JP2021169933A - Sensor, evaluation device for corrosion between dissimilar materials, and evaluation method for corrosion between dissimilar materials - Google Patents

Abstract

To provide a sensor used for evaluating corrosion between dissimilar materials, an evaluation device for corrosion between dissimilar materials that can easily evaluate corrosion between dissimilar materials, and an evaluation method for corrosion between dissimilar materials.SOLUTION: This sensor is used to evaluate corrosion between dissimilar materials. The sensor has a quartz crystal oscillator, an electrode provided on one surface of the quartz crystal oscillator, and two evaluation material parts provided on the electrode. The two evaluation material parts are composed of different materials and are in direct contact with each other.SELECTED DRAWING: Figure 2

Description

The present invention relates to a sensor, an evaluation device for corrosion between dissimilar materials, and an evaluation method for corrosion between dissimilar materials.

It is known that corrosion between dissimilar metals, that is, galvanic corrosion occurs between dissimilar metals in a state where dissimilar materials such as dissimilar metals are in contact with each other. It is known that the above-mentioned galvanic corrosion not only impairs the reliability and durability of the object, but also causes various problems. Therefore, it has been required to avoid galvanic corrosion by designing so that the chemical that mediates the corrosion does not cause galvanic corrosion when dissimilar metals come into contact with each other. For example, Non-Patent Document 1 proposes a method of obtaining charge transfer resistance at the interface between a metal and a CMP slurry by an AC impedance method and suppressing galvanic corrosion generated between dissimilar metals.

Electrochemical analysis of metal corrosion in semiconductor CMP process Chemical Times 2017 No.3 p13-17.

Galvanic corrosion is evaluated using electrochemical measurements such as the AC impedance method as described in Non-Patent Document 1 described above. In electrochemical measurement, corrosion potential, corrosion current, etc. were the main points of evaluation. However, the electrochemical method evaluates the degree of electron transfer associated with the oxidation of the metal, and covers all the phenomena that actually occur, such as metal oxidation, metal oxide complexation, and dissolution in the system. Not something to catch. Therefore, there is no perfect correlation between the result of the electrochemical measurement and the magnitude of galvanic corrosion that actually occurs, and it is only an index as a reference value. For example, after designing a chemical solution or the like, it was necessary to finally apply the degree of galvanic corrosion to the one actually used and confirm whether it is acceptable or not. In order to completely suppress the slight corrosion that occurs when dissimilar metals come into contact with each other, it is necessary to evaluate what is actually used. It is desired that corrosion between dissimilar materials such as galvanic corrosion can be easily evaluated.

An object of the present invention is to provide a sensor used for evaluating corrosion between dissimilar materials, an evaluation device for corrosion between dissimilar materials that can easily evaluate corrosion between dissimilar materials, and a method for evaluating corrosion between dissimilar materials.

In order to achieve the above object, the first aspect of the present invention is a sensor used for evaluating corrosion between dissimilar materials, which comprises a crystal oscillator and an electrode provided on one surface of the crystal oscillator. , The two evaluation material parts are provided with two evaluation material parts provided on the electrodes, and the two evaluation material parts provide a sensor which is composed of different materials and is in direct contact with each other.
A second aspect of the present invention is a sensor used for evaluating corrosion between dissimilar materials, which comprises a crystal transducer, a first electrode provided on one surface of the crystal transducer, and one of the crystal transducers. It has a second electrode provided on one surface and electrically insulated from the first electrode, and two evaluation material portions provided on the first electrode and the second electrode. The two evaluation material parts are composed of different materials and are in direct contact with each other, and at least one evaluation material part of the two evaluation material parts is provided on at least one of the first electrode and the second electrode. , Provides a sensor.
A third aspect of the present invention is a sensor used for evaluating corrosion between dissimilar materials, which comprises a crystal oscillator, a first electrode provided on one surface of the crystal oscillator, and one of the crystal oscillators. It has a second electrode provided on one surface and electrically insulated from the first electrode, and two evaluation material parts provided on the first electrode, and the two evaluation material parts are provided. Provided is a sensor, which is composed of different materials and is in direct contact with each other, and the second electrode is provided with an evaluation material portion which is corroded by corrosion between different materials among the two evaluation material portions. ..

A fourth aspect of the present invention is a sensor used for evaluating corrosion between dissimilar materials, which comprises a crystal transducer, a first electrode provided on one surface of the crystal transducer, and one of the crystal transducers. A second electrode provided on one surface and electrically insulated from the first electrode, and an electrode provided on one surface of the crystal transducer and electrically isolated from the first electrode and the second electrode. It has a third electrode in an insulated state and two evaluation material parts provided on the first electrode and the second electrode, and the third electrode has a different type of the two evaluation material parts. An evaluation material part that is corroded by inter-material corrosion is provided, and the two evaluation material parts are composed of different materials and are in direct contact with each other, and at least one of the two evaluation material parts has an evaluation material part. It provides a sensor provided on at least one of a first electrode and a second electrode.
A fifth aspect of the present invention is a sensor used for evaluating corrosion between dissimilar materials, which comprises a crystal transducer, a first electrode provided on one surface of the crystal transducer, and one of the crystal transducers. A second electrode provided on one surface and electrically insulated from the first electrode, and an electrode provided on one surface of the crystal transducer and electrically isolated from the first electrode and the second electrode. It has a third electrode in an insulated state and two evaluation material parts provided on the first electrode, and the two evaluation material parts are made of different materials and are in direct contact with each other. Provided is a sensor in which one of the two evaluation material parts is provided on the second electrode, and the other evaluation material part of the two evaluation material parts is provided on the third electrode. It is a thing.

A sixth aspect of the present invention is a sensor used for evaluating corrosion between dissimilar materials, which comprises a crystal transducer, a first electrode provided on one surface of the crystal transducer, and one of the crystal transducers. A second electrode provided on one surface and electrically insulated from the first electrode, and an electrode provided on one surface of the crystal transducer and electrically isolated from the first electrode and the second electrode. A third electrode in an insulated state and a fourth electrode provided on one surface of the crystal transducer and electrically insulated from the first electrode, the second electrode, and the third electrode. It has an electrode and two evaluation material parts provided on the first electrode and the second electrode, and one of the two evaluation material parts is provided on the third electrode, and the first evaluation material part is provided. The electrode 4 is provided with the other evaluation material part of the two evaluation material parts, and the two evaluation material parts are made of different materials and are in direct contact with each other, and at least one of the two evaluation material parts. The evaluation material section of the above provides a sensor provided on at least one of the first electrode and the second electrode.
The evaluation material section is a material selected from Au, Si, SiO ₂ , SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, Ru, Mo, Zn, oxides containing these, and alloys. It is preferably composed of.

A seventh aspect of the present invention is an evaluation device for evaluating corrosion between dissimilar materials to a target liquid, wherein the sensor of the first aspect of the present invention and an oscillating unit that vibrates the crystal oscillator of the sensor at a resonance frequency. Provided is an evaluation device for corrosion between different materials, which is connected to an electrode of a sensor and has a detection unit for detecting the amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material part due to the target liquid. be.
The eighth aspect of the present invention is an evaluation device for evaluating corrosion between dissimilar materials with respect to a target liquid, and includes a sensor according to the second aspect of the present invention and an oscillating unit that vibrates the crystal oscillator of the sensor at a resonance frequency. Corrosion between dissimilar materials, which is connected to the first electrode and the second electrode of the sensor and has a detection unit for detecting the amount of change in the resonance frequency of the crystal oscillator due to corrosion between dissimilar materials of the evaluation material portion due to the target liquid. It provides an evaluation device for.
A ninth aspect of the present invention is an evaluation device for evaluating corrosion between dissimilar materials with respect to a target liquid, wherein the sensor of the third aspect of the present invention and an oscillating unit that vibrates the crystal oscillator of the sensor at a resonance frequency. , Connected to the first electrode of the sensor and changed in the resonance frequency of the crystal unit due to corrosion between different materials in the evaluation material part by the target liquid, and connected to the second electrode and corroded by corrosion between different materials. It is an object of the present invention to provide an evaluation device for corrosion between dissimilar materials, which has a detection unit for detecting a change in the resonance frequency of a crystal unit due to a target liquid of the evaluation material unit.

A tenth aspect of the present invention is an evaluation device for evaluating corrosion between different materials with respect to a target liquid, and includes a sensor of the fourth aspect of the present invention and an oscillating unit that vibrates the crystal oscillator of the sensor at a resonance frequency. , Connected to the first and second electrodes of the sensor, the amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials in the evaluation material part by the target liquid, and connected to the third electrode, between different materials It is an object of the present invention to provide an evaluation device for corrosion between dissimilar materials, which has a detection unit for detecting the amount of change in the resonance frequency of the crystal oscillator due to the target liquid of the evaluation material unit corroded by corrosion.
The eleventh aspect of the present invention is an evaluation device for evaluating corrosion between different materials with respect to a target liquid, and includes a sensor of the fifth aspect of the present invention and an oscillating unit that vibrates the crystal oscillator of the sensor at a resonance frequency. Of the two evaluation material parts, which are connected to the first electrode of the sensor and connected to the second electrode, the amount of change in the resonance frequency of the crystal unit due to corrosion between different materials in the evaluation material part due to the target liquid. The amount of change in the resonance frequency of the crystal unit due to the target liquid of one evaluation material part and the resonance of the crystal unit due to the target liquid of the other evaluation material part of the two evaluation material parts connected to the third electrode. It is an object of the present invention to provide an evaluation device for corrosion between dissimilar materials, which has a detection unit for detecting the amount of change in frequency.
A twelfth aspect of the present invention is an evaluation device for evaluating corrosion between different materials with respect to a target liquid, and includes a sensor according to the sixth aspect of the present invention and an oscillating unit that vibrates the crystal oscillator of the sensor at a resonance frequency. , Connected to the first and second electrodes of the sensor, the amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material part by the target liquid, and connected to the third electrode, two evaluations Of the material parts, the amount of change in the resonance frequency of the crystal oscillator due to the target liquid of one evaluation material part and the target liquid of the other evaluation material part of the two evaluation material parts connected to the fourth electrode The present invention provides an evaluation device for corrosion between dissimilar materials, which has a detection unit for detecting a change in the resonance frequency of a crystal oscillator.

It may have a calculation unit for calculating the corrosion rate of corrosion between dissimilar materials based on the amount of change in the resonance frequency detected by the detection unit.
It is preferable to have a supply unit that supplies the target liquid to the sensor and brings the target liquid into contact with the sensor.
It is preferable that at least a part of the wetted portion in contact with the target liquid is made of a fluororesin.
Further, it is preferable to have a display unit for displaying the amount of change in the resonance frequency.
The supply unit preferably supplies the target liquid by flowing it through the sensor in one direction.
The supply unit circulates and supplies the target liquid to the sensor, and the circulation flow rate of the target liquid is preferably 0.01 to 1000 ml / s.
For example, the target liquid is a liquid containing at least one component and water, and the components are alkali metal halides, alkaline earth metal halides, hydroxylamines or derivatives thereof, hydrogen fluoride, amino. It is selected from the group consisting of alcohols, quaternary ammonium salts, and hydrogen peroxides.
The evaluation material part of the sensor is selected from Au, Si, SiO ₂ , SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, Ru, Mo, Zn, and oxides and alloys containing these. It is preferably composed of a new material.

The thirteenth aspect of the present invention is an evaluation method for evaluating corrosion between dissimilar materials with respect to a target liquid, in which the sensor of the first or second aspect of the present invention is brought into contact with the target liquid, and the crystal vibration of the sensor. The present invention provides a method for evaluating corrosion between dissimilar materials, which comprises a detection step of vibrating the child at a resonance frequency and detecting a change in the resonance frequency of the crystal oscillator due to corrosion between dissimilar materials in the evaluation material portion due to the target liquid. ..
The fourteenth aspect of the present invention is an evaluation method for evaluating corrosion between dissimilar materials with respect to a target liquid, in which the sensor of the third or fourth aspect of the present invention is brought into contact with the target liquid to vibrate the crystal of the sensor. The child is vibrated at the resonance frequency, and the amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials in the evaluation material part due to the target liquid and the amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials and the crystal oscillator due to the target liquid in the evaluation material part corroded by the target liquid. It provides a method for evaluating corrosion between dissimilar materials, which has a detection step of detecting a change amount of a resonance frequency.
A fifteenth aspect of the present invention is an evaluation method for evaluating corrosion between dissimilar materials with respect to a target liquid, in which the sensor of the fifth or sixth aspect of the present invention is brought into contact with the target liquid, and the crystal vibration of the sensor. The child is vibrated at the resonance frequency, and the amount of change in the resonance frequency of the crystal transducer due to corrosion between different materials in the evaluation material part by the target liquid and the crystal vibration due to the target liquid in one of the two evaluation material parts. Evaluation of corrosion between dissimilar materials, which has a detection step of detecting the amount of change in the resonance frequency of the child and the amount of change in the resonance frequency of the crystal transducer due to the target liquid of the other evaluation material part of the two evaluation material parts. It provides a method.

A step of calculating the corrosion rate of corrosion between dissimilar materials may be included based on the amount of change in the resonance frequency detected in the detection step.
It is preferable to supply the target liquid to the sensor to bring the target liquid into contact with the sensor.
It is preferable to supply the target liquid by flowing it through the sensor in one direction.
The supply unit circulates and supplies the target liquid to the sensor, and the circulation flow rate of the target liquid is preferably 0.01 to 1000 ml / s.
The evaluation material part of the sensor is selected from Au, Si, SiO ₂ , SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, Ru, Mo, Zn, and oxides and alloys containing these. It is preferably composed of a new material.
For example, the target liquid is a liquid containing at least one component and water, and the components are alkali metal halides, alkaline earth metal halides, hydroxylamines or derivatives thereof, hydrogen fluoride, amino. It is selected from the group consisting of alcohols, quaternary ammonium salts, and hydrogen peroxides.

According to the present invention, corrosion between dissimilar materials can be easily evaluated.

It is a schematic diagram which shows an example of the evaluation apparatus of corrosion between dissimilar materials of embodiment of this invention. It is a schematic cross-sectional view which shows the 1st example of the sensor of embodiment of this invention. It is a graph which shows an example of the calibration curve which shows the relationship between the corrosion amount and the resonance frequency of a crystal oscillator. It is a schematic diagram which shows an example of the flow cell unit of the evaluation apparatus of corrosion between dissimilar materials of embodiment of this invention. It is a schematic diagram which shows the 2nd example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 2nd example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 3rd example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 3rd example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 4th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 4th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 5th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 5th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 6th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 6th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 7th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 7th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 8th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 8th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 9th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 9th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the tenth example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the tenth example of the sensor of embodiment of this invention. It is a schematic diagram which shows the eleventh example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the eleventh example of the sensor of embodiment of this invention. It is a schematic diagram which shows the twelfth example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the twelfth example of the sensor of embodiment of this invention. It is a schematic diagram which shows the thirteenth example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the thirteenth example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 14th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 14th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the fifteenth example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the fifteenth example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 16th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 16th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 17th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 17th example of the sensor of embodiment of this invention. It is a schematic diagram which shows the 18th example of the sensor of embodiment of this invention. It is a schematic cross-sectional view which shows the 18th example of the sensor of embodiment of this invention.

Hereinafter, the sensor of the present invention, the evaluation device for corrosion between dissimilar materials, and the evaluation method for corrosion between dissimilar materials will be described in detail based on the preferred embodiments shown in the accompanying drawings.
It should be noted that the figures described below are exemplary for explaining the present invention, and the present invention is not limited to the figures shown below.
In the following, "~" indicating the numerical range includes the numerical values described on both sides. For example, when ε is a numerical value α to a numerical value β, the range of ε is a range including the numerical value α and the numerical value β, and is α ≦ ε ≦ β in mathematical symbols.
Here, dissimilar materials refer to materials having "different material types". More specifically, a dissimilar material is one that satisfies one or both of those having different chemical constituents and those having different physical properties. As a specific example of dissimilar materials, for example, Cu and CuO ₂ have different constituent components and different physical properties. Here, Cu has conductivity, but CuO ₂ has low conductivity and has characteristics close to those of an insulator. Therefore, these two kinds are different materials.
Further, Cu formed by plating and Cu formed by PVD (Physical Vapor Deposition) have the same chemical constituents. However, the physical properties are different. Cu formed by plating has a low Redox Potential, but Cu formed by PVD has different physical properties such as a relatively low Redox Potential. For this reason, these two types are included in "dissimilar metals", that is, dissimilar materials.

[Evaluator for corrosion between dissimilar materials]
FIG. 1 is a schematic view showing an example of an evaluation device for corrosion between dissimilar materials according to the embodiment of the present invention, and FIG. 2 is a schematic cross-sectional view showing a first example of the sensor according to the embodiment of the present invention.
The dissimilar material corrosion evaluation device 10 shown in FIG. 1 is a device that evaluates dissimilar material corrosion in dissimilar materials composed of different materials, and evaluates, for example, the corrosion rate and the like. Hereinafter, the evaluation device 10 for corrosion between dissimilar materials is simply referred to as the evaluation device 10.
The evaluation device 10 includes a flow cell unit 12, an oscillation unit 14, a detection unit 15, a calculation unit 16, a memory 18, a supply unit 20, and a control unit 22. The evaluation device 10 further includes a display unit 23, an output unit 24, and an input unit 25.
The control unit 22 controls the operations of the flow cell unit 12, the oscillation unit 14, the detection unit 15, the calculation unit 16, the memory 18, and the supply unit 20. Further, the control unit 22 controls each component of the evaluation device 10 based on the operation control of the display unit 23 and the output unit 24 and the input information from the input unit 25.

The flow cell unit 12 includes a sensor 26 having an evaluation material body 35 (see FIG. 2) for evaluating corrosion between dissimilar materials, and a temperature adjusting unit 28 for maintaining the temperature of the target liquid supplied to the flow cell unit 12. And have. The flow cell unit 12 will be described in detail later. As shown in FIG. 2, the evaluation material body 35 (see FIG. 2) is composed of two evaluation material parts, a first evaluation material part 36 and a second evaluation material part 38. The two evaluation material parts are composed of different materials and are in direct contact with each other. The sensor 26 is also a crystal oscillator sensor having a crystal oscillator 27.

As shown in FIG. 2, the oscillator 14 is electrically connected to the sensor 26. The oscillating unit 14 vibrates the crystal oscillator 27 at a resonance frequency. The oscillating unit 14 applies a high-frequency signal of a sine wave to the sensor 26 as a frequency signal, and has an oscillating circuit (not shown).
Further, the detection unit 15 is electrically connected to the oscillation unit 14. The detection unit 15 measures the resonance frequency of the crystal oscillator 27 and detects the amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material portion by the target liquid. The detection unit 15 may detect the amount of change in the resonance frequency of the crystal oscillator due to the target liquid of the evaluation material unit that is corroded by corrosion between different materials, which will be described later.

The detection unit 15 takes in the frequency signal of the oscillation unit 14, samples the frequency signal every second, for example, and stores it in the memory 18 as time series data. The memory 18 stores the measurement time and the frequency tolerance. The detection unit 15 measures the resonance frequency of the crystal oscillator 27 based on the measurement time and the allowable frequency value, and detects the amount of change in the resonance frequency of the crystal oscillator due to the contact of the target liquid.
The measurement time is the time required to obtain the amount of change in the resonance frequency due to the occurrence of corrosion between dissimilar materials in the two evaluation material bodies 35 constituting the evaluation material body 35. The measurement time is not particularly limited and is appropriately determined according to the supply flow rate of the target liquid and the like. For example, 3 minutes or more is preferable, and 15 minutes or more is more preferable. The upper limit is not particularly limited, but from the viewpoint of productivity, 3 hours or less is preferable, and 2 hours or less is more preferable.
The frequency permissible value is a threshold value for determining whether or not the value that is an index of frequency stabilization becomes a sufficiently small value corresponding to stabilization when determining whether or not the frequency is stable. The frequency tolerance is appropriately set according to, for example, the set measurement sensitivity. For example, when the resonance frequency is 30 MHz, the error range allowed in the measurement time when the measurement sensitivity is 5 Hz is, for example, It is set to 0.5 Hz. This corresponds to 0.0167 ppm. The permissible value corresponding to this error range is 1.67 × ^10-8 (0.0167 ppm) or less.

The detection unit 15 detects the frequency by, for example, a frequency counter which is a known circuit. In addition to this, for example, as described in Japanese Patent Application Laid-Open No. 2006-258787, a frequency signal is analog-digitally converted, processed by a carrier move to generate a rotation vector that rotates at the frequency of the frequency signal, and this rotation vector. The frequency may be detected by using a technique such as finding the speed of. In the detection unit 15, it is preferable to use such digital processing because the frequency detection accuracy is high.

The calculation unit 16 calculates the corrosion rate of corrosion between dissimilar materials based on the amount of change in the resonance frequency detected by the detection unit. The calculation unit 16 reads out the amount of change in the resonance frequency based on the previously measured corrosion between different materials stored in the memory 18, and the amount of change in the resonance frequency based on the degree of corrosion between different materials stored in the memory 18. The amount of change in the resonance frequency obtained by the detection unit 15 is compared with the amount of change in the resonance frequency to obtain the amount of corrosion between different materials. Then, the corrosion rate of the corrosion between different materials is calculated based on the time when the amount of corrosion of the corrosion between different materials is obtained. The corrosion rate of the above-mentioned corrosion between different materials calculated by the calculation unit 16 is displayed on the display unit 23. In addition to this, the corrosion rate of corrosion between dissimilar materials may be output to the output unit 24.

The memory 18 stores the amount of change in the resonance frequency based on the amount of corrosion between different materials measured in advance. In addition to this, the memory 18 may store the resonance frequency of the crystal oscillator and the like. Corrosion between dissimilar materials occurs in various material combinations. The amount of change in resonance frequency based on the amount of corrosion between dissimilar materials in various material combinations may be stored. Further, in the corrosion between dissimilar materials, at least the amount of change in the resonance frequency due to the corrosion of the evaluation material portion alone in which the corrosion occurs may be stored.

The amount of change in the resonance frequency stored in the memory 18 is, for example, as shown in FIG. 3, a calibration curve L showing the relationship with the resonance frequency of the crystal transducer 27 caused by corrosion between different materials by a specific target liquid. Based on this calibration curve L, the relationship between the amount of corrosion between dissimilar materials and the amount of change in resonance frequency caused by corrosion between dissimilar materials due to a specific target liquid can be obtained.
The amount of corrosion on the calibration curve L shown in FIG. 3 is the amount of reduction measured by, for example, using a scale by corroding the object to be measured for corrosion between different materials. More specifically, a calibration curve L can be obtained by actually causing corrosion between different materials and measuring the amount of decrease before and after corrosion and the resonance frequency before and after corrosion for the measurement target of corrosion between different materials.
The scale for measuring the amount of reduction is not particularly limited as long as it has a performance capable of measuring the amount of corrosion, and an electronic balance or the like can be used.

The display unit 23 displays the amount of change in the resonance frequency obtained by the calculation unit 16, and is composed of, for example, a display. The display is not particularly limited as long as it can display characters and images, and a liquid crystal display device or the like is used. Further, what is displayed on the display unit 23 is not limited to the amount of change in the obtained resonance frequency, but may be a resonance frequency, and as will be described later, a plurality of resonance frequencies obtained by using a plurality of electrodes. The difference in the amount of change in the above may be used, and various setting items and input information set by the evaluation device 10 may be displayed.
The output unit 24 displays on a medium the amount of change in the obtained resonance frequency, the resonance frequency, the corrosion rate of corrosion between dissimilar materials, and the like. More specifically, for example, at least one of characters, symbols and barcodes is used for display. The output unit 24 is composed of a printer or the like.
The input unit 25 is various input devices for inputting various information such as a mouse and a keyboard according to an operator's instruction. For example, the evaluation device 10 is set, data is called from the memory 18, and the like are made via the input unit 25.
The input unit 25 also includes an interface for inputting information to be stored in the memory 18, and the information is stored in the memory 18 through an external storage medium or the like.
If the amount of change in the resonance frequency is obtained, it is possible to determine corrosion. Therefore, the evaluation device 10 only needs to be able to obtain the obtained change amount of the resonance frequency, and is not necessarily required to have a configuration other than obtaining the change amount of the resonance frequency. From this, for example, the calculation unit 16 is necessary in the management method, but is not necessarily necessary in the evaluation device 10 for obtaining the amount of change in the resonance frequency. However, since the evaluation device 10 can calculate the corrosion rate of corrosion between different materials, the calculation unit 16 may be provided.

The flow cell unit 12 causes corrosion between dissimilar materials in the two evaluation material portions provided in the sensor 26. The flow cell unit 12 is connected to the supply unit 20 by using a first tube 29a and a second tube 29b. The target liquid passes through the first tube 29a by the supply unit 20, the target liquid is supplied to the crystal oscillator, the target liquid is passed through the second tube 29b, and the target liquid is collected. The supply unit 20 allows the target liquid to pass through the first tube 29a and the second tube 29b without coming into contact with the target liquid, and for example, a peristaltic type pump is used. The supply unit 20 is not particularly limited as long as it can supply the liquid without coming into contact with the target liquid, and for example, a syringe pump can be used.
The temperature adjusting unit 28 has, for example, a Perche element. The liquid temperature of the target liquid is maintained by the Perche element. As a result, the temperature of the target liquid can be kept constant, and the viscosity of the target liquid can be kept within a constant range. Fluctuations in measurement conditions for corrosion between dissimilar materials can be reduced. The configuration of the temperature adjusting unit 28 is not particularly limited as long as the temperature of the target liquid can be maintained.

[Sensor]
As described above, the sensor 26 has a crystal oscillator 27, and the crystal oscillator 27 has, for example, a disk shape, and is located between the front surface 27a, the back surface 27b facing the front surface 27a, and between the front surface 27a and the back surface 27b. Moreover, it has a side surface 27c provided along the outer edge of the front surface 27a and the back surface 27b. The side surface 27c is a circumferential surface. In the sensor 26, for example, the electrode 30 is provided on the front surface 27a of the crystal oscillator 27, and the back surface electrode 31 is provided on the back surface 27b. The electrode 30 may be provided on one surface of the sensor 26. Therefore, the arrangement position of the electrode 30 is not limited to the front surface 27a of the crystal oscillator 27, and may be any surface of the front surface 27a, the back surface 27b, and the side surface 27c of the crystal oscillator 27, for example. The side surface 27c may be used.
For example, the evaluation material body 35 is provided on the surface 27a of the crystal oscillator 27 and on the surface 30a of the electrode 30. The evaluation material body 35 is composed of two evaluation material units, a first evaluation material unit 36 and a second evaluation material unit 38. The first evaluation material portion 36 is provided on the surface 30a of the electrode 30, and the second evaluation material portion 38 is directly laminated on the surface 36a of the first evaluation material portion 36.
As the crystal oscillator 27, for example, an AT-cut type crystal oscillator is used. The AT-cut type crystal oscillator is an oscillator cut out at an angle of 35 ° 15'from the Z axis of the artificial quartz. The sensor 26 is not limited to the configuration shown in FIG.

The oscillating unit 14 is electrically connected to the electrode 30 and the back surface electrode 31. The oscillating unit 14 applies a sine wave high-frequency signal as a frequency signal to the electrode 30 and the back surface electrode 31, and has, for example, an oscillating circuit. The oscillating unit 14 causes the crystal oscillator 27 to vibrate at the resonance frequency. The resonance frequency of the crystal oscillator 27 is, for example, 27 MHz or 30 MHz.
The first evaluation material unit 36 and the second evaluation material unit 38 are composed of materials for evaluating corrosion between dissimilar materials. For example, Au, Si, SiO ₂ , SiOC, Cu, Co, W, Ti, Consists of materials selected from TiN, Ta, TaN, Ru, Mo, Zn, and oxides containing them, and alloys.
The first evaluation material part 36 and the second evaluation material part 38 can be formed by a vapor phase method such as a sputtering method or a CVD (chemical vapor deposition) method, or a coating method or the like.

In the sensor 26, the resonance frequency of the crystal oscillator 27 changes due to corrosion between different materials that occurs at the portion where the first evaluation material portion 36 and the second evaluation material portion 38 come into contact with each other. The amount of change in the resonance frequency can be obtained by measuring the resonance frequency before and after the contact with the target liquid for causing corrosion. The amount of change ΔF in the resonance frequency of the crystal oscillator 27 can be expressed by the following equation called the Sauerbrey equation. In the following equation, F ₀ is the resonance frequency, Δm is the amount of mass change, ρ is the density of the crystal, μ is the shear stress of the crystal, and A is the area of the electrode. From the following equation, by increasing the resonant frequency F ₀ of the crystal oscillator, to increase the mass sensitivity, i.e., it is possible to increase the measurement accuracy of the impurities.

[Flow cell unit]
FIG. 4 is a schematic view showing an example of a flow cell unit of the measuring device according to the embodiment of the present invention.
In the flow cell unit 12, for example, the sensor 26 is arranged on the temperature adjusting unit 28 via the seal unit 43. A seal portion 42 is provided on the sensor 26 along the periphery of the crystal oscillator 27. The block 40 is arranged on the seal portion 42. The block 40 is provided with a supply path 40a for supplying the target liquid to the sensor 26. The supply path 40a is connected to the first tube 29a. Further, the block 40 is provided with a discharge path 40b for discharging the target liquid from the sensor 26. The discharge path 40b is connected to the second tube 29b. That is, the flow cell unit 12 has a seal portion 42 arranged on the sensor 26, a supply path 40a arranged on the sensor 26 via the seal portion 42 and supplying the target liquid to the sensor 26, and the target liquid as a sensor. It further has a block 40 provided with a discharge path 40b for discharging from 26, and a liquid feeding section including a first tube 29a connected to the supply path 40a and a second tube 29b connected to the discharge path 40b.
The target liquid that has passed through the first tube 29a and the supply path 40a is supplied to the region 44 formed by being surrounded by the sensor 26, the seal portion 42, and the block 40. That is, the seal portion 42 is arranged outside the region 44. As a result, the target liquid comes into contact with the evaluation material body 35 on the surface 30a of the electrode 30 of the crystal oscillator 27 of the sensor 26. Further, the target liquid passes through the discharge path 40b and the second tube 29b, and is discharged from the region 44. A circulation line is formed by the first tube 29a and the discharge path 40b, and the second tube 29b and the discharge path 40b.

The movement of the target liquid in the first tube 29a and the supply path 40a and the second tube 29b and the discharge path 40b is performed by the supply unit 20 (see FIG. 1) as described above.
For example, the seal portion 42 and the seal portion 43 have the same size, and are composed of, for example, an O-ring. The target liquid is not supplied to the region 45 formed by being surrounded by the sensor 26, the seal portion 43, and the temperature adjusting portion 28.
Further, in the flow cell unit 12, by forming at least a part of the wetted portion in contact with the target liquid with a fluororesin, elution into the target liquid can be suppressed, and a decrease in measurement accuracy of corrosion between different materials can be suppressed. preferable.
In the evaluation device 10, the surface formed by being surrounded by the above-mentioned sensor 26, the seal portion 42, and the block 40 and forming the region 44 for holding the target liquid on the sensor 26 is a wetted portion in contact with the target liquid. It corresponds to a part of. In addition to the region 44, in the supply unit that brings the target liquid into contact with the sensor 26, the portion of the liquid feeding unit that sends the target liquid to the sensor that comes into contact with the target liquid is also a liquid contact portion. It is preferable that at least a part of these wetted parts is made of a fluororesin. Examples of the liquid feeding unit include a supply line that feeds the liquid in one direction and a circulation line that circulates and supplies the target liquid to the sensor.
More specifically, the liquid contact portion is a portion of the flow cell unit 12 that is in contact with the surface 40c of the block 40 in contact with the region 44, and a portion of the seal portion 42 that holds the target liquid arranged on the sensor 26 in the region 44. The surface 42a, the supply path 40a of the block 40, and the discharge path 40b of the block 40. Further, the inside of the first tube 29a and the inside of the second tube 29b are also wetted parts in contact with the target liquid, and the parts of the first tube 29a and the second tube 29b in contact with the target liquid are made of a fluororesin. It is preferable to do so.
Among them, at least a part of the wetted portion in contact with the target liquid of the seal portion 42, the wetted portion in contact with the target liquid of the block 40, and the wetted portion in contact with the target liquid of the liquid feeding portion is composed of a fluororesin. Is preferable.

The fluorine-based resin may be a resin containing a fluorine atom.
The fluorine-based resin is not particularly limited as long as it is a resin (polymer) containing a fluorine atom, and a known fluorine-based resin can be used. Examples of the fluororesin include polytetrafluoroethylene (PTFE, tensile strength: 20 to 35 MPa, Shore D hardness: 50 to 55), perfluoroalkoxyalkane, polychlorotrifluoroethylene, polyvinylidene fluoride, and ethylene tetrafluoroethylene. Examples thereof include copolymers, ethylene chlorotrifluoroethylene copolymers, perfluoroethylene propene copolymers, tetrafluoroethylene perfluoroalkyl vinyl ether copolymers, and cyclized polymers of perfluoro (butenyl vinyl ether) (Cytop®). ..

In particular, when the wetted portion (the portion in contact with the target liquid) of the block 40 of the flow cell unit 12 in contact with the target liquid is composed of a fluororesin, the tensile strength of the fluororesin may be 20 to 60 MPa. preferable. The shore D hardness of the fluororesin is preferably 60 to 80.
Examples of the fluororesin constituting the wetted portion in contact with the target liquid of the block 40 include perfluoroalkoxy alkane (PFA, tensile strength: 25 to 35 MPa, shore D hardness: 62 to 66), ethylene tetrafluoroethylene copolymer (ETFE,). Tensile strength: 38-42 MPa, Shore D hardness: 67-78), Perfluoroethylene propene copolymer (FEP, Tensile strength: 20-30 MPa, Shore D hardness: 60-65), Polychlorotrifluoroethylene (PCTFE, Tensile strength) : 31-41 MPa, shore D hardness: 75-80), or polychlorovinylidene (PVDF, tensile strength: 30-70 MPa, shore D hardness: 64-79) is preferable.
The tensile strength is measured according to JIS (Japanese Industrial Standards) K 7161.
The shore D hardness is measured according to JIS K 7215.

Further, the fluorine-based resin constituting the wetted part (the part in contact with the target liquid) in contact with the target liquid of the liquid feeding part for sending the target liquid to the region 44 includes fluorine atoms, carbon atoms, and fluorine atoms and carbon atoms. It is preferable to have a repeating unit containing other atoms other than the above (hereinafter, also simply referred to as “specific repeating unit”). Examples of the other atom include a hydrogen atom and a chlorine atom. That is, the specific repeating unit preferably contains a fluorine atom, a carbon atom, and at least one other atom selected from the group consisting of a hydrogen atom and a chlorine atom.
Examples of the fluororesin constituting the portion of the liquid feeding portion in contact with the target liquid include a ternary copolymer (THV soft fluororesin) of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, polyvinylidene fluoride, and ethylenetetra. Fluoroethylene copolymer or polychlorotrifluoroethylene is preferable.
The method for measuring the tensile strength and the shore D hardness is as described above.

The portion of the seal portion 42 that holds the target liquid arranged on the sensor 26 in contact with the target liquid (the surface 42a that is in contact with the region 44) is preferably made of a fluororesin.
The tensile strength of the fluororesin constituting the portion of the seal portion 42 in contact with the target liquid is preferably 20 to 40 MPa. Further, the shore D hardness of the fluororesin constituting the portion of the seal portion 42 in contact with the target liquid is preferably 56 to 70. Further, the flexural modulus of the fluororesin constituting the portion of the seal portion 42 in contact with the target liquid is preferably 0.5 to 3 GPa.
When the fluororesin constituting the portion of the seal portion 42 in contact with the target liquid satisfies the tensile strength, the shore D hardness, and the flexural modulus, the vibration of the sensor 26 is not hindered and more stable measurement is performed. be able to.
The method for measuring the tensile strength and the shore D hardness is as described above.
The flexural modulus is measured according to JIS K 7171.
Examples of the fluororesin constituting the portion of the seal portion 42 in contact with the target liquid include perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylenechlorotrifluoroethylene copolymer, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene, or , Polyfluoridene fluoride is preferred.

The supply unit 20 circulates the target liquid by using the first tube 29a and the second tube 29b, but the present invention is not limited to this, and a method in which the target liquid flows in one direction may be used. .. In this case, for example, a syringe pump can be used.
When the target liquid is circulated and supplied to the crystal oscillator 27, the circulation flow rate of the target liquid is preferably 0.01 to 1000 ml / s. When the circulation flow rate is 0.01 to 1000 ml / s, a sufficient amount of the target liquid can be supplied to the sensor 26 to cause corrosion between dissimilar materials.
The arrangement of the sensor 26 in the flow cell unit 12 is not particularly limited.

[Evaluation method for corrosion between dissimilar materials]
In the method for evaluating corrosion between dissimilar materials, the sensor 26 shown in FIG. 2 is brought into contact with the target liquid. Next, the crystal oscillator 27 of the sensor 26 is vibrated at the resonance frequency. Next, it has a detection step of detecting the amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material portion by the target liquid. Further, for example, there may be a step of calculating the corrosion rate of corrosion between dissimilar materials based on the amount of change in the resonance frequency detected in the detection step.
If the amount of change in the resonance frequency is obtained, it is possible to determine corrosion. Therefore, in the method for evaluating corrosion between dissimilar materials, the step of calculating the corrosion rate of corrosion between dissimilar materials based on the amount of change in the resonance frequency detected in the detection step is not always necessary, and the step of calculating the corrosion rate between dissimilar materials is not always necessary. There may be no step of calculating the corrosion rate. However, since the corrosion rate of corrosion between dissimilar materials can be calculated, there may be a step of calculating the corrosion rate of corrosion between dissimilar materials.

In the method for evaluating corrosion between dissimilar materials, as shown in the evaluation device 10 described above, at least a part of the wetted portion in contact with the target liquid is composed of a fluororesin in the detection step.
In the method for evaluating corrosion between dissimilar materials, the target liquid is brought into contact with the sensor 26 by sending the target liquid in the same manner as in the evaluation device 10 described above. The target liquid may be adhered to the sensor 26 by flowing the target liquid in one direction. Further, the target liquid may be circulated and supplied to the crystal oscillator 27, and the circulation flow rate of the target liquid may be 0.01 to 1000 ml / s.

Hereinafter, the method for evaluating corrosion between dissimilar materials will be described more specifically by taking the evaluation device 10 shown in FIG. 1 above as an example. In the method for evaluating corrosion between dissimilar materials, for example, the target liquid is circulated and supplied.
As described above, the target liquid is brought into contact with the sensor 26 provided with the evaluation material body 35 for evaluating the corrosion between different materials. The target liquid is stored in the supply unit 20 of the evaluation device 10.
Next, the target liquid is supplied from the supply unit 20 to the flow cell unit 12 through the supply passage 40a of the first tube 29a and the block 40 to the region 44, and passes through the discharge passage 40b and the second tube 29b of the block 40. Then, it is returned to the supply unit 20, passed through the supply path 40a of the first tube 29a and the block 40 again, and is repeatedly supplied to the region 44. As a result, the target liquid is circulated and supplied to the crystal oscillator 27 and brought into contact with the evaluation material body 35 of the crystal oscillator 27.

From the oscillating unit 14, a sinusoidal high-frequency signal is applied to the sensor 26 as a frequency signal, the crystal oscillator 27 is vibrated at a resonance frequency before the target liquid is supplied, and the resonance frequency before the target liquid is supplied is detected. Obtained in part 15. Then, for example, after supplying the target liquid to the crystal oscillator 27 for a predetermined time, the detection unit 15 obtains the resonance frequency, and then detects the amount of change in the resonance frequency (detection step). The amount of change in the resonance frequency obtained by the detection unit 15 is output to the calculation unit 16 and stored in the calculation unit 16.
The calculation unit 16 reads out the amount of change in the resonance frequency based on the amount of corrosion between different materials measured in advance stored in the memory 18, and obtains the amount of change in the resonance frequency stored in the memory 18 and the detection unit 15. The corrosion rate of corrosion between dissimilar materials is calculated by comparing with the amount of change in the resonance frequency obtained (calculation step). For example, the corrosion rate of the above-mentioned corrosion between different materials is displayed on the display unit 23.
In the evaluation method, the corrosion rate of corrosion between dissimilar materials can be easily obtained, and the corrosion between dissimilar materials can be controlled based on the obtained corrosion rate.
From the amount of change in the resonance frequency stored in the memory 18, for example, the amount of corrosion between different materials can be obtained based on the calibration curve L shown in FIG. 3 as described above.

[Other examples of sensors]
FIG. 5 is a schematic view showing a second example of the sensor according to the embodiment of the present invention, and FIG. 6 is a schematic cross-sectional view showing the second example of the sensor according to the embodiment of the present invention. FIG. 7 is a schematic view showing a third example of the sensor according to the embodiment of the present invention, and FIG. 8 is a schematic cross-sectional view showing a third example of the sensor according to the embodiment of the present invention. FIG. 9 is a schematic view showing a fourth example of the sensor according to the embodiment of the present invention, and FIG. 10 is a schematic cross-sectional view showing a fourth example of the sensor according to the embodiment of the present invention.
In the sensor 26 shown in FIGS. 5 to 10, the same components as the sensor 26 shown in FIG. 2 are designated by the same reference numerals, and detailed description thereof will be omitted. Further, in FIGS. 7 to 10, the sensor 26 is simply shown, the electrode configuration on the front surface 27a of the crystal oscillator 27 is shown, and the back surface electrode 31, the oscillation unit 14, and the detection unit 15 of the back surface 27b are shown. It is omitted.

The sensor 26 shown in FIG. 2 has a configuration in which one electrode 30 is provided on the surface 27a of the crystal oscillator 27, but the sensor 26 is not limited to this. As shown in FIGS. 5 and 6, the first electrode 50 and the second electrode 51 may be provided on the surface 27a of the crystal oscillator 27. The first electrode 50 and the second electrode 51 are formed of, for example, a rectangular conductive layer, and are arranged in parallel with each other at intervals. The first electrode 50 and the second electrode 51 are in a state of being electrically insulated from each other. An electrical insulating film may be provided between the first electrode 50 and the second electrode 51.
The evaluation material body 35 is provided across the surface 50a of the first electrode 50 and the surface 51a of the second electrode 51. The first evaluation material portion 36 is provided on the surface 50a of the first electrode 50, and the second evaluation material portion 38 is provided on the surface 51a of the second electrode 51. The first evaluation material unit 36 and the second evaluation material unit 38 are in direct contact with each other between the first electrode 50 and the second electrode 51.

The first electrode 50 and the back surface electrode 31 are electrically connected to the first oscillation unit 14a. The second electrode 51 and the back surface electrode 31 are electrically connected to the second oscillation unit 14b. The first oscillation unit 14a and the second oscillation unit 14b are provided in the oscillation unit 14, and are independent of each other, the first electrode 50 and the back surface electrode 31, and the second electrode 51 and the back surface electrode 31. In addition, a high-frequency signal of a sine wave can be applied as a frequency signal, whereby the crystal oscillator 27 can be oscillated at a resonance frequency.
Further, the first oscillation unit 14a and the second oscillation unit 14b are electrically connected to the detection unit 15, respectively. The detection unit 15 has a switch unit (not shown) for switching the connection between the first oscillation unit 14a and the second oscillation unit 14b. The switch unit alternately captures the frequency signal of the first oscillation unit 14a and the frequency signal of the second oscillation unit 14b into the detection unit 15. As a result, the detection unit 15 can obtain the resonance frequency of the first electrode 50 and the resonance frequency of the second electrode 51 independently of each other.

The first evaluation material portion 36 is provided on the surface 50a of the first electrode 50, and the second evaluation material portion 38 is provided on the surface 51a of the second electrode 51. In this case, the difference in the amount of change in the resonance frequency between the first electrode 50 and the second electrode 51 can be used. The amount of corrosion between different materials can be calculated by comparing the difference in the amount of change in the resonance frequency with the difference in the amount of change in the resonance frequency based on the corrosion between different materials due to the target liquid measured in advance. Then, the corrosion rate of the corrosion between different materials can be calculated based on the time when the amount of corrosion of the corrosion between different materials is obtained.

The sensor 26 shown in FIGS. 7 and 8 has a different arrangement of the evaluation material body 35 from the sensor 26 shown in FIGS. 5 and 6. In the sensor 26 shown in FIGS. 7 and 8, the first evaluation material portion 36 is provided so as to straddle the surface 50a of the first electrode 50 and the surface 51a of the second electrode 51. The second evaluation material portion 38 is provided in direct contact with the surface 36a of the first evaluation material portion 36.
The first electrode 50 and the second electrode 51 are provided with the same first evaluation material portion 36. In this case, the amount of change in the resonance frequency of the evaluation material body 35 can be obtained from the first electrode 50 and the second electrode 51, respectively.
In general, experimental errors occur. In order to ignore the experimental error and obtain the true value, it is necessary to measure repeatedly and grasp the statistical variation. In the sensor 26 shown in FIGS. 7 and 8, the first electrode 50 and the second electrode 51 are provided with the same first evaluation material portion 36, so that the first electrode 50 and the second electrode 51 are two. Repeated measurements can be made using the electrodes. As a result, statistical variations can be easily grasped.

The sensor 26 shown in FIGS. 9 and 10 has a different arrangement of the evaluation material body 35 from the sensor 26 shown in FIGS. 5 and 6. In the sensor 26 shown in FIGS. 9 and 10, a first evaluation material portion 36 and a second evaluation material portion 38 are provided across the surface 50a of the first electrode 50 and the surface 51a of the second electrode 51. There is. The first evaluation material portion 36 and the second evaluation material portion 38 are in direct contact with each other on the surface 50a of the first electrode 50 and the surface 51a of the second electrode 51.
The first electrode 50 and the second electrode 51 are provided with a first evaluation material section 36 and a second evaluation material section 38, respectively. In this case, the amount of change in the resonance frequency of the evaluation material body 35 can be obtained from the first electrode 50 and the second electrode 51, respectively.
As mentioned above, in order to ignore the experimental error and obtain the true value, it is necessary to measure repeatedly and grasp the statistical variation. In the sensor 26 shown in FIGS. 9 and 10, the first electrode 50 and the second electrode 51 are provided with the first evaluation material portion 36 and the second evaluation material portion 38, whereby the first electrode 50 and the second electrode 51 are provided. Repeated measurement can be performed using the two electrodes of the electrode 51 of 2. As a result, statistical variations can be easily grasped.

[Other examples of sensors]
FIG. 11 is a schematic view showing a fifth example of the sensor according to the embodiment of the present invention, and FIG. 12 is a schematic cross-sectional view showing the fifth example of the sensor according to the embodiment of the present invention. FIG. 13 is a schematic view showing a sixth example of the sensor according to the embodiment of the present invention, and FIG. 14 is a schematic cross-sectional view showing a sixth example of the sensor according to the embodiment of the present invention. FIG. 15 is a schematic view showing a seventh example of the sensor according to the embodiment of the present invention, and FIG. 16 is a schematic cross-sectional view showing the seventh example of the sensor according to the embodiment of the present invention. FIG. 17 is a schematic view showing an eighth example of the sensor according to the embodiment of the present invention, and FIG. 18 is a schematic cross-sectional view showing the eighth example of the sensor according to the embodiment of the present invention.
In the sensor 26 shown in FIGS. 11 to 18, the same components as those of the sensor 26 shown in FIGS. 5 and 6 are designated by the same reference numerals, and detailed description thereof will be omitted. Further, in FIGS. 11 to 18, the sensor 26 is simply shown, the electrode configuration on the front surface 27a of the crystal oscillator 27 is shown, and the back surface electrode 31, the oscillation unit 14, and the detection unit 15 of the back surface 27b are shown. It is omitted.

In the sensor 26 shown in FIGS. 11 and 12, the evaluation material body 35 is not provided across the first electrode 50 and the second electrode 51 as compared with the sensor 26 shown in FIGS. 5 and 6. In the sensor 26 shown in FIGS. 11 and 12, the first evaluation material portion 36 is provided on the surface 50a of the first electrode 50. The evaluation material body 35 is provided on the surface 51a of the second electrode 51. The second evaluation material portion 38 is arranged on the surface 51a of the second electrode 51, and the first evaluation material portion 36 is provided in direct contact with the second evaluation material portion 38. In the evaluation material body 35, of the two evaluation material parts, the first evaluation material part 36 is corroded by corrosion between different materials. Therefore, the first electrode 50 is provided with the first evaluation material unit 36 alone. As a result, the change in the first evaluation material portion 36 that corrodes can be measured together with the corrosion between dissimilar materials of the evaluation material body 35. By referring to the amount of change in the resonance frequency of the first evaluation material unit 36 obtained by the first electrode 50, the corrosion rate of corrosion between different materials can be calculated with higher accuracy.
In this case, the first evaluation material is obtained by subtracting the change in the resonance frequency of the first evaluation material unit 36 on the first electrode 50 from the change in the resonance frequency of the evaluation material body 35 on the second electrode 51. It is possible to eliminate the influence of the reaction with the target liquid other than the corrosion between different materials in the part 36.

The arrangement of the evaluation material body 35 in the second electrode 51 is not particularly limited, and for example, as in the sensor 26 shown in FIGS. 13 and 14, the first electrode 50 and the second electrode 51 are arranged. The first evaluation material portion 36 and the second evaluation material portion 38 may be provided on the surface 51a of the second electrode 51 in a state of being in direct contact with each other in a direction orthogonal to the opposite direction.
As in the sensor 26 shown in FIGS. 15 and 16, a state in which the first evaluation material portion 36 and the second evaluation material portion 38 are in direct contact with each other in the direction in which the first electrode 50 and the second electrode 51 face each other. Then, it may be provided on the surface 51a of the second electrode 51.
As in the sensor 26 shown in FIGS. 17 and 18, the first evaluation material unit 36 and the second evaluation material unit 38 are in a direction orthogonal to the direction in which the first electrode 50 and the second electrode 51 face each other. The first evaluation material portion 36 and the second evaluation material portion 38 may be provided on the surface 51a of the second electrode 51 in a state of being arranged alternately and in direct contact with the second evaluation material portion 38.
The larger the area of the interface between dissimilar metals in contact with the chemical solution, the larger the amount of change in the resonance frequency, and the more remarkable the amount of change in the resonance frequency can be measured. Therefore, among the sensor 26 shown in FIG. 12, the sensor 26 shown in FIG. 14, the sensor 26 shown in FIG. 16, and the sensor 26 shown in FIG. 18, the sensor 26 shown in FIG. 18 and the sensor 26 shown in FIG. The sensor 26 shown in FIG. 12, the sensor 26 shown in FIG. 12, and the sensor 26 shown in FIG. 14 are preferable in this order.

In the second example of the sensor to the eighth example of the sensor described above, the first electrode 50 and the second electrode 51 may be provided on one surface of the sensor 26. Therefore, the arrangement position of the first electrode 50 and the second electrode 51 is not limited to the front surface 27a of the crystal oscillator 27, and is any one of the front surface 27a, the back surface 27b, and the side surface 27c of the crystal oscillator 27. It may be the aspect of. For example, at least one of the first electrode 50 and the second electrode 51 may be arranged on the side surface 27c.

[Other examples of sensors]
FIG. 19 is a schematic view showing a ninth example of the sensor according to the embodiment of the present invention, and FIG. 20 is a schematic cross-sectional view showing the ninth example of the sensor according to the embodiment of the present invention. FIG. 21 is a schematic view showing a tenth example of the sensor according to the embodiment of the present invention, and FIG. 22 is a schematic cross-sectional view showing a tenth example of the sensor according to the embodiment of the present invention. FIG. 23 is a schematic view showing an eleventh example of the sensor according to the embodiment of the present invention, and FIG. 24 is a schematic cross-sectional view showing the eleventh example of the sensor according to the embodiment of the present invention. FIG. 25 is a schematic view showing a twelfth example of the sensor according to the embodiment of the present invention, and FIG. 26 is a schematic cross-sectional view showing the twelfth example of the sensor according to the embodiment of the present invention.
In the sensor 26 shown in FIGS. 19 to 26, the same components as those of the sensor 26 shown in FIGS. 5 and 6 are designated by the same reference numerals, and detailed description thereof will be omitted. Further, in FIGS. 21 to 26, the sensor 26 is simply shown, the electrode configuration on the front surface 27a of the crystal oscillator 27 is shown, and the back surface electrode 31, the oscillation unit 14, and the detection unit 15 of the back surface 27b are shown. It is omitted.

Like the sensor 26 shown in FIGS. 19 and 20, the first electrode 50, the second electrode 51, and the third electrode 52 may be provided on the surface 27a of the crystal oscillator 27.
The first electrode 50, the second electrode 51, and the third electrode 52 are formed of, for example, a rectangular conductive layer, and are arranged in parallel with each other at intervals. The first electrode 50, the second electrode 51, and the third electrode 52 are in a state of being electrically insulated from each other. An electrical insulating film may be provided between the first electrode 50, the second electrode 51, and the third electrode 52.
The first electrode 50 and the back surface electrode 31 are electrically connected to the first oscillation unit 14a. The second electrode 51 and the back surface electrode 31 are electrically connected to the second oscillation unit 14b. The third electrode 52 and the back surface electrode 31 are electrically connected to the third oscillation unit 14c. The first oscillation unit 14a, the second oscillation unit 14b, and the third oscillation unit 14c are provided in the oscillation unit 14, and are independent of each other, the first electrode 50, the back surface electrode 31, and the second electrode. A sinusoidal high frequency signal can be applied as a frequency signal to the third electrode 52 and the back surface electrode 31 to the 51 and the back surface electrode 31, whereby the crystal oscillator 27 can be oscillated at the resonance frequency. can.

Further, the first oscillation unit 14a, the second oscillation unit 14b, and the third oscillation unit 14c are electrically connected to the detection unit 15, respectively. The detection unit 15 has a switch unit (not shown) for switching the connection between the first oscillation unit 14a, the second oscillation unit 14b, and the third oscillation unit 14c. The switch unit alternately captures the frequency signal of the first oscillation unit 14a, the frequency signal of the second oscillation unit 14b, and the frequency signal of the third oscillation unit 14c into the detection unit 15. As a result, the detection unit 15 can independently obtain the resonance frequency of the first electrode 50, the resonance frequency of the second electrode 51, and the resonance frequency of the third electrode 52.

The first evaluation material portion 36 is provided on the surface 50a of the first electrode 50. The evaluation material body 35 is provided on the surface 51a of the second electrode 51. The second evaluation material portion 38 (one evaluation material portion) is arranged on the surface 51a of the second electrode 51, and the first evaluation material portion 36 is provided in direct contact with the surface 38a of the second evaluation material portion 38. .. A second evaluation material portion 38 (the other evaluation material portion) is provided on the surface 52a of the third electrode 52.
In the evaluation material body 35, of the two evaluation material parts, the first evaluation material part 36 is corroded by corrosion between different materials. Therefore, the first electrode 50 is provided with the first evaluation material unit 36 alone. Further, the second electrode 51 is provided with the second evaluation material portion 38 alone. Thereby, the change of the first evaluation material part 36 constituting the evaluation material body 35 and the change of the second evaluation material part 38 can be measured together with the corrosion between different materials of the evaluation material body 35. The amount of change in the resonance frequency of the first evaluation material unit 36 obtained by the first electrode 50 and the amount of change in the resonance frequency of the second evaluation material unit 38 obtained by the second electrode 51 are referred to. As a result, the corrosion rate of corrosion between dissimilar materials can be calculated with even higher accuracy.
In this case, from the amount of change in the resonance frequency of the evaluation material body 35 on the second electrode 51, the amount of change in the resonance frequency of the first evaluation material unit 36 on the first electrode 50 and the amount of change on the third electrode 52. By subtracting the amount of change in the resonance frequency of the second evaluation material part 38, the influence of the reaction with the target liquid other than the corrosion between different materials of the first evaluation material part 36 and the second evaluation material part 38 is eliminated. Can be done.

The arrangement of the evaluation material body 35 in the second electrode 51 is not particularly limited, and for example, as in the sensor 26 shown in FIGS. 21 and 22, the first electrode 50 and the second electrode 51 are arranged. The first evaluation material portion 36 and the second evaluation material portion 38 may be provided on the surface 51a of the second electrode 51 in a state of being in direct contact with each other in a direction orthogonal to the opposite direction.
As in the sensor 26 shown in FIGS. 23 and 24, the first evaluation material portion 36 and the second evaluation material portion 38 are in direct contact with each other in the direction in which the first electrode 50 and the second electrode 51 face each other. Then, it may be provided on the surface 51a of the second electrode 51.
Like the sensor 26 shown in FIGS. 25 and 26, the first evaluation material unit 36 and the second evaluation material unit 38 are arranged in a direction orthogonal to the direction in which the first electrode 50 and the second electrode 51 face each other. The first evaluation material portion 36 and the second evaluation material portion 38 may be provided on the surface 51a of the second electrode 51 in a state of being arranged alternately and in direct contact with the second evaluation material portion 38.
The larger the area of the interface between dissimilar metals in contact with the chemical solution, the larger the amount of change in the resonance frequency, and the more remarkable the amount of change in the resonance frequency can be measured. Therefore, among the sensor 26 shown in FIG. 20, the sensor 26 shown in FIG. 22, the sensor 26 shown in FIG. 24, and the sensor 26 shown in FIG. 26, the sensor 26 shown in FIG. 26 and the sensor 26 shown in FIG. The sensor 26 shown in FIG. 20, the sensor 26 shown in FIG. 20, and the sensor 26 shown in FIG. 22 are preferable in this order.

[Other examples of sensors]
FIG. 27 is a schematic view showing a thirteenth example of the sensor of the embodiment of the present invention, and FIG. 28 is a schematic cross-sectional view showing a thirteenth example of the sensor of the embodiment of the present invention. FIG. 29 is a schematic view showing a 14th example of the sensor according to the embodiment of the present invention, and FIG. 30 is a schematic cross-sectional view showing a 14th example of the sensor according to the embodiment of the present invention. FIG. 31 is a schematic view showing a fifteenth example of the sensor according to the embodiment of the present invention, and FIG. 32 is a schematic cross-sectional view showing a fifteenth example of the sensor according to the embodiment of the present invention.
In the sensor 26 shown in FIGS. 27 to 32, the same components as those of the sensor 26 shown in FIGS. 19 and 20 are designated by the same reference numerals, and detailed description thereof will be omitted. Further, in FIGS. 27 to 32, the sensor 26 is simply shown, the electrode configuration on the front surface 27a of the crystal oscillator 27 is shown, and the back surface electrode 31, the oscillation unit 14, and the detection unit 15 of the back surface 27b are shown. It is omitted.

The sensor 26 shown in FIGS. 27 and 28 has a first electrode 50, a second electrode 51, and a third electrode 52, similarly to the sensor 26 shown in FIGS. 19 and 20. In the sensor 26 shown in FIGS. 27 and 28, the first evaluation material portion 36 is provided on the surface 50a of the first electrode 50. The evaluation material body 35 is provided straddling the surface 51a of the second electrode 51 and the surface 52a of the third electrode 52. The first evaluation material portion 36 is provided on the surface 51a of the second electrode 51, and the second evaluation material portion 38 is provided on the surface 52a of the third electrode 52. The first evaluation material unit 36 and the second evaluation material unit 38 are in direct contact with each other.
The arrangement of the evaluation material body 35 on the second electrode 51 and the third electrode 52 is not particularly limited, and the surface of the second electrode 51 is, for example, as in the sensor 26 shown in FIGS. 29 and 30. The first evaluation material portion 36 may be provided across the 51a and the surface 52a of the third electrode 52. The second evaluation material portion 38 is provided in direct contact with the surface 36a of the first evaluation material portion 36. Further, as in the sensor 26 shown in FIGS. 31 and 32, the first evaluation material section 36 and the second evaluation material section 38 straddle the surface 51a of the second electrode 51 and the surface 52a of the third electrode 52. And may be provided. The first evaluation material portion 36 and the second evaluation material portion 38 are in direct contact with each other on the surface 51a of the second electrode 51 and the surface 52a of the third electrode 52.
The larger the area of the interface between dissimilar metals in contact with the chemical solution, the larger the amount of change in the resonance frequency, and the more remarkable the amount of change in the resonance frequency can be measured. Therefore, among the sensor 26 shown in FIG. 28, the sensor 26 shown in FIG. 30, and the sensor 26 shown in FIG. 32, the sensor 26 shown in FIG. 30, the sensor 26 shown in FIG. 28, and the sensor 26 shown in FIG. The sensor 26 shown in 32 is preferable in that order.

In the ninth example of the sensor to the fifteenth example of the sensor described above, the first electrode 50, the second electrode 51, and the third electrode 52 may be provided on one surface of the sensor 26. .. Therefore, the arrangement positions of the first electrode 50, the second electrode 51, and the third electrode 52 are not limited to the front surface 27a of the crystal oscillator 27, but the front surface 27a and the back surface 27b of the crystal oscillator 27. And any surface of the side surface 27c. For example, at least one of the first electrode 50, the second electrode 51, and the third electrode 52 may be arranged on the side surface 27c.
Further, in the first electrode 50, the second electrode 51, and the third electrode 52, one of the three first electrodes 50, the second electrode 51, and the third electrode 52 is attached to one of the electrodes. Two evaluation material parts are provided, one of the two evaluation material parts is provided on one of the remaining two electrodes, and the other of the two evaluation material parts is provided on the other electrode. The evaluation material section may be provided. For example, the first electrode 50 is provided with two evaluation material parts, the second electrode 51 is provided with one of the two evaluation material parts, and the third electrode 52 is provided with two evaluation material parts. Of these, the other evaluation material section may be provided.

[Other examples of sensors]
FIG. 33 is a schematic view showing a sixteenth example of the sensor according to the embodiment of the present invention, and FIG. 34 is a schematic cross-sectional view showing the sixteenth example of the sensor according to the embodiment of the present invention. FIG. 35 is a schematic view showing a 17th example of the sensor according to the embodiment of the present invention, and FIG. 36 is a schematic cross-sectional view showing a 17th example of the sensor according to the embodiment of the present invention. FIG. 37 is a schematic view showing an 18th example of the sensor according to the embodiment of the present invention, and FIG. 38 is a schematic cross-sectional view showing an 18th example of the sensor according to the embodiment of the present invention.
In the sensor 26 shown in FIGS. 33 to 38, the same components as those of the sensor 26 shown in FIGS. 19 and 20 are designated by the same reference numerals, and detailed description thereof will be omitted. Further, in FIGS. 35 to 38, the sensor 26 is simply shown, the electrode configuration on the front surface 27a of the crystal oscillator 27 is shown, and the back surface electrode 31, the oscillation unit 14, and the detection unit 15 of the back surface 27b are shown. It is omitted.

As in the sensor 26 shown in FIGS. 33 and 34, the surface 27a of the crystal oscillator 27 may be provided with the first electrode 50, the second electrode 51, the third electrode 52, and the fourth electrode 53. good.
The first electrode 50, the second electrode 51, the third electrode 52, and the fourth electrode 53 are formed of, for example, a rectangular conductive layer, and are arranged in parallel with each other at intervals. .. The first electrode 50, the second electrode 51, the third electrode 52, and the fourth electrode 53 are electrically insulated from each other. An electrical insulating film may be provided between the first electrode 50, the second electrode 51, the third electrode 52, and the fourth electrode 53.
The first electrode 50 and the back surface electrode 31 are electrically connected to the first oscillation unit 14a. The second electrode 51 and the back surface electrode 31 are electrically connected to the second oscillation unit 14b. The third electrode 52 and the back surface electrode 31 are electrically connected to the third oscillation unit 14c. The fourth electrode 53 and the back surface electrode 31 are electrically connected to the fourth oscillation unit 14d.
The first oscillation unit 14a, the second oscillation unit 14b, the third oscillation unit 14c, and the fourth oscillation unit 14d are provided in the oscillation unit 14, and the first electrode 50 and the back surface electrode 31 are independent of each other. A sinusoidal high-frequency signal can be applied as a frequency signal to the second electrode 51 and the back surface electrode 31, the third electrode 52 and the back surface electrode 31, and the fourth electrode 53 and the back surface electrode 31. As a result, the crystal oscillator 27 can be oscillated at the resonance frequency.

Further, the first oscillation unit 14a, the second oscillation unit 14b, the third oscillation unit 14c, and the fourth oscillation unit 14d are electrically connected to the detection unit 15, respectively. The detection unit 15 has a switch unit (not shown) for switching the connection between the first oscillation unit 14a, the second oscillation unit 14b, the third oscillation unit 14c, and the fourth oscillation unit 14d. By the switch unit, the frequency signal of the first oscillation unit 14a, the frequency signal of the second oscillation unit 14b, the frequency signal of the third oscillation unit 14c, and the frequency signal of the fourth oscillation unit 14d are alternately sent to the detection unit 15. It is captured. As a result, in the detection unit 15, the resonance frequency at the first electrode 50, the resonance frequency at the second electrode 51, the resonance frequency at the third electrode 52, and the resonance frequency at the fourth electrode 53 are mutually set. Can be obtained independently.

A first evaluation material portion 36 (one evaluation material portion) is provided on the surface 50a of the first electrode 50. A second evaluation material portion 38 (the other evaluation material portion) is provided on the surface 53a of the fourth electrode 53. The evaluation material body 35 is provided straddling the surface 51a of the second electrode 51 and the surface 52a of the third electrode 52.
The first evaluation material portion 36 is arranged on the surface 51a of the second electrode 51, and the first evaluation material portion 36 is provided on the surface 52a of the third electrode 52. The first evaluation material unit 36 and the second evaluation material unit 38 are in direct contact with each other.
In the evaluation material body 35, of the two evaluation material parts, the first evaluation material part 36 is corroded by corrosion between different materials. Therefore, the first electrode 50 is provided with the first evaluation material unit 36 alone. Further, the second evaluation material portion 38 alone is provided on the fourth electrode 53. Thereby, the change of the first evaluation material part 36 constituting the evaluation material body 35 and the change of the second evaluation material part 38 can be measured together with the corrosion between different materials of the evaluation material body 35. The amount of change in the resonance frequency of the first evaluation material unit 36 obtained by the first electrode 50 and the amount of change in the resonance frequency of the second evaluation material unit 38 obtained by the fourth electrode 53 are referred to. As a result, the corrosion rate of corrosion between dissimilar materials can be calculated with even higher accuracy.
In this case, the amount of change in the resonance frequency of the evaluation material body 35 on the second electrode 51 and the third electrode 52, the amount of change in the resonance frequency of the first evaluation material unit 36 on the first electrode 50, and the first By subtracting the amount of change in the resonance frequency of the second evaluation material part 38 on the electrode 53 of 4, the reaction of the first evaluation material part 36 and the second evaluation material part 38 with the target liquid other than the corrosion between different materials, etc. The influence of can be eliminated.

The arrangement of the evaluation material body 35 on the second electrode 51 is not particularly limited, and for example, as in the sensor 26 shown in FIGS. 35 and 36, the surface 51a of the second electrode 51 and the third electrode The first evaluation material portion 36 may be provided across the surface 52a of the 52. The second evaluation material portion 38 is provided in direct contact with the surface 36a of the first evaluation material portion 36. Further, as in the sensor 26 shown in FIGS. 37 and 38, the first evaluation material section 36 and the second evaluation material section 38 straddle the surface 51a of the second electrode 51 and the surface 52a of the third electrode 52. And may be provided. The first evaluation material portion 36 and the second evaluation material portion 38 are in direct contact with each other on the surface 51a of the second electrode 51 and the surface 52a of the third electrode 52.
The larger the area of the interface between dissimilar metals in contact with the chemical solution, the larger the amount of change in the resonance frequency, and the more remarkable the amount of change in the resonance frequency can be measured. Therefore, among the sensor 26 shown in FIG. 34, the sensor 26 shown in FIG. 36, and the sensor 26 shown in FIG. 38, the sensor 26 shown in FIG. 36, the sensor 26 shown in FIG. 34, and the sensor 26 shown in FIG. The sensor 26 shown in 38 is preferable in that order.

In the 16th example of the sensor to the 18th example of the sensor described above, the first electrode 50, the second electrode 51, the third electrode 52 and the fourth electrode 53 are on one surface of the sensor 26. It suffices if it is provided. Therefore, the arrangement positions of the first electrode 50, the second electrode 51, the third electrode 52, and the fourth electrode 53 are not limited to the surface 27a of the crystal oscillator 27, but the crystal oscillator 27. Any surface of the front surface 27a, the back surface 27b, and the side surface 27c may be used. For example, at least one of the first electrode 50, the second electrode 51, the third electrode 52, and the fourth electrode 53 may be arranged on the side surface 27c.
Further, in the first electrode 50, the second electrode 51, the third electrode 52, and the fourth electrode 53, the four first electrodes 50, the second electrode 51, the third electrode 52, and the fourth electrode 53 are used. Of the electrodes 53 of 4, two evaluation material parts are provided on two electrodes, one of the two evaluation material parts is provided on one of the remaining two electrodes, and one evaluation material part is provided on the other electrode. Of the two evaluation material parts, the other evaluation material part may be provided. For example, the first electrode 50 and the second electrode 51 are provided with two evaluation material parts, the third electrode 52 is provided with one of the two evaluation material parts, and the fourth electrode 53 is provided with one evaluation material part. Of the two evaluation material parts, the other evaluation material part may be provided.

The present invention is basically configured as described above. The sensor of the present invention, the evaluation device for corrosion between dissimilar materials, and the evaluation method for corrosion between dissimilar materials have been described in detail above, but the present invention is not limited to the above-described embodiment, and the present invention is not limited to the above-described embodiment and does not deviate from the gist of the present invention. Of course, various improvements or changes may be made.

[Target liquid]
Corrosion between dissimilar materials occurs due to moisture or the like. Therefore, it is preferable to evaluate the corrosion between dissimilar materials while the sensor is immersed in a liquid such as water.
As the target liquid, for example, a liquid containing at least one or more components and water can be used. The components are alkali metal halides, alkaline earth metal halides, hydroxylamines or derivatives thereof, hydrogen fluoride, aminoalcohol, quaternary ammonium salts, or hydrogen peroxide. The concentrations of the alkali metal halide and the alkaline earth metal halide are preferably 10 mass ppt or more, respectively.
The type of water is not particularly limited, and for example, distilled water, ion-exchanged water, and pure water can be used.
Water may be added to the target liquid, or may be inevitably mixed in the target liquid in the process of producing the target liquid. Examples of cases in which water is unavoidably mixed in the production process of the target liquid include water being contained in a raw material (for example, an organic solvent) used in the production of the target liquid, and mixing in the production process of the target liquid (for example). For example, contamination) and the like.
It is also possible to use a target liquid according to the evaluation target of corrosion between dissimilar materials. For example, a liquid that promotes corrosion between dissimilar materials, for example, an aqueous solution of sodium chloride (salt water), an aqueous solution of potassium chloride, or the like can be used as the target solution. In addition, a corrosive liquid such as an acid or an alkaline aqueous solution can be used as the target liquid.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
<Example 1>
In Example 1, corrosion between dissimilar metals in the brake pipe was evaluated. The brake pipe is a copper pipe coated with zinc by plating, and the copper and zinc are in direct contact with each other. Corrosion occurs between zinc and the underlying copper in the brake pipe.
In Example 1, the sensor 26 shown in FIGS. 19 and 20 was used.
The first evaluation material part 36 was a zinc-plated film, an alloyed zinc-plated film, or a hot-dip galvanized steel plate. The second evaluation material part 38 was made into a copper film. Evaluation of three combinations of zinc-plated film and copper film (hereinafter referred to as sample 1), alloyed zinc-plated film and copper film (hereinafter referred to as sample 2), and hot-dip galvanized steel plate and copper film (hereinafter referred to as sample 3). A material body was prepared.
A 1% by mass calcium chloride solution was circulated for 30 minutes under a flow rate condition of 100 ml / min, and the amount of change in the resonance frequency in the sensor was measured.
The 1% by mass calcium chloride solution imitates a mixture of calcium chloride sprayed as a snow melting agent during snowfall and the snow melting component (water) liquefied by the calcium chloride solution.
The amount of change in the resonance frequency was Sample 1 (1080 Hz)> Sample 2 (680 Hz)> Sample 3 (420 Hz). The amount of change in the resonance frequency of the copper film was 50 Hz or less. From this result, it was found that the plating applied to the brake pipe is preferably in the order of zinc plating <alloyed zinc plating <hot-dip galvanized steel sheet. This result was similar to the result shown in "Corrosion Protection Technology for Automotive Steel Materials, 28,645-653 (1979)".
In addition to the sensors shown in FIGS. 19 and 20 described above, even if the sensors shown in FIGS. 2, 5 to 18 and 21 to 38 are used, the same order as the sensors shown in 19 and 20 can be obtained. It was observed.

<Example 2>
In Example 2, corrosion between dissimilar metals was evaluated for the metal used on the semiconductor substrate.
There is a situation where Cu and Co are close to each other in the wiring metal formed on the semiconductor substrate.
As the target solution, citric acid and monoethanolamine are the main agents, and different anticorrosive agents (combination of heterocyclic compound and anionic surfactant) are added in the range of pH (hydrogen ion index) = 11 to 11.5. 4 was prepared.
When the corrosion potentials of the chemical solutions 1 to 4 were determined according to the usual electrochemical method, the chemical solution 1 (0.4 mV)> the chemical solution 2 (0.32 mV)> the chemical solution 3 (0.2 mV)> the chemical solution 4 (0.01 mV). Met.
Using the chemical solutions 1 to 4, the semiconductor substrate in which the Cu film and the Co film were in contact with each other was immersed at a temperature of 25 ° C. (room temperature) for 30 minutes.
As a result of the immersion treatment, corrosion at the interface between the Cu film and the Co film, that is, excessive corrosion of the Co film, is caused by chemical solution 3 (8 nm)> chemical solution 4 (5 nm)> chemical solution 1 (2 nm)> chemical solution 2 (<1 nm). It became. From this, it was confirmed that the electrochemical method and the actual corrosion at the interface between the Cu film and the Co film do not always match.

In Example 2, the sensor 26 shown in FIGS. 35 and 36 was used. The first evaluation material part 36 was made into a Co film, and the second evaluation material part 38 was made into a Cu film. The Co film and the Cu film were each formed by a sputtering method.
The chemical solutions 1 to 4 were each circulated for 30 minutes at a temperature of 25 ° C. (room temperature) and a flow rate condition of 100 ml / min, and the amount of change in the resonance frequency of the sensor was measured for each of the chemical solutions 1 to 4.
The amount of change in the resonance frequency of the Co film was chemical solution 3 (2620 Hz)> chemical solution 4 (1560 Hz)> chemical solution 1 (780 Hz)> chemical solution 2 (250 Hz). It was in good agreement with the result of the dipping treatment described above.
In addition to the sensors shown in FIGS. 35 and 36 described above, even if the sensors shown in FIGS. 2, 5 to 34, 37 and 38 are used, the same order as the sensors shown in 35 and 36 can be obtained. It was observed.

<Comparative example 1>
In Example 2 described above, a sensor in which a Cu single film and a Co single film were formed was prepared. The amount of change in the resonance frequency with respect to the chemical solutions 1 to 4 was measured for each sensor. The result of the obtained change amount of the resonance frequency indicates the dissolution rate for the Cu single film (converted to the amount of change in the resonance frequency) and the dissolution rate for the Co single film (converted to the amount of change in the resonance frequency). Even when the difference in the amount of change was calculated, no result was obtained that was consistent with the tendency of the corrosion rate of corrosion between dissimilar metals.

<Comparative example 2>
In Example 2 described above, a sensor prepared by preparing a Cu single film and a Co single film so that a gap portion is formed between the two metals at the time of film formation without contacting the two metals. Using a sensor, the amount of change in the resonance frequency with respect to the chemical solutions 1 to 4 was measured.
The obtained result is the dissolution rate (converted to the amount of change in resonance frequency) of each metal of Cu single film and Co single film, and even if the difference between these values is calculated, the tendency of corrosion rate of corrosion between dissimilar metals No results were obtained that matched.

<Example 3>
In Example 3, corrosion between dissimilar metals was evaluated for the metal used on the semiconductor substrate.
There is a situation where Co and TiN are close to each other in the wiring processing formed on the semiconductor substrate.
As the target solution, hydroxylamine, DBU (diazabicycloundecene), and citric acid, which are widely used as wet residue removing solutions, are used as main agents, and different anticorrosive agents (different benzotriazole derivatives and different anticorrosive agents) having a pH in the range of 8 to 9 are used. Chemical solutions 5 to 8 to which a combination of diazole compounds) was added were prepared.
When the corrosion potentials of the chemical solutions 5 to 8 were determined according to the usual electrochemical method, the chemical solution 6 (0.3 mV)> the chemical solution 5 (0.25 mV)> the chemical solution 8 (0.1 mV)> the chemical solution 7 (0.08 mV). Met.
Using the chemical solutions 5 to 8, the semiconductor substrate in which the Co film and the TiN film were in contact with each other was immersed at a temperature of 25 ° C. (room temperature) for 30 minutes.
As a result of the immersion treatment, corrosion at the interface between the Co film and the TiN film, that is, excessive corrosion of the Co film, is caused by chemical solution 6 (5 nm)> chemical solution 5 (4 nm)> chemical solution 8 (3.5 nm)> chemical solution 7 (2 nm). ). From this, it was confirmed that the electrochemical method and the actual corrosion at the interface between the Co film and the TiN film do not always match.

In Example 3, the sensor 26 shown in FIGS. 37 and 38 was used. The first evaluation material part 36 was made into a Co film, and the second evaluation material part 38 was made into a TiN film. The Co film and the TiN film were each formed by a sputtering method.
The chemical solutions 5 to 8 were each circulated for 30 minutes at a temperature of 25 ° C. (room temperature) and a flow rate condition of 100 ml / min, and the amount of change in the resonance frequency of the sensor was measured for each of the chemical solutions 5 to 8.
The amount of change in the resonance frequency of the Co film was: chemical solution 6 (1680 Hz)> chemical solution 5 (1430 Hz)> chemical solution 8 (1080 Hz)> chemical solution 7 (890 Hz). It was in good agreement with the result of the dipping treatment described above.
In addition to the sensors shown in FIGS. 37 and 38 described above, the same order as the sensors shown in FIGS. 37 and 38 was observed by using the sensors shown in FIGS. 2, 5 and 36.

<Example 4>
In Example 4, corrosion between dissimilar metals was evaluated for the metal used on the semiconductor substrate.
_{There is a situation where Ge and SiO 2} are close to each other in the process of creating a gate structure.
As the target liquid, it is commonly used as the residue-removing solution of the wet, HF, and a main agent of NH ₄ F, was prepared drug solution 10 to 13 obtained by changing the pH in the range of 3-6.
When the corrosion potentials of the chemical solutions 10 to 13 were determined according to a normal electrochemical method, the chemical solution 10 (0.5 mV)> the chemical solution 11 (0.45 mV)> the chemical solution 12 (0.3 mV)> the chemical solution 13 (0.1 mV). Met.
Using the chemical solutions 10 to 13, _{the semiconductor substrate in which the Ge film and the SiO 2} film were in contact with each other was immersed at a temperature of 25 ° C. (room temperature) for 30 minutes.
As a result of the immersion treatment, _{corrosion at the interface between the Ge film and the SiO 2} film, that is, excessive corrosion of the Ge film, is caused by chemical solution 11 (8 nm)> chemical solution 10 (6 nm)> chemical solution 13 (2 nm)> chemical solution 12 (0. 5 nm). From this, it was confirmed that the electrochemical method and the actual corrosion at the interface between the Ge film and the SiO ₂ film do not always match.

In Example 4, the sensor 26 shown in FIGS. 23 and 24 was used. The first evaluation material part 36 was made into a Ge film, and the second evaluation material part 38 was made into a SiO ₂ film. The Ge film and the SiO ₂ film were each formed by a sputtering method.
The chemical solutions 10 to 13 were each circulated for 30 minutes at a temperature of 25 ° C. (room temperature) and a flow rate condition of 100 ml / min, and the amount of change in the resonance frequency of the sensor was measured for each of the chemical solutions 10 to 13.
The amount of change in the resonance frequency of the Ge film was chemical solution 11 (2150 Hz)> chemical solution 10 (1850 Hz)> chemical solution 13 (420 Hz)> chemical solution 12 (210 Hz). It was in good agreement with the result of the dipping treatment described above.
In addition to the sensors shown in FIGS. 23 and 24 described above, even if the sensors shown in FIGS. 2, 5 to 22 and 25 to 38 are used, the same order as the sensors shown in 23 and 24 can be obtained. It was observed.

10 Evaluation device 12 Flow cell unit 14 Oscillator 14a 1st oscillator 14b 2nd oscillator 14c 3rd oscillator 14d 4th oscillator 15 Detector 16 Calculation unit 18 Memory 20 Supply unit 22 Control unit 23 Display unit 24 Output unit 25 Input unit 26 Sensor 27 Crystal oscillator 27a Front surface 27b Back surface 27c Side surface 28 Temperature control unit 29a First tube 29b Second tube 30 Electrodes 30a, 36a Front surface 31 Back surface electrode 35 Evaluation material body 36 First evaluation material unit 38 Second Evaluation material part 40 block 40a Supply path 40b Discharge path 40c, 42a Surface 42, 43 Seal part 44, 45 Region 50 First electrode 50a, 51a, 52a, 53a Surface 51 Second electrode 52 Third electrode 53 Fourth Electrode L calibration line

Claims (30)

A sensor used to evaluate corrosion between dissimilar materials.
Crystal oscillator and
Electrodes provided on one surface of the crystal unit and
It has two evaluation material parts provided on the electrode.
A sensor in which the two evaluation material parts are made of different materials and are in direct contact with each other. A sensor used to evaluate corrosion between dissimilar materials.
Crystal oscillator and
A first electrode provided on one surface of the crystal unit and
A second electrode provided on one surface of the crystal unit and electrically insulated from the first electrode.
It has a first electrode and two evaluation material parts provided on the second electrode.
The two evaluation material parts are composed of different materials and are in direct contact with each other.
A sensor in which at least one of the two evaluation material parts is provided on at least one of the first electrode and the second electrode. A sensor used to evaluate corrosion between dissimilar materials.
Crystal oscillator and
A first electrode provided on one surface of the crystal unit and
A second electrode provided on one surface of the crystal unit and electrically insulated from the first electrode.
It has two evaluation material parts provided on the first electrode.
The two evaluation material parts are composed of different materials and are in direct contact with each other.
A sensor in which the second electrode is provided with an evaluation material portion that is corroded by corrosion between different materials among the two evaluation material portions. A sensor used to evaluate corrosion between dissimilar materials.
Crystal oscillator and
A first electrode provided on one surface of the crystal unit and
A second electrode provided on one surface of the crystal unit and electrically insulated from the first electrode.
A third electrode provided on one surface of the crystal unit and electrically insulated from the first electrode and the second electrode.
It has a first electrode and two evaluation material parts provided on the second electrode.
Of the two evaluation material parts, the third electrode is provided with an evaluation material part that is corroded by corrosion between different materials.
The two evaluation material parts are composed of different materials and are in direct contact with each other.
A sensor in which at least one of the two evaluation material parts is provided on at least one of the first electrode and the second electrode. A sensor used to evaluate corrosion between dissimilar materials.
Crystal oscillator and
A first electrode provided on one surface of the crystal unit and
A second electrode provided on one surface of the crystal unit and electrically insulated from the first electrode.
A third electrode provided on one surface of the crystal unit and electrically insulated from the first electrode and the second electrode.
It has two evaluation material parts provided on the first electrode.
The two evaluation material parts are composed of different materials and are in direct contact with each other.
One of the two evaluation material parts is provided on the second electrode.
A sensor in which the third electrode is provided with the evaluation material portion of the other of the two evaluation material portions. A sensor used to evaluate corrosion between dissimilar materials.
Crystal oscillator and
A first electrode provided on one surface of the crystal unit and
A second electrode provided on one surface of the crystal unit and electrically insulated from the first electrode.
A third electrode provided on one surface of the crystal unit and electrically insulated from the first electrode and the second electrode.
A fourth electrode provided on one surface of the crystal unit and electrically insulated from the first electrode, the second electrode, and the third electrode.
It has a first electrode and two evaluation material parts provided on the second electrode.
One of the two evaluation material parts is provided on the third electrode.
The fourth electrode is provided with the evaluation material portion of the other of the two evaluation material portions.
The two evaluation material parts are made of different materials and are in direct contact with each other.
A sensor in which at least one of the two evaluation material parts is provided on at least one of the first electrode and the second electrode. The evaluation material section
It is composed of Au, Si, SiO ₂ , SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, Ru, Mo, Zn, oxides containing these, and materials selected from alloys. The sensor according to any one of claims 1 to 6. An evaluation device that evaluates corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 1 and
An oscillator that vibrates the crystal oscillator of the sensor at a resonance frequency,
An evaluation device for corrosion between different materials, which is connected to the electrode of the sensor and has a detection unit for detecting a change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material part due to the target liquid. An evaluation device that evaluates corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 2 and
An oscillator that vibrates the crystal oscillator of the sensor at a resonance frequency,
It has a detection unit connected to the first electrode and the second electrode of the sensor and detecting a change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material portion by the target liquid. , Evaluation device for corrosion between dissimilar materials. An evaluation device that evaluates corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 3 and
An oscillator that vibrates the crystal oscillator of the sensor at a resonance frequency,
The amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material portion by the target liquid, which is connected to the first electrode of the sensor.
Corrosion between dissimilar materials, which is connected to the second electrode and has a detection unit for detecting the amount of change in the resonance frequency of the crystal oscillator due to the target liquid of the evaluation material portion that is corroded by corrosion between dissimilar materials. Evaluation device. An evaluation device that evaluates corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 4 and
An oscillator that vibrates the crystal oscillator of the sensor at a resonance frequency,
The amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material portion by the target liquid, which is connected to the first electrode and the second electrode of the sensor.
Corrosion between dissimilar materials, which is connected to the third electrode and has a detection unit for detecting the amount of change in the resonance frequency of the crystal oscillator due to the target liquid of the evaluation material portion that is corroded by corrosion between dissimilar materials. Evaluation device. An evaluation device that evaluates corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 5 and
An oscillator that vibrates the crystal oscillator of the sensor at a resonance frequency,
The amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material portion by the target liquid, which is connected to the first electrode of the sensor.
The amount of change in the resonance frequency of the crystal unit due to the target liquid in one of the two evaluation material parts connected to the second electrode,
A dissimilar material connected to the third electrode and having a detection unit for detecting the amount of change in the resonance frequency of the crystal unit due to the target liquid of the other evaluation material unit among the two evaluation material units. Inter-corrosion evaluation device. An evaluation device that evaluates corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 6 and
An oscillator that vibrates the crystal oscillator of the sensor at a resonance frequency,
The amount of change in the resonance frequency of the crystal oscillator due to corrosion between different materials of the evaluation material portion by the target liquid, which is connected to the first electrode and the second electrode of the sensor.
The amount of change in the resonance frequency of the crystal unit due to the target liquid in one of the two evaluation material parts, which is connected to the third electrode,
A dissimilar material connected to the fourth electrode and having a detection unit for detecting the amount of change in the resonance frequency of the crystal unit due to the target liquid of the other evaluation material unit among the two evaluation material units. Inter-corrosion evaluation device. The evaluation of corrosion between dissimilar materials according to any one of claims 8 to 13, which has a calculation unit for calculating the corrosion rate of corrosion between dissimilar materials based on the amount of change in resonance frequency detected by the detection unit. Device. The evaluation device for corrosion between different materials according to any one of claims 8 to 14, further comprising a supply unit for supplying the target liquid to the sensor and bringing the target liquid into contact with the sensor. The evaluation device for corrosion between dissimilar materials according to claim 15, wherein at least a part of the wetted portion in contact with the target liquid is made of a fluororesin. The device for evaluating corrosion between dissimilar materials according to claim 15 or 16, further comprising a display unit for displaying the amount of change in the resonance frequency. The device for evaluating corrosion between dissimilar materials according to any one of claims 15 to 17, wherein the supply unit supplies the target liquid to the sensor in one direction. The supply unit circulates and supplies the target liquid to the sensor, and the circulation flow rate of the target liquid is 0.01 to 1000 ml / s, according to any one of claims 15 to 18. Evaluation device for corrosion between dissimilar materials. The target liquid is a liquid containing at least one component and water.
The component is selected from the group consisting of alkali metal halides, alkaline earth metal halides, hydroxylamines or derivatives thereof, hydrogen fluoride, aminoalcohol, quaternary ammonium salts, and hydrogen peroxide. Item 4. The apparatus for evaluating corrosion between dissimilar materials according to any one of Items 15 to 19. The evaluation material section of the sensor
It is composed of Au, Si, SiO ₂ , SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, Ru, Mo, Zn, oxides containing these, and materials selected from alloys. The device for evaluating corrosion between dissimilar materials according to any one of claims 15 to 20. This is an evaluation method for evaluating corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 1 or 2 is brought into contact with the target liquid, and the target liquid is brought into contact with the target liquid.
The crystal oscillator of the sensor is vibrated at a resonance frequency.
A method for evaluating corrosion between dissimilar materials, which comprises a detection step of detecting a change in the resonance frequency of the crystal oscillator due to corrosion between dissimilar materials in the evaluation material portion due to the target liquid. This is an evaluation method for evaluating corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 3 or 4 is brought into contact with the target liquid, and the target liquid is brought into contact with the target liquid.
The crystal oscillator of the sensor is vibrated at a resonance frequency.
The amount of change in the resonance frequency of the crystal unit due to corrosion between different materials of the evaluation material part by the target liquid, and
An evaluation method for evaluating corrosion between different materials, which comprises a detection step of detecting the amount of change in the resonance frequency of the crystal oscillator due to the target liquid in the evaluation material portion that is corroded by corrosion between different materials. This is an evaluation method for evaluating corrosion between dissimilar materials with respect to the target liquid.
The sensor according to claim 5 or 6 is brought into contact with the target liquid, and the target liquid is brought into contact with the target liquid.
The crystal oscillator of the sensor is vibrated at a resonance frequency.
The amount of change in the resonance frequency of the crystal unit due to corrosion between different materials of the evaluation material part by the target liquid, and
Of the two evaluation material parts, the amount of change in the resonance frequency of the crystal unit due to the target liquid in one of the evaluation material parts, and
A method for evaluating corrosion between dissimilar materials, which comprises a detection step of detecting the amount of change in the resonance frequency of the crystal oscillator due to the target liquid in the other evaluation material part of the two evaluation material parts. The method for evaluating corrosion between dissimilar materials according to any one of claims 22 to 24, which comprises a step of calculating the corrosion rate of corrosion between dissimilar materials based on the amount of change in resonance frequency detected in the detection step. .. The method for evaluating corrosion between dissimilar materials according to any one of claims 22 to 25, wherein the target liquid is supplied to the sensor and the target liquid is brought into contact with the sensor. The method for evaluating corrosion between dissimilar materials according to any one of claims 22 to 26, wherein the target liquid is flowed and supplied to the sensor in one direction. The supply unit circulates and supplies the target liquid to the sensor, and the circulation flow rate of the target liquid is 0.01 to 1000 ml / s, according to any one of claims 22 to 27. How to evaluate corrosion between dissimilar materials. The evaluation material section of the sensor
It is composed of Au, Si, SiO ₂ , SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, Ru, Mo, Zn, oxides containing these, and materials selected from alloys. The method for evaluating corrosion between dissimilar materials according to any one of claims 22 to 28. The target liquid is a liquid containing at least one component and water.
The component is selected from the group consisting of alkali metal halides, alkaline earth metal halides, hydroxylamines or derivatives thereof, hydrogen fluoride, aminoalcohol, quaternary ammonium salts, and hydrogen peroxide. Item 8. The method for evaluating corrosion between dissimilar materials according to any one of Items 22 to 29.

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