Degradation Mechanism Research Articles

Molecular Dynamics Simulation of the Interaction within the Carboxymethyl Cellulose-Modified Montmorillonite Lamellae at Aggressive CuCl2 Concentrations.

To elucidate the degradation mechanism of the CMC-modified MMT composite at aggressive Cu2+ concentrations, large scale molecular dynamics simulation was conducted for CuCl2 concentrations ranging from 0 to 800 mM. Both CMC and MMT followed the Langmuir isotherm for Cu2+ adsorption, and the adsorption capacity of CMC (8.75 mmol/g) was much higher than that of MMT (0.83 mmol/g). Despite the CMC mass ratio being only 4.1%, it adsorbed up to 34.3% of the total adsorbed Cu2+. The Cu2+ attraction ability hierarchy of oxygen-containing functional groups in the CMC is as follows: carboxylic oxygens > alcoholic oxygens > carbinolic oxygens > bridging oxygens > glucose oxygens. Carboxyls were the most effective in chelating and complexing with Cu2+, and they could be intentionally added in artificially synthesized polymer-MMT composites for Cu2+ containment. Formation of the Cu2+ cation bridge between CMC and MMT at aggressive CuCl2 concentrations contributed to the transition of CMC density distribution from unimodality to bimodality and enhanced resistance of polymer elution. As the CuCl2 concentration increased, the stoichiometric ratio between the chelated Cu2+ and carboxylic oxygens increased from 1:2 to 1:1, suggesting the evolution of the Cu2+ chelation mechanism.

Bearing Behavior of Engineered Cementitious Composite and Ultra-High-Performance Concrete Filled-In Double Steel Tubular Composite Columns Subjected to Eccentrical Load

To study the eccentric compression mechanical properties of ECC and UHPC filled-in double steel tubular (EUFDST) composite columns, 35 full-scale EUCFDST composite column specimens were designed by ABAQUS software with the slenderness ratio (λ), UHPC cylinder compressive strength (fcu), inner and outer steel tubular strength (fy1, fy2), inner and outer steel tubular thickness (t1, t2), inner and outer steel tubular diameter ratio (Ω), eccentricity (e), and fiber content (γ) as the main parameters. By comparison with the simulation of the existing test, the correctness of the finite element modeling is verified. The parameter analysis of 35 full-scale EUFDST composite columns was carried out to obtain the eccentric load-mid-span deflection curve of the specimens. The failure mechanism, ductility coefficient, and stiffness degradation of the composite columns under different parameters were analyzed, and the section of the composite column was verified to satisfy the plane section assumption. The variation trend of maximum load-bearing capacity and the ductility of composite columns under different parameter conditions was obtained. By introducing the eccentricity correction coefficient and slenderness ratio correction coefficient, the calculation equation of the eccentric maximum load-bearing capacity of EUCFDST composite columns is statistically regressed, which provides a basis for the practical use of these columns.

Elucidating the degradation mechanism of the nerve agent A-234 using various detergents: a theoretical investigation.

A-234 (ethyl N-[1-(diethylamino)ethylidene]phosphoramidofluoridate) is one of the highly toxic Novichok nerve agents, and its efficient degradation is of significant importance. The possible degradation mechanisms of A-234 by H2O, H2O2, NH3, and their combinations have been extensively investigated by using density functional theory (DFT) calculations. According to the initial intermolecular interaction and the proton transfer patterns between the detergent and the substrate A-234, the A-234 degradation reaction is classified into three categories, denoted as A, B, and C. In modes A and B, the degradation of A-234 by H2O2, H2O, and NH3 is initiated by the nucleophilic attack of the O or N atom of the detergent on the P atom of A-234, coupled with the proton transfer from the detergent to the O or N atom of A-234, whereas in mode C, the direct interaction of H2N-H with the F-P bond of A-234 triggers ammonolysis through a one-step mechanism with the formation of H-F and N-P bonds. Perhydrolysis and hydrolysis of A-234 can be remarkably promoted by introducing the auxiliary NH3, and the timely formed hydrogen bond network among detergent, auxiliary, and substrate molecules is responsible for the enhancement of degradation efficiency.

Effect of Hydrothermal, Chemical, and Mechanical Degradation on Flexural Strength and Phase Transformation of Ground, Glazed, and Polished Zirconia

Objectives: Evaluation of the effect of grinding on flexural strength of zirconia after low temperature degradation (LTD) and pH-cycling. Materials and Methods: Sixty-four bar-shaped specimens of yttria-stabilized tetragonal polycrystalline zirconia were milled, sintered, wet-polished, and divided into 8 groups (N=8). The four control groups were not aged while artificial aging was performed in the 4 experimental groups in three steps including LTD in steam for 40h, pH-cycling, and tooth brushing for artificial aging. All groups underwent surface preparations as follows: standard polishing without surface treatment (Sp), grinding with a blue-yellow band diamond instrument (Gr); grinding with a diamond rotary instrument (DRI) and then over-glazing (Gl); grinding with a DRI followed by two-step intraoral polishing (Po); standard polishing and aging (Sp-Ag); grinding and aging (Gr-Ag), grinding, over-glazing and aging (Gl-Ag); and grinding, polishing and aging (Po-Ag). Monoclinic content was assessed in one specimen of each group by X-ray diffraction (XRD). The 3-point flexural strength test was performed in a universal testing machine. The results were analyzed with two-way ANOVA and Tukey’s test (α=0.05). Results: Mean flexural strength (Mpa) was significantly higher in groups Gr and Po compared to group Sp (both, P<0.0001) and group Gl (both, P<0.0001). In XRD analyses, the highest monoclinic phase before aging was observed in group Gr (12.6%), and after aging in group Gr-Ag (51.2%). Conclusion: Grinding and polishing increased the flexural strength, while glazing did not exhibit any significant effect on this parameter. Furthermore, aging did not adversely affect flexural strength.

Method to Study Potential‐Induced Degradation of Perovskite Solar Cells and Modules in an Inert Environment

The efficiency of perovskite solar cells (PSCs) is advancing rapidly, yet their sensitivity to ambient conditions poses challenges. An additional degradation mechanism, potential‐induced degradation (PID), can emerge during field operation, but the understanding of PID within perovskite devices is limited. To exclude environmental stressors, this study is conducted in an inert environment at room temperature. PSCs and mini‐modules are subjected to a 324 h PID stress test at −1000 V, revealing relative efficiency losses of around 29% and 24% for the PSCs and mini‐modules, respectively, exposing subtle degradation differences. These degradation rates are notably lower than reported in the literature, suggesting possible additional degradation pathways arising from suboptimal encapsulation combined with ambient conditions. Subsequently, half of the stressed samples are subject to +1000 V for 523 h and recover to a reduced efficiency loss of 15% and 7.7% for the PSCs and module, respectively. In contrast, storing the stressed samples on the shelf increased the efficiency losses to 32% (PSCs) and 41% (module). Therefore, the post‐PID rates differ significantly between both groups, whereas both effects of voltage recovery and progressed degradation are more pronounced in modules compared to cells. This study contributes to a robust method for PID research.

Hsc70 promotes anti-tumor immunity by targeting PD-L1 for lysosomal degradation

Immune checkpoint inhibition targeting the PD-1/PD-L1 pathway has become a powerful clinical strategy for treating cancer, but its efficacy is complicated by various resistance mechanisms. One of the reasons for the resistance is the internalization and recycling of PD-L1 itself upon antibody binding. The inhibition of lysosome-mediated degradation of PD-L1 is critical for preserving the amount of PD-L1 recycling back to the cell membrane. In this study, we find that Hsc70 promotes PD-L1 degradation through the endosome-lysosome pathway and reduces PD-L1 recycling to the cell membrane. This effect is dependent on Hsc70-PD-L1 binding which inhibits the CMTM6-PD-L1 interaction. We further identify an Hsp90α/β inhibitor, AUY-922, which induces Hsc70 expression and PD-L1 lysosomal degradation. Either Hsc70 overexpression or AUY-922 treatment can reduce PD-L1 expression, inhibit tumor growth and promote anti-tumor immunity in female mice; AUY-922 can further enhance the anti-tumor efficacy of anti-PD-L1 and anti-CTLA4 treatment. Our study elucidates a molecular mechanism of Hsc70-mediated PD-L1 lysosomal degradation and provides a target and therapeutic strategies for tumor immunotherapy.

Exploring the Progress of Hyaluronic Acid Hydrogels: Synthesis, Characteristics, and Wide-Ranging Applications

This comprehensive review delves into the world of hyaluronic acid (HA) hydrogels, exploring their creation, characteristics, research methodologies, and uses. HA hydrogels stand out among natural polysaccharides due to their distinct features. Their exceptional biocompatibility makes them a top choice for diverse biomedical purposes, with a great ability to coexist harmoniously with living cells and tissues. Furthermore, their biodegradability permits their gradual breakdown by bodily enzymes, enabling the creation of temporary frameworks for tissue engineering endeavors. Additionally, since HA is a vital component of the extracellular matrix (ECM) in numerous tissues, HA hydrogels can replicate the ECM’s structure and functions. This mimicry is pivotal in tissue engineering applications by providing an ideal setting for cellular growth and maturation. Various cross-linking techniques like chemical, physical, enzymatic, and hybrid methods impact the mechanical strength, swelling capacity, and degradation speed of the hydrogels. Assessment tools such as rheological analysis, electron microscopy, spectroscopy, swelling tests, and degradation studies are employed to examine their attributes. HA-based hydrogels feature prominently in tissue engineering, drug distribution, wound recovery, ophthalmology, and cartilage mending. Crafting HA hydrogels enables the production of biomaterials with sought-after qualities, offering avenues for advancements in the realm of biomedicine.

Influence of Surfactant Types on the Anti-Corrosion Performance of Phosphate Chemical Conversion Coated Mg-8wt.%Li Alloy

In this work, the morphology, anti-corrosion performance and degradation mechanisms of two phosphate chemical conversion coatings containing the AEO (fatty alcohol polyoxyethylene ether) and AES (fatty alcohol polyoxyethylene ether sodium sulfate) on an as-cast Mg-8wt.%Li alloy were explored and compared. Although two coating layers had a petal-shaped structure and were composed of leaf-shaped particles, the coating layer of the AES-coated sample was relatively dense due to the smaller size of the formed petal-shaped structure. Based on the electrochemical data and hydrogen evolution measurements, the corrosion protectability of the coating layer on the AES-coated sample was better than that on the AEO-coated sample. The determined corrosion current densities (icorr) of the AES-coated and AEO-coated samples in the 3.5 wt.% NaCl solution were, respectively, 7.8 mA·cm−2 and 11.7 mA·cm−2, whereas the icorr value of the coated sample without a surfactant was 36.2 mA·cm−2.

Mechanistic study of visible light driven photocatalytic degradation of clofibric acid using Fe-based Metal Organic Frameworks (MOFs).

Although a series of past studies proved the potential usage of Fe-based metal-organic frameworks (MOFs) as photocatalysts, there remains a knowledge gap of the photocatalytic mechanism stemming from the challenge to separate the simultaneous sorption and photocatalytic degradation. Thus, this article aimed to suggest a novel approach by desorbing target molecules during photocatalysis to excavate the underlying mechanisms of sorption and photocatalytic degradation. In this study, two Fe-based MOFs, MIL-101(Fe) and MIL-101(Fe)-NH2, were selected to remove clofibric acid under visible light irradiation. Prior to photocatalysis, sorption mechanism was uncovered based on the sorption kinetic, isotherm, thermodynamic interpretation, and of its dependence on solution pH. The results inferred that the primary sorption mechanism was through the π-π interaction between the benzene ring of clofibric acid and the organic ligand of Fe-based MOFs. Based on these results, photocatalytic mechanism could be independently or jointly assessed during the photocatalytic degradation of clofibric acid. Subsequently, the application of the Tauc method and XPS spectra revealed that the bandgap structure of Fe-based MOFs had the potential to oxidize clofibric acid by producing ROS through the electron excitation upon visible-light illumination. On top of that, the amine functionalization of Fe-based MOF altered the structural moiety that led to an additional strong acid-base interaction with clofibric acid but a decrease in the bandgap limiting the ROS production during photocatalytic activity.

Development of a novel polydopamine-imprinted MOFs targeted for removal of refractory organic pollutants: Synergistic mechanisms of adsorption and degradation

In this study, a novel dopamine-imprinted MOFs (metal organic frameworks) was developed for the first time to achieve targeted degradation of refractory organic pollutants (ROPs) in advanced oxidation process. The targeted adsorption and degradation capacity of sulfamethoxazole (SMX) by molecularly imprinted catalyst (Fe-MOFs@MIP) was 3.17 times and 5.47 times that of Fe-MOFs, respectively. The results showed that the polydopamine (PDA) imprinted layer not only enhanced the targeted adsorption of SMX, but also improved the activity of the catalyst by promoting electron transfer. The physicochemical properties of Fe-MOFs@MIP were investigated. In situ Fourier transform infrared spectroscopy and molecular dynamics theory were used to investigate targeted adsorption mechanism. The active species were identified by quenching experiments and electron paramagnetic resonance (EPR). The reaction sites of SMX were predicted using density functional theory (DFT) and the possible degradation pathways of SMX were proposed. Finally, the targeted degradation mechanism of Fe-MOFs@MIP was elucidated. This study has a guiding significance for the deep removal of refractory organic pollutants in wastewater.

Durability Investigation of Low Pt-Loaded PEM Fuel Cells with Different Catalyst Layer Morphologies

This study investigates the durability of proton exchange membrane fuel cells against the Pt-dissolution degradation mechanism using a triangular accelerated stress test (AST) within the voltage range of 0.6-1 V. The electrochemical active surface area and polarization curves are reported throughout the AST for three different catalyst layers (CL), all featuring 0.1 mg/cm2 Pt loading but with different morphologies, which include the Pt/C weight percentages, dilution ratio, and thickness. In addition, a numerical model is employed to simulate the electrochemical performance of these samples at the beginning and end of life, considering the variations in the oxygen transport resistances and catalyst structure.

Unraveling the Degradation Mechanism and Interaction Mechanism of Ofloxacin Based on Reactive Oxygen Species via Electrochemically Activating Peroxymonosulfate

Unraveling the Degradation Mechanism and Interaction Mechanism of Ofloxacin Based on Reactive Oxygen Species via Electrochemically Activating Peroxymonosulfate

Revealing the Enhanced Visible-light-driven Photocatalytic Activity of In2S3/CeO2 Heterojunction: Bandgap Structure Analysis and Active Radicals Determination

Background: The widespread presence of persistent organic pollutants, such as dyes in effluent from printing and textile industries, poses a significant threat to aquatic life and human health. Photocatalytic degradation is widely recognized as a promising technology to address this pollution crisis. The efficiency of photocatalysis is intricately tied to both the active radicals and the band structure of the catalyst. These factors play a crucial role in governing the photodegradation of dye molecules. Methods: In2S3/CeO2 heterojunctions were synthesized using an in-situ precipitation method and subsequently analyzed through SEM, XRD, and XPS techniques. Notably, the bandgap structure of the heterojunctions was examined through UV-Vis DRS. The photocatalytic performance of the synthesized samples was assessed by studying the degradation of methyl orange. To further validate the photocatalytic process, EPR spectroscopy was employed to confirm the presence of radicals generated within the heterojunction. Results: The heterojunction displayed a characteristic type-II structure, enhancing light absorption and facilitating the separation of photoinduced carriers. Among the In2S3/CeO2 composites, the one with a 15 wt% CeO2 content exhibited the highest photocatalytic activity, achieving an 88% degradation of methyl orange after 90 min of exposure to visible light irradiation. Additionally, •O2 − is identified as the primary active species responsible for degradation. Conclusion: UV-Vis DRS illustrated the improved transfer and separation of photogenerated electrons attributed to the optimized band structure of the heterojunction. EPR spectroscopy yielded valuable information on active radicals, thereby proposing the photocatalytic degradation mechanism.

A path to make well-informed decisions when considering the decommissioning of subsea pipelines

Australia’s law mandates the removal of infrastructure once not in use unless the Titleholder can demonstrate an equal or superior safety and environmental outcome. Around 100 infield and export pipelines in Australian waters, with an approximate total length of 5000 km, are nearing their end-of-life period. Three common decommissioning options are considered for subsea pipelines: complete removal, partial removal, or in-situ abandonment. Decommissioning these pipelines will cost an estimated US$13 billion, ~33% of the cumulative Australian offshore decommissioning liability, should the full removal option be selected. When decommissioning subsea pipelines, it is essential to consider that they have been exposed to hazardous fluids and aggressive environments. Careful assessments should determine the recyclability of recovered materials, decontamination, and the environmental risks associated with each decommissioning option. A holistic approach is needed to identify and quantify contaminants in subsea pipelines. In the early stages of decommissioning, planning, sampling, and laboratory testing are necessary to identify plastic coating types, degradation mechanisms, constituents released to the environment, types and mechanisms related to mercury/naturally occurring radioactive materials, and chemical stability. This paper aims to identify and present effective methods for addressing the impact of pipeline constituents on the Marine Environment Assessment while assessing potential decommissioning options and explains how tools can support decision-making. In summary, decommissioning subsea pipelines requires careful assessment and planning to ensure environmental and safety compliance. The paper provides a guide to understanding the process, highlighting the importance of quality assurance, risk assessment, and the selection of appropriate decommissioning options.

Improving Thermal Stability of Perovskite Solar Cells by Suppressing Ion Migration

Ion migration presents a formidable obstacle to the stability and performance of perovskite solar cells (PSCs), hindering their progress toward commercial feasibility. Herein, the degradation mechanism of PSCs caused by iodide ion migration, which leads to abnormal changes in photoluminescence transients at the buried interface of perovskite films, is investigated. In light of this problem, a novel strategy is proposed to mitigate ion migration by introducing poly(2‐vinylnaphthalene) into poly[bis(4‐phenyl)(2,4,6‐trimethylphenyl)amine] as the hole transport layer with improved ion‐blocking capability. Consequently, this layer effectively reduces defect concentration, suppresses ion migration, and modulates energy level alignment, leading to an impressive efficiency exceeding 23% for doctor‐bladed FAPbI3 PSCs. Moreover, the corresponding unencapsulated devices demonstrate remarkable durability, maintaining over 80% of their initial value after undergoing rigorous stress tests in accordance with the International Electrotechnical Commission 61215 standard for temperature, humidity, and illumination. These tests include 1000 h of thermal cycling and a long‐term operational test lasting 600 h under maximum power point tracking.

Design of Phytic Acid Crosslinked Xerogels as Organic Photocatalysts for Visible Light‐Assisted Degradation of Dyes

AbstractExtensive research is being carried out on the degradation of water pollutants using various strategies to overcome the global water crisis. In the present study, xerogels as a better alternative is utilized to metal oxides for the photocatalytic degradation of toxic water pollutants such as dyes. Xerogels of polyaniline (PANI) and polypyrrole (PPy) are synthesized using phytic acid as a dopant as well as cross‐linker in the weight ratios of 1:1, 1:2, and 2:1 via simple chemical oxidative polymerization. The synthesized xerogels are analyzed for their spectral, morphological, thermal, and optical properties using FTIR, UV–vis, XRD, SEM, and TGA techniques. The xerogels are also tested for their photocatalytic activity against textile dyes – Methylene Blue (MB), Alizarin Red S, (ARS), Rhodamine B (RhB), and Methyl Orange (MO). Among all the composite xerogels, PANI/PPy‐2/1 showed excellent degradation efficiency of 91% for MB dye, 88% for RhB dye, 96% for ARS dye, and 92% for MO dye respectively. The composite PANI/PPy xerogels showed better degradation efficiency than their pristine counterparts. The fragments of the degraded dyes are examined using the LCMS technique and a tentative dye degradation mechanism is proposed.

Recent advances in micro-pixel light emitting diode technology

Display technology has developed rapidly in recent years, with III–V system-based micro-light-emitting diodes (μLEDs) attracting attention as a means to overcome the physical limitations of current display systems related to their lifetime, brightness, contrast ratio, response time, and pixel size. However, for μLED displays to be successfully commercialized, their technical shortcomings need to be addressed. This review comprehensively discusses important issues associated with μLEDs, including the use of the ABC model for interpreting their behavior, size-dependent degradation mechanisms, methods for improving their efficiency, novel epitaxial structures, the development of red μLEDs, advanced transfer techniques for production, and the detection and repair of defects. Finally, industrial efforts to commercialize μLED displays are summarized. This review thus provides important insights into the potential realization of next-generation display systems based on μLEDs.

Corrosion Enhancement of PM Processed Magnesium by Turning Native Oxide on Mg Powders into Carbonates

In addition to its use as a lightweight material, pure magnesium is a promising candidate for prospective bioimplants considering its excellent biocompatible properties. Regardless of what Mg application is used, the ultimate goal is to improve magnesium's mechanical properties and degradation behaviour. Because of the high affinity for oxygen native oxide layer of gas-atomized powders is naturally formed in contact with the atmosphere. S/TEM investigation of the native oxide of the Mg powder particles revealed a nonhomogeneous nano-crystalline MgO layer. MgO is relatively soluble in water and does not provide sufficient corrosion protection. Among various surface treatment methods, conversion of the non-protective magnesium oxide to carbonate products is possible depending on the environmental conditions. This work used a simple experimental method using CO2 and water vapour to achieve surface carbonation of Mg powders. Two carbonated samples and pure magnesium were prepared by direct extrusion. The samples after carbonation retained good mechanical properties and the layer of carbonates had a significant impact on corrosion resistance. 1 day carbonation resulted in transformation of native oxide into amorphous layer and reduction of corrosion rate. Longer carbonation (10 days) revealed layer growth and transformation of native oxide to crystalline nesquehonite structure.

Preparation of Newly Polymer-Coated Microbial Pellets and Their Adsorption and Degradation Properties for Oil-Containing Wastewater.

Water is the lifeblood of everything on earth, nourishing and nurturing all forms of life, while also contributing to the development of civilization. However, with the rapid development of economic construction, especially the accelerated process of modern industrialization, the pollution of oily sewage is becoming increasingly serious, affecting the ecological balance and human health. The efficient elimination of pollutants in sewage is, therefore, particularly urgent. In this paper, a core-shell microbial reactor (MPFA@CNF-SA-AM) was fabricated by using nanocellulose and sodium alginate (SA) particles embedded with microorganisms as the core and lipophilic and hydrophobic fly ash as the outer shell layer. Compared with that of free microorganisms and cellulose and SA aerogel pellets loading with microorganisms (CNF-SA-AM), which has a degradation efficiency of 60.69 and 82.89%, respectively, the MPFA@CNF-SA-AM possesses a highest degradation efficiency of 90.60% within 240 h. So that this self-floating microbial reactor has selective adsorption properties to achieve oil-water separation in oily wastewater and high effective degradation of organic pollutants with low cost. The adsorption curves of MPFA@CNF-SA-AM for diesel and n-hexadecane were studied. The results showed that the adsorption follows the Freundlich model and is a multimolecular layer of physical adsorption. In addition, the degradation mechanism of diesel oil was studied by gas chromatography-mass spectrometry. The results showed that diesel oil was selectively adsorbed to the interior of MPFA@CNF-SA-AM, and it was degraded by enzymes in microorganisms into n-hexadecanol, n-hexadecaldehyde, and n-hexadecanoic acid in turn, and finally converted to water and carbon dioxide. Compared with existing oily wastewater treatment methods, this green and pollution-free dual-functional core-shell microbial reactor has the characteristics of easy preparation, high efficiency, flexibility, and large-scale degradation. It provides a new, effective green choice for oily wastewater purification and on-site oil spill accidents.

Fluoro-Ethylene-Carbonate Plays a Double-Edged Role on the Stability of Si Anode-based Rechargeable Batteries during Cycling and Calendar Aging.

The energy storage density of Li-ion batteries could be improved by replacing graphite anodes with high-capacity Si-based materials, though instabilities have limited their implementation. Performance degradation mechanisms that occur in Si-anodes can be divided into cycling stability (capacity retention after repeated battery cycles) and calendar aging (shelf life). While the cycling stability and improvement strategies have been researched intensively, there is little known about the underlying mechanisms that cause calendar aging. In this work multiple electron microscope techniques were used to explore the mechanism that governs the calendar aging from sub-nanometer-to-electrode scale. Plasma focused ion beam tomography were used to create 3D reconstructions of calendar aged electrodes and revealed the growth of a LiF-rich layer at the interface between the copper current collector and silicon material, which can lead to delamination and increased interfacial impendence. The LiF layer appeared to derive from the fluoro-ethylene-carbonate electrolyte additive, which is commonly used to improve cycling stability in Si-based systems. The results reveal that additives necessary to improve cycling stability can cause performance degradation over the long-term during calendar aging. The results show that high performing, stable system require careful design to simultaneously mitigate both cycling and calendar aging instabilities. This article is protected by copyright. All rights reserved.