This work investigates the role of grain size and recrystallization texture in the corrosion behavior of pure iron in 0.1 M sulfuric acid solution. Annealing heat treatment was applied to obtain samples with different average grain sizes (26, 53 and 87 µm). Optical microscopy, X-ray diffraction and electron backscatter diffraction techniques were used to characterize the microstructure. The EBSD data analysis showed ferrite phase with no inclusions and very low geometrically necessary dislocation density, indicating strain-free grains constituting all samples. The crystallographic texture analysis of the samples revealed that the 26 µm grain size sample had a high volume fraction of {111} oriented grains parallel to the sample surface, while other samples exhibited nearly random crystallographic texture. The electrochemical results from potentiodynamic polarization and electrochemical impedance spectroscopy showed a decrease in corrosion resistance from 87 µm to 53 µm grain size sample and then an increase for the 26 µm grain size sample. This increase was attributed to the dominant effect of recrystallization texture on the corrosion behavior of the sample. The cathodic hydrogen evolution reaction kinetics was found to play a decisive role in the corrosion behavior of iron.@en

The role of prior austenite grain size (PAGS) on the passive layer properties of martensitic steels is studied. Electron backscatter diffraction analysis shows that PAGS between 5 and 66 µm were obtained after applying different heat treatments. The barrier properties of passive film deteriorate with grain refinement up to 28 µm, attributed to increased donor density and a decrease in the fraction of γ-Fe2O3 in passive films. However, the further refinement of PAGS to 5 µm leads to improvement in the barrier properties due to the changes within the martensite structure. This improvement stems from the increase in γ-Fe2O3 fraction. @en

Nanoparticles (NPs) have high multifunctional potential to simultaneously enhance implant osseointegration and prevent infections caused by antibiotic-resistant bacteria. Here, we present the first report on using plasma electrolytic oxidation (PEO) to incorporate different combinations of reduced graphene oxide (rGO) and silver (Ag) NPs on additively manufactured geometrically ordered volume-porous titanium implants. The rGO nanosheets were mainly embedded parallel with the PEO surfaces. However, the formation of ‘nano-knife’ structures (particles embedded perpendicularly to the implant surfaces) was also found around the pores of the PEO layers. Enhanced in vitro antibacterial activity against methicillin-resistant Staphylococcus aureus was observed for the rGO+Ag-containing surfaces compared to the PEO surfaces prepared only with AgNPs. This was caused by a significant improvement in the generation of reactive oxygen species, higher levels of Ag+ release, and the presence of rGO ‘nano-knife’ structures. In addition, the implants developed in this study stimulated the metabolic activity and osteogenic differentiation of MC3T3-E1 preosteoblast cells compared to the PEO surfaces without nanoparticles. Therefore, the PEO titanium surfaces incorporating controlled levels of rGO+Ag nanoparticles have high clinical potential as multifunctional surfaces for 3D-printed orthopaedic implants.@en

The role of microstructural defects (dislocation density and grain boundary areas) on the passive film properties formed on cold- and hot-rolled interstitial free (IF) steels is investigated in 0.1 M NaOH solution. Electron backscattered diffraction (EBSD) shows higher microstructural defect density on cold-rolled samples. Potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) results exhibit the lower barrier properties of passive films with the increase in microstructural defects. This is attributed to the increase in donor density measured with Mott-Schottky analysis and the lower relative quantity of protective γ-Fe₂O₃ in passive films (composed of Fe₃O₄,γ-Fe₂O₃ and FeO(OH)) with the increase in microstructural defect density.

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The effect of ferrite-pearlite and ferrite-martensite phase combinations on the passive layer properties of low carbon steel is investigated in a 0.1 M NaOH solution. Heat treatments were designed to obtain ferrite-pearlite and ferrite-martensite microstructures with similar ferrite volume fractions. Potentiostatic polarisation and electrochemical impedance spectroscopy (EIS) results demonstrated the lower barrier properties of passive films on ferrite-martensite microstructure compared to the ones formed on ferrite-pearlite microstructure. This was attributed to the higher donor density of the passive layer on ferrite-martensite samples, measured with Mott–Schottky analysis. This behaviour was explained by the complex microstructure morphology of the martensite phase that led to the formation of a more defective passive film@en

Direct metal printed (DMP) porous iron implants possess promising mechanical and corrosion properties for various clinical application. Nevertheless, there is a requirement for better co-relation between in vitro and in vivo corrosion and biocompatibility behaviour of such biomaterials. Our present study evaluates absorption of porous iron implants under both static and dynamic conditions. Furthermore, this study characterizes their cytocompatibility using fibroblastic, osteogenic, endothelial and macrophagic cell types. In vitro degradation was performed statically and dynamically in a custom-built set-up placed under cell culture conditions (37 °C, 5% CO2 and 20% O2) for 28 days. The morphology and composition of the degradation products were analysed by scanning electron microscopy (SEM, JSM-IT100, JEOL). Iron implants before and after immersion were imaged by μCT (Quantum FX, Perkin Elmer, USA). Biocompatibility was also evaluated under static and dynamic in vitro culture conditions using L929, MG-63, HUVEC and RAW 264.7 cell lines. According to ISO 10993, cytocompatibility was evaluated directly using live/dead staining (Live and Dead Cell Assay kit, Abcam) in dual channel fluorescent optical imaging (FOI) and additionally quantified by flow cytometry. Furthermore, cytotoxicity was indirectly quantified using ISO conform extracts in proliferation assays. Strut size of DMP porous iron implants was 420 microns, with a porosity of 64% ± 0.2% as measured by micro-CT. After 28 days of physiological degradation in vitro, dynamically tested samples were covered with brownish degradation products. They revealed a 5.7- fold higher weight loss than statically tested samples, without significant changes in medium pH. Mechanical properties (E = 1600–1800 MPa) of these additively manufactured implants were still within the range of the values reported for trabecular bone, even after 28 days of biodegradation. Less than 25% cytotoxicity at 85% of the investigated time points was measured with L929 cells, while MG-63 and HUVEC cells showed 75% and 60% viability, respectively, after 24 h, with a decreasing trend with longer incubations. Cytotoxicity was analysed by two-way ANOVA and post-hoc Tukey's multiple comparisons test. Under dynamic culture conditions, live-dead staining and flow cytometric quantification showed a 2.8-fold and 5.7-fold increase in L929 and MG-63 cell survival rates, respectively, as compared to static conditions. Therefore, rationally designed and properly coated iron-based implants hold potential as a new generation of absorbable Orthopaedic implants.@en

This work focuses on the effect of surface roughness and surface chemistry on the initial adhesion strength and corrosive de-adhesion properties of adhesive bonds. The adherend used in this study is a S690 low-alloy steel whereas the adhesive is a 2-component epoxy-amine adhesive (Araldite 2015). The steel surface is subjected to different surface pre-treatment methods such as mechanical abrasion, grit blasting, zirconium conversion treatment and silane treatment. The effect of these different pre-treatments on the surface morphology, roughness and chemistry is addressed. Single-lap joint tests were performed at ambient conditions to assess the initial bond strength of the joint. Static wedge tests were performed in saltwater immersions to study the environmental ageing of the adhesive joints. Unloaded delamination of adhesive films from the steel surface was studied by means of scanning Kelvin probe (SKP) at high relative humidity. This unique combination of different techniques allows thorough evaluations of the bond performance under different environmental and loading conditions. Experimental results indicate that surface roughening plays an important role in the initial adhesion in the single-lap joint test but a minor role in the durability of the bonded steel surfaces. The improved initial adhesion is mainly attributed to the increased interfacial bond area at higher surface roughness. The presence of complex texture or morphology shows a more profound effect than the average roughness on both the initial adhesion and the durability of the interfacial adhesion. The results from the static wedge test show the large contribution of mechanical interlocking, caused by texturing of the surface, on the durability of the interfacial adhesion. In the absence of complex texture, surfaces with altered chemistry by zirconium- or silane treatment exhibit a significant increase of the initial bonding strength due to enhanced physicochemical interactions across the interface. Assessment of the interfacial delamination kinetics by SKP show that despite the absence of any surface topography, chemically altered surfaces prove to have higher resistance to delamination.@en

The bonding properties of zirconium- and titanium-based conversion coatings were evaluated using model conversion solutions of H₂ZrF₆ and H₂TiF₆ with addition of various organic additives (PAA, PVA, PVP). Macroscopic testing techniques such as contact angle and pull-off adhesion measurements were performed on galvanized steel sheets. Complementary to this, molecular studies were performed on model zinc substrates using ATR-FTIR in the Kretschmann configuration. The macroscopic and molecular approaches showed a good correlation demonstrating ATR-FTIR in the Kretschmann configuration to be a valuable tool to gain fundamental insights in metal oxide-polymer interfacial phenomena. Zirconium-treated galvanized steel substrates were shown to have a higher bonding affinity for the polyester coil coat primer than titanium-treated galvanized steel substrates. The presence of organic additives did not further improve the bonding properties. Yet, organic additives initially improved the interfacial stability of titanium-treated substrates. However, on the long term, organic additives are shown to be detrimental for polyester coil coat adhesion. This adverse effect of organic additives on the long term was assigned to its selective dissolution during immersion and was most pronounced for titanium-treatments. The limited effect of organic additives in case of zirconium-treatments was attributed to the higher portion of chemical interfacial bonds, as well as its tendency for crosslinking reactions causing entanglement of polymeric compounds in the zirconium oxide structure.

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One of the main applications of SVET in corrosion research is the study of the corrosion inhibition effectiveness and the evaluation of the self-healing effect of inhibitor-containing coatings. The tip of the platinum/iridium vibrating electrode is electroplated with black platinum, which creates a large electrode surface and confers high capacitance to the tip. When studying organic inhibitors in aqueous solutions with SVET, inhibitor adsorption may occur at the tip, causing its contamination and the initial calibration conditions of the system might not be valid. This may lead to an incorrect interpretation of the results. This work is intended to study the effect of different inhibitors (cerium nitrate, 8-hydroxyquinoline, potassium 2,5-dimercapto-1,3,4-thiadiazolate, benzotriazole and mercaptobenzothiazole), typically used for corrosion protection of aluminum alloys, on the Pt probe signal during SVET measurements. The results reveal the detrimental effect of some corrosion inhibitors on the sensitivity of the vibrating probe, an effect that imposes a regular assessment of the electrode state during measurements. The increase of the signal noise was related to a decrease of the probe capacitance, while the false current density signal was a result of the potential drift between vibrating and reference electrodes.

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Additively manufactured (AM) topologically ordered porous metallic biomaterials with the proper biodegradation profile offer a unique combination of properties ideal for bone regeneration. These include a fully interconnected porous structure, bone-mimicking mechanical properties, and the possibility of fully regenerating bony defects. Most of such biomaterials are, however, based on magnesium and, thus, degrade too fast. Here, we present the first report on topologically ordered porous iron made by Direct Metal Printing (DMP). The topological design was based on a repetitive diamond unit cell. We conducted a comprehensive study on the in vitro biodegradation behavior (up to 28 days), electrochemical performance, time-dependent mechanical properties, and biocompatibility of the scaffolds. The mechanical properties of AM porous iron (E = 1600–1800 MPa) were still within the range of the values reported for trabecular bone after 28 days of biodegradation. Electrochemical tests showed up to ≈12 times higher rates of biodegradation for AM porous iron as compared to that of cold-rolled (CR) iron, while only 3.1% of weight loss was measured after 4 weeks of immersion tests. The biodegradation mechanisms were found to be topology-dependent and different between the periphery and central parts of the scaffolds. While direct contact between MG-63 cells and scaffolds revealed substantial and almost instant cytotoxicity in static cell culture, as compared to Ti-6Al-4V, the cytocompatibility according to ISO 10993 was reasonable in in vitro assays for up to 72 h. This study shows how DMP could be used to increase the surface area and decrease the grain sizes of topologically ordered porous metallic biomaterials made from metals that are usually considered to degrade too slowly (e.g., iron), opening up many new opportunities for the development of biodegradable metallic biomaterials. Statement of Significance: Biodegradation in general and proper biodegradation profile in particular are perhaps the most important requirements that additively manufactured (AM) topologically ordered porous metallic biomaterials should offer in order to become the ideal biomaterial for bone regeneration. Currently, most biodegradable metallic biomaterials are based on magnesium, which degrade fast with gas generation. Here, we present the first report on topologically ordered porous iron made by Direct Metal Printing (DMP). We also conducted a comprehensive study on the biodegradation behavior, electrochemical performance, biocompatibility, and the time evolution of the mechanical properties of the implants. We show that these implants possess bone-mimicking mechanical properties, accelerated degradation rate, and reasonable cytocompatibility, opening up many new opportunities for the development of iron-based biodegradable materials.

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