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1 第 16 回 助 成 研 究 発 表 会 要 旨 集 ( 平 成 16 年 7 月 ) 発 表 番 号 23(31) 電 位 ノイズ 法 を 用 いた 製 塩 プラント 局 部 腐 食 モニタリング 技 術 への 極 値 統 計 解 析 手 法 の 適 用 に 関 する 基 礎 的 研 究 助 成 研 究 者 : 井 上 博 之 ( 大 阪 府 立 大 学 大 学 院 工 学 研 究 科 ) 近 年 非 進 展 性 局 部 腐 食 ( 食 孔 萌 芽 や 微 小 き 裂 )の 生 成 と 再 不 働 態 化 の 過 程 で 発 生 する 電 位 ノイズを 解 析 し 孔 食 や 応 力 腐 食 割 れの 発 生 をモニタリングする 試 みがなされている 電 位 ノイズ 法 によるモニタリングでは 測 定 したノイズの 波 形 から 対 応 する 食 孔 萌 芽 のサイズを 推 定 する 次 に 実 験 室 試 験 等 で 予 め 求 めておいた 臨 界 食 孔 深 さ( 発 生 した 食 孔 が 進 展 性 となるための 最 小 深 さ)とを 比 較 し 現 在 の 環 境 条 件 が 孔 食 発 生 の 臨 界 条 件 にどの 程 度 接 近 しているかを 判 定 す る 電 位 ノイズによる 局 部 腐 食 モニタリングでは モニタリング 対 象 と 同 じ 材 料 で 作 成 した 小 面 積 の プローブ 電 極 が 用 いられる しかし 孔 食 発 生 は 確 率 過 程 を 含 んだ 現 象 であることから 小 面 積 の 電 極 で 発 生 した 食 孔 萌 芽 の 最 大 値 は 大 面 積 の 電 極 例 えばある 製 塩 装 置 全 体 での 最 大 値 より も 小 さい すなわち プローブ 電 極 上 では 臨 界 サイズ 以 下 の 食 孔 萌 芽 しか 発 生 していない 場 合 で も 装 置 のいずれかの 個 所 では 既 に 進 展 性 の 食 孔 が 生 成 している 可 能 性 がある 筆 者 は この 課 題 を 解 決 するために 極 値 統 計 法 を 用 いることを 着 想 した 本 研 究 では 電 位 ノイズ 法 による 孔 食 モ ニタリングへの 極 値 統 計 法 適 用 の 可 能 性 を 検 討 するため 塩 化 物 水 溶 液 中 において 電 極 上 で 生 成 した 萌 芽 食 孔 の 最 大 深 さが 極 値 分 布 の 一 つである Gumbel 分 布 に 従 うかを 検 討 した 6,7 ならびに 8 の 1mass%の NaCl 水 溶 液 中 に 表 面 積 1mm 2 の SUS34 鋼 試 験 片 を 浸 漬 させ それぞれの 条 件 下 において 複 数 回 48 時 間 の 電 位 ノイズ 測 定 をおこなった 測 定 には 高 精 度 のデジタル 電 圧 計 と 銀 塩 化 銀 電 極 を 用 い.5 秒 間 隔 で 連 続 して 試 験 片 の 腐 食 電 位 を 測 定 し た 各 測 定 毎 に 発 生 した 最 大 の 食 孔 深 さ を RPS 法 を 用 いた 電 位 ノイズの 解 析 結 果 から 推 定 した 得 られた 結 果 を Gumbel 分 布 の 確 率 紙 にプロットした( 右 図 ) 横 軸 は 食 孔 深 さ( 半 径 ), 縦 軸 は 累 積 分 布 関 数 を 示 す GEV 解 析 の 結 果 より 8 と 7 における 各 測 定 での 最 大 食 孔 半 径 は Gumbel 分 布 に 従 うことが 確 認 された 以 上 より 複 数 本 のプローブ 電 極 を 製 塩 のプロセス 流 体 中 に 挿 入 して 電 位 ノイ ズの 測 定 をおこなうことにより 大 面 積 の 製 塩 装 置 における 食 孔 の 最 大 深 さが 推 定 できる 可 能 性 があることが 示 せた

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6 3. RPS Q (2)r R(a)a E-Emin R(a) = a a a 3 (3) R(a) a m mv mv E-Emin (3) r m m Gumbel Q (2)7 8Gumbel GEV Gumbel Gumbel MVLUE 5 5 T - 7 -

7 MVLUE 87 1cm 2 1cm m m (5,6) 4. 1) 52, 444 (23) 2) H. Inoue, M. Kinoshita, Y. Maeda, Corrosion 24, Paper No.4452, (24) 3),,,,, (1996) 4), p.196, (1984) 5),, 36, 385 (1972). 6)

8 Table 1 Conclusion of the GEV analysis 6ºC 7ºC 8ºC Table 2 Probability for initiating propagating pits as a function of the specimen area and the solution temperature. The probability is shown as the ratio of the number of trial that propagating pits were initiated to the total trial number. Temperature / ºC Area / cm 2 Probability for initi-ating propagating pits 6 1 / / / / / 2 Estimated radius/m Amplitude, E-E/mV Fig.1 The relationship between the pit radius estimated by PRS method and the amplitudes of potential noises that generated each pit

9 Amplitude, E-E/ mv 8 14 Amplitude, E-E/ mv Fig.2 Histogram on the generation frequency of potential noise as a function of its amplitude 8 14 Amplitude, E-E/ mv Radius / m Radius / m Fig.3 Histogram on the generation frequency of potential noise as a function of the pit radius estimated from its amplitude Radius / m

10 Fig.4 Gambel plot of the maximum pit depths on the specimens as a function of solution temperatures Fig.5 The Gambel plot shown in Fig.4 and the critical radius for being initiated propagating pits at 7 and 8ºC supposing the minimum specimen area for that as 1cm

11 Basic approach to the application of extreme value statistics analysis to localized-corrosion monitoring technique using potential noise method for salt manufacturing plants Hiroyuki Inoue College of Engineering, Osaka Prefecture University Recently, many attempts have been made to monitoring the initiation of pitting and stress corrosion cracking by analyzing potential noise. The potential noise is generated from the initiation and the repassivation process of non-propagating localized corrosions. The potential noise measurement uses probe electrodes with small area, whose material are equivalent to the monitoring objective with large area, such as an equipment for salt manufacturing plants. Because the pit initiation is a phenomenon that includes stochastic process, the maximum pit depth on the probe electrode is always smaller than that over the monitoring objective. This means that a propagating pit might be initiated at a location on the monitoring objective, even under the conditions that only non-propagating pits are existing on the probe electrodes. In order to overcome this problem, the author came up with the idea of using extreme value statistics for the analysis of the potential noise. In this study, it was examined that whether the maximum pit depths on the electrodes follows Gumbel distribution, and it was investigated the possibility for the application of the extreme value statistics to the pitting monitoring using the potential noise method. The potential noise of SUS34 stainless steel specimens with 1mm 2 exposed area was measured in 1mass% NaCl solutions at 6, 7 or 8 C. The measurements were carried out several times under each conditions for 48 hours. The corrosion potential of the specimens were measured continuously every.5s with a precise digital voltmeter and a silver/silver chloride electrode. The maximum pit depths in each measurement were estimated from the analysis of measured potential noises by using the RPS method. The estimated depths were plotted on a Gumbel probability plotting paper. The results in GEV analysis showed that the maximum pit depths (radiuses) at 8 and 7 C would follow the Gumbel distribution. The obtained results might suggest the possibility of the application of extreme value statistics to a pitting-corrosion monitoring using the potential noise measurement

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