Investigation of coating delamination on steels by surface topography and Volta potential difference

Corrosion-induced delamination of an epoxy coating on the AISI/SAE 1045 carbon steel was studied under a humid atmospheric condition (temperature of 25 °C, one standard atmospheric pressure, and relative humidity of 90 %) by the technique of scanning Kelvin probe force microscopy (SKPFM). Surface-polished 1045 samples were first cold coated with the epoxy and then subject to the atmospheric corrosion under the humid atmospheric condition. At specified time intervals, surface Volta potential of the samples was measured using the SKPFM over the dry surface of epoxy coating. The map of Volta potentials demonstrated high contrasts among three characteristic zones: intact steel-epoxy interface, delaminated interface, and interface with active corrosion, which based on a rigorous calibration procedure were then linked to the actual corrosion potential of the steel (measured using a potentiostat w.r.t. a saturated calomel electrode). The SKPFM was found to be able to provide a mean of direct and nondestructive detection of early active corrosion and coating delamination of steels at a submicroscopic resolution, which outperformed the conventional electrochemical techniques for such purposes.     

Stressed Corrosion of an Austenitic Stainless Steel Studied by Scanning Kelvin Probe Force Microscopy

Under the ambient temperature (25°C) and pressure (one Standard Atmospheric Pressure) conditions, surface Volta potential of an austenitic stainless steel was measured using the Scanning Kelvin Probe Force Microscopy (SKPFM) to study its stressed-related corrosion behavior in a 0.5 M chloride solution. In an oxygen and water regulated environment (using a glovebox), the steel shows a map of Volta potentials with high contrasts among the different grains and grain boundaries, which was then linked to the actual corrosion potential (w.r.t. a saturated calomel electrode) based on a rigorous calibration procedure. Corrosion behavior of the steel under tensile stress was then compared to that of the same sample under no tensile stress in light of the measured Volta potential, which was found to be sensitive to the level of applied tensile stress, although the tested stainless steel in general is known for its high corrosion-resident capability. According to this study, surface Volta potential measured by SKPFM can be used as a high-accuracy indicator for localized corrosion of steels.     

水性环氧铝粉涂层/碳钢体系的腐蚀电化学行为

应用电化学阻抗谱(EIS)和扫描振动电极技术(SVET)研究了碳钢基体上含人造缺陷的水性环氧铝粉涂层浸泡在3.5%NaCl溶液中的腐蚀电化学行为.结果表明,浸泡初期,涂层缺陷处为阳极活性区,涂层阻抗随时间延长逐渐降低,活性区逐渐扩展;之后,由于腐蚀产物的自修复作用使整个涂层/金属界面电化学反应活性降低,导致涂层阻抗快速增加.浸泡后期,由于腐蚀介质渗入到涂层/基体界面,出现了更多的阳极活性区,涂层产生破坏剥离.     

A combined TEM and SKPFM investigation of the surface layers on rolled AA5050 aluminium alloy using ultra‐microtomy

This article studies the evolution of near‐surface morphology as a function of various thermo‐mechanical treatments along the fabrication line of rolled AA5050 aluminium alloy. Ultra‐microtomy has been used to prepare cross‐sectional thin foils for transmission electron microscopy (TEM) and proper surfaces for scanning Kelvin probe force microscopy (SKPFM) analysis. A slight increase in the Volta potential difference (between the inter‐metallics and the matrix) between the as‐cast surface and the surface obtained after the first hot‐mill pass, emphasized that the changes in surface micro‐structure, which in turn affect the corrosion and electrochemical properties of the finished product, had already occurred at that stage. The Volta potential difference during the subsequent hot‐mill pass remained relatively constant. As far as the near‐surface morphology was concerned, hot‐rolling resulted in the formation of a heavily deformed surface layer. Annealing of the hot‐rolled aluminium sheet resulted in partial re‐crystallization of the surface layer. Subsequent cold‐rolling re‐introduced deformation in the near‐surface region. Copyright © 2008 John Wiley & Sons, Ltd.     

X-ray photoelectron and scanning Auger electron spectroscopy study of electrodeposited ZnCr coatings on steel

Zn–Cr alloyed coatings electrochemically deposited are of high interest for leading steel manufacturing companies because of their novel properties and high corrosion resistance compared with conventional Zn coatings on steel. For tuning and optimizing the properties of the electrodeposited Zn–Cr coatings, a broad range of the deposition conditions must be studied. For this reason, two different types of material were investigated in this study, one with a low electrolyte temperature and one with an elevated electrolyte pH, compared with the standard values. Because different corrosion performance and delamination behaviour of the layers were observed for the two types, advanced surface analysis was conducted to understand the origin of this behaviour and to discover differences in the formation of the coatings. The topmost surface, the shallow subsurface region, and the whole bulk down to the coating–steel interface surface were analysed in detail by X-ray photoelectron spectroscopy (XPS) and high-resolution scanning Auger electron spectroscopy to determine the elemental and the chemical composition. For better understanding of the resulting layer structure, multiple reference samples and materials were measured and their Auger and XPS spectra were fitted to the experimental data. The results showed that one coating type is composed of metallic Zn and Cr, with oxide residing only on the surface and interface, whereas the other type contains significant amounts of Zn and Cr oxides throughout the whole coating thickness.     

Enhanced corrosion protection performance with MWCNT dispersed epoxy coating prepared under supercritical CO2 assistance

The corrosion protection performance of epoxy coatings could be enhanced by incorporation of nanofillers such as MWCNT. However, a homogeneous dispersion of MWCNT in epoxy polymer is still a teasing challenge. Herein, we report an environmentally benign single‐step supercritical CO₂ processing method to improve the dispersion of MWCNT in epoxy matrix in order to achieve an effective anticorrosive coating. The executed approach provides a cluster‐free uniform distribution of MWCNT in epoxy matrix as characterized with UV‐visible spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffraction, and surface analysis. The anticorrosive characteristics of MWCNT/epoxy coating were studied in NaCl as well as in photodegraded dye medium through electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. We observed the remarkable corrosion of model metal substrate in photodegraded dye medium besides NaCl medium. In both mediums, the protection efficacy of MWCNT/epoxy coating was deduced from the stable impedance arcs in Nyquist plot and increased impedance modulus. The electrochemical impedance spectra were best fitted with equivalent circuits showing the higher values of pore resistance. Also, the MWCNT/epoxy coating exhibited a positive shift of corrosion potential and possessed a lower corrosion rate as compared with neat epoxy coating. More direct evidence of the excellent barrier properties for MWCNT/epoxy coating was visualized in SEM images. The obtained results implied that the superior dispersion of MWCNT into epoxy matrix significantly reduces the porosity of coating and inhibits the permeability of corrosive ions. We expect supercritical CO₂ assisted dispersion method can offer an efficient, cost‐effective, and industrially viable route to develop high performance protective coatings for varied commercialized applications.     

阻抗谱定量分析金属/有机涂层界面粘接力

采用传输线类型的CR电路解析阻抗谱得到离散的电容参数,它们随离散特征频率变化的线性区间斜率与有机涂层/金属界面的瞬时脱层速率有关,不受缺陷位置腐蚀产物的影响,重现性好.建立了阻抗谱与粘结力的定量关系和数据处理方法,并进行了验证,说明了精度较高的原因.用硅烷直接预处理,或者磷化、热浸锌后再处理,会明显影响A3钢与环氧粉末涂层之间的粘结力.     

SECM and SKPFM Studies of the Local Corrosion Mechanism of Al Alloys – A Pathway to an Integrated SKP‐SECM System

Scanning Kelvin Probe Force Microscopy and Scanning Electrochemical Microscopy were applied for the investigation of localized corrosion on heterogeneous aiming on the investigation of the possible correlation between the local surface potential differences, measured by the Kelvin probe technique in ambient conditions, and corrosion during immersion in a corrosive electrolyte. A model sample mimicking the interaction of Al and Cu in Al alloys was chosen to demonstrate the complementary nature of the information received from SKPFM and SECM. The necessary prerequisites for a future integration of SKP and SECM into a single set‐up are discussed.     

Preparation,Characterization, and Evaluation of the Anticorrosion Performance of Submicron/Nanocarbon from Jute Sticks

Jute stick, one of the most commonly and abundantly available agricultural waste product, was converted to a value-added submicron/nano jute carbon by using pyrolysis and high-energy ball milling techniques. The submicron/nano jute carbon was characterized using FE-SEM, TEM, EDS, XRD, XPS and Raman spectroscopy. The anticorrosive performance of the submicron/nano jute carbon was investigated through electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP) and salt spray techniques, on mild steel plates coated with a mixture of epoxy resin and the submicron/nano jute carbon. The electrochemical impedance of the steel coated with the composite coating was two orders of magnitudes higher than that of the specimen coated with neat epoxy. Consequently, the corrosion rate of specimens coated with composite coating was 13–20 times higher than that of steel coated with neat epoxy coating. The salt spray results also indicate an improvement in the corrosion resistance performance of the composite coating compared to the neat epoxy. The uniform distribution of the submicron/nano jute carbon particles in the epoxy resin improved the denseness of the composite coating by acting as a barrier against the diffusion of chloride, moisture, and oxygen, thus, improving the corrosion resistance of the developed coating.     

Ultrafine grain formation and coating mechanism arising from a blast coating process: A transmission electron microscopy analysis

This article examines the substrate/coating interface of a coating deposited onto mild steel and stainless steel substrates using an ambient temperature blast coating technique known as CoBlast. The process uses a coincident stream of an abrasive blast medium and coating medium particles to modify the substrate surface. The hypothesis for the high bond strength is that the abrasive medium roughens the surface while simultaneously disrupting the passivating oxide layer of the substrate, thereby exposing the reactive metal that then reacts with the coating medium. The aim of this study is to provide greater insight into the coating/substrate bonding mechanism by analysing the interface between a hydroxyapatite coating on both mild and stainless steel substrates. The coating adhesion was measured via a tensile test, and bond strengths of approximately 45 MPa were measured. The substrate/coating interface was examined using transmission electron microscopy and selected area diffraction. The analysis of the substrate/coating interface revealed the presence of ultrafine grains in both the coating and substrate at interface associated with deformation at the interface caused by particle impaction during deposition. The chemical reactivity resulting from the creation of these ultrafine grains is proposed to explain the high adhesive strength of CoBlast coatings.     

Development of nanostructured polyaniline dispersed smart anticorrosive composite coatings

Modern engineering science and nanotechnology have hastened the development of high performance corrosion‐resistant coatings having a broad spectrum of effectivity under a wider range of hostile environments. The formulation of such coating systems is expected to cause a major revolution in the corrosion world. Conducting polymers have recently proved to be an effective alternative to phosphate–chromate pretreatment that is hazardous due to toxic hexavalent chromium. Moreover, improvements in environmental impact can be achieved by utilizing nanostructured particulates in coating and eliminating the requirement of toxic solvents. The paper reports some preliminary investigations on the corrosion resistance performance of nanostructured methyl orange (MO)‐doped polyaniline (PANI)/castor oil polyurethane (COPU) composite coatings on mild steel (MS). The nanostructure of the MO‐PANI was confirmed by transmission electron microscopy (TEM). The corrosion protective performance was evaluated by physico‐mechanical properties, corrosion rate, and open circuit potential measurements. These coatings were found to act as “corrosion sensors” by exhibiting different colors when placed in acid as well as alkaline media. The protective behavior of coatings was attributed to the formation of a passive iron oxide/dopant layer at the metal‐coating interface that impedes the penetration of the corrosive ions. Copyright © 2008 John Wiley & Sons, Ltd.     

Designing an epoxy composite coating having dual-barrier-active self-healing anti-corrosion functions using a multi-functional GO/PDA/MO nano-hybrid

The graphene oxide, functionalized with polydopamine (PDA) bio-polymers and molybdate (MO) ions, was incorporated into the epoxy coating. The FT-IR, Raman, UV-visible, XRD, and FE-SEM/EDS analyses were utilized for the GO/PDA/MO nanoparticle characterization. The sequence of inhibitors' release from the nano-hybrid and their effect on the electrochemical behavior of the steel sample was explored by the OCP, polarization, and, EIS analyses in the aquatic saline media. EIS analyses revealed inhibition efficiency of 88% for the sample immersed in the GO/PDA/MO-contained solution after 48 h immersion. The polarization results showed a 91% corrosion mitigation index for the sample submerged in the GO/PDA/MO extract-containing solution after 48 h immersion. An increase of the scratched coating Nyquist diameter, the lower corrosion product, and coating blister formation after exposure to the salt spray chamber, as well as the lower adhesion loss in the pull-off test (26%), revealed that the epoxy coating reinforced with GO/PDA/MO nano-hybrids could mitigate the mild steel corrosion by improving the barrier performance and active corrosion protection (self-healing mechanism) behavior.     

有机涂层失效过程的电化学阻抗和电位分布响应特征

结合使用电化学阻抗谱(EIS)和扫描Kelvin探针(SKP)技术研究了在质量分数为3.5%的NaCl溶液中的铁基有机涂层劣化过程特征. 结果表明, 根据EIS和SKP的响应特征, 可将涂层劣化过程分为3个主要阶段: (Ⅰ) 涂层渗水阶段. 此时, 涂层渗水阶段的EIS阻抗持续减小, 但保持单容抗弧特征, SKP特征是电位持续降低, 但分布保持均匀; (Ⅱ) 基底金属腐蚀发生阶段. 此时, EIS阻抗快速下降, 并产生第二时间常数; SKP特征为表面电位差增大; (Ⅲ) 基底金属腐蚀发展与涂层失效阶段. 此时, EIS出现扩散尾, SKP电位差保持较大数值. 实验结果表明, 在研究有机涂层劣化过程中, EIS和SKP的结合使用能够互相补充完善, 获得涂层劣化过程中更为准确\, 可靠的变化信息.     

Tribo-corrosion behavior of Zn-Ni-Cu and Zn-Ni-Cu-TiB2 coated mild steel

In this investigation , Zn-Ni-Cu and Zn-Ni-Cu-TiB₂ were coated on a mild steel specimen using a high velocity oxy fuel thermal spray (HVOF) process. The surface morphology and coated powder distribution of coated specimens were characterized using scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), and X-ray-Elemental mapping. The pin-on-disc (ASTM G99-17) method was used to examine the wear resistance of the coated and uncoated mild steel specimens. Both coated Zn-Ni-Cu and Zn-Ni-Cu-TiB2 on mild steel saw reduced wear volume loss than uncoated mild steel. The coated samples of Zn-Ni-Cu and Zn-Ni-Cu-TiB2 on Mild Steel were put through a scratch test to determine the adhesion strength of the coating with the substrate. The adhesion strength of coated Zn-Ni-Cu and Zn-Ni-Cu TiB2 mild steel was higher than that of untreated mild steel, indicating a solid link between the coating and substrate and minimal delamination. Using the Vickers hardness test to measure the hardness caused by the coating, it was shown that coated samples of Zn-Ni-Cu and Zn-Ni-Cu-TiB2 coated mild steel had significantly higher hardness than uncoated mild steel. Using ASTM G1-03 and ASTM G-31 standards, a 0.2 M HCl immersion cycle test was conducted for 28 days to test the corrosion resistance of coatings in an acidic media (672Hrs). When compared to Zn-Ni-Cu and Zn-Ni-Cu-TiB2 coated mild steel, the weight loss for the uncoated mild steel was significantly larger. Additionally, XRD examination showed that coated samples had less rust on their surface than uncoated samples. Both Zn-Ni-Cu and Zn-Ni-Cu-TiB2 on Mild Steel were anti-corrosive, as evidenced by increased corrosion potential and reduced corrosion current density when compared to uncoated mild steel, according to electrochemical impedance spectroscopy (EIS)/Tafel study in 0.2 MHCl. The outcomes of each test were very encouraging and demonstrated the durability of these coatings against wear and corrosion.     

Epoxy polymer coating to prevent the corrosion of aluminum nanoparticles

Aluminum nanoparticles were coated by epoxy polymer in order to prevent the corrosion reaction. The coverage of the epoxy polymer film was controlled from 0% to 100%, which changed the corrosion rate of nanoparticles quantitatively. The surface of the polymer coating was investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM), and the corrosion resistance of these nanoparticles was estimated by the wet/dry corrosion test on platinum (Pt) plate with a NaCl solution. From a TEM analysis, 10 mass% polymer‐coated Al particles in the synthesis were almost 100% covered on the surface by a polymer film of 10 nm thick. On the other hand, 3 mass% polymer‐coated Al was partially covered by a film. In the AFM–Kelvin force microscopy, the potential around the Al particles had a relatively low value by the polymer coating, which indicated that the conductivity of the Al was isolated from Pt plate by the polymer. Both the corrosion and H₂ evolution reaction rates were quantitatively reduced by the mass% of polymer coating. In the case of 10 mass% coated sample, there was very little corrosion of Al nanoparticles. This fact suggested that the electrochemical reaction was suppressed by the polymer coating. Thus, it was found that the corrosion reaction rate of Al nanoparticles could be quantitatively suppressed by the mass% of epoxy coating. Copyright © 2015 John Wiley & Sons, Ltd.     

Corrosion resistance of amorphous AlPO4 coating in salty atmospheres

The objective of the present study was to introduce a cost-effective and environmentally friendly coating to improve the corrosion resistance of the structures located in salt water. The coating solution, based on amorphous aluminum phosphate composition, was synthesized by sol–gel process and applied to AISI 304 stainless steel by dip coating technique. X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy analyses were employed to investigate the phase composition and morphology of the coating. Corrosion behavior of the uncoated and coated samples was investigated using standard salt spray test, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl solution. Salt spray test results for the bare substrate revealed a corrosion rate of six-time greater than that of the coated surface after 168 hr exposure time. Electrochemical test results declared that the amorphous AlPO₄ coating decreased the corrosion current density of the AISI 304 stainless steel by 10 orders of magnitude. Furthermore, according to the corresponding EIS measurements, the coated surface exhibited a superior anti-corrosion performance than uncoated sample. Overall, the results declared that the amorphous AlPO₄ coating could be a good choice for surface protection of stainless steel against electrochemical corrosion in salty environments.     

正十二硫醇自组装单层膜改善环氧涂层腐蚀防护性能的研究

通过在正十二硫醇自组装单层膜表面制备环氧树脂涂层的方法,在涂层/铜基体界面引入自组装界面层.采用X射线光电子能谱、电化学阻抗谱、阻抗-时间谱和相位角-时间谱等方法对硫醇自组装界面层及其对涂层腐蚀防护性能的影响进行了研究.结果表明,引入的自组装单层可极大地改善涂层的腐蚀防护性能.论文还对自组装单层改善涂层腐蚀防护性能的机理进行了探讨.     

三聚磷酸铝缓蚀性能的EIS研究(英文)

利用电化学阻抗谱研究了方解石及三聚磷酸铝环氧涂层的耐蚀性能 ,并提出了它们的作用机理 .结果表明 ,方解石只起体质颜料作用 ,不具备缓蚀性能 ;而三聚磷酸铝因在钢基表面作用形成致密的保护膜则表现出优良的缓蚀性能 .     

Microstructural and in-depth electrochemical characterization of Zn diffusion layers on aluminum 3xxx alloy

AA 3XXX alloys are widely used in heating, ventilation, and air conditioning (HVAC) field. Diffusion joining using a filler metal together with flux is employed in some applications as for heat exchangers. In this work, the effect of diffusion of a Zn-based flux on both microstructure and electrochemical behavior has been investigated. In particular, an AA3xxx was coated with a Zn-rich flux and subjected to controlled atmosphere brazing (CAB). Glow discharge optical emission spectroscopy (GDOES) composition profiles were acquired in order to determine the Zn distribution in the diffusion layer. The GDOES was also employed to produce a controlled erosion of the surface in order to obtain craters with defined depths in the Zn diffusion layer, in which electrochemical analyses could be performed. The Volta potential maps at different depths in the Zn diffusion layer were obtained by scanning Kelvin probe force microscope (SKPFM). The Zn diffusion layer was also investigated by means of Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy (SEM-EDXS) and the chemical composition of the phases present in the regions was investigated by SKPFM. Finally, the electrochemical microcell was used in the produced craters in order to determine the electrochemical behavior along the Zn diffusion profile. SKPFM and microcell results showed a correlation between the Zn content and the electrochemical properties. In particular, a higher Zn content in the diffusion layer leads to an increase of the Volta potential difference between the intermetallic particles and the matrix. The electrochemical measurements also showed that the Zn diffusion layer provides galvanic protection to the underlaying aluminum alloy.     

SECM Imaging of Interfacial Processes in Defective Organic Coatings Applied on Metallic Substrates Using Oxygen as Redox Mediator

Operation of the SECM in feedback mode over a coated metal allows changes in the state of the surface to be monitored using dissolved oxygen in the test environment as redox mediator. The system investigated consisted in mild steel samples coated with a polyurethane film in which a defect was deliberately introduced into it. Accurate approach curves under negative‐feedback condition were obtained using a platinum microelectrode over regions of the intact coating. Imaging experiments were also carried out over the artificial defect on the coating. Under these conditions, corrosion of the exposed metal substrate at the defects could be monitored.