Surface Chemistry of Passive Films on Ni-Free Stainless Steel: The Effect of Organic Components in Artificial Saliva.

The composition and thickness of the passive film formed on the surface of an austenitic Ni-free DIN 1.4456 stainless steel (18% Cr, 18% Mn, and 2% Mo) used in orthodontics were investigated by X-ray photoelectron spectroscopy following contact with three complex artificial saliva solutions containing different organic components. It was found that the synergistic action of low pH and the presence of sodium citrate and lactic acid in the Darvell formulation resulted in thin passive films strongly enriched in chromium phosphates and oxyhydroxides and depleted in iron oxide. The differences in the surface chemistry of the passive film formed upon contact with the different artificial saliva formulations can be related to the more intense alloy dissolution in the active/passive transition, as shown by the polarization curves. Citrates or lactic acid can complex iron and promote alloy dissolution. The corrosion rates diminish with time, and after 16 h, they are found to be about 0.5 µm/year for all saliva formulations examined.

Chloride-induced corrosion of steel in concrete-insights from bimodal neutron and X-ray microtomography combined with ex-situ microscopy.

The steel-concrete interface (SCI) is known to play a major role in corrosion of steel in concrete, but a fundamental understanding is still lacking. One reason is that concrete's opacity complicates the study of internal processes. Here, we report on the application of bimodal X-ray and neutron microtomography as in-situ imaging techniques to elucidate the mechanism of steel corrosion in concrete. The study demonstrates that the segmentation of the specimen components of relevance-steel, cementitious matrix, aggregates, voids, corrosion products-obtained through bimodal X-ray and neutron imaging is more reliable than that based on the results of each of the two techniques separately. Further, we suggest the combination of tomographic in-situ imaging with ex-situ SEM analysis of targeted sections, selected based on the segmented tomograms. These in-situ and ex-situ characterization techniques were applied to study localized corrosion in a very early stage under laboratory chloride-exposure conditions, using reinforced concrete cores retrieved from a concrete bridge. Several interesting observations were made. First, the acquired images revealed the formation of several corrosion sites close to each other. Second, the morphology of the corrosion pits was relatively shallow. Finally, only about half of the total 31 corrosion initiation spots were in close proximity to interfacial macroscopic air voids, and > 90% of the more than 160 interfacial macroscopic air voids were free from corrosion. The findings have implications for the mechanistic understanding of corrosion of steel in concrete and suggest that multimodal in-situ imaging is a valuable technique for further related studies. Supplementary Information: The online version contains supplementary material available at 10.1617/s11527-024-02337-7.

Kinetics of electrochemical dissolution of metals in porous media.

Metals embedded in porous media interact electrochemically with the liquid phase contained in the pores. A widespread form of this, adversely affecting the integrity of engineered structures, is corrosion of steel in porous media or in natural environments. While it is well documented that the rate of this electrochemical dissolution process can vary over several orders of magnitude, understanding the underlying mechanisms remains a critical challenge hampering the development of reliable predictive models. Here we study the electrochemical dissolution kinetics of steel in meso-to-macro-porous media, using cement-based materials, wood and artificial soil as model systems. Our results reveal the dual role of the pore structure (that is, the influence on the electrochemical behaviour through transport limitations and an area effect, which is ultimately due to microscopic inhomogeneity of the metal/porous material interface). We rationalize the observations with the theory of capillary condensation and propose a material-independent model to predict the corrosion rate.

Development of a Novel Methodology to Assess the Corrosion Threshold in Concrete Based on Simultaneous Monitoring of pH and Free Chloride Concentration.

Both the free chloride concentration and the pH of the concrete pore solution are highly relevant parameters that control corrosion of the reinforcing steel. In this paper, we present a method to continuously monitor these two parameters in-situ. The approach is based on a recently developed electrode system that consists of several different potentiometric sensors as well as a data interpretation procedure. Instrumented mortar specimens containing different amounts of admixed chlorides were exposed to accelerated carbonation, and changes in free chloride concentration and pH were monitored simultaneously over time. The results revealed the stepwise decrease in pH as well as corresponding increases in free chlorides, resulting from the release of bound chlorides. For a pH drop of about 1 unit (from pH 13.5 down to pH 12.5), the free chloride concentration increased up to 1.5-fold. We continuously quantified the ratio Cl-/OH- that increased steeply with time, and was found to exceed a critical corrosion threshold long before carbonation can be detected with traditional indicator spray testing, even at admixed chloride contents in the order of allowable limits. These results can strongly influence the decision-making in engineering practice and it is expected to significantly improve condition assessments of reinforced concrete structures.

Calcium carbonate as sorbent for lead removal from wastewaters.

Low-cost and largely available industrial by-products such as calcite (CaCO3) have been considered as sorbents to remediate wastewaters from toxic elements, such as lead, in compliance with the European circular economy strategy. To date few articles are reporting results on lead sorption at the calcite-water solution interface by X-ray photoelectron spectroscopy (XPS) and this investigation aims to clarifying the mechanism of the interaction of Pb2+ model solutions over a wide concentration range, from 0.1 µM to 80 mM, with commercial calcite. X-ray powder diffraction (XRPD), scanning electron microscopy (SEM, EDX) and XPS analysis indicate that when CaCO3 particles are soaked in Pb2+ 0.1 mM and 1 mM solutions, hexagonal platelets of hydrocerussite [(PbCO3)2 Pb(OH)2] precipitate on its surface. When the concentration of Pb2+ is equal or higher than 40 mM, prismatic acicula of cerussite [PbCO3] precipitate. Solution analysis by atomic emission spectroscopy (ICP-AES) and ICP-mass spectrometry (ICP-MS) indicate that Pb2+ removal efficiency is nearly 100%; when the initial Pb2+ concentration was equal to 0.1 µM it was below the limit of detection (LOD) and the efficiency could not be determined. The sorption capacity (qe) increases linearly with increasing initial Pb2+ concentration up to a value of 1680 (20) mg/g when the initial Pb2+concentration is 80 mM. These findings suggest that heterogeneous nucleation and surface co-precipitation occur and calcite can be well considered a very promising sorbent for Pb2+ removal from wastewaters within a wide initial concentration range.

Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques.

In this work, a multi-technical bulk and surface analytical approach was used to investigate the bioleaching of a pyrite and arsenopyrite flotation concentrate with a mixed microflora mainly consisting of Acidithiobacillus ferrooxidans. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy mineral surfaces investigations, along with inductively coupled plasma-atomic emission spectroscopy and carbon, hydrogen, nitrogen and sulphur determination (CHNS) analyses, were carried out prior and after bioleaching. The flotation concentrate was a mixture of pyrite (FeS(2)) and arsenopyrite (FeAsS); after bioleaching, 95% of the initial content of pyrite and 85% of arsenopyrite were dissolved. The chemical state of the main elements (Fe, As and S) at the surface of the bioreactor feed particles and of the residue after bioleaching was investigated by X-ray photoelectron and X-ray excited Auger electron spectroscopy. After bioleaching, no signals of iron, arsenic and sulphur originating from pyrite and arsenopyrite were detected, confirming a strong oxidation and the dissolution of the particles. On the surfaces of the mineral residue particles, elemental sulphur as reaction intermediate of the leaching process and precipitated secondary phases (Fe-OOH and jarosite), together with adsorbed arsenates, was detected. Evidence of microbial cells adhesion at mineral surfaces was also produced: carbon and nitrogen were revealed by CHNS, and nitrogen was also detected on the bioleached surfaces by XPS. This was attributed to the deposition, on the mineral surfaces, of the remnants of a bio-film consisting of an extra-cellular polymer layer that had favoured the bacterial action.

Model Protective Films on Cu-Zn Alloys Simulating the Inner Surfaces of Historical Brass Wind Instruments by EIS and XPS.

The present work focuses on the characterization of brass surfaces after contact with artificial saliva solution at pH 7.4 and phosphate buffer solution at pH 7 simulating two extreme conditions that might occur when playing ancient brass wind instruments in the context of historically informed performance practice. The composition and the morphology of the film formed following the contact with the solutions for 1, 3, and 16 h were investigated by ex situ X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to shed a light on the surface changes upon time. In situ electrochemical impedance spectroscopy (EIS) was used to study the mechanism of corrosion and protection of the alloys. The results could be interpreted using a reliable equivalent electrical circuit; they provided evidence that the alloys behave differently when in contact to the various solutions. In saliva solution the formation on the brass surface of a thick surface film was observed, composed of crystallites of about 200 nm size mainly composed of CuSCN and Zn3(PO4)2. This layer hinders the alloy dissolution. The contact of the alloys with the buffer solution originated a much thinner layer composed of Cu2O, ZnO, and a small amount of Zn3(PO4)2. This film is rapidly formed and does not evolve upon time in a protective film.

Electrochemistry and capillary condensation theory reveal the mechanism of corrosion in dense porous media.

Corrosion in carbonated concrete is an example of corrosion in dense porous media of tremendous socio-economic and scientific relevance. The widespread research endeavors to develop novel, environmentally friendly cements raise questions regarding their ability to protect the embedded steel from corrosion. Here, we propose a fundamentally new approach to explain the scientific mechanism of corrosion kinetics in dense porous media. The main strength of our model lies in its simplicity and in combining the capillary condensation theory with electrochemistry. This reveals that capillary condensation in the pore structure defines the electrochemically active steel surface, whose variability upon changes in exposure relative humidity is accountable for the wide variability in measured corrosion rates. We performed experiments that quantify this effect and find good agreement with the theory. Our findings are essential to devise predictive models for the corrosion performance, needed to guarantee the safety and sustainability of traditional and future cements.

The size effect in corrosion greatly influences the predicted life span of concrete infrastructures.

Forecasting the life of concrete infrastructures in corrosive environments presents a long-standing and socially relevant challenge in science and engineering. Chloride-induced corrosion of reinforcing steel in concrete is the main cause for premature degradation of concrete infrastructures worldwide. Since the middle of the past century, this challenge has been tackled by using a conceptual approach relying on a threshold chloride concentration for corrosion initiation (Ccrit). All state-of-the-art models for forecasting chloride-induced steel corrosion in concrete are based on this concept. We present an experiment that shows that Ccrit depends strongly on the exposed steel surface area. The smaller the tested specimen is, the higher and the more variable Ccrit becomes. This size effect in the ability of reinforced concrete to withstand corrosion can be explained by the local conditions at the steel-concrete interface, which exhibit pronounced spatial variability. The size effect has major implications for the future use of the common concept of Ccrit. It questions the applicability of laboratory results to engineering structures and the reproducibility of typically small-scale laboratory testing. Finally, we show that the weakest link theory is suitable to transform Ccrit from small to large dimensions, which lays the basis for taking the size effect into account in the science and engineering of forecasting the durability of infrastructures.

Experimental Protocol to Determine the Chloride Threshold Value for Corrosion in Samples Taken from Reinforced Concrete Structures.

The aging of reinforced concrete infrastructure in developed countries imposes an urgent need for methods to reliably assess the condition of these structures. Corrosion of the embedded reinforcing steel is the most frequent cause for degradation. While it is well known that the ability of a structure to withstand corrosion depends strongly on factors such as the materials used or the age, it is common practice to rely on threshold values stipulated in standards or textbooks. These threshold values for corrosion initiation (Ccrit) are independent of the actual properties of a certain structure, which clearly limits the accuracy of condition assessments and service life predictions. The practice of using tabulated values can be traced to the lack of reliable methods to determine Ccrit on-site and in the laboratory. Here, an experimental protocol to determine Ccrit for individual engineering structures or structural members is presented. A number of reinforced concrete samples are taken from structures and laboratory corrosion testing is performed. The main advantage of this method is that it ensures real conditions concerning parameters that are well known to greatly influence Ccrit, such as the steel-concrete interface, which cannot be representatively mimicked in laboratory-produced samples. At the same time, the accelerated corrosion test in the laboratory permits the reliable determination of Ccrit prior to corrosion initiation on the tested structure; this is a major advantage over all common condition assessment methods that only permit estimating the conditions for corrosion after initiation, i.e., when the structure is already damaged. The protocol yields the statistical distribution of Ccrit for the tested structure. This serves as a basis for probabilistic prediction models for the remaining time to corrosion, which is needed for maintenance planning. This method can potentially be used in material testing of civil infrastructures, similar to established methods used for mechanical testing.

Nanostructure of Surface Films on Ni18P Alloy in Sulfate Solutions by the Maximum Entropy Method.

NiP alloys are very often used in industry, due to their outstanding performance in corrosion and wear. Alloys with high phosphorus content (≥16 atom % P) are amorphous and show high corrosion resistance in both neutral and acidic solutions irrespective of the presence of chloride ions. The reason for this behavior is attributed to the formation of a "P-enriched surface layer" whose exact nature is still under debate. In this work, an iterative algorithm based on the application of maximum entropy method on nondestructive angle-resolved X-ray photoelectron spectroscopy data has been applied to the investigation of the surface layer grown on Ni18P alloys following mechanical polishing and anodic polarization in sulfate solutions. The results show that the outermost region of the examined alloy has a complex layered structure: (1) an uppermost hydrocarbon contamination layer about 1 nm thick, which includes also adsorbed water; (2) a nickel (poly)phosphate layer of about 1 nm; (3) a highly phosphorus-enriched interface being about 2 nm thick with a marked phosphorus concentration gradient, from 70 to 20 atom %; and (4) bulk alloy with the stoichiometric composition. These findings, together with the chemical state of the different phosphorus compounds, allow us to conclude that the high corrosion and wear resistance of NiP alloys might be ascribed to the presence of a thin, self-repairing nickel (poly)phosphate layer grown on a strongly P-enriched interface. Because the Auger parameter of P at the interface is similar to that of elemental P, it might be also concluded that the interface is enriched in elemental phosphorus.

The chemical state of arsenic in minerals of environmental interest--an XPS and an XAES study.

A systematic analytical study using X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) has been carried out to characterize the chemical state of arsenic in complex environmental samples. The conventional approach, which relies on the chemical shift of the core levels As3d, provides ambiguous results in determining the chemical environment of arsenic. A more accurate approach, based on the Auger parameter and on the Wagner (Chemical State) plot, which combines AsLMM kinetic energy and As3d binding energy, was adopted. This novel method for determining the chemical state of arsenic was employed to completely characterize arsenic in complex environmental samples.

Quantitative evaluation of oxidative stress, chronic inflammatory indices and leptin in cancer patients: correlation with stage and performance status.

In advanced cancer patients, the oxidative stress could take place either at the onset of disease or as a function of disease progression. To test this hypothesis, the following parameters were investigated: the erythrocyte activity of the enzymes superoxide dismutase (SOD) and glutathione peroxidase (GPx), the serum activity of glutathione reductase (GR) and the serum total antioxidant status (TAS). The total antioxidant capacity of plasma LMWA was evaluated by the cyclic voltammetry methodology. We further determined the serum levels of proinflammatory cytokines (IL-6 and TNFalpha), IL-2, leptin and C-reactive protein (CRP). All of these parameters have been correlated with the most important clinical indices of patients such as Stage of disease, ECOG PS and clinical response. Eighty-two advanced stage cancer patients and 36 healthy individuals used as controls were included in the study. Our findings show that SOD activity was significantly higher in cancer patients than in controls and GPx activity was significantly lower in cancer patients than in controls. Serum values of IL-6, TNFalpha and CRP were significantly higher in patients than in controls. Serum leptin values of cancer patients were significantly lower than controls. SOD activity increased significantly from Stage II/ECOG 0-1 to Stage IV/ECOG 0-1, whereas it decreased significantly in Stage IV/ECOG 3. GPx activity decreased significantly in Stage IV/ECOG 2-3. An inverse correlation between ECOG PS and serum leptin levels was found. Serum levels of IL-2 decreased from Stage II/ECOG 0-1 to Stage IV/ECOG 2-3. A direct correlation between Stage/ECOG PS and serum levels of both IL-6 and CRP was observed. Cisplatin administration induced a significant increase of GPx after 24 hr. In conclusion, this is the first study that shows that several "biological" parameters of cancer patients such as antioxidant enzyme activity, cytokines, leptin and CRP strictly correlate with the most important clinical parameters of disease such as Stage and ECOG PS.