WO2022085080A1 - Hydrogen content measuring method - Google Patents

Hydrogen content measuring method Download PDF

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WO2022085080A1
WO2022085080A1 PCT/JP2020/039413 JP2020039413W WO2022085080A1 WO 2022085080 A1 WO2022085080 A1 WO 2022085080A1 JP 2020039413 W JP2020039413 W JP 2020039413W WO 2022085080 A1 WO2022085080 A1 WO 2022085080A1
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metal
temperature
hydrogen
amount
procedure
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PCT/JP2020/039413
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French (fr)
Japanese (ja)
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龍太 石井
拓哉 上庄
昌幸 津田
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日本電信電話株式会社
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Priority to PCT/JP2020/039413 priority Critical patent/WO2022085080A1/en
Priority to JP2022556862A priority patent/JP7469708B2/en
Publication of WO2022085080A1 publication Critical patent/WO2022085080A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/202—Constituents thereof
    • G01N33/2022—Non-metallic constituents
    • G01N33/2025—Gaseous constituents
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/204—Structure thereof, e.g. crystal structure
    • G01N33/2045—Defects

Definitions

  • the present invention relates to a hydrogen amount measuring method for measuring the amount of hydrogen in a metal.
  • TDA measurement Thermal Desorption Analysis
  • the temperature rising gas desorption analyzer is generally composed of a heating unit that heats the metal to be measured and a measurement unit that analyzes the gas released from the inside of the metal.
  • gas chromatography is used to measure the amount of hydrogen contained in the gas released from the metal by heating.
  • the specific measurement method differs depending on the type of metal and the purpose of measurement.
  • the reason for cooling the metal to liquid nitrogen temperature is to prevent hydrogen from escaping from the metal during preparation for measurement.
  • FIG. 1 of Non-Patent Document 1 shows a hydrogen release curve.
  • the horizontal axis is expressed by temperature, it corresponds to the measurement time because it controls the rate of temperature rise. For example, if the heating rate is 20 ° C./min, it takes 20 minutes to reach 400 ° C. from 0 ° C.
  • the vertical axis is the amount of hydrogen released per unit time.
  • the area surrounded by the hydrogen release curve of " ⁇ " corresponds to the amount of hydrogen in the metal.
  • the amount of hydrogen in the metal can be measured by the above measurement method.
  • a metal broken due to hydrogen embrittlement in an actual environment may have impurities (for example, rust) such as metal oxides attached to a part or the whole of the metal.
  • impurities for example, rust
  • impurities and the metal may react with each other during heating to generate hydrogen.
  • a hydrogen release peak occurs near 50 ° C. and also occurs near 280 ° C.
  • the hydrogen release peak due to hydrogen in the metal that is originally desired to be measured one is the hydrogen release peak due to hydrogen in the metal that is originally desired to be measured, and the other is the hydrogen release peak due to hydrogen generated by the reaction between the metal and rust in the furnace.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a technique capable of accurately measuring the amount of hydrogen in a metal.
  • the method for measuring the amount of hydrogen in one aspect of the present invention is a method for measuring the amount of hydrogen in a metal, in which the temperature of the metal is raised from a low temperature to reach the reaction temperature between the metal and impurities adhering to the metal.
  • a procedure and a calculation procedure for calculating the total amount of measured hydrogen as the amount of hydrogen contained in the metal are performed.
  • the hydrogen amount measuring method of one aspect of the present invention is a hydrogen amount measuring method for measuring the amount of hydrogen in a metal, in which a dividing procedure for dividing a metal into a first metal and a second metal and the first metal from a low temperature are used.
  • the temperature is raised, the generation start temperature of the hydrogen release peak is determined based on the measurement result of the amount of hydrogen contained in the gas released from the first metal, and the holding temperature is lower than the generation start temperature of the hydrogen release peak.
  • the temperature of the second metal is raised from a low temperature, the temperature of the second metal is stopped when the temperature reaches the holding temperature, and the temperature at which the temperature is stopped is maintained.
  • a measurement procedure for measuring the amount of hydrogen contained in the gas released from the second metal until the gas is no longer released from the second metal, and the total amount of the measured hydrogen is calculated as the amount of hydrogen contained in the metal. And the calculation procedure to be performed.
  • FIG. 1 is a diagram showing a configuration example of a temperature rising gas desorption analyzer.
  • FIG. 2 is a diagram showing an example of a method for measuring the amount of hydrogen in a metal.
  • FIG. 3 is a diagram showing an example of the measurement result of the TDA measurement in the procedure 2.
  • FIG. 4 is a diagram showing an example of the measurement result of the TDA measurement in the procedure 3.
  • FIG. 5 is a diagram showing an example of the measurement result of the TDA measurement in the procedure 4 and subsequent steps.
  • FIG. 6 is a diagram showing a configuration example of a temperature rising gas desorption analyzer (measurement unit).
  • the fact that the reaction between an impurity and a metal is a chemical reaction and hydrogen is not generated unless the reaction temperature is reached is utilized. That is, in the present invention, the temperature of the metal is raised from a low temperature, the temperature of the metal is stopped immediately before reaching the reaction temperature between the metal and the impurities adhering to the metal, and the gas is released from the metal while maintaining the temperature. The amount of hydrogen contained in the gas released from the metal is measured until it is exhausted. This makes it possible to eliminate the influence of hydrogen due to the reaction between impurities and the metal, and it is possible to accurately measure the amount of hydrogen contained in the metal.
  • the conventional TDA measurement is performed using a part of the metal to be measured, the reaction temperature between the impurity and the metal is determined in advance based on the result of the TDA measurement, and the reaction temperature is lower than the reaction temperature.
  • the temperature immediately before is determined in advance as the temperature to be held. This makes it possible to measure the amount of hydrogen contained in the metal within a practical time.
  • FIG. 1 is a diagram showing a configuration example of a temperature rising gas desorption analyzer according to the present embodiment.
  • the temperature rising gas desorption analyzer is a device for measuring the amount of hydrogen in a metal by using a temperature rising gas desorption analysis method (TDA measurement), and is, for example, a heating unit 1, a measuring unit 2, and a furnace 3. , Equipped with.
  • the heating unit 1 is a device that controls the temperature of the furnace 3. For example, the heating unit 1 raises the temperature of the metal 100 arranged inside the furnace 3 from a low temperature. The heating unit 1 stops the temperature rise of the metal 100 before reaching the reaction temperature of the metal 100 and the impurities adhering to the metal 100, and maintains the temperature at which the temperature rise is stopped.
  • the heating unit 1 may use a heating mechanism built in the furnace 3, or may be a heating device separately prepared from the furnace 3.
  • the measuring unit 2 is a device that takes in the gas released from the inside of the metal 100 by heating and measures the amount of hydrogen contained in the gas. For example, the measuring unit 2 measures the amount of hydrogen contained in the gas released from the metal 100 (conventional TDA measurement). The measuring unit 2 determines the reaction temperature between the metal 100 and the impurities adhering to the metal 100 based on the measurement result of the hydrogen amount, and determines a temperature lower than the reaction temperature as the holding temperature of the metal 100. The measuring unit 2 measures the amount of hydrogen contained in the gas released from the metal 100 until the gas is no longer released from the metal 100 while maintaining the holding temperature. The measuring unit 2 calculates the total amount of measured hydrogen as the amount of hydrogen contained in the metal 100. The measuring unit 2 is, for example, gas chromatography.
  • the furnace 3 is, for example, a heating furnace and a heat retaining furnace.
  • FIG. 2 is a diagram showing a measuring method for measuring the amount of hydrogen in a metal.
  • the measurer divides the metal 100 to be measured into two by using a dividing means such as pliers. Of the two divided metals, one is the first metal and the other is the second metal.
  • the first metal is a metal for determining the temperature T 1 in the procedure 2, and may be of a size capable of measuring a sufficient amount of hydrogen for determining the temperature T 1 .
  • the first metal and the second metal do not have to have the same shape, the same amount, and the same volume.
  • the measurer repeatedly dries and wets to occlude hydrogen by corrosion, and divides the high-strength steel material to which rust is attached as an impurity into two.
  • Two high-strength steel materials prepared under exactly the same conditions may be used as the first metal and the second metal, but in order to make the conditions of the first metal and the second metal exactly the same, two high-strength steel materials are used. It is desirable to divide it into.
  • the measurer raises the temperature of the first metal from a low temperature by the heating unit 1, and measures the amount of hydrogen contained in the gas released from the first metal by the measuring unit 2.
  • the measurement of the amount of hydrogen performed in step 2 is the same as the conventional TDA measurement.
  • the measurement result at this time is illustrated in FIG.
  • Two hydrogen release peaks have occurred. One is the hydrogen release peak due to hydrogen in the metal that is originally desired to be measured. The other is the hydrogen release peak due to hydrogen produced by the reaction of metal and rust in the furnace. Of these two hydrogen release peaks, the hydrogen release peak on the low temperature side is regarded as the hydrogen release peak due to hydrogen generated by the reaction between metal and rust in the furnace.
  • the measuring unit 2 determines the generation start temperature T 1 ( ⁇ reaction temperature between the metal and the impurities adhering to the metal; about 40 ° C.) of the hydrogen emission peak on the low temperature side, and is about 5 ° C. to about 10 ° C. than the temperature T 1 .
  • the measurer heats the first metal cooled to the liquid nitrogen temperature to a maximum temperature of 800 ° C. to 900 ° C. at a heating rate of 10 ° C./min to 20 ° C./min, and performs emission gas analysis while heating.
  • the rising temperature of the hydrogen emission peak on the low temperature side is determined to be T 1
  • the temperature about 5 ° C to about 10 ° C lower than the temperature T 1 is determined to be T 2 . do.
  • the rising temperature of the hydrogen release peak is determined to be T 1
  • the temperature is about 5 ° C to about 5 ° C to about T 1 .
  • T 2 be a temperature 10 ° C. lower.
  • the constant value operating temperature T 2 may be within a range not exceeding the generation start temperature T 1 of the hydrogen release peak, but it is preferably as high as possible within that range. As a result, the hydrogen release rate is increased, and the measurement time is shortened. At this time, it is conceivable that the temperature T 2 is as low as the temperature T 1 to 5 ° C. or lower, but if the temperature T 2 is too close to the temperature T 1 , the possibility of hydrogen generation due to the chemical reaction increases. .. Further, it is conceivable that the temperature T 2 is as low as 10 ° C. or more from the temperature T 1 , but the measurement time becomes long. In consideration of these, it is preferable to set the temperature T 2 to be about 5 ° C. to about 10 ° C. lower than the temperature T 1 .
  • the constant value operating temperature T 2 may be determined based on the hydrogen release peak on the lowest temperature side among the three or more hydrogen release peaks.
  • the measurer raises the temperature of the second metal from a low temperature by the heating unit 1, and when the constant operating temperature T 2 ( ⁇ T 1 ) determined in advance in step 2 is reached, the measurer stops the heating of the second metal and heats it.
  • the measuring unit 2 measures the amount of hydrogen contained in the gas released from the second metal until the gas is no longer released from the second metal while maintaining the constant operating temperature T 2 when the temperature is stopped.
  • the measurement result at this time is illustrated in FIG. “ ⁇ ” is the temperature inside the furnace, and “ ⁇ ” is the amount of hydrogen released per unit time.
  • Step 4 (S4) Finally, the observer calculates the total amount of hydrogen released in each unit time measured in step 3 by the measuring unit 2, and the total amount of the released hydrogen is used as the amount of hydrogen contained in the metal 100 to be measured. decide. Specifically, the measuring unit 2 calculates the area surrounded by the hydrogen release curve of “ ⁇ ” shown in FIG. 4 as the amount of hydrogen in the metal. The value of the obtained hydrogen amount is purely hydrogen contained in the metal because it does not contain extra hydrogen due to the chemical reaction between the impurities and the metal.
  • a temperature equal to or lower than the reaction temperature between the impurity and the metal is set as the holding temperature T 2 . Since there is no change, the amount of hydrogen in the metal can be measured by the same procedure as steps 1 and 2 above.
  • FIG. 5 exemplifies the measurement results in which the temperature of the second metal is continuously raised thereafter. Data values for the amount of released hydrogen can be seen at around 450 ° C and around 600 ° C, but since hydrogen is not actually detected, it has been confirmed that all hydrogen in the steel material was detected in the previous procedure. .. It is considered that the error is due to the characteristics of the temperature rising gas desorption analyzer itself.
  • a hydrogen amount measuring method for measuring the amount of hydrogen in a metal which is performed by a temperature rising gas desorption analyzer including a heating unit 1, a measuring unit 2, and a furnace 3, the metal is used.
  • the temperature rises from a low temperature the temperature rise of the metal is stopped before the reaction temperature of the metal and the impurities adhering to the metal is reached, and the temperature at the time when the temperature rise is stopped is maintained until the gas is no longer released from the metal. Since the measurement procedure (S3) for measuring the amount of hydrogen contained in the gas released from the metal and the calculation procedure (S4) for calculating the total amount of the measured hydrogen amount as the amount of hydrogen contained in the metal are performed. The influence of hydrogen due to the reaction between impurities and the metal can be eliminated, and the amount of hydrogen contained in the metal can be accurately measured.
  • the reaction temperature is calculated based on the above, and the determination procedure (S2) for determining a temperature lower than the reaction temperature as the holding temperature is further performed, so that the amount of hydrogen contained in the metal is measured within a practical time. It will be possible.
  • the present invention is not limited to the above embodiment.
  • the present invention can be modified in a number of ways within the scope of the gist of the present invention.
  • the measuring unit 2 of the temperature rising gas desorption analyzer includes, for example, a CPU 901, a memory 902, a storage 903, a communication device 904, an input device 905, and an output device 906. It can be realized by using a general-purpose computer.
  • Heating part 2 Measuring part 3: Furnace 100: Metal 901: CPU 902: Memory 903: Storage 904: Communication device 905: Input device 906: Output device

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Abstract

In this hydrogen content measuring method for measuring the hydrogen content in metal, conducted are: a measurement step (S3) for heating metal from a low temperature, stopping the heating of the metal before the temperature of reaction between the metal and impurities attached to the metal is reached, and, while the temperature at which the heating has been stopped is maintained, measuring the hydrogen content in gas that is emitted from the metal until the gas is no longer emitted from the metal; and a calculation step (S4) for calculating the total amount of the measured hydrogen content as the hydrogen content in the metal.

Description

水素量測定方法Hydrogen amount measurement method
　本発明は、金属内の水素量を測定する水素量測定方法に関する。 The present invention relates to a hydrogen amount measuring method for measuring the amount of hydrogen in a metal.
　インフラ設備などの野外に設置された金属構造物では、腐食反応によって発生した水素が金属に侵入することで、金属が脆くなる水素脆化という現象が起こり、突如破断に至る場合がある。腐食反応によって金属に侵入する水素が増えるほど破断する確率が上がるため、金属内の水素量を正しく測定することは重要である。 In metal structures installed outdoors such as infrastructure equipment, hydrogen generated by the corrosion reaction invades the metal, causing the phenomenon of hydrogen embrittlement, which makes the metal brittle, which may lead to sudden breakage. It is important to measure the amount of hydrogen in the metal correctly because the probability of breakage increases as the amount of hydrogen that invades the metal due to the corrosion reaction increases.
　金属内の水素量を測定する方法には、昇温ガス脱離分析装置を用いて行う昇温ガス脱離分析法（ＴＤＡ測定：ＴｈｅｒｍａｌＤｅｓｏｒｐｔｉｏｎ Ａｎａｌｙｓｉｓ）がある。昇温ガス脱離分析装置は、一般に、測定対象金属を加熱する加熱部と、金属内から放出されたガスを分析する測定部と、で構成される。例えば、ガスクロマトグラフィーにより、加熱によって金属内から放出されたガスに含まれる水素量を測定する。 As a method for measuring the amount of hydrogen in a metal, there is a temperature rise gas desorption analysis method (TDA measurement: Thermal Desorption Analysis) performed by using a temperature rise gas desorption analyzer. The temperature rising gas desorption analyzer is generally composed of a heating unit that heats the metal to be measured and a measurement unit that analyzes the gas released from the inside of the metal. For example, gas chromatography is used to measure the amount of hydrogen contained in the gas released from the metal by heating.
　具体的な測定方法は、金属の種類や測定目的などによって異なる。一般的には、液体窒素温度まで冷却した金属を昇温速度１０℃／ｍｉｎ～２０℃／ｍｉｎで最高温度８００℃～９００℃まで加熱し、単位時間あたりに検出した水素量（＝放出水素量）についての測定総時間分の総和を求めることで、金属内の水素を定量分析する。金属を液体窒素温度まで冷却する理由は、測定準備中に水素が金属内から抜けないようにするためである。 The specific measurement method differs depending on the type of metal and the purpose of measurement. Generally, a metal cooled to the temperature of liquid nitrogen is heated to a maximum temperature of 800 ° C. to 900 ° C. at a heating rate of 10 ° C./min to 20 ° C./min, and the amount of hydrogen detected per unit time (= amount of hydrogen released). ) Is calculated for the total measurement time to quantitatively analyze hydrogen in the metal. The reason for cooling the metal to liquid nitrogen temperature is to prevent hydrogen from escaping from the metal during preparation for measurement.
　非特許文献１の図１には、水素放出曲線が示されている。横軸は、温度で表記されているが、昇温速度を制御しているので、測定時間に相当する。例えば、昇温速度２０℃／ｍｉｎであれば、０℃から４００℃に到達するのに２０分経過することになる。縦軸は、単位時間あたりの放出水素量である。「□」の水素放出曲線で囲まれる面積が金属内の水素量に相当する。 FIG. 1 of Non-Patent Document 1 shows a hydrogen release curve. Although the horizontal axis is expressed by temperature, it corresponds to the measurement time because it controls the rate of temperature rise. For example, if the heating rate is 20 ° C./min, it takes 20 minutes to reach 400 ° C. from 0 ° C. The vertical axis is the amount of hydrogen released per unit time. The area surrounded by the hydrogen release curve of "□" corresponds to the amount of hydrogen in the metal.
　測定対象金属に不純物が付着していない場合（例えば、電気化学的に水素がチャージされた金属である場合）には、上記測定方法で金属内の水素量を測定可能である。 When no impurities are attached to the metal to be measured (for example, when the metal is electrochemically charged with hydrogen), the amount of hydrogen in the metal can be measured by the above measurement method.
　しかし、実際の環境下で水素脆化により破断した金属には、その金属の一部または全体に金属酸化物などの不純物（例えば、錆）が付着している場合がある。この場合、上記測定方法を用いると、加熱中に不純物と金属とが反応して水素が発生してしまう場合がある。この水素は、本来測定したい金属に含まれている水素とは別の水素（＝金属に含まれていない水素）であるが、互いを区別できないため、結果として、金属内の水素量を多めに測定することになる（非特許文献２参照）。 However, a metal broken due to hydrogen embrittlement in an actual environment may have impurities (for example, rust) such as metal oxides attached to a part or the whole of the metal. In this case, if the above measuring method is used, impurities and the metal may react with each other during heating to generate hydrogen. This hydrogen is different from the hydrogen contained in the metal to be measured originally (= hydrogen not contained in the metal), but since they cannot be distinguished from each other, as a result, the amount of hydrogen in the metal is increased. It will be measured (see Non-Patent Document 2).
　例えば、錆が付着した金属からの放出水素量を測定すると、水素放出ピークが５０℃付近で発生し、２８０℃付近でも発生する。２つの水素放出ピークのうち、片方は本来測定したい金属内の水素による水素放出ピークであるが、もう片方は金属と錆が炉中で反応して出てきた水素による水素放出ピークである。しかし、どちらが本来測定したい水素による水素放出ピークなのかが不明である。２つの水素放出ピークをまとめて積算してしまうと、金属内の水素量を多めに測定してしまうことになる。また、２つの水素放出ピークが完全に分離できず、シングルピークのように見える場合もある。この場合も、そのまま積算してしまうと金属内の水素量を多めに測定してしまうこととなる。 For example, when the amount of hydrogen released from a metal with rust is measured, a hydrogen release peak occurs near 50 ° C. and also occurs near 280 ° C. Of the two hydrogen release peaks, one is the hydrogen release peak due to hydrogen in the metal that is originally desired to be measured, and the other is the hydrogen release peak due to hydrogen generated by the reaction between the metal and rust in the furnace. However, it is unclear which is the hydrogen release peak due to hydrogen that is originally desired to be measured. If the two hydrogen emission peaks are integrated together, the amount of hydrogen in the metal will be measured too much. In addition, the two hydrogen emission peaks may not be completely separated and may appear as a single peak. In this case as well, if the integration is performed as it is, the amount of hydrogen in the metal will be measured too much.
　本発明は、上記事情に鑑みてなされたものであり、本発明の目的は、金属内の水素量を正確に測定可能な技術を提供することである。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a technique capable of accurately measuring the amount of hydrogen in a metal.
　本発明の一態様の水素量測定方法は、金属内の水素量を測定する水素量測定方法において、金属を低温から昇温し、前記金属と前記金属に付着した不純物との反応温度に到達する前に前記金属の昇温を止め、前記昇温を止めたときの温度を保持しながら、前記金属からガスが放出されなくなるまで、前記金属から放出されるガスに含まれる水素量を測定する測定手順と、前記測定された水素量の総量を前記金属に含まれる水素量として算出する算出手順と、を行う。 The method for measuring the amount of hydrogen in one aspect of the present invention is a method for measuring the amount of hydrogen in a metal, in which the temperature of the metal is raised from a low temperature to reach the reaction temperature between the metal and impurities adhering to the metal. A measurement that measures the amount of hydrogen contained in the gas released from the metal until the gas is no longer released from the metal while maintaining the temperature at which the temperature rise of the metal is stopped before. A procedure and a calculation procedure for calculating the total amount of measured hydrogen as the amount of hydrogen contained in the metal are performed.
　本発明の一態様の水素量測定方法は、金属内の水素量を測定する水素量測定方法において、金属を第１金属と第２金属とに分割する分割手順と、前記第１金属を低温から昇温し、前記第１金属から放出されるガスに含まれる水素量の測定結果を基に水素放出ピークの発生開始温度を決定し、前記水素放出ピークの発生開始温度よりも低い温度を保持温度として決定する決定手順と、前記第２金属を低温から昇温し、前記保持温度に到達した時に前記第２金属の昇温を止め、前記昇温を止めたときの温度を保持しながら、前記第２金属からガスが放出されなくなるまで、前記第２金属から放出されるガスに含まれる水素量を測定する測定手順と、当該測定された水素量の総量を前記金属に含まれる水素量として算出する算出手順と、を行う。 The hydrogen amount measuring method of one aspect of the present invention is a hydrogen amount measuring method for measuring the amount of hydrogen in a metal, in which a dividing procedure for dividing a metal into a first metal and a second metal and the first metal from a low temperature are used. The temperature is raised, the generation start temperature of the hydrogen release peak is determined based on the measurement result of the amount of hydrogen contained in the gas released from the first metal, and the holding temperature is lower than the generation start temperature of the hydrogen release peak. The temperature of the second metal is raised from a low temperature, the temperature of the second metal is stopped when the temperature reaches the holding temperature, and the temperature at which the temperature is stopped is maintained. A measurement procedure for measuring the amount of hydrogen contained in the gas released from the second metal until the gas is no longer released from the second metal, and the total amount of the measured hydrogen is calculated as the amount of hydrogen contained in the metal. And the calculation procedure to be performed.
　本発明によれば、金属内の水素量を正確に測定可能な技術を提供できる。 According to the present invention, it is possible to provide a technique capable of accurately measuring the amount of hydrogen in a metal.
図１は、昇温ガス脱離分析装置の構成例を示す図である。FIG. 1 is a diagram showing a configuration example of a temperature rising gas desorption analyzer. 図２は、金属内の水素量の測定方法例を示す図である。FIG. 2 is a diagram showing an example of a method for measuring the amount of hydrogen in a metal. 図３は、手順２におけるＴＤＡ測定の測定結果例を示す図である。FIG. 3 is a diagram showing an example of the measurement result of the TDA measurement in the procedure 2. 図４は、手順３におけるＴＤＡ測定の測定結果例を示す図である。FIG. 4 is a diagram showing an example of the measurement result of the TDA measurement in the procedure 3. 図５は、手順４以降におけるＴＤＡ測定の測定結果例を示す図である。FIG. 5 is a diagram showing an example of the measurement result of the TDA measurement in the procedure 4 and subsequent steps. 図６は、昇温ガス脱離分析装置（測定部）の構成例を示す図である。FIG. 6 is a diagram showing a configuration example of a temperature rising gas desorption analyzer (measurement unit).
　以下、図面を参照して、本発明の実施形態を説明する。図面の記載において同一部分には同一符号を付し説明を省略する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the description of the drawings, the same parts are designated by the same reference numerals and the description thereof will be omitted.
　［発明の概要］
　金属に付着している不純物と金属との反応は化学反応であり、反応温度に到達しない限り水素は発生しない。一方、金属内の水素は、室温で放置していても徐々に放出される。例えば、ＴＤＡ測定を行った結果、２００℃～３００℃で水素放出ピークが検出されても、２００～３００℃に到達しなければ金属内から水素が抜けないわけではなく、２５℃～２８℃の室温でも時間さえかければ徐々に金属内から水素は抜けていく。 [Outline of the invention]
The reaction between impurities adhering to the metal and the metal is a chemical reaction, and hydrogen is not generated unless the reaction temperature is reached. On the other hand, hydrogen in the metal is gradually released even if it is left at room temperature. For example, even if a hydrogen release peak is detected at 200 ° C to 300 ° C as a result of TDA measurement, hydrogen does not escape from the metal unless it reaches 200 to 300 ° C, and it is 25 ° C to 28 ° C. Even at room temperature, hydrogen will gradually escape from the metal as long as it takes time.
　そこで、本発明では、不純物と金属との反応は化学反応であり、反応温度に到達しない限り水素は発生しない、という事実を利用する。つまり、本発明は、金属を低温から昇温し、金属と金属に付着した不純物との反応温度に到達する直前に金属の昇温を止め、その温度を保持しながら、金属からガスが放出されなくなるまで、金属から放出されるガスに含まれる水素量を測定する。これにより、不純物と金属との反応による水素の影響を排除可能となり、金属に含まれる水素量を正確に測定可能となる。 Therefore, in the present invention, the fact that the reaction between an impurity and a metal is a chemical reaction and hydrogen is not generated unless the reaction temperature is reached is utilized. That is, in the present invention, the temperature of the metal is raised from a low temperature, the temperature of the metal is stopped immediately before reaching the reaction temperature between the metal and the impurities adhering to the metal, and the gas is released from the metal while maintaining the temperature. The amount of hydrogen contained in the gas released from the metal is measured until it is exhausted. This makes it possible to eliminate the influence of hydrogen due to the reaction between impurities and the metal, and it is possible to accurately measure the amount of hydrogen contained in the metal.
　また、本発明は、測定対象金属の一部を用いて従来のＴＤＡ測定を行い、そのＴＤＡ測定の結果を基に不純物と金属との上記反応温度を事前に決定し、その反応温度よりも低い直前の温度を上記保持する温度として事前に決定しておく。これにより、金属に含まれる水素量を実用的な時間内で測定可能となる。 Further, in the present invention, the conventional TDA measurement is performed using a part of the metal to be measured, the reaction temperature between the impurity and the metal is determined in advance based on the result of the TDA measurement, and the reaction temperature is lower than the reaction temperature. The temperature immediately before is determined in advance as the temperature to be held. This makes it possible to measure the amount of hydrogen contained in the metal within a practical time.
　［昇温ガス脱離分析装置の構成］
　図１は、本実施形態に係る昇温ガス脱離分析装置の構成例を示す図である。昇温ガス脱離分析装置は、昇温ガス脱離分析法（ＴＤＡ測定）を用いて金属内の水素量を測定する装置であり、例えば、加熱部１と、測定部２と、炉３と、を備える。 [Structure of heated gas desorption analyzer]
FIG. 1 is a diagram showing a configuration example of a temperature rising gas desorption analyzer according to the present embodiment. The temperature rising gas desorption analyzer is a device for measuring the amount of hydrogen in a metal by using a temperature rising gas desorption analysis method (TDA measurement), and is, for example, a heating unit 1, a measuring unit 2, and a furnace 3. , Equipped with.
　加熱部１は、炉３の温度を制御する装置である。例えば、加熱部１は、炉３の内部に配置された金属１００を低温から昇温する。加熱部１は、金属１００と金属１００に付着した不純物との反応温度に到達する前に金属１００の昇温を止め、その昇温を止めたときの温度を保持する。加熱部１は、炉３に内蔵されている加熱機構を用いてもよいし、炉３とは別途用意した加熱装置でもよい。 The heating unit 1 is a device that controls the temperature of the furnace 3. For example, the heating unit 1 raises the temperature of the metal 100 arranged inside the furnace 3 from a low temperature. The heating unit 1 stops the temperature rise of the metal 100 before reaching the reaction temperature of the metal 100 and the impurities adhering to the metal 100, and maintains the temperature at which the temperature rise is stopped. The heating unit 1 may use a heating mechanism built in the furnace 3, or may be a heating device separately prepared from the furnace 3.
　測定部２は、加熱によって金属１００の内部から放出されたガスを取り込み、そのガスに含まれる水素量を測定する装置である。例えば、測定部２は、金属１００から放出されるガスに含まれる水素量を測定（従来のＴＤＡ測定）する。測定部２は、その水素量の測定結果を基に、金属１００と金属１００に付着した不純物との反応温度を決定し、その反応温度よりも低い温度を金属１００の保持温度として決定する。測定部２は、その保持温度を保持しながら、金属１００からガスが放出されなくなるまで、金属１００から放出されるガスに含まれる水素量を測定する。測定部２は、測定された水素量の総量を金属１００に含まれる水素量として算出する。測定部２は、例えば、ガスクロマトグラフィーである。 The measuring unit 2 is a device that takes in the gas released from the inside of the metal 100 by heating and measures the amount of hydrogen contained in the gas. For example, the measuring unit 2 measures the amount of hydrogen contained in the gas released from the metal 100 (conventional TDA measurement). The measuring unit 2 determines the reaction temperature between the metal 100 and the impurities adhering to the metal 100 based on the measurement result of the hydrogen amount, and determines a temperature lower than the reaction temperature as the holding temperature of the metal 100. The measuring unit 2 measures the amount of hydrogen contained in the gas released from the metal 100 until the gas is no longer released from the metal 100 while maintaining the holding temperature. The measuring unit 2 calculates the total amount of measured hydrogen as the amount of hydrogen contained in the metal 100. The measuring unit 2 is, for example, gas chromatography.
　炉３は、例えば、加熱炉、保熱炉である。 The furnace 3 is, for example, a heating furnace and a heat retaining furnace.
　［水素量の測定方法］
　図２は、金属内の水素量を測定する測定方法を示す図である。 [Measurement method of hydrogen amount]
FIG. 2 is a diagram showing a measuring method for measuring the amount of hydrogen in a metal.
　手順１（Ｓ１）；
　測定者は、ペンチなどの分割手段を用いて、測定対象である金属１００を２つに分割する。分割した２つの金属のうち一方を第１金属とし、他方を第２金属とする。第１金属は、手順２で温度Ｔ１を決定するための金属であり、温度Ｔ１を決定するために十分な水素量を測定可能な大きさであればよい。第１金属と第２金属とは、同じ形、同じ量、同じ体積である必要はない。 Step 1 (S1);
The measurer divides the metal 100 to be measured into two by using a dividing means such as pliers. Of the two divided metals, one is the first metal and the other is the second metal. The first metal is a metal for determining the temperature T 1 in the procedure 2, and may be of a size capable of measuring a sufficient amount of hydrogen for determining the temperature T 1 . The first metal and the second metal do not have to have the same shape, the same amount, and the same volume.
　例えば、測定者は、乾燥と湿潤とを繰返し行い腐食によって水素を吸蔵させ、不純物として錆が付着している高強度鋼材を２つに分割する。全く同じ条件で用意した２つの高強度鋼材を第１金属と第２金属としてもよいが、第１金属と第２金属との条件を全く同じにするには、１つの高強度鋼材を２つに分割することが望ましい。 For example, the measurer repeatedly dries and wets to occlude hydrogen by corrosion, and divides the high-strength steel material to which rust is attached as an impurity into two. Two high-strength steel materials prepared under exactly the same conditions may be used as the first metal and the second metal, but in order to make the conditions of the first metal and the second metal exactly the same, two high-strength steel materials are used. It is desirable to divide it into.
　手順２（Ｓ２）；
　次に、測定者は、第１金属を炉３の内部に配置する。測定者は、加熱部１により、第１金属を低温から昇温し、測定部２により、第１金属から放出されるガスに含まれる水素量を測定する。手順２で行う水素量の測定は、従来のＴＤＡ測定と同じである。このときの測定結果を図３に例示する。水素放出ピークが２つ発生している。片方は、本来測定したい金属内の水素による水素放出ピークである。もう片方は、金属と錆が炉中で反応して出てきた水素による水素放出ピークである。この２つの水素放出ピークのうち低温側の水素放出ピークを、金属と錆が炉中で反応して出てきた水素による水素放出ピークとみなす。測定部２は、低温側の水素放出ピークの発生開始温度Ｔ１（≒金属と金属に付着した不純物との反応温度；約４０℃）を決定し、温度Ｔ１よりも約５℃～約１０℃低い温度を定値運転温度Ｔ２（＝保持温度；約３０℃）として決定する。温度Ｔ２以下で手順３以降を実施することで、不純物と金属との化学反応による水素の発生を抑制可能となる。 Step 2 (S2);
Next, the measurer places the first metal inside the furnace 3. The measurer raises the temperature of the first metal from a low temperature by the heating unit 1, and measures the amount of hydrogen contained in the gas released from the first metal by the measuring unit 2. The measurement of the amount of hydrogen performed in step 2 is the same as the conventional TDA measurement. The measurement result at this time is illustrated in FIG. Two hydrogen release peaks have occurred. One is the hydrogen release peak due to hydrogen in the metal that is originally desired to be measured. The other is the hydrogen release peak due to hydrogen produced by the reaction of metal and rust in the furnace. Of these two hydrogen release peaks, the hydrogen release peak on the low temperature side is regarded as the hydrogen release peak due to hydrogen generated by the reaction between metal and rust in the furnace. The measuring unit 2 determines the generation start temperature T 1 (≈ reaction temperature between the metal and the impurities adhering to the metal; about 40 ° C.) of the hydrogen emission peak on the low temperature side, and is about 5 ° C. to about 10 ° C. than the temperature T 1 . The lower temperature is determined as the constant operating temperature T 2 (= holding temperature; about 30 ° C.). By carrying out step 3 and subsequent steps at a temperature of T 2 or less, it is possible to suppress the generation of hydrogen due to the chemical reaction between impurities and the metal.
　例えば、測定者は、液体窒素温度まで冷却した第１金属を昇温速度１０℃／ｍｉｎ～２０℃／ｍｉｎで最高温度８００℃～９００℃まで加熱し、加熱しながら放出ガス分析を実施する。このとき、２つの水素放出ピークが検出された場合には、低温側の水素放出ピークの立ち上がり温度をＴ１と決定し、温度Ｔ１から約５℃～約１０℃低い温度をＴ２と決定する。偶然にも２つの水素放出ピークが重なり１つの水素放出ピークのみ（シングルピーク）検出された場合には、その水素放出ピークの立ち上がり温度をＴ１と決定し、温度Ｔ１から約５℃～約１０℃低い温度をＴ２とする。 For example, the measurer heats the first metal cooled to the liquid nitrogen temperature to a maximum temperature of 800 ° C. to 900 ° C. at a heating rate of 10 ° C./min to 20 ° C./min, and performs emission gas analysis while heating. At this time, when two hydrogen emission peaks are detected, the rising temperature of the hydrogen emission peak on the low temperature side is determined to be T 1 , and the temperature about 5 ° C to about 10 ° C lower than the temperature T 1 is determined to be T 2 . do. If two hydrogen release peaks happen to overlap and only one hydrogen release peak is detected (single peak), the rising temperature of the hydrogen release peak is determined to be T 1 , and the temperature is about 5 ° C to about 5 ° C to about T 1 . Let T 2 be a temperature 10 ° C. lower.
　定値運転温度Ｔ２は、水素放出ピークの発生開始温度Ｔ１を超えない範囲内であればよいが、その範囲内で可能な限り高い方が好ましい。これにより、水素の放出速度が速くなるので、測定時間が短くなる。このとき、温度Ｔ１から５℃以下で低い温度を温度Ｔ２とすることも考えられるが、温度Ｔ２が温度Ｔ１にあまりに近づきすぎると、化学反応による水素が発生する可能性が高くなる。また、温度Ｔ１から１０℃以上も低い温度を温度Ｔ２とすることも考えられるが、測定時間が長くなってしまう。これらを勘案し、温度Ｔ１よりも約５℃～約１０℃低い温度を温度Ｔ２とすることが好ましい。 The constant value operating temperature T 2 may be within a range not exceeding the generation start temperature T 1 of the hydrogen release peak, but it is preferably as high as possible within that range. As a result, the hydrogen release rate is increased, and the measurement time is shortened. At this time, it is conceivable that the temperature T 2 is as low as the temperature T 1 to 5 ° C. or lower, but if the temperature T 2 is too close to the temperature T 1 , the possibility of hydrogen generation due to the chemical reaction increases. .. Further, it is conceivable that the temperature T 2 is as low as 10 ° C. or more from the temperature T 1 , but the measurement time becomes long. In consideration of these, it is preferable to set the temperature T 2 to be about 5 ° C. to about 10 ° C. lower than the temperature T 1 .
　金属に付着する不純物の種類が２つ以上あることで、水素放出ピークが３つ以上発生する可能性も考えられる。この場合には、３つ以上の水素放出ピークのうち最も低温側の水素放出ピークを基に定値運転温度Ｔ２を決定すればよい。 If there are two or more types of impurities adhering to the metal, it is possible that three or more hydrogen emission peaks will occur. In this case, the constant value operating temperature T 2 may be determined based on the hydrogen release peak on the lowest temperature side among the three or more hydrogen release peaks.
　手順３（Ｓ３）；
　次に、測定者は、第２金属を炉３の内部に配置する。測定者は、加熱部１により、第２金属を低温から昇温し、手順２で予め決定していた定値運転温度Ｔ２（＜Ｔ１）に到達した時に第２金属の加熱を止め、加熱を止めたときの定値運転温度Ｔ２を保持しながら、第２金属からガスが放出されなくなるまで、測定部２により、第２金属から放出されるガスに含まれる水素量を測定する。 Step 3 (S3);
Next, the measurer places the second metal inside the furnace 3. The measurer raises the temperature of the second metal from a low temperature by the heating unit 1, and when the constant operating temperature T 2 (<T 1 ) determined in advance in step 2 is reached, the measurer stops the heating of the second metal and heats it. The measuring unit 2 measures the amount of hydrogen contained in the gas released from the second metal until the gas is no longer released from the second metal while maintaining the constant operating temperature T 2 when the temperature is stopped.
　例えば、測定者は、液体窒素温度まで冷却した第２金属を昇温速度１０℃／ｍｉｎ～２０℃／ｍｉｎで加熱し、手順２で決定していた低温側の水素放出ピークの発生開始温度Ｔ１（＝約４０℃）に到達する前の定値運転温度Ｔ２（＝約３０℃）で昇温を停止して温度を保持し、水素が検出されなくなるまで第２金属からの放出ガス分析を実施する。このときの測定結果を図４に例示する。「△」は炉内温度であり、「●」は単位時間毎の放出水素量である。 For example, the measurer heats the second metal cooled to the liquid nitrogen temperature at a heating rate of 10 ° C./min to 20 ° C./min, and the generation start temperature T of the hydrogen release peak on the low temperature side determined in step 2. Stop the temperature rise at the constant operating temperature T 2 (= about 30 ° C) before reaching 1 (= about 40 ° C), maintain the temperature, and analyze the emitted gas from the second metal until hydrogen is no longer detected. implement. The measurement result at this time is illustrated in FIG. “△” is the temperature inside the furnace, and “●” is the amount of hydrogen released per unit time.
　手順４（Ｓ４）；
　最後に、観測者は、測定部２により、手順３で測定された各単位時間の放出水素量の総量を計算し、その放出水素量の総量を測定対象である金属１００に含まれる水素量として決定する。具体的には、測定部２は、図４に示された「●」の水素放出曲線で囲まれる面積を金属内の水素量として計算する。得られた水素量の値は、不純物と金属との化学反応による余分な水素を含んでいないので、純粋に金属に含まれている水素となる。 Step 4 (S4);
Finally, the observer calculates the total amount of hydrogen released in each unit time measured in step 3 by the measuring unit 2, and the total amount of the released hydrogen is used as the amount of hydrogen contained in the metal 100 to be measured. decide. Specifically, the measuring unit 2 calculates the area surrounded by the hydrogen release curve of “●” shown in FIG. 4 as the amount of hydrogen in the metal. The value of the obtained hydrogen amount is purely hydrogen contained in the metal because it does not contain extra hydrogen due to the chemical reaction between the impurities and the metal.
　なお、２つの水素放出ピークのうち高温側が不純物と金属との化学反応による水素放出ピークだった場合でも、シングルピークだった場合でも、不純物と金属との反応温度以下の温度を保持温度Ｔ２としていることに変わりはないため、上記手順１，２と同一の手順で金属内の水素量を測定可能である。 Whether the high temperature side of the two hydrogen release peaks is a hydrogen release peak due to a chemical reaction between an impurity and a metal or a single peak, a temperature equal to or lower than the reaction temperature between the impurity and the metal is set as the holding temperature T 2 . Since there is no change, the amount of hydrogen in the metal can be measured by the same procedure as steps 1 and 2 above.
　参考までに、第２金属をその後昇温し続けた測定結果を図５に例示する。４５０℃付近や６００℃付近で放出水素量のデータ値が見られるが、実際には水素は検出されていないため、鋼材中のすべての水素を前手順で検出していることが確かめられている。昇温ガス脱離分析装置自体の特性による誤差と考えられる。 For reference, FIG. 5 exemplifies the measurement results in which the temperature of the second metal is continuously raised thereafter. Data values for the amount of released hydrogen can be seen at around 450 ° C and around 600 ° C, but since hydrogen is not actually detected, it has been confirmed that all hydrogen in the steel material was detected in the previous procedure. .. It is considered that the error is due to the characteristics of the temperature rising gas desorption analyzer itself.
　［実施形態の効果］
　本実施形態によれば、加熱部１と、測定部２と、炉３と、を備えた昇温ガス脱離分析装置で行う、金属内の水素量を測定する水素量測定方法において、金属を低温から昇温し、金属と金属に付着した不純物との反応温度に到達する前に金属の昇温を止め、昇温を止めたときの温度を保持しながら、金属からガスが放出されなくなるまで、金属から放出されるガスに含まれる水素量を測定する測定手順（Ｓ３）と、測定された水素量の総量を金属に含まれる水素量として算出する算出手順（Ｓ４）と、を行うので、不純物と金属との反応による水素の影響を排除可能となり、金属に含まれる水素量を正確に測定可能となる。 [Effect of embodiment]
According to the present embodiment, in a hydrogen amount measuring method for measuring the amount of hydrogen in a metal, which is performed by a temperature rising gas desorption analyzer including a heating unit 1, a measuring unit 2, and a furnace 3, the metal is used. The temperature rises from a low temperature, the temperature rise of the metal is stopped before the reaction temperature of the metal and the impurities adhering to the metal is reached, and the temperature at the time when the temperature rise is stopped is maintained until the gas is no longer released from the metal. Since the measurement procedure (S3) for measuring the amount of hydrogen contained in the gas released from the metal and the calculation procedure (S4) for calculating the total amount of the measured hydrogen amount as the amount of hydrogen contained in the metal are performed. The influence of hydrogen due to the reaction between impurities and the metal can be eliminated, and the amount of hydrogen contained in the metal can be accurately measured.
　また、本実施形態によれば、金属を分割する分割手順（Ｓ１）と、分割した一部の金属を低温から昇温し、一部の金属から放出されるガスに含まれる水素量の測定結果を基に上記反応温度を算出し、反応温度よりも低い温度を上記保持する温度として決定する決定手順（Ｓ２）と、を更に行うので、金属に含まれる水素量を実用的な時間内で測定可能となる。 Further, according to the present embodiment, the division procedure (S1) for dividing the metal and the measurement result of the amount of hydrogen contained in the gas released from the gas released from the part of the metal by raising the temperature of the divided part of the metal from a low temperature. The reaction temperature is calculated based on the above, and the determination procedure (S2) for determining a temperature lower than the reaction temperature as the holding temperature is further performed, so that the amount of hydrogen contained in the metal is measured within a practical time. It will be possible.
　［その他］
　本発明は、上記実施形態に限定されない。本発明は、本発明の要旨の範囲内で数々の変形が可能である。昇温ガス脱離分析装置の測定部２は、例えば、図６に示すように、ＣＰＵ９０１と、メモリ９０２と、ストレージ９０３と、通信装置９０４と、入力装置９０５と、出力装置９０６と、を備えた汎用的なコンピュータを用いて実現できる。 [others]
The present invention is not limited to the above embodiment. The present invention can be modified in a number of ways within the scope of the gist of the present invention. As shown in FIG. 6, the measuring unit 2 of the temperature rising gas desorption analyzer includes, for example, a CPU 901, a memory 902, a storage 903, a communication device 904, an input device 905, and an output device 906. It can be realized by using a general-purpose computer.
　１：加熱部
　２：測定部
　３：炉
　１００：金属
　９０１：ＣＰＵ
　９０２：メモリ
　９０３：ストレージ
　９０４：通信装置
　９０５：入力装置
　９０６：出力装置 1: Heating part 2: Measuring part 3: Furnace 100: Metal 901: CPU
902: Memory 903: Storage 904: Communication device 905: Input device 906: Output device

Claims (5)

  1. 　金属内の水素量を測定する水素量測定方法において、
    　金属を低温から昇温し、前記金属と前記金属に付着した不純物との反応温度に到達する前に前記金属の昇温を止め、前記昇温を止めたときの温度を保持しながら、前記金属からガスが放出されなくなるまで、前記金属から放出されるガスに含まれる水素量を測定する測定手順と、
    　前記測定された水素量の総量を前記金属に含まれる水素量として算出する算出手順と、
    　を行う水素量測定方法。     In the hydrogen amount measuring method for measuring the amount of hydrogen in a metal,
    The temperature of the metal is raised from a low temperature, the temperature rise of the metal is stopped before the reaction temperature of the metal and the impurities adhering to the metal is reached, and the temperature at which the temperature rise is stopped is maintained while maintaining the temperature of the metal. A measurement procedure for measuring the amount of hydrogen contained in the gas released from the metal until the gas is no longer released from the metal.
    A calculation procedure for calculating the total amount of measured hydrogen as the amount of hydrogen contained in the metal, and
    How to measure the amount of hydrogen.
  2. 　前記金属を分割する分割手順と、
    　前記分割した一部の金属を低温から昇温し、前記一部の金属から放出されるガスに含まれる水素量の測定結果を基に前記反応温度を決定し、前記反応温度よりも低い温度を前記保持する温度として決定する決定手順と、
    　を更に行う請求項１に記載の水素量測定方法。     The division procedure for dividing the metal and
    The temperature of the divided partial metal is raised from a low temperature, the reaction temperature is determined based on the measurement result of the amount of hydrogen contained in the gas released from the partial metal, and the temperature lower than the reaction temperature is set. The determination procedure for determining the temperature to be held and
    The hydrogen amount measuring method according to claim 1.
  3. 　金属内の水素量を測定する水素量測定方法において、
    　金属を第１金属と第２金属とに分割する分割手順と、
    　前記第１金属を低温から昇温し、前記第１金属から放出されるガスに含まれる水素量の測定結果を基に水素放出ピークの発生開始温度を決定し、前記水素放出ピークの発生開始温度よりも低い温度を保持温度として決定する決定手順と、
    　前記第２金属を低温から昇温し、前記保持温度に到達した時に前記第２金属の昇温を止め、前記昇温を止めたときの温度を保持しながら、前記第２金属からガスが放出されなくなるまで、前記第２金属から放出されるガスに含まれる水素量を測定する測定手順と、
    　当該測定された水素量の総量を前記金属に含まれる水素量として算出する算出手順と、
    　を行う水素量測定方法。     In the hydrogen amount measuring method for measuring the amount of hydrogen in a metal,
    The division procedure for dividing a metal into a first metal and a second metal,
    The temperature of the first metal is raised from a low temperature, the generation start temperature of the hydrogen release peak is determined based on the measurement result of the amount of hydrogen contained in the gas released from the first metal, and the generation start temperature of the hydrogen release peak is determined. The decision procedure to determine the lower temperature as the holding temperature,
    The temperature of the second metal is raised from a low temperature, the temperature rise of the second metal is stopped when the temperature reaches the holding temperature, and the gas is released from the second metal while maintaining the temperature when the temperature rise is stopped. A measurement procedure for measuring the amount of hydrogen contained in the gas released from the second metal until it is no longer used.
    A calculation procedure for calculating the total amount of measured hydrogen as the amount of hydrogen contained in the metal, and
    How to measure the amount of hydrogen.
  4. 　前記決定手順では、
    　前記水素放出ピークが複数ある場合、最も低温側の水素放出ピークを基に前記保持温度を決定する請求項３に記載の水素量測定方法。     In the determination procedure,
    The hydrogen amount measuring method according to claim 3, wherein when there are a plurality of hydrogen release peaks, the holding temperature is determined based on the hydrogen release peak on the lowest temperature side.
  5. 　前記決定手順では、
    　前記水素放出ピークの発生開始温度よりも５℃～１０℃低い温度を前記保持温度として決定する請求項３または４に記載の水素量測定方法。     In the determination procedure,
    The hydrogen amount measuring method according to claim 3 or 4, wherein a temperature 5 ° C. to 10 ° C. lower than the generation start temperature of the hydrogen release peak is determined as the holding temperature.
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JP2009168612A (en) * 2008-01-16 2009-07-30 R-Dec Co Ltd Hydrogen amount measuring apparatus
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