Oxygen Diffusion Research Articles

Influence of Oxygen Vacancies Introduced via Acceptor (Gadolinium) Doping to the Pseudocapacitive Properties of Nano-Sized Cerium Oxide.

The voluntary introduction of defects can be considered an effective strategy for enhancing the electrochemical properties of metal oxide electrodes. In this study, the enhanced pseudocapacitive properties of an acceptor (Gd) doped cerium oxide nanoparticle-a sustainable metal oxide with low environmental and human toxicity-are investigated in depth using ex situ X-ray photoemission spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Interestingly, with 15at% Gd doping (15GDC), the specific capacitance of the nanoparticles measured at 1Ag-1 enhanced to 547.8Fg-1, which is fivefold higher than undoped CeO2 (98.7Fg-1 at 1Ag-1). The rate-dependent capacitance is also improved for 15GDC, which showed a 31.0% decrease in the specific capacitance upon a tenfold increase in the current density, while CeO2 showed a 49.9% decrease. The enhanced electrochemical properties are studied in depth via ex situ XPS and EIS analysis, which revealed that the oxygen vacancies at the surface of the nanoparticles played important roles in enhancing both the specific capacitance and the high-rate performance of 15GDC by acting as the active site for pseudocapacitive redox reaction and allowing fast diffusion of oxygen ions at the surface of 15GDC nanoparticles.

Microencapsulation of tomato oleoresin using tomato waste fibre and its application for orange juice fortification

SummaryFood waste by‐products contain many bioactive compounds, such as proteins, carbohydrates, polyphenols and carotenoids. The purposes of this study was to extract oleoresin from tomato waste, apply tomato pomace powder (TPP) as a new shell material for encapsulation of oleoresin and to fortify orange juice using the developed microcapsules. Microencapsulation was carried out based on different TPP (2% and 3%) and oleoresin (20% and 30%) concentrations by spray drying at two temperatures (130 and 140 °C). Different features of microcapsules such as the encapsulation load, encapsulation efficiency, moisture content, hygroscopicity, bulk and tapped densities and the Hausner ratio were analysed. Based on properties of microcapsules, samples containing 3% TPP and 30% oleoresin dried at 130 °C were selected as the best treatment and their characteristics such as morphology, chemical structure and thermal behaviour were investigated. Scanning electron microscopy indicated that spherical micron‐size particles were formed and their crack‐free fine surface showed their potential for encapsulation of anti‐oxidants to reduce oxygen diffusion. Microencapsulated oleoresin was then added to the orange juice and the samples' pH, acidity, total soluble solids and colour were evaluated and compared with pure orange juice. Free radical scavenging method was used to investigate the anti‐oxidant properties of orange juice during storage. The results indicated that at the end of the 30 days of storage the fortified orange juice had anti‐oxidant activity equal to pure fresh orange juice on day one. Sensory evaluation results showed no significant differences between appearance, colour, thickness and overall acceptance of fresh and the fortified juices (P < 0.05). The results of this study showed the potential application of food and agricultural waste in production of value‐added ingredients to be used as natural additives in food industries.

Tailoring oxidation resistance of Cantor alloy by addition of Ta and Al

High-entropy alloys are widely investigated for applications in the nuclear engineering field, the aerospace sector, and various other high-temperature applications. High-temperature oxidation behaviour is a typical issue in such applications. In the current work, an effort is made to tailor the oxidation behaviour of Cantor alloy (CoCrFeMnNi) in the air at 1000 °C with the addition of Ta and Al. Both CoCrFeMnNiTa as well as CoCrFeMnNiAl alloys exhibit considerable resistance to oxide scale spallation as well as develop multi-layered complex oxide scales. CoCrFeMnNiTa primarily forms rutile-type CrTaO4 oxide, which drastically reduces the inward diffusion of oxygen and nitrogen and suppresses the escape of other alloying elements. Nonetheless, the better result is obtained through the Al addition, as evidenced by the comparatively lower oxidation rate constant of CoCrFeMnNiAl in comparison to CoCrFeMnNiTa alloy. This is attributed to the superior oxidation resistance for CoCrFeMnNiAl could be related to the emergence of distinctive Cr2O3 and Al2O3 scales. Additionally, the oxide scale of CoCrFeMnNiTa was not completely smooth and showed some spallation whereas the oxide scales of CoCrFeMnNiAl remained smooth, continuous, and had stronger oxide-substrate interface adhesion.

Triphasic Oxygen Storage in Wet Nanoparticulate Polymer of Intrinsic Microporosity (PIM-1) on Platinum: An Electrochemical Investigation.

The triphasic interaction of gases with electrode surfaces immersed in aqueous electrolyte is crucial in electrochemical technologies (fuel cells, batteries, sensors). Some microporous materials modify this interaction locally via triphasic storage capacity for gases in aqueous environments linked to changes in apparent oxygen concentration and diffusivity (as well as activity and reactivity). Here, a nanoparticulate polymer of intrinsic microporosity (PIM-1) in aqueous electrolyte is shown to store oxygen gas and thereby enhance electrochemical signals for oxygen reduction in aqueous media. Oxygen reduction current transient data at platinum disk electrodes suggest that the reactivity of ambient oxygen in aqueous electrolyte (typically Doxygen = 2.8 × 10-9 m2 s-1; coxygen = 0.3 mM) is substantially modified (to approximately Dapp,oxygen = 1.6 (±0.3) × 10-12 m2 s-1; capp,oxygen = 50 (±5) mM) with important implications for triphasic electrode processes. The considerable apparent concentration of oxygen even for ambient oxygen levels is important. Potential applications in oxygen sensing, oxygen storage, oxygen catalysis, or applications associated with other types of gases are discussed.

Two-Dimensional Metal-Organic Frameworks/Epoxy Composite Coatings with Superior O2/H2O Resistance for Anticorrosion Applications.

Corrosion protection technology plays a crucial role in preserving infrastructure, ensuring safety and reliability, and promoting long-term sustainability. In this study, we combined experiments and various analyses to investigate the mechanism of corrosion occurring on the epoxy-based anticorrosive coating containing the additive of two-dimensional (2D) and water-stable zirconium-based metal-organic frameworks (Zr-MOFs). By using benzoic acid as the modulator for the growth of the MOF, a 2D MOF constructed from hexazirconium clusters and BTB linkers (BTB = 1,3,5-tri(4-carboxyphenyl)benzene) with coordinated benzoate (BA-ZrBTB) can be synthesized. By coating the BA-ZrBTB/epoxy composite film (BA-ZrBTB/EP) on the surface of cold-rolled steel (CRS), we found the lowest coating roughness (RMS) of BA-ZrBTB/EP is 2.83 nm with the highest water contact angle as 99.8°, which represents the hydrophobic coating surface. Notably, the corrosion rate of the BA-ZrBTB/EP coating is 2.28 × 10-3 mpy, which is 4 orders of magnitude lower than that of the CRS substrate. Moreover, the energy barrier for oxygen diffusion through BA-ZrBTB/EP coating is larger than that for epoxy coating (EP), indicating improved oxygen resistance for adding 2D Zr-MOFs as the additive. These results underscore the high efficiency and potential of BA-ZrBTB as a highly promising agent for corrosion prevention in various commercial applications. Furthermore, this study represents the first instance of applying 2D Zr-MOF materials in anticorrosion applications, opening up new possibilities for advanced corrosion-resistant coatings.

Cr-Substituted SrCoO3-δ Perovskite with Abundant Oxygen Vacancies for High-Energy and Durable Low-Temperature Antifreezing Flexible Supercapacitor.

Developing high-performance electrodes for flexible antifreezing energy storage devices has been a significant challenge with the increasing demand for portable components. In this work, Cr-substituted SrCoO3-δ perovskites were first proposed as potential low-temperature supercapacitor electrode materials. The high-valence Cr6+ ([Ne]3s23p6) substitution favors a high-spin state of Co ions with enhanced electronic repulsion effect, ultimately forming a stable cubic structure with high conductivity. Accordingly, the modification strategies of SrCoO3 through the p6 configuration cation substitution have been improved. As a result, the asymmetric SrCo0.95Cr0.05O3-δ@CC//PPy@CC device exhibited a high energy density of 44.90 Wh kg-1 at 902.01 W kg-1 and maintained a 95.8% specific capacitance after 10,000 cycles, demonstrating an ultralong cyclic stability. The dramatically improved electrochemical performance was attributed to the stabilized crystal structure, increased oxygen vacancy, and accelerated oxygen diffusion rate. Furthermore, a quasi-solid-state supercapacitor with ethylene glycol (EG)-modified KOH/PVA organohydrogel electrolyte was developed through an advance in situ-integrated strategy. After bending at 180° for 1000 cycles, only a 9.7% capacity decay was observed. Even under -40 °C, the supercapacitor has a large energy density of 46.94 μWh cm-2. The present work represents the initial investigation into utilizing perovskite materials for antifreezing energy storage device, thereby confirming their potential application as low-temperature electronic components.

DESCRIPTIVE AND TOPOGRAPHIC ANATOMY OF THE LUNGS OF DOMESTIC ANIMALS

The respiratory system is divided into respiratory pathways (nose, nasal cavity, pharynx, larynx, trachea, bronchi, and lungs) and gas exchange sites (respiratory bronchioles, alveolar ducts, alveolar sacs, and alveoli). The upper respiratory tract includes the nose and pharynx, while the lower respiratory tract encompasses the larynx, trachea, and lungs. All these organs contribute to the essential function of the system, which is the exchange of gases between the environment and the blood, transporting oxygen to the cells and removing carbon dioxide. The inspired air is filtered, humidified, and warmed before reaching the lungs, where the diffusion of oxygen into the blood and the expulsion of carbon dioxide occur. Therefore, the lungs are the organs that contain the structures responsible for gas exchange and are of utmost importance. Despite their similarity, lungs exhibit differences both within the same animal and across different species. In this context, this work aims to present the descriptive and topographic anatomy of domestic animals, highlighting the differences between species.

Characterizing PEM fuel cell catalyst layer properties from high resolution three-dimensional digital images, Part II: Oxygen effective diffusion and proton effective conductivity tensors

The oxygen effective diffusion and proton effective conductivity tensors of a cathode catalyst layer (CCL) are computed using a two-scale approach on CCL microstructure three-dimensional images obtained by focused ion beam-scanning electron microscopy (FIB-SEM) after reconstruction of the ionomer distribution. The results show that the obtained tensors are not isotropic. It is also found that some off-diagonal components are not negligible in the case of the proton effective conductivity tensor. The simulations confirm that Knudsen diffusion has a significant impact on oxygen diffusion. The results are comparable to those obtained in previous works on synthetic images as regards the oxygen effective diffusion through-plane component but differ as regards the proton conductivity through-plane component. Contrary to previous works using synthetic images which tend to underestimate the proton conductivity, they are globally in better agreement with experimental data. The results also show that the effective proton conductivity is heterogeneous at the scale of the computational domains typically considered in several previous works due to the variability in the ionomer distribution at this scale. The impact of liquid water in the primary pores on the proton transport is explored and found to have a significant impact.

Characterization of 3D oxygen concentrations in microfluidic systems combining astigmatic particle tracking with phosphorescence decay measurements

In this work, we combine astigmatic particle tracking with phosphorescence decay measurements to determine 3D-resolved oxygen concentration in microfluidic systems. In our experiments we achieve uncertainties in the out-of-plane position of less than 1 µm and uncertainties in oxygen concentration of less than 2 ppm. The calibrated measurement range covers oxygen concentrations of 0.6 ppm to 27.6 ppm. A method is presented to correct for measurement errors caused by photobleaching. For this, the excitation energy, the cumulative exposure time and the spatially varying intensity profile of the laser are taken into account in the correction. With this method, low measurement errors of less than 2ppm at ambient oxygen levels can be achieved even after thousands of excitation cycles. Hence, 3D oxygen concentrations are measured in an agarose hydrogel filled microfluidic chamber across which different pressure and oxygen gradients can be set independently. The results show that oxygen diffusion is superposed by an interstitial flow, which significantly alters the resulting oxygen concentration.

Characterization of 3D oxygen concentrations in microfluidic systems combining astigmatic particle tracking with phosphorescence decay measurements

In this work, we combine astigmatic particle tracking with phosphorescence decay measurements to determine 3D-resolved oxygen concentration in microfluidic systems. In our experiments we achieve uncertainties in the out-of-plane position of less than 1 µm and uncertainties in oxygen concentration of less than 2 ppm. The calibrated measurement range covers oxygen concentrations of 0.6 ppm to 27.6 ppm. A method is presented to correct for measurement errors caused by photobleaching. For this, the excitation energy, the cumulative exposure time and the spatially varying intensity profile of the laser are taken into account in the correction. With this method, low measurement errors of less than 2ppm at ambient oxygen levels can be achieved even after thousands of excitation cycles. Hence, 3D oxygen concentrations are measured in an agarose hydrogel filled microfluidic chamber across which different pressure and oxygen gradients can be set independently. The results show that oxygen diffusion is superposed by an interstitial flow, which significantly alters the resulting oxygen concentration.

Improving the wear and heat resistance of niobium substrate via reactive electrospark treatment using fusible AlCaSiY electrode

Protective coatings with a heterophase layered structure were obtained by reactive electrospark treatment (EST) of niobium substrate with a fusible AlCaSiY electrode. The effect of the frequency–energy modes of EST on the phase composition, structure and properties of the coatings was studied. A combination of high discharge current values (400A) and long pulses (100 μs) yields a double-layer coating with the total thickness of 80 μm, which consists of the (Al) matrix strengthened with Nb2CaAl20 particles and a hard (10 GPa) NbAl3 layer. The results of pin-on-plate tribological testing revealed that this structure made it possible to reduce the coefficient of friction from 0.42 to 0.24 and increase wear resistance 3.5-fold compared to those of niobium. Oxidative annealing of Nb plates in air at 700 °C causes their fracture due to the formation of Nb2O5. Indeed, oxidative annealing of the samples subjected to EST leads to in situ formation of a dense Ca12Al10Si4O35-oxide based near surface layer that inhibits oxygen diffusion into the bulk, thus suppressing Nb2O5 formation. Mass gain of the sample having a protective coating after 300-min isothermal exposure was 2.54 mg/cm2, which is 3.6-fold lower than that for the Nb substrate (9.04 mg/cm2).

Perpendicular magnetic anisotropy of Cr/CoFeB/MgO modulated by MgO thickness

The dependence of perpendicular magnetic anisotropy (PMA) on the MgO thickness in Cr/CoFeB/MgO/Ta films has been experimentally investigated. A clear PMA is observed in the as-deposited samples with 1.8 nm MgO while no as-deposited PMA is shown in those with 4.0 nm MgO. This may be attributed to the moderate oxidation degree of CoFeB and larger interfacial anisotropy energy density K i to overcome the volume magnetic anisotropy and demagnetization field. On the contrary, samples with 4.0 nm MgO demonstrate PMA only after annealing, which might be due to the oxygen and boron diffusion during the annealing process. These results would provide a method to optimize the design of CoFeB/MgO structures on 3d metals for future applications in perpendicular magnetic devices.

The impact of oxygen availability on steel corrosion considering the self-balance between anodic and cathodic corrosion cells

An advanced model is developed to elucidate relationship between availability of oxygen and active corrosion, considering the equilibrium between gaseous and dissolved oxygen, as well as the equilibrium of oxygen diffusion and consumption. This research notably incorporates self-regulation mechanisms of cathodes and anodes in both macrocell and microcell corrosion. Accelerated corrosion experiments were performed under simulated marine environment, monitoring variations in corrosive medium concentration and electrochemical corrosion processes. Results indicate significant reduction in oxygen concentration following the activation of rebar. Potential inaccuracies in predicting corrosion rate arise from the adoption of a static cathodic to anodic area ratio was highlighted.

Effect of atmospheric-pressure nitrogen plasma treatment at low temperature on fatigue properties of low-alloy steels

A device for parallel-plate-type atmospheric-pressure nitrogen plasma (APNP) treatment, which can generate plasma in a sealed environment with high-purity nitrogen gas, was developed. The objective of the present study was to use microstructural analyses to investigate the effect of APNP treatment at low temperatures on the fatigue properties of low-alloy steels. The APNP treatment was conducted at 473 K, which is lower than the common gas nitriding temperature. X-ray analyses revealed that a nitrogen–oxygen diffusion layer with high fatigue limit was formed on the steel by the APNP treatment at 473 K. Thus, the APNP treatment is an effective approach for increasing the fatigue limit of steels by increasing their surface hardness.

Development of an integrated fixed-film activated sludge (IFAS) reactor treating landfill leachate for the biological nitrogen removal through nitritation-denitritation

The current work investigated the performance of an Integrated Fixed-Film Activated Sludge Sequencing Batch Reactor (IFAS-SBR) for Biological Nitrogen Removal (BNR) from mature landfill leachate through the nitritation-denitritation process. During the experimental period two IFAS-SBR configurations were examined using two different biocarrier types with the same filling ratio (50%). The dissolved oxygen (DO) concentration ranged between 2 and 3 mg/L and 4–6 mg/L in the first (baseline-IFAS) and the second (S8-IFAS) setup, respectively. Baseline-IFAS operated for 542 days and demonstrated a high and stable BNR performance maintaining a removal efficiency above 90% under a Nitrogen Loading Rate (NLR) up to 0.45 kg N/m3-d, while S8-IFAS, which operated for 230 days, was characterized by a limited and unstable BNR performance being unable to operate sufficiently under an NLR higher than 0.20 kg N/m3-d. It also experienced a severe inhibition period, when the BNR process was fully deteriorated. Moreover, S8-IFAS suffered from extensive biocarrier stagnant zones and a particularly poor sludge settleability. The attached biomass cultivated in both IFAS configurations had a negligible content of nitrifying bacteria, probably attributed to the insufficient DO diffusion through the biofilm, caused by the low DO concentration in the liquid in the baseline case and the extensive stagnant zones in the S8-IFAS case. As a result of the high biocarrier filling ratio, the S8-IFAS was unstable and low. This was probably attributed to the mass transfer limitations caused by the biocarrier stagnant zones, which hinder substrate and oxygen diffusion, thus reducing the biomass activity and increasing its vulnerability to inhibitory and toxic factors. Hence, the biocarrier filling fraction is a crucial parameter for the efficient operation of the IFAS-SBR and should be carefully selected taking into consideration both the media type and the overall reactor configuration.

Enhanced Hydrogen Production in Microwave‐Driven Water‐Splitting Redox Cycles by Engineering Ceria Properties

AbstractSustainable hydrogen, produced from renewable sources such as solar or wind, plays a decisive role in driving industrial decarbonization. Among hydrogen production technologies, steam electrolysis, and solar‐driven thermochemical cycles using reducible solid oxides show promise but face challenges due to high operation temperatures. Microwave‐driven redox chemical looping enables the direct, contactless electrification of the process, reducing the operation temperature and complexity. Previous works showed that microwaves can efficiently drive reduction/water‐splitting cycles using Gd‐doped ceria at low temperatures (<250 °C), but adjustment of material properties is needed. Here, the key properties of materials are explored that affect the redox mechanism by screening a series of doped ceria materials to enhance microwave‐driven hydrogen production. Evaluation of trivalent dopants (La3+, Gd3+, Y3+, Yb3+, Er3+, and Nd3+) reveals that reduction correlates with lattice and electronic properties. The composition Ce0.9La0.1O2‐δ achieves 1.41 mL g−1, the highest hydrogen production among the studied series. Its narrower bandgap allows for reaching higher conductivity upon microwave‐driven reduction at lower temperatures, while a larger ionic lattice size boosts solid‐state oxygen diffusion. Overall, this research remarks on the critical properties of ceria‐based materials that enhance hydrogen production in microwave‐driven water‐splitting cycles, supporting the design of more efficient materials for sustainable chemical production technology.

Accounting for spatial variations during photopolymerization of 1,6‐hexane‐diol diacrylate in the presence of oxygen

AbstractA dynamic model is proposed for photopolymerization of 1,6‐hexane‐diol diacrylate (HDDA) with bifunctional initiator bis‐acylphosphine oxide (BAPO) in the presence of oxygen. This partial‐differential‐equation model predicts time and spatially varying vinyl‐group conversion as well as concentrations of monomer, initiator, oxygen, and seven types of radicals. Experiments to obtain diffusivities of oxygen, BAPO and HDDA are reported. Oxygen‐related parameters are estimated using real‐time Fourier‐transform infrared (FTIR) conversion data. FTIR experiments were conducted using a range of film thicknesses (), BAPO levels () and light intensities (). The model predicts qualitative trends. Conversion predictions for runs with high intensities () and high BAPO () are accurate with a root‐mean‐squared error (RMSE) of 0.04. Larger RMSE (0.13) for runs with lower intensities and BAPO indicates that improved parameter estimates are required. Parameter estimates will be updated in future using a model that accounts for shrinkage during polymerization.

Two-dimensional oxygen-diffusion modelling for FLASH proton therapy with pencil beam scanning - impact of diffusive tissue properties, dose, dose rate and scan patterns.

Oxygen depletion is generally believed to play an important role in the FLASH effect - a differential reduction of the radiosensitivity of healthy tissues, relative to that of the tumour under ultra-high dose-rate (UHDR) irradiation conditions. In proton therapy (PT) with pencil-beam scanning (PBS), the deposition of dose, and, hence, the degree of (radiolytic) oxygen depletion varies both spatially and temporally. Therefore, the resulting oxygen concentration and the healthy-tissue sparing effect through radiation-induced hypoxia varies both spatially and temporally as well. We propose and numerically solve a physical oxygen diffusion model to study these effects and their dependence on tissue parameters and the scan pattern in pencil-beam delivery. Since current clinical FLASH proton therapy (FLASH-PT) is based on 250 MeV shoot-through (transmission) beams, for which dose and dose rate hardly vary with depth compared to the variation transverse to the beam axis, we focus on the two-dimensional case. We numerically integrate the model to obtain the oxygen concentration in each voxel as a function of time and extract voxel-based and spatially and temporarily integrated metrics for oxygen (FLASH) enhanced dose. Furthermore, we evaluate the impact on oxygen enhancement of standard pencil-beam delivery patterns and patterns that were optimised on dose-rate. Our model can contribute to the identification of tissue properties and pencil-beam delivery parameters that are critical for FLASH-PT and it may be used for the optimisation of FLASH-PT treatment plans and their delivery. Our main findings are that: (i) the diffusive properties of oxygen are critical for the steady state concentration and therefore the FLASH effect, even more so in two dimensions when compared to one dimension. (ii) The FLASH effect through oxygen depletion depends primarily on dose and less on other parameters. (iii) At a fixed fraction dose there is a slight dependence on dose rate. (iv) Scan patterns optimised on dose rate slightly increase the oxygen induced FLASH effect.

POTENTIAL PARAMETERS FOR EVALUATING THE ACTIVATION CHARACTERISTICS OF ION DIFFUSION IN SOLID ELECTROLYTES BASED ON STABILIZED ZIRCONIUM OXIDE

The activation energy values of oxygen ion diffusion in yttria-stabilized zirconia (one of the most promising solid electrolytes for fuel cell technologies), estimated in molecular dynamics studies with the classical Buckingham potential, turn out to be significantly lower than experimental ones. A possible reason is the incorrect calibration of the potential, the parameters of which were selected earlier using simple model systems. In this paper, three sets of potential parameters have been developed based on the calibration of the interatomic potential based on the results of periodic DFT calculation in an extended system. The results of molecular dynamic modeling using the developed parameter sets reproduce much better the experimental values of activation energies with a variation of the molar fraction of the dopant in a solid electrolyte.

Supersonic hot jet ablative testing and analysis of boron nitride nanotube hybrid composites

Boron nitride nanotubes (BNNTs) are high-strength, high-modulus nanotubes with high thermal and oxidative stabilities. Two hybrid composites were prepared with satin weave carbon fiber (CF) and resole-type phenolic resin: one with surface layers of BNNTs and one with alternating interlayers of BNNTs. The samples were subjected to hot jet tests that simulate realistic high-pressure-temperature conditions to understand the behavior of BNNTs under high-pressure erosion. Adding BNNTs to CF/phenolic laminates enhanced the ablation resistance by reinforcing the char material and mitigated localized thermal damage. Hybrid laminates exhibited up to 14 % lower weight loss, 55 % increase in flexural modulus, higher thermal diffusivity, and improved char yield and microstructure compared to CF/phenolic samples. The surface layer hybrid had many surviving nanotubes reinforcing the char and crystalline oxide structures that could mitigate further oxygen diffusion. Various characterization methods were used to deduce possible mechanisms and their products, indicating that BNNTs could serve as growth templates for direct crystalline boron oxide formation. Overall, hybrid BNNT/CF/phenolic laminates displayed better ablation resistance and favorable microstructure evolution under high-pressure conditions.