Soft Sparking Research Articles

Effects of dispersed α-Al2O3 particles into a cold-sprayed aluminium coating on its subsequent oxidation by the PEO process

The present study focused on the use of a duplex surface treatment combining cold-spray deposition and plasma electrolytic oxidation (PEO) to produce an aluminium metal matrix composite coating, including dispersed α-Al2O3 particles, with improved tribological properties. Al/α-Al2O3 composite coatings were first deposited by cold-spray, with various thickness and proportion in α-Al2O3 particles, and, then partially oxidized by PEO under various processing durations and sparking regimes (arcs or soft regime). The feasibility of cold-spraying thick, compact and adherent aluminium coatings containing well-dispersed α-Al2O3 particles (up to 14 vol%) was demonstrated in this work. It was also pointed out that the addition of hard α-Al2O3 particles into the spray composition tends to densify the deposited aluminium coating. This was related to a stronger peening effect which, in turn, decreases the growth kinetic of the subsequent PEO oxide layer. The presence of dispersed α-Al2O3 particles was found to promote the formation of the corundum alumina phase in the PEO oxide layer by triggering the transition to the soft sparking regime earlier. It was also observed that dispersed α-Al2O3 particles remain unaffected throughout the PEO oxide layers formed within the conventional arcs sparking regime while they undergo a morphological transformation within the specific soft sparking regime. This was explained by considering the different type of micro-discharges that initiate during each regime. Finally, sliding wear tests revealed that the incorporation of α-Al2O3 particles into the cold-sprayed coating resulted in a slight decrease in the friction coefficient and the wear rate of the produced PEO layers.

Role of anodic precursor layer thickness on PEO coatings: Energy consumption and long-term corrosion performance

PEO coatings with different thickness of anodic precursor films (5, 10, 20 and 40 μm) were successfully developed on AA2024 with the aim of determining how the thickness of anodic films affects the development of PEO film, structural growth, surface morphology, phase composition, and associated long term corrosion resistance properties. Compared to direct PEO treatment, reductions in the energy consumption (kW.h.m2.μm−1) of 71 %, 41 %, and 17 % are obtained at similar PEO processing conditions for the pre-anodized specimens of 40 μm, 20 μm, and 10 μm film thickness, respectively, while the time to current drop for above specimens reduced to 86.2 %, 63.3 % and 33.3 %, associated to the early formation of the “soft sparking” regime. The results suggest the effectiveness of pre-anodization on the PEO coatings for minimum energy consumption, developed explicitly on 20 and 40 μm anodic film, whereas overall PEO on anodic precursors exhibited a thicker oxide layer, homogenous pore size distribution, and long-term corrosion protection comparable to the original PEO layer. Based on the energy consumption and corrosion resistance of PEO on anodic precursor, a model of PEO coating growth is proposed, which can be considered a thorough insight towards highly developing energy-efficient PEO for practical applications.

Growth pattern of soft-spark micro-arc oxide coating on titanium alloy in silicon anion electrolyte

Soft-spark micro-arc oxidation (MAO) is considered a potential solution for eliminating the porosity on the surface coating of titanium alloys during the MAO process. However, the mechanisms behind soft-sparking and the growth of coatings on Ti alloys are not yet fully understood. This study aimed to investigate the growth pattern of soft-spark MAO coating on titanium alloys by using sodium silicate as the electrolyte and manipulating the soft-sparking duration. The research focused on analyzing the positive and negative pulse voltage-time response curves, surface micromorphology, surface composition, cross-sectional structure, phase composition, dynamic potential polarization curve, microhardness, and thickness growth curve during the soft-spark process. The research findings revealed that soft spark discharges occurred in the plasma atmosphere near the surface of the external porous layer. The sparks penetrated the weak points of the amorphous interface layer (existing between the MAO coating and the substrate), forming filamentary discharges within the coating. This phenomenon led to the formation of a significant amount of rutile phases and bubble pores within the soft-spark coating, promoting the expansion of soft-sparks into the coating and facilitating the growth of the soft-spark coating. While the inner hardness of the soft-spark MAO film reached 1146 HV, the plasma atmosphere discharge also led to the formation of numerous filamentary channels and gas pores within the coating. Consequently, the coating's corrosion resistance did not show any improvement.

The Effects of the Pre-Anodized Film Thickness on Growth Mechanism of Plasma Electrolytic Oxidation Coatings on the 1060 Al Substrate.

To increase the density of the micro-arc oxide coating, AA 1060 samples were pretreated with an anodic oxide film in an oxalic acid solution. Plasma electrolytic oxidation (PEO) was performed to investigate the effect of the thickness of the pre-anodic oxide film on the soft-sparking mechanism. The experimental results revealed that the PEO coating phases with different thicknesses of the pre-anodized films contained both Al and gamma-alumina (γ-Al2O3). The pre-anodized film changes the final morphology of the coating, accelerating the soft sparking transition and retaining the soft sparking. At a pre-anodized film thickness of ≤7.7 μm, the anodized films thickened before being broken through. When the pre-anodized film thickness was ≥13.1 μm, partial dissolution of the anodized films occurred before they were struck through. Two growth mechanisms for PEO coatings with different pre-anodized film thicknesses were proposed.

Plasma electrolytic oxidation of tantalum in an aluminate electrolyte: Effect of cathodic polarization and frequency

The effect of cathodic polarization on plasma electrolytic oxidation (PEO) of the refractory metal of tantalum is investigated in 10 g/l NaAlO2+2 g/l KOH under 1000 and 100 Hz. Ceramic coatings are formed under various cathodic-to-anodic current densities ratios (R = jc/ja) of 0, 0.6, 1.3 and 2.3. For PEO under 1000 Hz, the plasma discharges intensify with the increase of R from 0 to 1.3, with optical emission from Ta being detected at later stage of PEO under cathodic polarization. However, excessive R ratio of 2.3 has caused early extinguishment of the plasma discharges. Correspondingly, thicker coatings are formed as the R ratio increases from 0 to 1.3, and the coating under R = 1.3 exhibits a most porous outer layer. A thin and compact coating is formed under R = 2.3. It is also found that the application of cathodic polarization increases the Na content in the resultant coatings, with a new crystalline phase NaTaO3 being formed under R = 2.3. Cathodic polarization also decreases the corrosion resistance of the coatings. Surface wettability tests show that the coatings formed under R = 1.3 are the most hydrophilic. PEO under 100 Hz shows some differences in discharge and coating formation. Larger sized discharges are also observed at the later stage under R = 0.6, but Ta species are detected at a delayed time. For the R values of 1.3 and 2.3, patches of soft sparking occur on the sample surface, leading to non-uniform coatings. This study shows that both cathodic polarization and frequency significantly affect the PEO process. Moreover, compared with the PEO of Al, tantalum responds quite differently to cathodic polarization. Mechanisms of coating formation have been illustrated: Protons and other cations are attracted by cathodic electric field into the coatings, where they undergo a series of reactions to significantly affect the PEO behaviors.

How carbon black nanoparticles affect the occurrence of soft-sparking during plasma electrolytic oxidation

The effect of dispersed carbon black nanoparticles in the electrolyte on the plasma electrolytic oxidation of aluminium under soft sparking regime is investigated. Increasing the concentration of particles reduces the breakdown voltage. It also makes the transition to soft sparking to occur earlier, which can favour a more homogeneous coating. However, it is shown that a too high concentration of particles can be detrimental to the coating morphology despite an apparent soft sparking regime characterized by a decrease in anodic voltage.

Fast formation of a black inner α‐Al2O3 layer doped with CuO on Al–Cu–Li alloy by soft sparking PEO process

AbstractForming high‐temperature α‐Al2O3 phase under soft sparking is an intriguing phenomenon in plasma electrolytic oxidation (PEO) of Al alloys, which contradicts the low energy input of the process. In this study, α‐Al2O3 doped with black CuO is formed beneath an amorphous white outer layer on Al–Cu–Li alloy by PEO in a dilute silicate electrolyte under soft sparking. In comparison, reddish coatings with dominating γ‐Al2O3 are formed under the conventional plasma discharges, although blackish inner layer with α‐Al2O3 can also be exposed by heavily polishing the samples. In order to know the underlying mechanism, temperatures at the coating surface and the underlying substrate have been monitored by a thermocouple under the conventional and soft sparking PEO regimes, respectively. Interestingly, high temperatures are detected in the case of soft sparking rather than PEO with strong discharges. The formation of CuO, quartz, and cristobalite within the soft sparking coating also supports the existence of high temperature. Hence, the formation of α‐Al2O3 under soft sparking can be resolved to the conventional thermal activation mechanism, without the need of seeking other plausible explanations. Thermal condition evaluation for soft sparking PEO suggests that values of the effective thermal conductivity during PEO process for the outer layer and the barrier layer at the coating/substrate interface might be lower than ∼0.05 and ∼0.0017 W m−1 K−1, respectively. It is believed that the amorphous structure of the outer and barrier layers effectively blocks the heat dissipation, facilitating the formation of a highly wear‐resistant inner layer with α‐Al2O3, CuO, and the other high‐temperature species under soft sparking.

Rational design of compact ceramic coating on SiCp/Al composites by tailoring soft sparking discharge of plasma electrolytic oxidation

The characteristics of PEO processes on SiCp/Al composite in aluminate electrolyte under the influence of negative pulse were comparatively investigated, aiming to tailor the soft sparking discharge states, thus achieving the compact ceramic coating and providing a deep understanding of the mechanisms involved. Tracking the variation trend of element optical emission intensity by OES technology reflects the influence of negative voltage on the evolution of the spark state, and the results show that large negative voltage accelerates the transition from arc sparking discharge to soft sparking discharge. When the PEO process completely enters the soft spark discharge state, the lowest electron density can also be kept at 1.06 × 1022 m−3, reaching the local thermodynamic equilibrium condition. At this time, the electron temperature in the plasma discharge zone is about 4000 K. In addition, the coating surface roughness value decreases with the increase of negative voltage, and the introduction of negative voltage effectively reduces the irregular convex structures and the macropores in the coating, due to inhibiting destructive high-intensity spark discharge by the soft sparking discharge.

Effects of soft sparking on micro/nano structure and bioactive components of microarc oxidation coatings on selective laser melted Ti6Al4V alloy

We used the soft sparking mode to fabricate microarc oxidation coatings containing micro/nano-scale pores and bioactive Ca/P components on Ti6Al4V alloy samples formed by selective laser melting. The effect of soft sparking on the microstructure and corrosion resistance of the coatings and the codeposition mechanism of the electrolyte anions in the soft sparking layer were investigated using different negative/positive charge ratios. The results showed that the negative charge significantly decreased the intensity of microarc discharge, resuling in the soft sparking phenomenon, which promotes the formation of a thin amorphous TiO2 layer at the barrier layer/substrate interface. In turn, this interface facilitated the electron tunneling and aggregation of the electrolyte anions, which leads to soft sparking at voltages significantly lower than the breakdown voltage of the anodic oxide film on the selective laser melted Ti alloys. Soft sparking promoted the codeposition of the electrolyte anions, including PO43− and Ca2+ ions, in the form of bulk amorphous phases in the coating formed by soft sparking. The soft sparking layer contained amorphous phases, which were corroded more readily than that the outer ceramic layer. However, the submicro/nano-scale pores in the soft sparking layer improved its corrosion resistance. With an increase in negative/positive charge ratio, the effect of soft sparking on the surface morphology of the MAO coating weakened, and the amounts of Ca and P codeposited in the soft sparking layer increased. Finally, the corrosion resistance of the coating was found to first increase and then decrease, reaching the maximum at the 1.1 ratio.

Циклические закономерности проявления акустической эмиссии при плазменно-электролитическом оксидировании Al–Mg сплава в биполярном режиме

The paper analyzes the features of the acoustic emission (AE) signal generation during plasma-electrolytic oxidation (PEO) of the AMg6 aluminum alloy in a bipolar (anode-cathode) pulsed mode within each cycle of voltage application. The authors studied the range of PEO modes that almost completely covers all standard technological modes for processing aluminum alloys by the current densities (6–18 A/dm2) and current ratio in half-cycles (0.7–1.3), which allowed fixing and studying the AE accompanying the formation of oxide layers for various purposes. For the first time, due to AE registration, a new PEO stage was identified, in which there was no microarc breakdown to the substrate, but which was accompanied by an increase in the layer thickness, and the nature of which has not yet been determined. According to the known features of the oxidation stages, the authors systematized the repetitive forms of AE manifestation in the cycles of exposure and identified their five types and three subtypes. The study shows that the approach used to establish the PEO stages by the “acoustic emission amplitude” parameter has poor accuracy, since it does not take into account the form of signals and the half-period of their registration. Therefore, the authors developed and tested a new approach for analyzing AE frames synchronously with the cycles of change in the forming voltage during PEO, and proposed a new “acoustic-emission median” parameter, which allows identifying the main types and subtypes of signals accompanying the oxidation stages. An experimental study of the proposed AE parameter was carried out to identify these PEO stages, which confirmed the operability, high accuracy and sensitivity of the proposed parameter to the subtypes of AE signals recorded at the cathode stage of “soft sparking”. The latter is of particular interest, since it is a means of studying a given oxidation stage with a resolution equal to the exposure cycle.

Corrosion and wear resistance of coatings produced on AZ31 Mg alloy by plasma electrolytic oxidation in silicate-based K2TiF6 containing solution: Effect of waveform

In this research, plasma electrolytic oxidation coatings were prepared on AZ31 Mg alloy in a silicate-based solution containing K 2 TiF 6 using bipolar and soft sparking waveforms with 10, 20, and 30% cathodic duty cycles. The coatings displayed a net-like surface morphology consisted of irregular micro-pores, micro-cracks, fused oxide particles, and a sintered structure. Due to the incorporation of TiO 2 colloidal particles and the cathodic pulse repair effect, most of the micro-pores were sealed. Long-term corrosion performance of the coatings was investigated using electrochemical impedance spectroscopy during immersion in 3.5 wt.% NaCl solution up to 14 days. The coating grown by the soft sparking waveform with a 20% cathodic duty cycle having the lowest porosity (6.2%) and a sharp layer concentrated in F element at the substrate/coating interface shows the highest corrosion resistance. The friction coefficient of this coating has remained stable during the sliding even under 5 N normal load, showing relatively higher wear resistance than other coatings. The coating produced using the equivalent unipolar waveform, as the reference specimen, showed the highest friction coefficient and the lowest wear resistance despite its highest micro-hardness.

Soft Sparking Discharge Mechanism of Micro-Arc Oxidation Occurring on Titanium Alloys in Different Electrolytes

Soft sparking during micro-arc oxidation can form a ceramic coating with high hardness and high bond strength on titanium alloy while avoiding the continuous strong micro-arc that can damage the substrate properties and the integrity of the coating. Existing studies have reported that the soft spark discharge is significantly influenced by the electrolyte anions, and the detailed mechanism of its influence remains unclear. Therefore, we considered four monolithic electrolytes, namely Na2B4O7, NaF, Na3PO4, and Na2SiO3, for the bipolar pulsed micro-arc oxidation (MAO) treatment of the Ti6Al4V alloy to investigate the mechanism of the soft sparking discharge and the affections of different electrolytes on the soft sparking discharge. The results showed that soft spark discharges were observed in both Na2SiO3 and Na3PO4 electrolytes while not in Na2B4O7 and NaF electrolytes. We attributed this situation to the fact that the deposition of Si and P elements in the coating changed the structure and passivation ability of the coating and affected the rate of ion transport and electron tunneling in the coating, resulting in forming a thick and dense, soft spark MAO inner layer. Additionally, the soft sparking discharge facilitated particle deposition and did not destroy the structure of the initial film layer, and also had no significant effect on the corrosion resistance.

A Systematic Study of the Role of Cathodic Polarization and New Findings on the Soft Sparking Phenomenon from Plasma Electrolytic Oxidation of an Al-Cu-Li Alloy

Understanding the role of cathodic polarization and soft sparking is critical for plasma electrolytic oxidation (PEO). In this study, PEO of an Al-Cu-Li alloy has been carried out under cathodic to anodic current density ratio (R) from 0 to 3.3. Controlled potential tests and electrochemical impedance microscopy are also adopted. The results show that increased cathodic polarization improves the long-term oxide growth efficiency until an optimum soft sparking regime is reached at R = 1.2, after that the efficiency decreases and damages to the coatings occur. Interestingly, anodic potential drop, which was considered one of the characteristics of soft sparking, is absent in some cases under R = 1.2, and the coatings under R = 1.2 is also featured by a white outer layer enriched with cations. Excessive cathodic polarization (R = ∼2.0–3.3) leads to the compact coatings with highest impedance values at the early PEO stage (300 s), but they deteriorated rapidly. The complex PEO behaviors with different cathodic polarization has been explained in terms of the intercalation of hydrogen species, mass transportation affected by H2 evolution, charge extraction and hydrogen induced stresses. Reciprocally, controlled potential tests indicate that anodic polarization also suppresses the subsequent cathodic hydrogen evolution.

Analysis of electrical response, gas evolution and coating morphology during transition to soft sparking PEO of Al

The soft sparking regime of Plasma Electrolytic Oxidation (PEO) of valve metals attracts increasing attention as it enables a better process control with improved energy efficiency and coatings with enhanced performance to be obtained. Here, the discharges softening phenomenon was characterised by evaluation of changes in electrical signal, composition of gaseous products and morphology of the metal-oxide interface in PEO coatings on Al. The coatings were formed using two electrical regimes retarding or promoting soft sparking conditions. Harmonic analysis of PEO process has been performed using independent evaluation of the positive and negative half-waves of polarisation signal. The composition of gas evolved during the PEO process was evaluated by a quantitative gas analyser. Coatings were characterised by scanning and transmission electron microscopy with energy dispersive spectroscopy and small area electron diffraction. It was found that discharge softening is accompanied with a decrease in oxygen evolution rate, an increase in equivalent capacitance of anodic process as well as structural and compositional changes near the metal-oxide interface. The experimental findings provide further support to the explanation of discharge softening phenomenon by narrowing the active zone at the metal-oxide interface due to intercalation of hydrogen species into anodic alumina under cathodic polarisation. Such mechanistic understanding allows rational regime selection, in-situ process control and optimisation of the coating properties to be performed that paves the way to intellectual manufacturing approach based on careful process monitoring in operando.

The effect of process current parameters on the properties of oxide layers under plasma electrolytic oxidation of AMg6 alloy

The effect of current density and current ratio in the cathodic and anodic half-cycles during prolonged (180 minutes) plasma electrolytic oxidation (PEO) of AMg6 wrought alloy on the oxide layer wear and corrosion resistance were studied. It was established that the best wear resistance is achieved in the oxide layers obtained in the “soft sparking” mode (negative-to-positive pulse ratios of 1.15–1.30) at current densities of 9–15 A dm−2, and the best set of wear resistance and corrosion resistance – in the oxide layers obtained in “symmetrical” mode (negative-to-positive pulse ratio of 1.00).

Preparation of Wear-Resistant Coating on Ti6Al4V Alloy by Cold Spraying and Plasma Electrolytic Oxidation

In order to improve the wear resistance of Ti6Al4V alloy, the alloy was first coated with alumina-reinforced aluminum coating (CS-coating) by cold spraying, and then the alloy with CS-coating was processed by plasma electrolytic oxidation (PEO) under unipolar mode and soft sparking mode, respectively, to prepare wear-resistant PEO coatings. For comparison, Ti6Al4V alloy without CS-coating was also subjected to PEO treatment. The microstructure, phase composition, hardness, and wear resistance of the PEO coatings formed on Ti6Al4V alloy with and without CS-coating were investigated. The results revealed that PEO coatings formed on Ti6Al4V alloy with CS-coating under soft sparking mode contained more α-Al2O3, possessed larger thickness, more compact microstructure, and higher microhardness than that formed under unipolar mode. The PEO coating formed on Ti6Al4V substrate was mainly composed of TiO2 and had pores and cracks. Among all these coatings, PEO coating formed on Ti6Al4V alloy with CS-coating under soft sparking mode exhibited the best wear resistance with a wear rate of 1.18 × 10−5 mm3/(Nm), which was only 15.28% of that of the Ti6Al4V substrate. The investigation indicated that the combination of cold spraying and PEO under soft sparking mode is a promising technique for improving the wear resistance of titanium alloy.

Toward rational design of ceramic coatings generated on valve metals by plasma electrolytic oxidation: The role of cathodic polarisation

Plasma electrolytic oxidation (PEO) has attracted significant attention as a promising eco-friendly technology for the deposition of ceramic-like oxide coatings with superior wear- and corrosion resistance as well as biomedical, catalytic, magnetic, dielectric and optical properties. However, the industrial implementation of PEO has been hindered by a poor understanding of the mechanisms underlying plasma-assisted electrochemical coating formation. This study compares the characteristics of PEO processes on different valve metals in a dilute aqueous solution of NaOH and Na2SiO3 under pulsed unipolar and bipolar polarisation conditions. The focus is given to the influence of the nature of the valve metal on the transition to the soft sparking regime characterised by reduced energy consumption whilst yielding sintered coating materials enriched with crystalline phases. In-situ dynamic voltammetry analysis was employed to study the effects of the net current ratio and local negative charge injection using diagnostic pulses embedded in the polarisation signal. It has been demonstrated that soft sparking is a characteristic feature of valve metals such as Mg, Al, Zr and Ta that form insulating surface oxides with negligible electronic conductivity, whereas Ti and Nb form semiconducting oxides, which do not exhibit a characteristic voltage drop, although some features of spark softening were detected. This generalisation paves a way for implementation of a model known as ‘digital twin’ to the rational design of the PEO processes for deposition of the functional ceramics.

The influence of EDTA‐2Na on microstructure and corrosion resistance of PEO coating for AA1060 alloy

AbstractIn this study, plasma electrolytic oxidation (PEO) process was applied to AA1060 aluminum alloy in an alkaline‐based electrolyte with different concentrations of EDTA‐2Na. The investigation of coatings was concentrated on sparks, phase, structure, morphology, and corrosion resistance. The whole process presented a “soft spark” regime which proved by the reduction of light and acoustic emission with increase of current. The results of SEM and EDS showed that more discharge channels were found under surface and the proportion of silicon in the inner layer increased for the sample treated in solution with 5 g/L EDTA‐2Na, which was attributed to D type discharge causing some light emission invisible on sample surface. The polarization test presented a better corrosion resistance with the increase of EDTA‐2Na. However, EIS measurement showed a bigger corrosion resistance for outer layer of sample prepared with the addition concentration up to 3 g/L that meant outer layer played a more critical role in terms of corrosion resistance.

Morphological evolution and burning behavior of oxide coating fabricated on aluminum immersed in etidronic acid at high current density

Micro arcs on metal surface immersed in alkaline electrolyte have been studied by many works, but that in acidic electrolyte are rarely reported. In this work, anodizing of aluminum was carried out in etidronic acid (HEDP) at high current density to investigate the formation behavior of coating. SEM images indicate that the burning of initial film is actually caused by local oxide cracking due to the increase of compressive stress. The soft spark would appear when voltage reached 300 V, then change to the micro arcs at 400 V, and finally manufacture the outer micro-arc oxide (MAO) layer. Hereafter, the automatic extinguishing of micro arcs gives rise to the formation of inner anodic aluminum oxide (AAO) layer. Moreover, it is evidenced that plasma discharge has few contributions to coating thickening. The barrier layer provides the raw materials for the growth of outer MAO layer. Based on these results, the growth behavior of coating processed in HEDP at high current density is proposed and discussed.

Corrosion Resistance of Plasma Electrolytic Oxidation Coatings on LD7 Alloy in Oxalate and Dihydrogen Phosphate Electrolytes

Two plasma electrolytic oxidation (PEO) coatings were fabricated on LD7 aluminum alloy in oxalate and dihydrogen phosphate electrolytes. The phase composition, morphology and corrosion resistant of the two PEO coatings were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical test. Both PEO coatings presented three-layer structure, i.e., a porous outer layer, a relative dense intermediate layer with nano-size micro-pores and an inner nanoscale barrier layer at the coating/substrate interface. It was found that the porosity of the coating in oxalate electrolyte was lower than that in dihydrogen phosphate electrolyte. The small quantity of the nanosize micro-pores might be attributed to the appearance of "soft spark" in oxalate electrolyte, whereas the large number of micro-pores and cracks should be related to intensive micro-discharges in dihydrogen phosphate electrolyte during PEO process. The compact coating with nano-size micropores in oxalate electrolyte provided better protection than that in dihydrogen phosphate electrolyte from corrosion.