead portion whose property value changes, and a lead portion that extends at both ends of the bead portion, wherein the lead portion is wound in a coil shape.
- the lead portion has the same configuration as the coil spring, in the contact combustion type gas sensor using the heater coil, an externally applied shock is applied to the spring of the lead portion. Absorbed by elasticity. Therefore, the impact transmitted to the combustion portion of the detection element is reduced, so that the catalyst layer is less likely to be lost, and the zero point of the contact combustion type gas sensor can be suppressed from greatly fluctuating due to the impact.
- a gas sensor detection element is a detection element used for a contact combustion type gas sensor, and generates at the time of gas combustion.
- a heater portion having a bead portion whose electrical characteristic value changes due to combustion heat generated, and a lead portion extending at both ends of the bead portion, a heat conductive layer covering the bead portion, and a surface of the heat conductive layer.
- a catalyst layer attached thereto, and for an integer n of 2 or more, the bead portion is further wound in a coil shape by winding a wire composed of a (n-1) double wound coil. It is characterized by being constituted by an n-fold wound coil.
- the effective length of the bead portion embedded in the combustion portion is replaced by the conventional single-wound coil. It becomes longer than the case where it comprises. Therefore, since the resistance of the heater coil is increased, the gas sensitivity is increased in the contact combustion type gas sensor using this detection element. In addition, since the heater coil receives a large amount of combustion heat and causes a resistance change efficiently, the contact combustion type gas sensor using this detection element has a high response speed. Further, since the size of the combustion part may be almost the same as the conventional one, the weight of the combustion part becomes almost the same as the conventional one. Therefore, it is possible to improve the gas sensitivity of the contact combustion type gas sensor and to increase the response speed without sacrificing the ability to support the sensing element at the lead portion.
- the gas sensor detection element according to the fourteenth aspect of the present invention is the gas sensor detection element according to the thirteenth aspect, wherein the sensing element is constituted by a (n-1) multiply wound coil of a lead portion of the heater coil.
- the feature is.
- the lead portion of the heater coil has the same configuration as that of the coil spring.
- the impact is absorbed by the spring elasticity of the lead portion. Therefore, since the impact transmitted to the combustion portion is reduced, the catalyst layer is less likely to be missing, and the zero point of the contact combustion type gas sensor can be suppressed from greatly changing due to the impact.
- the detection element for a gas sensor according to the invention of claim 15 is the invention according to claim 13 or 14, wherein a wire diameter of a non-coiled raw wire as a starting material of the heater coil is 1 ⁇ m. It is not less than 100 ⁇ m or less.
- the wire diameter of the original wire of the heater coil is 1 ⁇ m or more, it is possible to easily manufacture a heater coil having a bead portion formed of a multi-turn coil. . Therefore, the production of the sensing element becomes easy. Also, since the wire diameter of the heater coil is 100 / zm or less, a sensing element having a size suitable for use in a contact combustion type gas sensor can be obtained.
- the gas sensor sensing element according to the invention of claim 16 is the invention according to claim 13 or 14, wherein the wire diameter of the non-coiled raw wire as a starting material of the heater coil is 10 ⁇ m. Not less than 50 ⁇ m.
- a power supply circuit having an appropriate voltage / current value can be used as a power supply circuit for driving the control circuit of the catalytic combustion type gas sensor.
- the use of a suitable power supply circuit is important because the catalytic layer can be brought to an appropriate operating temperature when operating the catalytic combustion type gas sensor.
- the sensing element for a gas sensor according to the invention of claim 17 is the invention according to claim 13 or 14, wherein the wire diameter of the non-coiled raw wire as a starting material of the heater coil is 20 ⁇ m. Not less than 30 ⁇ m.
- the weight of the combustion part can be reduced to about 1 mg, so that the sensing element can be sufficiently supported by the lead part of the heater coil. Further, in the contact combustion type gas sensor using this detection element, the impact resistance is improved. Furthermore, since the bead portion of the heater coil is buried at a higher density in the combustion portion, the heater coil can receive more combustion heat. Thereby, the resistance change of the heater coil occurs even more efficiently. Therefore, in the contact combustion type gas sensor using this detection element, the response speed is further increased. Further, since the resistance of the heater coil is further increased, the power supply voltage can be further increased. Therefore, in the contact combustion type gas sensor using this detection element, the gas Sensitivity is further increased.
- the wire diameter of the heater coil wire is smaller than 20 ⁇ m, the yield decreases when the heater coil is manufactured.
- the wire diameter of the heater coil wire is 20 ⁇ m or more. Therefore, the heater coil can be easily manufactured. Therefore, a sensing element can be obtained with a high yield. That is, it is possible to manufacture a sensing element that does not lower the yield, and by using the manufactured sensing element, it is possible to further improve the gas sensitivity and the response characteristics of the contact combustion type gas sensor. From the above, considering the gas sensitivity and response characteristics of the contact combustion type gas sensor and the ease of manufacturing the heater coil, the wire diameter of the heater coil wire is 20 ⁇ m or more and 30 ⁇ m or less. Is best.
- the gas sensor detection element according to the eighteenth aspect of the present invention is the gas sensor detection element according to any one of the thirteenth to seventeenth aspects, wherein the heater coil has m weights for an integer m of 1 to n.
- the winding diameter of the wound coil is characterized in that it is 0.5 times or more and 20 times or less the diameter of the core metal used for winding into a coil when manufacturing an m- fold wound coil.
- the sensing element can be sufficiently supported by the lead portion of the heater coil.
- the amount of the heat conductive layer filled in the space inside the coil of the bead portion is reduced. This increases the weight of the combustion part, resulting in a decrease in the ability of the lead part to support the sensing element, and the impact resistance of the contact combustion type gas sensor may fall below a practically acceptable range, causing inconvenience. .
- the gas sensor detection element according to the nineteenth aspect of the present invention is the gas sensor detection element according to any one of the thirteenth to seventeenth aspects, wherein the heater coil has m weights for an integer m of 1 or more and n or less.
- the winding diameter of the wound coil is 1 to 10 times the diameter of the core used for winding the coil when forming the m- fold wound coil.
- the shape stability of the m-fold wound coil after winding processing is good, so that the heater coil can be obtained with high yield. Therefore, a yield detecting element can be obtained.
- the support performance of the sensing element by the lead portion can be obtained stably. Even if the winding diameter of the m-fold wound coil is less than 20 times the diameter of the core metal, if it exceeds 10 times, the shape stability of the m-fold wound coil after winding is slightly lower. Become. [0052]
- the detection element for a gas sensor according to the invention of claim 20 is the invention according to any one of claims 13 to 19, wherein the number of windings of the n-fold winding coil of the heater coil is 1 or more. It is characterized by the following.
- the sensing element can be sufficiently supported by the lead portion of the heater coil. If a heater coil having more than 30 turns is used, the combustion part becomes heavy, and the sensing element cannot be stably supported by the heater coil leads.
- the detection element for a gas sensor according to the invention of claim 21 is the invention according to any one of claims 13 to 20, wherein an n-fold winding of the heater coil is provided for an integer k of 1 or more.
- the length of the gap between the winding part of the k-th winding and the winding part of the (k + 1) -th winding is 0. It is characterized by being 5 times or more and 10 times or less.
- the contact combustion type gas sensor using this detection element in the contact combustion type gas sensor using this detection element, a sufficiently high-speed response characteristic can be obtained.
- the sensing element it is possible to prevent a short circuit between the winding part of the k-th winding and the winding part of the (k + 1) -th winding in the n-fold winding coil, and to prevent the bead part from being short-circuited.
- the catalyst layer can be formed by filling the space inside the coil with a heat conductive layer.
- a gas sensor detecting element according to the invention of claim 22 is the invention according to any one of claims 13-21, wherein the heater coil is made of a platinum wire.
- the gas sensor sensing element according to the invention of claim 23 is the invention according to any one of claims 13-21, wherein the heater coil is made of a platinum-based alloy wire rod! / It is characterized by
- the detection element for a gas sensor according to the invention of claim 24 is used for a contact combustion type gas sensor.
- a heater coil having a bead portion whose electrical characteristic value changes due to combustion heat generated at the time of combustion of a gas, a lead portion extending at both ends of the bead portion, and heat covering the bead portion.
- the lead portion of the heater coil has the same configuration as the coil spring, in the contact combustion type gas sensor using this detection element, an externally applied shock is applied to the lead portion. Is absorbed by the elasticity of the spring. Therefore, since the impact transmitted to the combustion portion is reduced, the catalyst layer is less likely to be missing, and the zero point of the contact combustion type gas sensor can be suppressed from greatly changing due to the impact.
- the contact combustion type gas sensor according to the invention of claim 25 has an electric characteristic value that changes due to combustion heat generated when gas is burned.
- a heater coil having a bead portion and a lead portion extending at both ends of the bead portion; a heat conductive layer covering the bead portion; and a catalyst layer attached to a surface of the heat conductive layer,
- the bead portion is a sensing element formed of an n-fold wound coil in which a wire formed of a (n-1) double-turn coil wound in a coil shape is further wound in a coil shape.
- a compensating element having a heater coil having the same configuration as the heater coil connected in series to the sensing element, a first resistive element, and a second resistive element connected in series to the first resistive element.
- the second resistance element constitutes a Wheatstone bridge circuit, and a connection node between the detection element and the compensation element, the first resistance element and the second A voltage between the resistor element and a connection node is output.
- the effective length of the bead portion embedded in the combustion portion is replaced by the conventional single-wound coil. It becomes longer than the case where it comprises. Accordingly, the resistance of the heater coil increases, and the gas sensitivity increases. In addition, since the heater coil receives more combustion heat and changes resistance efficiently, the response speed is increased. Furthermore, since the size of the combustion part can be almost the same as the conventional one, Also, the weight of the combustion part becomes almost the same as the conventional one. Therefore, it is possible to improve the gas sensitivity without sacrificing the support capability of the sensing element at the lead portion and to achieve a high response speed.
- a contact combustion gas sensor is the contact combustion type gas sensor according to the twenty-fifth aspect, wherein the heater coil is configured by a (n-1) multiply wound coil.
- the lead portion of the heater coil has a configuration similar to that of the coil spring, an externally applied impact is absorbed by the spring elasticity of the lead portion. Therefore, since the impact transmitted to the combustion part of the detection element is reduced, the lack of the catalyst layer or the like occurs, and the zero point can be prevented from largely fluctuating due to the impact.
- the contact combustion type gas sensor according to the invention of claim 27 is the invention according to claim 25 or 26, wherein the wire diameter of the non-coiled raw wire as a starting material of the heater coil is 1 ⁇ m. It is not less than 100 ⁇ m or less.
- the wire diameter of the original wire of the heater coil is 1 ⁇ m or more, it is possible to easily manufacture a heater coil having a bead portion formed of a multi-turn coil. . Therefore, the production of the sensing element becomes easy, and the production of the contact combustion type gas sensor becomes easy. Further, since the diameter of the original wire of the heater coil is 100 ⁇ m or less, a contact combustion type gas sensor having a detection element of an appropriate size can be obtained.
- a wire diameter of the non-coiled raw wire as a starting material of the heater coil is 10 ⁇ m. Not less than 50 ⁇ m.
- a power supply circuit having an appropriate voltage / current value can be used as a power supply circuit for driving the control circuit of the contact combustion type gas sensor. It is important to use a suitable power supply circuit because the catalytic layer can be brought to an appropriate operating temperature when operating the catalytic combustion type gas sensor.
- a wire diameter of a non-coiled raw wire as a starting material of the heater coil is 20 ⁇ m. Not less than 30 ⁇ m.
- the weight of the combustion part of the detection element is about lmg
- the sensing element can be sufficiently supported by the lead portion of the data coil. Further, in the contact combustion type gas sensor using the heater coil, the impact resistance is improved. Furthermore, since the bead portion of the heater coil is embedded at a higher density in the combustion portion, the heater coil can receive more combustion heat. Thereby, the resistance change of the heater coil occurs even more efficiently. Therefore, the response speed is further increased. In addition, since the resistance of the heater coil is further increased, the power supply voltage can be further increased. Therefore, the gas sensitivity is further increased.
- the wire diameter of the base wire of the heater coil becomes smaller than 20 ⁇ m, the yield decreases when the heater coil is manufactured.
- the wire diameter of the base wire of the heater coil is 20 ⁇ m or more. Therefore, the heater coil can be easily manufactured. Therefore, a contact combustion type gas sensor can be obtained with good yield. That is, it is possible to manufacture a contact combustion type gas sensor without lowering the yield, and it is possible to further improve gas sensitivity and response characteristics. From the above, considering the balance between gas sensitivity and response characteristics and ease of manufacturing a heater coil, it is optimal that the wire diameter of the original wire of the heater coil is 20 ⁇ m or more and 30 ⁇ m or less.
- the contact combustion type gas sensor according to the invention of claim 30 is the invention according to any one of claims 25 to 29, wherein the heater coil has m weights for an integer m of 1 or more and n or less.
- the winding diameter of the wound coil is characterized in that it is 0.5 times or more and 20 times or less the diameter of the core metal used for winding into a coil when manufacturing an m- fold wound coil.
- the combustion portion of the detection element does not become heavy! Therefore, the detection element can be sufficiently supported by the lead portion of the heater coil.
- the amount of the heat conductive layer filled in the space inside the coil of the bead increases.
- the combustion part becomes heavy, the performance of supporting the sensing element by the lead part is reduced, and if the impact resistance is sometimes reduced to a range that is practically allowable, a disadvantage occurs.
- the contact combustion type gas sensor according to the invention of claim 31 is the invention according to any one of claims 25 to 29, wherein the heater coil has m weights for an integer m of 1 or more and n or less.
- the winding diameter of the wound coil is used for winding in a coil shape when manufacturing an m- fold wound coil.
- the diameter of the cored bar is at least 1 and at most 10 times.
- the shape stability of the m-fold wound coil after winding processing is good, so that the heater coil can be obtained with high yield. Therefore, a yield contact gas sensor can be obtained. Further, the support performance of the sensing element by the lead portion can be obtained stably. Even if the winding diameter of the m-fold wound coil is less than 20 times the diameter of the core metal, if it exceeds 10 times, the shape stability of the m-fold wound coil after winding becomes slightly lower. Become.
- the contact combustion type gas sensor according to the invention of claim 32 is the invention according to any one of claims 25 to 31, wherein the number of turns of the n-fold coil of the heater coil is 1 or more. It is characterized by the following.
- the combustion portion of the detection element does not become heavy! Therefore, the detection element can be sufficiently supported by the lead portion of the heater coil.
- the combustion portion becomes heavy, and the detection element cannot be stably supported by the lead portion of the heater coil.
- the contact combustion type gas sensor according to the invention of claim 33 is the invention according to any one of claims 25 to 32, wherein the heater coil has n double windings for an integer k of 1 or more.
- the length of the gap between the winding part of the k-th winding and the winding part of the (k + 1) -th winding is 0. It is characterized by being 5 times or more and 10 times or less.
- a sufficiently high-speed response characteristic can be obtained.
- the sensing element it is possible to prevent a short circuit between the winding part of the k-th winding and the winding part of the (k + 1) -th winding in the n-fold winding coil, and to prevent the coil of the bead part
- a catalyst layer can be formed by filling the heat conductive layer in the inner space of the catalyst.
- a heater coil whose gap between the k-th winding and the (k + 1) -th winding is shorter than 0.5 times the diameter of the wire is used, In some cases, adjacent winding portions come into contact with each other to cause a short circuit.
- the contact combustion type gas sensor according to the invention of claim 34 is characterized in that, in the invention of any one of claims 25 to 33, the heater coil is made of a platinum wire. .
- the contact combustion type gas sensor according to the invention of claim 35 is the invention according to any one of claims 25 to 32, wherein the heater coil is made of a platinum-based alloy wire! / ⁇ It is characterized by that.
- a sensing element having a heater coil having: a heat conductive layer covering the bead portion; and a catalyst layer attached to a surface of the heat conductive layer, wherein the lead portion is wound in a coil shape.
- a compensation element having a heater coil having the same configuration as the heater coil, a first resistance element, a second resistance element connected in series to the first resistance element, A power supply for applying a DC voltage to both ends of each of a series connection of a detection element and the compensation element, and a series connection of the first resistance element and the second resistance element.
- the second resistor element and the second resistor element constitute a Wheatstone bridge circuit, and the Wheatstone bridge circuit connects a connection node between the sensing element and the compensation element, the first resistor element, and the second resistor. A voltage between the element and a connection node is output.
- the lead portion of the heater coil since the lead portion of the heater coil has the same configuration as the coil spring, an externally applied impact is absorbed by the spring elasticity of the lead portion. Therefore, since the impact transmitted to the combustion part of the detection element is reduced, the lack of the catalyst layer or the like occurs, and the zero point can be prevented from largely fluctuating due to the impact.
- the electric characteristic value of the heater coil changes due to the combustion heat generated by the combustion of the contacted gas, and based on the change in the characteristic value!
- a contact combustion type gas sensor for detecting the presence of flammable gas at least both ends of the heater coil are wound in a coil shape, and the heater coil is welded to the coil portions at both ends of the heater coil. And a sintered body covering a part of the heater coil.
- At a bonding interface between the heater coil and the electrode at least one metal element constituting the electrode is provided in a composition ratio of the electrode. Alloy layer containing a higher proportion than And features.
- the electric characteristic value of the heater coil changes due to the combustion heat generated by the combustion of the contacted gas, and based on the change in the characteristic value!
- a contact combustion type gas sensor for detecting the presence of flammable gas at least both ends of the heater coil are wound in a coil shape, and the heater coil is welded to the coil portions at both ends of the heater coil. And a sintered body covering a part of the heater coil.
- At a bonding interface between the heater coil and the electrode at least one metal element constituting the electrode is provided in a composition ratio of the electrode.
- alloy layer containing a higher proportion than the above, and only in the welding portion between the heater coil and the electrode, inside the coiled portion of the heater coil, the alloy layer is higher in the alloy layer than in the electrode! ⁇ ⁇ Included in percentage A core wire made of the metal element is provided.
- an alloy layer containing a metal element constituting the electrode at a higher ratio than the constituent ratio in the electrode is provided at the joining interface between the heater coil and the electrode (hereinafter, such an alloy layer is referred to as such Alloy layer is referred to as a rich layer), so that high bonding strength can be obtained.
- the rich layer is welded to the electrode while the end portion of the heater coil is wound around the core wire made of at least one metal element constituting the electrode, so that the metal material constituting the core wire is the metal material of the electrode. It is a result of alloying.
- the contact combustion type gas sensor according to the invention of claim 39 is, in the invention of claim 37 or 38, included in the alloy layer at a higher ratio than that in the electrode.
- the metal element is characterized in that the ion array is larger than the metal constituting the heater coil.
- the core wire can be melted by etching after welding to the electrode while the end portion of the heater coil is wound around the core wire, the core wire can be easily removed except for the rich layer. Can be extinguished.
- the heater coil is a coiled coil described later. Even if it is configured, the core wire can be easily removed after welding.
- the contact combustion gas sensor according to claim 40 is the invention according to claim 37 or 38, wherein the heater coil is made of platinum or a platinum alloy, and the electrode is made of an alloy containing nickel. And wherein the metal element contained in the alloy layer at a higher proportion than in the electrode is nickel.
- nickel is a metal lower than platinum or a platinum alloy
- the core wire is made of nickel, the core wire can be easily melted without leaving the heater coil. .
- the contact combustion type gas sensor according to the invention of claim 41 is the invention according to any one of claims 37 to 40, wherein at least a portion of the heater coil covered by the sintered body is provided.
- a part is characterized in that the wire is wound in a coil shape and a coil wire is further wound in a coil shape to form a coiled coil.
- the electric characteristic value of the heater coil changes due to the combustion heat generated by the combustion of the contacted gas, and based on the change in the characteristic value.
- a contact-combustion gas sensor that detects the presence of flammable gas.
- An alloy layer formed by alloying a metal element and at least one metal element constituting the electrode is present.
- the electric characteristic value of the heater coil changes due to the combustion heat generated by the combustion of the contacted gas, and based on the change in the characteristic value!
- a heater coil wound at least at both ends in a coil shape and a coil-shaped portion at both ends of the heater coil are provided.
- a sintered body covering a part of the heater coil, and a bonding interface between the heater coil and the electrode is included in a gap between the heater coil and the electrode.
- an alloy layer formed by alloying a metal element that is not present with at least one metal element that constitutes the electrode, and the coil of the heater coil is provided only at a welding portion between the heater coil and the electrode.
- a core wire made of the metal element is provided inside the shape of the metal layer, which is included in the alloy layer but included in the deviation of the heater coil and the electrode.
- the joining interface between the heater coil and the electrode includes the! / ⁇ ! Since there is an alloy layer formed by alloying with at least one metal element constituting the alloy, high bonding strength can be obtained.
- the alloy layer is welded to the electrode with the end of the heater coil wound around a core made of a metal element not included in either the heater coil or the electrode, thereby forming a metal material forming the core.
- irregularities in the winding portion of the heater coil at the welding portion during welding and deformation of the coil shape can be prevented, so that variation in the resistance value of the heater coil can be reduced.
- the contact combustion type gas sensor according to the invention of claim 44 is characterized in that, in the invention of claim 42 or 43, a force contained in the alloy layer is a deviation of the heater coil and the electrode.
- the metal element is characterized in that the metal element has a larger ionization depth than the metal constituting the heater coil.
- the core wire can be melted by etching after welding to the electrode while the end portion of the heater coil is wound around the core wire, the core wire can be easily formed without the alloy layer. Can be extinguished. Further, even when the heater coil is constituted by a coiled coil described later, the core wire can be easily eliminated after welding.
- the contact combustion type gas sensor according to the invention of Claim 45 is the invention according to any one of Claims 42 to 44, wherein the heater coil has a portion covered with the sintered body. At least a part thereof is characterized in that the wire is wound in a coil shape, and a coil wire is further wound in a coil shape.
- a method for manufacturing a contact combustion type gas sensor according to the invention of claim 46 is characterized in that the heater coil is heated by combustion heat generated by combustion of the contacted gas.
- the heater coil is heated by combustion heat generated by combustion of the contacted gas.
- the electric characteristic value of the heater coil changes due to combustion heat generated by the combustion of the contacted gas, and the characteristic value changes.
- a contact-combustion gas sensor that detects the presence of flammable gas based on the above, at least both ends are wound around a core wire to form a coil-shaped heater coil, and the coil is wound around the core wire.
- the core wire is made of a metal which is lower than a constituent material of the heater coil.
- the core wire eliminating step only the core wire is eliminated by etching.
- the core wire can be easily eliminated by etching after welding to the electrode while the end portion of the heater coil is wound around the core wire. Further, even when the heater coil is formed of a coiled coil described later, the core wire can be easily eliminated after welding.
- the core wire is made of nickel, and the heater coil is made of platinum or platinum. It is made of a platinum alloy, and in the core wire eliminating step, the core wire is annihilated by using an etching solution for nickel.
- nickel is a metal lower than platinum or a platinum alloy
- the core wire can be easily melted by leaving the heater coil by etching.
- the sintered body of the heater coil is provided in the invention according to any one of claims 46 to 50. At least a part of the portion covered by the coil is wound into a coil shape around the core wire to form a coiled coil.
- the wire constituting the heater coil becomes longer, and the heater coil has a longer length. Since the resistance increases, a sensor with high gas sensitivity can be obtained. In addition, the wire constituting the heater coil is buried longer in the sintered body, and the resistance change of the heater coil occurs efficiently, so that a sensor having a high response speed can be obtained.
- the core wire joins the heater coil and the electrode. It is characterized in that it also serves as a brazing filler metal.
- the heater coil for a gas sensor, the sensing element for a gas sensor, and the contact combustion type gas sensor according to the present invention exhibit an effect when the gas sensitivity is high and a contact combustion type gas sensor can be obtained. Further, there is an effect that a contact combustion type gas sensor having a high response speed can be obtained. Further, there is an effect that a contact combustion type gas sensor having a small zero point fluctuation due to an impact having a high impact resistance can be obtained.
- the method for manufacturing a contact combustion gas sensor according to the present invention includes a contact combustion gas sensor having a heater coil wound at least at both ends in a coil shape and having a small variation in the resistance value of the heater coil. Is obtained. Further, there is an effect that a contact combustion type gas sensor having a heater coil wound at least at both ends in a coil shape and having a high bonding strength between the heater coil and the electrode pin can be obtained. Furthermore, when manufacturing a contact combustion type gas sensor, handle a heater coil with at least both ends wound in a coil shape.
- FIG. 1 is a front view showing a configuration of a heater coil according to an embodiment of the present invention.
- FIG. 2 is a cross-sectional view illustrating a configuration of a sensing element according to an embodiment of the present invention.
- FIG. 3 is a partial cross-sectional view showing a configuration of a sensor main body of a catalytic combustion type gas sensor according to an embodiment of the present invention.
- FIG. 4 is a configuration diagram of a control circuit of a catalytic combustion type gas sensor according to an embodiment of the present invention. It is a circuit diagram showing composition.
- FIG. 5 is a flowchart showing a method for manufacturing a catalytic combustion type gas sensor according to an embodiment of the present invention.
- FIG. 6 is a partially enlarged view showing a state in the course of manufacturing the contact combustion type gas sensor according to the embodiment of the present invention.
- FIG. 7 is a partially enlarged view showing a state during the manufacture of the contact combustion gas sensor according to the embodiment of the present invention.
- FIG. 8 is an explanatory diagram showing an SEM image showing a surface state of a welded part in an example.
- FIG. 9 is an explanatory view showing an SEM image showing a cross-sectional state of a welded part in an example.
- FIG. 10 is a chart showing an XMA analysis result at point A in FIG. 9.
- FIG. 11 is a chart showing an XMA ⁇ vector at point B in FIG.
- FIG. 12 is a chart showing an XMA spectrum at point C in FIG. 9.
- FIG. 13 is a chart showing an XMA analysis result at point D in FIG. 9.
- FIG. 14 is a photograph showing the overall shape of the heater coil of the example.
- FIG. 15 is an explanatory diagram showing an SEM image showing the surface of a welded part in a comparative example.
- FIG. 16 is an explanatory diagram showing an SEM image showing a cross section of a welded part in a comparative example.
- FIG. 17 is a photograph showing the overall shape of a heater coil of a comparative example.
- FIG. 18 is a cross-sectional view showing a configuration of a conventional sensing element.
- FIG. 19 is a front view showing a configuration of a conventional heater coil.
- FIG. 1 is a front view showing a configuration of a heater coil according to an embodiment of the present invention.
- the bead portion 24 of the heater coil 22 is formed of, for example, a double-turn coil.
- the lead portion 25 of the heater coil 22 is formed of, for example, a single coil.
- a resistance wire (original wire) made of a normal non-coiled wire is wound around a primary core wire to manufacture a single-turn coil.
- this single-turn coil is used as a new wire, and a part of this wire is wound around a secondary core wire, and the portion to be the bead portion 24 is made into a double-turn coil.
- the secondary core wire may be a wire having the same diameter as the primary core wire or a wire having a different diameter.
- the lead portion 25 may be formed of a double or more wound coil, and the bead portion 24 may be formed of a triple or more wound coil.
- the lead portion 25 and the bead portion 24 are a double wound coil and a triple wound coil, respectively, first, the original wire is wound around the primary core wire to produce a single wound coil.
- a double-wound coil is produced by winding the coil around a secondary core wire using the coil as a primary wire (primary wire).
- the part may be wound around a tertiary core wire, and the part serving as the bead part 24 may be formed into a triple wound coil.
- the number of repetitions of the winding process for winding the element wire around the core wire may be increased.
- FIG. 2 is a cross-sectional view illustrating a configuration of a sensing element according to an embodiment of the present invention.
- the sensing element 2 has a configuration in which a bead portion 24 of a heater coil 22 is covered with a heat conductive layer 21 made of a sintered body, and a catalyst layer 23 is attached to the surface of the heat conductive layer 21.
- the heat conductive layer 21 is made of, for example, alumina (aluminum).
- the catalyst layer 23 is composed of a combustion catalyst made of an oxidized metal according to the flammable gas to be detected. The catalyst layer 23 is heated to a temperature corresponding to the flammable gas to be detected by applying a voltage to both ends of the heater coil 22.
- the gas to be detected for example, an organic component gas such as methane gas, hydrogen gas, LP gas (liquefied petroleum gas), propane gas, butane gas, ethylene gas, carbon monoxide gas, or ethanolic acetone is used. No. Then, for example, when the gas to be detected is S methane gas, the catalyst layer 23 is heated to about 450 ° C.
- FIG. 3 is a partial cross-sectional view showing the configuration of the sensor main body of the contact combustion type gas sensor according to the embodiment of the present invention.
- the sensor body 3 has external connection electrode pins 32 and 33 that penetrate a plate-shaped mount base 31 made of ceramic resin.
- the configuration is such that the lead portions 25 at both ends of the element 2 are fixed.
- a compensating element including a heater coil having the same configuration as the heater coil 22 of the detecting element 2 is provided alongside the detecting element 2.
- the compensating element and the detecting element 2 are surrounded by a mount base 31 and an explosion-proof structure 34 made of a gas-permeable metal mesh or a sintered body of metal or ceramic.
- FIG. 4 is a circuit diagram showing a configuration of a control circuit of the catalytic combustion type gas sensor according to the embodiment of the present invention.
- the control circuit of the catalytic combustion type gas sensor 5 includes a sensing element 2, a compensation element 4 connected in series with the sensing element 2, a first resistance element 51, and a first resistance element 51 connected in series. It has a second resistance element 52 and a power supply (power supply circuit) 53 connected thereto.
- These sensing element 2, compensating element 4, first and second resistance elements 51, 52 form a Wheatstone bridge circuit! /
- Power supply 53 applies a DC voltage to both ends of a series connection of sensing element 2 and compensation element 4 and a series connection of first resistance element 51 and second resistance element 52, respectively. .
- the power of the Wheatstone bridge circuit also depends on the connection node between the sensing element 2 and the compensating element 4 (indicated by A in FIG. 4) and the connection node between the first resistive element 51 and the second resistive element 52 ( Figure 4 B) is output. Assuming that the current-carrying resistance values of the detection element 2, the compensation element 4, the first resistance element 51, and the second resistance element 52 are R, R, R, and R,
- each heater coil 22 of the detecting element 2 and the compensating element 4 When a rated voltage is applied to each heater coil 22 of the detecting element 2 and the compensating element 4 by the power supply 53, each heater coil 22 generates heat, and the detecting element 2 and the compensating element 4 respond to the gas to be detected.
- the operating temperature is reached, and the gas sensor 5 obtains an output voltage V depending on the current-carrying resistance value obtained from the equilibrium temperature with the environment. And when the detection target gas is detected out
- the output voltage V increases to the + (plus) side by an amount corresponding to the gas sensitivity.
- the operating temperature of the catalyst for causing the detection target gas to contact burn with high efficiency is selected based on the gas type.
- a heater coil having a higher resistance value is used, a higher power supply voltage is required to obtain a desired catalyst operating temperature. Due to the nature of the bridge circuit, the power supply voltage and the output voltage V are in a proportional relationship, so the heater with a higher resistance value out
- the gas sensitivity when using a coil has a higher value. That is, since the heater coil 22 having the above-described configuration has a higher resistance value than that of the conventional heater coil as described later, the use of the heater coil 22 provides a high gas sensitivity.
- the raw wire constituting the heater coil 22 for example, platinum or a platinum alloy wire, an alloy wire based on platinum or a platinum alloy such as platinum or a platinum alloy rhodium alloy, or an iron-palladium alloy wire may be used. it can.
- the wire diameter of the original wire is not less than m and not more than 100 / z m. The reason is that if the wire diameter of the wire is less than 1 ⁇ m, it is difficult to manufacture a double-wound coil that constitutes the bead portion 24, while the wire diameter of the wire exceeds 100 m This is because the combustion part of the detection element 2 becomes too large.
- the diameter of the original wire is preferably 10 m or more and 50 m or less.
- the power supply 53 having an appropriate voltage / current value can be used, so that the catalyst layer 23 can be set to an appropriate operating temperature when the catalytic combustion type gas sensor 5 operates.
- the wire diameter is 50 m
- the voltage-current value is 0.75 V-400 m A power supply can be used.
- the diameter of the original wire is 10 m
- a power supply with a voltage and current value of 12 V to 25 mA can be used.
- the diameter of the original wire is more preferably 20 / zm or more and 30 / zm or less.
- the volume occupied by the bead portion 24 is reduced and the weight of the combustion portion of the detection element 2 is reduced to about 1 mg, so that the detection element 2 is sufficiently supported by the lead portion 25 of the heater coil 22. Because they can do it.
- the impact resistance of the contact combustion type gas sensor 5 is improved.
- the bead portion 24 of the heater coil 22 can be buried at a higher density in the combustion portion of the sensing element 2, the ability of the heater coil 22 to receive the heat of combustion is increased, and the heater coil 22 is capable of receiving heat during combustion.
- the resistance change occurs more efficiently, and the response speed of the catalytic combustion gas sensor 5 increases.
- the resistance of the heater coil 22 is increased by the thin wire and the power supply voltage can be further increased as described above, so that the gas sensitivity of the contact combustion type gas sensor 5 increases. .
- Table 1 shows the relationship between the diameter of the base wire of the heater coil 22, the weight of the combustion part of the sensing element 2, the gas sensitivity of the contact combustion gas sensor 5, and the response time of the contact combustion gas sensor 5. This is shown below.
- the relative weight (au), relative gas sensitivity (au), and relative response time (au) of each wire diameter range are all based on heater coils based on platinum wire with a wire diameter of 30 ⁇ m. It is a relative value to the weight of the combustion part (lmg), gas sensitivity (40mV) and response time (5 seconds) when using.
- the bead portion 24 and the lead portion 25 are a double wound coil and a single wound coil, respectively.
- the gas sensitivity is the sensitivity to 4000 ppm of hydrogen gas
- the response time is the time required to reach 90% or more of the stable output value at 4000 ppm of hydrogen gas.
- the winding diameter of the single-turn coil is 0.5 times or more and 20 times or less the diameter of the core metal (primary core wire) used for winding the original wire in a coil shape.
- the winding diameter of the double wound coil is 0.5 times or more and 20 times or less the diameter of the core used to further wind the single wound coil (element wire) in a coil shape.
- the winding diameter exceeds 20 times, the amount of the heat conductive layer 21 filled in the inner space of the coil of the bead portion 24 increases and the combustion portion becomes heavy, so that the lead portion 25 supports the sensing element 2 by the lead portion 25. And the impact resistance of the contact combustion type gas sensor 5 may be lower than a practically allowable range.
- the winding diameter of the single-wound coil is preferably not less than 1 and not more than 10 times the diameter of the core metal used for winding the original wire in a coil shape.
- the winding diameter of the double-wound coil is preferably not less than 1 and not more than 10 times the diameter of the core used for further winding the single-wound coil (element wire) into a coil. .
- the reason is that the shape stability of the coil after winding is good, so that the heater coil 22 can be obtained with good yield, and the force that can stably obtain the support performance of the sensing element 2 by the lead portion 25. It is.
- the winding diameter is 20 times or less, if the winding diameter exceeds 10 times, the shape stability of the coil after winding becomes slightly lower.
- the number of turns of the double spiral coil as the final spiral is 1 or more and 30 or less. The same applies when the final spiral is a wound coil having three or more turns. The reason is that the combustion of sensing element 2 This is because the lead portion 25 of the heater coil 22 can sufficiently support the sensing element 2 because the portion does not become heavy. If the number of turns exceeds 30, the combustion portion becomes heavy, and the sensing element 2 cannot be stably supported by the lead portion 25 of the heater coil 22. In particular, it is appropriate that the number of turns of the double wound coil is four to ten.
- the length of the gap between a certain winding portion 26 and the winding portion 27 adjacent to this winding portion 26 is 0.5 times or more and 10 times or less the diameter of the wires.
- the first reason is the ability to obtain sufficiently fast response characteristics.
- the catalyst layer 23 can be formed by filling the space inside the coil of the bead portion 24 with the heat conductive layer 21.
- the length of the gap between the winding part 26 and the adjacent winding part 27 is generally determined by the distance between the wires called the pitch and the pitch of the spiral. It is the distance except half of the thickness of each of the part 26 and the winding part 27.
- Table 2 shows the relationship between the gap distance between the wires of the heater coil 22 and the response time of the contact combustion type gas sensor 5.
- the gap distance between the wires is expressed as a magnification relative to the diameter of the wires.
- the relative response time (a.u.) of each inter-wire gap distance range is a relative value with respect to the response time when using a heater coil in which the inter-wire gap distance is equal to the diameter of the wire.
- the bead portion 24 and the lead portion 25 are a double wound coil and a single wound coil, respectively.
- Table 3 shows a comparison result of gas sensitivity.
- the value obtained by subtracting the output voltage value in air from the output voltage value in gas was used as the gas sensitivity, and two comparisons were made: sensitivity comparison for 4000 ppm hydrogen gas and 4000 ppm methane gas.
- the gas sensitivity of the sample of the example was about three times that of the sample of the conventional example.
- Table 4 shows a comparison result of the response speed.
- Table 4 shows the response time, which is the time required to reach 90% or more of the stable output value at 1800 ppm of hydrogen gas.
- the response time of the sample of the example was approximately half of the response time of the sample of the conventional example. That is The response speed of the sample of the embodiment is approximately twice that of the sample of the conventional example.
- Table 5 shows a comparison result of zero point fluctuation (converted value of hydrogen concentration) generated after a drop impact.
- the contact combustion type gas sensors of the embodiment and the conventional example were freely dropped from a height of lm onto a cedar board having a thickness of 30 mm.
- the zero point fluctuation after the drop impact was converted to a hydrogen concentration, which was less than 2000 ppm in the example, but exceeded 2000 ppm in the conventional example.
- FIG. 5 is a flowchart showing a manufacturing procedure.
- 6 and 7 are partially enlarged views showing a state in the course of manufacturing the catalytic combustion type gas sensor 5.
- FIG. First prepare a normal non-coiled resistance wire, This is wound around a primary core wire to produce a single wound coil (step S1).
- the primary core wire may be a wire rod made of a metal lower than the resistance wire used. This is because it is necessary to melt the primary core wire while leaving the resistance wire in the subsequent wet etching process.
- the primary core is made of nickel, aluminum, copper or a stainless alloy.
- the diameter of the primary core wire is suitably 20-60 / z m. In a single-turn coil, the length of the gap between a certain winding part 28 and the winding part 29 adjacent to this winding part 28 (see FIG. 7), that is, the gap distance between the wires It is appropriate that the diameter be 0.5 times or more and 10 times or less of the diameter of the strand.
- a part of the single wound coil that is, a part to be the bead portion 24 is wound around a secondary core wire to produce a double wound coil, which is the heater coil 22 (Step S2).
- the material of the secondary core wire is not particularly limited, but is, for example, carbide or hardened steel.
- the diameter of the secondary core wire is suitably 100-300 ⁇ m.
- the element wire is a platinum or platinum alloy wire having a diameter
- the primary core wire is a nickel wire having a diameter of 40 m.
- the gap distance between the strands is preferably 20 m.
- the diameter of the primary wire composed of the single-wound coil is 80 m (20 m (diameter of the wire) +40 m (—diameter of the core wire) +20 m (the diameter of the wire) Diameter))).
- the gap distance between the single-wound coil and the strand is preferably 80 ⁇ m! / ,.
- the lead portions 25 at both ends of the heater coil 22 are welded to the electrode pins 32, 33 projecting from the mount base 31 by a resistance welding method, a laser welding method, a thermocompression bonding method, or the like. (Step S3). At this point, the primary core wire 6 remains as shown in FIG.
- the electrode pins 32 and 33 are made of, for example, nickel or nickel-copper alloy (monel). Alternatively, the electrode pins 32 and 33 may be made of a nickel-chromium molybdenum alloy such as Inconel Hastelly (trade name), a stainless steel alloy such as SUS316L, titanium or a titanium alloy, or a combination thereof to improve corrosion resistance. it can. Electrode pin 3 Most preferred as material 2 and 33 is Hastelloy (trade name). Although not particularly limited, for example, the diameter of the electrode pins 32, 33 is about 600 / zm.
- any method may be used, but a resistance welding method is preferable.
- the resistance welding method can stably control the energization time on the order of milliseconds, at which the voltage of the welding equipment rises extremely rapidly, so that different materials are welded together as in the present embodiment. It is suitable for welding thin metal wires.
- the resistance welding method When the resistance welding method is performed, a well-known transistor-type resistance welding machine can be used.
- the welding conditions in this case are not particularly limited.
- the voltage is 2.0-3. OV
- the energizing time is 3 milliseconds
- the head load is 0.5-5 kgf. is there.
- the voltage value is preferably 2.3 V.
- Step S4 the one obtained by welding the heater coil 22 to the electrode pins 32 and 33 is immersed in an etchant to dissolve and extinguish the primary core wire 6.
- the welding portion between the heater coil 22 and the electrode pins 32 and 33 may be covered and etched to leave the primary core wire 6 only at the welding portion.
- the etching solution is, for example, a mixed aqueous solution of nitric acid (30%), sulfuric acid (3%) and hydrogen peroxide (2%), or a ferric chloride solution (40% aqueous solution).
- the bath temperature is preferably room temperature (for example, 25 ° C)
- the immersion time is suitably 60 minutes.
- a ferric salt solution for example, it is appropriate to set the bath temperature to 40 ° C. and the immersion time to 3 minutes.
- FIG. 7 shows a state in which the primary core wire has disappeared by etching.
- Step S8 a slurry such as a heat conductive material and a combustion catalyst is applied to the bead portion 24 of the heater coil 22, and the slurry is heated and fired (Step S8).
- the sensor main body 3 is assembled by mounting the explosion-proof structure 34 and the like (step S9).
- a non-coiled platinum or platinum alloy wire having a diameter of 20 m is used as a strand, and this is wound around a primary core wire 6 made of a nickel wire having a diameter of 40 ⁇ m with a gap distance between the strands of 20 m. A single wound coil was manufactured.
- the single-wound coil was wound 6 times on a secondary core wire made of a 150 m-diameter cemented wire at a gap distance of 80 / zm between wires, thereby producing a double-wound coil in the bead portion 24.
- the lengths of the lead portions 25 at both ends of the bead portion 24 were each lmm.
- the electrode pins 32 and 33 were made of Hastelloy having a diameter of 600 ⁇ m, and a resistance welding method was used. The welding conditions were as described above, except that the head weight was 1.5 kgf and the voltage value was 2.3 V. Then, an etching treatment was performed for 60 minutes using a mixed aqueous solution of nitric acid, sulfuric acid and hydrogen peroxide at a bath temperature of room temperature.
- FIG. 8 and FIG. 9 are photographs of the surface and cross section of the welded part of the example, respectively, observed with a scanning electron microscope.
- 15 and 16 are photographs obtained by observing the surface and cross section of the welded portion of the comparative example with a scanning electron microscope.
- each winding portion of the lead portion 25 of the heater coil 22 is regularly and sufficiently crushed and joined to the electrode pins 32 and 33 as compared with the comparative example. You can see that there is. Also, comparing FIG. 9 and FIG. 16, it can be seen that the example is partially alloyed at the bonding interface where the bonding area is wider than the comparative example. The alloying is also apparent from the analytical results shown in Figs. FIGS. 10, 11, 12 and 13 show X-rays at the locations indicated by “A”, “B”, “C” and “D” in the cross-sectional photograph of the embodiment shown in FIG. 9, respectively. 5 is a chart showing a result of analysis by a micro analyzer (XMA).
- XMA micro analyzer
- Point “C” which is a portion near the heater coil 22 at the junction interface between the heater coil 22 and the electrode pins 32, 33, and the electrode pins 32, 33 at the junction interface between the heater coil 22 and the electrode pins 32, 33.
- point “D” which is a closer part, peaks of platinum or a platinum alloy, nickel, and chromium are observed. This is because the nickel of the primary core wire 6 functions as a brazing material at the bonding interface between the heater coil 22 and the electrode pins 32 and 33, and the heater coil 22 and the primary core wire 6 and the electrode pins 32 and 33 are alloyed. Is shown.
- the vicinity of the point “D” is a rich layer in which the nickel content is higher than that of the balta of the electrode pins 32 and 33 because the nickel primary core wire 6 is present during welding.
- step S1 and step S2 in FIG. 5 were performed, and step S4 was performed first to perform the primary operation. After the core wire 6 has disappeared, welding in step S3 is performed, and after the steps from step 5 to step S7, the heater coil 22 is pulled vertically between the electrode pins 32 and 33, respectively. 22 or the strength at the time of fracture of the welded part was measured.
- FIG. 14 and FIG. 17 show the overall shape of the heater coil 22 in the example and the comparative example, respectively. From FIG. 14, it can be seen that in the example, the bead portion 24 of the heater coil 22 has no distortion. On the other hand, in the comparative example, the bead portion 24 of the heater coil 22 is distorted, and it can be seen that the adjacent winding portions of the bead portion 24 are almost in contact with each other. The cause of such distortion is that when welding is performed without a primary core wire, the coil of the heater coil 22 is wound. Inadvertently crushing the part or damaging the coil shape.
- the effect of the bead part 24 embedded in the combustion part of the heater coil 22 is obtained.
- the length is longer than when the bead portion 24 is formed of a conventional single-turn coil. Accordingly, the resistance of the heater coil 22 increases, so that the gas sensitivity of the contact combustion type gas sensor 5 increases, and the SZN ratio improves.
- the heater coil 22 receives more combustion heat and causes a resistance change efficiently, the response speed of the contact combustion type gas sensor 5 is increased. Further, since the size of the combustion part may be almost the same as the conventional one, the weight of the combustion part becomes almost the same as the conventional one. Therefore, the gas sensitivity of the contact combustion type gas sensor 5 can be improved and the response speed can be increased without sacrificing the ability to support the detection element 2 at the lead portion 25 of the heater coil 22.
- the resistance of the heater coil 22 increases due to the thinning of the original wire of the heater coil 22, current consumption can be reduced.
- the lead portion 25 has the same configuration as the coil spring, an externally applied impact is absorbed by the spring elasticity of the lead portion 25. Therefore, the impact transmitted to the combustion part of the detection element 2 is reduced, so that the catalyst layer 23 is less likely to be lost, and the zero point can be suppressed from greatly changing due to the impact.
- the heater coil 22 having a coiled coil has a small variation in resistance value of the heater coil 22, and the bonding strength between the heater coil 22 and the electrode pins 32, 33 is high.
- the contact combustion type gas sensor 5 is obtained. Further, when manufacturing the contact combustion type gas sensor 5, it is easy to handle the heater coil 22 composed of a coiled coil.
- the welding method and its conditions, or the etching method and its conditions can be appropriately changed.
- the various numerical values and materials described above are examples, and are not limited thereto. There is no.
- the heater coil for a gas sensor, the sensing element for a gas sensor, the contact combustion type gas sensor, and the method for manufacturing the contact combustion type gas sensor, which are effective in the present invention, are useful for a gas leak detection device for home use or industrial use. It is suitable for a device for detecting a flammable gas used in a fuel cell.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006512011A JP4688794B2 (ja) | 2004-03-30 | 2005-03-24 | ガスセンサ用ヒータコイル、ガスセンサ用検知素子、接触燃焼式ガスセンサおよび接触燃焼式ガスセンサの製造方法 |
KR1020067020512A KR101099070B1 (ko) | 2004-03-30 | 2005-03-24 | 가스센서용 히터코일, 가스센서용 검지소자, 접촉 연소식가스센서 및 접촉 연소식 가스센서의 제조방법 |
US10/594,006 US7713480B2 (en) | 2004-03-30 | 2005-03-24 | Heater coil for gas sensor, detection element for gas sensor, contact combustion type gas sensor, and method for manufacturing contact combustion type gas sensor |
EP05727120.7A EP1731900B1 (en) | 2004-03-30 | 2005-03-24 | Detecting element for gas sensor and catalytic combustion gas sensor comprising detecting element |
US12/730,680 US8246913B2 (en) | 2004-03-30 | 2010-03-24 | Heater coil for gas sensor, detecting element for gas sensor, catalytic combustion gas sensor, and manufacturing method of catalytic combustion gas sensor |
US12/730,703 US8257656B2 (en) | 2004-03-30 | 2010-03-24 | Heater coil for gas sensor, detecting element for gas sensor, catalytic combustion gas sensor, and manufacturing method of catalytic combustion gas sensor |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2004101537 | 2004-03-30 | ||
JP2004101539 | 2004-03-30 | ||
JP2004-101539 | 2004-03-30 | ||
JP2004-101537 | 2004-03-30 |
Related Child Applications (3)
Application Number | Title | Priority Date | Filing Date |
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US10/594,006 A-371-Of-International US7713480B2 (en) | 2004-03-30 | 2005-03-24 | Heater coil for gas sensor, detection element for gas sensor, contact combustion type gas sensor, and method for manufacturing contact combustion type gas sensor |
US12/730,680 Division US8246913B2 (en) | 2004-03-30 | 2010-03-24 | Heater coil for gas sensor, detecting element for gas sensor, catalytic combustion gas sensor, and manufacturing method of catalytic combustion gas sensor |
US12/730,703 Division US8257656B2 (en) | 2004-03-30 | 2010-03-24 | Heater coil for gas sensor, detecting element for gas sensor, catalytic combustion gas sensor, and manufacturing method of catalytic combustion gas sensor |
Publications (1)
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WO2005098405A1 true WO2005098405A1 (ja) | 2005-10-20 |
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PCT/JP2005/005407 WO2005098405A1 (ja) | 2004-03-30 | 2005-03-24 | ガスセンサ用ヒータコイル、ガスセンサ用検知素子、接触燃焼式ガスセンサおよび接触燃焼式ガスセンサの製造方法 |
Country Status (5)
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US (3) | US7713480B2 (ja) |
EP (1) | EP1731900B1 (ja) |
JP (1) | JP4688794B2 (ja) |
KR (1) | KR101099070B1 (ja) |
WO (1) | WO2005098405A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005315845A (ja) * | 2004-03-30 | 2005-11-10 | Citizen Watch Co Ltd | ガスセンサ用検知素子および接触燃焼式ガスセンサ |
JP2010066174A (ja) * | 2008-09-11 | 2010-03-25 | Citizen Finetech Miyota Co Ltd | ガスセンサ |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US20170079089A1 (en) * | 2014-06-06 | 2017-03-16 | Panasonic Intellectual Property Management Co., Ltd. | Electrostatic grip detection device |
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- 2005-03-24 JP JP2006512011A patent/JP4688794B2/ja not_active Expired - Fee Related
- 2005-03-24 EP EP05727120.7A patent/EP1731900B1/en not_active Expired - Fee Related
- 2005-03-24 US US10/594,006 patent/US7713480B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
US8257656B2 (en) | 2012-09-04 |
EP1731900A4 (en) | 2011-05-11 |
JPWO2005098405A1 (ja) | 2008-02-28 |
EP1731900A1 (en) | 2006-12-13 |
US8246913B2 (en) | 2012-08-21 |
US20100175995A1 (en) | 2010-07-15 |
JP4688794B2 (ja) | 2011-05-25 |
KR101099070B1 (ko) | 2011-12-26 |
EP1731900B1 (en) | 2018-10-17 |
US20070209936A1 (en) | 2007-09-13 |
US7713480B2 (en) | 2010-05-11 |
US20100176094A1 (en) | 2010-07-15 |
KR20060131957A (ko) | 2006-12-20 |
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