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The development of organic coatings for corrosion protection is an elaborate process with a multitude of often interminable investigations and tests of protection properties. Electrochemical methods support the processes of development to a great extent and help to understand mechanisms of action and failure. They are usually carried out on applied coating systems with a completed formulation. An examination possibility is presented in this publication that enables the characterization of waterbased coatings with different formulation variations in the liquid (aqueous) state with the aid of electrochemical noise technique. Thus, selection of binders, pigments, and other additives is supported essentially and made more efficient in a very early Phase of formulation development. The paper shows that a unique insight into the dynamic processes of a metal in contact with an aqueous coating dispersion is possible using the example of the development of zinc-free corrosion-inhibiting pigments for waterbased coatings. In addition, it is presented in which way the results correlate with the performance of applied coatings.
In the last years, new approaches for the evaluation of the corrosion resistance of martensitic stainless steels were developed, which allow nearly non-destructive as well as short-term corrosion testing. This work analyzes the sensitive influence of microstructure and surface treatment on the corrosion resistance. The effect of alloy composition and microstructure, which is always present in addition to the influence of various surface treatments will be evaluated and discussed. The corrosion behavior was investigated with conventional evaluation of the pitting potential, electrochemical potentiodynamic reactivation (EPR), electrochemical noise (EN), and the 'KorroPad' (KP) technique. EPR provided information about the passivation ability and the extent of chromium content reduction due to chromium carbide precipitation in the microstructure. The use of EN and KP aims to detect the influence of different surface treatment parameters on the corrosion resistance in a nearly non-destructive way. Furthermore the results shall demonstrate the functionality and convenience of the short-term corrosion test methods EN and KP in order to gain more acceptance within the scientific community. The results will allow the extraction of surface treatment effects on the corrosion behavior of the martensitic stainless steels 1.4116, 1.4034, and 1.4021.
Sixteen laboratories have performed electrochemical noise (EN) measurements based on two systems. The first uses a series of dummy cells consisting of a 'star' arrangement of resistors in order to validate the EN measurement equipment and determine its baseline noise performance, while the second system, based on a previous round-robin in the literature, examines the corrosion of aluminium in three environments. All participants used the same measurement protocol and the data reporting and analysis were performed with automatic procedures to avoid errors. The measurement instruments used in the various laboratories include commercial general-purpose potentiostats and custom-built EN systems. The measurements on dummy cells have demonstrated that few systems are capable of achieving instrument noise levels comparable to the thermal noise of the resistors, because of its low level. However, it is of greater concern that some of the instruments exhibited significant artefacts in the measured data, mostly because of the absence of anti-aliasing filters in the equipment or because the way it is used. The measurements on the aluminium samples involve a much higher source noise level during pitting corrosion, and most (though not all) instruments were able to make reliable measurements. However, during passivation, the low level of noise could be measured by very few systems. The round-robin testing has clearly shown that improvements are necessary in the choice of EN measurement equipment and settings and in the way to validate EN data measured. The results emphasise the need to validate measurement systems by using dummy cells and the need to check systematically that the noise of the electrochemical cell to be measured is significantly higher than the instrument noise measured with dummy cells of similar impedance.
The main problem limiting the application of magnesium alloys as biodegradable implant material is its high degradation rate. In order to slow down the corrosion rate an extrusion process and specific coating systems based on plasma-chemical oxidation (PCO) and organic dip coating with poly(ʟ-lactid-co-caprolacton) (PLLC) were applied on Mg–1Ca magnesium alloy. The additional PLLC coating is used to delay the start of substrate corrosion, while the purpose of the PCO coating is to decrease the substrate corrosion rate. The corrosion behaviour was investigated in synthetic body fluid (SBF) through measurement of the hydrogen evolution rate in long term tests and polarisation and electrochemical noise measurements in short term tests. The results showed significant differences between the cast and extruded alloys and a decrease of the corrosion rate due to corrosion product formation. The combination of both coating systems resulted in a significant delay of metal substrate corrosion and all coating systems showed good correlation between short and long term tests. The combination of the three investigation methods provides the possibility to gain more information about the degradation behaviour and break down of protective coatings.
An important possibility to improve the corrosion behaviour of magnesium alloys is the application of protective coatings. The quality of such coatings depends mainly on the pretreatment and the exposure conditions after pretreatment. Since magnesium surfaces change much faster under atmospheric conditions than those of almost any other technical material, it is necessary to pay special attention to this particular feature. The activity of acid-pickled surfaces of the magnesium alloys AZ31 and AZ91 in dependence on the exposure time and the humidity conditions was investigated with electrochemical noise (EN) measurements. In addition to pickling, plasma chemical vapour deposition processes open new possibilities for an economical, as well as ecologically quite safe, pretreatment. The results of EN investigations after acid pickling as well as specific plasma oxidation treatments of the two magnesium alloys after exposure to air with different humidities are presented.
The determination of critical pitting temperatures (CPT) in various test solutions like ferric chloride solution according to ASTM G48 or 'Green Death' solution is a common test method for the comparative assessment of the pitting corrosion resistance of highly alloyed steels and Ni–Cr–Mo alloys. In addition to the well-known disadvantages of standard methods, like long test times, subjective examination, and large scatter, for the highest alloyed Ni–Cr–Mo alloys no stable pitting corrosion can initiate even at the highest test temperatures. This paper describes the limitations of standard test methods and shows how these problems can be solved by an alternative test solution and an adjusted test method. By capturing and examining the current noise under potentiostatic conditions during continuous heating in a 4.5 M calcium chloride solution the transition from metastable to stable pitting corrosion as a criterion for CPT can be detected in a reproducible way.
Electrochemical noise (EN) enables corrosion research and monitoring in real time and with high sensitivity. In the case of submicroscopic nucleation events of pitting corrosion it has been observed that the cathodic process plays a decisive role in the mechanism as well as in the origin of EN signals, which depend not only on the metallic dissolution reaction but also on the electron-consuming process. EN signals arising from the nucleation process of localized corrosion on stainless steels can only be recorded due to the inhibition effect on the cathodic process achieved by the spontaneous formation of the passive layer. In consequence, passive layer stability becomes a significant factor in influencing EN signals. The way in which the passive layer stability affects the acquisition and analysis of EN signals arising from pitting corrosion on stainless steels is discussed in detail.
Pitting corrosion is one of the most common mechanisms of surface damage on stainless steels. Electrochemical methods have been preferentially applied for the evaluation of the pitting corrosion resistance of stainless steels in the laboratory. Nevertheless, some of them are not reliable enough and in general the application of electrochemical methods in the field becomes difficult because of required deep understanding of corrosive phenomena and measurement technology. Therefore, new approaches for the evaluation of the pitting corrosion susceptibility of stainless steel surfaces in the laboratory as well as in the field are necessary. In the present paper two novel strategies including electrochemical noise measurements under anodic polarization for laboratory testing, and an indicator test to assess the susceptibility of stainless steel surfaces to pitting corrosion in the field are introduced. Experimental results concerning the influence of surface treatments on the pitting corrosion resistance on stainless steels have confirmed that final surface condition has a significant effect on their future pitting corrosion susceptibility. In addition, the pitting corrosion resistance of stainless steel surfaces was observed being specifically dependent on the achieved surface topography and in some cases independent on the roughness parameters of the surface.
Surface treatments usually are used to modify the appearance and properties of stainless steel surfaces. Simultaneously, the corrosion resistance of the stainless steel surface being related intrinsically to the spontaneous formation of a passive layer also will be affected. In this respect, the influence of different surface treatments on the corrosion resistance of Type 304 (UNS S30400) stainless steel to pitting corrosion has been evaluated by means of potentiostatic electrochemical noise measurements and surface characterization. Typical industrial treatments including mechanical grinding, glass blasting, and pickling were taken into account. Additionally, special consideration was put on the effect of aging conditions of the passive layer after surface treatments, in particular on the relative humidity. Benefits and limitations of the different applied surface treatments concerning protectiveness of the stainless steel surface were determined and discussed.
Unwanted corrosive phenomena on stainless steel surfaces like rouging had been observed for years occurring at certain service conditions. Rouging consists in the formation of a colored surface film containing mainly iron on metallic surfaces in contact with high-purity waters. In spite of numerous hypotheses and experimental examinations a clear explanation about the origin of rouging on stainless steels is currently still lacking. Because rouging occurs even at well passivated stainless steel surfaces the origin of this corrosive phenomenon should be related to the weakness of the stability of the passive film. In the present paper electrochemical noise measurements regarding the stability of the passive layer of alloy 904L (1.4539, X1NiCrMoCu25-20-5) in high-purity water at 70 °C depending on the cathodic process are presented. In addition, the importance of the cathodic reaction on the passivation and stability of the passive layer is discussed.
Electrochemical noise measurements on unalloyed steel in chloride-containing alkaline environment
(2007)
The investigations discussed in this paper aim to clarify whether electrochemical noise measurements (ENM) are capable for application in concrete and mortar, particularly with regard to pitting initiation in such environment. For these purposes, the results of several different test series are compared and discussed. Based on investigations on passivity and pitting corrosion in alkaline solutions with different chloride contents further results in cement paste, mortar and concrete are evaluated.