Surfaces

As a promising polymer for the production of biomaterials and drug delivery systems, poly(lactic acid) (PLA) is characterized by its relative hydrophobicity, as well as its chemical and biological inertness. Here, we aimed to improve the biological properties of PLA-based materials via the covalent attachment of a hydrophilic biocompatible glycopolymer, namely poly(2-deoxy-N-methacrylamido-D-glucose) (PMAG) on their surface. PMAG is a water-soluble polymer that contains glucose units in its side chains, which are responsible for good biocompatibility and the ability to attach bioactive molecules. In the developed protocol, PMAG was synthesized by controlled radical polymerization in the presence of a reversible addition–fragmentation chain transfer (RAFT) agent, followed by the conversion of glycopolymer terminal dithiobenzoate functionality into a primary amino group (PMAG-NH₂). PLA-based films served as model aliphatic polyester materials for developing the surface biofunctionalization protocol. According to that, PMAG-NH₂ covalent immobilization was carried out after alkali treatment, allowing the generation of the surface-located carboxyl groups and their activation. The developed modification method provided a one-point attachment of hydrophilic PMAG to the hydrophobic PLA surface. PMAG samples, which differed by the degree of polymerization, and the variation of polymer concentration in the reaction medium were applied to investigate the modification efficacy and grafting density. The developed single-point polymer grafting approach provided the efficient functionalization with a grafting density in the range of 5–23 nmol/cm². The neat and modified polymer films were characterized by a number of methods, namely atomic force microscopy, thermogravimetric analysis, ellipsometry, and contact angle measurements. In addition, an ArgGlyAsp-containing peptide (RGD peptide) was conjugated to the PMAG macromolecules grafted on the surface of PLA films. It was shown that both surface modification with PMAG and with PMAG-RGD peptide enhanced the adhesion and growth of mesenchymal stem cells as compared to a neat PLA surface. Full article

Many interesting materials in a broad range of applications have in their composition the coexistence of zinc and iron. Their characterization by XPS should identify and quantify both elements. The most intense regions for these elements Zn 2p and Fe 2p are, therefore, used to accomplish that purpose. By using sphalerite as an example of a material where Zn and Fe may coexist and using XPS with two different X radiation sources to study them, it is demonstrated that the Fe 2p region, when the iron is the minor component, may be seriously affected by the Auger Zn L₃M₁M₂₃ structure. The sphalerite (Zn_1−xFe_xS) here studied has x ≈ 0 and is a good example to show how an XPS spectrum obtained with the X-ray Al Kα, the most used radiation in monochromatic equipment, leads to a wrong assignment of the structures existing in the binding energy region of Fe 2p. The simultaneous use of Mg Kα radiation showed that the Fe 2p is below the XPS detection in this specific sample of sphalerite. Its attested absence reveals that the structure detected, when using Al Kα in the “Fe 2p” region, is assigned to a zinc Auger multiple peak and not to the expected 2p photoelectron doublet peak of iron. Full article

High-quality, reproducible tip coatings are essential for minimizing faradaic currents in electrochemical scanning tunneling microscopy (EC-STM), especially during in situ and operando measurements. The variability inherent in manual coating methods, influenced by the operator’s skill and a lack of standardization, can lead to inconsistent results, increased research costs, and a greater workload. This study introduces an Automated Tip Coater (ATC) designed to automate and standardize the tip coating process. The ATC features a tip movement system using stepper motors, a rotation module with a DC motor, and a heating block based on a soldering iron. It is controlled by an Arduino development board, supported by motor drivers, and has a user-friendly interface with an OLED display and encoder. The ATC coating mechanism includes a redesigned plate with a reduced gap size and a milled tray to precisely control the amount of insulating material applied to the tip. A fast cyclic voltammetry test in a 0.1 M HClO₄ electrolyte demonstrated that over 75% of ATC-coated tips achieved excellent insulation with leakage currents below ±50 pA—and 30% below ±10 pA—suitable for highly sensitive experiments. Further measurements with EC-STM using the newly coated tips investigated the electrochemical behavior of highly oriented pyrolytic graphite (HOPG), revealing detailed atomic structures under dynamic electrochemical conditions. The ATC significantly enhances reproducibility, reduces dependency on operator skills, and lowers research costs while improving the accuracy and reliability of EC-STM measurements. Full article

The generation of electrocharged microbubbles is very important for several separation processes (e.g., water treatment, paper industry, and mineral processing). However, their rising terminal velocities are not fully understood. This work presents a laboratory study of the terminal velocity of single microbubbles (bubble diameter ($D_b$) < 100 µm) rising in stagnant aqueous solutions with different pH levels (from 2 to 12) and reagent types (frother and collector; 30 ppm). The measurements were compared with the respective predicted velocities computed from the Stokes and Hadamard–Rybczynski models. It was found that the terminal velocities of electrocharged microbubbles were larger than the respective predictions from the Stokes equation. A regression equation was proposed to predict the terminal velocity as a function of the bubble diameter, which showed considerable dispersion depending on the type of reagent adsorbed on its surface, the concentration of these reagents, and the physical characteristics that the boundary layer acquires by modifying the zeta potential of the microbubbles; this effect has not yet been addressed in the literature. Full article

This paper reports on the successful preparation of a low absorption–emission thermal control coating on the surface of LAZ933 magnesium–lithium alloy using the micro-arc oxidation method. This study analyzed the microstructure, phase composition, and thermal control properties of the coating using Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), UV–visible near-infrared spectroscopy (UV-VIS-NIR) and infrared emissivity measurements. The results indicate that the hemispherical emissivity of the coating remains unaffected with an increase in temperature and holding time, while the solar absorption ratio gradually increases. The thermal control performance of the coating after a high-temperature experiment was found to be related to the diffusion of the Li metal element in the magnesium lithium alloy matrix, as determined by X-ray photoelectron spectroscopy (XPS), flame graphite furnace atomic absorption spectrometry (GFAAS) and Glow Discharge Optical Emission Spectroscopy (GD-OES). As the holding time is extended, the coating structure gradually loosens under thermal stress. The Li metal element in the substrate diffuses outward and reacts with O₂, H₂O and CO₂ in the air, forming LiO₂, LiOH, Li₂CO₃ and other products. This reaction affects the coating’s solar absorption ratio in the end. Full article

In this work, we report a detailed scheme of computational optimization of solar cell structures and parameters using PC1D and AFORS-HET codes. Each parameter’s influence on the properties of the components of heterojunction silicon-based solar cells (HIT) has been thoroughly examined. The proposed approach follows a stringent sequence of steps to optimize various parameters of the studied HITs. Furthermore, we have revealed the effects of the metal-semiconductor contact, and a model of a photocell with an ohmic contact and a Schottky contact has been simulated. The optimal model of HIT for available materials has been proposed and fabricated based on the results of these simulations. A comparison of predicted and measured performance unequivocally demonstrates the efficiency of the proposed scheme in developing silicon-based HITs, providing reassurance about its practical application. Full article

The drive for the development of systems that can simultaneously investigate chemical and morphological information comes from the requisite to fully understand the structure and chemical reactivity relationships of materials. This is particularly relevant in photocatalysis, a field ruled by surface interactions. An in-depth understanding of these complex interactions could lead to significant improvements in materials design, and consequently, in photocatalytic performances. Here, we present a first approach to a combined atomic force microscopy (AFM) and Raman spectroscopy characterization of anodic TiO₂ nanotubes arrays decorated with Ag nanoparticle electrodeposition from either the same anodizing organic electrolyte or from an aqueous one. Photocatalytic substrates were used in up to 15 consecutive photocatalysis tests to prove their possible deterioration with reuse. Sample aging can, in principle, produce changes in both the morphology and the chemical compounds that characterize the photocatalyst surface. Adopting multiple characterization techniques, such as a combination of AFM and Raman spectroscopy in an original setup, can profitably enable the observation of surface contamination. A significant drop in photocatalytic activity was observed after 10 cycles on samples where silver was deposited from the organic electrolyte, while the others remained stable. Such a drop was ascribed to photocatalyst deactivation. While in other cases, a simple recovery treatment allowed the initial photoactivity to be restored, this deactivation was not restored even after chemical and thermal cleaning treatments. Full article

The properties of coatings obtained using two surface preparation methods were compared: heating and etching by ion bombardment with plasma generation by arc evaporators and heating and etching by a glow discharge. A Ti-TiN-(Ti,Cr,Al)N coating was deposited. The use of a glow discharge provides better resistance of the coating to destruction during the scratch test and wear resistance of metal-cutting tools when turning steel. As the cutting speed increases, the advantage in wear resistance of the coating deposited using a glow discharge increases. During the process of heating and etching by ion bombardment with metal ions, a nanolayer rich in cobalt and tooling elements (iron, molybdenum) is formed in the area of the interface of the coating and the carbide substrate. When heated and etched by a glow discharge, such a layer does not form. When using both methods, there is identical diffusion of tungsten into the coating and diffusion of chromium and possibly titanium into the substrate. Thus, the glow-discharge heating and etching method can be effectively used in the process of PVD coating deposition. Full article

Cerium dioxide (CeO₂) is a promising material for photoelectrochemical applications, requiring a thorough understanding of the interplay between its properties and structure for optimal performance. This study investigated the photoelectrochemical performance of CeO₂ photoanodes immobilized by electrodeposition on glass substrates, focusing on the correlation between the annealing temperature and structural, optical, and electrical changes. CeO₂ coatings were obtained via chronoamperometry in an aqueous solution of 25 mM CeCl₃ and 50 mM NaNO₃. The photoelectrochemical characterization included the evaluation of photoactivity, current density, stability, and recombination using linear sweep voltammetry (LSV) and chronoamperometry (CA). Charge transfer resistance, flat-band potential, and capacitance were assessed through impedance spectroscopy. The optimal annealing temperature for this material was found to be 600 °C as it resulted in the lowest charge transfer resistance and increased photocurrent, which was attributed to enhanced crystallinity and variations in the Ce³⁺/Ce⁴⁺ ratio. Full article

The use of pesticides causes significant environmental problems, which drives the search for natural and non-toxic alternatives. In this study, a glycolipid biosurfactant (BS), produced by the yeast Starmerella bombicola ATCC 22214, was utilized as an active ingredient in natural agricultural defensive blends. The mixtures were tested for their fungicidal potential against phytopathogenic fungi isolated from fruits such as papaya, orange, and banana, demonstrating strong inhibition of fungal growth. The genera Penicillium, Colletotrichum, and Aspergillus were the pathogens present in the deterioration of the fruits used in the experiment. The biosurfactant was produced in a fermenter, yielding 10 g/L and reducing the surface tension to 31.56 mN/m, with a critical micelle concentration (CMC) of 366 mg/L. Blends of BS with oleic acid (T1) and lemongrass oil (T2) were found to be effective in controlling fungi. Additionally, the phytotoxicity of these formulations was assessed using Cucumis anguria (gherkin) seeds, where the blend of BS with castor oil (T4) showed the best performance, promoting seed germination. These results indicate the potential of such mixtures as natural alternatives for fungal control in plants and for application in sustainable agricultural systems. Full article

Colloidal bismuth nanoparticles (NPs) were synthesized in sodium chloride (NaCl) solutions at different concentrations using the laser ablation of solids in liquids technique. The obtained materials were characterized using various techniques. The morphology, size, and crystalline phases were determined through scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and Fourier-transform infrared spectroscopy (FTIR). The optical properties were studied using UV–visible spectroscopy, employing the Tauc method to determine the band gap of the particles. Two types of materials were identified depending on the NaCl concentration: spherical nanoparticles of α-Bi₂O₃ and the coexistence of α-Bi₂O₃ and BiOCl particles with irregular morphology. NaCl concentrations higher than 11.6% enable the coexistence of α-Bi₂O₃ and BiOCl. The photocatalytic response of the colloids was evaluated by the degrading rhodamine B under visible light irradiation. The sample synthesized at a NaCl concentration of 31.6% showed the best photocatalytic activity. Full article

As society moves away from heavy industry, large metallic structures will be abandoned. As an alternative to dismantling, these structures could be repurposed. Beyond being a practical solution, the conservation of these structures would serve as an ode to the role of these industries in shaping modern society. Conservation, however, requires suitable coatings that hinder corrosion long-term while not significantly altering the outward appearance. Traditionally, the stability of coatings has been tested by comparing fresh samples to those aged naturally or in a UV chamber. This method of testing provides no temporal information. Additionally, measuring many different conditions, e.g., UV, humidity, temperature, and pollutants, is tedious. In this review, we highlight how by implementing infrared spectroscopy in different configurations, temporally resolved information about the coating chemistry, the metal–coating interface chemistry, and gas emissions could be gained during degradation. These insights would be essential to enable the intentional design of coatings while simultaneously revealing their environmental impact. Full article

Branched fluorinated surfactants with creatively introduced acrylate in the hydrophilic group were designed and prepared by adopting perfluoro-2-methyl-2-pentene as the raw substrate. These new compounds showed excellent surface properties, and the surface tension of their aqueous solution at 25 °C could be below 20.00 mN/m at the critical micelle concentration. Compared with similar structures we have synthesized previously, these synthesized compounds exhibit a great improvement with regard to their molecular arrangement at the gas–liquid interface, their polymerizability, and the antibacterial properties of their polymer form, which can provide new ideas in the work to replace perfluorooctane sulfonate/perfluorooctanoic acid. Full article

The paper examines the possibility of increasing the wear and corrosion resistance of a CP-Ti surface by duplex plasma electrolytic treatment (borocarburizing and polishing). The structure and composition of diffusion layers, their microhardness, surface morphology and roughness, wear resistance during dry friction and corrosion resistance in Ringer’s solution were studied. The formation of a surface-hardened layer up to 200 μm thick with a microhardness of up to 950 HV, including carbides and a solid solution of boron and carbon, is shown. Subsequent polishing makes it possible to reduce surface roughness and remove weak areas of the porous oxide layer, which are formed during high-temperature oxidation in aqueous electrolyte vapor during borocarburizing. Changing the morphology and structural-phase composition of the CP-Ti surface helps reduce weight wear by a factor of three (the mode of frictional interaction changes from microcutting to oxidative wear) and corrosion current density by a factor of four after borocarburizing in a solution of boric acid, glycerin and ammonium chloride at 950 °C for 5 min and subsequent polishing in an ammonium fluoride solution at a voltage of 250 V for 3 min. Full article

Bipolar plates are one of the main components of proton exchange membrane fuel cells (PEMFCs). Their functions include distributing reactants, supporting the cell, and conducting heat and electricity. They account for a significant proportion of the fuel cell stack’s weight and volume. The main materials currently used for bipolar plates are graphite and stainless steel. Aluminium has a much lower density than steel and is easier to form than both steel and graphite. Its use, therefore, would allow fuel cells with higher power densities but is hindered due to it being prone to corrosion. This work focused on the development of corrosion-resistant and conductive coatings to address this issue. Carbon coatings with Ti and Cr adhesion layers were deposited on aluminium substrates using closed-field unbalanced magnetron sputtering. These coatings were tested for corrosion properties and performance on the cathode side of a single-cell fuel cell. Coated aluminium samples were also tested for their ability to maintain their corrosion protection after being formed. Coating with a Cr adhesion layer outperformed that with a Ti adhesion layer in both forming and fuel cell tests, demonstrating much lower performance degradation after accelerated stress testing. Full article

Accelerated synthesis of gold nanoparticles (AuNPs) in charged microdroplets produced by electrospray ionization (ESI) was exploited to modify the surface of graphite screen-printed electrodes (GSPEs). The deposited AuNPs were then functionalized by the charged microdroplets deposition of 6-ferrocenyl-hexanethiol (6Fc-ht) solutions that act as reducing and stabilizing agents and provide electrochemical properties for the modified electrodes. The morphology and composition of the AuNPs were characterized by scanning electron microscopy (SEM). Cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical behavior of the modified electrodes. The results showed that the ESI microdroplets deposition technique produces uniform and well-dispersed AuNPs on GSPE, and optimal conditions for deposition were identified, enhancing GSPE electrocatalytic performance. Further functionalization by ESI microdroplets of AuNPs with 6Fc-ht demonstrated improved redox properties compared with the conventional self-assembled monolayer (SAM) method, highlighting the technique’s potential for the easy and fast functionalization of electrochemical sensors. Full article

The extensive global use of rubber results in significant microplastic pollution from the release of tire wear particles and microplastic leachate, impacting the environment, human health, and ecosystems. Waste tires are normally recycled and used for the production of new products, such as rubber tiles. The presented study aims to show the possibility of further decrease in the negative environmental impact of materials based on recycled rubber. This paper presents the modification of rubber tiles with a titanium dioxide (TiO₂) coating, focusing on surface integrity, rubber particle wear release, and the consequent environmental impact of leachate release. Both reference and modified rubber tiles were subjected to artificial accelerated aging in a solar simulator for 4, 6, and 8 weeks, followed by an abrasion test. The carbonyl index was calculated from FTIR characterization after each time frame to indicate the degradation of organic compounds and chemical changes caused by UV exposure. A 24 h leaching test with a liquid-to-sample ratio of 1:20 was performed on both rubber tile samples prior to and after 8 weeks of aging along with the aged wear particles for the purpose of the non-target screening of released organic leachate by LC/MS QTOF. The results of carbonyl indices showed that the TiO₂ coating contributes to the stabilization of polymer degradation and, to a certain extent, reduces the leaching of organic compounds, such as phthalates. However, the increased wear and release of rubber particles and the subsequent degradation of organic leachates require further in-depth research. Full article

The optical characteristics and electrical behavior of zinc oxide nanorods (ZnO-NRs) and silver nanoparticles (Ag-NPs) were investigated using advanced scanning probe microscopy techniques. The study revealed that the ZnO nanorods had a length of about 350 nm, while the Ag nanoparticles were spherical with heights ranging from 5 to 14 nm. Measurements with Kelvin probe force microscopy (KPFM) showed that the work functions of ZnO nanorods were approximately 4.55 eV, higher than that of bulk ZnO, and the work function of Ag nanoparticles ranged from 4.54 to 4.56 eV. The electrical characterization of ZnO nanorods, silver nanoparticles, and their hybrid was also conducted using conductive atomic force microscopy (C-AFM) to determine the local current-voltage (I-V) characteristics, which revealed a characteristic similar to that of a Schottky diode. The current-voltage characteristic curves of ZnO nanorods and Ag nanoparticles both showed an increase in current at around 1 V, and the hybrid ZnONRs/AgNP exhibited an increase in turn-on voltage at around 2.5 volts. This suggested that the presence of Ag nanoparticles enhanced the electrical properties of ZnO nanorods, improving the charge carrier mobility and conduction mechanisms through a Schottky junction. The investigation also explored the optical properties of ZnO-NRs, AgNPs, and their hybrid, revealing absorption bands at 3.11 eV and 3.18 eV for ZnO-NRs and AgNPs, respectively. The hybrid material showed absorption at 3.13 eV, indicating enhanced absorption, and the presence of AgNP affected the optical properties of ZnO-NR, resulting in increased photoluminescence intensity and slightly changes in peak positions. Full article

Polymer-based molecular tweezers have emerged as a prominent research area due to their enhanced ability to form host–guest complexes, driven by advancements in their design and synthesis. The impact of the spacer structure on the tweezers is predominant. They can be rigid, flexible, and stimuli-responsive. Herein, a new generation of molecular tweezers is introduced as polymer-based molecular tweezers. The integration of molecular tweezers onto biopolymers has significantly expanded their potential applications, making them promising candidates, especially in drug delivery, owing to their biocompatibility, adaptive structural features, and versatile interaction capabilities. The unique structure of polymer-based molecular tweezers, particularly when integrated with biopolymers, creates a unique nano-environment that enhances their interaction with guest molecules. This minireview focuses on the synthesis and applications of polymer-based molecular tweezers and examines how the incorporation of various spacers affects their binding affinity and specificity. These features highlight the advancement of these polymer-based systems, emphasizing their potential applications, particularly in drug delivery, water treatment technology, and future research opportunities. Full article