炔醇類有機物對碳鋼高溫酸洗腐蝕抑制作用

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：121

、訪客IP：3.148.106.0

姓名

王俊堯(Jyun-yao Wang) 查詢紙本館藏

畢業系所

機械工程學系

論文名稱

炔醇類有機物對碳鋼高溫酸洗腐蝕抑制作用
(Inhibition of steel corrosion in 2M HCl at 85℃ by acetylenic alcohols)

相關論文

★ 銅導線上鍍鎳或錫對遷移性之影響及鍍金之鎳/銅銲墊與Sn-3.5Ag BGA銲料迴銲之金脆研究	★ 單軸步進運動陽極在瓦茲鍍浴中進行微電析鎳過程之監測與解析
★ 光電化學蝕刻n-型（100）單晶矽獲得矩陣排列之巨孔洞研究	★ 銅箔基板在H2O2/H2SO4溶液中之微蝕行為
★ 助銲劑對迴銲後Sn-3Ag-0.5Cu電化學遷移之影響	★ 塗佈奈米銀p型矽(100)在NH4F/H2O2 水溶液中之電化學蝕刻行為
★ 高效能Ni80Fe15Mo5電磁式微致動器之設計與製作	★ 銅導線上鍍金或鎳/金對遷移性之影響及鍍金層對Sn-0.7Cu與In-48Sn BGA銲料迴銲後之接點強度影響
★ 含氮、硫雜環有機物對鍋爐鹼洗之腐蝕抑制行為研究	★ 銦、錫金屬、合金與其氧化物的陽極拋光行為探討
★ n-型(100)矽單晶巨孔洞之電化學研究	★ 鋁在酸性溶液中孔蝕行為研究
★ 微陽極引導電鍍與監測	★ 鍍金層對Bi-43Sn與Sn-9Zn BGA銲料迴銲後之接點強度影響及二元銲錫在不同溶液之電解質遷移行為
★ 人體血清白蛋白構形改變之電化學及表面電漿共振分析研究	★ 光電化學蝕刻製作n-型(100)矽質微米巨孔陣列及連續壁結構

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

至系統瀏覽論文 ( 永不開放)

摘要(中)

本論文在研究含有-OH基及C≡C三鍵之炔醇類有機抑制劑，在2M鹽酸85℃環境下對鋼鐵酸洗之腐蝕抑制作用。研究方法採用重量損失法、直流極化法、交流頻譜法，鋼鐵表面使用FTIR及XPS分析。研究結果顯示影響炔醇類抑制效率之因素有三：(1)鄰接C≡C之碳鍊長度增加，其抑制效率增加。(2) C≡C三鍵位結構末端具有較高抑制效率。(3) C≡C三鍵所鍵結之官能基，以氫氧基（2-Butyne-1,4-diol）與苯環(3-Phenyl-2-propyn-1-ol)皆比單純接一碳鍊(2-Butyn-1-ol)抑制效率好。
由電化學研究得知炔醇類抑制劑屬於陰極型抑制劑，其在鋼鐵上的吸附屬於Langmuir等溫吸附。由活化能之計算得知，添加炔醇類抑制劑活化能下降（Addition free105.9kJmol-1> 2-Butyn-1-ol 90.4 kJmol-1）推測抑制劑之吸附屬於化學吸附。
長鏈型炔醇類（2-Nonyn-1-ol）在腐蝕環境中之抑制效率隨時間增長而大幅下降，且在三價鐵離子存在下抑制效率更差。
FTIR表面分析之結果顯示，2-Nonyn-1-ol 在鋼材表面形成C＝C、C＝O鍵結。XPS表面分析之C1s結果顯示，抑制劑能在鋼材表面吸附形成C-H、C-C、C-O的化學鍵結；偵測Fe2p2/3訊號時，可以得到試片表面呈現相同的鍵結，但經Ar+離子濺渡蝕刻30秒後，在高抑制效率系統中(2-Propyn-1-ol與2-Nonyn-1-ol)鋼鐵表面偵測到0價鐵的訊號，推測抑制劑分子保護鋼材表面使其較不易被氧化，生成氧化物也較薄。

摘要(英)

The inhibiting effect of some acetylenic alcohols has been investigated on the corrosion of low carbon steel (iron in 2M HCl at 85℃. Coupon test (weight loss measurement) and electrochemical techniques (including linear polarization resistance, Tafel extrapolation and electrochemical impedance spectroscopy) were applied to estimate the corrosion rate of steel and the inhibition efficiency of the inhibitors. The inhibition efficiency (Ef%) was defined as Ef% =100 (i-io)/io where I and io are the corrosion rate of steel in the presence of and in absence of inhibitors. The inhibition efficiency of the acetylenic alcohols was found to depend on their chemical formulae: (1) The Ef% increases with increasing the number of carbon chain linked to the C≡C triple bond. (2) The Ef% is higher for the alcohols with a terminal C≡C triple bond than that in the internal. (3) Substitution the —CH3 in 2-Butyn-1-ol by －CH2OH group (i.e., 2-Butyn-1,4-diol) by benzene ring (—C6H5) (i.e., 3-Penyl-2-propyn-1-ol) increases the Ef%.
Resulting from Tafel extrapolation, almost all the alcohols cause a negative shift of the corrosion potential and reduced the corrosion current. This surmises that the inhibitors belonged to cathodic type. The activation energies were estimated to be 105.9 and 90.4 kJmol-1 in the absence of inhibitors and in the presence of 2-butyn-1-ol, respectively, using Arrhenius plot. It suggests that the lower activation energy caused by 2-butyn-1-ol is resultant from its chemisorption on steel. The adsorption of acetylenic alcohols on the steel surface in 2M HCl solution obeyed the Langmuir adsorption isotherm.
The inhibition efficiency decreases with time for the inhibitors with long carbon chain (e.g., 2-Nonyn-1-ol). More vigorous is the tendency for in the addition of ferric ions (Fe3+).
Analysis through FTIR spectra showed that there are adsorption bands of C＝C、C＝O present on steel surface caused by the addition of 2-Nonyn-1-ol as an inhibitor. XPS spectra of the inhibited steel display the existence of C-C and C-H species adsorbed on the steel surface. XPS analysis on Fe2p 3/2 depicted a similar chemical state on the steel surface whether or not present an inhibitor. After etching by sputtering Ar+ for 30 s, the steel surface effectively inhibited exposed their metallic peak. In comparison, the exposed surface was still in the oxide forms of iron for the inefficient inhibition.

關鍵字(中)

★ 炔醇類抑制劑
★ 高溫酸洗
★ 低碳鋼
★ 電化學分析

關鍵字(英)

★ Chemical cleaning
★ Electrochemical analysis
★ Corrosion inhibitor

論文目次

中文摘要 Ⅰ
英文摘要 Ⅲ
致謝 Ⅴ
目錄 Ⅵ
表目錄 Ⅹ
圖目錄 ⅩⅠ
第一章前言 1
第二章文獻回顧 3
2.1鋼材酸洗流程 3
2.2酸洗除銹機制 4
2.3腐蝕抑制劑之特性與分類 6
2.3.1腐蝕行為 6
2.3.2腐蝕抑制劑與侵蝕性離子間之競爭吸附特性 7
2.3.3腐蝕抑制劑之分類 8
2.4抑制劑吸附方式 11
2.4.1物理吸附 11
2.4.2 化學吸附 12
2.5抑制劑吸附類型與活化能 12
2.5.1抑制劑吸附類型 12
2.5.2活化能 14
2.6電化學相關理論 14
2.6.1直流電化學法 14
2.6.2交流阻抗頻譜法(AC impedance) 15
2.6.3等效電路圖及模擬 17
第三章實驗方法 19
3.1 試片選擇 19
3.2 試片製作 19
3.3抑制劑藥品選擇 19
3.4重量損失法實驗 20
3.5 電化學實驗 20
3.5.1直流電化學 21
3.5.2交流電化學 22
3.6表面分析儀器 22
第四章結果 23
4.1炔醇類有機抑制劑抑制效率測試 23
4.1.1重量損失法 23
4.1.2線性極化 24
4.1.3 Tafel極化法 24
4.1.4交流阻抗頻譜分析（EIS）與等效電路模擬 26
4.2活化能與吸附型態 27
4.2.1溫度效應 27
4.2.2濃度效應 28
4.3酸洗環境對抑制效率之影響 28
4.3.1抑制劑穩定性測試 28
4.3.2三價鐵離子對抑制效率造成之影響 30
4.4表面分析 31
4.4.1 FTIR表面分析 31
4.4.2 XPS表面分析 31
第五章討論 33
5.1抑制效率測試 33
5.1.1抑制效率受到鄰近C≡C三鍵之碳鍊長度不同之影響 33
5.1.2 C≡C三鍵所在位置之影響 35
5.1.3 與C≡C三鍵所接不同官能基之比較 36
5.2溫度效應與濃度效應 37
5.2.1溫度效應 37
5.2.2濃度效應 37
5.3酸洗環境對抑制效率之影響 38
5.3.1藥品熱安定性測試 38
5.3.2抑制劑受到酸與熱之影響 38
5.3.3二價鐵離子與三價鐵離子環境所造成的影響 40
5.4 表面分析 41
5.4.1試片表面FTIR分析 41
5.4.2添加抑制劑酸洗後試片表面XPS分析 42
第六章結論 45
參考文獻 47

參考文獻

1. 陳森德，杜清芳，李建明”有機化合物對不鏽鋼在鹽酸，硫酸之酸洗抑制效率探討”，1990年12月，中鋼資料.
2. 張耀南，”熱軋鋼捲軋延銹皮與氧化銹皮之研究”，防蝕工程第十卷第四期，pp.234-242，民國85年12月。.
3. 張志哲，陳火坤，”酸洗設備與製程控制介紹”，中鋼技術與訓練22卷2期1997年4月.
4. 施漢章，洪耀宗，林洪霄”不同官能基酸洗抑制劑對多樣剛種的抑制效果研究”，1992年8月，中鋼資料
5. 李建明”酸洗製程簡介及抑制劑原理與選用”材料腐蝕與防蝕研究班，民國94年11月.
6. N. Hackerman and E. Mc Cafferty,”Adsorption and corrosion inhibition with Flexible organic diameters”,Corrosion ,Vol.4,1964,p.542
7. N.Sato,”Some concepts of corrosion fundamentals”,Corrosion Sci,Vol.4,1987,p.421
8. K. Trethewey,”Corrosion control by evironomental change”,Corrosion for students of Science and Engineering,1988,pp.221-229
9. An Introsuction to Corrosion and Protection of Materials,1985,p.165.
10. I.L.Rozenfeld,”Theoretical aspects of corrosion inhibitors and inhibition”,Corrosion Inhibitors,McGrraw-Hill Inc.1981
11. 曹楚南” 腐蝕電化學原理” 化學工業出版社2004
12. W. S. Tait,”An introduction to electrochemical corrosion testing for practicing engineers and scientists”,p.55
13. W. D. Callister,”Materials science and engineering an introsuction”,1997,p.448.
14. M.Gojic,” The Effect of Propargylic Alcohol on the corrosion inhibition of low ally CrMo steel in sulphuric acid” Corrosion sci 43,2001,pp.919-929
15. K.B.Samardzija,C.Lupu,N.Hackerman*”Inhibitive properties, adsorption and surface study of butyn-1-ol and pentyn-1-ol alcohols as corrosion inhibitors for iron in HCl”.J Mater Chem 15,2005,pp.1908-1916
16. M.Lebrini,F.Bentiss,H.Vezin,M.Lagrenee.” The inhibition of mild steel corrosion in acidic solution by 2,3-bis(4-pyridyl0-1,3,4-thiadiazole:Structure-activity correlation”. Corrosion science 48,2006,pp.1279-1291
17. D.A.Jones,”Principles and prevention of corrosion”,1996,p.90
18. A.M.shamseldin,R.A.arain, “Thermometric,gravimetric,and potentiometric study of corrosion of iron under conditions of reaction Fe+2Fe3+=3Fe2+” Br. Corros. J. Vol. 33, No.3, 1998, p.189
19. F.B.Growcock and V.R.Lopp , ”Inhibition of steel corrosion in hydrochloric acid with 3-PHENYL-2-PROPYN-1-OL”, Corrosion Sci Vol 28, No.4, 1988, pp.397-410
20. P.Kutej,J.Vosta,J.Pancir and N.Hackerman,” Electrochemical and Quantum Chemical Study of Propargyl Alcohol Adsorption on Iron”, J.Electrochem. Soc Vol.142, No.6, 1995, pp.1847-1850
21. G.W.Poling,”Infrared studies of protective films formed by acetylenic corrosion inhibitors”, J.Electrochem. Soc Vol.114,No.12,1967,pp.1209-1214
22. C.FIAUD,A.HARCH,D.MALLOUH AND M.TZINMANN,” The inhibition of iron corrosion by acetylenic alcohols in acid solution at high temperature”, Corrosion Sci Vol.35,,1993,pp.1437-1444
23. M.Bartos,S.D.Kapusta and N.Hackerman,” Solid-State science and technology a study of polymerization of propargyl alcohol on steel”, J.Electrochem. Soc Vol.140, No9,1993, pp.2604-2605

指導教授

林景崎(Jing-chie Lin)

審核日期

2007-7-18

推文