Surfaces, Volume 7, Issue 2 (June 2024) – 10 articles

Silicon is the most commonly used material in the microelectronics industry, due to its inherent advantages of high natural abundance, low cost, and high purity, coupled with the chemical and electrical stability at the interface with its oxide. For molecular electronics applications, oxide-free Si surfaces are widely used because of the relative ease of removing the oxide (SiO_x) by chemical means, yielding a surface which forms strong covalent bonds with a wide range of chemical functional groups; another advantage is that these surfaces remain oxide-free in the absence of oxidising agents. Standard procedures require the use of either HF, NH₄F, or a mixture of both as the etching solution; however, these two chemicals are highly corrosive and toxic, posing a significant risk to the experimentalist. Here, we report that for silicon wafers etched by using potassium fluoride, a less toxic chemical, the resulting surface is free of oxides and can be functionalized by self-assembled monolayers of 1,8-nonadiyne. To demonstrate this, Si/SiO_x wafers were etched by using either KF or NH₄F, followed by hydrosilylation with 1,8-nonadiyne and a click reaction of the terminal alkyne with azidomethylferrocene. The surface coverages and electron transfer kinetics of the ferrocene-terminated KF-etched surfaces are comparable to those formed by acidic fluoride etching procedures. This is the first study comparing the differences between surfaces functionalized by self-assembled monolayers of 1,8-nonadiyne which were etched by KF and NH₄F. KF could be used as a replacement chemical for etching silicon wafers when a less corrosive and toxic chemical is required. Full article

Improvement of the surface quality of machined parts is essential in order to avoid excessive and costly post-processing. Although non-conventional processes can efficiently carry out the machining of difficult-to-cut materials with high productivity, they may also, for various reasons, be related to increased surface roughness. In order to optimize the surface quality of generated surfaces in a reliable way, surface profiles obtained during these processes must be adequately modeled. However, given that most studies have focused on Ra or Rz indicators or are based on the assumption of a normal distribution for the profile heights, relevant models cannot accurately represent the surface characteristics that exist in a real machined surface with a high degree of accuracy. Thus, in the present study, a new modeling approach based on the use of a statistical probability distribution for the surface profile height is proposed. After six different distributions were evaluated on the basis of a three-stage procedure involving different roughness indicators pertaining to the abrasive waterjet (AWJ) milling of pockets, it was found that, although it is not possible to model the nominal values of every roughness parameter simultaneously, in several cases, it is possible to approximate the values of critical indicators such as Ra, Rz, Rsk, Rku and Rp/Rv ratio by Weibull distribution with a sufficient degree of accuracy. Full article

In this review, we have assessed the possibility of metal–perovskite interfacial engineering to enhance the catalytic activity and selectivity in a range of heterogeneous catalytic reactions. We embarked on a literature screening of different perovskite material classes and reactions to show the versatility of the perovskite structures to induce the formation of such hetero-interfaces and the widespread nature of the phenomenon in catalytic research. There is almost no limitation on the chemical composition of the used perovskites and the nature of the catalyzed reaction, be it under reduction or oxidation conditions. We attempted to classify the perovskite materials, discuss the different strategies leading to the hetero-interfaces, and detail the synergistic action of the components of the respective interfaces. We also provide a critical assessment of the large body of data that is available in terms of a knowledge-based approach to the comparison of differently prepared interfaces with varying interfacial extent to gain a deeper understanding of the bi-functional operation of the interfaces and the urgent necessity to study and characterize such interfaces under realistic operation conditions. Full article

Diffusion barrier composite films based on microfibrillated cellulose (MFC) and clay were developed with attention paid to the influence of thermal annealing and a fluorine-free surface silylation on their microstructure, water contact angle (WCA), mechanical properties, oxygen transmission rate (OTR), and water vapor transmission rate (WVTR). The OTR of MFC at 23 °C increased from 1.2 to 25.3 cm³/m²/day/bar as relative humidity increased from 50% to 80%. Annealing increased the film’s crystallinity, surface roughness, and hydrophobicity, while decreasing its OTR by 20% at 80%RH. The addition of clay led to a 30% decrease of OTR at 80%RH due to partial exfoliation and to a 50% decrease when combined with annealing. Silylation increased the hydrophobicity of surface of the film and its combination with clay and annealing led to a WCA of 146.5°. The combination of clay, annealing, and silylation considerably reduced the OTR at 80%RH to a value of 8 cm³/m²/day/bar, and the WVTR at 23 °C and 50%RH from 49 g/m²/day for MFC to 22 g/m²/day. The reduction of OTR and WVTR was found to correlate with the increase in surface hydrophobicity of the film, which was attributed to the reduced access of water molecules within the MFC network. Full article

Solid–liquid interfacial phenomena play an essential role in our everyday lives and are often regarded as the outcome of interactions at the solid–liquid interface. However, the intricately intrinsic mechanism underlying interfacial interactions renders in situ simulations and direct measurements challenging. As an effective analytic method for studying solid–liquid interfacial interactions, microcalorimetry can provide the most basic thermodynamic information (including changes in enthalpy, entropy, and Gibbs free energy during solid–liquid binding/separation processes), which is extremely crucial for understanding interaction directionality and limitation. This review is dedicated to highlighting the pivotal role of microcalorimetry in studying solid–liquid immersion and adsorption processes. Specifically, we provide an overview of the commonly employed microcalorimetric methods, including differential scanning calorimetry (DSC), isothermal titration calorimetry (ITC), and immersion microcalorimetry (IM), and delve into the influence factors of enthalpy change, and finally discuss the specific applications of microcalorimetry in studying various solid–liquid binding processes. There remains a vast expanse of thermodynamic information regarding solid–liquid interactions that await exploration via calorimetry. Full article

Water–ethanol mixtures are largely exploited for many different applications, from industrial processes to pharmaceutical formulations. Surfactants are often added to tune their interfacial properties. Sustainability concerns require redesigning such blends to minimize their environmental impact. A successful approach is to replace synthetic oil-based components with affordable unpurified bio-derived alternatives. In this respect, we have characterized aqueous mixtures of bioethanol, obtained by the fermentation of algae, and rhamnolipids, biosurfactants of microbial origin. The physico-chemical characterization of water–bioethanol binary mixtures in terms of refractive index, density, viscosity, and surface tension indicates that bioethanol behaves like pure ethanol with negligible effects of impurities. Analysis of tensiometric titrations shows that, at bioethanol contents higher than 20–30% bioethanol mass percent, rhamnolipid aggregation is impaired, whereas surface adsorption at the water–air interface remains poorly affected. Overall, bio-derived components can be proposed as a promising alternative to oil-derived chemicals in eco-sustainable formulations. Full article

This study focused on manufacturing efficient automobile sound-absorbing materials through alkaline treatment and dimple processing of recycled polyethylene terephthalate (rPET) nonwoven fabric. The rPET nonwoven fabric was produced with a sound-absorbing material through compression molding. It was improved through the development of porous sound-absorbing materials through alkaline treatment and resonant sound-absorbing materials through dimple processing. As a result of morphological analysis, alkaline treatment showed that pore size and air permeability increased according to temperature and concentration increase conditions. On the other hand, dimple processing caused a decrease in air permeability and a decrease in pores due to yarn fusion, and as the dimple diameter increased, the sound-absorbing coefficient increased in the 5000 Hz band. Finally, it was judged that effective sound absorption performance would be improved through a simple process through alkaline treatment and dimple processing, and thus there would be applicability in various industrial fields. Full article

Superhydrophobic coating is widely used due to its waterproof and self-cleaning properties. Carbon soot (CS) nanoparticles are naturally superhydrophobic and non-toxic which are superior to other superhydrophobic coating. However, the weak binding force of the CS nanoparticle layers hinders their practical application. In this study, micro-nanostructured PET-CS superhydrophobic coatings were prepared by a simple method. The obtained coatings presented durable superhydrophobicity and underwater stability, which are superior to PDMS-CS coatings and CS layers. The coating surfaces demonstrated superhydrophobicity under a water pressure of 13.72 kPa for up to 16 days. The surface could withstand water flush for more than 15 min. The coatings also demonstrated good mechanical stability and maintained superhydrophobicity after an abrasion length of 8 m. The stable long-lasting underwater superhydrophobic surface is of great importance for marine applications. Full article

Waste seashell (scallop shell)-based adsorbent was prepared via mechanochemical reaction with sodium oxalate using ball milling. The oxalate-modified seashell-based adsorbents (OS) were prepared by varying the molar ratio of calcium and oxalate to 0.5, 1, and 2. Sodium oxalate was used as the aqueous solution in ball milling. Lead ion adsorption was conducted with the prepared adsorbent. The adsorption behavior of lead ions was investigated in terms of adsorption kinetics and adsorption equilibrium. The time course of the amount of Pb adsorbed agreed well with Langmuir rate equation. The adsorption equilibrium relationship of OS adsorbent and Pb agreed well with the Langmuir adsorption isotherm. Increasing with the molar ratio, the saturated amount of Pb adsorbed increased slightly from 5.45 × 10⁻³ to 6.23 × 10⁻³ mol/g. Under the present experimental conditions, the maximum equilibrium adsorption was 5.93 × 10⁻³ mol/g, which is greater than that reported in the literature. Full article

Nickel films of 40 nm thickness were obtained by means of magnetron sputtering on a single-crystalline silicon substrate. The films were subjected to rapid thermal treatment (RTT) for 7 s until the temperature increased from 200 to 550 °C. By means of the X-ray diffraction method, the structural-phase composition of nickel films before and after RTT was explored. The atomic force microscopy method due to direct contact with the surface under study, made it possible to accurately define the microstructure, roughness, specific surface energy and grain size of the nickel films before and after RTT, as well as to establish the relationship of these parameters with the phase composition and electrical properties of the films. Surface specific resistance was measured using the four-probe method. Based on XRD results, formation of Ni₂Si and NiSi phases in the film was ascertained after RTT at 300 °C. At RTT 350–550 °C, only the NiSi phase was formed in the film. The microstructure and grain size significantly depend on the phase composition of the films. A correlation has been established between specific surface energy and resistivity with the average grain size after RTT at 350–550 °C, which is associated with the formation and constant restructuring of the crystal structure of the NiSi phase. Full article