Name: determining the chemical composition of corrosion inhibitor/metal interfaces with xps: minimizing post immersion oxidation
Uploaded: 2017-03-15T13:00:00.000+00:00
Duration: 7 min 44 s
Description: Watch this Scientific Journal Video about Determining the Chemical Composition of Corrosion Inhibitor/Metal Interfaces with XPS: Minimizing Post Immersion Oxidation at JoVE.com

这项工作是由阿克苏诺贝尔通过与曼彻斯特大学合作协议的支持。 PMG是感谢丰多扇形国家科学技术委员会 - SENER Hidrocarburos和研究所的墨西哥德Peteróleo财政支持。 TB感谢Mellitah石油与天然气Companyfor资助她的助学金。 KK确认来自通过材料的EPSRC（EP / L01680X / 1）财政支持要求苛刻的环境中心博士培训。"PAL感谢国家科学技术委员会的财政支持她在曼彻斯特的时光。最后，所有的作者承认本·斯宾塞对他的技术支持和建议。

1.基板/溶液的制备<ol><li> 碳制基板的制备 <ol><li>从一圆柱形碳钢杆（10±2毫米直径）3毫米厚的盘，使用精密切割机 - 剪切一个约2。采用在切割过程中的冷却流体，以尽量减少机械损伤。 </li><li>研磨既圆形面，并且与一系列的SiC砂纸盘形样品的边缘， 即 600目，800号粒度，1200号粒度的2400砂砾，和4000号粒度。 </li><li>得到波兰两个圆形面，并且所述盘形样品与任一金刚石糊剂或氧化铝粉末（3微米和/或1微米），直到一镜面光洁度的边缘。 </li><li>超声处理在室温下大约10分钟的样品中的每一个下面的:去离子水，丙酮，乙醇，最后再次去离子水。 </li><li>干燥的空气流下的样品的所有表面。 </li><li>在商店的样品或者干燥器或真空干燥器直到需要。理想情况下，最终制成碳钢基体之前，为了溶液浸泡。 </li></ol></li><li> 抑制的1M HCl溶液中制备 <ol><li>添加10.2 M盐酸到去离子水中以产生的1M HCl溶液中。注意:盐酸是有害的，有腐蚀性。承接在通风橱这一步，穿着合适的个人防护装备。 </li><li>在1M HCl溶液溶解选定的有机-Cl（ 如 X =0.300克2-巯基苯并咪唑）的XG以产生含有x毫有机-Cl（ 例如 X = 2毫摩尔2-巯基苯并咪唑）中的1M HCl溶液。 </li></ol></li></ol> 2.底物浸入抑制的酸溶液<ol><li>倒入一个小体积-中的1M HCl + X毫（ 例如 X = 2毫摩尔2-巯基苯并咪唑）有机-Cl溶液到一个小玻璃烧杯中（一般为25 50毫升）中。 </li><li>拾起盘形碳钢样品与陶瓷或复astic镊子是至1M的HCl抗性。只摸与镊子将样品的边缘。 </li><li>引入样品进入含有的1M HCl + X毫有机-Cl溶液的玻璃烧杯中。定向样品以便圆柱面是在垂直平面上。沉积样品直接到烧杯的底部，或顶上的短玻璃管的开口端。确保样品完全浸没。 </li></ol> 3.样品转移<ol><li> 手套箱准备 <ol><li>定位在手套箱的底部的圆形样品转移开口到该XPS加载互锁法兰安装。保证手套箱和装载锁定凸缘之间的密封是正确形成。 </li><li>手套箱连接到惰性气体筒（不管是N 2或Ar）。 </li><li>坚持双面碳（导电）带的一个小广场上XPS样吧。 </li><li>插入所需样品转移到XPS仪器硬件通过手套箱开放端口，附有碳纤维带，塑料/陶瓷镊子，丁腈手套，实验室组织，塑料石蜡膜，空/干洗瓶带嘴和玻璃烧杯即样品条含〜200克Na 2 CO 3粉末。 </li><li>含碳钢样品中的1M HCl + X毫（ 例如 X = 2毫摩尔2-巯基苯并咪唑）手套箱内有机-Cl溶液代替玻璃烧杯中。确保样品始终在这一步完全浸没。 </li><li>密封在手套箱的所有端口/入口点，并开始与N 2（或Ar）清除。 </li><li>不断清除手套箱直到样品传输完成。 </li></ol></li><li> 从溶液中的XPS分析室 <ol><li>允许样品中的1 M盐酸+所需浸渍期间离开Xmm有机-Cl溶液保持淹没， 如 4小时，作为用于该XPS数据如下。 </li><li>检查RELA手套箱内略去湿度被最小化，其通常实现后60 - 发起吹扫90分钟。 8％的相对湿度的值与样品传输继续之前必需的;清除前值通常是35 - 40％。 注意:通常情况下，有手套箱内没有专用的 O 2传感器，而试验测量结果与这样的设备指示该清洗过程由〜1000倍导致的 O 2浓度的降低。 </li><li>引进双手放进手套箱手套，再涂戴手套的手与位于手套箱内丁腈手套。这一步骤减少了污染的样品处理过程中的可能性，以及增加了便于样品操纵。 </li><li>取下的1M HCl + X毫（ 例如 X = 2毫摩尔2-巯基苯并咪唑）有机-Cl溶液的碳钢试样，使用陶瓷材料/塑料镊子。只摸与镊子将样品的边缘。 </li><li> Immediat伊利再现后，通过引导惰性气体流，反复挤空/干洗瓶位于手套箱内，到样品表面产生吹样品干燥。 注:在此阶段用溶剂漂洗未进行，以尽量减少损坏抑制界面， 例如除去抑制剂或接口氧化的电位。 </li><li>含有1M的HCl + X毫有机-Cl塑料石蜡膜溶液覆盖烧杯中。 </li><li>加盖样品连接到XPS样品条双面碳（导电）胶带的小广场。请勿触摸到的XPS被探测的表面。 </li><li>泄该XPS加载互锁真空室到N 2 /氩。确保相关的涡轮/机械泵组合执行此操作前关闭。 </li><li>打开负载锁定凸缘。 </li><li>转移样品条放入装载室并将其推到试样固定插脚。 </li><li>关闭负载锁凸缘。 </li><li>开关关于涡轮/旋转泵组合抽空装载室。 </li><li>一旦在装载锁定腔室的压力达到至少约5×10 -7毫巴，手动样品使用传送臂传送到中间室。 </li><li>等到在中间室的压力达到约1×10 -8毫巴，然后使用第二传送臂在分析室样品手动转移到样品操纵器。 </li></ol></li></ol> 4. XPS数据采集<ol><li>样品的取向角，使用小键盘来驱动样品操纵器马达，以期望的光电子发射角， 例如 0°（沿表面法线发射），作为用于以下提出的XPS数据。 </li><li>通过点击位于桌面上的图标打开的XPS数据采集软件。打开仪器手动控制窗口。 </li><li>输入端10 mA和分别为15千伏，作为阳极排放和阳极HT参数的值。然后，单击"X射线枪"部分的单色化的AlKαX射线源功率达"中"按钮。在此之后，点击"中和剂"部分中的"ON"按钮打开充电中和剂。 </li><li>选择电子分析仪"的频谱/混合"测量距离"模式"模式和"镜头"下拉菜单中的"分析"部分。 </li><li>输入所需的动能/结合能范围内，通过能源（IES），步长（s）和停留时间（s）到"采集/扫描控制"部分。例如输入参数值:1200 - 0 eV的结合能范围，80 eV的通能，0.5 EV步长大小，和0.1秒停留时间获取概述谱。 </li><li>通过调整样本机械手的位置，使用键盘驱动样品操纵电机优化样品位置，最大限度地从选定的核心层面， 例如 C 1或铁2P信号。 </li><li>在XPS数据采集启动数据采集获得X射线光电子能谱软件。 </li></ol>

<ol>
	<li>Sastri, V. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Corrosion Inhibitors: Principles and Applications. , (1998).</li><li>Lindsay, R., Lyon, S. B., Cottis, R. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Introduction+to+Control+of+Corrosion+by+Environmental+Control.">Introduction to Control of Corrosion by Environmental Control.</a> In: Shreir's Corrosion, Vol. 4, Management and Control of Corrosion. , 2891-2899 (2010).</li><li>Oguzie, E. E., Li, Y., Wang, S. G., Wang, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Understanding+corrosion+inhibition+mechanisms+-+Experimental+and+theoretical+approach.">Understanding corrosion inhibition mechanisms - Experimental and theoretical approach.</a> RSC Advances. 1 (5), 866-873 (2011).</li><li>Kokalj, A., Peljhan, S., Fin&#353;gar, M., Milo&#353;ev, I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=What+determines+the+inhibition+effectiveness+of+ATA,+BTAH,+and+BTAOH+corrosion+inhibitors+on+copper?.">What determines the inhibition effectiveness of ATA, BTAH, and BTAOH corrosion inhibitors on copper?.</a> Journal of the American Chemical Society. 132 (46), 16657-16668 (2010).</li><li>Kokalj, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Formation+and+structure+of+inhibitive+molecular+film+of+imidazole+on+iron+surface.">Formation and structure of inhibitive molecular film of imidazole on iron surface.</a> Corrosion Science. 68, 195-203 (2013).</li><li>Briggs, D., Seah, M. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Practical surface analysis: by auger and x-ray photo-electron spectroscopy. 1, (1996).</li><li>Fin&#353;gar, M., Jackson, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Application+of+corrosion+inhibitors+for+steels+in+acidic+media+for+the+oil+and+gas+industry:+A+review.">Application of corrosion inhibitors for steels in acidic media for the oil and gas industry: A review.</a> Corrosion Science. 86, 17-41 (2014).</li><li>Fin&#353;gar, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=2-Mercaptobenzimidazole+as+a+copper+corrosion+inhibitor:+Part+II.+Surface+analysis+using+X-ray+photoelectron+spectroscopy.">2-Mercaptobenzimidazole as a copper corrosion inhibitor: Part II. Surface analysis using X-ray photoelectron spectroscopy.</a> Corrosion Science. 72, 90-98 (2013).</li><li>Morales-Gil, P., Walczak, M. S., Cottis, R. A., Romero, J. M., Lindsay, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Corrosion+inhibitor+binding+in+an+acidic+medium:+Interaction+of+2-mercaptobenizmidazole+with+carbon-steel+in+hydrochloric+acid.">Corrosion inhibitor binding in an acidic medium: Interaction of 2-mercaptobenizmidazole with carbon-steel in hydrochloric acid.</a> Corrosion Science. 85, 109-114 (2014).</li><li>Olivares-Xometl, O., Likhanova, N. V., Mart&#237;nez-Palou, R., Dom&#237;nguez-Aguilar, M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrochemistry+and+XPS+study+of+an+imidazoline+as+corrosion+inhibitor+of+mild+steel+in+an+acidic+environment.">Electrochemistry and XPS study of an imidazoline as corrosion inhibitor of mild steel in an acidic environment.</a> Materials and Corrosion. 60 (1), 14-21 (2009).</li><li>Flores, E. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sodium+phthalamates+as+corrosion+inhibitors+for+carbon+steel+in+aqueous+hydrochloric+acid+solution.">Sodium phthalamates as corrosion inhibitors for carbon steel in aqueous hydrochloric acid solution.</a> Corrosion Science. 53 (12), 3899-3913 (2011).</li><li>Zarrok, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Corrosion+control+of+carbon+steel+in+phosphoric+acid+by+purpald+-+Weight+loss,+electrochemical+and+XPS+studies.">Corrosion control of carbon steel in phosphoric acid by purpald - Weight loss, electrochemical and XPS studies.</a> Corrosion Science. 64, 243-252 (2012).</li><li>Morales-Gil, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Corrosion+inhibition+of+carbon-steel+with+2-mercaptobenzimidazole+in+hydrochloric+acid.">Corrosion inhibition of carbon-steel with 2-mercaptobenzimidazole in hydrochloric acid.</a> Corrosion Science. 101, 47-55 (2015).</li><li>Popova, A., Christov, M., Raicheva, S., Sokolova, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Adsorption+and+inhibitive+properties+of+benzimidazole+derivatives+in+acid+mild+steel+corrosion.">Adsorption and inhibitive properties of benzimidazole derivatives in acid mild steel corrosion.</a> Corrosion Science. 46 (6), 1333-1350 (2004).</li><li>Gupta, R. P., Sen, S. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Calculation+of+multiplet+structure+of+core+p+-vacancy+levels+II.">Calculation of multiplet structure of core p -vacancy levels II.</a> Physical Review B. 12 (1), 15-19 (1975).</li><li>Shirley, D. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-resolution+x-ray+photoemission+spectrum+of+the+valence+bands+of+gold.">High-resolution x-ray photoemission spectrum of the valence bands of gold.</a> Physical Review B. 5 (12), 4709-4714 (1972).</li><li>Al-Refaie, A. A., Walton, J., Cottis, R. A., Lindsay, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photoelectron+spectroscopy+study+of+the+inhibition+of+mild+steel+corrosion+by+molybdate+and+nitrite+anions.">Photoelectron spectroscopy study of the inhibition of mild steel corrosion by molybdate and nitrite anions.</a> Corrosion Science. 52 (2), 422-428 (2010).</li><li>Liu, X., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+study+of+self-assembled+films+of+triazole+on+iron+electrodes+using+electrochemical+methods,+XPS,+SEM+and+molecular+simulation.">The study of self-assembled films of triazole on iron electrodes using electrochemical methods, XPS, SEM and molecular simulation.</a> Electrochemistry Communications. 9 (4), 813-819 (2007).</li><li>Zhang, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Corrosion+inhibition+of+mild+steel+in+hydrochloric+acid+solution+by+quaternary+ammonium+salt+derivatives+of+corn+stalk+polysaccharide+(QAPS).">Corrosion inhibition of mild steel in hydrochloric acid solution by quaternary ammonium salt derivatives of corn stalk polysaccharide (QAPS).</a> Desalination. 372, 57-66 (2015).</li></ol>

The authors declare that they have no competing financial interests.

XPS光谱显示在图1和2清楚地表明，样品转移过程中所用的惰性气氛是至关重要的，以避免这些碳钢/有机-Cl接口的交浸入氧化。在此基础上，从其他类似的XPS研究的结果（ 如 18，19），其中所涉及的抑制基底到环境实验室气氛的曝光，应该严格重新评估，作为界面化学可能是通过氧化改性。应当指出的是，没有理由假定所有有机顺吸附到在酸性溶液中的氧化物/氢氧化物自由表面。在某些情况下，这种相可确实促进有机-Cl表面结合。区分后浸入氧化这种情况并非如此简单。一个可能的解决方案是获得来自参考抑制接口XPS数据（ <eM&gt;如1 M盐酸+ 2mM的MBI）在与感兴趣的样品以检查后浸入氧化串联是不是一个问题。 以确保成功的结果，以样品传输的程序，它是必不可少的手套箱完全用惰性气体（N 2 /氩）置换，即在手套箱中的 O 2浓度被最小化。应注意，以验证在手套箱端口/入口点的所有密封件被正确地形成，包括手套箱和XPS装载锁定凸缘之间的密封。理想情况下， 在原位传感器应该被用来直接监测O 2的浓度，虽然不是必要的，由我们自己的工作所证明。如步骤3.3.2所示，我们通常使用一个相对湿度传感器作为时承接了样品转移的指南。 与手套箱环境中的一个进一步的潜在问题是挥发性的溶液成分的存在，其可污染以下从溶液中并在插入之前移除到负载锁定样品表面。例如，在手套箱中的1M HCl溶液中的存在导致的HCl蒸气，它可与碳的钢试样导致不定C1信号在XPS数据起反应的演化。为了尽量减少这样的污染是显著的可能性，盐酸溶液小体积应采用与样品传输应尽可能快地完成。在此基础上，作为协议中所指出的，通常只有一个烧杯/样品被插入到为在任一时刻样品转移手套箱。此外，应尽量减少HCl溶液的表面积，以及覆盖下面的示例再现的烧杯中。 的 Na 2 CO 3粉末（步骤3.1.4）被插入到手套式操作箱中试图控制的HCl蒸气量。此外，它可以用来清理任何酸性溶液溢漏。 除了手套的B小心控制牛的环境中，样品处理也是获得XPS光谱的完整性至关重要。人们不应从已接触到任何固体物体， 如镊子或手套接触的任何表面获取XPS数据。此外，在除去从溶液的样品，应当立即吹入干燥的惰性气体（步骤3.2.5）。此过程进行的，以防止蒸发和溶液组分的后续物理沉积到样品表面上，这可能导致数据的误解。作为附加的预防措施，还可以考虑用新鲜对取代的腈手套（步骤3.2.3）对样品棒转移到加载互锁真空室， 即前到步骤3.1.10。 最后，鉴于此处所述的方法的有效性，我们期望它在腐蚀可以应用于其他主题（ 即除了缓蚀），其中XPS数据的从空气敏感接口采集将添加到understanding。此外，这样的做法应该在XPS测量从形成于液体环境空气敏感的接口进行的其他领域加以考虑。显然，该过程并不限于XPS，但也可以从先前已经浸入在液体中的表面， 例如 ，扫描探针显微术应用到任何其他基于UHV-测量。

腐蚀抑制剂（CI）的是物质，当引入侵蚀性环境，通过在固/液界面1，2，3，4，5诱导的变化降低的金属材料的腐蚀速率。这种方法来腐蚀控制被广泛用于工业，具有高性能的CI具有用于各种应用已研制成功。但是仍然存在，相当缺乏的表现CI基本认识，阻碍了以知识为基础的优化。例如，通过有机顺腐蚀性酸性溶液形成接口的确切性质目前还不清楚。 鉴于假设有机顺通形成中吸附的2-D层2的抑制酸性腐蚀，表面敏感的技术是必需的牛逼Ø描述这些接口。因此，X射线光电子能谱（XPS）6已成为选择的技术来探测这些界面的元素/化学组成易地 7，8，9; XPS测量典型地执行在，或接近，超高真空（UHV）。各种见解已声称，包括一个表面的氧化物或氢氧化物的存在，以促进有机-Cl结合到金属基片10，11，12。该接口描述的有效性，但是，是值得怀疑的XPS数据是从已被从抑制溶液和引入到UHV-XPS光谱仪暴露于实验室气氛中去除之间的样本获得的。这样的程序可能会导致接口氧化，破坏了有关结论界面的化学组成。另一种方法是必需的，这对于后浸入氧化的可能性降至最低。 在本文中，我们详细设计了一个方法，让一个从没有经过氧化以下从酸性溶液中再现有机-CI /金属界面获取XPS数据。的手套箱中，用惰性气体吹扫，这是直接附连到UHV-XPS仪器的真空加载互锁采用。我们的方法的效用是通过XPS数据的呈现从以下除了足够的CI以显著降低在水性1M盐酸（HCl）的溶液在基板的腐蚀速率的形成的两个有机-CI /碳钢接口验证。

<table><tbody><tr><td>Mild steel C1010</td><td>RCSL, BAC Corrosion Control Ltd.</td><td>n/a</td><td></td></tr><tr><td>Polycrystallline iron 99.99+%</td><td>Goodfellow Cambridge Ltd.</td><td>FE007948</td><td></td></tr><tr><td>Silicon Carbide Grinding papers</td><td>Spectrographic Limited</td><td>T13316, T13317, T13318, T13156, T13153</td><td></td></tr><tr><td>Polishing Cloth</td><td>Spectrographic Limited</td><td></td><td></td></tr><tr><td>Monocrystalline Diamond compound</td><td>Spectrographic Limited</td><td>G22003</td><td></td></tr><tr><td>OmegaPol TWIN 250 mm Metallurgical Polisher</td><td>Spectrographic Limited</td><td>n/a</td><td></td></tr><tr><td>BRILLANT 220 - Wet Abrasive Cut-Off Machine</td><td>ATM GmbH Advanced Materialography</td><td>n/a</td><td></td></tr><tr><td>Ultrasonic Bath</td><td>NICKEL-ELECTRO LTD.</td><td>SW3H</td><td></td></tr><tr><td>Heat gun, D100/200 Mfg</td><td>Mar Equipment Ltd</td><td>n/a</td><td></td></tr><tr><td>Vacuum Desiccator</td><td>DURAN</td><td>24 782 57</td><td></td></tr><tr><td>Low form beaker 25 mL</td><td>Fisher Scientific</td><td>FB33170</td><td></td></tr><tr><td>Regulator for N&lt;sub&gt;2&lt;/sub&gt; gas cylinders</td><td>Freshford Ltd.</td><td>MS-10B-N2</td><td></td></tr><tr><td>Nitrogen Purge Glove Box</td><td>Terra Universal, Inc</td><td>n/a</td><td></td></tr><tr><td>Dual Purge System</td><td>Terra Universal, Inc</td><td>1606-61</td><td></td></tr><tr><td>NitroWatch System with sensor</td><td>Terra Universal, Inc</td><td>9500-00A, 9500-02A</td><td></td></tr><tr><td>SEFRAM LOG 1620 Data Logger, 50000</td><td>SEFRAM</td><td>2475144 from Farnell Element14</td><td></td></tr><tr><td>Big Digit Hygro-Thermometer</td><td>FLIR Commercial Systems, Inc. Extech Instruments Division</td><td>445703</td><td></td></tr><tr><td>Kratos Axis Ultra</td><td>Kratos Analytical Ltd</td><td>n/a</td><td></td></tr></tbody></table>

determining the chemical composition of corrosion inhibitor/metal interfaces with xps: minimizing post immersion oxidation

用于获取从腐蚀抑制剂/金属界面更可靠的X射线光电子能谱法数据的方法进行说明。更具体而言，重点是在浸渍在含有有机腐蚀抑制剂的酸性溶液金属基材，因为这些系统可以如下从溶液中除去是对氧化特别敏感。为了尽量减少这样的降解的可能性，将样品从用惰性气体吹扫的手套箱内溶液中除去，或者N 2或Ar。手套箱被直接附着到超高真空X射线光电子能谱仪器的加载互锁，避免任何暴露于实验室环境的气氛，从而降低交浸入底物氧化的可能性。在此基础上，人们可以更确信所观察到的X射线光电子能谱特征很可能是代表的原位淹没的情况下， 例如第m的氧化态等人没有被修改。

图1显示了概述，澳1S和Fe 2P XPS数据碳钢样本收购已浸泡4小时，在两个不同的1M HCl + X毫米有机-CI的解决方案之一，并转移了XPS测量上面详细。从抛光样品类似数据也被显示。碳钢具有C（0.08-0.13），锰（0.30-0.50），P（0.04），S（0.05）的标称重量％的组合物，和Fe（平衡量）。研究了两种有机顺有:2-巯基苯（MBI）和（Z）-2-2（2-（十八碳-9-烯-1-基）-4,5-二氢-1H-咪唑-1-基）乙胺（OMID）。在所使用的浓度（MBI:2毫米; OMID:1毫米）的腐蚀速率的测量13,14表明所有物种的显著抑制碳钢， 即抑制效率（η％）2&gt; 90％的腐蚀。最适合向O 1和铁2P光谱图也显示。光电子峰用高斯洛伦兹（GL）线的形状的功能（30％洛伦兹）建模，用金属铁，其中使用洛伦兹不对称线形状与尾阻尼（LF）中的Fe 2P级除外。阳离子铁X +的状态，用由3和4 GL功能的Fe 2+和Fe 3+，15多峰信封建模。一个雪莉型功能16被用来描述非弹性散射电子的背景。 重点概述XPS数据（ 图1（a）），从抛光样品获得的光谱显示三个主峰， 即铁2P，澳1S，和C 1秒。这些特征可以如下分配:铁2P源于碳钢，O- 1秒从同时具有表面氧化膜和吸附物派生，以及C 1秒信号以不定碳水化合物是由于上。淹没在任何给相应的频谱概述变化显著的1 M盐酸+ X毫米有机-CI方案的结果。分配给N 1s电子出现的水平，这是与抑制剂的表面吸附一致的特征; MBI和OMID都包含N.此外，O1s的核心层信号显著减少。 如从抛光的衬底方面Ô1秒的数据（ 图1（b）），该简档可以配备四个组件。在较低的结合能的两种组分（BE），〜530.0 eV和〜531.3 eV的，可以分配到铁氧化物（O 2-）和氢氧化（OH - ）相，分别两个较高结合能的组件，标记为O 1（BE〜532.2 EV）和O 2（BE〜533.3电子伏特），很可能与吸附OH（O 1）和不定碳物种（O 1和O 2）17相关联。沉浸在任的t他的1M HCl + X毫米有机-CI方案导致O 2-和OH完全淬火-组件。在此基础上，可以得出结论认为，腐蚀抑制剂被吸附在氧化物/氢氧化物自由表面。在图1（c）该铁的2p光谱是一致的这个结果，因为只有一个金属的Fe（铁0）峰是在抑制衬底显而易见。 的 Fe 2+和Fe 3+特征存在于抛光样品，由于表面氧化物/氢氧化物。 Ò1和铁的2p芯能级的XPS谱图从浸入的1M HCl + 2毫MBI两个碳-钢样在图2中进行了比较。一个样品用一个充分的 N 2 -purged手套箱传送，而另一个是从溶液中去除到部分N 2 -purged手套箱， 即 O 2的浓度比目标值显著高。对于后者样品，我t是显而易见已经发生交浸入氧化， 即 的 Fe 2 + / 3 +和O 2- / OH -功能都存在。 <img alt="图1" src="/files/ftp_upload/55163/55163fig1.jpg" /> 从抛光和抑制碳钢样品 图1. XPS谱。 （ 一 ）概述（ 二 ）O 1S，和（c）铁2P XPS光谱。在每个面板中表示的数据是从已被浸渍4小时在一个的两个不同的1M HCl + X毫有机-Cl溶液， 即 2毫MBI，和1mM OMID碳钢样品获得的。光谱所有以0°（沿表面法线发射）的光电子发射角（θE）获得的。为（b）和（c）该最佳拟合（浅蓝色的标记）的实验数据（实心黑色线）也被显示，与GL的组合来实现（碎红色线），LF（破ř<html>编线），和Shirley型（破灰线）的功能。山顶标签在正文中说明。 <a href="https://ecsource-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/55163/55163fig1large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图2" src="/files/ftp_upload/55163/55163fig2.jpg" /> 图 2. XPS光谱后浸泡氧化的影响。 （ 一 ）O 1S和（b）铁2P XPS光谱。数据是从已被浸渍于1 M盐酸+ 2mM的MBI溶液（η（％）= 99％）4小时碳钢样品获得的。谱在θE = 0°收购。在每个面板，下部（上部）的频谱是从通过一个完全（部分） 的 N 2 -purged手套箱转移样品。山顶标签在正文中说明。 （参考文献中的修改版图5。9）OAD / 55163 / 55163fig2large.jpg"目标="_空白"&gt;点击此处查看该图的放大版本。

Watch this Scientific Journal Video about Determining the Chemical Composition of Corrosion Inhibitor/Metal Interfaces with XPS: Minimizing Post Immersion Oxidation at JoVE.com

Determining the Chemical Composition of Corrosion Inhibitor/Metal Interfaces with XPS: Minimizing Post Immersion Oxidation

A protocol to avoid the oxidation of metallic substrates during sample transfer from an inhibited acidic solution to an X-ray photoelectron spectrometer is presented.

确定缓蚀剂/金属界面的化学成分与XPS:最小化后浸入氧化

An approach for acquiring more reliable X-ray photoelectron spectroscopy data from corrosion inhibitor/metal interfaces is described. More specifically, ...

determining-chemical-composition-corrosion-inhibitormetal-interfaces

Universidad San Sebastian

Research

JoVE Journal

Chemistry

15.7K 次观看.  The University of Manchester. A protocol to avoid the oxidation of metallic substrates during sample transfer from an inhibited acidic solution to an X-ray photoelectron spectrometer is presented. 

视频: Determining the Chemical Composition of Corrosion Inhibitor/Metal Interfaces with XPS: Minimizing Post Immersion Oxidation

Potentiodynamic Corrosion Testing

Different metallic materials have different polarization characteristics as dictated by the open circuit potential, breakdown potential, and passivation potential of the material. The detection of these electrochemical parameters identifies the corrosion factors of a material. A reliable and well-functioning corrosion system is required to achieve this.
Corrosion of the samples was achieved via a potentiodynamic polarization technique employing a three-electrode configuration, consisting of reference, counter, and working electrodes. Prior to commencement a baseline potential is obtained. Following the stabilization of the corrosion potential (Ecorr), the applied potential is ramped at a slow rate in the positive direction relative to the reference electrode. The working electrode was a stainless steel screw. The reference electrode was a standard Ag/AgCl. The counter electrode used was a platinum mesh. Having a reliable and well-functioning in vitro corrosion system to test biomaterials provides an in-expensive technique that allows for the systematic characterization of the material by determining the breakdown potential, to further understand the material's response to corrosion. The goal of the protocol is to set up and run an in vitro potentiodynamic corrosion system to analyze pitting corrosion for small metallic medical devices.

Here, we present a protocol to set up and run an in vitro potentiodynamic corrosion system to analyze pitting corrosion for small metallic medical devices.

动电位腐蚀试验

Different metallic materials have different polarization characteristics as dictated by the open circuit potential, breakdown potential, and passivation ...

科研

环境科学

A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where interfacial tension is a dominant force. A variety of methods exist for controlling the interfacial tension of aqueous and organic liquids on this scale; however, these techniques have limited utility for liquid metals due to their large interfacial tension.
Liquid metals can form soft, stretchable, and shape-reconfigurable components in electronic and electromagnetic devices. Although it is possible to manipulate these fluids via mechanical methods (e.g., pumping), electrical methods are easier to miniaturize, control, and implement. However, most electrical techniques have their own constraints: electrowetting-on-dielectric requires large (kV) potentials for modest actuation, electrocapillarity can affect relatively small changes in the interfacial tension, and continuous electrowetting is limited to plugs of the liquid metal in capillaries.
Here, we present a method for actuating gallium and gallium-based liquid metal alloys via an electrochemical surface reaction. Controlling the electrochemical potential on the surface of the liquid metal in electrolyte rapidly and reversibly changes the interfacial tension by over two orders of magnitude ( &#820;500 mN/m to near zero). Furthermore, this method requires only a very modest potential (&#60; 1 V) applied relative to a counter electrode. The resulting change in tension is due primarily to the electrochemical deposition of a surface oxide layer, which acts as a surfactant; removal of the oxide increases the interfacial tension, and vice versa. This technique can be applied in a wide variety of electrolytes and is independent of the substrate on which it rests.

We present a method to control the interfacial energy of a liquid metal in an electrolyte via electrochemical deposition (or removal) of a surface oxide layer. This simple method can control the capillary behavior of gallium-based liquid metals by tuning the interfacial energy rapidly, significantly, and reversibly using modest voltages.

方法通过表面氧化还原操纵液态金属的表面张力

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where ...

化学

Metal Corrosion and the Efficiency of Corrosion Inhibitors in Less Conductive Media

Material corrosion can be a limiting factor for different materials in many applications. Thus, it is necessary to better understand corrosion processes, prevent them and minimize the damages associated with them. One of the most important characteristics of corrosion processes is the corrosion rate. The measurement of corrosion rates is often very difficult or even impossible especially in less conductive, non-aqueous environments such as biofuels. Here, we present five different methods for the determination of corrosion rates and the efficiency of anti-corrosion protection in biofuels: (i) a static test, (ii) a dynamic test, (iii) a static test with a reflux cooler and electrochemical measurements (iv) in a two-electrode arrangement and (v) in a three-electrode arrangement. The static test is advantageous due to its low demands on material and instrumental equipment. The dynamic test allows for the testing of corrosion rates of metallic materials at more severe conditions. The static test with a reflux cooler allows for the testing in environments with higher viscosity (e.g., engine oils) at higher temperatures in the presence of oxidation or an inert atmosphere. The electrochemical measurements provide a more comprehensive view on corrosion processes. The presented cell geometries and arrangements (the two-electrode and three-electrode systems) make it possible to perform measurements in biofuel environments without base electrolytes that could have a negative impact on the results and load them with measurement errors. The presented methods make it possible to study the corrosion aggressiveness of an environment, the corrosion resistance of metallic materials, and the efficiency of corrosion inhibitors with representative and reproducible results. The results obtained using these methods can help to understand corrosion processes in more detail to minimize the damages caused by corrosion.

The testing of processes associated with material corrosion can often be difficult especially in non-aqueous environments. Here, we present different methods for short-term and long-term testing of corrosion behavior of non-aqueous environments such as biofuels, especially those containing bioethanol.

金属腐蚀与腐蚀抑制剂在低导电介质中的效率

Material corrosion can be a limiting factor for different materials in many applications. Thus, it is necessary to better understand corrosion processes, ...

The Evolution of Silica Nanoparticle-polyester Coatings on Surfaces Exposed to Sunlight

Corrosion of metallic surfaces is prevalent in the environment and is of great concern in many areas, including the military, transport, aviation, building and food industries, amongst others. Polyester and coatings containing both polyester and silica nanoparticles (SiO2NPs) have been widely used to protect steel substrata from corrosion. In this study, we utilized X-ray photoelectron spectroscopy, attenuated total reflection infrared micro-spectroscopy, water contact angle measurements, optical profiling and atomic force microscopy to provide an insight into how exposure to sunlight can cause changes in the micro- and nanoscale integrity of the coatings. No significant change in surface micro-topography was detected using optical profilometry, however, statistically significant nanoscale changes to the surface were detected using atomic force microscopy. Analysis of the X-ray photoelectron spectroscopy and attenuated total reflection infrared micro-spectroscopy data revealed that degradation of the ester groups had occurred through exposure to ultraviolet light to form COO&#903;, -H2C&#903;, -O&#903;, -CO&#903; radicals. During the degradation process, CO and CO2 were also produced.

Two types of surfaces, polyester-coated steel and polyester coated with a layer of silica nanoparticles, were studied. Both surfaces were exposed to sunlight, which was found to cause substantial changes in the chemistry and nanoscale topography of the surface.

表面上的纳米硅聚酯涂料暴露在阳光下的演变

Corrosion of metallic surfaces is prevalent in the environment and is of great concern in many areas, including the military, transport, aviation, ...

工程学

Determining Tribocorrosion Rate and Wear-Corrosion Synergy of Bulk and Thin Film Aluminum Alloys

The increasing complexity and severity of service conditions in areas, such as aerospace and marine industries, nuclear systems, microelectronics, batteries, and biomedical devices, etc., impose great challenges on the reliable performance of alloys exposed to extreme conditions where mechanical and electrochemical attack co-exist. Finding ways for alloys to mitigate the combined attack of wear and corrosion (i.e., tribocorrosion) under such extreme conditions is thus highly critical for improving their reliability and service lifetime when used in such conditions. The challenge lies in the fact that wear and corrosion are not independent of each other, but rather work synergistically to accelerate the total material loss. Thus, a reliable method to evaluate the tribocorrosion resistance of metals and alloys is needed. Here, a protocol for measuring the tribocorrosion rate and wear-corrosion synergy of Al-based bulk and thin film samples in a corrosive environment under room temperature is presented.

Here, we present a protocol to measure the tribocorrosion rate and wear-corrosion synergy of thin film and bulk Al alloys in simulated sea water at room temperature.

Tribocorrosion 和薄膜铝合金的磨损与腐蚀协同性测定

The increasing complexity and severity of service conditions in areas, such as aerospace and marine industries, nuclear systems, microelectronics, ...

A Continuous-flow Photocatalytic Reactor for the Precisely Controlled Deposition of Metallic Nanoparticles

In this work, a novel photocatalytic reactor for the pulsed and controlled excitation of the photocatalyst and the precise deposition of metallic nanoparticles is developed. Guidelines for the replication of the reactor and its operation are provided in detail. Three different composite systems (Pt/graphene, Pt/TiO2, and Au/TiO2) with monodisperse and uniformly distributed particles are produced by this reactor, and the photodeposition mechanism, as well as the synthesis optimization strategy, are discussed. The synthesis methods and their technical aspects are described comprehensively. The role of the ultraviolet (UV) dose (in each excitation pulse) on the photodeposition process is investigated and the optimum values for each composite system are provided.

For a continuous and scalable synthesis of noble-metal-based nanocomposites, a novel photocatalytic reactor is developed and its structure, operation principles, and product quality optimization strategies are described.

一种用于金属纳米粒子精确控制沉积的连续流动光催化反应器

In this work, a novel photocatalytic reactor for the pulsed and controlled excitation of the photocatalyst and the precise deposition of metallic ...

Imaging Corrosion at the Metal-Paint Interface Using Time-of-Flight Secondary Ion Mass Spectrometry

Corrosion developed at the paint and aluminum (Al) metal-paint interface of an aluminum alloy is analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS), illustrating that SIMS is a suitable technique to study the chemical distribution at a metal-paint interface. The painted Al alloy coupons are immersed in a salt solution or exposed to air only. SIMS provides chemical mapping and 2D molecular imaging of the interface, allowing direct visualization of the morphology of the corrosion products formed at the metal-paint interface and mapping of the chemical after corrosion occurs. The experimental procedure of this method is presented to provide technical details to facilitate similar research and highlight pitfalls that may be encountered during such experiments.

Time-of-flight secondary ion mass spectrometry is applied to demonstrate the chemical mapping and corrosion morphology at the metal-paint interface of an aluminum alloy after being exposed to a salt solution compared with a specimen exposed to air.

利用飞行时二次离子质谱法成像金属颜料界面的腐蚀

Corrosion developed at the paint and aluminum (Al) metal-paint interface of an aluminum alloy is analyzed using time-of-flight secondary ion mass ...

Preparation of Nanoparticles for ToF-SIMS and XPS Analysis

Nanoparticles have gained increasing attention in recent years due to their potential and application in different fields including medicine, cosmetics, chemistry, and their potential to enable advanced materials. To effectively understand and regulate the physico-chemical properties and potential adverse effects of nanoparticles, validated measurement procedures for the various properties of nanoparticles need to be developed. While procedures for measuring nanoparticle size and size distribution are already established, standardized methods for analysis of their surface chemistry are not yet in place, although the influence of the surface chemistry on nanoparticle properties is undisputed. In particular, storage and preparation of nanoparticles for surface analysis strongly influences the analytical results from various methods, and in order to obtain consistent results, sample preparation must be both optimized and standardized. In this contribution, we present, in detail, some standard procedures for preparing nanoparticles for surface analytics. In principle, nanoparticles can be deposited on a suitable substrate from suspension or as a powder. Silicon (Si) wafers are commonly used as substrate, however, their cleaning is critical to the process. For sample preparation from suspension, we will discuss drop-casting and spin-coating, where not only the cleanliness of the substrate and purity of the suspension but also its concentration play important roles for the success of the preparation methodology. For nanoparticles with sensitive ligand shells or coatings, deposition as powders is more suitable, although this method requires particular care in fixing the sample.

A number of different procedures for preparing nanoparticles for surface analysis are presented (drop casting, spin coating, deposition from powders, and cryofixation). We discuss the challenges, opportunities, and possible applications of each method, particularly regarding the changes in the surface properties caused by the different preparation methods.

用于ToF-SIMS和XPS分析的纳米颗粒的制备

Nanoparticles have gained increasing attention in recent years due to their potential and application in different fields including medicine, cosmetics, ...

Co-localizing Kelvin Probe Force Microscopy with Other Microscopies and Spectroscopies: Selected Applications in Corrosion Characterization of Alloys

Kelvin probe force microscopy (KPFM), sometimes referred to as surface potential microscopy, is the nanoscale version of the venerable scanning Kelvin probe, both of which measure the Volta potential difference (VPD) between an oscillating probe tip and a sample surface by applying a nulling voltage equal in magnitude but opposite in sign to the tip-sample potential difference. By scanning a conductive KPFM probe over a sample surface, nanoscale variations in surface topography and potential can be mapped, identifying likely anodic and cathodic regions, as well as quantifying the inherent material driving force for galvanic corrosion.
Subsequent co-localization of KPFM Volta potential maps with advanced scanning electron microscopy (SEM) techniques, including back scattered electron (BSE) images, energy dispersive spectroscopy (EDS) elemental composition maps, and electron backscattered diffraction (EBSD) inverse pole figures can provide further insight into structure-property-performance relationships. Here, the results of several studies co-localizing KPFM with SEM on a wide variety of alloys of technological interest are presented, demonstrating the utility of combining these techniques at the nanoscale to elucidate corrosion initiation and propagation.
Important points to consider and potential pitfalls to avoid in such investigations are also highlighted: in particular, probe calibration and the potential confounding effects on the measured VPDs of the testing environment and sample surface, including ambient humidity (i.e., adsorbed water), surface reactions/oxidation, and polishing debris or other contaminants. Additionally, an example is provided of co-localizing a third technique, scanning confocal Raman microscopy, to demonstrate the general applicability and utility of the co-localization method to provide further structural insight beyond that afforded by electron microscopy-based techniques.

Kelvin probe force microscopy (KPFM) measures surface topography and differences in surface potential, while scanning electron microscopy (SEM) and associated spectroscopies can elucidate surface morphology, composition, crystallinity, and crystallographic orientation. Accordingly, the co-localization of SEM with KPFM can provide insight into the effects of nanoscale composition and surface structure on corrosion.

开尔文探针力显微镜与其他显微镜和光谱学共定位:合金腐蚀表征中的选定应用

Kelvin probe force microscopy (KPFM), sometimes referred to as surface potential microscopy, is the nanoscale version of the venerable scanning Kelvin ...

Corrosion

The degradation of metals due to natural electrochemical processes is known as corrosion. Rust formation on iron, tarnishing of silver, and the blue-green patina that develops on copper are examples of corrosion. Corrosion involves the oxidation of metals. Sometimes it is protective, such as the oxidation of copper or aluminum, wherein a protective layer of metal oxide or its derivatives forms on the surface, protecting the underlying metal from further oxidation. In other cases, corrosion is damaging to the metal, such as the rusting of iron.
Undesirable Redox Reaction: The Rusting of Iron
Rusting occurs due to exposure of iron to oxygen and water. Rust formation involves the creation of a galvanic cell at the surface of iron, which results in the generation of iron(II). The relevant redox reactions that occur at the anodic (oxidation of iron) and cathodic (reduction of oxygen) regions formed on the iron surface include:
<img alt="Eq1" src="/files/ftp_upload/11440/11440_Equation_1.png" style="text-align: center; height: 150px;" />
The iron(II) further reacts with humid air, forming an iron(III) oxide hydrate, commonly known as rust.
<img alt="Eq2" src="/files/ftp_upload/11440/11440_Equation_2.png" style="text-align: center; height: 50px;" />
The hydrate&#39;s stoichiometry varies with the amount of water to which iron(II) is exposed, as indicated by the use of x in the compound formula. Moisture, the presence of acids and electrolytes increases the rate of formation of rust. Unlike the patina on copper, the formation of rust does not create a protective layer, and so corrosion of the iron continues as the rust flakes off and exposes fresh iron to the atmosphere.
Prevention of Corrosion
Various methods can be used to prevent corrosion. One way is to keep the metal surface painted to avoid contact with water and oxygen. Alloying of metals, like mixing iron with small amounts of chromium in stainless steel, is another effective method to prevent corrosion. The chromium collects near the surface and undergoes oxidation, thus, effectively protecting the iron from corrosion.
Iron and other metals may also be protected from corrosion by galvanization, a process in which the metal to be protected is coated with a layer of a more readily oxidized metal, usually zinc. When the zinc layer is intact, it prevents air from contacting the underlying iron and thus prevents corrosion. If the zinc layer is breached by either corrosion or mechanical abrasion, the iron may still be protected from corrosion by a cathodic protection process, which is described in the next paragraph.
Cathodic protection utilizes the principle of converting the metal to be protected into a cathode in an electrochemical reaction. This is achieved by connecting the protected metal to a more active or easily oxidized metal such as zinc or magnesium, known as the sacrificial anode. The anode corrodes and gets used up protecting the metal that serves as the cathode. Cathodic protection is most commonly used in household appliances such as water heaters and underground water storage tanks. Importantly, cathodic protection can be used for metals other than just iron.
This text is adapted from <a href="https://openstax.org/books/chemistry-2e/pages/17-6-corrosion">OpenStax, Chemistry 2e, Chapter 17.6: Corrosion</a>.

Corrosion: Rodox Reaction in Rusting of Iron; Prevention

腐蚀

The degradation of metals due to natural electrochemical processes is known as corrosion. Rust formation on iron, tarnishing of silver, and the blue-green ...