醇酸清漆保护性的电化学加速评价

将目前一种电化学阻抗谱和负电位极化相结合的AC/DC/AC技术拓展成正电位阳极极化加速与电化学阻抗评价相结合的技术,并用醇酸清漆/碳钢体系验证了该技术确实能加速涂层/金属体系的腐蚀破坏、快速评价涂层的保护性,不仅适用于阴极保护条件下的涂层,也可用于自然腐蚀甚至被阳极极化的体系。通过实验分析了该技术测得的阻抗数据及样品表面形貌的变化,研究了其加速破坏的机理,建立了涂层加速破坏失效的物理模型。对比浸泡实验、AC/阴极DC/AC循环加速实验及AC/阳极DC/AC循环加速实验阻抗变化规律和腐蚀破坏形貌。结果表明:结合阴极极化和阳极极化将是未来获得一种既快速又合理的有机涂层性能评价技术的途径之一。     

循环压力对环氧涂层在模拟深海环境中失效行为的影响

在模拟深海环境下,利用电化学阻抗技术并结合重量法,研究了循环压力对纯环氧涂层在3.5mass%NaCl溶液中失效行为的影响。结果表明,循环压力条件下,涂层的阻抗行为呈周期性变化规律:在高压条件下浸泡时,有机涂层电容较高、涂层电阻较低;而常压条件下两者都较高。循环压力增大,腐蚀介质更容易扩散到涂层内部,使得涂层吸水量增加,涂层电阻降低,涂层防护性能恶化。     

Zn粉含量及表面沾污对环氧富Zn漆电化学行为的影响

采用腐蚀电位、电化学阻抗谱(EIS)评价了Zn粉含量以及涂层／基体界面污染程度对环氧富Zn涂层的防腐蚀性能的影响并探索了富Zn涂层的失效机制。实验结果表明，当涂层中Zn含量较少时，Zn粉没有有效的阻挡作用。通过对可能的阻抗模型的分析，认为富Zn涂层的电化学阻抗谱的低频段是由Zn^2 从金属表面穿过腐蚀产物的扩散控制。涂层／基体界面污染不仅影响了环氧富Zn涂层的防腐蚀性能的发挥，也加速了钢铁基体的腐蚀。     

核电站钢制安全壳无机锌涂层的大气腐蚀行为

通过盐雾加速腐蚀试验和电化学测试,对比分析了核电站钢制安全壳用无机锌(IOZ)涂层与热喷锌(TSZ)涂层的耐蚀性进行研究。结果表明:与TSZ涂层相比,IOZ涂层在经过不同时间盐雾加速腐蚀后,涂层缺陷及其表面附着的盐斑均较少,涂层结构致密且腐蚀速率较低;两种涂层的腐蚀产物均以Zn_5(OH)_8Cl_2H_2O为主;随着腐蚀时间的延长,IOZ涂层的阻抗增大,表明其不仅具有阴极保护性能和屏蔽性能,耐蚀性也更加优异和持久。     

有机涂层在模拟沙漠大气环境下的加速试验研究

目的在较短的时间内获得有机涂层在沙漠大气环境下的腐蚀失效规律。方法针对有机涂层中应用比较广泛的丙烯酸聚氨酯涂层,采用紫外暴晒与吹沙试验相结合的加速试验环境谱进行实验室模拟沙漠大气环境加速老化试验,通过分析涂层质量、厚度、光泽度、表面形貌及电化学阻抗的变化,研究有机涂层的老化失效过程。结果随着加速试验周期的延长,丙烯酸聚氨酯涂层发生了一系列变化,表现为涂层质量减小,厚度减薄,光泽度降低,表面微观缺陷增多,电化学低频阻抗模值减小,防护性能下降。结论通过加速试验,可以快速获得有机涂层在沙漠大气环境下的老化失效规律。     

两种水性聚氨酯涂层在3种加速老化试验中的性能对比

目的 研究目前水性涂料中两种应用广泛的水性脂肪族聚氨酯涂层与水性丙烯酸聚氨酯涂层的耐候性与防腐性能的差异,探讨加速老化方法对涂层性能的影响.方法 利用3种加速老化试验(中性盐雾、紫外-冷凝以及中性盐雾-紫外冷凝循环试验)对涂层进行240 d的加速老化.通过涂层的失光率、色差以及红外吸收光谱变化,研究涂层老化情况.利用交流阻抗法判断涂层防腐性能强弱,分析两种涂层体系在不同加速老化试验中的性能变化.结果 在各加速老化试验条件下,水性脂肪族聚氨酯涂层相比于水性丙烯酸聚氨酯涂层,失光率与色差变化小,阻抗下降较少,涂层基体官能团分解程度小,说明水性脂肪族聚氨酯涂层老化程度小,防腐性能更好.3种老化加速试验对涂层阻抗影响顺序为:中性盐雾试验>循环试验>紫外-冷凝试验.对涂层色差、失光率影响顺序为:紫外-冷凝试验>循环试验、中性盐雾试验.结论 连续的盐雾渗透对涂层的防腐屏蔽性能影响最严重.紫外线对涂层官能团分解具有加速作用,是涂层老化的主要原因.水性脂肪族聚氨酯涂层比水性丙烯酸聚氨酯涂层具有更好的耐候性以及防腐性能,可以应用在强紫外线、高湿热的环境.     

承载作用下铁红环氧脂底漆失效过程的电化学响应特征

采用局部电化学阻抗(LEIS)技术和电化学阻抗(EIS)技术研究了不同承载条件下,海水介质中铁红环氧脂底漆失效过程的电化学响应特征。结果表明:在不同的承载力作用下,铁红环氧脂底漆的失效过程呈阶段性变化,且应力加载过程加速了涂层的失效。在300 MPa屈服应力作用下,腐蚀介质可以沿着细小的裂缝快速渗透涂层,与基体接触,缩短涂层的失效时间。涂层失效后,整体阻抗值明显降低,同时试样表面随机分布的高阻抗点数量有所减少,涂层防护性能明显下降,基材发生腐蚀。     

模拟海洋大气环境下铝合金表面锌黄环氧底漆/丙烯酸聚氨酯面漆涂层体系失效过程研究

目的研究5A06型铝基材所使用的锌黄环氧底漆/丙烯酸聚氨酯面漆涂层体系的失效过程。方法设计"紫外/冷凝3 d+中性盐雾3 d+低温暴露1 d"为一个周期的实验室循环加速试验,采用交流阻抗谱法,结合光泽度、色差值、红外光谱等数据,研究涂层体系性能。结果循环加速试验进行到16周,该过程中面漆的失光率、色差值上升,达到轻微失光等级和轻微变色等级。面漆的表面形貌及涂层的低频阻抗发生明显变化,第12周时在光学显微镜下明显可见微小鼓泡,涂层0.1 Hz阻抗保持在109W·cm~2以上,但此后鼓泡数量增加,部分鼓泡破损,颜填料流出;第14周时,0.1 Hz阻抗下降到108W·cm~2,此后鼓泡数量进一步增加,部分鼓泡处面漆脱落;第16周时,0.1 Hz阻抗下降到约为107W·cm~2。结论丙烯酸聚氨酯面漆树脂基体特征官能团、聚合物链发生断裂,面漆的完整性遭到破坏,这可能与紫外线照射相关。这将加速涂层中腐蚀性介质(如水、氧和侵蚀性氯离子)渗透,促进涂层的失效。     

ES150型纳米改性有机硅涂料的防护作用及其应用

采用物理混合的方法制备了ES150型纳米改性有机硅涂料,并采用电化学阻抗技术、盐雾腐蚀实验和浸泡实验研究了涂层的防腐蚀性能。结果表明,清漆涂层存在大量的微孔,严重影响涂层的防护性能。纳米改性复合涂层的致密度显著提高,经6000 h盐水浸泡和5000 h中性盐雾腐蚀实验,涂层未出现起泡、剥落等破坏,涂层下的基体镁合金未发生腐蚀。在浸泡过程中涂层的阻抗保持在109Ω·cm2以上,具有优异的耐腐蚀性能。SO2加速腐蚀实验表明,ES150型纳米复合有机硅涂料实现了对飞机零部件在恶劣环境中的有效防护,实际应用效果显著。     

结合WBE与EIS技术研究环氧涂层下碳钢与铜合金在海水中的电偶腐蚀

目的 研究环氧涂层下碳钢与铜合金在海水中的电偶腐蚀行为及涂层整体和局部区域的劣化过程。方法 使用丝束电极（WBE）技术和电化学阻抗谱（EIS）技术研究丝束电极表面的电流密度分布和涂层阻抗谱演化,同时对比分析碳钢区域与铜合金区域涂层的阻抗谱特征。结果 阳极电流峰首先出现在碳钢局部区域,而电流密度较大的阴极电流峰主要集中出现在铜合金区域的边缘。当浸泡至122 h时,铜合金区域的涂层阻抗明显低于碳钢区域的涂层阻抗,且EIS响应出现了Warburg扩散阻抗特征。在浸泡456 h后,单根钢电极发生由阴极向阳极的极性转换。结论 涂层下碳钢与铜合金在海水中发生电偶腐蚀时,铜合金作为阴极被保护,但铜合金区域的涂层在阴极剥离的作用下加速劣化。在涂层劣化过程中,碳钢区域的涂层缺陷处成为腐蚀反应的阳极区,而主要的阴极区位于铜合金的边缘区域,这与溶解氧的“竞争效应”有关。由于涂层发生阴极剥离现象使得基底金属被腐蚀,从而导致涂层下单根钢电极的电流发生由阴极向阳极的极性转换。     

电流密度对镁合金微弧氧化过程及氧化陶瓷膜性能的影响

在含有硅酸钠、氟化钠、甘油的电解液中以恒电流方式对镁合金进行微弧氧化。考察了电流密度对放电电压、起火时间及陶瓷膜厚度的影响。利用扫描电镜观察了在不同电流密度下形成的陶瓷膜的表面形貌；通过电化学交流阻抗测量了不同电流密度下得到的陶瓷氧化膜的耐蚀性能。结果表明：在恒电流微弧氧化过程中，依据电压．时间曲线，可简单地分为电压持续增长阶段和电压基本稳定阶段，且随着电流密度的增加，曲线斜率逐渐增大：电流密度的增大，可以降低起火时间，增加陶瓷氧化膜的厚度，但对放电电压并没有明显的影响：随着电流密度的增大，陶瓷层表面微孔数量减少．孔径增大，呈现出的熔融状态更为明显；陶瓷氧化膜的耐蚀性随着电流密度的升高呈现先增强后减弱的趋势。     

Corrosion properties of plasma-polymerized methylcyclohexane films using electrochemical methods

Three types of methylcyclohexane (MCH) coating were deposited as interlayer dielectrics on copper using plasma-enhanced chemical vapor deposition (PECVD) at three different RF plasma power levels. The coating performance was then evaluated by an electrochemical im pedance spectroscopy (EIS) and a potentiodynamic polarization test in 3.5 wt.% NaCl solution. An atomic force microscopy (AFM) and Fourier transform infrared reflection (FT-IR) spectroscopy were also conducted to analyze the coatings. The MCH coatings showed a lower corrosion rate than the copper substrate in the potentiodynamic tests. The EIS results showed that the corrosion resistance of the coatings increased with an increasing plasma power. Thus, the MCH films with an increasing plasma power improved the corrosion resistance due to the formation of a low-porosity coating, the enhanced formation of C−H, C−C, and C≡C stretching configurations, and the improved smooth surfaces.     

电化学阻抗谱研究达克罗在海水中的腐蚀行为

测量了达克罗涂层在海水中全浸不同时间的电化学阻抗谱（EIS）,并用等效电路Ro(RpC)(RDQ)进行解析。结果表明：腐蚀过程中试样的极化电阻Rp、双电层电容C、扩散电阻RD均不断增大,且RD/Rp也一直增大。达克罗涂层的腐蚀初期为金属Zn的溶解,随着腐蚀的进行,腐蚀产物在膜内的累积导致钝化膜的有效厚度增加,Zn粉的牺牲阳极作用受到了限制;腐蚀后期主要是机械的壁垒保护作用,直到扩散和溶解作用超过壁垒作用后,涂层以点蚀的形式发生破坏。     

水、氯离子在丙烯酸聚氨酯涂层中的扩散传输行为

采用渗水率测试技术、渗氯离子浓度测试方法及交流阻抗测试技术研究了水、氯离子在丙烯酸聚氨酯涂层中的扩散传输行为.结果表明:在渗透初期,水在涂层中的传输符合Fick扩散定律,之后涂层渗水量达到饱和,随涂膜厚度的增加,涂层渗水量达到饱和的时间相对延长,饱和渗水量随膜厚的增加而降低;Cl-在涂层中的扩散在起始阶段呈一定值,达到某一临界点后(漆膜结构发生变化),透过涂层的Cl-的量突然呈线性增加,由直线斜率可求得氯离子在涂层中的扩散系数,随涂膜厚度的增加,溶液中Cl-浓度保持平衡的时间相对延长,涂层的平衡透氯离子浓度降低,Cl-在涂层中的扩散系数也随膜厚的增加而降低;采用EIS技术,据涂层、膜下金属阻抗及电容的变化及体系第二个时间常数出现的时间,可研究电解质溶液在涂层中的扩散渗透及膜下金属的腐蚀情况.     

EIS STUDY ON THE EFFECTS OF HEAT TREATMENT ON CORROSION BEHAVIOR OF NICKEL BASE ALLOY COATING

采用超音速火焰喷涂(HVOF)方法在碳钢基体上制备了NiCrBSi喷涂层, 对包覆样 品进行900 ℃保温2 h或10 min热处理, 利用电化学阻抗谱(EIS)研究了涂层在3.5%NaCl 水溶液中的腐蚀失效过程和耐蚀性的变化规律. EIS图谱分析表明, 喷态涂层抗介质渗透能力 差, 腐蚀20 h后介质可渗达碳钢基体;900 ℃, 2 h保温热处理涂层腐蚀 15 h后EIS谱发生明 显变化, 产生局部腐蚀;而900 ℃, 10 min处理涂层为均匀腐蚀, EIS谱形可长时间保持稳定. 利用等效电路拟合, 获取了涂层界面反应阻力(腐蚀抗力)随时间变化的关系, 显示高温短 时(10 min)热处理涂层的界面反应阻力高且稳定, 其耐蚀性和抗介质渗透能力远优于喷态 涂层, 但2 h保温热处理涂层的耐蚀性比喷态涂层的差. 利用组织结构分析解释了热处理影响 涂层腐蚀行为的原因.     

Electrochemical Impedance Spectroscopy of protective coatings

Electrochemical impedance spectroscopy (EIS) carried out over a wide frequency range (10⁵ to 10^?2 Hz) allows us to obtain mechanistic information concerning corrosion protection by coatings. Examples are given for polymer coatings on an Al alloy as a function of surface petreatment and for anodized Al alloys. For polymer coatings on metals, information concerning the coating's properties and its changes with exposure time can be obtained from the high and medium frequency regions of the impedance spectrum, while the corrosion reaction at the metal/coating interface can be evaluated from the low frequency part. The pore resistance of the coating and its changes with exposure time have been used to rank different pretreatment procedures for a given metal/coating combination. For Al alloys, pronounced differences in corrosion resistance between a conversion coating and an anodized layer under a polyurethane coating have been observed. The use of a segmented electrode allows measurements of the impedance across as well as under a coating. From these data, information concerning delamination can be obtained. An example is given for an epoxy coating on steel. The use of EIS as a quality control and corrosion test for anodized Al alloys is discussed. The effects of the anodization procedure (sulfuric acid and chromic acid), sealing procedure (hot water and dichromate) and alloy chemistry (Al 2024, 6061 and 7075) have been studied during exposure to aerated 0.5 N NaCl. All these parameters play an important role in the corrosion resistance of the alloys. The sealing process can be evaluated from the high frequency part of the spectrum. Pronounced differences in the spectra for the two sealing procedures are observed. The corrosion behavior is reflected in the low frequency part, which is essentially dominated by barrier layer properties.     

Role of thickness on electrochemical behaviour of Ni2Si coatings in NaCl solution

Abstract

Ni₂Si intermetallic coatings were deposited on a substrate of 420 stainless steel using a high velocity oxy-fuel (HVOF) process. The electrochemical corrosion behaviour of the coatings in 3.5% NaCl solution was investigated by means of Tafel polarisation tests and electrochemical impedance spectroscopy (EIS) measurements. Two coatings with different thicknesses, 55 and 115?μm, were investigated. The results showed that the corrosion rate of the thicker coating was lower than that of stainless steel by one order of magnitude. Local attack of the substrate was observed after the polarisation test of this coating, while the coating was still intact. The thinner coating and the stainless steel substrate showed similar corrosion rates. In this case, the substrate was severely attacked after the polarisation test. Two time constants were observed in the EIS spectra of both coatings which were related to charge transfer processes and pore resistance, respectively.     

镀铝锌彩涂板与镀锌彩涂板耐蚀性能对比研究

目的：研究热浸镀彩涂板常用金属镀层（铝锌合金镀层与纯锌镀层）对彩涂板耐蚀性能的影响。方法通过断面金相、SEM及EDS能谱、循环腐蚀试验和电化学阻抗测试(EIS)等方法,全面对比研究相同单面镀层厚度的镀铝锌与镀锌彩涂板的耐蚀性能。结果在长达250个循环（共计2000 h）的腐蚀试验中,镀锌彩涂板出现了严重的红色锈迹,而镀铝锌彩涂板并未出现明显腐蚀。在 EIS 测试中,两种彩涂板最初的阻抗值约为2×109Ω· cm2,浸泡2 d后镀锌彩涂板阻抗值急剧下降至1.165×108Ω· cm2;浸泡前期,镀铝锌彩涂板阻抗值缓慢下降,15 d后从6.979×108Ω·cm2急剧下降至2.984×107Ω·cm2。EIS等效电路拟合参数表明,镀铝锌彩涂板的电荷转移电阻比镀锌彩涂板高,相应的双电层电容低。SEM和EDS测试结果显示,铝锌合金镀层由底层合金层和外层的富铝和富锌的两相结构组成,而纯锌镀层则由底层合金层和外层纯锌层组成。结论铝锌合金镀层具有独特的富铝和富锌两相结构,使得同等镀层厚度的镀铝锌彩涂板比镀锌彩涂板具有更高的耐蚀性能。     

Corrosion and surface study of sputtered Al–W coatings with a range of tungsten contents

The corrosion behaviour of sputter-deposited, Al–W coatings with three different concentrations of tungsten (0.6, 3.5 and 11 at.% W) on AA7075 aluminium alloy substrates was investigated in chloride media using EIS, salt-fog tests and surface analyses. The surface analyses were performed with XPS/AES, SEM/EDS and TEM microscopy. The presence of W reduces the thickness of the oxide layer formed after the EIS test, as proved by the compositional depth profile. From the EIS data of the investigated Al–W_x coatings, the polarisation resistance (R_p) and the capacitive behaviour as a function of the immersion time were obtained. A small increase in R_p suggested improved corrosion properties over time. However, the extent of the improvement depends on the content of W and the coating-surface morphology (the presence of growth defects on the coating surface). The capacitive behaviour observed at high frequencies was related to the dielectric properties and the thickness of the barrier oxide film formed. The salt-fog tests to some extent supported the results from the EIS measurements. However, there was a difference between the corrosion EIS and salt-fog test results in the case of the Al₈₉W₁₁ coatings. The thickest oxide layer and the “layering” into the three regions (porous, semi-porous and intact) were observed when the salt-fog corrosion test was performed on the Al₈₉W₁₁ coating. Galvanic corrosion, probably due to the local compositional and structural inhomogeneities, takes place. However, this was not unambiguously observed during the EIS corrosion test.     

Effect of Al additions in WC-(Cr1−xAlx)N coatings on the corrosion resistance of coated AISI D2 steel in a deaerated 3.5 wt.% NaCl solution

Multilayered WC-(Cr_1−xAl_x)N coatings were deposited on AISI D2 steel using cathodic arc ion plating (CAIP) process. Five kinds of WC-(Cr_1−xAl_x)N coatings were prepared: WC-Cr_0.6Al_0.4N, WC-Cr_0.57Al_0.43N, WC-Cr_0.53Al_0.47N, WC-Cr_0.48Al_0.52N and WC-Cr_0.45Al_0.55N. The Al concentration could be controlled by using evaporation source for Al targets and fixing the evaporation rate of the other metals (WC alloy and Cr). In this study, the corrosion behavior in deaerated 3.5 wt.% NaCl solution was investigated by electrochemical corrosion tests (potentiodynamic polarization test, galvanic corrosion test, electrochemical impedance spectroscopy (EIS)) and surface analyses (glow discharge optical emission spectroscopy, X-ray diffractometry, scratch adhesion test, scanning electron microscopy, electron probe micro-analyzer).

The results of potentiodynamic polarization test showed that the WC-Cr_0.48Al_0.52N coating with lower porosity exhibited the lower corrosion current density. The galvanic corrosion current between the coating and the substrate showed low values. In EIS measurements, the charge transfer resistance (R_ct) value of WC-Cr_0.48Al_0.52N coating only increased with the immersion time, when compared to the other coatings. It can be due to the corrosion products plugging the pores and increasing the pathway resistance.