Silane Coatings for Corrosion and Microbiologically Influenced Corrosion Resistance of Mild Steel: A Review

Mild steel continues to be the most extensively used construction material in several industries and constructions. However, corrosion of mild steel in aggressive environments is a major concern. Under the tremendously increasing demand for improving the coatings strategies because of the environmental concerns due to some of the traditional coatings, silane pre-treatments have been emerging as one of the effective solutions, among other strategies. Different approaches, such as adding particles of metal oxide (such as SiO₂, ZrO₂, Al₂O₃, TiO₂ and CeO₂), incorporating plant extracts and impregnating 2D materials into the coatings, have been employed for durable corrosion resistance, including for mitigating enhanced corrosion due to the presence of bacteria. This review discusses the critical mechanistic features of silane coatings such as the role of hydrolysis and condensation in the bonding of silanes with metal surfaces. The factors that influence the performance of the silane coatings for corrosion resistance of mild steel are discussed. In particular, this review provides insight into silane coatings for mitigating microbiologically influenced corrosion (MIC) of mild steel.     

Mechanical Behavior of Bi-Layer and Dispersion Coatings Composed of Several Nanostructures on Ti13Nb13Zr Alloy

Titanium implants are commonly used because of several advantages, but their surface modification is necessary to enhance bioactivity. Recently, their surface coatings were developed to induce local antibacterial properties. The aim of this research was to investigate and compare mechanical properties of three coatings: multi-wall carbon nanotubes (MWCNTs), bi-layer composed of an inner MWCNTs layer and an outer TiO₂ layer, and dispersion coatings comprised of simultaneously deposited MWCNTs and nanoCu, each electrophoretically deposited on the Ti13Nb13Zr alloy. Optical microscopy, scanning electron microscopy, X-ray electron diffraction spectroscopy, and nanoindentation technique were applied to study topography, chemical composition, hardness, plastic and elastic properties. The results demonstrate that the addition of nanocopper or titanium dioxide to MWCNTs coating increases hardness, lowers Young’s modulus, improves plastic and elastic properties, wear resistance under deflection, and plastic deformation resistance. The results can be attributed to different properties, structure and geometry of applied particles, various deposition techniques, and the possible appearance of porous structures. These innovative coatings of simultaneously high strength and elasticity are promising to apply for deposition on long-term titanium implants.     

The Influence of Nanometals,Dispersed in the Electrophoretic Nanohydroxyapatite Coatings on the Ti13Zr13Nb Alloy,on Their Morphology and Mechanical Properties

In this work, nanohydroxyapatite coatings with nanosilver and nanocopper have been fabricated and studied. The presented results concern coatings with a chemical composition that has never been proposed before. The present research aims to characterize the effects of nanosilver and nanocopper, dispersed in nanohydroxyapatite coatings and deposited on a new, non-toxic Ti13Zr13Nb alloy, on the physical and mechanical properties of coatings. The coatings were obtained by a one-stage electrophoretic process. The surface topography, and the chemical and phase compositions of coatings were examined with scanning electron microscopy, atomic force microscopy, X-ray diffractometry, glow discharge optical emission spectroscopy, and energy-dispersive X-ray spectroscopy. The mechanical properties of coatings were determined by nanoindentation tests, while coatings adhesion was determined by nanoscratch tests. The results demonstrate that copper addition increases the hardness and adhesion. The presence of nanosilver has no significant influence on the adhesion of coatings.     

Production and Characterization of the Third-Generation Oxide Nanotubes on Ti-13Zr-13Nb Alloy

In the group of vanadium-free titanium alloys used for applications for long-term implants, the Ti-13Zr-13Nb alloy has recently been proposed. The production of a porous layer of oxide nanotubes (ONTs) with a wide range of geometries and lengths on the Ti-13Zr-13Nb alloy surface can increase its osteoinductive properties and enable intelligent drug delivery. This work concerns developing a method of electrochemical modification of the Ti-13Zr-13Nb alloy surface to obtain third-generation ONTs. The effect of the anodizing voltage on the microstructure and thickness of the obtained oxide layers was conducted in 1 M C₂H₆O₂ + 4 wt% NH₄F electrolyte in the voltage range 5–35 V for 120 min at room temperature. The obtained third-generation ONTs were characterized using SEM, EDS, SKP, and 2D roughness profiles methods. The preliminary assessment of corrosion resistance carried out in accelerated corrosion tests in the artificial atmosphere showed the high quality of the newly developed ONTs and the slight influence of neutral salt spray on their micromechanical properties.     

The Influence of Casein Coatings on the Corrosion Behavior of Mg-Based Alloys

This article discusses the influence of conversion casein coatings with a thickness of about 20 µm on the structure and the corrosion behavior of two magnesium alloys: MgCa2Zn1 and MgCa2Zn1Gd3. Casein is a protein that, along with whey protein, is a part of milk. Casein coatings are appropriate for bone growth because they contain high amounts of calcium and phosphorus. In this work, casein coatings and casein-free coatings were applied on Mg-based alloys using the conversion process. The structure and topography observations were presented. The corrosion behavior was determined by electrochemical and immersion tests, and electrochemical impedance spectroscopy (EIS) in chloride-rich Ringer solution. The obtained results show that conversion casein coatings effectively protect Mg-based alloys against corrosion. This was confirmed by higher corrosion potentials (E_corr), polarization resistances (R_p) derived from Tafel’s and EIS analysis, as well as low hydrogen release. The volume of hydrogen released after 216 h of immersion for casein coatings applied to MgCa2Zn1 and MgCa2Zn1Gd3 alloys was 19.25 and 12.42 mL/cm², respectively. The improvement in corrosion resistance of casein coatings was more significant for Mg alloy dopped with gadolinium. The lower corrosion rate of casein conversion coatings is explained by the synergistic effect of the addition of Gd in the Mg-based alloy and the formation of dense, tight conversion casein coatings on the surface of this alloy.     

A Comparative Study of Aluminium and Titanium Warm Sprayed Coatings on AZ91E Magnesium Alloy

Aluminium (Al) and titanium (Ti) coatings were applied on AZ91E magnesium alloy using a low-pressure warm spray (WS) method. The deposition was completed using three different nitrogen flow rates (NFR) for both coatings. NFR effects on coating microstructure and other physical properties were systematically studied. Microstructural characterization was performed using scanning electron microscopy (SEM), and the porosity was estimated using two methods—image analysis and X-ray microtomography. The coating adhesion strength, wear resistance, and hardness were examined. The protective properties of the coatings were verified via a salt spray test. Decreasing NFR during coating deposition produced more dense and compact coatings. However, these conditions increased the oxidation of the powder. Al coatings showed lower hardness and wear resistance than Ti coatings, although they are more suitable for corrosion protection due to their low porosity and high compactness.     

Corrosion Properties of S-Phase/Cr2N Composite Coatings Deposited on Austenitic Stainless Steel

In order to study the suitability of the S-phase layers as the interlayer for Cr₂N chromium nitride coatings, a number of composite coatings were deposited by the reactive magnetron sputtering (RMS) method on austenitic steel substrates with various initial surface conditions (as delivered and polished) and their corrosion resistance was assessed. Coatings with S-phase interlayer were deposited at three different nitrogen contents in the working atmosphere (15%, 30%, and 50%), which influenced the nitrogen concentration in the S-phase. Coatings with chromium, as a traditional interlayer to improve adhesion, and uncoated austenitic stainless steel were used as reference materials. Detailed microstructural and phase composition studies of the coatings were carried out by means of scanning electron microscopy (SEM), optical microscopy (LM), and X-ray diffraction (XRD) and were discussed in the context of results of corrosion tests carried out with the use of the potentiodynamic polarization method conducted in a 3% aqueous solution of sodium chloride (NaCl). The performed tests showed that the electrochemical potential of the S-phase/Cr₂N composite coatings is similar to that of Cr/Cr₂N coatings. It was also observed that the increase in the nitrogen content in the S-phase interlayer causes an increase in the polarization resistance of the S-phase/Cr₂N composite coating. Moreover, with a higher nitrogen content in the S-phase interlayer, the polarization resistance of the S-phase/Cr₂N coating is higher than for the Cr/Cr₂N reference coating. All the produced composite coatings showed better corrosion properties in relation to the uncoated austenitic stainless steel.     

The Comparative Analysis of the Coatings Deposited on the Automotive Parts by the Cataphoresis Method

The paper presents preliminary research focused on the determination of the influence of surface preparation on the quality of the paint coating obtained by the cataphoresis method (KTL). The tests were carried out on steel parts used in the construction of trailers and truck bodies. The first research group consisted of cold-rolled and chemically cleaned parts, the second group were mechanically cleaned with abrasive blasting. In order to determine the influence of surface treatment on the corrosion resistance of the tested coatings, besides a corrosion test, roughness measurements were also carried out. Tests were performed on the crude surface and after coating deposition. Moreover, tests were supplemented by measuring the thickness of the coating using the magnetic induction method and the hardness with the use micro and nano hardness testers. Measurements of the tribological parameters under dry friction conditions were performed using a T11 tester. The corrosion resistance of the applied coatings was determined in a salt spray test. The obtained results were compared to those that were determined for different zinc coatings. It has been shown that the method of base steel surface preparation affects every measured parameter and property of tested paint coatings. The quality of the coating deposited on the steel base after chemical cleaning is much better than the one applied to the sandblasted surface. The measured corrosion resistance of the tested paint coatings is only greater than the corrosion resistance of the lamellar zinc coating. The other zinc coatings (galvanic, hot-dip, sherardized) show corrosion resistance by an order of magnitude higher.     

Corrosion Resistance and Surface Bioactivity of Ti6Al4V Alloy after Finish Turning under Ecological Cutting Conditions

The influence of cooling conditions and surface topography after finish turning of Ti6Al4V titanium alloy on corrosion resistance and surface bioactivity was analyzed. The samples were machined under dry and minimum quantity lubrication (MQL) conditions to obtain different surface roughness. The surface topographies of the processed samples were assessed and measured using an optical profilometer. The produced samples were subjected to electrochemical impedance spectroscopy (EIS) and corrosion potential tests (E_corr) in the presence of simulated body fluid (SBF). The surface bioactivity of the samples was assessed on the basis of images from scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) analysis. The inspection of the surfaces of samples after turning under dry and MQL conditions revealed unevenly distributed precipitation of hydroxyapatite compounds (Ca/P) with a molar ratio in the range of 1.73–1.97. Regardless of the cutting conditions and surface roughness, the highest values of E_corr ~0 mV were recorded on day 7 of immersion in the SBF solution. The impedance characteristics showed that, compared to the MQL conditions, surfaces machined under dry conditions were characterized by greater resistance and the presence of a passive layer on the processed surface. The main novelty of the paper is the study of the effect of ecological machining conditions, namely, dry and MQL cutting on the corrosion resistance and surface bioactivity of Ti6Al4V titanium alloy after finish turning. The obtained research results have practical significance. They can be used by engineers during the development of technological processes for medical devices made of Ti6Al4V alloy to obtain favorable functional properties of these devices.     

Influence of the Nb and V Addition on the Microstructure and Corrosion Resistance of the Fe-B-Co-Si Alloy

The paper presents a comparison of the results of the corrosion resistance for three Fe-B-Co-Si-based newly developed alloys with the addition of Nb and V. The corrosion performance differences and microstructure variations were systematically studied using scanning electron microscope, electric corrosion equipment, X-ray diffractometer, and differential calorimeter. It has been shown that each alloying addition increased the corrosion resistance. The highest corrosion resistance obtained by potentiodynamic polarization was found for the alloy with both Nb and V addons (Fe₅₇Co₁₀B₂₀Si₅Nb₄V₄) and lowest in the case of the basic four-element Fe₆₂Co₁₅B₁₄Si₉ material. This shows that the proper choice of additions is of significant influence on the final performance of the alloy and allows tailoring of the material for specific applications.     

Effect of Electrodeposition Parameters on the Morphology,Topography and Corrosion Resistance of Epoxy Resin/Zinc Hybrid Coatings

The paper presents the morphology, topography and corrosion behavior of epoxy resin/zinc hybrid coatings obtained by electrodeposition from zinc sulphate electrolyte. The effect of current density and mean diameter size of polymer particles used for electrodeposition of the epoxy resin/zinc coatings on the morphology, topography and roughness of the surfaces were investigated by Scanning Electron Microscopy and Atomic Force Microscopy. The corrosion behavior of the hybrid coatings in 0.5 M sodium chloride solution was evaluated using electrochemical methods. For microbiological corrosion, the effect of sulphate reducing bacteria (SRB) on the surfaces was evaluated using epifluorescence microscopy. The surface roughness before and after bacteria attachment was evaluated using Atomic force microscopy. Polymer particles provide an influence in restricting the growth of zinc crystals as well as a catalytic role in nucleation sites increase. The results of electrochemical tests indicate a very good corrosion resistance of hybrid coatings comparing with zinc coatings. Epifluorescence images demonstrate that hybrid coating surfaces are slightly attacked by sulphate reducing bacteria.     

Effect of Corrosive Medium and Surface Defect-Energy on Corrosion Behavior of Rolled ZK61M Alloy

Magnesium alloys have been widely used as lightweight engineering structural materials, but their service performances are severely restricted by corrosion failure. In this paper, the influence of corrosive medium and surface defect energy on the corrosion behavior of rolled ZK61M alloy was investigated. The corrosion tests were conducted in different concentrations of sodium chloride solution for different durations, and the polarization curves and electrochemical impedance spectroscopy were reported. The surface morphology of rolled ZK61M alloy before and after corrosion tests were analyzed. The results showed that the corrosion tendency became stronger with the increase of the concentration of corrosive medium and the number of surface defects of ZK61M alloy. Moreover, the initial corrosion pattern was the pitting caused by micro galvanic corrosion at the surface defect, which gradually developed into uniform corrosion. Furthermore, the main damage occurred at the grain boundary, resulting in the destruction of grain bonding force and the removal of material along the rheological layer. The oxidation corrosion mechanism was mainly the anodic dissolution mechanism.     

Review of the Effect of Surface Coating Modification on Magnesium Alloy Biocompatibility

Magnesium alloy, as an absorbable and implantable biomaterial, has been greatly developed in the application field of biomaterials in recent years due to its excellent biocompatibility and biomechanics. However, due to the poor corrosion resistance of magnesium alloy in the physiological environment, the degradation rate will be unbalanced, which seriously affects the clinical use. There are two main ways to improve the corrosion resistance of magnesium alloy: one is by adding alloying elements, the other is by surface modification technology. Compared with adding alloy elements, the surface coating modification has the following advantages: (1) The surface coating modification is carried out without changing the matrix elements of magnesium alloy, avoiding the introduction of other elements; (2) The corrosion resistance of magnesium alloy can be improved by relatively simple physical, chemical, or electrochemical improvement. From the perspective of corrosion resistance and biocompatibility of biomedical magnesium alloy materials, this paper summarizes the application and characteristics of six different surface coating modifications in the biomedical magnesium alloy field, including chemical conversion method, micro-arc oxidation method, sol-gel method, electrophoretic deposition, hydrothermal method, and thermal spraying method. In the last section, it looks forward to the development prospect of surface coating modification and points out that preparing modified coatings on the implant surface combined with various modification post-treatment technologies is the main direction to improve biocompatibility and realize clinical functionalization.     

Effect of Functionalization of Reduced Graphene Oxide Coatings with Nitrogen and Sulfur Groups on Their Anti-Corrosion Properties

Electrophoretic production of anticorrosion carbonaceous coatings on copper could be successfully performed by anodic oxidation of negatively charged graphene platelets suspended in an aqueous solution. The various platelets were synthesized by Hummer’s method followed by a hydrothermal reduction in the presence of NH₄SCN which was expected to substitute some parts of graphene structure with nitrogen and sulfur groups. X-ray photoelectron spectroscopy analysis confirmed that the graphene precursors, as well as the coatings, contained typical nitrogen groups, such as pyridinic and pyrrolic, and sulfur groups, such as thiol, thiophene, or C-SO₂. However, due to oxidation during deposition, the qualitative and quantitative composition of the graphene coatings changed relative to the composition of the precursors. In particular, the concentration of nitrogen and sulfur dropped and some thiophene groups were oxidized to C-SO₂. Studies showed the functionalized coatings had a uniform, defect-free, hydrophobic, more adhesive surface than nonmodified films. The corrosion measurements demonstrated that these coatings had better protective properties than the ones without these heteroatoms. This behavior can be assigned to the catalytic activity of nitrogen towards oxidation of C-SO₂ groups to C-SO₃H with oxygen.     

Influence of Tantalum Addition on the Corrosion Passivation of Titanium-Zirconium Alloy in Simulated Body Fluid

Ti-15%Zr alloy and Ti-15%Zr-2%Ta alloy were fabricated to be used in biomedical applications. The corrosion of these two alloys after being immersed in simulated body fluid for 1 h and 72 h was investigated. Different electrochemical methods, including polarization, impedance, and chronoamperometric current with time at 400 mV were employed. Also, the surface morphology and the compositions of its formed film were reported by the use of scanning electron microscope and energy dispersive X-ray. Based on the collected results, the presence of 2%Ta in the Ti-Zr alloy passivated its corrosion by minimizing its corrosion rate. The polarization curves revealed that adding Ta within the alloy increases the corrosion resistance as was confirmed by the impedance spectroscopy and current time data. The change of current versus time proved that the addition of Ta reduces the absolute current even at high anodic potential, 400 mV. The results of both electrochemical and spectroscopic methods indicated that pitting corrosion does not occur for both Ti-Zr and Ti-Zr-Ta alloys, even after their immersion in SBF solutions for 72 h.     

The Effect of Solidification Rate on the Corrosion Resistance of Die-Cast AZ91 Magnesium Alloy

To increase the utilization of die-cast Mg alloys with various shapes in a variety of environments, the corrosion behaviors of commercial die-cast Mg alloys with different thicknesses were investigated in neutral and alkali solutions at ambient temperature. A decrease in the thickness of a specimen leads to an increase in cooling and solidification rates, which, in turn, decreases the size of the eutectic β phases and the interphase distance, thus improving the hardness of the specimen. Specimens with relatively large β phases were more corroded under neutral conditions due to severe galvanic corrosion at the interface between α-Mg and the β phases, whereas they were protected by passivation films formed on the substrate in the alkaline solution. However, in the case of the alloy with thin thickness and high solidification rate, the fine β phases improved corrosion resistance by forming a net structure that acted as a barrier to corrosion propagation of the α matrix. These results suggest that the size and distribution of the eutectic phases should be appropriately controlled, depending on the environment.     

The Influence of Pd and Zr Co-Doping on the Microstructure and Oxidation Resistance of Aluminide Coatings on the CMSX-4 Nickel Superalloy

Pd + Zr co-doped aluminide coatings were deposited on the CMSX-4 nickel superalloy, widely used in the aircraft industry, in order to investigate their microstructure and improvement of oxidation resistance. Palladium was deposited by the electrochemical method, whereas zirconium and aluminum by the chemical vapor deposition (CVD) method. Coatings consist of two zones: the additive and the interdiffusion one. The additive zone contains β–(Ni,Pd)Al phase with some zirconium-rich precipitates close to the coating’s surface, whereas the interdiffusion zone consists of the same β–(Ni,Pd)Al phase with inclusions of refractory elements that diffused from the substrate, so called topologically closed-packed phases. Palladium dissolves in the β–NiAl phase and β–(Ni,Pd)Al phase is being formed. Pd + Zr co-doping improved the oxidation resistance of analysed coatings better than Pd mono-doping. Mechanisms responsible for this phenomenon and the synergistic effect of palladium and zirconium are discussed.     

Effect of Heat Treatments on the Corrosion Resistance of a High Strength Mg-Gd-Y-Zn-Zr Alloy

Magnesium-rare earth (Mg-Re) alloys are very promising structural materials in lightweight industries, while the poor corrosion resistance limits their widespread application. In this work, to provide insights into the functions of precipitate characteristics on the corrosion behaviors of Mg-Re alloys, the influence of heat treatments on the corrosion behavior of Mg-11.46Gd-4.08Y-2.09Zn-0.56Zr alloy was investigated via an immersion test, electrochemical experiment and scanning electron microscope (SEM). The results showed that the corrosion rate of Mg-11.46Gd-4.08Y-2.09Zn-0.56Zr alloy specimens decreased by 17.58% and 20.44% after T5 and T6 heat treatment, respectively. In the heat-treated specimens, the corrosion did not extend further into the matrix but formed fine corrosion grooves along the extrusion direction. The improved homogeneity reduced the residual stress and the β’ precipitate introduced as a corrosion barrier after T5 and T6 heat treatment reduced the corrosion rate of the studied Mg alloy. In addition, the volume fraction of the long-period stacking-ordered (LPSO) phase decreased after heat treatment, which effectively reduced galvanic corrosion and enhanced the protective effect on the Mg matrix.     

Microstructural Evolution and Surface Mechanical Properties of the Titanium Alloy Ti-13Nb-13Zr Subjected to Laser Shock Processing

As a progressive surface-hardening technology, laser shock processing (LSP) can enhance the mechanical properties and extend fatigue life for metallic components through laser-generated high-pressure plasma shock waves. In this work, LSP was used to treat titanium alloy Ti-13Nb-13Zr experimental coupons, and the microstructural response and surface mechanical properties of the Ti-13Nb-13Zr experimental coupons were investigated. After the LSP treatment, the X-ray diffraction (XRD) peaks were shifted without any new phase formation. The surface roughness of the experimental coupons increased, which can be explained by the LSP-induced severe plastic deformation. The LSP treatment effectively enhanced the surface compressive residual stress of Ti-13Nb-13Zr. Meanwhile, the microhardness of the Ti-13Nb-13Zr was also obviously increased after the LSP treatment. The experimental results also showed that the number of shocks times is an important factor in the improvement of surface mechanical properties. LSP treatment with multiple shocks can lead to more severe plastic deformation. The surface roughness, surface compressive residual stress and microhardness of the Ti-13Nb-13Zr experimental coupons shocked three times are higher than those after one shock. What is more, grain refinement accounts for the mechanical properties’ enhancements after the LSP treatment.     

Effect of Al Concentration on Microstructure and Properties of AlNbTiZr Medium-Entropy Alloy Coatings

The AlNbTiZr medium-entropy alloy (MEA) coatings with different Al contents were prepared on N36 zirconium alloy substrates by RF magnetron co-sputtering. The morphology, microstructure, mechanical properties, surface wettability and corrosion resistance of the AlNbTiZr MEA coatings were studied to evaluate the surface protection behavior of zirconium alloy cladding under operation conditions of a pressurized water reactor. The results showed that all the coatings were composite structures with amorphous and bcc-structured nanocrystals. With the increase of Al content, both the elastic modulus and hardness decreased first and then increased. The hydrophobicity of the coatings was enhanced compared with that of the substrate. The 10.2 at.% Al AlNbTiZr coating had the best corrosion resistance and the minimum oxygen penetration depth, which originated from the formation of a denser oxide layer consisting of Nb₂Zr₆O₁₇ and ZrO₂. This study provides an improved idea for the design and development of Al-containing MEA coating materials for accident tolerant fuel.