Time-of-flight Secondary Ion Mass Spectrometry Research Articles

Progressive quenching of luminescence from quantum dot thin films in proximity with ZnMgO in unencapsulated stacks

ZnMgO nanoparticles (NPs) are being increasingly used as the electron transport layer (ETL) in state-of-the-art quantum-dot light-emitting devices (QLEDs) instead of ZnO. However, the impact of ZnMgO on the luminescence properties of quantum dots (QDs) is much less understood. Here, we compare ZnMgO and ZnO NPs for their quenching effect on Cd-based QDs photoluminescence (PL), immediately and over time. Time-resolved photoluminescence (TRPL) and steady-state PL results show that ZnMgO NPs decreases the QDs’ luminescence more than ZnO NPs and that the behavior continues progressively over time. The surface topography of the samples containing different ETLs is studied using atomic force microscopy (AFM) and optical PL images. Additionally, time of flight secondary ion mass spectroscopy (TOF-SIMS) measurements are conducted to investigate the potential diffusion of some species from ETL into the QDs layer. The results confirm that morphological changes and out-diffusion of some species from the ZnMgO layer can likely play a role in the QDs PL quenching. This study sheds light on the limitations of ZnMgO for the long-term stability of QLEDs, specifically for blue QLEDs where using ZnMgO is essential for efficient electron injection.

Time-of-Flight Secondary Ion Mass Spectrometry Coupled with Unsupervised Methods for Advanced Saffron Authenticity Screening.

Saffron, renowned for its aroma and flavor, is susceptible to adulteration due to its high value and demand. Current detection methods, including ISO standards, often fail to identify specific adulterants such as safflower or turmeric up to 20% (w/w). Therefore, the quest continues for robust screening methods using advanced techniques to tackle this persistent challenge of safeguarding saffron quality and authenticity. Advanced techniques such as time-of-flight secondary ion mass spectrometry (TOF-SIMS), with its molecular specificity and high sensitivity, offer promising solutions. Samples of pure saffron and saffron adulterated with safflower and turmeric at three inclusion levels (5%, 10%, and 20%) were analyzed without prior treatment. Spectral analysis revealed distinct signatures for pure saffron, safflower, and turmeric. Through principal component analysis (PCA), TOF-SIMS effectively discriminated between pure saffron and saffron adulterated with turmeric and safflower at different inclusion levels. The variation between the groups is attributed to the characteristic peaks of safflower and the amino group peaks and mineral peaks of saffron. Additionally, a study was conducted to demonstrate that semi-quantification of the level of safflower inclusion can be achieved from the normalized values of its characteristic peaks in the saffron matrix.

Matrices to enhance the ion yield of OLED molecules in ToF-SIMS: An interesting alchemist solution

Since the early days of time of flight secondary ion mass spectrometry (ToF-SIMS), increasing the ion signal has been crucial. It is even more crucial when performing tandem mass spectrometry experiments. To achieve this goal, many developments have been made over the years, which are divided into two categories: instrumental development and sample modification. The latter involves sample metallization, matrix deposition, or changing the temperature of the measurement. In this study, the possibility of using matrices to enhance the signals of organic light emitting device (OLED) molecules was explored. Seven molecules commonly used in OLEDs were separately deposited on Si wafers: Alq3, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, 1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile, Ir(mppy)3, N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)benzidine, 2,2′,7,7′-tetra(N,N-ditolyl)-amino-spiro-bifluor (STTB), and tris(4-carbazoyl-9-ylphenyl)amine. Using the same solvent, three different matrices with different thicknesses, common in matrix assisted light desorption ionization time of flight mass spectrometry, α-cyano-4-hydroxycinnamic acid, 2,5-dihydrobenzoic acid (DHB), and dihydrochloride N-(1-Naphthyl)ethylenediamine, were sprayed on these surfaces. Spectra were acquired for all compounds and spraying conditions in static ToF-SIMS experiments for Alq3 chemical imaging and depth profiling were performed. This allowed the investigation of the fragmentation pattern of the chosen matrices in ToF-SIMS and, thus, obtained a reference for these molecules. The results show that matrices can enhance the signal of fragments of the studied molecules, for example, the signal of STTB is increased with DHB spraying. Samples sprayed only with the solvent were also prepared to verify the impact of the matrices on the signal. Spraying with the solvent alone can enhance the signal even more than the matrices up to four times in the case of Alq3. This result opens new possibilities in the field of matrix-enhanced ToF-SIMS in terms of applications and matrix choices.

Mesoporous architectural magnetic halloysite-polymer beads for removing toxic streptomycin from water: A sustainable remediation approach

Streptomycin (STR) is a widely used antibiotic to treat various infectious diseases in humans and animals. Increased STR production and distribution result in harmful residue in soil and water. Consequently, STR exists in biotic- and abiotic-counterpart of the environment and poses potential toxicity and risk due to its bioaccumulation and biomagnification properties. Sustainable remediation of STR from wastewater requires selective, minimal, low-cost, regenerable, and reusable materials as adsorbents. In this study, magnetic-halloysite incorporated polymer composite beads (SPHM) were synthesized and used for the efficient clean-up of toxic STR from wastewater. SPHM has a mesoporous structure with an abundance of oxygen-containing functional groups and exhibits a synergistic STR clean up performance (qm = 235.71 ± 13.98 mg/g). Sorption and interfacial studies revealed that diffusion, hydrophobic and ionic interactions, including electrostatic interaction, are involved in STR remediation. Electrostatic interaction plays a vital role alongside the physical sorption mechanism due to the presence of hydroxyl and carboxyl groups induced from poly (vinyl alcohol) and sodium alginate. Moreover, X-ray photoelectron spectroscopy (XPS) and Time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses confirm the involvement of opposing charged groups of SPHM and STR in adsorption. SPHM can be magnetically separated in just 20 s and is regenerable and reusable up to 10 times, with outstanding performance and stability. The sorption process requires only a minimal amount of SPHM, i.e., 0.5 g/L for STR clean-up. Even the natural surface water composition did not affect its performance. Hence, natural nanoclay-based, biocompatible and low-cost SPHM has a great potential for the sustainable remediation of streptomycin and other similar antibiotics from wastewater.

Benchmarking diamond surface preparation and fluorination via inductively coupled plasma-reactive ion etching

Diamond, renowned for its exceptional semiconducting properties, stands out as a promising material for high-performance power electronics, optics, quantum, and biosensing technologies. This study methodically investigates the optimization of polycrystalline diamond (PCD) substrate surfaces through Inductively Coupled Plasma Reactive Ion Etching (ICP-RIE). Various parameters, including gaseous species, flow rate, coil power, and bias power were tuned to understand their impact on surface morphology and chemistry. A thorough characterization, encompassing chemical, spectroscopic, and microscopic methods, shed light on the effects of different ICP-RIE conditions on surface properties. CF4/O2 plasma emerged as a viable treatment for achieving smooth PCD surfaces with minimal etch pit formation. Most notably, surface fluorination, a critical aspect of increasing chemical and thermal stability, was successfully accomplished using CF4, SF6, and other F-containing plasmas. The fluorine concentration and surface chemistry variations were studied, with high resolution X-ray Photoelectron Spectroscopy unveiling differences amongst the sp2 C phase, sp3 C phase, C–O, CO, and C–F bonds. Time-of-flight secondary Ion Mass Spectrometry (ToF-SIMS) and depth-profile analysis unveiled a consistent surface fluorination pattern with CF4/O2 treatment. Furthermore, contact angle measurements showcased heightened hydrophobicity. This study provides valuable insights into precise diamond surface engineering, important for the development of future diamond-based semiconductor technologies.

Study on the effects of a novel imidazoline siliconophilic collector in the desilication process of magnesite: Separation experiments, adsorption mechanisms, and separation model

This study innovatively introduced heptadecenyl amine ethyl imidazoline quaternary ammonium salt (ODD) as a siliconophilic flotation collector, effectively facilitating the achievement of high-efficiency separation of magnesite from quartz. ODD exhibits unique properties such as high selectivity and environmental friendliness. Through a comprehensive series of experiments, including flotation tests, zeta potential characterization, atomic force microscopy (AFM) imaging, Fourier-transform infrared (FTIR) spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS), the flotation performance and selective adsorption mechanisms of ODD were thoroughly investigated. The experiments demonstrated that at a pH of 7.00 and an ODD concentration of 40 mg/L, quartz achieved a flotation recovery rate of 95.16 %, while magnesite was only 2.99 %, underscoring the high selectivity of ODD in mineral separation. Zeta potential measurements indicated that ODD exhibits strong adsorption interactions with quartz over magnesite. AFM observations confirmed that ODD forms significant adsorption structures on quartz surfaces, in contrast to weaker interactions with magnesite. FTIR analysis further revealed the robust interactions between ODD and quartz through hydrogen bonds and electrostatic forces, which were significantly diminished on magnesite surfaces. ToF-SIMS analysis provided direct evidence of ODD’s selective adsorption on quartz, contributing to a better understanding of the flotation mechanisms involved. This research not only offers a novel approach for the purification of magnesite and effective removal of quartz but also demonstrates the potential of ODD as an eco-friendly collector in mineral processing, potentially advancing a green transformation in the industry. The findings provide a solid theoretical and experimental basis for future industrial applications and innovative development of flotation collectors.

Recyclable Organic Radical Electrodes for Metal-Free Batteries.

Organic batteries are one of the possible routes for transitioning to sustainable energy storage solutions. However, the recycling of organic batteries, which is a key step toward circularity, is not easily achieved. This work shows the direct recycling of poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl) (PTMA) and poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl acrylamide) (PTAm) based composite electrodes. After charge-discharge cycling, the electrodes are deconstructed using a solubilizing-solvent and then reconstructed using a casting-solvent. The electrochemical properties of the original and recycled electrodes are compared using cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) cycling, from which it is discovered using time-of-flight secondary ion mass spectrometry (ToF-SIMS) that recycling can be challenged by the formation of a cathode electrolyte interphase (CEI). In turn, an additive is proposed to modify the CEI layer and improve the properties after recycling. Last, an anionic rocking chair battery consisting of PTAm electrodes as both positive and negative electrodes is demonstrated, in which the electrodes are recycled to form a new battery. This work demonstrates the recycling of composite electrodes for organic batteries and provides insights into the challenges and possible solutions for recycling the next-generation electrochemical energy storage devices.

Morphological and chemical changes in nuclear graphite target under vacuum and high-temperature conditions

Nuclear-grade graphite is a high-efficiency material, widely used for vacuum applications in nuclear reactors and accelerators as targets facing particle beams. In these contexts, graphite is often exposed to extreme thermal stresses altering its physical and chemical properties. The thermal-induced release of volatile contaminants from targets and the damage of structural components are critical issues that can affect the safety and operation efficiency of beamline facilities. Here, we provide for the first time a detailed picture of the chemical and morphological changes occurring in a nuclear-grade graphite target, obtained through Electrical Discharge Machining (EDM), when exposed in vacuum to high temperatures. The radial temperature gradient induced by the impact of a pulsed energetic (MeV- GeV range) focused particle beams was reproduced by cyclically heating, in the 1300–1800 K temperature range, a disc-shaped graphite target in a vacuum setup. An accurate surface and in-depth chemical analysis of the graphite target was obtained thanks to the high sensitivity (ppm/ppb) of the Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) technique. The chemical maps clearly show the presence of several metal oxides and impurities in the surface and subsurface regions of the untreated sample. Such contaminants were removed because of the thermal treatment in vacuum more or less efficiently, as demonstrated by Thermogravimetric analysis (TGA), X-ray Photoelectron Spectroscopy (XPS), and ToF-SIMS. However, Raman spectroscopy and SEM-EDS revealed that the high-temperature treatment induces a decrease in the crystallite size of the graphite as well as changes in the target surface porosity with the appearance of microvoids, leading the graphite target to be more prone to the breakage.

Comparison of Nitriding Behavior for Austenitic Stainless Steel 316Ti and Super Austenitic Stainless Steel 904L

In situ X-ray diffraction (XRD) was used to compare nitrogen low-energy ion implantation (LEII) into austenitic stainless steel 316Ti and super austenitic stainless steel 904L. While the diffusion and layer growth were very similar, as derived from the decreasing intensity of the substrate reflection, strong variations in the observed lattice expansion—as a function of orientation, the steel alloy, and nitriding temperature—were observed. Nevertheless, a similar resulting nitrogen content was measured using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Furthermore, for some conditions, the formation of a double layer with two distinct lattice expansions was observed, especially for steel 904L. Regarding the stability of expanded austenite, 316Ti had already decayed in CrN during nitriding at 500 °C, while no such effect was observed for 904L. Thus, the alloy composition has a strong influence only on the lattice expansion and the stability of expanded austenite—but not the diffusion and nitrogen content.

Microglial activation induces nitric oxide signalling and alters protein S-nitrosylation patterns in extracellular vesicles.

Neuroinflammation is an underlying feature of neurodegenerative conditions, often appearing early in the aetiology of a disease. Microglial activation, a prominent initiator of neuroinflammation, can be induced through lipopolysaccharide (LPS) treatment resulting in expression of the inducible form of nitric oxide synthase (iNOS), which produces nitric oxide (NO). NO post-translationally modifies cysteine thiols through S-nitrosylation, which can alter function of the target protein. Furthermore, packaging of these NO-modified proteins into extracellular vesicles (EVs) allows for the exertion of NO signalling in distant locations, resulting in further propagation of the neuroinflammatory phenotype. Despite this, the NO-modified proteome of activated microglial EVs has not been investigated. This study aimed to identify the protein post-translational modifications NO signalling induces in neuroinflammation. EVs isolated from LPS-treated microglia underwent mass spectral surface imaging using time of flight-secondary ion mass spectrometry (ToF-SIMS), in addition to iodolabelling and comparative proteomic analysis to identify post-translation S-nitrosylation modifications. ToF-SIMS imaging successfully identified cysteine thiol side chains modified through NO signalling in the LPS treated microglial-derived EV proteins. In addition, the iodolabelling proteomic analysis revealed that the EVs from LPS-treated microglia carried S-nitrosylated proteins indicative of neuroinflammation. These included known NO-modified proteins and those associated with LPS-induced microglial activation that may play an essential role in neuroinflammatory communication. Together, these results show activated microglia can exert broad NO signalling changes through the selective packaging of EVs during neuroinflammation.

Enhancing ToF-SIMS OLED Data Analysis with Neural Networks and Mathematical Spectral Mixing.

This study presents a method employing artificial neural networks (ANN) for automated interpretation and depth profiling of organic multilayers using a limited set of time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra. To overcome the challenges of acquiring massive data sets for OLEDs, training data was generated by combining existing ToF-SIMS data sets with mathematically generated spectra. The classification model achieved an impressive 99.9% accuracy in identifying the mixed layers of the OLED dyes. The study demonstrates the synergy of ToF-SIMS and ANN analysis for effective classification and depth profiling of the OLED layers, providing valuable insights for the development and optimization of organic electronic devices.

From surface to core: Comprehensive ToF-SIMS insights into pharmaceutical tablet analysis

This study presents an innovative approach to pharmaceutical analysis using time-of-flight secondary ion mass spectrometry (ToF-SIMS) to investigate tablets containing paracetamol in the solid state without the need for traditional pretreatment methods (dissolution, filtration, etc.). Employing both MS1 and MS2 ToF-SIMS spectra, signals characteristic of paracetamol and a fragmentation mechanism were assigned. Some findings challenge previous interpretations of certain ToF-SIMS signals attributed to paracetamol, highlighting the need for reevaluation. Moreover, as the sample was used without any pretreatment (a purchased tablet), which has a complex matrix, the resulting ToF-SIMS mass spectra can suffer from spectral interferences. The use of multivariate statistical analysis resulted in the assignment of unique signals for paracetamol. Additionally, ToF-SIMS imaging was utilized with high mass and lateral resolution, employing the delayed-extraction ToF analyzer mode, to image the two-dimensional distribution of species on the tablet’s surface with an emphasis on paracetamol distribution. The use of a gas cluster ion beam (GCIB) sputtering source in association with ToF-SIMS enabled the visualization of the three–dimensional distribution of species within the tablet. This thorough investigation advances knowledge regarding the characterization of paracetamol and offers the examination of pharmaceuticals without sample pretreatment with elemental and molecular-specific information.

Selective depression mechanism of polyaspartic acid and calcium oxide on arsenopyrite after copper ions activation and its effect on flotation separation performance

The arsenopyrite activated by copper ions have similar flotation properties to chalcopyrite. Polyaspartic acid (PASP) and calcium oxide (CaO) using as combination depressants for the selective separation of copper-activated arsenopyrite and chalcopyrite were carried out by micro-flotation experiments, contact angle measurements, surface adsorption capacity tests, zeta potential measurements, X-ray photoelectron spectroscopy (XPS) analyses, inductively coupled plasma-optical emission spectrometer (ICP-OES) tests and time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses, and its depression mechanism was investigated. The results of flotation experiments showed that the recovery of arsenopyrite after addition of the depressants reached only 7.80 %, while the recovery of chalcopyrite reached 94.02 %. The results of contact angles, adsorption capacity tests and zeta potential measurements showed that the PASP-CaO can selectively enhance the hydrophilicity of arsenopyrite surface, but has little effect on the chalcopyrite. XPS analyses and ICP-OES tests further verified that the depressants first eliminated the activation of copper ions and then selectively adsorbed on the surface of arsenopyrite. ToF-SIMS analyses showed that the PASP-CaO would achieve selective depression of arsenopyrite in the form of PASP, PASP-Ca complexes and Ca(OH)+, respectively. Finally, the mechanism diagram of PASP-CaO selectively depressing arsenopyrite was derived. These results will provide an excellent theoretical reference for the flotation separation of copper arsenic sulfide ore.

Investigation on nanoindentation and TOF-SIMS applications in the hydrogen and oxygen absorption behavior of Zr-Sn-Nb alloys

This paper focuses on nanoindentation and TOF-SIMS (time-of-flight secondary ion mass spectrometry) small-scale test methods in the study of hydrogen absorption and oxygenation behavior analysis of Zr-Sn-Nb oxidized at 650°C −1200 °C. The CSM (Continuous Stiffness Method) test demonstrates the hardness fluctuations caused by element proliferation in post-high temperature oxidation microstructures. The deformation resistance ability of typical microstructures is as follows: β-Zr layer > α-Zr(O) layer > ZrO2 layer. In addition, hydrogen-induced softening occurred in steam-containing hydrogen conditions (HIT=2～3Gpa), compared to steam (HIT=5～16Gpa). The 1200℃ load-displacement curve demonstrates that the pop-in (or pop-out) effect exists in the Zr-Sn-Nb alloy, related to the influence of hydrogen charge, essentially to dislocation nucleation, winding, and movement. TOF-SIMS provides an effective method for small molecular chemical elements, such as H and O, while ZrO, ZrO2, ZrO2H, ZrO3H, OH, and O2 ions also be found. Based on these results, this study also hypothesizes the OH- dominated oxidation reaction equation.

Enhancement imaging of developed latent blood fingerprints using TOF-SIMS

As one of the most common types of evidence in violent cases, blood fingerprints play an important role in identifying suspects. Typically, Latent blood fingerprints from a crime scene require the application of chemical development reagents followed by photographing to visualize the ridge detail. However, conventional development techniques are not effective in the visualization of poor latent blood fingerprints due to the formation conditions. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a surface analysis technique that combines high mass resolution and high spatial resolution to recover through mass spectrometry imaging (MSI) to reveal fingerprints that are invisible to the naked eye, especially conventional visualization methods. In this study, an enhancement method for latent blood fingerprints was established by analyzing blood fingerprints that showed poor visibility using conventional methods (acid yellow, amido black 10B, tetramethylbenzidine) on plastic sheets, aluminum foil, various papers, and other objects. Additionally, blood samples were diluted with distilled water at concentration gradients of 1:5, 1:10, 1:20, and 1:100 to test the method's sensitivity. Latent fingerprints of blood that aged 14, 30, and 54 days were also examined. Results showed that this method not only enhances the development of fingerprints under challenging conditions but also allows for the recovery of incomplete fingerprints and the separation of overlapping fingerprints. Compared to conventional methods, this approach significantly improves the development effect of latent blood fingerprints while maintaining universality, reliability and practicality.

Mixed-cation, mixed-halide perovskite ToF-SIMS spectra

We report positive and negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra of metal-halide perovskite (MHP) films used for photovoltaic applications. This ToF-SIMS spectral library is of importance because it identifies the major peaks in most MHP films from organic [formamidinium (FA+)] and inorganic (Cs+) cations and anions (I− and Br−).

Precise determination of oxygen content in SmBa2Cu3O7-δ thin film samples using x-ray diffraction

Abstract The superconducting properties of SmBa2Cu3O7-δ (SmBCO) thin films are predominantly influenced by the oxygen deficiency δ. Yet, the established methods to determine δ such as iodometric titration or thermogravimetry cannot be applied to thin films due to their very small volume.
Therefore, an alternative way to determine δ for SmBCO thin film samples using X-ray diffraction (XRD) is presented. Main point of this analysis is the structural relationship between the a, b and c lattice parameters and δ. A linear relationship between c and δ is found in SmBCO powder samples for both the orthorhombic and tetragonal phases.
Furthermore, an attempt is made to quantify the chemical composition using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). This attempt was inconclusive because of drastically changing ion yields due to δ influencing the valence state of the analyzed ions.
The found crystal structural relationship gathered from the powder samples is applied to thin film samples. Thereby, it becomes clear that thermal strain is affecting the crystal structure of the thin films. A simple correction model is used to correct for thermal strain and a good match between powder, literature and thin film data is achieved and thus a non-destructive way for the determination of δ using XRD.


Exploring chitosan-plant extract bilayer coatings: Advancements in active food packaging via polypropylene modification

UV-ozone activated polypropylene (PP) food films were subjected to a novel bilayer coating process involving primary or quaternary chitosan (CH/QCH) as the first layer and natural extracts from juniper needles (Juniperus oxycedrus; JUN) or blackberry leaves (Rubus fruticosus; BBL) as the second layer. This innovative approach aims to redefine active packaging (AP) development. Through a detailed analysis by surface characterization and bioactivity assessments (i.e., antioxidant and antimicrobial functionalities), we evaluated different coating combinations. Furthermore, we investigated the stability and barrier characteristics inherent in these coatings. The confirmed deposition, coupled with a comprehensive characterization of their composition and morphology, underscored the efficacy of the coatings. Our investigation included wettability assessment via contact angle (CA) measurements, X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), which revealed substantial enhancements in surface concentrations of elements and functional groups of CH, QCH, JUN, and BBL. Scanning electron microscopy (SEM) unveiled the coatings' heterogeneity, while time-of-flight secondary ion mass spectrometry (ToF-SIMS) and CA profiling showed moderately compact bilayers on PP, providing active species on the hydrophilic surface, respectively. The coatings significantly reduced the oxygen permeability. Additionally, single-layer depositions of CH and QCH remained below the overall migration limit (OML). Remarkably, the coatings exhibited robust antioxidative properties due to plant extracts and exceptional antimicrobial activity against S. aureus, attributed to QCH. These findings underscore the pivotal role of film surface properties in governing bioactive characteristics and offer a promising pathway for enhancing food packaging functionality.

Synergistic inhibition of Mikania micrantha extract with iodide ion on the corrosion of cold rolled steel in trichloroacetic acid medium

The corrosion inhibition behavior of Mikania micrantha extract (MME) and iodide ion in a synergistic system consisting of 0.10 M trichloroacetic acid (Cl3CCOOH, TCA) on cold rolled steel (CRS) materials and its mechanism was fully investigated by weightlessness, electrochemical, and surface analysis measurements. The results show that MME/I− performs higher inhibition than either MME or I− with a peak inhibition efficiency of 96.3 %. The adsorption of MME, I− and MME/I− on CRS follow with Langmuir isotherm. MME/I− retards both anodic and cathodic reactions. With the MME/I− complex inhibitor, the capacitance arc radius reaches a maximum. The results of scanning electron microscopy (SEM), atomic force microscopy (AFM), and confocal laser scanning microscopy (CLSM) showed that there were obvious adsorbent films on the surface of the suppressed CRS. Compositional analysis of surface adsorbates on CRS by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (TOF-SIMS) revealed that the main components of the adsorption film on the surface of CRS contained a large number of polar compounds, notably the formation of chemical bonds by iron atoms.

Application of operando ORP-EIS for the in-situ monitoring of acid anion incorporation during anodizing

Operando odd random phase electrochemical impedance spectroscopy (ORP-EIS) is applied to monitor the anodizing process of AA2024 in acidic media. The impedance data reveals the presence of inductive behavior during the process. We correlate this inductive behavior to the acid anion incorporation during anodizing using the surface charge approach. Moreover, the impact of anodizing parameters – including anodizing DC potential, electrolyte type and concentration – is studied on the inductive behavior, and consequently on the acid anion adsorption and incorporation. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is employed to support the operando ORP-EIS results. We conclude that operando ORP-EIS during anodizing can predict acid anion incorporation into the oxide layer.