Surfaces

This study reports a route to obtaining a novel and cost-effective rice husk-derived lignin/thiophene chalcone green composite for application in forensic science as a fingermark developer through high energy milling. The material was properly characterized by UV-Vis, IR, fluorescence, X-ray diffraction and scanning electron microscopy. The product provided clear and sharp images of latent fingermarks with minimal background staining, revealing all ridge details. Thus, the composite presented good performance as a fingermark developer, becoming an interesting alternative to being applied as a technological, reproducible and renewable product. Full article

Recently, titania nanotubes (TNTs) have been extensively studied because both their functional properties and highly controllable morphology make them important building blocks for understanding nanoscale phenomena and realizing nanoscale devices. Compared with sol–gel and template-assisted methods, electrochemical anodization is a simple, cost-effective, and low-temperature technique offering additional advantages such as straightforward processing and ease of scale-up. This review focuses on the process modalities and underlying mechanism of electrochemical anodization to achieve a different set of TNTs for a variety of applications. Finally, important applications of TNTs are highlighted including biomedical devices, water purification, and solar cells. Full article

The present paper describes the technological peculiarities relevant to the nucleation and further epitaxial growth of the metastable epsilon phase of iron oxide by means of pulsed laser deposition (PLD). The orthorhombic epsilon ferrite ε-Fe₂O₃ is an exotic member of a large family of iron oxide polymorphs, which attracts extensive attention nowadays due to its ultra-high magneto-crystalline anisotropy and room temperature multiferroic properties. Continuing the series of previous publications dedicated to the fabrication of ε-Fe₂O₃ films on GaN, this present work addresses a number of important requirements for the growing conditions of these films. Among the most sensitive technological parameters, the growth temperature must be high enough to aid the nucleation of the orthorhombic phase and, at the same time, low enough to prevent the thermal degradation of an overheated ε-Fe₂O₃/GaN interface. Overcoming the contradicting growth temperature requirements, an alternative substrate-independent technique to stabilize the orthorhombic phase by mild aluminum substitution is proposed. The advantages of this technique are demonstrated by the example of ε-Fe₂O₃ films PLD growth carried out on sapphire—the substrate that possesses a trigonal lattice structure and would normally drive the nucleation of the isostructural and energetically more favorable trigonal α-Fe₂O₃ phase. The real-time profiling of high-energy electron diffraction patterns has been extensively utilized throughout this work to keep track of the orthorhombic-to-trigonal balance being the most important feed-back parameter at the growth optimization stage. Full article

Three ternary metal composites (TMCs) with iron nitrate, aluminum nitrate, and copper nitrate (Fe-TMC-N, Al-TMC-N, Cu-TMC-N) were synthesized and their physicochemical properties were investigated. Characterization of the TMCs was achieved by elemental analysis (XPS), infrared (IR) spectroscopy and thermogravimetric analysis (TGA). The surface charge of the TMCs was estimated from the point-of-zero-charge (PZC), which depended on the type of metal nitrate precursor. The adsorption properties of the TMCs showed the vital role of the metal center, where methylene blue (MB) is a cationic dye probe that confirmed the effects of surface charge for effective methyl orange (MO) anion dye uptake. MB uptake was negligible for Al-TMC-N and Cu-TMC-N, whereas moderate MB uptake occurs for Fe-TMC-N (26 mg/g) at equilibrium. The adsorption capacity of MO adopted the Langmuir isotherm model, as follows: Al-TMC-N (422 mg/g), Cu-TMC-N (467 mg/g) and Fe-TMC-N (42 mg/g). The kinetic adsorption profiles followed the pseudo-second order model. Generally, iron incorporation within the TMC structure is less suitable for MO anion removal, whereas Cu- or Al-based materials show greater (10-fold) MO uptake over Fe-based TMCs. The dye uptake results herein provide new insight on adsorbent design for controlled adsorption of oxyanion species from water. Full article

The removal of model hydrocarbon oil systems (4-nitrophenol (PNP) and naphthalene) from laboratory water was evaluated using a ferric sulfate and a lime-softening coagulant system. This study addresses the availability of a methodology that documents the removal of BTEX related compounds and optimizes the ferric-based coagulant system in alkaline media. The Box–Behnken design with Response Surface Methodology enabled the optimization of the conditions for the removal (%) of the model compounds for the coagulation process. Three independent variables were considered: coagulant dosage (10–100 mg/L PNP and 30–100 mg/L naphthalene), lime dosage (50–200%), and initial pollutant concentration (1–35 mg/L PNP and 1–25 mg/L naphthalene). The response optimization showed a 28% removal of PNP at optimal conditions: 74.5 mg/L ferric sulfate, 136% lime dosage, and initial PNP concentration of 2 mg/L. The optimal conditions for naphthalene removal were 42 mg/L ferric sulfate, 50% lime dosage, and an initial concentration of naphthalene (16.3 mg/L) to obtain a 90% removal efficiency. The coagulation process was modeled by adsorption isotherms (Langmuir for PNP; Freundlich for Naphthalene). The surface properties of flocs were investigated with pH_pzc, solid-state UV absorbance spectra, and optical microscopy to gain insight into the role of adsorption in the ferric coagulation process. Full article

Counter-surfaces for radial shaft seals are usually finished by infeed grinding to avoid macro twist structures on the surface since they can impose a conveying action on the lubricant. This can lead to either leakage or starved lubrication and subsequent thermal damage depending on the direction of said conveying action. Turning processes can offer a more cost-effective surface finish, but conventional methods cause twist structures, which can impair the leakage prevention of the sealing system. An approach for the production of twist-free surfaces was developed based on new kinematics for turning. However, the surfaces produced with this approach using case hardened specimens made from the steel 16MnCr5 show deviating structural characteristics compared to the kinematic simulation. The causes of this and the resulting influence on the conveying value are the subjects of the research work. For this purpose, in addition to hardened steel, two other materials are considered: the steel 16MnCr5 in the unhardened hot rolled delivery condition and brass as a material with good machinability. The results clearly show that there is a deviation in the machining behavior of the steel materials compared to the kinematic surface simulations, especially in the repeatedly turned areas. This is mainly due to elastic–plastic deformation effects. Despite the actually twist-free surface profile, certain characteristics result in an anisotropic structure, which partially has an influence on the conveying value. Full article

Microfouling is the deposition of inorganic and organic material on surfaces and can cause economic losses. This deposition affects the performance of vessels, causes corrosion, clogging of equipment and contaminates the surfaces of medical items and the surface of machinery that handles food; it is controlled by cleaning products that contain synthetic surfactants in their formulations. Biobased products provide a promising basis to produce sustainable chemicals such as surfactants. In the present study, the biobased surfactants glyceryl laurate and hydroxystearic acid were synthesized and evaluated for stability at different pH values, salinity and temperatures. In addition, bioactivity tests against Pseudomonas aeruginosa (UCP 0992) and Bacillus cereus (UCP 1516) were also performed. Biobased surfactants glyceryl laurate and hydroxystearic acid showed excellent stability against temperature, pH, salinity and emulsifying activities for different kinds of oils; prevented bacterial adhesion by almost 100%; and affected the production of EPS by both bacteria and their consortium when compared to a synthetic surfactant SDS. The results showed the potential of these substances for application as an alternative antifouling non-biocide. Full article

Poly(2-methoxyethyl acrylate) (PMEA) is a US FDA-approved biocompatible polymer, although there is insufficient work on human umbilical vein endothelial cells (HUVECs) and platelet interaction analysis on PMEA-analogous polymers. In this study, we extensively investigated HUVEC–polymer and platelet–polymer interaction behavior by measuring the adhesion strength using single-cell force spectroscopy. Furthermore, the hydration layer of the polymer interface was observed using frequency-modulation atomic force microscopy. We found that endothelial cells can attach and spread on the PMEA surface with strong adhesion strength compared to other analogous polymers. We found that the hydration layers on the PMEA-analogous polymers were closely related to their weak platelet adhesion behavior. Based on our results, it can be concluded that PMEA is a promising candidate for the construction of artificial small-diameter blood vessels owing to the presence of IW and a hydration layer on the interface. Full article

Owing to the light weight and high energy, the “All-aluminum engine” can reduce fuel consumption and pollutant emissions, showing a great significance in saving resources and protecting the environment, and becoming a research hotspot. However, the aluminum alloy cylinder liners have difficulty withstanding extremely harsh working conditions, such as strong friction and wear, making the engine extremely easy to damage. In this work, Al-25Si wear-resistant coating was deposited by inner hole supersonic plasma spraying technique to improve the wear resistance of the aluminum alloy cylinder liner. The microstructure, phase composition, mechanical properties and tribological properties were tested by SEM, XRD, tribological machine, etc. The results indicated that the coating exhibited an excellent bonding strength of 44.1 MPa, and the average hardness and average friction coefficient of the coating are 267.09 ± 14.85 HV_0.2, and 0.20, respectively. The total wear amount, the wear scar width and the wear scar depth of the coating are 2.77 × 10⁻³ mm³, 654.3 μm and 8.95 μm, respectively, which showed that the coating can significantly improve the tribological properties of the “All-aluminum engine”. The wear mechanism of the coating was mainly interpreted by furrow cutting, extrusion and spalling in two-body abrasive wear, three-body abrasive wear and a small amount of oxidative wear. Full article

Supercapacitors have played an important role in electrochemical energy storage. Recently, researchers have found many effective methods to improve electrode materials with more robust performances through the increasing volume of scientific publications in this field. Though nickel cobaltite (NiCo₂O₄), as a promising electrode material, has substantially demonstrated potential properties for supercapacitors, its composites usually show much better performances than the pristine NiCo₂O₄. The combination of carbon-based materials and NiCo₂O₄ has been implemented recently due to the dual mechanisms for energy storage and the unique advantages of carbon materials. In this paper, we review the recent research on the hybrids of NiCo₂O₄ and carbon nanomaterials for supercapacitors. Typically, we focused on the reports related to the composites containing graphene (or reduced graphene oxide), carbon nanotubes, and amorphous carbon, as well as the major synthesis routes and electrochemical performances. Finally, the prospect for the future work is also discussed. Full article

To facilitate future novel devices incorporating rare earth metal films and III-V semiconductors on Si substrates, this study investigates the mechanisms of growth via molecular beam epitaxy of gadolinium (Gd) on aluminum nitride (AlN) by determining the impact of substrate temperature on microstructure. The Gd films underwent extensive surface analysis via in situ reflective high energy electron diffraction (RHEED) and ex-situ SEM and AFM. Characterization of the surface features of rare earth metal films is important, as surface geometry has been shown to strongly impact magnetic properties. SEM and AFM imaging determined that Gd films grown on AlN (0001) from 80 °C to 400 °C transition from wetting, nodular films to island–trench growth mode to reduce in-plane lattice strain. XRD and Raman spectroscopy of the films revealed that they were primarily comprised of GdN, Gd and Gd₂O₃. The samples were also analyzed by a vibrating sample magnetometer (VSM) at room temperature. From the room temperature magnetic studies, the thick films showed superparamagnetic behavior, with samples grown between 240 °C and 270 °C showing high magnetic susceptibility. Increasing GdN (111) 2θ peak position and single-crystal growth modes correlated with increasing peak magnetization of the thin films, suggesting that lattice strain in single-crystal films was the primary driver of enhanced magnetic susceptibility. Full article

This investigation is motivated by the numerous advantages of electrophoretic deposition (EPD) for the fabrication of polyvinylidene fluoride (PVDF) and composite coatings and the various applications of such coatings. It is demonstrated that gallic acid (GA), caffeic acid (CFA), cholic acid (CA) and 2,3,4 trihydroxybenzoic acid (THB) can be used as charging and dispersing agents for the EPD of PVDF. The deposition yield of PVDF increases in the following order: THB < CFA < CA < GA. Test results indicate that the chemical structure of the dispersants exerts influence on the deposition efficiency. Potentiodynamic and impedance spectroscopy studies show the corrosion protection properties of PVDF coatings. GA is used for the co-EPD of PVDF with nanosilica and micron-size silica. The silica content in the composite coatings is varied by the variation of silica content in the suspensions. The ability to use GA as a charging and dispersing agent for the co-EPD of materials of different types paves the way for the fabrication of advanced organic–inorganic composites using EPD. Full article

The electrical discharge machine (EDM) has been one of the most widely used non-traditional machines in recent decades, primarily used for machining hard materials into various complex shapes and different sizes and, nowadays, used for surface modifications/hard coatings. In this study, the SWOT (strengths, weaknesses, opportunities and threats) of electrical discharge coating was analyzed by conducting a case study. For the purpose of the case study, copper was deposited on the titanium alloy surface (Ti6Al4V). Three electrodes of different copper alloy materials, viz., brass, bronze and copper, were selected for coating the Ti6Al4V surface. Input parameters such as current, pulse-on, pulse-off, flushing pressure and the electrode material were optimized to develop a uniform coating. Experiments were designed according to the L18 orthogonal array, and among them, the samples that showed proper coating, as seen with the naked eye, were selected for morphological and elemental analyses by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX. Further, the output responses, viz., the material deposition rate (MDR), electrode wear rate (EWR), surface roughness (SR), elemental data (copper (Cu) and zinc (Zn)) and coating thickness (CT), were considered for the optimization of coatings. Implementing the Technique for Order Performance by Similarity to Ideal Solution, copper coating with a thickness of 20.43 µm, developed with an MDR with input parameters of 20 A current, 600 µs pulse-on, 120 µs pulse-off, 0.5 bar flushing pressure and the brass electrode, was selected as the optimum coating. The most influential parameters in this coating process were the current and pulse-on time. In this study, a SWOT table was developed to depict the strengths, weaknesses, opportunities and threats of electrical discharge coating. Full article

The mechanism of adsorption of p-cresol over activated carbon adsorbent and the specific role of oxygen functional groups on cresol adsorption were studied using density functional theory (DFT) calculations. All the energy calculations and geometry optimization pertaining to DFT calculations were done using the B3LYP hybrid functional at basis set 6-31g level of theory in a dielectric medium of ε = 80 (corresponding to water). The interaction of cresol with different activated carbon models, namely pristine activated carbon, hydroxyl functionalized activated carbon, carbonyl functionalized activated carbon, and carboxyl functionalized activated carbon, were considered, and their adsorption energies corresponded to −416.47 kJ/mol, −54.73 kJ/mol, −49.99 kJ/mol, and −63.62 kJ/mol, respectively. The high adsorption energies suggested the chemisorptive nature of the cresol-activated carbon adsorption process. Among the oxygen functional groups, the carboxyl group tended to influence the adsorption process more than the hydroxyl and carbonyl groups, attributing to the formation of two types of hydrogen bonds between the carboxyl activated carbon and the cresol simultaneously. The outcomes of this study may provide valuable insights for future directions to design activated carbon with improved performance towards cresol adsorption. Full article

Activated carbons play an essential role in developing new electrodes for renewable energy devices due to their electrochemical and physical properties. They have been the subject of much research due to their prominent surface areas, porosity, light weight, and excellent conductivity. The performance of electric double-layer capacitors (EDLCs) is highly related to the morphology of porous carbon electrodes, where high surface area and pore size distribution are proportional to capacitance to a significant extent. In this work, we designed and synthesized several activated carbons based on lignin for both supercapacitors and Li-S batteries. Our most favorable synthesized carbon material had a very high specific surface area (1832 m²·g⁻¹) and excellent pore diameter (3.6 nm), delivering a specific capacitance of 131 F·g⁻¹ in our EDLC for the initial cycle. This translates to an energy density of the supercapacitor cell at 55.6 Wh·kg⁻¹. Using this material for Li-S cells, composited with a nickel-rich phosphide and sulfur, showed good retention of soluble lithium polysulfide intermediates by maintaining a specific capacity of 545 mA·h·g⁻¹ for more than 180 cycles at 0.2 C. Full article

Kinetic Monte Carlo simulations of a model of thin film heteroepitaxy are performed to investigate the effects of the deposition temperature in the initial growth stages. Broad ranges of the rates of surface processes are used to model materials with several activation energies and several temperature changes, in conditions of larger diffusivity on the substrate in comparison with other film layers. When films with the same coverage are compared, the roughness increases with the deposition temperature in the regimes of island growth, coalescence, and initial formation of the continuous films. Concomitantly, the position of the minimum of the autocorrelation function is displaced to larger sizes. These apparently universal trends are consequences of the formation of wider and taller islands, and are observed with or without Ehrlich-Schwöebel barriers for adatom diffusion at step edges. The roughness increase with temperature qualitatively matches the observations of recent works on the deposition of inorganic and organic materials. In thicker films, simulations with some parameter sets show the decrease of roughness with temperature. In these cases, a re-entrance of roughness may be observed in the initial formation of the continuous films. Full article

The adsorption of 4-mercaptobenzoic acid (4-MBA) on anatase (101) and rutile (110) TiO₂ surfaces has been studied using synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy techniques. Photoelectron spectroscopy results suggest that the 4-MBA molecule bonds to both TiO₂ surfaces through the carboxyl group, following deprotonation in a bidentate geometry. Carbon K-edge NEXAFS spectra show that the phenyl ring of the 4-MBA molecule is oriented at 70° ± 5° from the surface on both the rutile (110) and anatase (101) surfaces, although there are subtle differences in the electronic structure of the molecule following adsorption between the two surfaces. Full article

In this work, we studied dispersion correction, adsorption and substitution of chalcogen dopants (O, S, Se and Te) on the surface of graphene using density functional theory. The results reveal that a single oxygen atom is more preferred for adsorption onto the graphene surface than the other dopants, with an adsorption energy of −0.84 eV. The preference of this dopant is evidenced by a greater charge transfer of 0.34 electrons from the graphene surface to the oxygen. The substitutional doping of oxygen is energetically more favourable than the doping of other atoms. While nitrogen activation is enhanced by the adsorption, the activation is not significant with the doping of chalcogen atoms. Full article