The effects of surface preparations on oxidation kinetics and oxide scale morphology for the commercially available Ni-based superalloy IN 713C have been investigated. The ground and polished samples were exposed in air at 800-1100C. The ground specimens were found to demonstrate lower oxidation kinetics compared to those after polishing. The grinding also affected the oxide scale morphology, resulting in a protective alumina scale, while the polished samples developed Ni-/Cr-rich mixed oxides on the surface. Better oxidation resistance of the ground surfaces is related to a higher concentration of defects in the nearsurface region introduced by cold working. These defects facilitate the outward transport of the scaleforming element Al and thus are beneficial for protective oxidation. The oxidation mechanism at lower temperatures was introduced. The model based on the generalized Darken method and multiphase approximation was proposed.
High oxidation potential indicates anodes have high oxidation power and high current efficiency for organics oxidation. In this paper, we prepared Ti/Cu-SnO2 anodes using spray pyrolysis method. The Ti/Cu-SnO2 anodes have an ultra-high oxidation potential of about 2.7 V vs NHE, suitable for use in wastewater treatment. The Ti/Cu-SnO2 anodes exhibit the preferred orientation along (110) plane at high Cu doped concentration. First-principles calculations suggest that work function of Cu-SnO2 increases with the Cu doping concentration. It is obtained that the preferred (110) plane and the high wo…
The effect of isothermal pre-oxidation treatments on the \b{eta}-(Ni,Pt)Al + René N5 system degradation is here reported. The oxidation treatments were carried out from 900 (mostly θ-Al2O3 growing conditions) to 1200°C (mainly α-Al2O3 growing conditions) for 5 h, under a purified Ar-stream with a fixed pO2= 1 x 10-5 atm. Results are discussed based on the correlation between the structural, microstructural and chemical properties of the \b{eta}-(Ni,Pt)Al BC showing that pre-oxidation parameters have an important effect on the multi-elemental counter diffusion phenomena along BC. For instance, …
We report first-principles static and dynamic calculations that clarify the microscopic mechanism of carbon annihilation due to phosphorous treatment upon oxidation of silicon carbide (SiC). We identify the most stable form of the phosphorus (P) in the oxide as the four-fold coordinated with the dangling PO unit and find that the unit attracts carbon ejected from the interface, thus operating as a carbon absorber. This finding provides a microscopic reasoning for the first time for the promotion of the oxidation reaction on one hand and the annihilation of the C-related defects at the interfac…
Fe based alloys are commonly used in almost every sector of human life. For different reasons, the surfaces of the real parts are prepared using different methods, e.g., mirror-like polishing, grit-blasting, etc. The purpose of the present work is to answer the question how the surface preparation influences the oxidation behavior of Fe-based alloys. To answer this question, a high purity model alloy, Fe 5 wt Al, was isothermally oxidized in a thermogravimetrical furnace. The post-exposure analysis included SEM/EDS (WDS) and XRD. The surface roughness was determined by a contact and laser prof…
The Zr-based MAX phases have attracted considerable attention for their outstanding irradiation behavior and high neutron transparency relevant to nuclear power generation technologies. In spite of increased understanding of physical behavior crystalline MAX phases, the high-temperature oxidation behavior and reaction mechanism of disordered MAX phases both from theory and experiments are not well understood due to increased system complexity. Here, we present a detailed comparative assessment of high-temperature thermodynamic-stability and oxidation behavior (reaction-products and chemical ac…
In the present work the effect of surface roughness on oxidation behavior during the early stages of high temperature exposure of Ni-base superalloy IN 625 is described. The surface roughness was described using standard contact profilometer as well as novel method, fractal analysis. It was found that the different surface preparation resulted in a difference in roughness with a parameter increase of at least one order of magnitude for the ground sample as compared with the polished sample. The oxidation test was performed in a horizontal tube furnace. Post exposure analyses including glow dis…
It has been widely accepted that the introduction of titanium carbides into titanium-based alloys can significantly enhance the oxidation resistance due to their superior physicochemical stability at elevated temperatures. The present study reported for the first time that the ordered C vacancies within titanium carbides could lead to an uncommon phenomenon particularly at the very initial stage of oxidation. The intrinsic micro-to-macro oxidation mechanisms were systematically clarified with the aids of transmission electron microscope and ab-initio molecular dynamics simulation.
The effect of temperature in high purity Ar (low oxygen partial pressure) on the oxidation and crystal phase evolution of c-Al0.66Ti0.33N arc-PVD coatings was investigated. High temperature tribology in Ar jet and adhesion behavior of the oxidized coating were addressed. The use of Ar protects the coating from the oxidation reactions and allowed to shed light into the details and paths of the nitride oxidation process. The c-Al0.66Ti0.33N nitrides were slightly oxidized in Ar even at high temperature. The surface chemistry evaluation shows very thin Al- and Ti-based oxide layers formation afte…
Recent experiments revealed an anomalous dependence of carbon monoxide oxidation at Ru(0001) on oxygen pressure and a particularly high reaction rate. Below we report density functional theory calculations of the energetics and reaction pathways of the speculated mechanism. We will show that the exceptionally high rate is actuated by a weakly but nevertheless well bound (1x1) oxygen adsorbate layer. Furthermore it is found that reactions via scattering of gas-phase CO at the oxygen covered surface may play an important role. Our analysis reveals, however, that reactions via adsorbed CO molecul…
Reducible oxides are widely used catalyst supports that can increase oxidation reaction rates by transferring their lattice oxygen at the metal-support interface. The interfacial oxidation process is typically described in terms of a Mars-van Krevelen mechanism. However, many outstanding questions remain unanswered regarding the atomic-scale structure and dynamic meta-stability (i.e., fluxional behavior) of the interface $\textit{during catalysis}$. Here, we employ aberration-corrected $\textit{operando}$ electron microscopy to visualize the structural dynamics occurring at and near Pt/CeO$_{2…
In-depth understanding of the retarded oxidation phenomenon observed during the oxidation of silicon nanostructures is proposed. The wet thermal oxidation of various silicon nanostructures such as nanobeams, concave/convex nanorings and nanowires exhibits an extremely different and complex behavior. Such effects have been investigated by the modeling of the mechanical stress generated during the oxidation process explaining the retarded regime. The model describes the oxidation kinetics of silicon nanowires down to a few nanometers while predicting reasonable and physical stress levels at the …
The mechanical behaviour and deformation mechanisms of magnetron-sputtered Zr/Nb nanoscale multilayers were analysed as a function of the periodicity (L = 10 and 75 nm) and annealing time at 350C (2-336 hrs). The strength of the as-deposited multilayers was independent of the layer thickness and it was controlled by the co-deformation of the Zr and Nb layers. Annealing led to transformation of the Zr layers into ZrO2 after a few hours, while the Nb layers oxidised at a much slower rate. The volumetric expansion associated with the oxidation led to the formation of cracks at the interfaces and …
Open-porous scaffolds of WE43 Mg alloy with a body-center cubic cell pattern were manufactured by laser powder bed fusion with different strut diameters. The geometry of the unit cells was adequately reproduced during additive manufacturing and the porosity within the struts was minimized. The microstructure of the scaffolds was modified by means of thermal solution and ageing heat treatments and was analysed in detail by means of X-ray microtomography, optical, scanning and transmission electron microscopy. Moreover, the corrosion rates and the mechanical properties of the scaffolds were meas…
We present a first-principles based multiscale modeling approach to heterogeneous catalysis that integrates first-principles kinetic Monte Carlo simulations of the surface reaction chemistry into a fluid dynamical treatment of the macro-scale flow structures in the reactor. The approach is applied to a stagnation flow field in front of a single-crystal model catalyst, using the CO oxidation at RuO2(110) as representative example. Our simulations show how heat and mass transfer effects can readily mask the intrinsic reactivity at gas-phase conditions typical for modern in situ experiments. For …
Investigation on oxidation resistance of two-dimensional (2D) materials is critical for many of their applications, because 2D materials could have higher oxidation kinetics than their bulk counterparts due to predominant surface atoms and structural distortions. In this study, the oxidation behavior of high-quality boron nitride (BN) nanosheets of 1-4 layer thick has been examined by heating in air. Atomic force microscopy and Raman spectroscopy analyses reveal that monolayer BN nanosheets can sustain up to 850 °C and the starting temperature of oxygen doping/oxidation of BN nanosheets only s…
Generally hydrogen will adopt the +1, 0 or -1 oxidation state in solids depending upon the chemical environment it occupy. Typically, there are some exceptional cases in which hydrogen exhibits both anionic and cationic behavior in the same structural frame works. In this study we briefly explore an amphoteric behavior of hydrogen present in ammine bimetallic borohydrides with the chemical formula M1M2 (BH4)3 (NH3)2 (M1= Na; M2 = Zn, Mg) using the state-of-the-art density functional calculations. In order to establish the amphoteric behavior of hydrogen in M1M2 (BH4)3 (NH3)2, we have made deta…
The present study deals with oxidation behavior under residual stress of shot-peened plates of "commercially pure" zirconium exposed for 30 min at 650 C. The influence of the shot-peening on a pre-oxidized material is presented. The results have been used to determine the influences of these chemical (preoxidation) and mechanical (shot-peening) treatments on the high temperature oxidation of zirconium. The oxygen profile was revealed using micro-hardness techniques and confirmed by SEM-EDS techniques. After pre-oxidation the samples were first resurfaced then shot-peened in order to introduce …
NiTi-based high-temperature shape memory alloys (HTSMAs) such as NiTiHf have been utilized in a broad range of applications due to their high strength and work output, as well as, their ability to increase the transformation temperatures (TTs). Recently, additive manufacturing techniques (AM) have been widely used to fabricate complex shape memory alloy components without any major modifications or tooling and has paved the way to tailor the manufacturing and fabrications of microstructure and critical properties of their final parts. NiTi alloys properties such as transformation temperatures …
High entropy materials, which include high entropy alloys, carbides, and borides, are a topic of substantial research interest due to the possibility of a large number of new material compositions that could fill gaps in application needs. There is a current need for materials exhibiting high temperature stability, particularly oxidation resistance. A systematic understanding of the oxidation behavior in high entropy materials is therefore required. Prior work notes large differences in the thermodynamic favorability between oxides formed upon oxidation of high entropy materials. This work use…
In our work, a novel processing strategy for the continuous fabrication and surface modification of wires from Magnesium alloy WE43 by means of plasma-electrolytic oxidation (PEO) is presented. In the first step, wires with a strong basal texture and small grain size ($\approx$ 1 $μ$m) were manufactured by combined cold drawing and in-line stress-relief heat treatment steps that optimized the mechanical properties (in terms of strength and ductility) by means of annealing. In a second step, and to the best of our knowledge for the first time ever, the wires were continuously surface-modified w…
Growing uniform oxides with various thickness on TMDs is one of the biggest challenges to integrate TMDs into complementary metal oxide semiconductor (CMOS) logic circuits. Here, we report a layer-by-layer oxidation of atomically thin MoTe2 flakes via ozone (O3) exposure. The thickness of MoOx oxide film could be tuning with atomic-level accuracy simply by varying O3 exposure time. Additionally, MoOx-covered MoTe2 shows a hole-dominated transport behavior. Our findings point to a simple and effective strategy for growing homogenous surface oxide film on MoTe2, which is promising for several pu…
Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metal- insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth c…
We show a general two-step method to grow hydroxide and oxide nanocrystals of the iron family elements (Ni, Co, Fe) on graphene with two degrees of oxidation. Drastically different nanocrystal growth behaviors were observed on low-oxidation graphene sheets (GS) and highly oxidized graphite oxide (GO) in hydrothermal reactions. Small particles pre-coated on GS with few oxygen-containing surface groups diffused and recrystallized into single-crystalline nickel hydroxide Ni(OH)2 hexagonal nanoplates or iron oxide Fe2O3 nanorods with well defined morphologies. In contrast, particles pre-coated on …
We present first-principles kinetic Monte Carlo (1p-kMC) simulations addressing the CO oxidation reaction at Pd(100) for gas-phase conditions ranging from ultra-high vacuum (UHV) to ambient pressures and elevated temperatures. For the latter technologically relevant regime there is a long-standing debate regarding the nature of the active surface. The pristine metallic surface, an ultra-thin (sqrt5xsqrt5)R27^o PdO(101) surface oxide, and thicker oxide layers have each been suggested as the active state. We investigate these hypotheses with 1p-kMC simulations focusing on either the Pd(100) surf…
Polyimides, due to their superior mechanical behavior at high temperatures, are used in a variety of applications that include aerospace, automobile and electronic packaging industries, as matrices for composites, as adhesives etc. In this paper, we extend our previous model in [S. Karra, K. R. Rajagopal, Modeling the non-linear viscoelastic response of high temperature polyimides, Mechanics of Materials, In press, doi:10.1016/j.mechmat.2010.09.006], to include oxidative degradation of these high temperature polyimides. Appropriate forms for the Helmholtz potential and the rate of dissipation …
We found that carbon-associated byproducts formed at the dry-oxidized SiO2/SiC(0001) interface could be decomposed and be taken out to the SiO2 side by high-purity Ar annealing. We evaluated the concentration of the ejected carbon atoms in the SiO2 by secondary ion mass spectrometry, and discovered that it clearly depends on the condition of oxide formation (dry-oxidation, nitridation treatment, and phosphorus treatment). This work provides an indirect but unambiguous evidence for the carbon-byproducts existing at the SiO2/SiC interfaces, and also indicates that the phosphorus treatment remove…
The Langmuir-Hinshelwood barrier (ELH) and the pre-exponential factor ($ν$LH) for CO oxidation have been measured at high temperature on hexagonal arrays of Pd clusters supported on an ultrathin alumina film on Ni3Al(111). The Pd clusters have a sharp size distribution and the mean sizes are: 174$\pm$13, 360$\pm$19 and 768$\pm$28 atoms. ELH and $ν$LH are determined from the initial reaction rate of a CO molecular beam with a saturation layer of adsorbed oxygen on the Pd clusters, measured at different temperatures (493$\le$T (K) $\le$613). The largest particles (3.5 nm) give values of ELH and …
The localized dielectric breakdown had been considered as the driving force for growth of plasma electrolytic oxide (PEO) coatings for several decades. However, the TEM study here reveals the dielectric breakdown behavior has little contribution for coating thickening. The presented evidences show the nature of PEO coating growth in all three consecutive stages I-III is ionic migration behavior inside the amorphous alumina layer (AAL) at the coating/matrix interface. The evolution of morphological characterizations in the PEO process is attributed to the interfacial reactions of AAL/alkaline (…
In recent years due to improvements in calculation methods and increased computer power, it has become possible to perform first-principles investigations for ``simple'' chemical reactions at surfaces. We have carried out such studies for the catalytic oxidation of CO at transition metal surfaces, in particular, at the ruthenium surface for which unusual behavior compared to other transition metal catalysts has been reported. High gas pressure catalytic reactor experiments have revealed that the reaction rate over Ru for oxidizing conditions is the highest of the transition metals considered -…
FeCrAl alloys are proposed and being intensively investigated as alternative accident tolerant fuel (ATF) cladding for nuclear fission application. Herein, the influence of major alloy elements (Cr and Al), reactive element effect and heating schedules on the oxidation behavior of FeCrAl alloys in steam up to 1500°C was examined. In case of transient ramp tests, catastrophic oxidation, i.e. rapid and complete consumption of the alloy, occurred during temperature ramp up to above 1200°C for specific alloys. The maximum compatible temperature of FeCrAl alloys in steam increases with raising Cr a…
We present first-principles calculations of the structural and electronic properties of Si(001)-SiO2 interfaces. We first arrive at reasonable structures for the c-Si/a-SiO2 interface via a Monte-Carlo simulated annealing applied to an empirical interatomic potential, and then relax these structures using first-principles calculations within the framework of density-functional theory. We find a transition region at the interface, having a thickness on the order of 20Å, in which there is some oxygen deficiency and a corresponding presence of sub-oxide Si species (mostly Si^+2 and Si^+3). Distri…
Although of practical importance, there is no established modeling framework to accurately predict high-temperature cyclic oxidation kinetics of multi-component alloys due to the inherent complexity. We present a data analytics approach to predict the oxidation rate constant of NiCr-based alloys as a function of composition and temperature with a highly consistent and well-curated experimental dataset. Two characteristic oxidation models, i.e., a simple parabolic law and a statistical cyclic-oxidation model, have been chosen to numerically represent the high-temperature oxidation kinetics of c…
Oxidation-resilient structural modifications in Nickel-functionalized 3D-graphene for hydrogen storage applications
Istituto Nanoscienze–CNR（意大利国家研究委员会纳米科学研究所）；NEST-Scuola Normale Superiore（新实验科学与技术学院-高等师范学校）；Department of Physical Science, Earth, and Environment, University of Siena（锡耶纳大学地球与环境物理科学系）；Institute of Sensor and Actuator Systems, TU Wien（维也纳工业大学传感器与致动器系统研究所）；CNR - Istituto Officina dei Materiali (IOM)（意大利国家研究委员会材料工厂研究所）
Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the first use of aberration-corrected scanning transmission electron micr…
In the present paper, the analysis of polishing, grinding and sand-blasting processes on oxidation behavior of nickel, copper and nickel-copper alloy has been investigated. Surface roughness has been measured using two methods: by contact profilometer and by fractal analysis. It has been proved that sand-blasting process influences the surface roughness the most but also contaminates the surface with alumina particles. The oxidation tests were performed in thermogravimetrical furnace. The obtained mass gain plots, SEM microphotographs of cross-sections and SEM EDS analysis of the samples prove…
The corrosion, mechanical degradation and biological performance of cold-drawn WE43 Mg wires were analyzed as a function of thermo-mechanical processing and the presence of a protective oxide layer created by continuous plasma electrolytic oxidation (PEO). It was found that the corrosion properties of the non-surface-treated wire could be optimized by means of thermal treatment within certain limits, but the corrosion rate remained very high. Hence, strength and ductility of these wires vanished after 24 h of immersion in simulated body fluid at 37$^\circ$C and, as a result of that rather quic…
We performed density-functional theory calculations using the generalized gradient approximation for the exhange-correlation functional to investigate the unusual catalytic behavior of Ru under elevated gas pressure conditions for the carbon monoxide oxidation reaction, which includes a particularly high CO_2 turnover. Our calculations indicate that a full monolayer of adsorbed oxygen actuates the high rate, enabling CO_2 formation via both scattering of gas-phase CO molecules as well as by CO molecules adsorbed at oxygen vacancies in the adlayer, where the latter mechanism is expected to be v…
In recent times,there has been a significant volume of work on Eutectic High Entropy Alloys (EHEAs) owing to their remarkable castability combined with excellent mechanical properties,which aids in clearing obstacles for their technological applications. One of the most common EHEAs,which has been of enormous interest at present, primarily owing to its solidification and tensile behavior, is AlCoCrFeNi$_{2.1}$. However,to aim for high-temperature applications,oxidation behaviour of material is one of the major aspects that needs to be extensively investigated.To this end,the present work aims …
We report fluorescence investigations and Raman spectroscopy on colloidal nanodiamonds (NDs) obtained via bead assisted sonic disintegration (BASD) of a polycrystalline chemical vapor deposition film. The BASD NDs contain in situ created silicon vacancy (SiV) centers. Whereas many NDs exhibit emission from SiV ensembles, we also identify NDs featuring predominant emission from a single bright SiV center. We demonstrate oxidation of the NDs in air as a tool to optimize the crystalline quality of the NDs via removing damaged regions resulting in a reduced ensemble linewidth as well as single pho…
Our recent modelling works and corresponding numerical simulations realized to describe the UO2 oxidation processes confirm the theory showing that an applied mechanical strain can strongly affect the local oxygen diffusion in a stressed solid. This result allows us to assume that stress field, previously applied at the surface of a metallic sample on several microns, will delay the degradation during its oxidation. Considering this hypothesis, we implemented a FEM simulation code developed in our laboratory to numerically investigate some different stress fields applied on a sample sub-surfac…
The activity and stability of a platinum nanoparticle (NP) is not only affected by its size but additionally depends on its shape. To this end, simulations can identify structure-property relationships to make a priori decisions on the most promising structures. While activity is routinely probed by electronic structure calculations on simplified surface models, modeling the stability of NP model systems in electrochemical reactions is challenging due to the long timescale of relevant processes such as oxidation beyond the point of reversibility. In this work, a routine for simulating electroc…
Liquid metals exhibit remarkable mechanical properties, in particular large surface tension and low viscosity. However, these properties are greatly affected by oxidation when exposed to air. We measure the viscosity, surface tension, and contact angle of gallium (Ga) and a eutectic gallium-indium alloy (eGaIn) while controlling such oxidation by surrounding the metal with an acid bath of variable concentration. Rheometry measurements reveal a yield stress directly attributable to an oxide skin that obscures the intrinsic behavior of the liquid metals. We demonstrate how the intrinsic viscosit…
Electronic structure and oxidation states in high-pressure synthesized isostructural CeCN$_5$ and TbCN$_5$
Linköping University（林雪平大学）；École polytechnique, Institut Polytechnique de Paris（巴黎综合理工学院，巴黎理工学院）；CNRS（法国国家科学研究中心）；Collège de France, Université PSL（法兰西学院，巴黎文理研究大学）
A beam experiment is presented to study heterogeneous reactions relevant to plasma-surface interactions. Atom and ion beams are focused onto the sample to expose it to quantified beams of oxygen, nitrogen, hydrogen, noble gas ions and metal vapor. The heterogeneous surface processes are monitored in-situ and in real time by means of a quartz crystal microbalance (QCM) and Fourier transform infrared spectroscopy (FTIR). Two examples illustrate the capabilities of the particle beam setup: oxidation and nitriding of aluminum as a model of target poisoning during reactive magnetron sputtering, and…
Formation Gibbs free energy of point defects and oxygen clusters in uranium dioxide at high-pressure high-temperature conditions are calculated from first principles, using the LSDA+U approach for the electronic structure and the Debye model for the lattice vibrations. The phonon contribution on Frenkel pairs is found to be notable, whereas it is negligible for the Schottky defect. Hydrostatic compression changes the formation energies drastically, making defect concentrations depend more sensitively on pressure. Calculations show that, if no oxygen clusters are considered, uranium vacancy bec…
