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- Electrochemical noise (7)
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- Magnesium (4)
- Pitting corrosion (4)
- KorroPad (3)
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An unusual feature known as the negative difference effect (NDE) can be observed in magnesium when recording corrosion current density–potential curves. More hydrogen is evolved at a more positive potential which does not occur in conventional metals. Several models have been proposed in the literature in order to explain the phenomenon of NDE. They succeed in explaining some effects, and fail to deal with others. A new model, which explains the NDE by two electron consuming processes, is presented in this paper. By potentiostatic investigations of magnesium in a chloride electrolyte, measurements of hydrogen evolution and chemical analysis of the electrolyte the new model was experimentally verified.
Long term corrosion behavior of clad aluminium materials under different atmospheric conditions
(2013)
Aluminum materials roll-plated on both sides are combinations of metals, which consist of clad layers on a core. To document the long term behavior of roof profiles of Alclad 3004 after long term exposure of about 40 years, evaluations were made at three locations in Germany with different climatic conditions. Locations with typical rural-urban, coastal-urban, and industrial climates were selected. The corrosion progress as a function of time and climatic type could be characterized by cross-sections of roof specimens. To interpret the protective mechanism of the clad layer, the corrosion behavior of Alclad 6025 was characterized by electrochemical investigations. The results show that the passive clad material easily undergoes pitting in media containing specific amounts of chlorides. In case of contact of both cladding and core with an electrolyte the core alloy was protected because of the pitting corrosion of the cladding. This guarantees long-time corrosion protection of constructions like facades or roofs under different atmospheric conditions.
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.
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 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.
The use of electrochemical noise (EN) measurements for the investigation and monitoring of corrosion has allowed many interesting advances in the corrosion science in recent years. A special advantage of EN measurements includes the possibility to detect and study the early stages of localized corrosion. Nevertheless, the understanding of the electrochemical information included in the EN signal is actually very limited. The role of the cathodic process on the EN signals remains uncertain and has not been sufficiently investigated to date. Thus, an accurate understanding of the influence of the cathodic process on the EN signal is still lacking. On the basis of different kinetics of the oxygen reduction it was established that the anodic amplitude of transients arising from pitting corrosion on stainless steel can be decreased by the corresponding electron consumption of the cathodic process. Therefore, the stronger the electron consumption, the weaker the anodic amplitude of the EN signal becomes. EN signals arising from pitting corrosion on stainless steel can be measured because the cathodic process is inhibited by the passive layer. This was confirmed by means of EN measurements under cathodic polarisation. Since the cathodic process plays a decisive role on the form of transients arising from pitting corrosion, its influence must be considered in the evaluation and interpretation of the EN signals.
The degradation behaviour of an Mg-1Ca alloy is investigated in vitro to figure out the possibilities of influencing the degradation behaviour of such an alloy by applying heat treatment as well as the use of a coating system based on plasma-chemical oxidation. It is shown that an optimised solution annealing (T4-heat treatment) can reduce the degradation rate while an additional ageing between 240 and 300 °C (T6-heat treatment) increases it. A coating generated by plasma-chemical oxidation reduces the degradation rate in the immersion test. Its effect is depending on the former heat treatment of the Mg-1Ca alloy as well as on the parameter during plasma-chemical oxidation.
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.
Investigation on defect morphology and corrosion behaviour of TiMgN hard coatings on steel substrate
(2014)
Nitride hard coatings, such as Titanium nitride and chromium nitride coatings are widely used for applications focussing on wear protection and decorative purposes. Also these coatings are often applied on low alloyed steel substrates. The inevitable contact of the coated components with the environment through pores and coating defects bears the danger of corrosion of the steel substrate followed by further delamination of the coating and a loss of function of the component. A new attempt to increase the corrosion behaviour of those physically deposited hard coating systems is the implementation of magnesium. The positive effect of magnesium could be verified already electrochemically. Performed experiments on TiMgN have shown that corrosion resistance could drastically improved with increasing Mg content of the TiMgN up to 30 at% compared to steel substrates with applied titanium nitride hard coatings. Besides the clarification of the electrochemical and phenomenological effect of the magnesium on the corrosion behaviour, an additional aim of this work is the investigation of the coating defects, defect morphologies and their influence on the local corrosion behaviour. For this the incorporation of the magnesium and its effects on the coating material, the influence of coating growth related defects and the effect of the coating structure on the corrosion behaviour should be experimental examined by using innovative surface and material analysis methods such as FIB and TEM. Furthermore the evolution of the coating defects should be investigated by combing confocal microscopy with a new developed exposure test method using the electrochemical indication test KorroPad. The function of the KorroPad test, which was developed and patented [1] at the BAM for the detection of corrosion sensitive steel surfaces by indicating dissolution of iron ions [1], allows the detection and identification of critical coating defects for further microscopic investigation. Additional to that the KorroPad test simulates an accelerated exposure test by simultaneous absence of the disadvantages of typical short time exposure test like salt spray tests. Thus it allows a monitoring and analysis of the evolution of the critical coating defects and their influence on the local corrosion behaviour and the overall corrosion mechanisms. The results of this work should contribute to the development of new hard coatings with improved corrosion protection properties and also to a better understanding of the corrosion mechanisms of coated steel substrates.
In the last years, new approaches for the evaluation of the corrosion resistance of stainless steels were developed which allow short term corrosion testing with increased information content. This work analyses the extensive influence of heat treatment on microstructure and the resulting corrosion resistance of the martensitic stainless steels 1.4034 and 1.4021 with advanced methods. Different heat treatments at various austenitization temperatures up to 1100°C and the effect of different cooling rates were evaluated; the last has not yet been studied in literature at all. The resulting corrosion behaviour in relation to the different carbon content in the two used alloys and the applied heat treatment will be presented and discussed. The applied methods of investigation were conventional evaluation of the critical pitting corrosion potential (PP), modified electrochemical potentiodynamic reactivation (mEPR) and the "KorroPad" (KP) technique. The performance of modified EPR and its interpretation were optimized to provide additional information about the general passivation ability and the extent of chromium depletion as result of applied heat treatment. The aim using PP and KP was the correlation between the Parameters of the mEPR with the changes in the pitting corrosion resistance. Furthermore the results will demonstrate the functionality and usability of the short term corrosion test methods mEPR and KP in order to increase their acceptance within the scientific community. The results indicate a surprisingly large influence of both austenitization temperature and cooling rate on the corrosion resistance within all three used test methods, which can explain the different corrosion behaviour of martensitic stainless steels in earlier investigations.