The delamination of polymeric coatings from steel Part 3: Effect of the oxygen partial pressure on the delamination reaction and current distribution at the metal/polymer interface

Leng, Andreas; Streckel, H.; Hofmann, Konstantin; Stratmann, M.

doi:10.1016/s0010-938x(98)00168-1

Cited by 185 publications

(126 citation statements)

References 15 publications

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“…Here degradation implies a local deadhesion of the interface due to the oxygen reduction, most likely due to reactive intermediates. 2 This degradation leads to a more reactive interface, with the presence of underfilm Pd-water interfaces (presumably in the form of nanoscopic pockets, this is subject of current research) supporting higher ORR currents after successive runs as compared to the original intact adherent PVB-Pd interface. Further, the preparation procedure outlined in this work involving the use of 5 and 10 wt% PVB solutions for spin coating as well as an intermediate annealing step results in different coatings with different interfaces which slightly changes the derived I(U) curves as compared to those reported in our earlier work.…”

Section: Resultsmentioning

confidence: 97%

“…The Scanning Kelvin Probe (SKP) provides direct information of the corrosion potential underneath coatings at buried interfaces, but, it does not provide information about interfacial reaction rates. [2][3][4] Recently, inspired by earlier work on controlling the potential on one side of a palladium membrane by applying a potential on the other side to control the defined hydrogen activity across the sample, [13][14][15][16] a new potentiometric approach using hydrogen permeation as a tool to measure interfacial oxygen reduction rates at this buried metal/organic coating interface has been developed. 17 In this method, the classical Devanathan-Stachurski technique has been adapted, wherein hydrogen permeation from the back side of the sample is used to quantitatively measure the oxygen reduction rate at the metal/organic coating interface on the other side.…”

mentioning

confidence: 99%

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Probing the Buried Metal-Organic Coating Interfacial Reaction Kinetic Mechanisms by a Hydrogen Permeation Based Potentiometric Approach

Vijayshankar

Altin

Merola

et al. 2016

J. Electrochem. Soc.

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Corrosion driven delamination of coatings is crucially determined by the rate of the cathodic oxygen reduction reaction at the buried metal-organic coating interface. Quantitative measurement of this rate at such interfaces by conventional techniques is impeded due to the blocking of ion transport by the coating. A new approach where hydrogen permeation is used as a tool to measure the oxygen reduction rate underneath coatings has been recently introduced. This permeation based potentiometry approach measures the rate of the oxygen reduction reaction by correlating the open circuit potential established as a consequence of the dynamic electrochemical equilibrium between hydrogen oxidation and oxygen reduction reactions on the coated exit side with the hydrogen uptake rate on the entry side. In this work, the interfacial reaction kinetics of the oxygen reduction reaction causing delamination of the coating are investigated by this hydrogen permeation based potentiometric approach. Moreover, thus performed prolonged cathodic polarizations of the palladium/coating interface have been found to destroy the interface, just like it is the case in the cathodic delamination process. Initial results obtained on ultra-thin films of iron on palladium are also presented, showing that the technique is applicable also on technically more relevant metal surfaces. Corrosion driven degradation of the buried metal/organic coating interface is of utmost interest in the contemporary space of coatings science. Earlier studies have shown conclusively that the oxygen reduction reaction (ORR) plays a fundamental role in the destruction of this buried metal/organic coating interface. The role of the interface between organic coating and metal has been object of intense research over last decades. Leidheiser et al.1 pointed out the key role of the cathodic ORR for the degradation process and also showed that diffusion processes such as water and oxygen transport through the coating can influence this delamination rate. Stratmann and co-workers 2-4 proposed a detailed delamination mechanism for a basic polymer coating on steel where galvanic coupling between the defect site of metal dissolution (local anode) and delamination site of electrochemical oxygen reduction (local cathode) supported by cation migration along the polymer/metal interface lead to the progressive deadhesion of the polymer from the underlying metal based on comprehensive analysis of the local electrode potential at the metal/polymer interface using primarily the Scanning Kelvin Probe (SKP) technique along with complementary Auger electron spectroscopy and mechanical deadhesion tests. Fürbeth and Stratmann 5-7 extended their studies to coated zinc (or galvanized steel), which also involves anodic processes at the interface. Also other works by Brewis et al. 8 and Dickie et al. 9 show the importance of interfacial electrochemical reactions on metal/polymer adhesion. Up to now our knowledge about the reactions and how they are determined by the interface itself is too rest...

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Section: Resultsmentioning

confidence: 97%

mentioning

confidence: 99%

Probing the Buried Metal-Organic Coating Interfacial Reaction Kinetic Mechanisms by a Hydrogen Permeation Based Potentiometric Approach

Vijayshankar

Altin

Merola

et al. 2016

J. Electrochem. Soc.

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“…The pioneering work of cathodic delamination was performed by Stratmann et al [113][114][115][116][117][118][119][120]. The delamination of film-substrate (steel) near an artificial defect investigated using Scanning Kelvin Probe showed that the galvanic coupling (A galvanic couple is a corrosive cell that is developed when two different materials are separated by electrolyte) in film results in the defect in film due to the high permeability of the film to oxygen.…”

Section: Cathodic Delaminationmentioning

confidence: 99%

“…The first comprehensive mathematical model for cathodic delamination comprising of a non-linear porosity-pH relationship was developed by Allahar et al [128,129] based upon the experimental results [113][114][115][116][117][118][119][120]. The interfacial porosity which depends on hydroxyl OH-ions formation decides the interfacial bonding and bond breakage of film and substrate [130].…”

Section: Cathodic Delaminationmentioning

confidence: 99%

A review of theoretical analysis techniques for cracking and corrosive degradation of film-substrate systems

Nazir

Khan

2017

Engineering Failure Analysis

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This paper contains a review of the most vital concepts regarding the analysis and design of film systems. Various techniques have been presented to analyse and predict the failure of films for all common types of failure: fracture, delamination, general yield, cathodic blistering, erosive and corrosive wear in both organic and inorganic films. Interfacial fracture or delamination is the loss of bonding strength of film from substrate, and is normally analysed based on the fracture mechanics concepts of bi-material systems. Therefore, keeping the focus of this review on bonding strength, the emphasis will be on the interfacial cracking of films and the corresponding stresses responsible for driving the delamination process. The bi-material characteristics of film systems make the nature of interfacial cracks as mixed mode, with cracks exhibiting various complex patterns such as telephone cord blisters. Such interfacial fracture phenomenon has been widely studied by using fracture mechanics based applicable analysis to model and predict the fracture strength of interface in film systems. The incorporation of interfacial fracture mechanics concepts with the thermodynamics/diffusion concepts further leads to the development of corrosive degradation theories of film systems such as cathodic blistering. This review presents the suggestions for improvements in existing analysis techniques to overcome some of the limitations in film failure modelling. This comprehensive review will help researchers, scientists, and academics to understand, develop and improve the existing models and methods of film-substrate systems.

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“…app D is an apparent diffusion coefficient, taking into account that the transport of the ions is facilitated by an electrical field gradient [2,3] between anode and cathode resulting from the cathodic reaction [17]. This behaviour can be expressed using the Nernst-Planck equation.…”

Section: Introductionmentioning

confidence: 99%

Investigation of delamination mechanisms in polymer coatings by scanning acoustic microscopy

Alig¹,

Bargmann²,

Oehler³

et al. 2010

J. Phys. D: Appl. Phys.

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Scanning acoustic microscopy (SAM) was used to investigate disbonding, delamination and blister formation in polymer coatings for different layer structures and initial defect depths during exposure to a corrosive environment. The time evolution of disbonding and blister initiation and their growth was investigated by analysing the SAM images exposure to an electrolyte solution (Harrison solution). From investigations of a model system of coatings on steel substrates, it was possible to differentiate between water and/or ion transport (i) through the coating and (ii) along the coating-steel interface. For samples without clear coat randomly distributed blisters appeared at the coating-steel interface after exposure to the electrolyte solution, irrespective of the location of initial defects. The random distribution of growing blisters is related to diffusion of water and/or ions through the coating and "nucleation" at weak points of the substrate or within the polymer. For samples with clear coat a propagating migration front along the coating-steel interface of 3-4 µm height -starting from initial defects -was detected. The linear propagation of this front cannot be explained by Fickian diffusion. Therefore, it is discussed in terms of an accelerated diffusion or crack growth kinetics. Since blistering starts only at sites, where the migration front has passed, the presence of a thin water layer at the coating-steel interface, the loss of adhesion and the following corrosive processes are prerequisites for the nucleation of blisters. The blister growth shows a square-root time dependence which was related to a diffusion controlled transport mechanism.

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The delamination of polymeric coatings from steel Part 3: Effect of the oxygen partial pressure on the delamination reaction and current distribution at the metal/polymer interface

Cited by 185 publications

References 15 publications

Probing the Buried Metal-Organic Coating Interfacial Reaction Kinetic Mechanisms by a Hydrogen Permeation Based Potentiometric Approach

Probing the Buried Metal-Organic Coating Interfacial Reaction Kinetic Mechanisms by a Hydrogen Permeation Based Potentiometric Approach

A review of theoretical analysis techniques for cracking and corrosive degradation of film-substrate systems

Investigation of delamination mechanisms in polymer coatings by scanning acoustic microscopy

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