Search Results (77)

Epoxy polymers modified with nanoparticles are increasingly employed due to their enhanced performance in aggressive environments, characterized by mechanical stress, radiation exposure, and extreme temperatures. The mechanical failure of these polymers is attributed to the fracturing of atomic and molecular bonds, that subsequently excites electrons having the capability to be emitted from the nanolayer of the material. The present study demonstrates that the relationship between mechanical loading and electron emission over time serves as an indicator of surface loading and durability. By utilizing the Kinetic Nature of Solid Material Strength (KSMS) theory alongside near-threshold electron emission measurements, the article presents the behavior of epoxy polymers modified with SiO₂ nanoparticles under tensile loading. The results indicate that as mechanical load is applied, photoelectron emission (PE) pulses emerge. Notably, the pulse spectrum highest frequency (fmax) correlates with the time of atomic fluctuations (τ), defined by τ = 1/fmax. Furthermore, ultraviolet (UV) irradiation of the nanoparticles prior to mixing with the polymer is shown to influence the parameter of KSMS responsible for local stress concentration. This suggests that PE is connected with the homogeneity of the composite too. The achieved results demonstrate that PE contactless measurements can be used to detect mechanical destruction of the epoxy polymer composite surface nanolayer, as well as to assess its durability and corresponding activation energy. The results presented in the article may contribute to the development of more reliable epoxy polymer composites and durability measurements of their mechanically loaded surface layer or nanofilms. Full article

Hyperthermia is a promising medical treatment that uses controlled heat to target and destroy cancer cells while minimizing damage to the surrounding healthy tissue. Unlike conventional methods, it offers reduced risks of infection and shorter recovery periods. This study focuses on the integration of carbon nanotubes (CNTs) within the blood to enable precise heat transfer to tumors. The central idea is that by adjusting the concentration, shape, and size of CNTs, as well as the strength of an external magnetic field, heat transfer can be controlled for targeted treatment. A theoretical model is developed to analyze laminar natural convection within a simplified rectangular porous enclosure resembling a tumor, considering the composition of blood, and the geometric characteristics of CNTs, including the interfacial nanolayer thickness. Using an asymptotic expansion method, ordinary differential equations for mass, momentum, and energy balances are derived and solved. Results show that increasing CNT concentration decelerates fluid flow and reduces heat transfer efficiency, while elongated CNTs and thicker nanolayers enhance conduction over convection, to the detriment of heat transfer. Finally, increased tissue permeability—characteristic of cancerous tumors—significantly impacts heat transfer. In conclusion, although the model simplifies real tumor geometries and treatment conditions, it provides valuable theoretical insights into hyperthermia and nanofluid applications for cancer therapy. Full article

We used high-power impulse magnetron sputtering (HiPIMS) to deposit tungsten carbide films for superior wear protection in abrasive environments. In order to sample different W-to-C ratios more efficiently, a combinatorial approach was chosen. A single sputter target with two equal segments was used, consisting of an upper tungsten and lower graphite segment. This allowed us to vertically sample various elemental compositions in just one deposition run without creating graphitic nano-layers by rotating the substrate holder. The substrate bias voltage, being one of the most effective process parameters in physical vapor deposition (PVD), was applied in both constant and pulsed modes (the latter synchronized to the target pulse). A direct comparison of the different modes has not been performed so far for HiPIMS W-C (separated W and C targets). The resulting coating properties were mainly analyzed by nano-hardness testing and X-ray diffraction. In general, the W₂C phase prevailed in tungsten-rich coatings with pulsed bias, leading to slightly higher tungsten contents. Hardness reached maximum values of up to 35 GPa in the center region between the two segments, where a mix of W₂C and WC_1-x phases occurs. With pulsed bias, voltage hardnesses are slightly higher, especially for tungsten-rich films. In those cases, compressive stress was also found to be higher when compared to constant bias. Erosive wear testing by blasting with alumina grit showed that the material removal rate followed basically the coating’s hardness but surprisingly reached minimum wear loss for W₂C single-phase films just before maximum hardness. In contrast to previous findings, low friction that requires higher carbon contents of at least 50 at. % is not favorable for this type of wear. Full article

Traditional binary coatings like TiN and CrN display limited thermal stability and wear resistance under extreme conditions. High-entropy alloy nitride (HEAN) coatings offer a promising solution due to their customizable composition and unique properties, including high hardness, corrosion resistance, and thermal stability. This study focused on (AlCrNbTaTi)N HEAN coatings to address a critical need for materials capable of enduring extreme mechanical and tribological demands by examining the impact of aluminum content on their structural and mechanical properties, providing insights for optimizing coatings in harsh conditions through a self-assembled nanolayer structure with enhanced resilience and performance. The coatings were deposited via a cathodic arc by employing an AlCrNbTaTi alloy target composed of aluminum (20, 50, 60, 70%) and equal molar ratios of Cr, Nb, Ta, and Ti. The coatings were characterized through grazing incidence X-ray diffraction, SEM, HR-TEM, a nano-indentation test, and a friction and wear test. The results indicated that with increasing Al content, the structure of (AlCrNbTaTi)N coatings shifted from FCC to an amorphous state, leading to a reduction in the hardness and elastic modulus, accompanied by an increase in the wear rate and friction coefficient. The (AlCrNbTaTi)N coating, with an equal atomic ratio of metallic elements, showed potential as a hard tool coating. It demonstrated outstanding mechanical and tribological properties, with a 34.5 GPa hardness, 369 GPa modulus, 0.35 friction coefficient, and 8.2 × 10⁻¹⁹ m²·N⁻¹ wear rate. The findings highlight the potential of (AlCrNbTaTi)N coatings to extend tool life and improve operational efficiency, helping advance materials engineering for industrial applications. Full article

The highly selective and sensitive determination of pesticide residues in food is critical for human health protection. Herein, the specific selectivity of molecularly imprinted polymers (MIPs) was proposed to construct an electrochemical sensor for the detection of carbendazim (CBD), one of the famous broad-spectrum fungicides, by combining with the synergistic effect of bioelectrocatalysis and nanocomposites. Gold nanoparticle-reduced graphene oxide (AuNP-rGO) composites were electrodeposited on a polished glassy carbon electrode (GCE). Then the MIP films were electropolymerized on the surface of the nanolayer using CBD as the template molecule and o-phenylenediamine (OPD) as the monomer. The detection sensitivity of CBD on the heterogeneous structure films was greatly amplified by AuNP-rGO composites and the bioelectrochemical oxidation of glucose, which was catalyzed by glucose oxidase (GOD) with the help of mediator in the underlying solution. The developed sensor showed high selectivity, good reproducibility, and excellent stability towards CBD with the linear range from 2.0 × 10⁻⁹ to 7.0 × 10⁻⁵ M, and the limit of detection (LOD) of 0.68 nM (S/N = 3). The expected system would provide a new idea for the development of simple and sensitive molecularly imprinted electrochemical sensors (MIESs). Full article

This study, based on our previous research, aims to quantitatively determine the enhanced protection of austenitic stainless steels against pitting corrosion in NaCl solution by self-assembled molecular (SAM) layers, in their original form and after γ-irradiation. This study focuses on four stainless steels of varying compositions, covered by self-assembled undecenyl phosphonic acid layers. The metal dissolution in corrosion experiments was measured by a special, highly sensitive analytical technique using the inductively coupled plasma–optical emission spectrometry (ICP-OES). The comparison of the dissolved metal ion concentrations measured in the presence of different metals with and without nanocoatings allowed the evaluation of the anticorrosion effectiveness of nanofilms as well as the importance of the alloying elements. The ICP-OES results demonstrated that the quality of layers have a significant impact on anticorrosion efficacy. The γ-irradiated self-assembled layers were the most effective in controlling the dissolution of stainless steels. The mechanisms of the inhibition in the presence of these nanolayers were elucidated by infrared spectroscopy. First of all, it revealed the differences in the adsorption of the undecenyl phosphonic acid self-assembled layer, both with and without γ-irradiation. The other important observation that confirmed the increased anticorrosion efficiency after γ-irradiation proved the formation of a more compact, polymer-like layer over the metal surface. The increased anticorrosion efficacy, defined as the enhancement in Pitting Resistance Equivalent Numbers (PRENs) in the presence of self-assembled layers (either pre- or post-γ-irradiation), can be documented. Full article

To obtain materials or metamaterials with desired elastic properties that are tailor-made for a particular application, it is necessary to design a new material or composite (which may be cumbersome) or to modify the structure of existing materials in order to change their properties in the desired direction. The latter approach, although also not easy, seems favourable with respect to parameters like costs and time-to-market. Despite the fact that elastic properties are one of the oldest studied physical parameters of matter, our understanding of the processes at the microstructural level, that are behind these properties, is still far from being complete. The present work, with the help of Monte Carlo computer simulations, aims to broaden this knowledge. The previously studied model crystal of hard spheres, containing a combined nanolayer and nanochannel inclusions, is revisited. This periodic model crystal has been extended to include a degree of disorder in the form of degenerate crystalline phase by introducing a degenerate crystalline phase within its structure. The inclusion has been transformed (without changes to its shape, size, or orientation) by randomly connecting the neighbouring spheres into di-atomic molecules (dumbbells). The impact of this modification on elastic properties has been investigated with the help of the Parrinello–Rahman approach in the isothermal–isobaric ensemble ($NpT$). It has been shown, that the presence of the degenerate crystalline phase of hard dumbbells in the system leads to a significant decrease in the Poisson’s ratio in $\left[110\right]$-direction ($\nu =-0.235$) and an overall enhancement of the auxetic properties. Full article

The fracture strength was compared in a scratch test of coatings based on the ZrN system with the introduction of Ti, Nb and Hf, which were deposited on a titanium alloy substrate. The coatings were deposited using Controlled Accelerated Arc (CAA-PVD) technology. In coatings that simultaneously include Zr and Ti, a nanolayer structure is formed, while in coatings without Ti, the formation of a monolithic single-layer structure is observed. The comparison was carried out according to two parameters: adhesion strength to the substrate and overall coating strength. The (Zr,Hf)N coating showed better resistance to destruction, but had worse adhesion to the substrate. As a result, although the coating is retained directly in the scribing groove, a large area of delamination and destruction is formed around the groove. The (Ti,Zr,Nb)N coating, with its somewhat lower strength, has a high adhesion to the substrate; no noticeable delamination is observed along the groove boundary. In this paper, not only is the fracture resistance of various coatings deposited on a titanium alloy substrate compared, but the nature of this fracture is also investigated depending on the composition of the coatings. Full article

To endow an implant surface with enhanced properties to ensure an appropriate seal with the host tissue for inflammation/infection resistance, next-generation bone implant collagen–polyphenol nanolayers were built on conventional titanium surfaces through a multilayer approach. X-ray Photoelectron Spectroscopy (XPS) analysis was performed to investigate the chemical arrangement of molecules within the surface layer and to provide an estimate of their thickness. A short-term (2 and 4 weeks) in vivo test of bone implants in a healthy rabbit model was performed to check possible side effects of the soft surface layer on early phases of osteointegration, leading to secondary stability. Results show the building up of the different nanolayers on top of titanium, resulting in a final composite collagen–polyphenol surface and a layer thickness of about 10 nm. In vivo tests performed on machined and state-of-the-art microrough titanium implants do not show significant differences between coated and uncoated samples, as the surface microroughness remains the main driver of bone-to-implant contact. These results confirm that the surface nanolayer does not interfere with the onset and progression of implant osteointegration and prompt the green light for specific investigations of the potential merits of this bioactive coating as an enhancer of the device/tissue seal. Full article

Renewable, green, and safe natural biopolymer-derived materials are highly desired for the purification of pollutants, but significantly improving their performance without the introduction of additional harmful chemicals remains a huge challenge. Based on the concept of “structure optimization design”, environment-friendly composite beads (named SA/PASP/RE) with excellent adsorption performance and recyclability were rationally constructed through a green ionic crosslinking route, using the completely green biopolymer sodium alginate (SA), sodium salt of polyaspartic acid (PASP), and the natural nanoclay rectorite (RE) as starting materials. The nano-layered RE was embedded in the polymer matrix to prevent the polymer chain from becoming over-entangled so that more adsorption sites inside the polymer network were exposed, which effectively improved the mass transfer efficiency of the adsorbent and the removal rate of contaminants. The composite beads embedded with 0.6% RE showed high adsorption capacities of 211.78, 197.13, and 195.69 mg/g for Pb(II) and 643.00, 577.80, and 567.10 mg/g for methylene blue (MB) in Yellow River water, Yangtze River water, and tap water, respectively. And the beads embedded with 43% RE could efficiently adsorb Pb(II) and MB with high capacities of 187.78 mg/g and 586.46 mg/g, respectively. This study provides a new route to design and develop a green, cost-effective, and efficient adsorbent for the decontamination of wastewater. Full article

Polyvinylidene fluoride (PVDF) membranes were coated with TiO₂ and TiO₂-Ag to enhance their efficiency for oil-in-water emulsion separation. The photocatalytic activities of the two modified membranes and their filtration performances were compared in detail. The significantly enhanced photocatalytic activity of the TiO₂-Ag composite was proved using a methyl orange (MO) solution (c = 10⁻⁵ M) and a crude oil emulsion (c = 50 mg·L⁻¹). The TiO₂-Ag-coated membrane reduced the MO concentration by 87%, whereas the TiO₂-modified membrane reached only a 46% decomposition. The photocatalytic reduction in the chemical oxygen demand of the emulsion was also ~50% higher using the TiO₂-Ag-coated membrane compared to that of the TiO₂-coated membrane. The photoluminescence measurements demonstrated a reduced electron/hole recombination, achieved by the Ag nanoparticle addition (TiO₂-Ag), which also explained the enhanced photocatalytic activity. A significant improvement in the oil separation performance with the TiO₂-Ag-coated membrane was also demonstrated: a substantial increase in the flux and flux recovery ratio (up to 92.4%) was achieved, together with a notable reduction in the flux decay ratio and the irreversible filtration resistance. Furthermore, the purification efficiency was also enhanced (achieving 98.5% and 99.9% COD and turbidity reductions, respectively). Contact angle, zeta potential, scanning electron microscopy (SEM), and atomic force microscopy (AFM) measurements were carried out to explain the results. SEM and AFM images revealed that on the TiO₂-Ag-coated membrane, a less aggregated, more continuous, homogeneous, and smoother nanolayer was formed due to the ~50% more negative zeta potential of the TiO₂-Ag nanocomposite compared to that of the TiO₂. In summary, via Ag addition, a sufficiently hydrophilic, beneficially negatively charged, and homogeneous TiO₂-Ag-coated PVDF membrane surface was achieved, which resulted in the presented advantageous filtration properties beyond the photocatalytic activity enhancement. Full article

In the present study, (Cr,Al)N nanolayer coatings with different Al/Cr atomic ratios were deposited by magnetron sputtering on different substrate materials (H11 and D2 tool steel, alumina). To prepare the (Cr,Al)N coatings with different Al/Cr atomic ratios in the same batch, we used two targets composed of two triangle-like segments together with two standard Al and Cr targets. This approach enabled us to study the evolution of structural and mechanical properties in dependence on composition. The elemental composition of the coatings was determined by energy-dispersive X-ray analysis (EDS). The phase composition of the (Cr,Al)N coatings was determined utilizing X-ray diffraction (XRD), while scanning electron microscopy (SEM) was employed to assess their morphology and microstructure. The coating surface topography was analyzed by atomic force microscopy (AFM). In order to evaluate the effect of the Al/Cr atomic ratio on the oxidation behavior, the (Cr,Al)N coatings were oxidized in ambient atmospheres at temperatures between 700 and 850 °C and subsequently analyzed by means of cross-sectional SEM and transmission electron microscopy (TEM). The oxidation rate, determined by weight gain over time, was utilized to quantify the oxidation process. The oxidation tests showed that the Al-rich (Cr,Al)N nanolayer coatings exhibit a considerably better oxidation resistance than the Cr-rich ones. We found that the oxide scale formed on the Al-rich coating is composed of double layers: a Cr-oxide top layer and an inner (Cr,Al) mixed oxide layer. In contrast, the oxide scale of the Cr-rich coating mainly consists of the Cr₂O₃ layer. In particular, we focused on the oxidation process occurring at the locations of growth defects. We noticed that the first oxidation products on the coated substrate occurred at a temperature that was much lower than the temperature for the (Cr,Al)N coating oxidation initiation. These products (iron oxides) formed only at the sites of those growth defects that extended through the entire coating thickness. Full article

Cellulose has been a go-to material for its dielectric properties from the onset of capacitor development. The demand for an energy storage solution continues to grow, but the supply remains limited and relies too often on fossil and mined materials. This work proposes a fully sustainable and green method with which to produce dielectric thin films made of renewable and degradable materials. Cellulose nanocrystals (CNC) made an excellent matrix for the dispersion of proteins and the fabrication of robust transparent thin films with enhanced dielectric permittivity. A range of proteins sources, additives and concentrations allowed for us to control the dielectric permittivity from ε_r = 4 to 50. The proteins screened came from animal and plant sources. The films were formed from drying a water suspension of the CNC and proteins through evaporation-induced self-assembly. This yielded nano-layered structures with very high specific surface areas, ideal for energy storage devices. The resulting films were characterized with respect to the electrical, mechanical, piezoelectric, and optical properties to be compared. Electrically conductive (σ = 1.53 × 10³ S/m) CNC films were prepared with carbon nanotubes (CNT). The fabricated films were used to make flexible, sustainable, and degradable capacitors by layering protein-based films between CNC–CNT composite films. Full article

This study is focused on polytetrafluoroethylene (PTFE) porous nanotextile and its modification with thin, silver sputtered nanolayers, combined with a subsequent modification with an excimer laser. The KrF excimer laser was set to single-shot pulse mode. Subsequently, the physico chemical properties, morphology, surface chemistry, and wettability were determined. Minor effects of the excimer laser on the pristine PTFE substrate were described, but significant changes were observed after the application of the excimer laser to the polytetrafluoroethylene with sputtered silver, where the formation of a silver nanoparticles/PTFE/Ag composite was described, with a wettability similar to that of a superhydrophobic surface. Both scanning electron microscopy and atomic force microscopy revealed the formation of superposed globular structures on the polytetrafluoroethylene lamellar primary structure, which was also confirmed using energy dispersive spectroscopy. The combined changes in the surface morphology, chemistry, and thus wettability induced a significant change in the PTFE’s antibacterial properties. Samples coated with silver and further treated with the excimer laser 150 mJ/cm² inhibited 100% of the bacterial strain E. coli. The motivation of this study was to find a material with flexible and elastic properties and a hydrophobic character, with antibacterial properties that could be enhanced with silver nanoparticles, but hydrophobic properties that would be maintained. These properties can be used in different types of applications, mainly in tissue engineering and the medicinal industry, where water-repellent materials may play important roles. This synergy was achieved via the technique we proposed, and even when the Ag nanostructures were prepared, the high hydrophobicity of the system Ag-polytetrafluorethylene was maintained. Full article

As the mechanical properties of resin-based dental composite materials are highly relevant in clinical practice, diverse strategies for their potential enhancement have been proposed in the extant literature, aiming to facilitate their reliable use in dental medicine. In this context, the focus is primarily given to the mechanical properties with the greatest influence on clinical success, i.e., the longevity of the filling in the patient’s mouth and its ability to withstand very strong masticatory forces. Guided by these objectives, the goal of the present study was to ascertain whether the reinforcement of dental composite resins with electrospun polyamide (PA) nanofibers would improve the mechanical strength of dental restoration materials. For this purpose, light-cure dental composite resins were interspersed with one and two layers comprising PA nanofibers in order to investigate the influence of such reinforcement on the mechanical properties of the resulting hybrid resins. One set of the obtained samples was investigated as prepared, while another set was immersed in artificial saliva for 14 days and was subsequently subjected to the same set of analyses, namely Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). Findings yielded by the FTIR analysis confirmed the structure of the produced dental composite resin material. They also provided evidence that, while the presence of PA nanofibers did not influence the curing process, it strengthened the dental composite resin. Moreover, flexural strength measurements revealed that the inclusion of a 16 μm-thick PA nanolayer enabled the dental composite resin to withstand a load of 3.2 MPa. These findings were supported by the SEM results, which further indicated that immersing the resin in saline solution resulted in a more compact composite material structure. Finally, DSC results indicated that as-prepared as well as saline-treated reinforced samples had a lower glass transition temperature (Tg) compared to pure resin. Specifically, while pure resin had a Tg of 61.6 °C, each additional PA nanolayer decreased the Tg by about 2 °C, while the further reduction was obtained when samples were immersed in saline for 14 days. These results show that electrospinning is a facile method for producing different nanofibers that can be incorporated into resin-based dental composite materials to modify their mechanical properties. Moreover, while their inclusion strengthens the resin-based dental composite materials, it does not affect the course and outcome of the polymerization reaction, which is an important factor for their use in clinical practice. Full article