Corrosion environment monitoring device and method

Abstract

The present invention provides a corrosion environment monitoring device and method, which suppress the reduction of the measurement accuracy of the corrosiveness of the environment at the beginning of monitoring, and measure the corrosiveness of the environment with high accuracy and continuously for a long time during the entire monitoring period, even in an environment with very serious corrosiveness. The corrosion environment monitoring device of the present invention is characterized in that it has: a stacked body, which has an insulating plate, a base metal film formed on the insulating plate and is difficult to be corroded by corrosive substances, and a sensing metal film formed on the base metal film and is easily corroded by corrosive substances; and a shell, which encloses the stacked body and has an opening in the side direction, forming a gas passage for the above-mentioned corrosive substances inside, wherein the sensing metal film is formed on a part of the base metal film.

Description

Technical Field

[0001] The invention relates to a corrosion environment monitoring device and method.

[0002] In particular, the present invention relates to a corrosion environment monitoring device and method for measuring the degree of corrosion in the environment and a corrosion environment monitoring device and method for measuring the concentration of corrosive gas in the environment according to the degree of corrosion in the environment.

[0003] In particular, the present invention relates to a corrosion environment monitoring device and method for measuring the degree of corrosion in the environment caused by corrosive gases present in the environment, taking the installation environment, storage environment, and transportation environment of electronic appliances as the objects, and a corrosion environment monitoring device and method for measuring the concentration of corrosive gases in the environment according to the degree of corrosion in the environment.

[0004] Moreover, the present invention relates to a corrosion environment monitoring device and method for measuring the degree of corrosion in the environment caused by corrosive gases present in the environment, taking the test environment of a gas corrosion test device and a gas release test device generated by organic materials as the object, and a corrosion environment monitoring device and method for measuring the concentration of corrosive gases in the environment according to the degree of corrosion in the environment. Background Art

[0005] As background technology in this technical field, there is WO2017-061182 (Patent Document 1).

[0006] Patent document 1 describes a corrosion environment monitoring device, which is composed of a shell having an opening on one surface, sealing surfaces other than the opening surface to form a space portion inside, and a first thin film metal that is difficult to be corroded by corrosive substances and is arranged from the depth side of the space portion toward the opening portion, and a second thin film metal that serves as a measuring component that is easily corroded by corrosive substances and is arranged along the first thin film metal from the depth side of the space portion toward the opening portion using the first thin film metal as a supporting component, and terminals to which an external voltage is applied that are arranged on both sides of the first thin film metal, and the second thin film metal is arranged from the depth side of the space portion toward the opening.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: WO2017-061182 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Social infrastructure equipment such as power, sewers, and factories requires stable operation because failures can affect social activities. In particular, for equipment that operates in a harsh, corrosive environment, it is important to ensure the corrosion resistance of the equipment itself and also of electronic equipment such as information equipment and control equipment installed together.

[0012] Appropriate anti-corrosion measures are taken in electronic equipment installed together with equipment that is expected to have corrosion failures, but there is a possibility of new corrosion failures in equipment with few installation examples and insufficient anti-corrosion measures. In order to implement appropriate anti-corrosion measures in such equipment, it is effective to quickly measure and diagnose the local environment, and a corrosion environment monitoring device that can measure the corrosiveness of the environment continuously over a long period of time is required.

[0013] The corrosion environment monitoring device described in Patent Document 1 can continuously measure the corrosiveness of the environment over a long period of time even in an extremely corrosive environment (IC5 level according to ISO 11844-1 standard).

[0014] However, Patent Document 1 does not describe a corrosion environment monitoring device that can improve the measurement accuracy of the corrosiveness of the environment at the initial stage of monitoring.

[0015] Therefore, the present invention provides a corrosion environment monitoring device and method for suppressing the reduction in measurement accuracy of environmental corrosivity at the beginning of monitoring and measuring the environmental corrosivity with high accuracy and continuously for a long time during the entire monitoring period, even in an environment with extremely severe corrosivity.

[0016] Methods for solving problems

[0017] In order to solve the above-mentioned problems, the corrosion environment monitoring device of the present invention comprises: a stacked body, which has an insulating plate, a base metal film formed on the insulating plate and which is not easily corroded by corrosive substances, and a sensing metal film formed on the base metal film and which is easily corroded by corrosive substances; and a shell, which encloses the stacked body and has an opening in the side direction, forming a gas passage for the above-mentioned corrosive substances inside, wherein the sensing metal film is formed in a partial area on the base metal film.

[0018] In addition, in order to solve the above-mentioned problems, the corrosion environment monitoring method of the present invention uses the above-mentioned corrosion environment monitoring device to measure the degree of corrosion in the environment; it is characterized in that the expansion speed of the area where corrosion products are generated in a part of the area is faster.

[0019] Effects of the Invention

[0020] According to the present invention, a corrosion environment monitoring device and method can be provided which can suppress the reduction in measurement accuracy of environmental corrosivity at the beginning of monitoring and can continuously measure the environmental corrosivity with high accuracy over a long period of time during the entire monitoring period, even in an environment with extremely severe corrosivity.

[0021] In addition, problems, structures, and effects other than those described above will be described through the following embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 1 and 2 : (a) a top view, (b) a side view of the AA section, and (c) a front view of a conventional corrosion environment monitoring device 1 .

[0023] Figure 2 1 and 2 are (a) a top view, (b) a side view of the AA cross section, and (c) a front view of the conventional corrosion environment monitoring device 1 after exposure.

[0024] Figure 3 It is a front view showing the corrosion condition of a stacked body consisting of an insulating plate, a base metal film, and a sensing metal film in a conventional corrosion environment monitoring device 1 before exposure, at time A after exposure, at time B after exposure, and at time C after exposure, and a curve graph showing the relationship between the exposure time and the resistance value corresponding to the corrosion condition.

[0025] Figure 4 It is a top view and a front view showing the corrosion condition of a stacked body consisting of an insulating plate, a base metal film, and a sensing metal film at time a after exposure, time b after exposure, and time c after exposure in a conventional corrosion environment monitoring device 1, and a curve chart showing the relationship between the exposure time and the resistance value corresponding to the corrosion condition.

[0026] Figure 5 1 and 2 . The corrosion environment monitoring device 1 of Example 1 is shown in (a) a top view, (b) a side view of the AA section, and (c) a front view.

[0027] Figure 6 1 and 2. The corrosion environment monitoring device 1 of Example 2 is shown in (a) a top view, (b) a side view of the AA section, and (c) a front view.

[0028] Figure 7 1 and 2 are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 3.

[0029] Figure 8 1 and 2 . These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 4.

[0030] Fig. 91 and 2 . These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 5.

[0031] Fig.10 These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 6.

[0032] Fig.11 These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 7.

[0033] Fig.12 These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 8.

[0034] Fig.13 These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 9. DETAILED DESCRIPTION

[0035] Hereinafter, embodiments of the present invention will be described using the drawings. However, substantially the same or similar structures are given the same reference numerals, and when the description is repeated, the description may be omitted.

[0036] In the following, in this embodiment, a corrosion environment monitoring device and method are described for suppressing the reduction in measurement accuracy of the corrosiveness of the environment at the beginning of monitoring and measuring the corrosiveness of the environment with high accuracy and continuously for a long time during the entire monitoring period, even in an environment with extremely severe corrosiveness.

[0037] In addition, in this embodiment, a corrosion environment monitoring device and method for measuring the degree of corrosion in the environment (the presence or absence of corrosive gas) are particularly described.

[0038] <Existing example>

[0039] First, before describing this embodiment, Figure 1 , Figure 2 , Figure 3 , Figure 4 , describing a conventional corrosion environment monitoring device.

[0040] Figure 1 1 and 2 : (a) a top view, (b) a side view of the AA section, and (c) a front view of a conventional corrosion environment monitoring device 1 .

[0041] The corrosion environment monitoring device 1 has the following structure.

[0042] (1) A sensor chip 20, which is composed of an insulating plate 4, a base metal film 2 made of a material that is not easily corroded by a corrosive gas 10 present in the environment and has a small resistance temperature change, and a U-shaped sensing metal film 3 formed in the entire area of ​​the base metal film 2 and made of a material that is easily corroded by the corrosive gas 10, using the base metal film 2 as a supporting member;

[0043] (2) a substrate 5 on which the sensor chip 20 is formed;

[0044] (3) a housing 6 containing a substrate 5, having an opening 7 for a gas passage 8 in a side direction (one surface), and sealing surfaces other than the surface of the one opening 7, thereby forming a gas passage 8 for a corrosive gas 10 in the interior;

[0045] (4) The lead electrodes 9 are formed at both ends of the sensor chip 20 and the resistance value is measured.

[0046] Here, the U-shaped portion has a short side portion formed with a predetermined width on the opening 7 side, and a deep side ( Figure 1 (a) and Figure 1 (c) (right side) has two long sides formed with a predetermined width.

[0047] That is, the corrosion environment monitoring device 1 has a shell 6 with an opening 7 on one surface, and the surfaces in other directions other than the surface of the opening 7 are sealed to form a gas passage 8 for the corrosive gas 10 inside, and a base metal film 2 formed from one side of the opening 7 to the deep side of the gas passage 8 and is difficult to be corroded by the corrosive gas 10, and a sensing metal film 3 as a measuring component that uses the base metal film 2 as a supporting component and is formed along the base metal film 2 from one side of the opening 7 to the deep side of the gas passage 8 and is easily corroded by the corrosive gas 10, and lead-out electrodes 9 formed on both sides of the base metal film 2 for measuring the resistance value.

[0048] Figure 2 1 and 2 are (a) a top view, (b) a side view of the AA cross section, and (c) a front view of the conventional corrosion environment monitoring device 1 after exposure.

[0049] When the corrosion environment monitoring device 1 of the prior art is exposed to the environment, Figure 2 As shown, the corrosive gas 10 existing in the environment invades from the opening 7, and the corrosion area of ​​the sensing metal film 3 (the area where the corrosion product 31 is generated) expands from the opening 7 where the concentration flux of the corrosive gas 10 is high to the deep side (right side) of the gas passage 8.

[0050] The expansion of the corrosion area is explained as follows. That is, when the corrosion product 31 generated by the corrosion of the sensing metal film 3 reaches the lower surface of the sensing metal film 3 (the interface with the base metal film 2), it will not corrode further toward the lower surface. Therefore, the corrosive gas 10 is not consumed toward the lower surface during the corrosion reaction, but is consumed toward the deep side of the gas passage 8. The corrosive gas 10 corrodes the sensing metal film 3 toward the deep side of the gas passage 8.

[0051] At this time, the upper surface of the sensing metal film 3 (the surface in contact with the gas passage 8) is as follows: Figure 2 As shown in (c), the corrosion progresses faster than the lower surface of the sensing metal film 3. The variation of the corrosion is achieved by limiting the diffusion direction of the corrosive gas 10 and controlling the corrosion rate of the sensing metal film 3 by the gas passage 8.

[0052] In addition, if Figure 2 As shown in (a), a part of the sensing metal thin film 3 is transformed into a corrosion product 31 by corrosion, so the resistance value between the extraction electrodes 9 formed at both ends of the sensor chip 20 increases after exposure compared to before exposure (initial value).

[0053] Here, the metal used in the sensing metal film 3 (sensing metal) has a relatively low resistivity, and the generated corrosion product 31 has a relatively high resistivity. Furthermore, the metal used in the base metal film 2 (base metal) has a relatively high resistivity compared to the sensing metal.

[0054] In addition, by determining in advance the relationship between the corrosion amount of the sensing metal film 3 and the resistance value between the lead-out electrode 9, the corrosion amount can be estimated from the measured resistance value. In addition, by determining in advance the relationship between the corrosion amount of the sensing metal film 3 and the concentration of corrosive gas in the environment, the concentration of corrosive gas can be estimated from the measured resistance value.

[0055] Figure 3 It is a front view showing the corrosion condition of a stacked body consisting of an insulating plate, a base metal film, and a sensing metal film in a conventional corrosion environment monitoring device 1 before exposure, at time A after exposure, at time B after exposure, and at time C after exposure, and a curve graph showing the relationship between the exposure time and the resistance value corresponding to the corrosion condition.

[0056] Here, the change in resistance value between the lead-out electrodes 9 formed at both ends of the sensor chip 20 corresponding to the corrosion conditions before exposure, at post-exposure time A, post-exposure time B, and post-exposure time C (post-exposure time A < post-exposure time B < post-exposure time C) of the existing example of the corrosion environment monitoring device 1 is schematically described.

[0057] In addition, about Figure 1The corrosion environment monitoring device 1 of the conventional example shown is described using the sensor chip 20 . Here, for simplicity of description, an I-type (rectangular) sensor chip is used for description. Figure 3 , the opening 7 side of the I-type sensor chip is shown in an enlarged manner. In addition, regarding the resistance value, it is assumed that the resistance value is measured at both ends of the I-type sensor chip.

[0058] Before exposure, both the base metal film 2 and the sensing metal film 3 are not corroded.

[0059] The resistance value of the sensor chip before exposure is calculated by using the resistance R of the base metal film 2. BM1 The resistance R of the sensing metal film 3 SM1 Parallel circuit representation of .

[0060] Then, since the resistivity of the sensing metal is smaller than that of the base metal, the resistance value of the sensor chip before exposure is equal to the resistance value of the sensing metal film 3 (resistance R SM1 )express.

[0061] At time A after exposure, due to the corrosive gas 10 in the environment, corrosion products 31 are formed from the upper surface of the sensing metal film 3 connected to the gas passage 8. The corrosive gas 10 intrudes from the opening 7 (left side) to the deep side (right side) of the gas passage 8, so the sensing metal film 3 is corroded from the opening 7 where the concentration flux of the corrosive gas 10 is high.

[0062] At the time A after the exposure, a corrosion product 31 is partially formed at the left end of the sensing metal thin film 3, and only L of the sensing metal thin film 3 remains.

[0063] The resistance value of the sensor chip at time A after exposure is expressed as follows: BM2 and resistor R BM3 , the resistance R of the sensing metal film 3 SM2 and resistor R SM3 , the resistance R of the corrosion product 31 CP2 The equivalent circuit representation of .

[0064] Furthermore, according to the magnitude relationship between the resistivity of the base metal, the resistivity of the sensing metal, and the resistivity of the corrosion product 31, the resistance value of the sensor chip at time A after exposure becomes as shown by the dotted arrow, which can be expressed by the resistance R of the sensing metal film 3. SM2 With resistor R SM3 In addition, the change between the resistance value of the sensor chip at time A after exposure and the resistance value of the sensor chip before exposure is still small.

[0065] At time B after exposure, due to the corrosive gas 10 present in the environment, corrosion products 31 are formed from the upper surface of the sensing metal film 3 connected to the gas passage 8. The corrosive gas 10 further intrudes from the opening 7 (left side) to the deep side of the gas passage 8, so the sensing metal film 3 is further corroded from the opening 7 where the concentration flux of the corrosive gas 10 is high.

[0066] At the time B after the exposure, at the left end of the sensing metal film 3, the corrosion product 31 reaches the lower surface of the sensing metal film 3, and no sensing metal film 3 remains.

[0067] The resistance value of the sensor chip at time B after exposure is expressed as follows: BM4 and resistor R BM5 , the resistance R of the sensing metal film 3 SM4 and resistor R SM5 , the resistance R of the corrosion product 31 CP4 The equivalent circuit representation of .

[0068] Furthermore, according to the magnitude relationship between the resistivity of the base metal, the resistivity of the sensing metal, and the resistivity of the corrosion product 31, the resistance value of the sensor chip at time B after exposure becomes as shown by the dotted arrow, which can be expressed by the resistance R of the sensing metal film 3. SM4 With resistor R SM5 In addition, the change between the resistance value of the sensor chip at time B after exposure and the resistance value of the sensor chip before exposure is still small.

[0069] In addition, the change in the resistance value of the sensor chip increases with the post-exposure time B as the boundary.

[0070] At the time C after exposure, due to the corrosive gas 10 in the environment, corrosion products 31 are formed from the upper surface of the sensing metal film 3 connected to the gas passage 8. The corrosive gas 10 further intrudes from the opening 7 (left side) to the deep side of the gas passage 8, so the sensing metal film 3 is further corroded from the opening 7 where the concentration flux of the corrosive gas 10 is high.

[0071] At time C after exposure, at the left end of the sensing metal film 3, the corrosion product 31 reaches the lower surface of the sensing metal film 3, and no sensing metal film 3 remains. Furthermore, on the lower surface of the sensing metal film 3, the corrosion product 31 is also formed toward the deep side of the gas passage 8.

[0072] The resistance value of the sensor chip at the time C after exposure is expressed as follows: BM6 and resistor R BM7 and resistor R BM8 , the resistance R of the sensing metal film 3SM7 and resistor R SM8 , the resistance R of the corrosion product 31 CP6 and resistor R CP7 The equivalent circuit representation of .

[0073] Furthermore, according to the magnitude relationship between the resistivity of the base metal, the resistivity of the sensing metal, and the resistivity of the corrosion product 31, the resistance value of the sensor chip at the time C after exposure becomes as shown by the dotted arrow, which can be calculated by the resistance R of the base metal film 2. BM6 , and the resistance R of the sensing metal film 3 SM7 and R SM8 In addition, the resistance value of the sensor chip at time C after exposure and the resistance value of the sensor chip before exposure vary greatly.

[0074] Figure 4 It is a top view and a front view showing the corrosion condition of a stacked body consisting of an insulating plate, a base metal film, and a sensing metal film at time a after exposure, time b after exposure, and time c after exposure in a conventional corrosion environment monitoring device 1, and a curve chart showing the relationship between the exposure time and the resistance value corresponding to the corrosion condition.

[0075] Here, a problem that the measurement accuracy of the corrosiveness of the environment decreases at the beginning of monitoring in the corrosion environment monitoring device 1 will be described.

[0076] At time a after exposure, on the left side of the sensor metal film 3, the corrosion product 31 reaches the lower surface of the sensor metal film 3, and no sensor metal film 3 remains. Furthermore, on the lower surface of the sensor metal film 3, the corrosion product 31 is also formed toward the deep side (right side) of the gas passage 8. That is, on the left side of the sensor metal film 3, an area where no sensor metal film 3 remains is confirmed.

[0077] However, in the conventional corrosion environment monitoring device 1 using the sensor chip 20, although corrosion progresses in this way, Figure 4 Even if a small amount of the sensing metal thin film 3 remains in the region 1 (the portion having the width of the short side) in the middle, the resistance value of the sensor chip 20 is almost unchanged.

[0078] That is, at the time a after the exposure, the change in the resistance value of the sensor chip 20 is small. Therefore, the initial measurement accuracy of monitoring the corrosiveness of the environment is reduced.

[0079] On the other hand, Figure 4 Area 1 in the whole corroded ( Figure 4With the exposure time b (when no sensing metal film 3 remains in the region 1) as the boundary, the change in the resistance value of the sensor chip 20 increases, and at the exposure time c, the change in the resistance value of the sensor chip 20 is relatively large.

[0080] (Example 1)

[0081] Next, the corrosion environment monitoring device 1 of the first embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the first embodiment.

[0082] Figure 5 1 and 2 . The corrosion environment monitoring device 1 of Example 1 is shown in (a) a top view, (b) a side view of the AA section, and (c) a front view.

[0083] The corrosion environment monitoring device 1 of Example 1 has the following structure.

[0084] (1) A sensor chip (laminate) 20, which comprises an insulating plate 4, a base metal film 2 formed on the insulating plate 4 and made of a material that is not easily corroded by a corrosive gas 10 (e.g., corrosive substances such as SO2, NO2, H2S, S8) present in the environment and has a small resistance-temperature change, and a sensing metal film 3 (with a thickness of 1 μm or less) as a measuring component formed on the base metal film 2 and made of a material that is easily corroded by the corrosive gas 10, with the base metal film 2 as a supporting member;

[0085] (2) a substrate 5 on which the sensor chip 20 is formed;

[0086] (3) a housing 6 containing a sensor chip 20, having an opening 7 (with a width of 10 mm or less and a height of 5 mm or less) in a lateral direction (one surface), and sealing surfaces other than the surface of the one opening 7, thereby forming a gas passage 8 for the corrosive gas 10 in the interior; and

[0087] (4) The lead electrodes 9 are formed at both ends of the sensor chip 20 and the resistance value is measured.

[0088] That is, the corrosion environment monitoring device 1 of Example 1 includes a shell 6 having an opening 7 on one surface, sealing the surfaces in other directions other than the opening 7 to form a gas passage 8 for the corrosive gas 10 inside, and a base metal film 2 formed from one side of the opening 7 to the deep side (right side) of the gas passage 8 and difficult to be corroded by the corrosive gas 10, and a sensing metal film 3 as a measuring component which is supported by the base metal film 2 and is formed at two long sides (3a and 3b) along the base metal film 2 from one side of the opening 7 to the deep side of the gas passage 8 and is easily corroded by the corrosive gas 10, and lead-out electrodes 9 for measuring resistance values ​​formed on both sides of the base metal film 2.

[0089] Thus, in the corrosion environment monitoring device 1 of Example 1, in particular, the base metal film 2 is formed by a short side portion on the insulating plate 4, which is formed with a prescribed width on one side of the opening 7, and two long sides on both sides of the short side portion, which are formed with a prescribed width from one side of the opening 7 to the depth side of the gas passage 8, and the sensing metal film 3 is formed by two long sides on the base metal film 2, which are located on both sides of the short side portion, which are formed with a prescribed width from one side of the opening 7 to the depth side of the gas passage 8.

[0090] That is, in the corrosion environment monitoring device 1 of Example 1, the short side portion on the opening side 7 is a stacked portion consisting of the insulating plate 4 and the base metal film 2, and the two long sides (3a and 3b) are a stacked portion consisting of the insulating plate 4, the base metal film 2 and the sensing metal film 3.

[0091] Here, the partial region on the base metal thin film 2 refers to two long sides formed from the opening 7 side toward the deep side of the gas passage 8 excluding the short sides.

[0092] In addition, in the corrosion environment monitoring device 1 of Example 1, the opening 7 side of the sensing metal thin film 3 has a shape parallel to the opening 7 .

[0093] The sensing metal is a metal with a relatively low resistivity and a relatively high resistivity of the generated corrosion product 31. Examples of the sensing metal include copper, copper alloys, silver, silver alloys (such as silver-palladium alloys), aluminum, iron, zinc, lead, and the like, and the metal and the corrosion product 31 thereof have different resistance values.

[0094] The base metal is a metal having a higher resistivity than the sensing metal, for example, titanium, chromium, gold, palladium, stainless steel, or the like.

[0095] In addition, as the corrosion product 31, for example, when silver is used as the sensor metal and the corrosive gas 10 is, for example, H2S, S8, etc., silver sulfide is generated.

[0096] In addition, in the corrosion environment monitoring method of Example 1, such a corrosion environment monitoring device 1 is used to measure the degree of corrosion in the environment, and by forming a partial area on the sensing metal film 3, the expansion speed of the area where corrosion products are generated in the partial area is accelerated.

[0097] Thus, according to Example 1, it is possible to suppress the decrease in the measurement accuracy of the environmental corrosivity at the beginning of monitoring. Moreover, even in an extremely corrosive environment, the environmental corrosivity can be measured continuously and accurately over a long period of time during the entire monitoring period.

[0098] In addition, the base metal film 2 is formed to be biased from the opening 7 to the deep side of the gas passage 8, and the sensing metal film 3 is formed to be further biased from the opening 7 to the deep side of the gas passage 8 than the base metal film 2. Thus, the measurement accuracy of the corrosiveness of the environment can be stabilized at the initial stage of monitoring.

[0099] In order to form the sensing metal thin film 3 in a partial region on the base metal thin film 2, the following process is used.

[0100] (1) On the insulating plate 4, the base metal thin film 2 is formed by sputtering or plating.

[0101] (2) Next, a mask is applied to the area other than the area where the sensing metal thin film 3 is to be formed (two long sides formed with a predetermined width from one side of the opening 7 to the deep side of the gas passage 8 on both sides of the short side), and the sensing metal thin film 3 is formed by sputtering or plating.

[0102] In order to form the sensing metal thin film 3 in a partial region on the base metal thin film 2, the following process is used.

[0103] (1) On the insulating plate 4, the base metal thin film 2 and the sensor metal thin film 3 are formed by sputtering or plating.

[0104] (2) Next, a mask is applied to the region where the sensing metal thin film 3 is formed (two long sides formed with a predetermined width from the opening 7 side to the deep side of the gas passage 8 on both sides of the short side), and the sensing metal thin film 3 is removed by etching. In the etching, a solution that is inactive to the base metal thin film 2 and active only to the sensing metal thin film 3 is used.

[0105] In order to form the sensing metal film 3 in a partial region on the base metal film 2, screen printing or inkjet printing can also be used.

[0106] Furthermore, the corrosion environment monitoring device 1 of the first embodiment can also be used as a highly reliable gas sensor for detecting changes in the corrosive gas concentration of the corrosive gas 10 .

[0107] (Example 2)

[0108] Next, the corrosion environment monitoring device 1 of the second embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the second embodiment.

[0109] Figure 6 1 and 2. The corrosion environment monitoring device 1 of Example 2 is shown in (a) a top view, (b) a side view of the AA section, and (c) a front view.

[0110] The corrosion environment monitoring device 1 of the second embodiment is different from the corrosion environment monitoring device 1 of the first embodiment in that the shape of the front end of the opening 7 of the sensing metal film 3 is different.

[0111] In the corrosion environment monitoring device 1 of the second embodiment, unlike the corrosion environment monitoring device 1 of the first embodiment, the opening 7 side of the sensing metal film 3 has a region (reference numeral 1 ) where the width of the sensing metal film 3 is narrower than the region (region with a constant cross-sectional area) on the deep side of the gas passage 8. Figure 6 (a)). That is, in the sensing metal film 3 formed in a part of the base metal film 2, a region where the width of the sensing metal film 3 is narrower than that of the region on the deep side of the gas passage 8 is formed on the side of the opening 7 (sharp portion: a region where the width of the sensing metal film 3 continuously increases from the side of the opening 7 toward the deep side of the gas passage 8).

[0112] Alternatively, the sharp portion may be a region where the width of the sensing metal film 3 increases in a stepwise manner.

[0113] The sharp portion is a region where the cross-sectional area increases from the opening 7 side to the deep side of the gas passage 8, and is a region where the width of the sensing metal film 3 increases continuously from the opening 7 side to the deep side of the gas passage 8. The sharp portion is a region with a smaller cross-sectional area than the region on the deep side of the gas passage 8.

[0114] The concentration flux of the corrosive gas 10 invading from the opening 7 is concentrated on the sharp portion of the sensing metal film 3 where the width is narrower. Therefore, the time until the sensing metal film 3 is corroded and the corrosion product 31 is generated is shorter. The expansion speed of the area where the corrosion product 31 is generated is faster at the sharp portion than the area on the deeper side of the gas passage 8 relative to the sharp portion.

[0115] Therefore, according to Example 2, the time from before exposure to time B after exposure can be shortened, and the reduction in measurement accuracy of the corrosiveness of the environment at the initial stage of monitoring can be suppressed.

[0116] (Example 3)

[0117] Next, the corrosion environment monitoring device 1 of the third embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the third embodiment.

[0118] Figure 7 1 and 2 are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 3.

[0119] The corrosion environment monitoring device 1 of the third embodiment is different from the corrosion environment monitoring device 1 of the first embodiment in that the shape of the front end of the opening 7 of the sensing metal film 3 is different.

[0120] In the corrosion environment monitoring device 1 of the third embodiment, unlike the corrosion environment monitoring device 1 of the first embodiment, the film thickness of the sensing metal film 3 is thinner than the area on the deep side of the gas passage 8 (the area with a constant cross-sectional area) on the side of the opening 7 of the sensing metal film 3 (reference Figure 7 (c)). That is, in the sensing metal film 3 formed in a part of the base metal film 2, a region where the film thickness of the sensing metal film 3 is thinner than that of the region on the deep side of the gas passage 8 is formed on the side of the opening 7 (sharp portion: a region where the height of the sensing metal film 3 increases stepwise or continuously from the side of the opening 7 toward the deep side of the gas passage 8).

[0121] The region where the film thickness of the sensing metal thin film 3 is thinner is a region having a smaller cross-sectional area than the region on the deep side of the gas passage 8 .

[0122] The concentration flux of the corrosive gas 10 invading from the opening 7 is concentrated in the area where the film thickness of the sensing metal film 3 is thinner. Therefore, the time from the corrosion of the sensing metal film 3 to the generation of the corrosion product 31 is shorter, and the area where the corrosion product 31 is generated expands faster than the area on the deeper side of the gas passage 8 relative to the area with thinner film thickness.

[0123] In Example 3, the sharp portion is a region where the height of the sensing metal film 3 is lower than the region on the deep side of the gas passage 8. The sharp portion may be a region where the height of the sensing metal film 3 increases stepwise from the opening 7 side toward the deep side of the gas passage 8, or may be a region where the height of the sensing metal film 3 increases continuously.

[0124] Therefore, according to Example 3, the time from before exposure to time B after exposure can be shortened, and the reduction in measurement accuracy of the corrosiveness of the environment at the initial stage of monitoring can be suppressed.

[0125] (Example 4)

[0126] Next, the corrosion environment monitoring device 1 of the fourth embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the fourth embodiment.

[0127] Figure 8 1 and 2 . These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 4.

[0128] The corrosion environment monitoring device 1 of the fourth embodiment is different from the corrosion environment monitoring device 1 of the first embodiment in that a coating film 41 is formed on the opening 7 side of the sensing metal film 3 .

[0129] In the corrosion environment monitoring device 1 of Example 4, unlike the corrosion environment monitoring device 1 of Example 1, a coating film 41 is formed on the sensing metal film 3 on the side of the opening 7 of the sensing metal film 3. That is, in Example 4, there is a region on the side of the opening 7 of the sensing metal film 3 where the coating film 41 is formed.

[0130] In addition, the coating film 41 is made of a material that is not easily corroded by the corrosive gas 10 and has a small resistance temperature change, similar to the base metal film 2. In addition, the coating film 41 is not limited to a metal material, and may be an organic material as long as the corrosive gas 10 does not penetrate the coating film 41 and corrode the sensing metal film 3 formed thereunder.

[0131] The concentration flux of the corrosive gas 10 invading from the opening 7 is concentrated on the side portion (front end portion) of the opening 7 of the sensing metal film 3. Therefore, the time from the corrosion of the sensing metal film 3 to the generation of the corrosion product 31 is short, and the area where the coating film 41 is formed and the corrosion product 31 is generated expands faster than the area on the deeper side of the gas passage 8 relative to the area where the coating film 41 is formed.

[0132] Therefore, according to Example 4, the time from before exposure to time B after exposure can be shortened, and the reduction in measurement accuracy of the corrosiveness of the environment at the initial stage of monitoring can be suppressed.

[0133] (Example 5)

[0134] Next, the corrosion environment monitoring device 1 of the fifth embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the fifth embodiment.

[0135] Fig. 9 1 and 2 . These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 5.

[0136] The corrosion environment monitoring device 1 of the fifth embodiment is different from the corrosion environment monitoring device 1 of the first embodiment in that the shape of the front end of the opening 7 of the sensing metal film 3 is different.

[0137] In the corrosion environment monitoring device 1 of Example 5, unlike the corrosion environment monitoring device 1 of Example 1, on the side of the opening 7 of the sensing metal film 3, there is a region where the width of the sensing metal film 3 is narrower than the region on the deep side of the gas passage 8 (region with a constant cross-sectional area) (reference Fig. 9 (a)). That is, in the sensing metal film 3 formed in a part of the base metal film 2, a region where the width of the sensing metal film 3 is narrower than that of the region on the deep side of the gas passage 8 is formed on the side of the opening 7 (sharp portion: a region where the width of the sensing metal film 3 increases stepwise from the side of the opening 7 toward the deep side of the gas passage 8).

[0138] Alternatively, the sharp portion may be a region where the width of the sensing metal thin film 3 continuously increases.

[0139] The sharp portion is a region where the cross-sectional area increases from the opening 7 side to the deep side of the gas passage 8, and is a region where the width of the sensing metal film 3 increases stepwise from the opening 7 side to the deep side of the gas passage 8. The sharp portion is a region with a smaller cross-sectional area than the region on the deep side of the gas passage 8.

[0140] The concentration flux of the corrosive gas 10 invading from the opening 7 is concentrated on the sharp portion of the sensing metal film 3 where the width is narrower. Therefore, the time until the sensing metal film 3 is corroded and the corrosion product 31 is generated is shorter. The expansion speed of the area where the corrosion product 31 is generated is faster at the sharp portion than the area on the deeper side of the gas passage 8 relative to the sharp portion.

[0141] Therefore, according to Example 5, the time from before exposure to time B after exposure can be shortened, and the reduction in measurement accuracy of the corrosiveness of the environment at the initial stage of monitoring can be suppressed.

[0142] (Example 6)

[0143] Next, the corrosion environment monitoring device 1 of the sixth embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the sixth embodiment.

[0144] Fig.10 These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 6.

[0145] The corrosion environment monitoring device 1 of the sixth embodiment is different from the corrosion environment monitoring device 1 of the first embodiment in that the shape of the front end portion 42 of the sensing metal thin film 3 on the side of the opening 7 is provided.

[0146] In the corrosion environment monitoring device 1 of Example 6, unlike the corrosion environment monitoring device 1 of Example 1, on the side of the opening portion 7 of the sensing metal film 3, there is a region where the width of the base metal film 2 and the sensing metal film 3 is narrower than the region on the deep side of the gas passage 8 (region with a constant cross-sectional area) (reference Fig.10 That is, in the base metal film 2 and the sensor metal film 3 formed in a part of the region on the insulating plate 4, a region (front end portion 42) having a narrower width of the base metal film 2 and the sensor metal film 3 than the region on the deep side of the gas passage 8 is formed on the side of the opening 7 thereof.

[0147] The tip portion 42 is formed in a partial region on the insulating plate 4 by partially removing the base metal film 2 and the sensor metal film 3 on the side of the opening 7. The tip portion 42 can also be formed by mechanical cutting in addition to sputtering with a mask and etching with a mask.

[0148] The front end portion 42 is a region having a smaller cross-sectional area than a region on the back side of the gas passage 8 .

[0149] In Example 6, the front end portion 42 is a region where the widths of the base metal film 2 and the sensor metal film 3 continuously increase compared to the region on the deep side of the gas passage 8 .

[0150] The concentration flux of the corrosive gas 10 invading from the opening 7 is concentrated in the front end portion 42, so the time from the corrosion of the sensing metal film 3 to the generation of the corrosion product 31 is short, and the expansion speed of the area where the corrosion product 31 is generated is faster in the front end portion 42 than in the area on the deeper side of the gas passage 8 relative to the front end portion 42.

[0151] Therefore, according to Example 6, the time from before exposure to time B after exposure can be shortened, and due to the effect of the base metal with relatively large resistance, the reduction in measurement accuracy at the initial stage of monitoring due to the corrosiveness of the environment can be further suppressed.

[0152] (Example 7)

[0153] Next, the corrosion environment monitoring device 1 of the seventh embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the seventh embodiment.

[0154] Fig.11 These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 7.

[0155] The corrosion environment monitoring device 1 of the seventh embodiment is different from the corrosion environment monitoring device 1 of the first embodiment in that the shape of the front end portion 43 of the sensing metal thin film 3 on the side of the opening 7 is provided.

[0156] In the corrosion environment monitoring device 1 of Example 7, unlike the corrosion environment monitoring device 1 of Example 1, on the side of the opening portion 7 of the sensing metal film 3, there is a region where the width of the base metal film 2 and the sensing metal film 3 is narrower than the region on the deep side of the gas passage 8 (region with a constant cross-sectional area) (reference Fig.11 That is, in the base metal film 2 and the sensor metal film 3 formed in a part of the region on the insulating plate 4, a region (front end portion 43) having a narrower width of the base metal film 2 and the sensor metal film 3 than the region on the deep side of the gas passage 8 is formed on the side of the opening 7 thereof.

[0157] The tip portion 43 is formed in a partial region on the insulating plate 4 by partially removing the base metal film 2 and the sensor metal film 3 on the side of the opening 7. The tip portion 43 can also be formed by mechanical cutting in addition to sputtering with a mask and etching with a mask.

[0158] The front end portion 43 is a region having a smaller cross-sectional area than a region on the back side of the gas passage 8 .

[0159] In Example 7, the front end portion 43 is a region where the widths of the base metal film 2 and the sensor metal film 3 increase stepwise compared to the region on the deep side of the gas passage 8 .

[0160] The concentration flux of the corrosive gas 10 invading from the opening 7 is concentrated in the front end portion 43, so the time from the corrosion of the sensing metal film 3 to the generation of the corrosion product 31 is short, and the expansion speed of the area where the corrosion product 31 is generated is faster in the front end portion 43 than in the area on the deeper side of the gas passage 8 relative to the front end portion 43.

[0161] Therefore, according to Example 7, the time from before exposure to time B after exposure can be shortened, and due to the effect of the base metal with relatively large resistance, the reduction in measurement accuracy at the initial stage of monitoring due to the corrosiveness of the environment can be further suppressed.

[0162] (Example 8)

[0163] Next, the corrosion environment monitoring device 1 of the eighth embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the eighth embodiment.

[0164] Fig.12 These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 8.

[0165] The corrosion environment monitoring device 1 of Example 8 is different from the corrosion environment monitoring device 1 of Example 1 in the opening shape of the opening 7 of the housing 6 .

[0166] In the corrosion environment monitoring device 1 of Example 8, unlike the corrosion environment monitoring device 1 of Example 1, there is a region 81 (reference numeral 81) in which the height (cross-sectional area) of the gas passage 8 formed in the region on the side of the opening 7 is higher (cross-sectional area is larger) than the height (cross-sectional area) of the gas passage 8 formed in the region on the deep side of the gas passage 8 (region with a constant cross-sectional area). Fig.12 (c)).

[0167] The high region 81 of the gas passage 8 is a region with a larger cross-sectional area than a region on the deep side of the gas passage 8 .

[0168] In Example 8, since the high region 81 of the gas passage 8 is formed, the total amount of the corrosive gas 10 intruding from the opening 7 increases, and the corrosive gas 10 is concentrated on the sensing metal film 3 on the side of the opening 7. Therefore, the sensing metal film 3 on the side of the opening 7 corrodes, and the high region 81 of the gas passage 8 expands faster than the region on the deep side of the gas passage 8 to generate the corrosion product 31.

[0169] In Example 8, a higher height region 81 of the gas passage 8 is formed. The higher height region 81 of the gas passage 8 may be a region whose height decreases stepwise from one side of the opening 7 toward the depth side of the gas passage 8, or may be a region whose height decreases continuously.

[0170] Therefore, according to Example 8, the time from before exposure to time B after exposure can be shortened, and the reduction in measurement accuracy of the corrosiveness of the environment at the initial stage of monitoring can be suppressed.

[0171] (Example 9)

[0172] Next, the corrosion environment monitoring device 1 of the thirteenth embodiment will be described. The basic structure of the corrosion environment monitoring device 1 of the conventional example is also applicable to the ninth embodiment.

[0173] Fig.13 These are (a) a top view, (b) a side view of the AA section, and (c) a front view of the corrosion environment monitoring device 1 of Example 9.

[0174] The corrosion environment monitoring device 1 of Example 9 is different from the corrosion environment monitoring device 1 of Example 1 in the opening shape of the opening 7 of the housing 6 .

[0175] In the corrosion environment monitoring device 1 of Example 9, unlike the corrosion environment monitoring device 1 of Example 1, there is a region 91 (reference numeral 91) in which the width (cross-sectional area) of the gas passage 8 formed in the region on the side of the opening 7 is wider (the cross-sectional area is larger) than the width (cross-sectional area) of the gas passage 8 formed in the region on the deep side of the gas passage 8 (the region with a constant cross-sectional area). Fig.13 (a)).

[0176] The wide region 91 of the gas passage 8 is a region having a larger cross-sectional area than a region on the deep side of the gas passage 8 .

[0177] In Example 9, since the wider area 91 of the gas passage 8 is formed, the total amount of the corrosive gas 10 intruding from the opening 7 increases, and the corrosive gas 10 is concentrated on the sensing metal film 3 on the side of the opening 7. Therefore, the sensing metal film 3 on the side of the opening 7 corrodes, and the area where the corrosion product 31 is generated in the wider area 91 of the gas passage 8 expands faster than the area on the deep side of the gas passage 8.

[0178] In Example 9, a wider region 91 of the gas passage 8 is formed. The wider region 91 of the gas passage 8 may be a region whose width decreases stepwise from one side of the opening 7 toward the depth side of the gas passage 8, or may be a region whose width decreases continuously.

[0179] Therefore, according to Example 9, the time from before exposure to time B after exposure can be shortened, and the reduction in measurement accuracy of the corrosiveness of the environment at the initial stage of monitoring can be suppressed.

[0180] In addition, the present invention is not limited to the above-described embodiments, and includes various modified examples. For example, the above-described embodiments are specifically described in order to explain the present invention in an easy-to-understand manner, and are not limited to necessarily having all the described structures.

[0181] In addition, a part of the structure of a certain embodiment can be replaced with a part of the structure of another embodiment. In addition, a part of the structure of another embodiment can be added to a part of the structure of a certain embodiment. In addition, a part of the structure of each embodiment can be deleted, added with a part of another structure, or replaced with a part of another structure.

[0182] Description of Reference Numerals

[0183] 1……Corrosion environment monitoring device

[0184] 2...Base metal film

[0185] 3……Sensing metal film

[0186] 4...Insulation board

[0187] 5...Substrate

[0188] 6……Housing

[0189] 7... Opening

[0190] 8...Gas passage

[0191] 9...Leader electrode

[0192] 10...Corrosive gases

[0193] 20...Sensor chip

[0194] 31……Corrosion products

[0195] 41……Coating film

[0196] 42……Front end

[0197] 43……Front end

[0198] 81 ... a higher area of ​​the gas passage 8

[0199] 91 is a region where the width of the gas passage 8 is relatively wide.

Claims

1. A corrosion environment monitoring device, characterized in that: have: A laminate having an insulating plate, a base metal film which is difficult to be corroded by a corrosive substance and is formed on the insulating plate and in contact with the insulating plate, and a sensing metal film which is easily corroded by a corrosive substance and is formed on the base metal film and in contact with the base metal film; and The housing has the stacked body therein and has an opening in the side direction, and a gas passage for the corrosive substance is formed inside. The base metal film includes: a short side portion formed to have a predetermined width on the opening side; and two long sides formed at both sides of the short side with a predetermined width from the opening side toward the depth side of the gas passage, The sensing metal film is formed only on two long sides of the base metal film but not on the short sides.

2. The corrosion environment monitoring device according to claim 1, characterized in that: The sensing metal film forms a sharp portion on one side of the opening. The sharp portion is a region where the width or height of the sensing metal thin film increases continuously or stepwise from the opening side toward the depth side of the gas passage.

3. The corrosion environment monitoring device according to claim 1, characterized in that: On one side of the opening of the two long sides of the base metal film formed on the insulating plate and the sensor metal film formed on the base metal film, there is a front end portion whose width is narrower than the area on the deep side of the gas passage.

4. The corrosion environment monitoring device according to claim 1, characterized in that: The cross-sectional area of ​​the gas passage in a region formed on one side of the opening is larger than the cross-sectional area of ​​the gas passage in a region formed on a deeper side of the gas passage.

5. A corrosion environment monitoring device, characterized in that: have: A laminate having an insulating plate, a base metal film which is difficult to be corroded by a corrosive substance and is formed on the insulating plate and in contact with the insulating plate, and a sensing metal film which is easily corroded by a corrosive substance and is formed on the base metal film and in contact with the base metal film; and The housing has the stacked body therein and has an opening in the side direction, and a gas passage for the corrosive substance is formed inside. The base metal film includes: a short side portion formed to have a predetermined width on the opening side; and two long sides formed at both sides of the short side with a predetermined width from the opening side toward the depth side of the gas passage, The sensing metal film is formed on the short side and two long sides of the base metal film, and a coating film that is difficult to be corroded by corrosive substances is formed only on the short side of the base metal film.

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