NiP (P > 10 wt.%) coatings are amorphous coatings whose structure can be transformed by heat treatment into a crystalline structure and hardened by precipitation of Ni3P. In this study, NiP coatings and composite ones with SiC nanoparticles were produced by electrodeposition, and their structural transformation by heat treatment was studied using differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The microhardness and the scratch and corrosion resistance of the coatings were evaluated and compared before and after different heat treatments. The results showed that in as-plated condition, the addition of SiC particles in the coatings did not modify the microstructure, microhardness, or electrochemical behavior. However, the SiC particles’ role was disclosed in combination with heat treatment. Composite coatings that were heat treated at 300◦C had higher microhardness and scratch resistance than the pure NiP one. In addition, composite coatings maintained their scratch resistance up to 400◦C, while in the case of the NiP ones, there was a reduction in scratch resistance by heating at 400◦C. It was also concluded that heating temperature has the main role in hardness and corrosion resistance of NiP and composite coatings, rather than heating time. The optimum heat-treatment protocol was found to be heating at 360◦C for 2 h, which resulted in a maximum microhardness of about 1500 HV0.02 for NiP and its composite coating without sacrificing the corrosion resistance.

Electrodeposition of NiP composite coatings with nano and sub-micron sized SiC has been carried out to investigate the possibility of replacing hard chromium coatings. The composition and structure of the coatings were evaluated by energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) analysis, respectively. Microhardness was measured by Vickers indentation and polarization measurements were carried out to study the corrosion behavior of the coatings. The results showed that submicron particles can be codeposited with a higher content as compared to nano sized ones. However, even if a smaller amount of the nano-sized SiC particles are incorporated in the coating, the contribution to an increasing microhardness was comparable with the submicron sized particles, which can be related to the higher density of codeposited particles. SiC particles did not change the anodic polarization behavior of NiP coatings in a 3.5% NaCl solution. Finally, the effect of heat-treatment on the coatings properties at 400 °C for 1 h was studied to investigate the contribution of particles and heat-treatment on hardness and corrosion properties. It was found that the heat-treatment doubled the microhardness and changed the anodic polarization behavior of the coatings from passive to active with respect to the as-plated conditions.

High-pressure torsion (HPT) processing was applied to cast pure Mg pieces and its effects on microstructure, hardness and tensile properties as well as corrosion resistance were evaluated. The microstructure of the processed samples was examined by electron backscatter diffraction (EBSD) and the mechanical properties were determined by microhardness and tensile tests. Corrosion resistance of the samples was studied via electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. The results showed that HPT refined the grain size of Mg very effectively from millimeters in the cast structure to a few micrometers homogeneously through the thickness and created a basal texture on the surface. One or five turns of HPT produced no significant difference in the grain size of the processed Mg but the hardness was a maximum after one turn. The yield strength of the cast Mg was increased by seven times whereas the corrosion resistance was not affected by the HPT processing.

High-pressure torsion (HPT) processing was applied to cast pure magnesium, and the effects of the deformation on the microstructure, hardness, tensile properties and corrosion resistance were evaluated. The microstructures of the processed samples were examined by electron backscatter diffraction, and the mechanical properties were determined by Vickers hardness and tensile testing. The corrosion resistance was studied using electrochemical impedance spectroscopy in a 3.5% NaCl solution. The results show that HPT processing effectively refines the grain size of Mg from millimeters in the cast structure to a few micrometers after processing and also creates a basal texture on the surface. It was found that one or five turns of HPT produced no significant difference in the grain size of the processed Mg and the hardness was a maximum after one turn due to recovery in some grains. Measurements showed that the yield strength of the cast Mg increased by about seven times whereas the corrosion resistance was not significantly affected by the HPT processing. 

This study aimed to deposit high entropy alloy (HEA) coatings with five different elements, Ni, Co, Cu, Mo, and W, from a single aqueous bath. The influence of pH, current density, and complex agent on the composition of deposited coating was examined. It was shown that Mo and W were codeposited mainly with Ni and Co. pH had the most impact on the codeposition of reluctant elements like Mo and W, while current density had the minimum effect. The deposited coating had a metallic, dense, and nodular morphology with configurational entropy of around 1.6 R.

The purpose of the study is to assess the influence of SiC particles and heat treatment on the wear behaviour of Ni–P coatings when in contact with a 100Cr6 steel. Addition of reinforcing particles and heat treatment are two common methods to increase Ni–P hardness. Ball-on-disc wear tests coupled with SEM investigations were used to compare as-plated and heat-treated coatings, both pure and composite ones, and to evaluate the wear mechanisms. In the as-plated coatings, the presence of SiC particles determined higher friction coefficient and wear rate than the pure Ni–P coatings, despite the limited increase in hardness, of about 15%. The effect of SiC particles was shown in combination with heat treatment. The maximum hardness in pure Ni–P coating was achieved by heating at 400◦C for 1 h while for composite coatings heating for 2 h at 360◦C was sufficient to obtain the maximum hardness. The difference between the friction coefficient of composite and pure coatings was disclosed by heating at 300◦C for 2 h. In other cases, the coefficient of friction (COF) stabilised at similar values. The wear mechanisms involved were mainly abrasion and tribo-oxidation, with the formation of lubricant Fe oxides produced at the counterpart.

Selective laser melting is one of the additive manufacturing technologies that have been known for building various and complicated shapes. Despite numerous advantages of additive manufacturing technologies, they strongly influence the microstructure and typically show a relatively high surface roughness. In this study, maraging steel was produced by selective laser melting (SLM), and its microstructure, hardness and corrosion behavior before and after heat treatment were studied and compared to traditionally manufactured ones (wrought, forged samples). In addition, the effect of electropolishing on the surface roughness was evaluated. The microstructural study was carried out by scanning electron microscopy equipped with electron backscattered diffraction in three different sections: parallel to the top surface (xy), transverse cross section (xz) and longitudinal cross section (yz). The same characterization was applied to heat-treated samples, austenitized and quenched as well as the aged ones. The results showed that selective laser melting produced a fine grain martensitic structure (in the as-printed condition) with a surface roughness (R-a) of about 10 mu m. There was no sign of preferred texture or anisotropy in the microstructure of as-print SLM materials. The SLM microstructure was similar in all 3 sections (xy, xz and yz). Despite finer microstructure, nano-hardness and corrosion behavior of SLM and conventional wrought maraging steel in heat-treated conditions were similar. Aging resulted in the maximum nano-hardness and the minimum corrosion potential values. Precipitation has the main role in both hardness and corrosion behavior. Electropolishing was optimized and reduced the surface roughness (R-a) by 65%.

In this study, electrodeposition of Ni-P composite coatings has been carried out to investigate the possibility of replacing hard chromium coatings. Therefore, electrodeposition of Ni-P based composite coating with different SiC particle size (50 nm, 100 nm and 500 nm) or B4C (500 nm) was performed. The coating’s composition was evaluated by energy dispersive spectroscopy (EDS), microhardness of the coatings was measured by Vickers indentor and polarization measurements were carried out to study the corrosion behavior of the coatings. The results showed that B4C particles can codeposit in higher percent respect to SiC ones. Ceramic particles increased microhardness of Ni-P coatings to 700HV0.01. The polarization behavior of all the coatings in 3.5% NaCl was similar in as plated state proving that particles did not hindered the passive behaviour. Finally, the effect of heat-treatment (at 400 ºC for 1 hour) on the coating’s properties was studied to compare the contribution of particles and heat-treatment on mechanical and corrosion properties of the coatings. Heat-treatment increased the coating’s microhardness and changed the anodic polarization behavior of the coatings respect to the as plated conditions.

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.

This study is focused on finding optimised conditions for electrodeposition of NiP and NiP/SiC coatings, which enhance the coatings' microhardness. Both the effect of particles and the effect of heat treatment at 400°C for 1 h on the microhardness of the coating were studied. The effects of pulse electrodeposition parameters including duty cycle, frequency, and peak current density on the composition of NiP and NiP/SiC composite coatings were examined, and the results were compared with those from direct current plating. Pulse plating increased the current efficiency of NiP deposition while decreasing the phosphorus content of these coatings in comparison to direct plating, resulting in higher microhardness values. It was also shown that wt.%P in NiP coating depends not only on peak current density but also on bath charge of pulse plating. Pulse plating parameters (duty cycle and frequency) and the low incorporation of SiC particles did not affect microstructure or the microhardness of the coatings, while heat treatment was the main factor that increased microhardness.

In this study, electrodeposition of NiP composite coatings with the addition of SiC 100 nm was carried out on low carbon steel studying the effect of additives (sodium dodecyl sulfate, saccharin), particles load (10 or 20 g/L) and current density (1, 2 and 4 A/dm2). As a benchmark, coatings from an additive-free bath were also deposited, despite additives being essential for a good quality of the coatings. The coating's morphology and composition were evaluated by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS). It was shown that by addition of sodium dodecyl sulfate (SDS), pure NiP coating with a higher P content was achieved, and their morphology changed to nodular. SDS also reduced the codeposited fraction of SiC particles, while saccharin increased it. SiC loading and current density had less impact respect to the additives on codeposition of SiC particles. Finally, the microhardness of NiP coatings did not increase linearly by codeposition of SiC particles. 

This study aimed to investigate the influence of process parameters on crack formation in laser alloying or cladding of grey cast iron. For this purpose, the effects of laser power and feeding rate of Ni-based alloying powders were examined. The microstructure and hardness of the coating and the interface of the coating with cast iron (bonding zone) were studied. The results showed that the dilution ratio is crucial in crack formation, explaining the challenges in achieving a defect-free laser alloying coating on cast iron. The higher dilution ratio of laser alloying resulted in higher dissolved carbon and bigger (Nb, Ti)C carbides formation than in laser cladding coatings. In this study, cracks appeared in the coating due to the combination of the high amount of carbide in the layer and a sharp hardness gradient at the interface with the cast iron substrate. An empirical relation was proposed for dilution ratio as a function of specific energy density, which combined the most critical process parameters on crack formation.

Commercially pure copper rod was successfully subjected to severe plastic deformation by applying the continuous equal channel angular pressing (ECAP-Conform) method at room temperature. Microstructural characterizations of copper rod samples at various stages of plastic deformation were carried out by optical microscopy and electron backscatter diffraction methods. X-ray diffractometry and Kernal average misorientation were used for dislocation density estimations. Microstructural evaluations revealed grain size change of 30 mm for the initial annealed copper rod to less than 5 mm and even 100 nm for severely deformed samples. Mechanical behaviors of samples after different deformation stages were characterized using tensile and hardness tests. The ultimate tensile strength of the severely deformed copper rod was increased threefold by ECAP-Conform while elongation halved in comparison to the initial annealed copper. Low-temperature annealing of severely plastic deformed samples led to bi-modal grain size distribution and lowering of strength accompanied by the increase of elongation. Tensile properties of severely deformed and then annealed copper samples showed around a 40% increase in both ultimate tensile strength and elongation in comparison to the initial annealed copper rod.

The paper reveals benefits of multi-disciplinary computer simulation and parametric studies in the design of silver plating process for improved coating distribution. A finite element model of direct current silver plating is experimentally validated for an Assaf panel without agitation. The model combines tertiary current distribution with Butler–Volmer electrode kinetics and computational fluid dynamics at a very low flow-rate. The effect of charge transfer coefficients on the throwing power of the process is quantified for the studied geometry, and variation of cathodic current density and exchange current density is investigated. A simpler model based on secondary current distribution is employed to quantify the effect of electrolyte conductivity on the throwing power of the process. A model combining tertiary current distribution and computational fluid dynamics has been developed and experimentally validated for simulation of complex telecom component electroplating in agitated electrolyte. The effect of current density on the process throwing power is quantified. Recommendations regarding modeling methodology and the effect of electrochemical and process parameters on the thickness distribution have been developed.

The use of recycled (hereafter called secondary) aluminum alloys is increasing more and more in light of sustainability as the energy needed for their production is much lower than in the case of the primary alloys and they may have mechanical properties comparable to those of the latter. Most of the secondary aluminum alloys are used to fabricate parts through casting processes, which may need further machining operations to get the part's final shape. While the mechanical properties of the secondary aluminum alloys have been comprehensively addressed in the literature and correlated to the different intermetallic particles that characterize their microstructure, the same is not true when addressing machinability. In this framework, the paper investigates the machinability of one primary and two secondary aluminum alloys in terms of cutting forces and surface finish after turning trials carried out at fixed cutting parameters. A detailed characterization of the alloys’ microstructure was carried out making use of both optical and scanning electron microscopy to identify the size, morphology, and distribution of intermetallics. The highest cutting force was registered when machining the primary alloy, being characterized by the highest specific cutting energy. The surface damage in terms of tearings induced by cutting was comparable between the primary and secondary alloys. In contrast, the different roughness features that characterize the machined surfaces of the considered alloys can be partly ascribed to the different intermetallics they present. Nevertheless, the surface topography analysis results must be interpreted based on the specific application.

This work studies the particular mechanism of environmental stress corrosion cracking (SCC) that has been described to interest stainless steel products, like climbing anchors, installed in sea areas. The failure analysis of several broken anchors was carried out. The samples were collected in different parts of the world, always from climbing structures close to the sea. The analysis confirmed the stress corrosion mechanism of degradation, giving also important information about the specific environments causing the metal fracture. These results are in agreement with a few previous works about this subject and are in the frame of the larger topic of SCC of austenitic stainless steel at room temperature. Moreover, some corrosion tests were carried out on stainless steel samples simulating the operation conditions, after contamination with electrolytes at different concentration. The tests are performed in order to better understand the degradation mechanism and to evaluate the influence of some environmental parameters over the susceptibility to SCC. With these experimental data, a possible interpretation model has been proposed together with some reasonable solutions for the material selection process, considering the problem's characteristics and the multiple alternatives available nowadays for climbing materials.

Cerium-based conversion coatings have been considered as an effective alternative to hazardous and carcinogenic chromate-based coatings used in the treatment of metal surfaces such as aluminium alloys. However, there is still considerable debate over the mechanism by which these coatings are formed on different alloys and microstructure features. In the current work, Ce-based conversion coatings were deposited on Rheo-HPDC Al-Si alloys by immersion in water-based solutions of cerium nitrate. Effect of deposition parameters including immersion time and Ce(NO3)3.6H2O concentration on the corrosion resistance and the morphology of coatings was investigated. In addition in some experiments, NaCl was added to the cerium based solution in order to accelerate the deposition of the conversion coating and also to understand the coating formation mechanism. Electrochemical behaviour of the treated aluminium alloys was evaluated in the solution of 0.05 mol/L NaCl using polarization test and electrochemical impedance spectroscopy (EIS) measurements. The morphology and distribution of the cerium-based conversion coatings on the aluminium alloys were studied using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS) and X-ray photoelectron spectroscopy (XPS). Conversion treated substrates in all solutions were shown to possess improved corrosion resistance in comparison to the untreated samples. Immersion time and Ce(NO3)3.6H2O concentration slightly affect the deposition and the passivation capability of the cerium hydroxide/oxide layers. SEM images revealed that the deposition of cerium is more favoured in some cathodic areas including iron-based intermetallics and/or eutectic silicon phase. This phenomenon helps to block the active interfaces between these cathodic sites and the aluminium matrix, which is prone to localized corrosion in chloride ion containing environments. 

The electrochemical behavior of a low silicon aluminum alloy cast by the conventional and rheo-high-pressure die cast processes is evaluated using polarization test and electrochemical impedance spectroscopy in 0.01 M, 0.05 M, 0.1 M, and 0.6 M sodium chloride solutions. Compared to the conventional high-pressure die cast process, rheocasting introduces some alterations in the microstructure including the presence of aluminum grains with different sizes, formed at different solidification stages. According to the results of the anodic polarization test, conventional cast and rheocast samples show similar breakdown potentials. However, the rheocast samples present enhanced oxygen reduction kinetics compared to the conventional cast sample. Based on scanning electron microscopy examinations, localized microgalvanic corrosion is the main corrosion mechanism for both alloys and it initiates at the interface of aluminum with iron-rich intermetallic particles which are located inside the eutectic regions. The corrosion further develops into the eutectic area. Although the rate of the cathodic reaction can be influenced by the semisolid microstructure, according to the results of anodic polarization and electrochemical impedance spectroscopy tests, the corrosion behavior is not meaningfully affected by the casting process.

Electropolymerization of polypyrrole coatings in the presence and absence of sodium nitrate was applied on rheo-cast Al-4.5% Si alloy and pure aluminum. The results showed that the eutectic silicon phase and intermetallic particles in the alloy's microstructure increase the electrodeposition rate in comparison to the pure aluminum substrate. The electrochemical and microstructural studies show that the polypyrrole coatings are able to protect the surface due to the barrier properties and the passivation protection provided by the reduction of the conductive polymer. The coating electrodeposited from sodium nitrate-containing electrolyte presented improved protection for longer immersion time. Localized formation of a thick oxide layer as a result of the drastic galvanic coupling at the polypyrrole/aluminum interface leads to blister formation and failure of the coating. It was revealed that the coating could be deposited into the porosities produced by the casting related defects, but in most cases, this affects the corrosion protection leading to imminent failure.

Cerium-based conversion coatings were deposited on Rheo-High Pressure Die Cast (HPDC) Al-Si alloys by immersion in cerium nitrate aqueous solutions. Rheocast Al-Si alloys have a heterogeneous microstructure and present a challenge for the conversion treatment. Different parameters were studied to optimize the conversion coating, and NaCl or H2O2 were also added to the solution to modify or accelerate the deposition process. The mechanism of the coating formation was studied by means of focused ion beam milling (FIB) assisted SEM. The results show that applying cerium-based conversion coating to Al-Si alloys, is possible and a preferential deposition is obtained due to the presence of iron-rich intermetallic particles inside the eutectic region. The formation mechanism of selectively deposited cerium-based conversion coating includes dissolution of aluminium matrix, selective dissolution of aluminium from the noble intermetallic particles, oxidation of iron from the intermetallic particles, and the deposition of cerium hydroxide/oxide layer. The results reveal that the improvement in corrosion resistance in the presence of selectively deposited cerium-based conversion coating is more significant compared to the homogenous coating deposited from the conversion solution containing H2O2. 

Cerium-based conversion coatings were deposited on high pressure die cast (HPDC) Al-Si alloys using an immersion method. Hydrogen peroxide and sodium chloride were added to the conversion solution to accelerate the coating formation and to understand its formation mechanism. These studies showed that the deposition of cerium hydroxide/ oxide conversion layer starts from iron-rich intermetallic particles, which are located inside the eutectic region and then the coating growth continues to cover the entire alloy surface. This phenomenon passivates the active interfaces between iron-rich intermetallic particles and/ or the eutectic silicon phase and the aluminum matrix, which are prone to localized corrosion in chloride ions containing environments. Accordingly, values of the total impedance in EIS measurements significantly increased for the treated substrates. Morphologies of the conversion coatings and the oxidation state of cerium compounds were found to be dependent on the composition of the solution and the presence of chloride ions and/ or hydrogen peroxide. Aluminum alloy with higher silicon content showed a more active surface during immersion in the conversion solution. This makes it more difficult to be treated using aggressive conversion solutions. 

The effect of the electrolyte composition and the deposition potential range on the physical properties and possible corrosion protection effect of polypyrrole coatings on rheocast aluminum–2.5 % silicon alloy is investigated. Solutions with different concentrations of sodium nitrate and an electron transfer mediator reagent were used for the electrodeposition. Polypyrrole coating is able to hinder the entrance of electrolyte. Upon the penetration of chloride ions, the coating can induce passivation of the alloy's surface by its reduction. The thickness of the coating and its ion-barrier properties, controlled by the electrodeposition conditions, are shown as the important factors influencing the protection efficiency. However, localized drastic galvanic coupling at the polypyrrole/aluminum interface forms blisters, causes failure, and limits the possible protection.

Effect of solution chemistry on the electropolymerization and the electrochemical properties of polypyrrole coatings on aluminum is studied by means of electrochemical techniques, scanning electron microscopy (SEM), and x-ray photoelectron spectroscopy. It is shown that the protection effect of the coating in long-term exposures and when exposed to more concentrated NaCl solutions depends on the chemistry of electropolymerization electrolyte. The results show that nitrate anions passivate the aluminum substrate during the electropolymerization process. The resulting coating is less prone to blistering in a NaCl solution and probably due to its higher electrochemical activity presents a higher anodic protection effect. The galvanic interaction of polypyrrole coating with aluminum in a NaCl solution is directly observed using focused ion beam-assisted SEM.

Novel layered double hydroxides (LDHs) based coatings developed in-situ on aluminum alloys are recognized to provide the substrate with improved corrosion protection. LDH layers have gained prominent attention due to their barrier properties and ions exchange capability, together with compositional flexibility and low environmental impact. In this work, diverse MgAl LDHs layers are developed on AA5005 as a surface conversion treatment prior to applying an acrylic clearcoat. The work aims to assess the potential LDH layers of to improve the filiform corrosion (FFC) resistance of the AA500 substrate. The effect of the synthesis time and the presence of urea on the FFC susceptibility are investigated. The performance of the different synthesis conditions was compared and shown to be more effective to increase FFC resistance when well-defined crystals are formed. The findings suggest that MgAl-LDHs mitigate the extent of filiform corrosion of acrylic paint coated AA5005. The FFC inhibition was found to be qualitatively proportional to the pitting potential measured over the LDHs conversion layers.

Coatings incorporating nanoparticles of molybdenum and tungsten disulfide (MoS2 and WS2)—known for their lubricating properties—are applied to orthodontic stainless steel wires to verify if there is an improvement in terms of tribological properties during the sliding of the wire along the bracket. To simulate in vitro sliding of the wire along the bracket and evaluate friction 0.019 × 0.025 inches orthodontic stainless steel (SS) wires were subjected to the application, by electrodeposition, of Ni, Ni + MoS2, and Ni + WS2 . The samples produced were analyzed with scanning electron microscopy and assessment of resistance to bending. Thirty-two test conditions have been analyzed, arising from the combination of four types of coatings (SS bare wires and strings with three types of coating), two types of self-ligating bracket (Damon Q, Ormco and In-Ovation R, GAC International), two bracket-wire angles (0◦ and 5◦), two environments (dry and wet). Analyses carried out on the samples show acceptable coatings incorporating MoS2 and WS2 and a resistance of coatings after a minimum bending. In “dry conditions” a statistically significant decrease in friction occurs for wires coated with MoS2 and WS2 if associated with the In-Ovation bracket. In “wet conditions” this decrease is observed only in isolated test conditions. Analysis of the wires after sliding tests show little wear of the applied coatings. Nanoparticles are acceptable and similar in their behavior. Improvements in terms of friction are obtained pairing coatings incorporating MoS2 and WS2 with the In-Ovation bracket in dry conditions. 

MgAl-layered double hydroxides (LDHs) thin films, exhibiting two distinct surface morphologies (Platelet and Cauliflower-like), were synthesized directly on the aluminum substrate. The as-prepared films were further modified with graphene due to the chemical inertness of graphene and its capability to act as a possible physical barrier against ionic media. The morphology and structure of MgAl-LDH/graphene composite films are fully characterized. The corrosion resistance properties were analyzed through Electrochemical impedance spectroscopy and the results were further fitted using “ZSimpWin” software to evaluate coating behavior. The graphene was found to interact with the LDH structure and provide another pathway for the corrosion reactions and results in improve LDHs corrosion resistance properties. The sealing effect of graphene resists the aggressive media penetration and caused an increase of one order magnitude in impedance modulus of MgAl-LDHs. The enhancement in corrosion resistance properties is attributed to the graphene impermeable behavior against corrosive species confirmed by physical and electrochemical characterizations.

Overly fast corrosion degradation of biodegradable magnesium alloys has been a major problem over the last several years. The development of protective coatings by using biocompatible, biodegradable, and non-toxic material such as chitosan ensures a reduction in the rate of corrosion of Mg alloys in simulated body fluids. In this study, chitosan/TiO₂ nanocomposite coating was used for the first time to hinder the corrosion rate of Mg19Zn1Ca alloy in Hank's solution. The main goal of this research is to investigate and explain the corrosion degradation mechanism of Mg19Zn1Ca alloy coated by nanocomposite chitosan-based coating. The chemical composition, structural analyses, and corrosion tests were used to evaluate the protective properties of the chitosan/TiO₂ coating deposited on the Mg19Zn1Ca substrate. The chitosan/TiO₂ coating slows down the corrosion rate of the magnesium alloy by more than threefold (3.6 times). The interaction of TiO₂ (NPs) with the hydroxy and amine groups present in the chitosan molecule cause their uniform distribution in the chitosan matrix. The chitosan/TiO₂ coating limits the contact of the substrate with Hank's solution.

The Assaf panel arrangement was used for evaluating pulse reverse plating processes and optimisation of the throwing power (TP) of complex three-dimensional (3D) geometries. Two different electroplating processes were investigated: an acid copper bath and a cyanide silver bath without additives. It has not been possible to establish a direct correlation factor for TP obtained with the Assaf panel and the 3D objects included in the trials. Nevertheless, the Assaf panel was found to be a useful tool for preliminary process parameter optimisation. The copper bath needs agitation to deposit coatings of good quality, whereas the silver bath obtains the best throwing power without agitation. The latter is probably due to inhibition by adsorbed cyanide.

The influence of electroplating parameters on throwing power (TP) is studied in additive-free silver cyanide solutions under direct current and pulse reverse electroplating conditions. It is found that the best TP is obtained when no agitation of the electrolyte is applied. The most important parameters for controlling the TP are the cathodic current density, the anodic to cathodic charge ratio, and the ratio between the anodic and cathodic current densities. Guidelines for process optimisation are given.

This paper discusses how anodic pulses and periodic current reversion influence electrodeposition. Depending on the involved metal and electrolyte, very different effects can be observed and taken advantage of. The Wagner number, Wa, describing the current distribution is shown to be useful for predicting the throwing power at low frequencies of current reversion, even in complex electrochemical systems, but is less useful at higher frequencies. Passivation can occur due to oxide formation, super-saturation of metal salts or depletion of complexing agents at the electrode surface. Furthermore, dissolution and desorption processes in the anodic period can have strong influence on the succeeding cathodic electrocrystallisation affecting preferred crystal orientation, intrinsic stress and current efficiency. A literature survey is combined with experiments from silver plating from a cyanide bath.

mCBEEs is an acronym for: Advanced integrative solutions to Corrosion problems beyond micro-scale: towards long-term durability of miniaturised Biomedical, Electronic and Energy systems. It is a doctoral student training network funded by the European Commission under the Marie Sklodowska-Curie Action scheme in the same way as the recently reported training network SELECTA that is focusing on smart electrodeposited alloys for environmentally sustainable applications.

Additive manufacturing opens new possibilities for designing light-weight structures using aluminium alloys. The microstructure of two Al alloys and their corrosion resistance in NaCl and natural seawater environments were investigated. The newly designed Al-Mn-Cr-Zr based alloy showed a higher corrosion resistance than reference AlSi10Mg alloy in both environments in as printed and heat-treated conditions. The corrosion initiated in the Al matrix along the precipitates in the alloys where the Volta potential difference was found the highest. The coarser microstructure and precipitate composition of the new Al-alloy led to the formation of a resistant passive film which extended the passivity region of the Al-Mn-Cr-Zr alloy compared to the AlSi10Mg alloy. The effect of heat treatment could be seen in the microstructure as more precipitates were found in between the melt pool boundaries, which affected the corrosion initiation and slightly the pitting resistance. Overall, this study shows that a newly designed Al-alloy for additive manufacturing has a suitable corrosion resistance for applications in marine environments.

Corrosion properties of two Al–Si alloys processed by Rheo-high pressure die cast (HPDC) method were examined using polarization and electrochemical impedance spectroscopy (EIS) techniques on as-cast and ground surfaces. The effects of the silicon content, transverse and longitudinal macrosegregation on the corrosion resistance of the alloys were determined. Microstructural studies revealed that samples from different positions contain different fractions of solid and liquid parts of the initial slurry. Electrochemical behavior of as-cast, ground surface, and bulk material was shown to be different due to the presence of a segregated skin layer and surface quality.

This study analysed the influence of the codeposition of SiC particles with different sizes: 50 nm, 500 nm and 5 μm, and the type of bath agitation (stirring or ultrasonic) on the electrocrystallisation of nickel coatings. The composites matrix microstructure was analysed by means of SEM, EBSD and XRD, to evaluate the grain size, crystal orientation, and internal stresses and was benchmarked against pure nickel samples electrodeposited in equivalent conditions. The codeposition of nano- and microsize particles with an approximate content of 0.8 and 4 vol.%, respectively, caused only a minor grain refinement and did not vary the dominant < 100 > crystal orientation observed in pure Ni. The internal stress was, however, increased by particles codeposition, up to 104 MPa by nanoparticles and 57 MPa by microparticles, compared to the values observed in pure nickel (41 MPa). The higher codeposition rate (11 vol.%) obtained by the addition of submicron-size particles caused a change in the grain growth from columnar to equiaxial, resulting in deposits with a fully random crystal orientation and pronounced grain refinement. The internal stress was also increased by 800% compared to pure nickel. The ultrasound (US) agitation during the deposition caused grain refinement and a selective particle inclusion prompting a decrease in the content of the particles with the larger particles. The deposits produced under US agitation showed an increase in the internal stresses, with double values compared to stirring. The increase in the deposits microhardness, from 280 HV in pure Ni to 560 HV in Ni/SiC submicron-US, was linked to the microstructural changes and particles content.

The present paper describes the study of the synergism between the matrix microstructure and reinforcement phase in electrodeposited nanocomposite coatings. Adding hard nanoparticles into the metallic matrix leads to hardening of the coating. The effects of particle load, size and dispersion on hardening as well as their influence on metal microstructure refinement were studied. The relative contributions of strengthening factors in Ni/nano-SiC composites, namely, Hall–Petch strengthening, Orowan strengthening, enhanced dislocation density and particles incorporation, were evaluated. The production of various coatings under different stirring conditions and powders resulted in dissimilarities in the incorporation of particles. The Hall–Petch relationship for pure nickel was determined using samples produced under different current densities. Additionally, the grain refinement resulting from the particle codeposition and agitation mode were identified as influential factors in grain-size strengthening. Dislocation density strengthening was significant in electrodeposits produced using ultrasonic agitation, while it was negligible in layers produced under other conditions. Particles codeposition affected the magnitude of Orowan strengthening, resulting in cases where strengthening was negligible despite the presence of particles. The sum of contributions and the modified Clyne methods were used to calculate the hardness of the composites based on the contribution of each strengthening factor, and the calculation results were in good agreement with experimental data. The wear behavior of the composites was analyzed by pin-on-disk measurements, and the results correlated with the strengthening mechanisms. Particle size, dispersion and content increased the strengthening effects as well as the hardness and wear resistance of the coatings.

This work has explored the surface modification of SiC submicron- and nanoparticles, and its influence on the particles' chemical behaviour and deposition rate in the electroplating of composite Ni/SiC coatings. SiC particles with different sizes (50, 60, 300 and 500 nm) were codeposited in their “as-produced” state. The ζ-potential measurements and alkaline titration for the “as-produced” particles showed differences in chemical behaviour for particles of different sizes, reporting pH buffering effect, even though the particles were inert and chemically the same (SiC). A surface treatment (ST) based on nitric acid was developed in an attempt to set a similar surface state, therefore a similar chemical behaviour in all particles. The ζ-potential measurements and alkaline titration of the “surface treated” particles showed similar results, independently of the size of particles. The pH buffering effect also decreased considerably by the ST. The codeposition rate was modified by the ST differently for each size compared to their as-produced state. The content of SiC50 and SiC500 was doubled (≈2% and ≈19%), tripled for SiC300 (≈7%) and more than halved for SiC60 (≈2%). The microhardness of these composite deposits was linked to the changes in the SiC codeposition.

This work has explored the potential of using pulse reverse (PR) plating for increasing the deposited fraction of SiC nanoparticles. Two PR waveforms were selected, a short pulse (500 Hz) waveform and a newly modified and adapted pulsed sequence that equals the plating thickness to the particles’ diameter (50 nm) for the on-time and half-diameter during the anodic time. The pulse waveforms were designed with 4 and 10 A⋅dm⁻² as the average current density and cathodic peak current density, respectively. Direct current (DC) deposits at the same values were also produced as reference. In all cases, the codeposition of nano-SiC particles influenced the microstructure. The electroplating under DC 10 A⋅dm⁻² showed the strongest grain refinement and increased the content of the particles (up to 2% vol.) PR using high-frequency achieved a similar codeposition. The maximum particle incorporation was achieved by the proposed adapted pulse waveform, doubling the SiC content produced by other set-ups (up to 4% vol.); increasing the microhardness of the deposits to 400 HV, despite no grain refinement compared to the pure metal. From these results, it was observed a relationship between the influence of the plating method on the microstructure, the particle content, and the material's hardness.