Surfaces, Volume 7, Issue 3 (September 2024) – 21 articles

This paper investigates the enhancement of the microstructure and properties of Ag-10La_0.7Sr_0.3CoO₃ composites, prepared by powder metallurgy, through the application of high-current pulsed electron beam (HCPEB) irradiation. The X-ray diffraction results showed that the irradiated samples exhibited selective orientations on the surface of their (200) and (311) crystal planes. Microstructural observations revealed a dense remelted layer on the samples’ surface after HCPEB irradiation. The surface hardness of the samples increased after 15 treatments, showing an improvement of 36.76%. This is primarily attributed to fine-grain strengthening, surface remelting, and recrystallization. Further, the electrical conductivity of the samples treated 15 times increased by 74.8% compared to that of the original samples. Electrochemical test results showed that the samples treated 15 times showed the lowest corrosion current density in a 3.5 wt.% NaCl solution. This improved corrosion resistance is attributable to the refinement of the surface’s microstructure and the introduction of residual compressive stress. This study demonstrates the significant impact of HCPEB irradiation on the regulation of the properties of Ag-10La_0.7Sr_0.3CoO₃ composites. Full article

High density portable energy storage is desirable owing to the energy requirements of portable electronics and electric vehicles. The Li-ion battery’s high energy density could be even further improved through the utilization of alternative materials (instead of carbon) for the anode, such as Sn or Si. Nonetheless, the large volume expansion upon lithiation, up to ~300% for Li₂₂Si₅, causes pulverization and rapid capacity degradation during cycling. Sn also forms a Li₂₂Sn₅ compound with the equivalent stoichiometric Li capacity but with enhanced ductility. Nano-sized Si and Sn have demonstrated distinctive nanoscale properties, facilitating the retention of higher capacities, particularly when coated with carbon, which improves mechanical stability. To date, the methods of synthesizing coated Si, Sn, or Si-Sn alloyed nanoparticles are complicated, costly, and not readily scalable to meet the demands of cost-effective manufacturing. Spark plasma erosion in a hydrocarbon dielectric has been explored as a one-step process to produce Sn-Si alloy nanoparticles coated with a thin carbon film, offering a scalable and cost-effective processing route. The resulting Sn-Si particles exhibited a bi-modal size distribution at ~5 nm and ~500 nm and were carbon-coated, as intended, from the hydrocarbon dielectric breakdown. The spark-eroded nanoparticles were thoroughly characterized using TEM/EDS, XPS, AES, SSNMR, and TGA, and their improved electrochemical performance was assessed through half-cell experiments. Full article

The surfaces of ceramic products are replete with numerous defects, such as those that appear during the diamond grinding of sintered SiAlON ceramics. The defective surface layer is the reason for the low effectiveness of TiZrN coatings under abrasive and fretting wear. An obvious solution is the removal of an up to 4-µm-thick surface layer containing the defects. It was proposed in the present study to etch the layer with fast argon atoms. At the atom energy of 5 keV and a 0.5 mA/cm² current density, the ions were converted into fast atoms and the sputtering rate for the SiAlON samples reached 20 μm/h. No defects were observed in the microstructures of coatings deposited after beam treatment for half an hour. The treatment reduced the volumetric abrasive wear by five times. The fretting wear was reduced by three to four times. Full article

Bismuth oxide (Bi₂O₃) and Bi₂O₃–supported Kaolin were synthesized using household microwave–assisted methods (350 W, 5 min), with catalyst characteristics analyzed. XRD patterns confirmed the monoclinic structure of Bi₂O₃. Incorporating 20%w/w Kaolin increased the specific surface area of Bi₂O₃ from 6.2879 to 16.1345 m²/g, observed in FESEM images showing a hierarchical flower-like morphology resembling French fries alongside Kaolin plates. XRF analysis identified elements in Kaolin contributing to self–doping in band structure of Bi₂O₃, reducing its band gap and PL intensity. Kaolin/Bi₂O₃ composites demonstrated enhanced photocatalytic degradation of tetracycline (TC) under visible light, attributed to Bi₂O₃-generated radicals and increased surface area. The composite photocatalyst can be recycled up to three times. This research not only enhances the photocatalytic activity of Bi₂O₃ but also increases the value of a local waste material, Kaolin clay. Such enhancements could potentially extend to other metal oxides and abundant waste materials within the country. Full article

Atmospheric pressure microplasma is a simple, cost-effective, efficient, and eco-friendly procedure, which is superior to the traditional nanomaterials synthesis techniques. It generates high yields and allows for a controlled growth rate and morphology of nanomaterials. The silver (Ag) nanomaterials, with their unique physical and chemical properties, exhibit outstanding antibacterial and antifungal properties. Similarly, zinc oxide (ZnO) nanomaterials, known for their low toxicity and relatively lower cost, find wide applications in wound repair, bone healing, and antibacterial and anticancer applications. The use of core–shell nanomaterials in certain situations where some nanoparticles can cause serious harm to host tissues or organs is a testament to their potential. A benign material is coated over the core to reduce toxicity in these cases. This review compares the numerous configurations of microplasma systems used for synthesizing nanomaterials and their use in producing Ag, ZnO, and their core–shell (Ag-ZnO) nanomaterials for biomedical applications. The summary also includes the effect of control parameters, including cathode diameter, gas flow rate, precursor concentration, voltage, and current, on the nanomaterial’s characteristics and applications. In addition, it provides a research gap in the synthesis of Ag, ZnO, and core–shell nanomaterials by this technique, as well as the development and limitations of this technique and the use of these nanoparticles for biomedical applications. Full article

Hypromellose (HM) is a cellulose-derived polymer of pharmaceutical grade that forms easily from thin films and coatings. As few studies concern HM-formulated systems, this study focuses on the formulation of HM films by incorporating a fatty acid additive, making it possible to control surface properties such as wetting and slip behavior for pharmaceutical or medical applications. The results show that the addition of a very small amount (from 0.1 to 1% w/w) of fatty acid additive reduces HM film affinity for water and water vapor transmission rate, while film appearance and gloss are rather preserved. Surface properties were probed using wettability measurements, Tapping Mode AFM, ATR-FTIR spectrometry, and friction measurements. Tapping Mode AFM images show that the surface roughness reduces by up to 65%. Wettability results show that the surface energy decreases from 43 to 31 mJ.m⁻², whereas surface FTIR spectrometry measurements demonstrate that fatty acid molecules migrate on the surface of the formulated films, the driving force being the microphase separation between the polar HM macromolecules and the hydrophobic additive, leading to the formation of a weak boundary layer with poor cohesion. As a consequence, the surface coefficient of friction significantly reduces from 0.38 to 0.08, and fatty acid molecules thus act as a lubricant, improving the sliding properties of HM-based coatings. Full article

Background: Electrodeposition of functional films from polyphenol-containing solutions has emerged as a new field of surface functionalization from bio-sourced molecules. There is, however, almost no knowledge about the chemical structure of such complex films. It is the aim of this research to use the known electrodeposition of films made from catechol and resorcinol, two isomers of dihydroxybenzene, to understand the electrodeposition of a more complex polyphenol, quercetin, which is constituted from a fused catechol and resorcinol moiety. The aim of this article is hence to introduce some methodology in the interpretation of the electrochemical behavior of complex polyphenols starting from their building blocks. Methods: Cyclic voltammetry (CV) is used to deposit films from quercetin and from equimolar blends of catechol and resorcinol on amorphous carbon and gold working electrodes. The main experimental parameter was the potential sweep rate used during the CVs. Results: The CV of quercetin is not the exact sum of the CV of the catechol + resorcinol blends, but the major features are conserved, namely the presence of two main oxidation peaks affiliated to those of catechol and resorcinol but shifted to less anodic potentials. In addition, the anodic electron transfer coefficients of the two oxidation waves of quercetin are higher than those measured in the catechol resorcinol blend. However, film deposition ability is reduced with quercetin compared to catechol + resorcinol blend in probable relationship to steric hindrance occurring during the non-electrochemical crosslinking of the deposit. The quercetin-based films deposited at 10 mV·s⁻¹ on gold electrodes are conformal and display some antioxidant activity. Full article

With the recent ban on the production and use of long-chain perfluorinated compounds, the development of alternative approaches to prepare liquid-repellent surfaces that avoids the use of such compounds has become an urgent issue. We have succeeded in the development of fish-mimicking hydrophilic transparent hydrogel-based films with long-lasting anti-oil adhesion properties. Such films could be prepared by simply mixing poly(vinylpyrrolidone) (PVP), nanoclay particles (NCPs), and a waterborne aminosilane (AOS) using an integral blend (IB) method. When submerged in water, these films displayed underwater superoleophobicity (advancing and receding contact angles (CAs) of diiodomethane were ~171°/~163°) with low CA hysteresis (less than 8°), because the hydrophilic nature of the films promoted the formation of a thin layer of adsorbed water on the topmost film surfaces, similar to fish scales. Furthermore, when our films were coated onto the inside of poly(ethylene terephthalate) (PET) bottles and pre-wetted using 80 °C hot water vapors, these film surfaces could effectively repel various oils and were able to maintain their oil-repellent properties for more than 5 weeks. These water-driven, non-perfluorinated transparent hydrogel-based films are expected to increase recycling of PET bottles for oils that are generally incinerated or landfilled. Full article

This comprehensive review examines the phenomena of stress corrosion cracking (SCC) and chloride-induced stress corrosion cracking (Cl-SCC) in materials commonly used in the oil and gas industry, with a focus on austenitic stainless steels. The study reveals that SCC initiation can occur at temperatures as low as 20 °C, while Cl-SCC propagation rates significantly increase above 60 °C, reaching up to 0.1 mm/day in environments with high chloride concentrations. Experimental methods such as Slow Strain Rate Tests (SSRTs), Small Punch Tests (SPTs), and Constant-Load Tests (CLTs) were employed to quantify the impacts of temperature, chloride concentration, and pH on SCC susceptibility. The results highlight the critical role of these factors in determining the susceptibility of materials to SCC. The review emphasizes the importance of implementing various mitigation strategies to prevent SCC, including the use of corrosion-resistant alloys, protective coatings, cathodic protection, and corrosion inhibitors. Additionally, regular monitoring using advanced sensor technologies capable of detecting early signs of SCC is crucial for preventing the onset of SCC. The study concludes with practical recommendations for enhancing infrastructure resilience through meticulous material selection, comprehensive environmental monitoring, and proactive maintenance strategies, aimed at safeguarding operational integrity and ensuring environmental compliance. The review underscores the significance of considering the interplay between mechanical stresses and corrosive environments in the selection and application of materials in the oil and gas industry. Low pH levels and high temperatures facilitate the rapid progression of SCC, with experimental results indicating that stainless steel forms passive films with more defects under these conditions, reducing corrosion resistance. This interplay highlights the need for a comprehensive understanding of the complex interactions between materials, environments, and mechanical stresses to ensure the long-term integrity of critical infrastructure. Full article

In the study, a hybrid lubricant was prepared by introducing graphene into a polyphosphate lubricant. In the tribological test of a steel/steel friction pair at the high temperature of 800 °C, the addition of a small proportion of graphene significantly enhances the lubrication performance of polyphosphate at elevated temperatures. The coefficient of friction and the wear were obviously held down while the surface quality of the high-temperature friction pair was enhanced effectively with the graphene-strengthened polyphosphate lubricant, compared with the dry sliding condition. Through scanning electron microscopy and Raman spectroscopy analysis, the formation mechanism of tribofilm and the antiwear performance of the hybrid lubricant are further explained. This lubricant effectively combines the advantages of both; the combination of polyphosphate melted at elevated temperature with graphene and metal surfaces ensures the self-sealing of the friction contact area and brings better high-temperature oxidation resistance. At the same time, the presence of graphene provides excellent strength to the friction film and ensures the anti-wear and wear-resistant performance of the lubricant at high temperatures. Full article

Doping titanium dioxide has become a strategy for enhancing its properties and reducing its recombination issues, with the aim of increasing its efficiency in photocatalytic processes. In this context, this work studied its deposition over glass substrates using a sol–gel dip coating methodology. The effect of doping TiO₂ with Zirconium cations in low molar concentrations (0.01, 0.05, 0.1%) in terms of its structural and optical properties was evaluated. The structural characterization confirmed the formation of amorphous thin films with Zr introduced into the TiO₂ cell (confirmed by XPS characterization), in addition to increasing and defining the formed particles and their size slightly. These changes resulted in a decrease in the transmittance percentage and their energy band gap. Otherwise, their photocatalytic properties were evaluated in hydrogen production using ethanol as a sacrificial agent and UV irradiation. The hydrogen evolution increased as a function of the Zr doping, the sample with the largest Zr concentration (0.1% mol) being the most efficient, evolving 38.6 mmolcm⁻² of this gas. Zr doping favored the formation of defects in TiO₂, being responsible for this enhancement in photoactivity. Full article

The iron (Fe) specimens selected as the substrate metal for this study were surface-treated using fluorine gas, and their wettability with liquid sodium (Na) was evaluated using the sliding angle. Additionally, the surface morphology and binding state were analyzed, and the applicability of wettability control with liquid sodium by fluorination was discussed using the analysis results. Fluorination formed a fluoride layer comprising FeF₂ and FeF₃ bonds on the iron surface. The composition of the fluoride layer varied, depending on the treatment conditions. The surface of the specimen that contains a lot of FeF₃ bonds had a small sliding angle for the liquid sodium droplet and was harder to wet than the untreated specimen. In contrast, the surface of the specimen that contains a lot of FeF₂ bonds had a large sliding angle for the liquid sodium droplet and was easier to wet than the untreated specimen. These results indicate that fluorination is an effective surface modification technique that can be applied to control the wettability of iron with liquid sodium. Full article

Biosurfactants are amphipathic molecules with considerable potential for application in different industries due to their biochemical characteristics, low toxicity as well as greater biodegradability and stability compared to chemical surfactants when submitted to adverse environmental conditions. The aim of the present study was to investigate the production of a biosurfactant by Candida lipolytica UCP 0988 grown in a medium containing 4.0% molasses, 2.5% used soybean frying oil, and 2.5% corn steep liquor for 144 h at 200 rpm. The biosurfactant was characterized; its stability and toxicity were investigated, and the compound was applied in oil removal tests. In the C. lipolytica growth and biosurfactant production studies, the surface tension of the medium was reduced from 72 mN/m to 25 mN/m, the critical micellar concentration (CMC) was 0.5 g/L (w/v), and the yield was 12 g/L. Tests under extreme conditions of temperature, pH, and NaCl indicated the stability of the biosurfactant. Fourier-transform infrared and nuclear magnetic resonance spectroscopy of the chemical structure of the purified biosurfactant suggested that the biosurfactant is a glycolipid. The anionic biosurfactant exhibited no toxicity to the microcrustacean Artemia salina or vegetable seeds (Brassica oleracea). Dispersion tests in seawater demonstrated 100% efficiency of the biomolecule against motor oil. The biosurfactant was efficient at removing oil from sand in static and kinetic tests at concentrations of ½ CMC (0.25 g/L), CMC (0.5 g/L), and 2 × CMC (1.0 g/L), with removal rates of 70 to 96%, whereas the synthetic surfactants tested removed only 10 to 18% of the oil. Based on the findings, the biosurfactant analyzed has considerable potential for the remediation of contaminated coastal and marine environments due to oil spills. Full article

In this study, we investigated the surface-confined coupling reactions of 1,8-dibromobiphenylene (BPBr₂) on Cu(111) to elucidate the details of the organometallic intermediates via Ullmann reactions. We used scanning tunneling microscopy (STM) to characterize the resulting organometallic intermediates. Moreover, submolecular resolution of the non-contact atomic force microscopy (nc-AFM) qPlus technique enables the bond-resolving within the organometallic dimer product. Our findings reveal the debromination of BPBr₂ on Cu(111), leading to the formation of an organometallic dimer intermediate at room temperature. Through nc-AFM measurements, we confirm and visualize the formation of the C-Cu-C bond. These insights enhance our understanding of Ullmann reaction and hold potential implications for the design of novel two-dimensional electronic devices. Full article

Degradable and high-barrier plastic packaging materials draw more attention with the development of a social economy and the demands of environmental protection. In this study, poly(propylene carbonate phthalate) (PPC-P) and poly(butylene adipate-co-terephthalate) (PBAT) blends with different ratios were designed and prepared, marked as PPC-P/PBAT. Chain extenders were introduced into the blends, and the mechanical properties, thermal properties, and barrier properties of the composites were studied. The 75PPC-P/PBAT with 2% extenders represent the best performance. The addition of the chain extender has significantly improved the thermal stability and tensile elongation of PPC-P/PBAT. On this basis, the PPC-P/PBAT composite film was coated with PVA and borax using the dipping and pulling method. The oxygen barrier properties have been further improved for the composite film with a coating layer. Considering the characteristics of biodegradability and a high-barrier property, the 75PPC-P/PBAT/2MDI@Gly blend coated with 2 wt% PVA and 3 wt% borax exhibits potential as a superior food/pharmaceutical plastic packaging material with excellent tensile and barrier properties. Full article

This study uses a hybrid concept to propose an optimal textured surface morphology for enhancing water condensation. The natural phenomenon-inspired morphology, which combined different degrees of wettability presented on the surface, documented their advantage in water harvesting compared to untreated surfaces. These superiorities might be explained by the appropriate combination of nucleation and water-driven ability facilitated by the superhydrophobic surrounding area. The uniform condensed droplets are effectively agglomerated to achieve the critical size. The best combination was found on a superhydrophobic-hydrophilic hybrid sample that improved water collection efficiency by up to 50% compared to bare Al. Condensation performance also illustrated an interesting tendency that revealed the great contribution of wettability on hydrophilic dots and the water-driven ability of the high-hydrophobicity area. The results were supported by a theoretical model which predicts the critical volume of a single droplet before it has departed from the surface. The findings reveal a good level of agreement between theory and real-time measurement, demonstrating the potential of combinations of hybrid samples to induce water collection efficiency. Full article

One of the major problems facing humanity in all parts of the world is water pollution. Since carbon nanoparticles (CPs) are known for their excellent absorbability, this study explored preparing CPs via a facilitated ball-milling protocol. Four CP products were prepared with the friction enhancer being variated, typically 0-CPs, 2.5-CPs, 5-CPs, and 10-CPs. The four sorbents were characterized using TEM, EDX, XRD, BET, and FTIR methods. The 0-CPs, 2.5-CPs, 5-CPs, and 10-CPs possessed a BET surface area of 113, 139, 105, and 98.5 m² g⁻¹, respectively, and showed a sorption capacity of 55.6, 147.0, 65.8, and 24.6 mg g⁻¹ when tested with chlorohexidine (CH). Therefore, the 2.5-CPs were selected as the best sorbents among the prepared nanomaterials and employed for further sorption investigations. The CH sorption on the 2.5-CPs followed the pseudo-second-order, and the liquid–film diffusion controlled the CH sorption onto the 2.5-CPs. The Langmuir isotherm model was followed, and the Dubinin–Radushkevich energy was 3.0 kJ mole⁻¹, indicating a physisorption process. The thermodynamic outputs suggested that CH sorption by 2.5-CPs was favorable. Furthermore, the 2.5-CPs sorbent was tested for treating water samples contaminated with 20 mg L⁻¹ of ciprofloxacin, dextromethorphan, guaifenesin, metronidazole, ibuprofen, chlorzoxazone, chlorpheniramine malate paracetamol, and hydro-chlorothiazide. The 2.5-CPs showed an average removal efficiency of 94.1% with a removal range of 92.1% to 98.3% and a 2.21 standard deviation value. Full article

Anti-fogging coatings/surfaces have attracted much attention lately because of their practical applications in a wide variety of engineering fields. In this study, we successfully developed transparent anti-fogging surfaces using a non-volatile and hygroscopic ionic liquid (IL), bis(hydroxyethyl)dimethylammonium methanesulfonate ([BHEDMA][MeSO₃]), with a high surface tension (HST, 66.4 mN/m). To prepare these surfaces, a layer of highly transparent, superhydrophilic silica (SiO₂) nano-frameworks (SNFs) was first prepared on a glass slide using candle soot particles and the subsequent chemisorption of tetraethoxysilane (TEOS). This particulate layer of SNFs was then used as the support for the preparation of the [BHEDMA][MeSO₃] layer. The resulting IL-infused SNF-covered glass slide was highly transparent, superhydrophilic, hygroscopic, and had self-healing and reasonable reversible/repeatable anti-fogging/frosting properties. This IL-infused sample surface kept its excellent anti-fogging performance in air for more than 8 weeks due to the IL’s non-volatile, HST, and hygroscopic nature. In addition, even if the water absorption limit of [BHEDMA][MeSO₃] was reached, the anti-fogging properties could be fully restored reversibly/repeatably by simply leaving the samples in air for several tens of minutes or heating them at 100 °C for a few minutes to remove the absorbed water. Our IL-based anti-fogging surfaces showed substantial improvement in their abilities to prevent fogging when compared to other dry/wet (super)hydrophobic/(super)hydrophilic surfaces having different surface geometries and chemistries. Full article

Monodisperse Pt nanoparticles supported on carbon (Pt/C) were prepared via an impregnation method. By changing the concentration of the platinum precursor in the initial reagent mixture, the average particle size (d) could be controlled to within a narrow range of less than 2 nm. The specific activity (SA) of these materials, when applied to the oxygen reduction reaction (ORR), increased rapidly with d in the range below 1.8 nm, with a maximum SA at d = 1.3 nm. This value is approximately four times that of a commercial Pt/CB catalyst. The electrochemical active area, ECAA (electrochemical surface area (ECSA)/specific surface area (SSA) × 100), decreased drastically from 100% with decreases in d below 1.3 nm. In this study, we present a correlation between SA and ECAA as a means of determining the appropriate d for polymer electrolyte fuel cells (PEFCs) and propose an optimal size. Full article

The recyclable paper based on photochromic materials not only reduces the pollution in the paper manufacture process, but also reduces the pollution caused by the use of ink, which receives wide attention. In this paper, a series of phosphomolybdic acid–phosphotungstic acid/ZnO/polyvinylpyrrolidone (PMoA-PWA/ZnO/PVP) hybrid films, which had different ratio of PMoA/PWA, was prepared by the ultrasonic composite method. The results indicated that the hybrid film prepared when the ratio of PMoA to PWA was 3 had the best photochromic performance. In this system, ZnO was the photosensitizer, while PMoA/PWA was the chromophore. The photochromic mechanism of the PMoA-PWA/ZnO/PVP hybrid film was based on the photogenerated electron transfer mechanism. ZnO generated photoelectron under the excitation of visible light, then PMoA and PWA obtained the photoelectron and produced photoreduction reaction to generate heteropolyblue. The visible light photochromic paper was prepared by loaded PMoA-PWA/ZnO/PVP hybrid film (A₃) on A4 paper. Application tests showed that the prepared paper had extremely stable, excellent and reversible visible light photochromic properties, whether it was printing patterns or words, and could replace ordinary paper to realize the reuse of paper. Full article

Modern catalysts are complex systems whose performance depends both on space and time domains and, most importantly, on the operational environment. As a direct consequence, understanding their functionalities requires sophisticated techniques and tools for measurement and simulation, addressing the proper spatial and temporal scale and being capable of mimicking the working conditions of every single component, such as catalyst supports, electrodes, electrolytes, as well as of the entire assembly, e.g., in the case of fuel cells or batteries. Scanning photoelectron spectro-microscopy (SPEM) is one of the approaches that allow combining X-ray photoelectron spectroscopy with sub-micron spatial resolution; in particular, the SPEM hosted at the ESCA Microscopy beamline at Elettra has been upgraded to conduct in situ and operando experiments. Three different case studies are presented to illustrate the capabilities of the SPEM in the investigation of catalytic materials in different conditions and processes. Full article