Interfacial and Electronic Modulation of M-Bridged Heterostructures with L-Tryptophan and Transition Metallic Oxides: Enhancing Corrosion Resistance and Photocatalytic Activity.

Despite remarkable advancements in multilayer composite materials, achieving controlled growth on stationary platforms for optimal corrosion protection and photocatalytic capabilities remains a challenge. In this study, we introduce an innovative approach by integrating bifunctional metal-organic frameworks (MOFs) into plasma-electrolyzed layers made on AZ31 Mg alloy. Metallic oxides of Zr, Ti, and W serve as new pivotal centers for MOF formation, while L-tryptophan (Trp) acts as an organic linker. This innovative approach establishes an efficient electron transport system that acts as a functional pathway for creating highly effective and versatile materials. The tunable structure of the MOF/plasma electrolyzed layer enables it to concurrently display electrochemical stability and photocatalytic activity for the photodegradation of organic pollutants. Remarkably, the WOF complex emerges as a standout performer, effectively shielding the substrate from corrosive anion attacks. This sample showcases exceptional photocatalytic efficiency of 99.61% for crystal violet solution, with sustained performance after five cycles and a 72 h corrosion test (96.55% and 98.39% degradation, respectively). Moreover, DFT calculations elucidate the fundamental bonding modes between MOFs and inorganic constituents, delivering comprehensive insights into their structural formation. Our research addresses the critical challenge of achieving controlled growth for enhanced corrosion resistance and photocatalytic activity, demonstrating a novel pathway for creating multifunctional materials with practical applications across various fields.

Microstructural Changes Caused by the Creep Test in ZK60 Alloy Reinforced by SiCp at Intermediate Temperature after KOBO Extrusion and Aging.

In this study, we investigated the creep properties of ZK60 alloy and a ZK60/SiCp composite at 200 °C and 250 °C in the 10-80 MPa stress range after the KOBO extrusion and precipitation hardening process. The true stress exponent was obtained in the range of 1.6-2.3 for both the unreinforced alloy and the composite. The apparent activation energy of the unreinforced alloy was found to be in the range of 80.91-88.09 kJ/mol, and that of the composite was found to be in the range of 47.15-81.60 kJ/mol, and this indicated the grain boundary sliding (GBS) mechanism. An investigation of crept microstructures using an optical microscope and scanning electron microscope (SEM) showed that at 200 °C, the predominant strengthening mechanisms at low stresses were the formation of twin, double twin, and shear bands, and that by increasing the stress, kink bands were activated. At 250 °C, it was found that a slip band was created in the microstructure, and this effectively delayed GBS. The failure surfaces and adjacent regions were examined using SEM, and it was discovered that the primary cause of failure was cavity nucleation around precipitations and reinforcement particles.

Cu@Fe-Redox Capacitive-Based Metal-Organic Framework Film for a High-Performance Supercapacitor Electrode.

A metal-organic framework (MOF) is a highly porous material with abundant redox capacitive sites for intercalation/de-intercalation of charges and, hence, is considered promising for electrode materials in supercapacitors. In addition, dopants can introduce defects and alter the electronic structure of the MOF, which can affect its surface reactivity and electrochemical properties. Herein, we report a copper-doped iron-based MOF (Cu@Fe-MOF/NF) thin film obtained via a simple drop-cast route on a 3D-nickel foam (NF) substrate for the supercapacitor application. The as-deposited Cu@Fe-MOF/NF electrodes exhibit a unique micro-sized bipyramidal structure composited with nanoparticles, revealing a high specific capacitance of 420.54 F g-1 at 3 A g-1 which is twice compared to the nano-cuboidal Fe-MOF/NF (210 F g-1). Furthermore, the asymmetric solid-state (ASSSC) supercapacitor device, derived from the assembly of Cu@Fe-MOF/NFǁrGO/NF electrodes, demonstrates superior performance in terms of energy density (44.20 Wh.kg-1) and electrochemical charge-discharge cycling durability with 88% capacitance retention after 5000 cycles. This work, thus, demonstrates a high potentiality of the Cu@Fe-MOF/NF film electrodes in electrochemical energy-storing devices.

Synchronized Improvements in the Protective and Bioactive Properties of Plasma-Electrolyzed Layers via Cellulose Microcrystalline.

This study reports synchronized improvements in the protective and bioactive properties of Ti-6Al-4V alloy through the formation of titania-based inorganic layers by considering the role of cellulose microcrystalline (CMC) additive into account. Acetate-phosphate-based electrolyte with cellulose CMC is formulated for the first time to modify the porous structure of the oxide layers made via plasma electrolysis of Ti-6Al-4V alloy. The presence of CMC (0, 1, 2, 3 g/L) changed the characteristics of plasma discharges where porous oxide layers with different pore sizes and surface roughness were obtained. A rough oxide layer with large pores was found in the 3 g/L CMC, while a slightly smoother oxide layer with smaller pores was obtained in the case of 2 g/L CMC. The -OH groups in CMC would facilitate the formation of an adsorption layer on the substrate surface, affecting the sparking behavior during plasma electrolysis (PE). Due to a synergy between controlled microstructure, surface roughness, and the insertion of bioactive phases, the coated samples in CMC-containing electrolytes displayed protective and bioactive properties simultaneously. Based on the obtained results, the samples coated in CMC-containing electrolytes can be used as safe implants to replace missing teeth in dental applications.

Performance of PEO/Polymer Coatings on the Biodegradability, Antibacterial Effect and Biocompatibility of Mg-Based Materials.

Magnesium (Mg) alloys have recently attracted attention in biomedicine as biodegradable materials with non-toxic degradable products. Such compounds have become a frontier in the study of biodegradable materials because of their remarkable biomechanical compatibility and superior biocompatibility. The use of Mg-based implants reduces the negative consequences of permanent biological implants by eliminating the necessity for biomaterial surgery following the healing process. However, the quick deterioration, formation of considerable gas of hydrogen volumes and a rise in the body environment pH are obstacles in the application of Mg as an implant material. Hence, compelling advances for erosion resistance and biocompatibility of magnesium and its alloys are noteworthy. Surface modification may be a practical approach because it improves the erosion resistance compared with extensive preparation of a treated surface for progressed bone recovery and cell attachment. Coating produced by plasma electrolytic oxidation (PEO) seems a compelling method in order to enhance magnesium and the properties of its alloys. PEO-formed coatings cannot provide long-term protection in the physiological environment due to their porous nature. Thus, a polymer coating is applied on the porous PEO-formed coating, which is steadily applied on the surface. Polymer coatings improve the biocompatibility properties of Mg and its alloys and increase corrosion resistance. In this article, the most recent advancements in PEO/polymer composite coatings are reviewed, and the biocompatibility of such coatings is examined.

The Role of COVID-19 Vaccine Perception, Hope, and Fear on the Travel Bubble Program.

The travel bubble program presented an appealing strategy for reopening international travel safely. However, a full vaccination regime is the foremost prerequisite of the program. Therefore, vaccination and the travel bubble are inextricably linked. This study investigated the roles of perceived vaccine efficacy, attitude towards the COVID-19 vaccine, and attitude toward the travel bubble on travel bubble intention. More importantly, the study also examined the mediating role of hope and fear among unvaccinated Korean adults between 20 and 29 years old. A total of 535 samples were collected to test the proposed conceptual model using structural equation modeling. In general, the results supported the proposed hypotheses. Notably, the intention to travel to a bubble destination was explained by 57% of the variance. Furthermore, hope mediated the relationship between vaccine attitude and travel bubble intention. Whereas fear mediated the relationship between perceived vaccine efficacy and intention. Hence, the findings suggest doubts around the vaccine efficacy and that a positive attitude towards the vaccine also install hope among the research samples.

Bimetallic Cu/Fe MOF-Based Nanosheet Film via Binder-Free Drop-Casting Route: A Highly Efficient Urea-Electrolysis Catalyst.

Developing efficient electrocatalysts for urea oxidation reaction (UOR) can be a promising alternative strategy to substitute the sluggish oxygen evolution reaction (OER), thereby producing hydrogen at a lower cell-voltage. Herein, we synthesized a binder-free thin film of ultrathin sheets of bimetallic Cu-Fe-based metal-organic frameworks (Cu/Fe-MOFs) on a nickel foam via a drop-casting route. In addition to the scalable route, the drop-casted film-electrode demonstrates the lower UOR potentials of 1.59, 1.58, 1.54, 1.51, 1.43 and 1.37 V vs. RHE to achieve the current densities of 2500, 2000, 1000, 500, 100 and 10 mA cm-2, respectively. These UOR potentials are relatively lower than that acquired by the pristine Fe-MOF-based film-electrode synthesized via a similar route. For example, at 1.59 V vs. RHE, the Cu/Fe-MOF electrode exhibits a remarkably ultra-high anodic current density of 2500 mA cm-2, while the pristine Fe-MOF electrode exhibits only 949.10 mA cm-2. It is worth noting that the Cu/Fe-MOF electrode at this potential exhibits an OER current density of only 725 mA cm-2, which is far inconsequential as compared to the UOR current densities, implying the profound impact of the bimetallic cores of the MOFs on catalyzing UOR. In addition, the Cu/Fe-MOF electrode also exhibits a long-term electrochemical robustness during UOR.

Improving the Chemical Stability of Al Alloy through the Densification of the Alumina Layer Assisted by SiF62- Anion Hydrolysis.

In this work, a high-density alumina layer with high chemical stability was successfully developed by controlling the hydrolysis of hexafluorosilicate (SiF62-) anions through the addition of various concentrations of sodium citrate (SCi) into the electrolyte of plasma electrolysis (PE). To achieve this aim, the substrate samples were anodized in alkaline aluminate-SiF62--based electrolytes with 0, 5, and 10 g/L of SCi. The presence of SCi anions in the electrolyte led to the formation of a thick adsorbed electrochemical double layer (EDL) on the substrate surface. The EDL not only affected the movement of SiF62- anions towards the anode but also influenced their hydrolysis reaction, which in turn led to a controllable sealing of structural defects with the hydrolysis products, namely SiO2 and AlF3. Among three different oxide layers, the oxide layer obtained from the electrolyte with 5 g/L SCi showed the highest chemical stability in a corrosive solution, which was linked to the fact that a considerable increase in the compactness of the oxide layers was obtained by the incorporation of SiO2 and AlF3. The mechanism underlying the effects of SCi on triggering the hydrolysis of SiF62- anions and factors affecting chemical stability are discussed based on the experimental data and computational analysis.

Macro and micro thermal investigation of nanoarchitectonics-based coatings on cotton fabric using new quaternized starch.

Implementation of a new cationizing reagent and its incorporation onto the backbone of starch was performed successfully, confirmed from the remarkable micro- and macro anti-flammable properties. The morphologies and localized compositional analysis of the modified starch-based LBL coatings on the cotton surface were carried out using LV-SEM and EDX: highly uniform coating layers and uptake of solution species for intermediate implant reagent concentrations were confirmed. The subject samples were further analyzed through thermogravimetric analysis (TGA), microcombustion experiments (MCC), flame testing (VFT) and afterburn measurements. The peak range of the degradation was highly improved from the lower range to the higher range (329.92-394.48 °C), together with significant mass residue for TBAB-0.7-17.02%. Moreover, a significant decrease in the absolute heat loss (THR ∼ 30%), heat dissipation competence (HRC ∼ 27.86%), and peak heat output (PHRR ∼ 23%) was achieved for a TBAB loading of ∼0.7 g. The results were further confirmed from the increase in the limiting oxygen index (LOI) to a higher rate of ∼23.2, improved structural integrity and higher quality of char obtained in the VFT and after-burn analysis.

A Review on Synthesis, Properties, and Applications of Polylactic Acid/Silica Composites.

Polylactic acid (PLA)/silica composites as multifunctional high-performance materials have been extensively examined in the past few years by virtue of their outstanding properties relative to neat PLA. The fabrication methods, such as melt-mixing, sol-gel, and in situ polymerization, as well as the surface functionalization of silica, used to improve the dispersion of silica in the polymer matrix are outlined. The rheological, thermal, mechanical, and biodegradation properties of PLA/silica nanocomposites are highlighted. The potential applications arising from the addition of silica nanoparticles into the PLA matrix are also described. Finally, we believe that a better understanding of the role of silica additive with current improvement strategies in the dispersion of this additive in the polymer matrix is the key for successful utilization of PLA/silica nanocomposites and to maximize their fit with industrial applications needs.

Surface Properties of Graphene Functionalized TiO2/nHA Hybrid Coatings Made on Ti6Al7Nb Alloys via Plasma Electrolytic Oxidation (PEO).

Nano-hydroxyapatite (nHA)-matrix coatings containing graphene nanosheets (GNS)-nHA were coated on Ti6Al7Nb alloys by plasma electrolytic oxidation (PEO) treatment for the improvement of their surface properties. Crystallographic properties, functional groups, and elemental analysis of coatings were characterized by XRD, ATR-FTIR, and EDS analysis. Surface morphological changes of the coated surfaces were investigated by AFM and SEM. The electrochemical corrosion behavior of the coatings was examined by using the potentiodynamic scanning (PDS) tests under in-vitro conditions in simulated body fluid (SBF). The results showed that the GNS was successfully deposited in ceramic matrix coatings on Ti6Al7Nb alloys. Also, the microstructural observations revealed that the coatings have a porous and rough structure. The XRD and ATR-FTIR quantitative analysis have proved the appearance of HA and GNS in the coating layers. An increase in the coating thickness, surface hardness, and anatase/rutile transformation rate was determined, while the GNS ratio in the coating layers was increased. The microhardness of the nHA coating reinforced with 1.5 wt% GNS was measured at 862 HV, which was significantly higher than that of GNS-free (only nHA) coating (584 HV). The best in-vitro resistance to corrosion in SBF was observed in the nHA/1.5GNS wt% coating.

Enhancement of Mixing Performance of Two-Layer Crossing Micromixer through Surrogate-Based Optimization.

Optimum configuration of a micromixer with two-layer crossing microstructure was performed using mixing analysis, surrogate modeling, along with an optimization algorithm. Mixing performance was used to determine the optimum designs at Reynolds number 40. A surrogate modeling method based on a radial basis neural network (RBNN) was used to approximate the value of the objective function. The optimization study was carried out with three design variables; viz., the ratio of the main channel thickness to the pitch length (H/PI), the ratio of the thickness of the diagonal channel to the pitch length (W/PI), and the ratio of the depth of the channel to the pitch length (d/PI). Through a primary parametric study, the design space was constrained. The design points surrounded by the design constraints were chosen using a well-known technique called Latin hypercube sampling (LHS). The optimal design confirmed a 32.0% enhancement of the mixing index as compared to the reference design.

A Review on LDH-Smart Functionalization of Anodic Films of Mg Alloys.

This review presents an overview of the recent developments in the synthesis of layered double hydroxide (LDH) on the anodized films of Mg alloys prepared by either conventional anodizing or plasma electrolytic oxidation (PEO) and the applications of the formed composite ceramics as smart chloride traps in corrosive environments. In this work, the main fabrication approaches including co-precipitation, in situ hydrothermal, and an anion exchange reaction are outlined. The unique structure of LDH nanocontainers enables them to intercalate several corrosion inhibitors and release them when required under the action of corrosion-relevant triggers. The influences of different variables, such as type of cations, the concentration of salts, pH, and temperature, immersion time during the formation of LDH/anodic film composites, on the electrochemical response are also highlighted. The correlation between the dissolution rate of PEO coating and the growth rate of the LDH film was discussed. The challenges and future development strategies of LDH/anodic films are also highlighted in terms of industrial applications of these materials.

Poly(Lactic Acid) Composites.

Polylactic acid-based materials have gained great interest within the scientific community due to their biodegradability, good performance, and suitability for a number of applications. Therefore, this Special Issue "Poly(lactic acid) Composites" is proposed to cover the important advances in poly (lactic acid) composites, ranging from their design, fabrication, and material properties to the potential applications of these materials. Therefore, we believe that the present Issue can convey beneficial information to scientists and engineers in numerous fields, including polymer science and biomedical engineering.

Review of Recent Advances in Polylactic Acid/TiO2 Composites.

Polylactic acid/titanium oxide (PLA/TiO2) composites as multifunctional materials have been studied extensively by couple of research groups owing to their outstanding mechanical, thermal, photocatalytic, and antimicrobial properties. This review describes the experimental approaches used to improve the compatibility of PLA/TiO2 composites. The mechanical, thermal, photocatalytic, and antimicrobial properties of PLA/TiO2 composites are discussed. The potential applications arising from the structural and functional properties of PLA/TiO2 composites were also reviewed. Finally, it is concluded that a deep understanding of the impacts of TiO2 filler with available improvement approaches in the dispersibility of this filler in the PLA matrix would be the key for the effective usage of PLA/TiO2 composites and to expand their suitability with worldwide application requirements.

Effect of starch on the corrosion behavior of Al-Mg-Si alloy processed by micro arc oxidation from an ecofriendly electrolyte system.

In addition to being environmentally friendly and ecologically acceptable, starch-based materials are inexpensive, readily available and renewable. The capability of starch, therefore, to inhibit the corrosion of Al-Mg-Si alloy processed via micro arc oxidation (MAO) process was investigated. For this aim, MAO coating was carried out on the present sample under AC conditions in an alkaline electrolyte with and without starch. The oxide layer formed on an Al-Mg-Si alloy created from electrolyte with starch was denser and thicker than that without starch. Whilst the oxide layer formed from electrolyte without starch was only composed of γ-Al2O3, the addition of starch into the electrolyte helped to decelerate the rate of cooling during the solidification of molten alumina, resulting in the formation of α-Al2O3 as well. Accordingly, the inhibiting action in the sample coated from the electrolyte containing starch was superior to that without starch.

A novel composite system composed of zirconia and LDHs film grown on plasma electrolysis coating: Toward a stable smart coating.

A novel composite system composed of zirconia and double hydroxide layers (LDHs) was successfully fabricated on the plasma electrolysis (PE) coating. For this aim, the molybdate-loaded LDHs film grown on the PE film of aluminum alloy was modified additionally by zirconia nanoparticles via a facile dip-coating method. The MoO42- anions which were obtained by anion exchange process from the precursor CeMgAl-LDH film, led to decrease the distance between the flakes of LDHs film where a flower-like structure was successfully developed. Moreover, the inclusion of zirconia helped to decrease the size of pores present in the LDHs films. Accordingly, a superior smart protective film was obtained due to the possible synergetic effects between the MoO42- and Ce3+ ions released from LDHs film as well as the high chemical stability of zirconia. The LDHs film modified by zirconia can be regarded as a stable smart coating, meaning that it has the ability to control the release of corrosion inhibitors and providing an excellent long-term electrochemical performance as well.

Toward a nearly defect-free coating via high-energy plasma sparks.

A nearly defect-free metal-oxide-based coating structure was made on Al-Mg-Si alloy by plasma electrolytic oxidation at high current density accompanying high-energy plasma sparks. The present coatings were performed at two different current densities of 50 and 125 mA/cm2 in the alkaline-phosphate-based electrolytes with different concentrations of sodium hexafluoroaluminate (Na3AlF6). The addition of (Na3AlF6) to the electrolyte used in this study would result in a decrease in the size of the micropore, and a reasonably defect-free coating structure was achieved in the sample treated at high current density of 125 mA/cm2. This was attributed mainly to the hydrolysis of AlF63- triggered by intense plasma sparks, which resulted in a uniform distribution of fluorine throughout the coating. Accordingly, the corrosion performance of the coating formed in the electrolyte containing 1.5 g/L Na3AlF6 at 125 mA/cm2 was improved significantly as confirmed by electrochemical impedance analysis. In addition, the formation mechanism of the nearly defect-free coating in the presence of Na3AlF6 was discussed.

Soft plasma electrolysis with complex ions for optimizing electrochemical performance.

Plasma electrolytic oxidation (PEO) was a promising surface treatment for light metals to tailor an oxide layer with excellent properties. However, porous coating structure was generally exhibited due to excessive plasma discharges, restraining its performance. The present work utilized ethylenediaminetetraacetic acid (EDTA) and Cu-EDTA complexing agents as electrolyte additives that alter the plasma discharges to improve the electrochemical properties of Al-1.1Mg alloy coated by PEO. To achieve this purpose, PEO coatings were fabricated under an alternating current in silicate electrolytes containing EDTA and Cu-EDTA. EDTA complexes were found to modify the plasma discharging behaviour during PEO that led to a lower porosity than that without additives. This was attributed to a more homogeneous electrical field throughout the PEO process while the coating growth would be maintained by an excess of dissolved Al due to the EDTA complexes. When Cu-EDTA was used, the number of discharge channels in the coating layer was lower than that with EDTA due to the incorporation of Cu2O and CuO altering the dielectric behaviour. Accordingly, the sample in the electrolyte containing Cu-EDTA constituted superior corrosion resistance to that with EDTA. The electrochemical mechanism for excellent corrosion protection was elucidated in the context of equivalent circuit model.