This paper aims to develop a proper and valid simulation model for electroplating complex geometries. Since many variables influence the quality of the deposited coating and its thickness distribution, it is challenging to conduct efficient research only through experiments. In contrast, simulation can be an efficient way to optimize the electroplating experiments. Despite its potential, simulation has seen limited commercial use in the electroplating industry due to its inherent complexity and difficulty in achieving accurate precision for intricate geometries. The present study addresses the aspects that can enhance the electroplating simulation's accuracy, which has been typically overlooked in the literature, such as the effect of current efficiency and its dependency on the current density, the input data for the electrode kinetics, the surface topology changes, and the differences between 2 and 3D simulations. The simulation model was validated by experimental results related to the coating thickness of Ni plating on a T-joint geometry. The results showed good agreement with the experimental ones, confirming the model's ability to precisely predict the coating thickness and distribution and promote its broader utilization in the industry. Finally, the developed model was used to determine the optimal current density regime for achieving uniform coating thickness distribution on a T-joint sample.

The process of cold flat rolling is a widespread industrial technique to manufacture semi-finished products, e.g., for the automotive or homewares industry. Basic knowledge of the process regarding dimensioning and adjustment of defined characteristics is already state of the art. However, a detailed consideration and analysis with respect to local inhomogeneous residual stresses in several process steps mostly remains disregarded. A broad understanding of the process due to the distribution of residual stresses in the workpiece and the direction of the stress tensors allows for a definition of the characteristics of the workpiece even before the actual manufacturing process. For that purpose, it is necessary to perform numerical investigations by means of the finite element analysis (FEA) of cold flat rolling processes. Within this contribution, several approaches for the calibration of the FEA with the real flat rolling process will be addressed and discussed. To ensure that the numerical consideration provides realistic results, this calibration is indispensable. General parameters such as geometry, height reduction, rolling temperature, process time, and the rolling speed are considered as well as a photogrammetric survey, and calculated residual stresses with results of X-ray diffraction (XRD) will be compared. In the course of the experiments, a good agreement between the stress results of the FEA and the XRD was found in the center of the specimen. In combination with the allocation of the stress orientations, the agreement close to the edges is also fine. Some issues that cause differences between the FEA and the experiment are dis-cussed. 

Self-tapping aluminium screws are an innovative joining technology for the assembly of lightweight components in industrial scale. It has been established in the past that porous anodic oxide coatings in many cases reduce the fatigue strength of specimens without notches. In the present work, the fatigue behaviour of notched specimens, i.e. self-tapping screws made from aluminium alloys EN AW-6056, 6082 (both in a conventional state and in a fine-grained state produced by equal channel angular pressing - ECAP) and 7068 with and without oxide coatings is examined. The coatings are produced by hard anodising and are necessary for the thread-forming process during assembly. While the coatings do not affect the static tensile strength, they reduce the fatigue strength for the specimens of the 6056 and the 6082 alloy. For the 7068 alloy a slight increase in fatigue strength is discovered on a low load horizon. The scatter of endured fatigue cycles until fracture of specimens is generally reduced by the anodic oxide coatings. 

Anodic oxidation of aluminium and its alloys is often used as protection against material wearout and corrosion. Therefore, anodic oxidation of aluminium is applied to produce functional oxide layers. The structure and properties of the oxide layers can be influenced by various factors. These factors include for example the properties of the substrate material, like alloy elements and heat treatment or process parameters, like operating temperature, electric parameters or the type of the used electrolyte. In order to avoid damage to the work-piece surface caused by covering materials in masking applications, to minimize the use of resources and to modify the surface in a targeted manner, the anodic oxidation has to be localised to partial areas. Within this study a proper alternative without preparing the substrate by a mask is investigated for generating locally limited anodic oxidation by using a continuous electrolyte jet. Therefore aluminium material EN AW 7075 is machined by applying a continuous electrolyte jet of oxalic acid. Experiments were carried out by varying process parameters like voltage or processing time. The realised oxide spots on the aluminium surface were investigated by optical microscopy, SEM and EDX line scanning. Furthermore, the dependencies of the oxide layer properties from the process parameters are shown.

Due to their outstanding specific mechanical properties, high-strength, age-hardenable aluminum alloys offer a high potential for lightweight security-related applications. However, the use of copper-alloyed aluminum is limited because of their susceptibility to selective corrosion and their low wear resistance. These restrictions can be overcome and new applications can be opened up by the generation of protective anodic aluminum oxide layers. In contrast to the anodic oxidation of unalloyed aluminum, oxide layers produced on copper-rich alloys exhibit a significantly more complex pore structure. It is the aim of the investigation to identify the influence of microstructural parameters such as size and distribution of the strengthening precipitations on the coating microstructure. The aluminum alloy EN AW-2024 (AlCu4Mg1) in different heat treatment conditions serves as substrate material. The influence of the strengthening precipitations' size and distribution on the development of the pore structure is investigated by the use of high-resolution scanning electron microscopy. Integral coating properties are characterized by non-destructive and light-microscopic thickness measurements and instrumented indentation tests. 

Due to their outstanding specific mechanical and high-temperature properties, titanium aluminides exhibit a high potential for lightweight components exposed to high temperatures. However, their application is limited through their low wear resistance and the increasing high-temperature oxidation starting from about 750 °C. By the use of oxide ceramic coatings, these constraints can be set aside and the possible applications of titanium aluminides can be extended. The plasma electrolytic oxidation (PEO) represents a process for the generation of oxide ceramic conversion coatings with high thickness. The current work aims at the clarification of different electrolyte components' influences on the oxide layer evolution on alloy TNM-B1 (Ti43.5Al4Nb1Mo0.1B) and the creation of compact and wear resistant coatings. Model experiments were applied using a ramp-wise increase of the anodic potential in order to show the influence of electrolyte components on the discharge initiation and the early stage of the oxide layer growth. The production of PEO layers with technically relevant thicknesses close to 100 μm was conducted in alkaline electrolytes with varying amounts of Na2SiO3•5H2O and K4P2O7 under symmetrically pulsed current conditions. Coating properties were evaluated with regard to morphology, chemical composition, hardness and wear resistance. The addition of phosphates and silicates leads to an increasing substrate passivation and the growth of compact oxide layers with higher thicknesses. Optimal electrolyte compositions for maximum coating hardness and thickness were identified by statistical analysis. Under these conditions, a homogeneous inner layer with low porosity can be achieved. The frictional wear behavior of the compact coating layer is superior to a hard anodized layer on aluminum. 

Aluminum Matrix Composites (AMCs) consisting of high-strength alloys and ceramic reinforcement phases exhibit a high potential for security relevant lightweight components due to their high specific mechanical properties. However, their application as tribologically stressed components is limited because of their susceptibility against fatigue wear and delamination wear. Oxide ceramic protective coatings produced by plasma electrolytic oxidation (PEO) can solve these problems and extend the possible applications of AMCs. The substrate material was powder metallurgically processed using alloy EN AW 2017 and SiC or Al2O3 particles. The influence of material properties like particle type, size and volume fraction on coating characteristics is clarified within this work. An alkaline silicate electrolyte was used to produce PEO coatings with technically relevant thicknesses under bipolar-pulsed current conditions. Coating properties were evaluated with regard to morphology, chemical composition, hardness and wear resistance. The particle type proved to have the most significant effect on the coating properties. Whereas compactness and thickness are not deteriorated by the incorporation of thermodynamically stable alumina particles, the decomposition of silica particles during the PEO processes causes an increase of the porosity. The higher silica particle content decreases also the coating thickness and hardness, which leads in particular to reduction of the wear resistance of the PEO coatings. Finally, different approaches for the reduction of the coating porosity of silica reinforced AMCs are discussed. 

An appropriate corrosion protection is required for transport and storage of high-quality goods and semi-finished parts made from metals. The application of volatile corrosion inhibitors (VCI) as a means of temporary corrosion protection is based on the release of corrosion inhibitors from films, papers, diffusers or oils to the gaseous phase. By adsorption on the metal surface, the inhibitors prevent the degradation of the primary oxide layer and hence impede corrosion. In principle, the anticorrosive effect is independent of the part geometry, because the protected surfaces do not need direct contact with the VCI material. Also, the VCI method does not require costly cleaning of parts prior to further use after transport and storage. The EXCOR jar test is a common method to examine the efficiency of VCI. A metallic sample and a VCI material are exposed in a jar. After conditioning in dry and humid atmosphere, corrosive stress is applied to the sample. To clarify the VCI's mechanism of action, the test steps, their duration and the type of inhibitors were varied. Thus, the operating principle of VCI during the test was identified. The acquired knowledge enables to understand and tailor the corrosion protection by VCI in service.

The influence of adding alfa-Al2O3 nanoparticles with different concentrations into Watt's bath under the application of ultrasound during electrodeposition was investigated by means of electrochemical impedance spectroscopy (EIS) in the galvanostatic mode. The characteristics of the double layer during nickel deposition were affected by the existence of Al2O3 nanoparticles in the electrolyte. In this study, the results of the impedance were correlated with the layer properties, e.g. the mean grain size, the incorporation of particles in the deposit and the strengthening performance. It became obvious that there is a good relationship between the EIS data and layer properties, which makes the impedance spectroscopy a reliable tool for predicting the properties in dispersion coatings. 

This paper introduces a phenomenological calculation approach for the electrolytic pulse deposition of nickel under high polarisation based on an equivalent electrical circuit. In a quasistationary state of the deposition, the electrolyte resistance and double layer parameters are identified by electrochemical impedance spectroscopy and galvanostatic polarisation. The charge-transfer resistance of both the anodic and cathodic electrode double layer is inversely proportional to the current density. This means the overpotentials over the electrode double layers are independent of the current density. For short pulse on-times and off-times (up to 10 ms), the behaviour of the electrolytic cell is mainly determined by the double layer characteristics and the calculation approach therefore allows the prediction of the current-potential behaviour during pulse deposition under high polarisation. For larger pulse widths, the time-dependent evolution of the overpotentials occurring at the electrode/electrolyte interface becomes a determining factor for the cell potential. 

The anodic oxidation process is commonly used to refine the surface of aluminium and its alloys. Compared to the substrate, the alumina layers produced by anodising exhibit an increased hardness and chemical resistance. Thus, the corrosion and wear resistance are generally improved. The coatings are also electrically isolating and may serve decorative purposes. Applying a time-variant, dynamic electrical process control by pulse-current or current-steps is a promising approach to improve the coating properties, which is partially deployed in an industrial scale. In the present work, the influence of dynamic electrical process control on the coating properties is examined by means of a design of experiments (DOE). The effects of various electrolyte compositions and temperatures as well as processing time are considered with regard to coating thickness, hardness, wear resistance and the electrical energy consumption during the formation of the coatings. Information about the statistical significance of the effects of the parameters on the considered properties is obtained by an analysis of variance (ANOVA).

An appropriate corrosion protection is required for transport and storage of high-quality goods and semi-finished parts made from metals. The application of volatile corrosion inhibitors (VCI) as a means of temporary corrosion protection is based on the release of corrosion inhibitors from films, papers, diffusers or oils to the gaseous phase. By adsorption on the metal surface, the inhibitors prevent the degradation of the primary oxide layer and hence impede corrosion. In principle, the anticorrosive effect is independent of the part geometry, because the protected surfaces are not in direct contact with the VCI material. Further, the VCI method does not require costly cleaning of parts prior to further use after transport and storage. A new approach for the evaluation of VCI is presented. A metallic sample is exposed in a chamber filled with air along with a VCI-containing product. In the course of the test, the air is humidified and the sample is then cooled down below the dew point, which leads to condensation of humidity. Electrochemical DC and AC methods, namely polarization resistance measurements and electrochemical impedance spectroscopy, are applied to characterize the state of the metallic surface under the condensed water film. The time-resolved analysis of the measurements provides a basis for the quantitative evaluation of the VCI's anticorrosive effect or a possible corrosion attack. The present work focusses on establishing the interrelations between the electrochemical response of the system and the test regime including initial exposition time of the dry sample along with the VCI in the test volume, the amount of VCI and the dwelling time of the sample under condensed humidity. The validity of the measurements is verified and the range of deviation is estimated. Exemplarily, the anticorrosive effect of various VCI-containing products on mild steel is evaluated. In summary, the presented application-oriented test is proven as a suitable method for the quantified assessment of VCI-containing products.

Volatile corrosion inhibitors (VCI) are a means of temporary corrosion protection based on the release of inhibitors from films, papers, diffusers or oil to the gaseous phase. By adsorption on a metal surface, the inhibitors prevent degradation of the primary oxide layer and impede corrosion. Thus, VCI provide corrosion protection for high-quality goods and semi-finished parts made from metals during transportation and storage. The application of oil on the metal surface for corrosion protection and its removal can be avoided. Due to rapid volatilization of the VCI after unpacking, no costly cleaning of parts prior to further use is required. In a new approach for evaluation of the protective effect of VCI, a metallic sample is exposed in a small chamber filled with air alongside a VCI-containing product. The air is humidified and the sample is cooled down under dewpoint, which leads to condensation of humidity and represents corrosive stress. The state of the metallic surface under the condensed water film is characterized by electrochemical methods. The present work demonstrates the evaluation of the anticorrosive effect of various VCI-films on mild steel. In summary, the application-oriented test allows for quick and quantified evaluation of VCI-containing products with a tabletop device.

Volatile corrosion inhibitors (VCI), which are incorporated in packaging materials like films, papers, plastic racks etc., are a suitable means for temporary corrosion protection during transport and storage of metallic products. For the evaluation of the corrosion protection effect of VCI-containing products, numerous tests are established. In most cases, principally, a metallic sample is exposed to a climatic stress in presence of a VCI-containing product and the protection effect of the VCI is evaluated afterwards by visually assessing the occurrence/absence of corrosion products at the sample surface. In a newly proposed test method and a dedicated device, the evaluation of the VCI-containing product is based on electrochemical measurements at the interface between the metallic sample and a film of condensed water. The water film is precipitated during the test by actively cooling the metallic sample below the dew point, which imposes a corrosive stress on the sample surface. With a simple direct current potentiostat for polarization resistance measurement, the state of the metallic surface (corrosion-active, passive) is registered objectively during the test and thus the corrosion protection effect of the VCI is evaluated. In the present paper, the test method and the dedicated device are disclosed in detail. On the basis of a statistical analysis of a sample of independently repeated tests, limit values are established for the quality assessment of VCI products. Different commercially available VCI films are evaluated and the results are compared to the state-of-the-art jar test procedure based on German TL 8135. In conclusion, the proposed test reproducibly provides objective and quantitative information on the corrosion protection effect of VCI-containing products. 

In the recent decades, various process windows have been found for plasma anodising of aluminium surfaces to produce wear-resistant alumina coatings. The coatings offer a high hardness and provide an excellent bonding to the substrate material, thus preventing spallation under mechanical or tribological load. In the present study, coatings with a high abrasive wear resistance and a hardness of up to 12GPa were produced in an electrolyte of 5g/l sodium metasilicate and 5g/l potassium hydroxide at a current density of 30A/dm2. To understand the reasons for the high wear resistance, the morphology as well as the phase composition and distribution within the coating were examined globally and locally using X-ray diffraction with conventional and grazing incidence and electron backscatter diffraction. The analyses show that the coating globally is comprised of approximately one third of α-alumina, one third of γ-alumina and one third of amorphous alumina with locally varying phase content. 

The increasing multi-functionality of parts and assemblies in several fields of engineering demands, amongst others, highly functionalised surfaces. For the different applications, on the one hand, there is a need to scale up surface modification processes originating in the nano- and micro-scale. On the other hand, conventional macro-scale surface refinement methods offer a huge potential for application in the said nano- and micro-scale. The anodic oxidation process, which is established especially for aluminium and its alloys, allows the formation of oxide ceramic layers on the surface. The build-up of an oxide ceramic coating comes along with altered chemical, tribological and electrical surface properties. As a basis for further investigations regarding the use of the anodic oxidation process for micro-scale-manufacturing, the scale effects of oxalic acid anodising on commercially pure aluminium as well as on the AlZn5.5MgCu alloy are addressed in the present work. The focus is on the amount of oxide formed during a potentiostatic process in relation to the exchanged amount of charge. Further, the hardness of the coating as an integral measure to assess the porous oxide structure is approached by nano-indentation technique. 

The anodic oxidation process is a common method for the surface modification of aluminium and its alloys. The increasing application of high-strength aluminium alloys therefore represents a challenge, since alloying elements, amongst them copper, significantly disturb the coating formation during anodising. Hence, flaws arise in the oxide layers and lead to the deterioration of their performance. Recent investigations have indicated the possibility of extenuating the negative influence of the alloying elements on the coating formation by applying time-variable electrical regimes. In case of the current density as the control factor in the coating process, this approach is related to as dynamic current control. For the anodic oxidation of AlCu4Mg1 (EN AW-2024), the effect of dynamic current control on the oxide layer properties is investigated by using a design of experiments (DOE). The parameter variation includes starting ramps, a step-wise change of the current density in the process and pulse current at electrolyte temperatures of 5 °C and 15 °C. A solution of 20 vol% sulphuric acid with an addition of oxalic acid or nitric acid is used as the electrolyte. The produced oxide coatings are examined with regard to their thickness, hardness, their performance in the scratch test and their current density-potential behaviour in diluted NaCl solution. Further, the electrical energy consumption during the anodisation is considered. The results are evaluated with the help of an analysis of variance (ANOVA).

The application of Al/Mg compound materials for lightweight structures is limited by their corrosion susceptibility. The primary corrosion attack takes place at the Mg component. This may partly be caused by galvanic corrosion and partly by the insufficient formation of a natural passive layer on magnesium. Therefore, oxide coatings were produced on the co-extruded Al/Mg compounds by simultaneous plasma electrolytic oxidation (PEO). A silicate-alkaline and a silicate-phosphate-alkaline electrolyte were used for the coincident production of coatings with a thickness of several 10 microns on both the aluminum and the magnesium component. The inherent flaws of the coating (pores, cavities) allow for the infiltration with an epoxy-based sealant. The electrochemical behavior of the magnesium component covered with the oxide coatings with and without sealing was compared with reference to the unmodified surface. The surface modification (PEO w/wo sealing) significantly decreases the corrosion susceptibility of the Mg component, and thus of the compound.

The anodic oxidation process is an established means for the improvement of the wear and corrosion resistance of high-strength aluminum alloys. For high-strength aluminum-copper alloys of the 2000 series, both the current efficiency of the anodic oxidation process and the hardness of the oxide coatings are significantly reduced in comparison to unalloyed substrates. With regard to this challenge, recent investigations have indicated a beneficial effect of nitric acid addition to the commonly used sulphuric acid electrolytes both in terms of coating properties and process efficiency. The present work investigates the anodic oxidation of the AlCu4Mg1 alloy in a sulphuric acid electrolyte with additions of nitric acid as well as oxalic acid as a reference in a full-factorial design of experiments (DOE). The effect of the electrolyte composition on process efficiency, coating thickness and hardness is established by using response functions. A mechanism for the participation of the nitric acid additive during the oxide formation is proposed. The statistical significance of the results is assessed by an analysis of variance (ANOVA). Eventually, scratch testing is applied in order to evaluate the failure mechanisms and the abrasion resistance of the obtained conversion coatings. 

In recent years, the growing environmental awareness has led to the development of energy-efficient products, for example by the replacement of steel as construction material by aluminium to save weight and thus increase the energy-efficiency of mobile systems. However, to address the energy-efficiency of a product holistically, the energy consumption of the production process also has to be considered. For the anodic oxidation process of the AlMgSi1 aluminium alloy, the influence of the sulphuric acid concentration, the glycolic acid concentration, the electrolyte temperature and current density on coating thickness, hardness, ductility and wear resistance (scratch test), as well as on the consumption of electrical energy and process costs for the oxide coating formation are investigated using a design of experiments (DOE). An analysis of variance (ANOVA) is conducted to assess the significance of the parameters for the coating and process properties. For the considered range of the process parameters a significant enhancement of thickness, hardness and wear resistance of the coatings alters also energy consumption during anodic oxidation and process costs, which are assessed by material flow cost accounting (MFCA). 

Enhanced use of lightweight materials, namely aluminium and magnesium, requires the application of appropriate production techniques. Self-tapping screws represent an innovative joining technology. High-strength aluminium alloys can be used as screw material. Stringent requirements regarding the wear resistance of screw surfaces result from the thread-forming process. These requirements are met by oxide ceramic conversion layers produced by hard anodizing. Based on application-oriented testing methods, the influence of hard anodized layers on the screwing behaviour and susceptibility to stress corrosion cracking of high-strength aluminium screws is examined. 

With the progress in materials science and production technology and the establishment of light-weight design in many fields of the industry, the application of light metals no longer requires only mechanical strength, but also a significant protection of the material against wear and corrosion. Hard and wear-resistant oxide coatings on aluminium are produced by plasma electrolytic oxidation (PEO). During PEO, a conversion of the aluminium substrate to a ceramic oxide takes place. While the role of strength-giving alloying elements like Cu, Mg/Si, Zn, and Zn/Cu on the PEO process has selectively been subject of investigation in the past, the significance of the alloy composition for the service properties of the coatings is still unknown. Therefore, the performance of PEO coatings produced on the widely used commercial high-strength alloys AlCu4Mg1 (EN AW-2024), AlMgSi1 (EN AW-6082), and AlZn5.5MgCu (EN AW-7075) is examined with regard to their behaviour in the rubber-wheel test according to ASTM G65 and the current density-potential behaviour of the substrates with undamaged and worn coatings in dilute NaCl solution. To give a reference to the unalloyed material the testings were carried out also on Al 99.5 (EN AW-1050) which was treated in an adjusted PEO process. Although differences in the conversion of intermetallic phases during PEO and the phase composition of the coatings on the various substrates are determined, the service properties are hardly depending on the alloying elements of the investigated aluminium materials. The wear rates in the rubber-wheel test are low for all the alloyed samples. The current density-potential curves show a decrease of the corrosion current density by approximately one order of magnitude compared to the bare substrate. Eventually, previous wear of the coatings does not deteriorate the corrosion behaviour. PEO layers on technically pure aluminum can resist the testing regimes if they are prepared in an electrolyte with an elevated silicate content and without additional hydroxide ions, during a longer process time.

Plasma electrolytic oxidation (PEO) is a common means for the surface modification of light metals. However, PEO of magnesium substrates in dilute electrolytes generally leads to the formation of coatings consisting of unfavorable MgO magnesium oxide. By incorporation of electrolyte components, the phase constitution of the oxide coatings can be modified. Coatings consisting exclusively of MgAl2O4 magnesium-aluminum spinel are produced by PEO in an electrolyte containing hydroxide, aluminate, and phosphate anions. The hardness of the coatings is 3.5 GPa on Martens scale on average. Compared to the bare substrate, the coatings reduce the corrosion current density in dilute sodium chloride solution by approx. one order of magnitude and slightly shift the corrosion potential toward more noble values. 

Magnesium and its alloys are increasingly in use as lightweight construction materials. However, their inappropriate corrosion and wear resistance often prevent their direct practical use. The plasma electrolytic oxidation (PEO) is a promising, environmentally friendly method to improve the surface characteristics of magnesium materials by the formation of oxide coatings. These PEO layers contain components of the applied electrolyte and can be shifted in their composition by increasing the concentration of the electrolyte constituents. Therefore, in contrast to the use of conventional low concentrated electrolytes, the process results in more stable protective coatings, in which electrolyte species are the dominating constitutes. In the present work, the influence of the composition of highly concentrated alkaline silicate electrolytes with additives of phosphate and glycerol on the quality of PEO layers on the magnesium alloy AZ31 was examined. The effect of ultrasound coupled into the electrolyte bath was also considered. The process was monitored by recording the electrical process variables with a transient recorder and by observation of the discharge phenomena on the sample surface with a camera. The study was conducted on the basis of a design of experiments. The effects of the process parameter variation are considered with regard to the coatings thickness, hardness and corrosion resistance. Information about the statistical significance of the effects of the parameters on the considered properties is obtained by an analysis of variance (ANOVA). 

Plasma electrolytic oxidation (PEO), also called micro-arc oxidation (MAO), is an innovative method in producing oxide-ceramic coatings on metals, such as aluminum, titanium, magnesium, zirconium, etc. The process is characterized by discharges, which develop in a strong electric field, in a system consisting of the substrate, the oxide layer, a gas envelope, and the electrolyte. The electric breakdown in this system establishes a plasma state, in which, under anodic polarization, the substrate material is locally converted to a compound consisting of the substrate material itself (including alloying elements) and oxygen in addition to the electrolyte components. The review presents the process kinetics according to the existing models of the discharge phenomena, as well as the influence of the process parameters on the process, and thus, on the resulting coating properties, e.g., morphology and composition. 

Plasma electrolytic oxidation (PEO), also called plasma anodizing or micro arc oxidation (MAO), is an appropriate method to improve surface characteristics of valve metals. Micro arc discharges, which appear at the working piece in an aqueous electrolyte under strong anodic polarization, are typical for this process. The discharge initiation is discussed controversially. Contradicting theories, which are mainly based on investigations of tantalum, exist concerning the meaning of electrolytic anions, which are initially incorporated in the anodic film. Dual step polarization and PEO experiments were carried out on aluminum, magnesium, and titanium, which are in practical use as lightweight construction materials. For Al 99.5, AZ31, and TiAl6V4 it could be shown that the incorporation of electrolytic anions in the anodic film is not required for the ignition process. Also, the influence of electrolyte conductivity on the ignition voltage was investigated by polarization experiments with silicate, aluminate, and hydroxide solutions using the example of AZ31. It has been demonstrated that not the electrical electrolyte conductivity, but its specific electron injection ability at the electrolyte/substrate interface defines the ignition voltage. This injection ability depends on the kind and concentration of the electrolytic anions.

Plasma electrolytic oxidation (PEO) is a method to obtain protective coatings on metallic light-weight construction materials. Here, the workpiece receives a strong anodic polarisation in a suitable aqueous electrolyte, which leads to the formation of a passive layer and a gaseous shell. Afterwards, plasma electrolytic discharges appear on the substrate surface and convert it into a ceramic layer. The properties of the passive layer are influenced by the selected substrate/electrolyte combination and are essential for the PEO process-initiation and characteristics. In this work, a new method for the systematic investigation of the substrate/electrolyte interactions during the pre-discharge stage is presented. The procedure is carried out by a polarisation experiment and allows for a quantitative characterisation of the passivation behavior, based on a small electrolyte volume. The method is used to investigate a literature-known electrical conduction mechanism on passive films formed on magnesium, by cross-comparison between different Mg and Al materials. In addition, the influence of phosphate, glycerol, and fluoride on the passivation behaviour of the Mg alloy AZ31 in an alkaline environment is considered and quantified. The results provide an explanatory approach for the positive influence of toxic fluorides within the electrolyte on the morphology of PEO layers on magnesium.