JP2019184585A - Hydrogen filling method and hydrogen embrittlement characteristic evaluation method - Google Patents
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 104
- 239000001257 hydrogen Substances 0.000 title claims abstract description 104
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000011156 evaluation Methods 0.000 title claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
- Investigating Strength Of Materials By Application Of Mechanical Stress (AREA)
Abstract
Description
本発明は、水素充填方法および水素脆化特性評価方法に関する。 The present invention relates to a hydrogen filling method and a hydrogen embrittlement characteristic evaluation method.
高強度鋼の開発において、水素により強度および靭性が劣化する水素脆化が大きな問題となっている。しかし、水素脆化に関係する材料組織的な変化は定かでなく、水素脆化のメカニズム解明が求められている。そして、そのためには、効率的に水素を鋼中に充填する方法の確立が必要となる。 In the development of high-strength steel, hydrogen embrittlement, whose strength and toughness deteriorate due to hydrogen, has become a major problem. However, material structural changes related to hydrogen embrittlement are not clear, and elucidation of the mechanism of hydrogen embrittlement is required. For this purpose, it is necessary to establish a method for efficiently filling hydrogen into steel.
鋼中に水素を充填する方法として、電気化学的に水素チャージを行う方法が一般的に用いられている（例えば、特許文献１〜４を参照。）。 As a method of filling hydrogen in steel, a method of electrochemically charging hydrogen is generally used (see, for example, Patent Documents 1 to 4).
上記の方法においては、電解液中に試料および対極を浸漬し、それらの間に電位差を生じさせることによって、電気化学的に水素を試料に充填する。しかしながら、上記の文献においては、水素チャージを行う際の試験条件について十分に検討がなされておらず、より効率的に水素を試料中に充填するためには、改善の余地が残されている。 In the above-described method, the sample and the counter electrode are immersed in an electrolytic solution, and a potential difference is generated therebetween, thereby electrochemically filling the sample with hydrogen. However, in the above-mentioned documents, the examination conditions for performing hydrogen charging have not been sufficiently studied, and there remains room for improvement in order to more efficiently fill the sample with hydrogen.
本発明は、上記の問題を解決し、試料に効率的に水素を充填することができる方法、およびそれにより水素が充填された試料の水素脆化特性を評価する方法を提供することを目的とする。 An object of the present invention is to solve the above problems and to provide a method capable of efficiently filling a sample with hydrogen, and a method for evaluating the hydrogen embrittlement characteristics of the sample filled with hydrogen thereby. To do.
本発明は、上記の問題を解決するためになされたものであり、下記の水素充填方法および水素脆化特性評価方法を要旨とする。 The present invention has been made to solve the above-described problems, and the gist of the present invention is the following hydrogen filling method and hydrogen embrittlement characteristic evaluation method.
（１）金属相中にｂｃｃ相およびｂｃｔ相から選択される１種以上を、合計の体積％で、９５％以上含む金属からなる試料への水素充填方法であって、
（ａ）前記試料および対極を電解液に浸漬する工程と、
（ｂ）前記電解液の温度Ｔｃ（℃）を、前記試料の厚さｔ（ｍｍ）との関係で、下記（ｉ）式を満足するように調整する工程と、
（ｃ）前記試料と前記対極との間に電位差を生じさせて、前記試料に電気化学的に水素を充填する工程と、を備える、
水素充填方法。
Ｔｃ＜２０×ｌｎ（ｔ）＋５５ ・・・（ｉ）
(1) A hydrogen filling method for a sample made of a metal containing 95% or more of a total volume% of one or more selected from a bcc phase and a bct phase in a metal phase,
(A) immersing the sample and the counter electrode in an electrolytic solution;
(B) adjusting the temperature Tc (° C.) of the electrolyte so as to satisfy the following formula (i) in relation to the thickness t (mm) of the sample;
(C) generating a potential difference between the sample and the counter electrode, and electrochemically filling the sample with hydrogen.
Hydrogen filling method.
Tc <20 × ln (t) +55 (i)
（２）前記（ｂ）の工程において、前記電解液の温度を、さらに下記（ii）式を満足するように調整する、
上記（１）に記載の水素充填方法。
Ｔｃ＜１０×ｌｎ（ｔ）＋３０ ・・・（ii）
(2) In the step (b), the temperature of the electrolytic solution is further adjusted to satisfy the following formula (ii).
The hydrogen filling method according to (1) above.
Tc <10 × ln (t) +30 (ii)
（３）前記（ｂ）の工程において、前記電解液の温度を、さらに下記（iii）式を満足するように調整する、
上記（１）または（２）に記載の水素充填方法。
Ｔｃ≦１８ ・・・（iii）
(3) In the step (b), the temperature of the electrolytic solution is further adjusted so as to satisfy the following formula (iii):
The hydrogen filling method according to the above (1) or (2).
Tc ≦ 18 (iii)
（４）前記（ｂ）の工程において、前記電解液の温度を、前記電解液中の溶質のイオンの質量モル濃度ｍ（ｍｏｌ／ｋｇ）との関係で、さらに下記（iv）式を満足するように調整する、
上記（１）から（３）のいずれかに記載の水素充填方法。
−１．８６×ｍ＜Ｔｃ ・・・（iv）
(4) In the step (b), the temperature of the electrolytic solution further satisfies the following formula (iv) in relation to the molar mass m (mol / kg) of solute ions in the electrolytic solution. To adjust,
The hydrogen filling method according to any one of (1) to (3) above.
−1.86 × m <Tc (iv)
（５）前記（ｂ）の工程において、前記試料と前記対極との距離を、０ｍｍを超えて１００ｍｍ以下に調整する、
上記（１）から（４）までのいずれかに記載の水素充填方法。
(5) In the step (b), the distance between the sample and the counter electrode is adjusted to be greater than 0 mm and not greater than 100 mm.
The hydrogen filling method according to any one of (1) to (4) above.
（６）試料の水素脆化特性を評価する方法であって、
上記（１）から（５）までのいずれかに記載される（ａ）〜（ｃ）の工程と、
（ｄ）前記試料に含まれる水素濃度を測定する工程と、を備える、
水素脆化特性評価方法。
(6) A method for evaluating hydrogen embrittlement characteristics of a sample,
The steps (a) to (c) described in any one of (1) to (5) above;
(D) measuring the concentration of hydrogen contained in the sample,
Hydrogen embrittlement characteristic evaluation method.
（７）試料の水素脆化特性を評価する方法であって、
上記（１）から（５）までのいずれかに記載される（ａ）〜（ｃ）の工程と、
（ｅ）前記試料に対して応力を負荷する工程と、を備える、
水素脆化特性評価方法。
(7) A method for evaluating the hydrogen embrittlement characteristics of a sample,
The steps (a) to (c) described in any one of (1) to (5) above;
(E) applying a stress to the sample,
Hydrogen embrittlement characteristic evaluation method.
本発明によれば、試料に水素を効率的に充填することが可能となる。 According to the present invention, it is possible to efficiently fill a sample with hydrogen.
本発明の一実施形態に係る水素充填方法および水素脆化特性評価方法について、詳細に説明する。 A hydrogen filling method and a hydrogen embrittlement characteristic evaluation method according to an embodiment of the present invention will be described in detail.
本発明の一実施形態に係る水素充填方法は、（ａ）浸漬工程、（ｂ）調整工程、および（ｃ）水素充填工程を備える。各工程について詳しく説明する。 A hydrogen filling method according to an embodiment of the present invention includes (a) an immersion step, (b) an adjustment step, and (c) a hydrogen filling step. Each step will be described in detail.
（ａ）浸漬工程
浸漬工程においては、試料および対極を電解液に浸漬する。本発明において、試料は、金属相中にｂｃｃ相およびｂｃｔ相から選択される１種以上を、合計の体積％で、９５％以上含む金属からなるものである。すなわち、金属相中に含まれるｆｃｃ相の体積率は５％以下となる。なお、ｂｃｃ相にはフェライト、低炭素マルテンサイト等が含まれ、ｂｃｔ相には高炭素マルテンサイトが含まれる。また、ｆｃｃ相としては、オーステナイトが挙げられる。また、試料の形状については特に制限はない。例えば、板状であってもよいし、円柱状であってもよい。
(A) Immersion step In the immersion step, the sample and the counter electrode are immersed in the electrolytic solution. In the present invention, the sample is made of a metal containing 95% or more in a total volume% of one or more selected from the bcc phase and the bct phase in the metal phase. That is, the volume ratio of the fcc phase contained in the metal phase is 5% or less. The bcc phase includes ferrite, low carbon martensite, and the like, and the bct phase includes high carbon martensite. An example of the fcc phase is austenite. Moreover, there is no restriction | limiting in particular about the shape of a sample. For example, a plate shape may be sufficient and a column shape may be sufficient.
試料の寸法についても特に制限はないが、水素濃度測定の精度を安定させる観点から、０．５ｇ以上であるのが好ましく、１ｇ以上であるのがより好ましい。なお、試料表面に汚れまたは酸化皮膜等が付着していると、水素の充填が阻害されるおそれがある。そのため、試料表面は洗浄し、汚れおよび酸化皮膜等は除去しておくことが望ましい。 Although there is no restriction | limiting in particular also about the dimension of a sample, From a viewpoint of stabilizing the precision of hydrogen concentration measurement, it is preferable that it is 0.5 g or more, and it is more preferable that it is 1 g or more. If dirt or an oxide film adheres to the sample surface, filling of hydrogen may be hindered. Therefore, it is desirable to clean the sample surface and remove dirt, oxide film, and the like.
また、対極の材質についても特に制限はないが、例えば白金を用いることができる。対極の形状については特に制限はなく、例えば、線状（棒状）または板状のものを用いればよい。なお、試料全体に効率的に水素を充填するためには、試料の表面積に対する対極の表面積が下記（ａ）式を満足することが好ましい。
Ｓ２／Ｓ１≧０．１ ・・・（ａ）
但し、（ａ）式中の各記号の意味は以下のとおりである。
Ｓ１：試料の表面積（ｍｍ２）
Ｓ２：対極の表面積（ｍｍ２）
The material of the counter electrode is not particularly limited, but platinum can be used, for example. There is no restriction | limiting in particular about the shape of a counter electrode, For example, what is necessary is just to use a linear (bar shape) or plate-shaped thing. In order to efficiently fill the entire sample with hydrogen, the surface area of the counter electrode with respect to the surface area of the sample preferably satisfies the following formula (a).
S2 / S1 ≧ 0.1 (a)
However, the meaning of each symbol in the formula (a) is as follows.
S1: Sample surface area (mm 2 )
S2: Surface area of the counter electrode (mm 2 )
さらに、電解液の成分については特に制限はなく、酸性、中性またはアルカリ性のいずれでも構わない。簡便に準備できかつ導電しやすいものとしてＮａＣｌ水溶液が好ましい。この時、導通が取れればＮａＣｌの濃度は問わないが、例えば、０．５質量％以上とすることが好ましい。 Furthermore, there is no restriction | limiting in particular about the component of electrolyte solution, Any of acidic, neutral, or alkaline may be sufficient. A NaCl aqueous solution is preferable as a material that can be easily prepared and easily conducts electricity. At this time, the concentration of NaCl is not limited as long as conduction is obtained, but it is preferably 0.5% by mass or more, for example.
加えて、水素をより多量に充填したい場合は、ＨＣｌ、Ｈ２ＳＯ４などの酸を用いてもよく、また、触媒毒であるチオシアンアンモニウム（ＮＨ４ＳＣＮ）、チオ尿素などを水溶液に加えてもよい。一方、試料の腐食抑制の観点から、ＮａＯＨなどのアルカリ水溶液を用いてもよい。 In addition, when it is desired to charge a larger amount of hydrogen, an acid such as HCl or H 2 SO 4 may be used, and a catalyst poison such as thiocyanammonium (NH 4 SCN) or thiourea is added to the aqueous solution. Also good. On the other hand, an alkaline aqueous solution such as NaOH may be used from the viewpoint of inhibiting corrosion of the sample.
（ｂ）調整工程
調整工程においては、電解液の温度を調整する。上述のように、本発明において、試料はｂｃｃ相および／またはｂｃｔ相を主体とする金属からなるものを対象としている。ｂｃｃ相および／またはｂｃｔ相に充填される水素の多くは転位等の欠陥にトラップされており、低温ほどトラップ水素量は増加する。
(B) Adjustment process In an adjustment process, the temperature of electrolyte solution is adjusted. As described above, in the present invention, the sample is intended to be made of a metal mainly composed of the bcc phase and / or the bct phase. Most of the hydrogen charged in the bcc phase and / or the bct phase is trapped by defects such as dislocations, and the amount of trapped hydrogen increases as the temperature decreases.
一方、後述の水素充填工程終了後、水素脆化特性評価のため水素量測定等を行うまでの間に、試料表面からの水素の放散が起こる。しかし、試料の温度を低くすることにより、試料からの水素の放散を低減することができる。そして、電解液の温度を低くするほど、試料の温度は低くなる。 On the other hand, after the hydrogen filling step described later is completed, hydrogen is diffused from the sample surface until the hydrogen amount is measured for evaluating the hydrogen embrittlement characteristics. However, by lowering the temperature of the sample, hydrogen emission from the sample can be reduced. And the temperature of a sample becomes low, so that the temperature of electrolyte solution is made low.
ここで、試料の厚さが薄いほど、水素の放散による試料中の平均水素濃度の低下は大きい。したがって、試料の厚さが薄いほど、効率的な水素充填のために、水素充填量の増加および水素放散の低減が求められる。以上より、本発明者らが検討を行った結果、試料の厚さに応じて電解液の温度を低く調整することにより、水素を効率的に充填できることが分かった。 Here, the thinner the sample is, the greater the decrease in the average hydrogen concentration in the sample due to hydrogen diffusion. Therefore, as the sample thickness is thinner, an increase in hydrogen filling amount and a reduction in hydrogen diffusion are required for efficient hydrogen filling. From the above, as a result of investigations by the present inventors, it has been found that hydrogen can be efficiently charged by adjusting the temperature of the electrolytic solution to be low according to the thickness of the sample.
具体的には、電解液の温度をＴｃ（℃）、試料の厚さをｔ（ｍｍ）とした場合において、電解液の温度を、下記（ｉ）式を満足するように調整する。
Ｔｃ＜２０×ｌｎ（ｔ）＋５５ ・・・（ｉ）
Specifically, when the temperature of the electrolytic solution is Tc (° C.) and the thickness of the sample is t (mm), the temperature of the electrolytic solution is adjusted so as to satisfy the following formula (i).
Tc <20 × ln (t) +55 (i)
また、電解液の温度は、さらに下記（ii）式を満足するように調整することが好ましく、下記（iii）式を満足するように調整することがより好ましい。
Ｔｃ＜１０×ｌｎ（ｔ）＋３０ ・・・（ii）
Ｔｃ≦１８ ・・・（iii）
Moreover, it is preferable to adjust so that the temperature of electrolyte solution may further satisfy | fill following (ii) Formula, and it is more preferable to adjust so that the following (iii) Formula may be satisfied.
Tc <10 × ln (t) +30 (ii)
Tc ≦ 18 (iii)
なお、電解液の温度は、０℃以下の温度であってもよい。ただし、電解液の温度を凝固点以上とするためには、電解液の温度Ｔｃ（℃）を、電解液中の溶質のイオンの質量モル濃度ｍ（ｍｏｌ／ｋｇ）との関係で、下記（iv）式を満足するように調整することが好ましい。
−１．８６×ｍ＜Ｔｃ ・・・（iv）
The temperature of the electrolytic solution may be 0 ° C. or lower. However, in order to make the temperature of the electrolytic solution equal to or higher than the freezing point, the temperature Tc (° C.) of the electrolytic solution is related to the mass concentration m (mol / kg) of solute ions in the electrolytic solution as follows (iv It is preferable to adjust so as to satisfy the formula.
−1.86 × m <Tc (iv)
本発明においては、強酸と強塩基とから生成する塩については電離度を１とし、弱酸と弱塩基、弱酸と強塩基、または強酸と弱塩基から生成する塩については電離度から、イオンの質量モル濃度を計算するものとする。 In the present invention, the ionization degree is set to 1 for a salt formed from a strong acid and a strong base, and the ion mass is determined from the ionization degree for a salt generated from a weak acid and a weak base, a weak acid and a strong base, or a strong acid and a weak base. The molar concentration shall be calculated.
電解液の冷却は、投げ込み式クーラーまたは冷媒循環装置などを用い、設定した温度に維持する。また、設定温度に対して室温が上下に変化する場所で実施する場合は、ヒーターおよびクーラーを同時に稼働できるように装置を組み立てる等により、温度が維持できるように注意する。 Cooling of the electrolytic solution is maintained at a set temperature by using a throw-in cooler or a refrigerant circulation device. In addition, when it is carried out in a place where the room temperature changes up and down with respect to the set temperature, care is taken so that the temperature can be maintained by assembling the apparatus so that the heater and the cooler can be operated simultaneously.
ここで、本発明において、試料の内部の任意の点から試料表面までの長さが最短となる距離をＬとし、Ｌの最大値をＬｍａｘとした時に、２Ｌｍａｘを試料の厚さと定義する。すなわち、試料が板状の場合には板厚が、また、円柱状の場合には直径が、それぞれの厚さとなる。 In the present invention, the distance that the length from any point within the sample to the sample surface is the shortest and L, the maximum value of L is taken as L max, a 2L max for thickness and definition of the sample . That is, the thickness is the thickness when the sample is plate-shaped, and the diameter is the thickness when the sample is cylindrical.
さらに、ｂｃｃ相およびｂｃｔ相の合計体積率は、試料が鋼の場合は、以下の方法により求めるものとする。まず、試料を１２００番エミリー紙で研磨し、次いで、室温のフッ酸および過塩素酸の混酸溶液に浸漬して化学研磨することにより、厚さの４分の１を除去する。次に、研磨を施した試料表面に、矢澤武男ら（鉄と鋼、Ｖｏｌ．８３（１９９７）Ｎｏ．１、ｐｐ．６０−６５）に準拠した方法でＸ線回折測定（Ｃｕ対陰極、管電圧３０ｋＶ、管電流１００ｍＡ）を実施し、ｆｃｃ相に関しては（１１１）、（２００）および（２２０）、ｂｃｃ相またはｂｃｔ相に関しては（１１０）、（２００）および（２１１）のピーク強度を求め、矢澤武男らに準拠した方法でｆｃｃ相の体積率を算出する。そして、得られた値を１００％から差し引くことによって、ｂｃｃ相およびｂｃｔ相の合計体積率を求める。 Further, the total volume ratio of the bcc phase and the bct phase is determined by the following method when the sample is steel. First, the sample is polished with # 1200 Emily paper, and then immersed in a mixed acid solution of hydrofluoric acid and perchloric acid at room temperature for chemical polishing to remove a quarter of the thickness. Next, X-ray diffraction measurement (Cu counter cathode, tube) was applied to the polished sample surface by a method in accordance with Takeo Yazawa et al. (Iron and Steel, Vol. 83 (1997) No. 1, pp. 60-65). The peak intensity of (111), (200) and (220) for the fcc phase, and (110), (200) and (211) for the bcc phase or the bct phase. The volume fraction of the fcc phase is calculated by a method based on Takeo Yazawa et al. Then, the total volume ratio of the bcc phase and the bct phase is obtained by subtracting the obtained value from 100%.
また、試料が鋼以外の金属の場合は、上記と同様の方法により研磨およびＸ線回折測定を行い、１００％からｆｃｃ相およびｈｃｐ相の体積率を差し引くことにより、ｂｃｃ相およびｂｃｔ相の合計体積率を求める。 When the sample is a metal other than steel, polishing and X-ray diffraction measurement are performed in the same manner as described above, and the volume ratio of the fcc phase and the hcp phase is subtracted from 100% to obtain the total of the bcc phase and the bct phase. Obtain the volume ratio.
調整工程においては、さらに、試料と対極との距離を調整してもよい。これまで、試料と対極との距離については、実験結果に大きく影響を及ぼす要素としては考えておらず、特別な検討はなされてこなかった。また、一般的には、発生する電界の均一性の観点からある程度の距離を確保すべきと考えられてきた。 In the adjustment step, the distance between the sample and the counter electrode may be further adjusted. So far, the distance between the sample and the counter electrode has not been considered as a factor that greatly affects the experimental results, and no special consideration has been made. In general, it has been considered that a certain distance should be secured from the viewpoint of the uniformity of the generated electric field.
しかしながら、本発明者らが、試料および対極の距離と水素充填量との関係について検討を行った結果、従来の考えとは異なり、接触しない範囲で距離が近いほど水素充填量が増加する傾向にあることを見出した。 However, as a result of studying the relationship between the distance between the sample and the counter electrode and the hydrogen filling amount, the present inventors have found that the hydrogen filling amount tends to increase as the distance is shorter in the non-contact range, unlike the conventional idea. I found out.
そのため、本発明においては、調整工程において、試料と対極との距離を、０ｍｍを超えて１００ｍｍ以下に調整することが好ましい。上記の距離は短ければ短い方が好ましく、５０ｍｍ以下であることが好ましく、１０ｍｍ以下であることがより好ましく、５ｍｍ以下であることがさらに好ましい。なお、試料と対極との接触を避ける必要があるため、その距離は１ｍｍ以上であることが好ましい。 Therefore, in this invention, it is preferable to adjust the distance of a sample and a counter electrode to 100 mm or less exceeding 0 mm in an adjustment process. The shorter the distance, the better. The distance is preferably 50 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less. In addition, since it is necessary to avoid contact with a sample and a counter electrode, it is preferable that the distance is 1 mm or more.
ここで、本発明において、試料と対極との距離とは、試料の表面上の任意の点と対極の表面上の任意の点との最短距離を指すものとする。 Here, in the present invention, the distance between the sample and the counter electrode refers to the shortest distance between an arbitrary point on the surface of the sample and an arbitrary point on the surface of the counter electrode.
（ｃ）水素充填工程
水素充填工程においては、試料と対極との間に電位差を生じさせて、試料に電気化学的に水素を充填する。具体的には、試料および対極を、電線等を介して外部電源に接続し、試料と対極との間に電位差を生じさせて、試料を対極に対して負電位にすることによって、試料に水素が充填される。この際、例えば、外部電源にポテンショ／ガルバノスタットを用いることで、水素の充填を電流制御（定電流）で行うことができる。
(C) Hydrogen filling step In the hydrogen filling step, a potential difference is generated between the sample and the counter electrode, and the sample is electrochemically filled with hydrogen. Specifically, the sample and the counter electrode are connected to an external power source via an electric wire or the like, a potential difference is generated between the sample and the counter electrode, and the sample is set to a negative potential with respect to the counter electrode. Is filled. At this time, for example, by using a potentio / galvanostat as an external power source, hydrogen can be charged by current control (constant current).
（ｄ）水素濃度測定工程
本発明の一実施形態に係る水素脆化特性評価方法においては、上述の（ａ）〜（ｃ）の工程に加えて、試料に含まれる水素濃度を測定する工程を備える。水素濃度の測定は、上述の方法によって試料に水素を充填した後に行ってもよいし、水素充填の前後の両方で行ってもよい。水素脆化特性を評価するための重要なパラメータの１つである試料中の水素濃度を測定することにより、試料の水素脆化特性を評価することが可能となる。
(D) Hydrogen concentration measurement step In the hydrogen embrittlement characteristic evaluation method according to one embodiment of the present invention, in addition to the steps (a) to (c) described above, a step of measuring the hydrogen concentration contained in the sample is performed. Prepare. The measurement of the hydrogen concentration may be performed after the sample is filled with hydrogen by the above-described method, or may be performed both before and after the hydrogen filling. By measuring the hydrogen concentration in the sample, which is one of important parameters for evaluating the hydrogen embrittlement characteristics, the hydrogen embrittlement characteristics of the sample can be evaluated.
試料中の水素濃度の測定方法については特に制限はなく、例えば、ガスクロマトグラフ式昇温脱離水素分析装置（ＴＤＡ）を用いて、試料を１００℃／ｈの昇温速度で４００℃まで加熱した後、放出された水素量を測定することにより求めることができる。 The method for measuring the hydrogen concentration in the sample is not particularly limited. For example, the sample was heated to 400 ° C. at a temperature increase rate of 100 ° C./h using a gas chromatographic temperature-programmed desorption hydrogen analyzer (TDA). Later, it can be determined by measuring the amount of hydrogen released.
（ｅ）応力負荷工程
本発明の他の実施形態に係る水素脆化特性評価方法においては、上述の（ａ）〜（ｃ）の工程に加えて、試料に対して応力を負荷する工程を備える。試料に対する応力の負荷は、上述の方法によって試料に水素を充填した後に行ってもよいし、水素充填しながら行ってもよい。試料に負荷する応力の種類については特に制限されず、引張応力、圧縮応力、曲げ応力、ねじり応力のいずれであってもよい。そして、例えば、破断が生じた際の応力を測定することによって、試料の水素脆化特性を直接的に評価することが可能である。
(E) Stress loading step In the hydrogen embrittlement characteristic evaluation method according to another embodiment of the present invention, in addition to the steps (a) to (c) described above, a step of applying stress to the sample is provided. . The stress load on the sample may be performed after the sample is filled with hydrogen by the above-described method, or may be performed while filling with hydrogen. The type of stress applied to the sample is not particularly limited, and may be any of tensile stress, compressive stress, bending stress, and torsional stress. For example, the hydrogen embrittlement characteristics of the sample can be directly evaluated by measuring the stress when the fracture occurs.
以下、実施例によって本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples.
低合金鋼であり、ｂｃｃ相の体積率が９５％以上であるＪＩＳ ＳＣＭ４３５鋼を試料として用いて、水素の充填を行った。試料の寸法および形状は、長さ２０ｍｍ、幅１０ｍｍ、厚さ０．２〜１．０ｍｍの薄板状とした。対極には、長さ３０ｍｍ、幅１０ｍｍ、厚さ０．２ｍｍの薄板状の白金を用いた。そして、電解液には、試験Ｎｏ．１〜９では３％ＮａＣｌ、試験Ｎｏ．１０〜１２では５％ＮａＣｌ水溶液を使用し、表１に示す温度に調整した。 JIS SCM435 steel, which is a low alloy steel and has a volume ratio of bcc phase of 95% or more, was used as a sample for hydrogen filling. The size and shape of the sample was a thin plate having a length of 20 mm, a width of 10 mm, and a thickness of 0.2 to 1.0 mm. As the counter electrode, a thin plate-like platinum having a length of 30 mm, a width of 10 mm, and a thickness of 0.2 mm was used. And, in the electrolyte, the test No. 1-9, 3% NaCl, test no. 10-12 used 5% NaCl aqueous solution and adjusted to the temperature shown in Table 1.
そして、電解液に上記の試料および対極を浸漬した後、試料と対極とが互いに平行であり、距離が３０ｍｍとなるようにそれぞれ配置した。そして、外部電源を用いて試料と対極との間に電位差を生じさせて、試料を対極に対して負電位にした。なお、外部電源としてはポテンショ／ガルバノスタットを用い、電流密度を１．０ｍＡ／ｃｍ２とした。また、充填時間は２４時間で一定とした。 And after immersing said sample and a counter electrode in electrolyte solution, the sample and the counter electrode were mutually arrange | positioned so that a distance might be set to 30 mm. Then, a potential difference was generated between the sample and the counter electrode using an external power source, and the sample was set to a negative potential with respect to the counter electrode. Note that a potentio / galvanostat was used as the external power source, and the current density was 1.0 mA / cm 2 . The filling time was constant at 24 hours.
その後、各試料中に充填された水素濃度の測定を行った。具体的には、ＴＤＡを用いて、試料を１００℃／ｈの昇温速度で４００℃まで加熱した後、放出された水素量を測定することにより、試料中に充填された水素濃度を求めた。その結果を表１に併せて示す。 Thereafter, the concentration of hydrogen charged in each sample was measured. Specifically, using TDA, the sample was heated to 400 ° C. at a rate of temperature increase of 100 ° C./h, and then the hydrogen concentration filled in the sample was determined by measuring the amount of released hydrogen. . The results are also shown in Table 1.
表１を参照して、電解液の温度が（ｉ）式を満足しない試験Ｎｏ．３、７および９においては、充填された水素濃度がそれぞれ０．１６ｐｐｍ、０．１１ｐｐｍおよび０．１５ｐｐｍと低い結果となった。それに対して、（ｉ）式を満足する本発明例の試験Ｎｏ．１、２、４〜６、８および１０〜１２では、水素濃度が０．２０ｐｐｍ以上となり良好な結果となった。特に電解液の温度を１８℃以下にした試験Ｎｏ．１、５、８および１０〜１２では、水素濃度が０．３０ｐｐｍ以上となり著しく良好な結果となった。 With reference to Table 1, test No. in which the temperature of electrolyte solution does not satisfy Formula (i). In 3, 7, and 9, the charged hydrogen concentrations were low, 0.16 ppm, 0.11 ppm, and 0.15 ppm, respectively. On the other hand, test No. of the present invention example satisfying the formula (i). In 1, 2, 4-6, 8, and 10-12, the hydrogen concentration was 0.20 ppm or more, and good results were obtained. In particular, test no. In 1, 5, 8 and 10-12, the hydrogen concentration was 0.30 ppm or more, and extremely good results were obtained.
本発明によれば、試料に水素を効率的に充填することが可能となる。また、本発明に係る水素充填方法を採用することにより、水素脆化特性の評価を効率的に行うことが可能となり、水素脆化のメカニズム解明に寄与することができる。 According to the present invention, it is possible to efficiently fill a sample with hydrogen. In addition, by adopting the hydrogen filling method according to the present invention, it becomes possible to efficiently evaluate the hydrogen embrittlement characteristics and contribute to elucidation of the mechanism of hydrogen embrittlement.
Claims (7)
（ａ）前記試料および対極を電解液に浸漬する工程と、
（ｂ）前記電解液の温度Ｔｃ（℃）を、前記試料の厚さｔ（ｍｍ）との関係で、下記（ｉ）式を満足するように調整する工程と、
（ｃ）前記試料と前記対極との間に電位差を生じさせて、前記試料に電気化学的に水素を充填する工程と、を備える、
水素充填方法。
Ｔｃ＜２０×ｌｎ（ｔ）＋５５ ・・・（ｉ） A method for filling hydrogen into a sample comprising a metal containing 95% or more of a total volume% of one or more selected from a bcc phase and a bct phase in a metal phase,
(A) immersing the sample and the counter electrode in an electrolytic solution;
(B) adjusting the temperature Tc (° C.) of the electrolyte so as to satisfy the following formula (i) in relation to the thickness t (mm) of the sample;
(C) generating a potential difference between the sample and the counter electrode, and electrochemically filling the sample with hydrogen.
Hydrogen filling method.
Tc <20 × ln (t) +55 (i)
請求項１に記載の水素充填方法。
Ｔｃ＜１０×ｌｎ（ｔ）＋３０ ・・・（ii） In the step (b), the temperature of the electrolytic solution is further adjusted so as to satisfy the following formula (ii):
The hydrogen filling method according to claim 1.
Tc <10 × ln (t) +30 (ii)
請求項１または請求項２に記載の水素充填方法。
Ｔｃ≦１８ ・・・（iii） In the step (b), the temperature of the electrolytic solution is further adjusted so as to satisfy the following formula (iii):
The hydrogen filling method according to claim 1 or 2.
Tc ≦ 18 (iii)
請求項１から請求項３のいずれかに記載の水素充填方法。
−１．８６×ｍ＜Ｔｃ ・・・（iv） In the step (b), the temperature of the electrolytic solution is adjusted so as to further satisfy the following formula (iv) in relation to the molar concentration m (mol / kg) of ions of the solute in the electrolytic solution. To
The hydrogen filling method according to any one of claims 1 to 3.
−1.86 × m <Tc (iv)
請求項１から請求項４までのいずれかに記載の水素充填方法。 In the step (b), the distance between the sample and the counter electrode is adjusted to more than 0 mm and not more than 100 mm.
The hydrogen filling method according to any one of claims 1 to 4.
請求項１から請求項５までのいずれかに記載される（ａ）〜（ｃ）の工程と、
（ｄ）前記試料に含まれる水素濃度を測定する工程と、を備える、
水素脆化特性評価方法。 A method for evaluating the hydrogen embrittlement characteristics of a sample,
The steps (a) to (c) described in any one of claims 1 to 5,
(D) measuring the concentration of hydrogen contained in the sample,
Hydrogen embrittlement characteristic evaluation method.
請求項１から請求項５までのいずれかに記載される（ａ）〜（ｃ）の工程と、
（ｅ）前記試料に対して応力を負荷する工程と、を備える、
水素脆化特性評価方法。 A method for evaluating the hydrogen embrittlement characteristics of a sample,
The steps (a) to (c) described in any one of claims 1 to 5,
(E) applying a stress to the sample,
Hydrogen embrittlement characteristic evaluation method.
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