Surface Oxidation Research Articles

A comprehensive electrochemical analysis revealing the surface oxidation behavior difference between pyrite and arsenopyrite

This study systematically investigated the surface oxidation behavior differences between pyrite and arsenopyrite under neutral and alkaline pH conditions using various electrochemical measurements. These measurements include open circuit potential (OCP), cyclic voltammetry (CV), potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and Mott-Schottky analyses. Key electrochemical parameters have been obtained. The OCP, oxidation potential (Eox), and charge transfer resistance (Rct) of arsenopyrite and pyrite declined as the solution pH increased, but oxidation current density (jox) and carrier concentration (ND) increased, suggesting that a high solution pH is thermodynamically and dynamically favorable for the oxidation of both pyrite and arsenopyrite. Compared to pyrite, arsenopyrite has a higher Fermi level, lower OCP and Eox, a larger jox, and a smaller Rct at the same pH conditions, suggesting that arsenopyrite oxidation has a higher thermodynamic preference and occurs at a faster rate than pyrite oxidation under neutral and alkaline pH conditions. This comprehensive study enhances our understanding of the oxidation difference between pyrite and arsenopyrite and offers important guidance for the pyrite-arsenopyrite flotation separation when using the selective surface oxidation method.

Spectroscopic analysis of color origins in titanium-based thin films deposited by cathodic arc deposition

The distinctive colors observed in titanium-based (Ti-based) decorative coatings fabricated by cathodic arc deposition originate from the unique electronic, morphological, and chemical properties of these films. Most Ti-based film colors arise from their surface band gaps, as measured by electron energy loss spectroscopy, with the exception of the lowest brightness (TLB) and green hues. The green color in titanium dioxide films typically results from interference between light reflected from the film and substrate interfaces. In contrast, the black color in Ti-based coatings stems from the chemical structure, specifically the presence of Ti-C and C=C(sp2) bonds within the film. Moreover, the large band gap of the TLB film surface is attributed to surface oxidation, as detected by soft X-ray spectroscopy. Significantly, the film thickness and surface roughness are characterized by field emission secondary electron microscopy and atomic force microscopy, respectively.

Influencing the surface quality of free-standing wurtzite gallium nitride in ultra-high vacuum: Stoichiometry control by ammonia and bromine adsorption

Gallium nitride (GaN), a wide bandgap semiconductor with absorption and emission in the ultraviolet/visible range, is proposed as an alternative to metallic surfaces for assembling organic molecular structures aiming at optoelectronic applications. However, the formation of a persistent surface oxide layer in air considerably limits the use of GaN for well-defined interfaces. In this work, we have investigated, characterized and processed n-type free-standing c-plane hexagonal wurtzite GaN crystals grown by hydride vapor phase epitaxy and ammonothermal growth methods. Surface cleaning and full removal of the oxide layer on GaN surfaces could be reproducibly achieved via sputtering and annealing cycles, as evidenced by X-ray photoelectron spectroscopy and low-energy electron diffraction. Scanning tunneling microscopy, however, indicated substantial roughening of the GaN surface and the formation of unwanted Ga-rich islands and clusters. Although ammonia (NH3) and bromine (Br) treatments compensated the N/Ga atoms ratio reduced by sputtering, the surface morphology remained rough, exhibiting randomly shaped and distributed hillocks. In addition, we studied the effect of electron bombardment on the surface quality of GaN during NH3 annealing, on-surface debromination and polymerization of 1,3,5-tris(4-bromophenyl) benzene on GaN, and the removal of Ga atoms by Br atoms during the desorption.

Environmental stability and ageing of ScN thin films from XPS Ar+ depth profiling

A basic knowledge on chemical stability and reactivity of a wide band gap ScN semiconductor in the presence of air atmosphere, where O2 and H2O represent the main degradation or corrosive agents, is of vital importance for a long-term performance of ScN-based devices for thermoelectric applications. Here, we present a systematic XPS Ar+ depth profiling analysis and optical and TEM characterizations of naturally room temperature air-aged thin ScN films prepared by a high-temperature DC sputtering on MgO(001) and SiO2 substrates. We find that superior crystalline quality ScN/MgO films degrade weakly after their quick initial surface oxidation and/or hydrolysis. Their oxidation is rather local and associated with the film-penetrating void-like interfaces. Significant initial surface oxidation and subsequent bulk oxidation after ageing is, however, observed for polycrystalline ScN/SiO2 films. Ab initio calculations of pure ScN and ScN with diluted nitrogen vacancies and/or substitutional oxygen impurities, which assist our experimental research, reveal pronounced impact of these defects on the ScN electronic structure. The modeled compositions reflect homogeneously and weakly oxidized films, while the real films correspond to relatively pure ScN crystallites with interfaces rich in oxygen.

Enhanced Electrocatalysis on Copper Nanostructures: Role of the Oxidation State in Sulfite Oxidation.

The influence of surface morphology and the oxidation state on the electrocatalytic activity of nanostructured electrodes is well recognized, yet disentangling their individual roles in specific reactions remains challenging. Here, we investigated the electrooxidation of sulfite ions in an alkaline environment using cyclic voltammetry on copper oxide nanostructured electrodes with different oxidation states and morphologies but with similar active areas. To this aim, we synthesized nanostructured Cu films made of nanoparticles or nanorods on top of glassy carbon electrodes. Our findings showed an enhanced sensitivity and a lower detection threshold when utilizing Cu(I) over Cu(II). Density functional theory-based thermochemical analysis revealed the underlying oxidation mechanism, indicating that while the energy gain associated with the process is comparable for both oxide surfaces, the desorption energy barrier for the resulting sulfate molecules is three times higher on Cu(II). This becomes the limiting step of the reaction kinetics and diminishes the overall electrooxidation efficiency. Our proposed mechanism relies on the tautomerization of hydroxyl groups confined on the surface of Cu-based electrodes. This mechanism might be applicable to electrochemical reactions involving other sulfur compounds that hold technological significance.

Manganese doped La0.8Ba0.2FeO3 perovskite oxide as an efficient electrode material for supercapacitor

In this study, L0.8Ba0.2Fe1-xMnxO3 (LBFM-x, x = 0.0, 0.2, 0.5, 0.8) perovskite materials were synthesized by a Sol-Gel combustion method and were investigated as an electrode material for a supercapacitor device. The morphology, crystalline structure and electrochemical performance of the samples were studied in detail. The active points, where the electrochemical redox reaction takes place to store faradaic energy, are the oxygen vacancies on the surface of perovskite oxides. Partial substitution in the B-site of the perovskite structure, which is directly related to the oxygen vacancy in BO6 octahedral, is effective in optimizing the electrochemical performance. Based on the results of structural analysis, LBFM-0.2 has the highest concentration of oxygen vacancies; thus, it showed a higher electrochemical performance compared to other samples. The supercapacitors prepared with this electrode material should have an acceptably high specific capacitance of 685 F.g−1 at a current density of 2.0 A.g−1. The partial substitution of Mnn+ at the B-site increases the oxidation state of Fe cations and the mobility of oxygen ions through the oxygen vacancy sites. The electrochemical stability of LBFM-0.2, was evaluated by applying long charge-discharge cycles. After 3000 charge-discharge cycles, the supercapacitor was able to maintain about 94 % of its initial capacity.

Biochar assisted synthesis of α-MnO2 nanowires with superior performance for non-radical activation of peroxymonosulfate

Non-radical activation of peroxymonosulfate (PMS) is a promising water treatment technology for removing refractory organics, but its mechanism is still ambiguous and the development of highly efficient catalyst is still a challenge. Herein, α-MnO2 nanowires were synthesized by a hydrothermal method with the assistance of biochar and their performance for PMS activation was studied. The characterization results show that the addition of biochar had little effect on the crystal phase and valence state of MnO2 but significantly reduced the size of nanowires. These nanowires had mesoporous structure, high surface area and oxidation ability, resulting in their superior performance for removing organic pollutants with PMS activation. The degradation of phenol by α-MnO2-PMS followed first order kinetics with an activation energy of 14.82 kJ mol−1. Electron paramagnetic resonance and radical scavenging experiments demonstrated that this activation process followed the non-radical mechanism. The quenching effect of scavengers led to the misleading role of singlet oxygen. In fact, surface activated PMS (MnO2–PMS*) rather than singlet oxygen was the reactive species. Weak acidic condition was conducive for the formation of MnO2–PMS* complexes. This catalyst exhibited good reusability and high activity for removing various organic pollutants, and the common substances in real water had little effect on its performance, suggesting its potential application in wastewater treatment.

Biodegradation, Antibacterial Performance, and Cytocompatibility of a Novel ZK30-Cu-Mn Biomedical Alloy Produced by Selective Laser Melting.

In the present study, an antibacterial biomedical magnesium (Mg) alloy with a low biodegradation rate was designed, and ZK30-0.2Cu-xMn (x = 0, 0.4, 0.8, 1.2, and 1.6 wt%) was produced by selective laser melting, which is a widely applied laser powder bed fusion additive manufacturing technology. Alloying with Mn evidently influenced the grain size, hardness, and biodegradation behavior. On the other hand, increasing Mn content to 0.8 wt% resulted in a decrease of biodegradation rate which is attributed to the decreased grain size and relatively protective surface layer of manganese oxide. Higher Mn contents increased the biodegradation rate attributed to the presence of the Mn-rich particles. Taken together, ZK30-0.2Cu-0.8Mn exhibited the lowest biodegradation rate, strong antibacterial performance, and good cytocompatibility.

Arsenate adsorption, desorption, and re-adsorption on Fe–Mn binary oxides: Impact of co-existing ions

Fe–Mn binary oxides have demonstrated impressive arsenate removal efficiencies as adsorbents. However, their interaction with co-existing ions can lead to arsenate desorption, complicating the remediation process. The dynamics of both desorption and subsequent readsorption of arsenate on these oxides under the influence of various ions remain largely unexplored. This study illuminates these processes through a detailed six-month batch experiment, examining the behavior of arsenate in the presence of both single and multiple competing ions. Our findings demonstrate varied desorption impacts by different ions. Notably, the desorption effects induced by bicarbonate (HCO3−) and phosphate (PO43−) were the most significant, with maximum desorption rates reaching 21.8 % and 20.8 %, respectively. Following desorption, As(V) exhibited varying re-adsorption rates; notably, As(V) desorbed by HCO3− and PO43− achieved nearly complete re-adsorption at rates of 100 % and 97.8 % respectively after 150 days. The dynamics altered substantially in the presence of multiple ions. Specifically, the co-presence of Ca2+ and Mg2+ significantly reduced the desorption of As(V) by HCO3−, with maximum desorption rates decreasing to 0 % and 2.9 %, respectively. Moreover, the inclusion of silicate (SiO32−) in the system markedly enhanced the re-adsorption of As(V), surpassing rates observed in the presence of HCO3− alone. In contrast, when PO43−and HCO3− were present together, almost no re-adsorption of As(V) occurred, leading to a higher final desorption rate of 27.4 %. These results highlight the complex and significant role that specific ions and their combinations play in the desorption and re-adsorption of As(V) on Fe–Mn binary oxide surfaces. The study emphasizes the importance of considering the types and interactions of co-existing ions in environmental settings when utilizing Fe–Mn binary oxides for efficient arsenic removal.

Cristobalite formation on high-temperature oxidation of 4H-SiC surface based on silicon atom sublimation

Two innovative high-temperature oxidation methods for 4H-SiC were developed, with observations made via Optical Microscope, Scanning Electron Microscope and Raman spectrum. We successfully fabricated fully crystallized cristobalite films through oxidation and annealing processes, unveiling the lateral growth mechanisms of crystal planes during annealing. The study also delved into the unusual effects of Si sublimation on the oxidation rate of cristobalite during its formation and investigated the stress-induced cracking phenomena observed when the film thickness exceeds 1 μm. Additionally, a novel step oxidation technique was introduced to suppress vapor phase oxidation of Si at high temperatures by employing a barrier layer, facilitating the swift production of amorphous SiO2 thick films. The exceptional surface and interface flatness exhibited by these films underscore their significant potential for applications in the realm of functional films.

Development of a Pb(Zr,Ti)O3 capacitor employing an IrO x /Ir bottom electrode for highly reliable ferroelectric random access memories

A highly {111}-oriented metal-organic CVD Pb(Zr,Ti)O3 (PZT) is successfully developed using IrOx/Ir instead of Ir as the bottom electrode. The {111} PZT orientation strongly depends on the IrOx thickness and the O2 content of the atmosphere (PO2) during IrO x deposition. During PZT deposition, the Ir surface easily oxidizes and becomes rough, resulting in poor {111} PZT orientation. IrO x prevents Ir surface oxidation and transforms the Ir metal via O2 reduction after the PZT deposition completion. Highly {111}-oriented PZT can be obtained by optimizing the IrO x thickness and PO2 content.

Laser processing effects on Ti−45Nb alloy surface, corrosive and biocompatible properties

The Ti−45Nb (wt.%) alloy properties were investigated in relation to its potential biomedical use. Laser surface modification was utilized to improve its performance in biological systems. As a result of the laser treatment, (Ti,Nb)O scale was formed and various morphological features appeared on the alloy surface. The electrochemical behavior of Ti−45Nb alloy in simulated body conditions was evaluated and showed that the alloy was highly resistant to corrosion deterioration regardless of additional laser surface modification treatment. Nevertheless, the improved corrosion resistance after laser treatment was evident (the corrosion current density of the alloy before laser irradiation was 2.84×10−8 A/cm2, while that after laser treatment with 5 mJ was 0.65×10−8 A/cm2) and ascribed to the rapid formation of a complex and passivating bi-modal surface oxide layer. Alloy cytotoxicity and effects of the Ti−45Nb alloy laser surface modification on the MRC-5 cell viability, morphology, and proliferation were also investigated. The Ti−45Nb alloy showed no cytotoxic effect. Moreover, cells showed improved viability and adherence to the alloy surface after the laser irradiation treatment. The highest average cell viability of 115.37% was attained for the alloy laser-irradiated with 15 mJ. Results showed that the laser surface modification can be successfully utilized to significantly improve alloy performance in a biological environment.

Role of catalyst oxidation states in the selective detection of reducing gases: A comparative study of nanocomposites based on Au and chemically/thermally reduced graphene oxide

Catalyst-loaded reduced graphene oxide (rGO) is a promising material for developing high-performance gas sensors. In this work, surface functionalization is achieved by loading different quantities of nanogold (Au) on chemically and thermally reduced graphene oxide (CRGO and TRGO). These materials showed selective gas response toward reducing gases such as hydrogen (H2), carbon monoxide (CO), and methane (CH4) in the temperature range RT to 150 °C. The quantity of Au catalysts and their oxidation states in the films influenced the selectivity attributes of the studied sensors. The surface oxidation states of the Au catalyst are different for CRGO-Au and TRGO-Au films. It is apparent from the results that the difference in the Au oxidation states is due to the variation in surface oxygen functionalities of the base matrix CRGO and TRGO. The experimental results are tallied with the proposed gas selectivity mechanism of CRGO-Au and TRGO-Au films.Novelty of the Work:In reduced graphene oxide based gas sensors, the combined influence of the graphene oxide reduction method, gold (Au) catalyst quantity, and valence oxidation states (in the Au catalyst) on the gas selectivity is rarely reported. The available reports only focus on examining the metallic gold (Au0) phase of the catalyst. However, it is necessary to note that Au can also exist in various higher oxidation states (Au+1, Au+2, Au+3, etc.), which provide selective gas adsorption sites. Therefore, this work addresses the above issue by employing chemically reduced graphene oxide (CRGO) and thermally reduced graphene oxide (TRGO) decorated with Au nanoparticles (Au wt% = 1 %, 50 % & 90 %) for the selective sensing of reducing gases.

Strength, microstructure and bonding mechanism of borosilicate glass-to-SA105 carbon steel seals

The bonding strengths, microscopic characteristics and fracture properties of borosilicate glass-to-SA105 carbon steel seals were investigated, and two different glass-to-metal bonding mechanisms were compared. First, a mechanical interlocking mechanism was found via precipitates formed from chemical reactions at the interface of the seal bonded to unoxidized SA105 carbon steel. Second, a transitional layer mechanism was proven by the dissolution of metal oxides, which was on the surface of preoxidized SA105 carbon steel, into the glass. The bonding strength results showed that both mechanisms effectively contributed to the joining of dissimilar phases, but the effect of the latter mechanism was more prominent than that of the former mechanism. Various microstructures and chemical compositions of the surface oxide scales were obtained by applying different preoxidation conditions to SA105 carbon steel. Additionally, different sealing interfaces were reported through this process. The width of the interfacial transitional layer ranged from 0.5 μm to 1.5 μm, and the strength of the seal was closely related to this width. The sealing of SA105 carbon steel that was preoxidized at 800 °C for 30 min with a moderate width of the transitional layer had an optimal shear strength of 25.4 MPa. However, a wide transitional layer composed of the remaining oxide scales deteriorated the strength of the seal. In addition, fracture analysis of the seals after the shear test was conducted, and the intrinsic correlations between the macroscopic shear strength and microscopic bonding mechanism were established. The present work should provide a reference for the characterization of bonding strength in joining dissimilar materials.

Significant improvement in hot corrosion resistance of Inconel 690 by laser shock peening

The effects of laser shock peening (LSP) with different peening times on the hot corrosion behavior (molten salt of 75 wt% Na2SO4 + 25 wt% NaCl) of Inconel 690 at three different temperatures (700 °C, 800 °C, 900 °C) were investigated. The corrosion conditions of the three specimens were also compared in the extreme case, i.e. after 900 °C, 300 h of hot corrosion. The results showed that LSP effectively prevented the surface oxides from shedding. As times of LSP increased, the strengthening effect improved and the rate of weight loss gradually slowed down. The dense oxide film generated by the high Cr content of the material itself, LSP-induced high-density dislocation structure, mechanical twinning and grain refinement is one of the key factors in improving the hot corrosion resistance of Inconel 690. The CRS layer and microhardness layer are another key factor in preventing the cracking of the oxide film to enhance the hot corrosion resistance. Under extreme conditions, the hot corrosion resistance of LSPed specimens is still better than that of unLSPed specimen.

Crude oil-water separation with the aid of carbon based materials

Carbon-based materials are commonly utilized in water filtration and purification due to their affordability and environmental friendliness. This study investigates the effectiveness of four different carbon-based materials: activated carbon (AC), graphene oxide (GO), reduced graphene oxide (rGO), and polyethylene (PE) in crude oil–water separation. To test the effectiveness of the separation, light transmission measurements were carried out with the aid of Arduino UNO using a red, green, and blue (RGB) light spectral sensor. The results revealed that the emulsions with AC was the most effective material in the separation, followed by rGO, and GO was the least effective. To explain the mechanism behind the separation performance, the carbon materials have been characterized by x-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR). The effectiveness of AC and rGO in the separation process was directly related to the quantity of surface oxides. The experimental results are perfectly agreed with published Density functional theory (DFT) calculations of HOMO–LUMO gap energies. AC shows the best performance and the smallest gap, which indicates that it requires less energy for electrons transition between the HOMO and LUMO. This phenomenon can be attributed to the affinity towards hydrogen in the hydrocarbon chains in crude oil.

Improving interactions at the electrochromic polymer‐transparent oxide electrode interface using alkyl phosphonic acid modifiers

AbstractAs new synthetic methods for the preparation of solution processable electrochromic polymers are explored, including increasing synthetic scale beyond that of the research laboratory, it is expected that polymer intermolecular and intramolecular interactions will be affected. In this study, we explore the use of four different alkyl phosphonic acids of differing chain lengths as an interfacial treatment on ITO transparent electrodes to improve the polymer‐electrode interactions to mitigate the loss of film integrity and resulting electrochromic properties (current density, optical properties, and effective switch rates) during repeated oxidation/reduction and swelling/deswelling of the film. It was found that the phosphonic acid layer allows for a compatibilization of the polarity of the electrode surface with the polymer layer while also improving surface energy uniformity. We evaluated two electrochromic polymers (ECPs), and while a near complete delamination was observed on untreated ITO, film integrity was maintained beyond 25 repeated cycles, with polymer optical contrast maintained at all switching rates when coated onto dodecylphosphonic acid. Additionally, we show that electrochromic polymer film integrity is maintained over a range of film thicknesses. This method can be extended to applications using a variety of solution processable electroactive polymers in contact with metal oxide surfaces.

Simultaneous tracking of ultrafast surface and gas-phase dynamics in solid-gas interfacial reactions.

Real-time detection of intermediate species and final products at the surface and near-surface in interfacial solid-gas reactions is critical for an accurate understanding of heterogeneous reaction mechanisms. In this article, an experimental method that can simultaneously monitor the ultrafast dynamics at the surface and above the surface in photoinduced heterogeneous reactions is presented. This method relies on a combination of mass spectrometry and femtosecond pump-probe spectroscopy. As a model system, the photoinduced reaction of methyl iodide on and above a cerium oxide surface is investigated. The species that are simultaneously detected from the surface and gas-phase present distinct features in the mass spectra, such as a sharp peak followed by an adjacent broad shoulder. The sharp peak is attributed to the species detected from the surface, while the broad shoulder is due to the detection of gas-phase species above the surface, as confirmed by multiple experiments. By monitoring the evolution of the sharp peak and broad shoulder as a function of the pump-probe time delay, transient signals are obtained that describe the ultrafast photoinduced reaction dynamics of methyl iodide on the surface and in the gas-phase. Finally, SimION simulations are performed to confirm the origin of the ions produced on the surface and in the gas-phase.

Unraveling the Role and Impact of Alumina on the Nucleation and Reversibility of β‐LiAl in Aluminum Anode Based Lithium‐Ion Batteries

AbstractAluminum, due to its high abundance, very attractive theoretical capacity, low cost, low (de−) lithiation potential, light weight, and effective suppression of dendrite growth, is considered as a promising anode candidate for lithium‐ion batteries (LIBs). However, its practical application is hindered due to multiple detrimental challenges, including the formation of an amorphous surface oxide layer, pulverization, and insufficient lithium diffusion kinetics in the α‐phase. These outstanding intrinsic challenges need to be addressed to facilitate the commercial production of Al‐based batteries. The native passivation layer, Al2O3, plays a critical role in the nucleation and reversibility of lithiating aluminum and is thoroughly investigated in this study using high precision electrochemical micro calorimetry. The enthalpy of crystallization of β‐LiAl is found to be 40.5 kJ mol−1, which is in a strong agreement with the value obtained by calculation using Nernst equation (40.04 kJ mol−1). Surface treatment of the active material by the addition of 25 nm of alumina increases the nucleation energy barrier by 83 % over the native oxide layer. After the initial nucleation, the added alumina does not negatively impact the reversibility at 0.1 C rate, suggesting the removal of alumina is not necessary for improving the cyclability of aluminum anode based lithium‐ion batteries. Moreover, the coulombic efficiencies are also found to be slightly higher in the alumina treated samples compared to the untreated ones.

Investigation of deformation behavior during electric pulse assisted incremental forming of Ti-6Al-4V sheet with a water-cooling system

Electric pulse assisted incremental sheet forming (E-ISF) has been proven to enhance the formability of Ti-6Al-4 V sheet. However, the high electro-thermal effect induced by electric pulse could result in severe surface oxidation and excessively coarse grains of the final parts. In this study, a water-cooling system was employed to fabricate high-quality Ti-6Al-4 V parts during electric pulse assisted incremental forming. The excellent surface finish of Ti-6Al-4 V parts fabricated using water-cooling system can be attributed to the low forming temperature. Additionally, the activated non-basal slip can lead to the texture transition from {0001} 〈01−10〉 to {11−20} 〈0001〉 texture, together with the dynamic recrystallization of α and β grains, resulting in forming heights larger than 15 mm. This study indicates that the water-cooling system is an effective strategy for achieving low surface roughness, high formability, and geometric accuracy in Ti-6Al-4 V parts during the electric pulse assisted incremental sheet forming.