Search Results (15)

Recent observations of superconductivity in low-dimensional systems composed of twisted, untwisted, or rhombohedral graphene have attracted significant attention. One-dimensional moiré superlattices and flat bands have interestingly been identified in collapsed chiral carbon nanotubes (CNTs), opening up new avenues for the tunability of the electronic properties in these systems. The nucleation of hexagonal moiré superlattices and other types of stacking faults has also been demonstrated in partially collapsed and uncollapsed carbon nano-onions (CNOs). Here, we report a novel investigation on the dynamics of stacking fault nucleation within the multilayered lattices of micrometer-scale vertically oriented films of multiwall CNTs (MWCNTs), resulting from the pyrolysis of molecular precursors consisting of ferrocene or dimethyl ferrocene, at low vapor flow rates of ~5–20 mL/min. Interestingly, local nucleation of moiré-like superlattices (as stacking faults) was found when employing dimethyl ferrocene as the pyrolysis precursor. The morphological and structural properties of these systems were investigated with the aid of scanning and transmission electron microscopies, namely SEM, TEM, and HRTEM, as well as X-ray diffraction (XRD) and Raman point/mapping spectroscopy. Deconvolution analyses of the Raman spectra also demonstrated a local surface oxidation, possibly occurring on defect-rich interfaces, frequently identified within or in proximity of bamboo-like graphitic caps. By employing high-temperature Raman spectroscopy, we demonstrate a post-growth re-graphitization, which may also be visualized as an alternative way of depleting the oxygen content within the MWCNTs’ interfaces through recrystallization. Full article

Calcium phosphate (CaP)-based materials are largely explored in orthopedics, to increase osseointegration of the prostheses and specifically in spine surgery, to permit better fusion. To address these aims, nanostructured biogenic apatite coatings are emerging, since they better mimic the characteristics of the host tissue, thus potentially being better candidates compared to their synthetic counterpart. Here, we compare hydroxyapatite (HA) nanostructured coatings, obtained by ionized jet deposition, starting from synthetic and natural sources. The starting materials and the corresponding films are characterized and compared from a compositional and morphological point of view, then their stability is studied after post-treatment annealing. Although all the films are formed by globular aggregates and show morphological features at different scales (from nano to micro), significant differences are found in composition between the synthetic and naturally derived HA in terms of magnesium and sodium content, carbonate substitution and Ca/P ratio, while differences between the coatings obtained by the different natural HA sources are minor. In addition, the shape of the aggregates is also target-dependent. All coatings have a good stability after over 14 days of immersion in medium, with natural apatite coatings showing a better behavior, as no cracking and detachments are observed during immersion. Based on these results, both synthetic and naturally derived apatitic materials appear promising for applications in spine surgery, with coatings from natural sources possessing physiochemical properties more similar to the mineral phase of the human bone tissue. Full article

Thin copper and carbon coatings of electrodes of lithium-ion batteries (LIBs) have the potential to improve LIB operation by preserving electrode integrity during cycling, by developing a proper solid-electrolyte interphase (SEI) layer (e.g., by increasing the de-solvation rate), and by enhancing electric conductivity. In the structures, the thin coatings, e.g., copper thin films, must be permeable to Li⁺ ions in order to facilitate Li⁺ uptake and Li⁺ release in the electrochemically active material of coated electrodes beneath. The influences of copper and carbon thin coatings on LIB-electrode performance were investigated in this work by electrochemically cycling a [C(16 nm)/Cu(17 nm)] × 10 multilayer (ML) up to lithium plating. The C/Cu ML was deposited onto a copper current collector using ion beam sputtering. The rate capability and the long-time cycling were compared to the corresponding ones for the cycling of the bare copper substrate and 16 nm and 230 nm carbon single films (without Cu coating). The bare copper electrode does not store Li⁺ ions, which is as expected because copper is electrochemically inactive with respect to lithiation. The Li⁺ uptake and Li⁺ release in thin carbon layers capped by thin copper layers within the C/Cu ML is compared to that of uncapped carbon single thin films. All electrodes exhibited a good rate capability and long-term cycling stability. Under fast cycling, the amount of reversible Li⁺ uptake and Li⁺ release was largest for the case of the C/Cu ML, which pointed to the beneficial influence of the capping Cu layers. The higher Li kinetics in the C/Cu ML was confirmed using impedance analysis. The C/Cu ML behaves as a supercapacitor possessing a differential charge plot nearly independent of potential. At lower currents, the specific capacity of the C/Cu ML is only 20% of that of the thin carbon single films, with that of the latter being the same as that of graphite. On the one hand, this evidences a disadvantageous influence of the thin Cu layers, which block the Li⁺ permeation, that is necessary to reach deeper carbon layers of the C/Cu ML electrode. On the other hand, the differential capacity plots reveal that the carbon material in the interior of the C/Cu ML is electrochemically cycled. Microscopy, Raman scattering, depth profiling with X-ray reflectometry (XRR), and secondary ion mass spectrometry (SIMS) were applied to get deep insights and a comprehensive examination of the contradiction. The XRR examination revealed a non-altered ML after more than 542 electrochemical cycles, after the washing procedure, and even after 15 months of air exposure. This observation suggests that the copper layers block contamination as well as the Li insertion. The analyses of microscopy, Raman, and SIMS affirm the ML intactness but also reveal the participation of some portions of the interior of the C/Cu ML in electrochemical cycling. The low capacity of carbon in the C/Cu ML may stem from the mechanical stress inside the C/Cu ML, which reduces the Li⁺ uptake and Li⁺ release. Full article

In this work, colloidal perovskite nanocrystals (PNCs) are used to sensitize the photoconductivity of nanocrystalline ZnO films in the visible range. Nanocrystalline ZnO with a crystallite size of 12–16 nm was synthesized by precipitation of a zinc basic carbonate from an aqueous solution, followed by annealing at 300 °C. Perovskite oleic acid- and oleylamine-capped CsPbBr₃, CsPb(Cl/Br)₃ and CsPb(Br/I)₃ PNCs with a size of 6–13 nm were synthesized by a hot injection method at 170 °C in 1-octadecene. Photoconductive nanocomposites were prepared by applying a hexane sol of PNCs to a thick (100 μm) polycrystalline conductive ZnO layer. The spectral dependence of the photoconductivity, the dependence of the photoconductivity on irradiation, and the relaxation of the photoconductivity of the obtained nanocomposites have been studied. Sensitization of ZnO by CsPbBr₃ and CsPb(Cl/Br)₃ PNCs leads to enhanced photoconductivity in the visible range, the maximum of which is observed at 460 and 500 nm, respectively; close to the absorption maximum of PNCs. Nanocomposites ZnO/CsPb(Br/I)₃ turned out to be practically not photosensitive when irradiated with light in the visible range. The data obtained are discussed in terms of the position of the energy levels of ZnO and PNCs and the probable PNCs photodegradation. The structure, morphology, composition, and optical properties of the synthesized nanocrystals have also been studied by XRD, TEM, and XPS. The results can be applied to the creation of artificial neuromorphic systems in the visible optical range. Full article

The aim of the study was to analyze the chemical–physical properties and bioactivity (apatite-forming ability) of three recently introduced premixed bioceramic root canal sealers containing varied amounts of different calcium silicates (CaSi): a dicalcium and tricalcium silicate (1–10% and 20–30%)-containing sealer with zirconium dioxide and tricalcium aluminate (CERASEAL); a tricalcium silicate (5–15%)-containing sealer with zirconium dioxide, dimethyl sulfoxide and lithium carbonate (AH PLUS BIOCERAMIC) and a dicalcium and tricalcium silicate (10% and 25%)-containing sealer with calcium aluminate, tricalcium aluminate and tantalite (NEOSEALER FLO). An epoxy resin-based sealer (AH PLUS) was used as control. The initial and final setting times, radiopacity, flowability, film thickness, open pore volume, water absorption, solubility, calcium release and alkalizing activity were tested. The nucleation of calcium phosphates and/or apatite after 28 days aging in Hanks balanced salt solution (HBSS) was evaluated by ESEM-EDX, vibrational IR and micro-Raman spectroscopy. The analyses showed for NeoSealer Flo and AH Plus the longest final setting times (1344 ± 60 and 1300 ± 60 min, respectively), while shorter times for AH Plus Bioceramic and Ceraseal (660 ± 60 and 720 ± 60 min, respectively). Radiopacity, flowability and film thickness complied with ISO 6876/12 for all tested materials. A significantly higher open pore volume was observed for NeoSealer Flo, AH Plus Bioceramic and Ceraseal when compared to AH Plus (p < 0.05), significantly higher values were observed for NeoSealer Flo and AH Plus Bioceramic (p < 0.05). Ceraseal and AH Plus revealed the lowest solubility. All CaSi-containing sealers released calcium and alkalized the soaking water. After 28 days immersion in HBSS, ESEM-EDX analyses revealed the formation of a mineral layer that covered the surface of all bioceramic sealers, with a lower detection of radiopacifiers (Zirconium for Ceraseal and AH Plus Bioceramic, Tantalum for NeoSealer Flo) and an increase in calcium, phosphorous and carbon. The calcium phosphate (CaP) layer was more evident on NeoSealer Flo and AH Plus Bioceramic. IR and micro-Raman revealed the formation of calcium carbonate on the surface of all set materials. A thin layer of a CaP phase was detected only on AH Plus Bioceramic and NeoSealer Flo. Ceraseal did not show CaP deposit despite its highest calcium release among all the tested CaSi-containing sealers. In conclusion, CaSi-containing sealers met the required chemical and physical standards and released biologically relevant ions. Slight/limited apatite nucleation was observed in relation to the high carbonation processes. Full article

A new electrochemical DNA biosensor based on mercaptopropionic acid (MPA)-capped ZnS quantum dots (MPA-ZnS QDs) immobilization matrix for covalent binding with 20-base aminated oligonucleotide has been successfully developed. Prior to the modification, screen-printed carbon paste electrode (SPE) was self-assembled with multilayer gold nanoparticles (AuNPs) and cysteamine (Cys). The inclusion of MPA-ZnS QDs semiconducting material in modified electrodes has enhanced the electron transfer between the SPE transducer and DNA leading to improved bioanalytical assay of target biomolecules. Electrochemical studies performed by cyclic voltammetry (CV) and differential pulsed voltammetry (DPV) demonstrated that the MPA-ZnS QDs modified AuNPs electrode was able to produce a lower charge transfer resistance response and hence higher electrical current response. Under optimal conditions, the immobilized synthetic DNA probe exhibited high selectivity towards synthetic target DNA. Based on the DPV response of the reduction of anthraquinone monosulphonic acid (AQMS) redox probe, the MPA-ZnS QDs-based electrochemical DNA biosensor responded to target DNA concentration from 1 × 10⁻⁹ μM to 1 × 10⁻³ μM with a sensitivity 1.2884 ± 0.12 µA, linear correlation coefficient (R²) of 0.9848 and limit of detection (LOD) of 1 × 10⁻¹¹ μM target DNA. The DNA biosensor exhibited satisfactory reproducibility with an average relative standard deviation (RSD) of 7.4%. The proposed electrochemical transducer substrate has been employed to immobilize the aminated Arowana fish (Scleropages formosus) DNA probe. The DNA biosensor showed linearity to target DNA from 1 × 10⁻¹¹ to 1 × 10⁻⁶ µM (R² = 0.9785) with sensitivity 1.1251 ± 0.243 µA and LOD of 1 × 10⁻¹¹ µM. The biosensor has been successfully used to determine the gender of Arowana fish without incorporating toxic raw materials previously employed in the hazardous processing conditions of polypyrrole chemical conducting polymer, whereby the cleaning step becomes difficult with thicker films due to high levels of toxic residues from the decrease in polymerization efficacy as films grew. Full article

Carbon-based hole transport material (HTM)-free perovskite solar cells have exhibited a promising commercialization prospect, attributed to their outstanding stability and low manufacturing cost. However, the serious charge recombination at the interface of the carbon counter electrode and titanium dioxide (TiO₂) suppresses the improvement in the carbon-based perovskite solar cells’ performance. Here, we propose a modified sequential deposition process in air, which introduces a mixed solvent to improve the morphology of lead iodide (PbI₂) film. Combined with ethanol treatment, the preferred crystallization orientation of the PbI₂ film is generated. This new deposition strategy can prepare a thick and compact methylammonium lead halide (MAPbI₃) film under high-humidity conditions, which acts as a natural active layer that separates the carbon counter electrode and TiO₂. Meanwhile, the modified sequential deposition method provides a simple way to facilitate the conversion of the ultrathick PbI₂ capping layer to MAPbI₃, as the light absorption layer. By adjusting the thickness of the MAPbI₃ capping layer, we achieved a power conversation efficiency (PCE) of 12.5% for the carbon-based perovskite solar cells. Full article

A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionalization of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230 °C) without any catalyst between the sp² network of carbon nanotubes, which acted as dienophile, and the diphenylethylene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt % of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm⁻²). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM). Full article

Surface bubbles are present in many industrial processes and in nature, as well as in carbonated beverages. They have motivated many theoretical, numerical and experimental works. This paper presents the current knowledge on the physics of surface bubbles lifetime and shows the diversity of mechanisms at play that depend on the properties of the bath, the interfaces and the ambient air. In particular, we explore the role of drainage and evaporation on film thinning. We highlight the existence of two different scenarios depending on whether the cap film ruptures at large or small thickness compared to the thickness at which van der Waals interaction come in to play. Full article

This work attempts to understand the behaviour of Ge-induced cytotoxicity of germanium-doped hydrogen-free diamond-like carbon (DLC) films recently thoroughly studied and published by Jelinek et al. At a low doping level, the films showed no cytotoxicity, while at a higher doping level, the films were found to exhibit medium to high cytotoxicity. We demonstrate, using surface-sensitive methods—two-angle X-ray-induced core-level photoelectron spectroscopy (ARXPS) and Low Energy Ion Scattering (LEIS) spectroscopy, that at a low doping level, the layers are capped by a carbon film which impedes the contact of Ge species with tissue. For higher Ge content in the DLC films, oxidized Ge species are located at the top surface of the layers, provoking cytotoxicity. The present results indicate no threshold for Ge concentration in cell culture substrate to avoid a severe toxic reaction. Full article

Bone grafts and bone-based materials are widely used in orthopedic surgery. However, the selection of the bone type to be used is more focused on the biological properties of bone sources than physico-chemical ones. Moreover, although biogenic sources are increasingly used for deposition of biomimetic nanostructured coatings, the influence of specific precursors used on coating’s morphology and composition has not yet been explored. Therefore, in order to fill this gap, we provided a detailed characterization of the properties of the mineral phase of the most used bone sources for allografts, xenografts and coating deposition protocols, not currently available. To this aim, several bone apatite precursors are compared in terms of composition and morphology. Significant differences are assessed for the magnesium content between female and male human donors, and in terms of Ca/P ratio, magnesium content and carbonate substitution between human bone and different animal bone sources. Prospectively, based on these data, bone from different sources can be used to obtain bone grafts having slightly different properties, depending on the clinical need. Likewise, the suitability of coating-based biomimetic films for specific clinical musculoskeletal application may depend on the type of apatite precursor used, being differently able to tune surface morphology and nanostructuration, as shown in the proof of concepts of thin film manufacturing here presented. Full article

Porous silicon (PSi) is a versatile matrix with tailorable surface reactivity, which allows the processing of a range of multifunctional films and particles. The biomedical applications of PSi often require a surface capping with organic functionalities. This work shows that visible light can be used to catalyze the assembly of organosilanes on the PSi, as demonstrated with two organosilanes: aminopropyl-triethoxy-silane and perfluorodecyl-triethoxy-silane. We studied the process related to PSi films (PSiFs), which were characterized by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF-SIMS) and field emission scanning electron microscopy (FESEM) before and after a plasma patterning process. The analyses confirmed the surface oxidation and the anchorage of the organosilane backbone. We further highlighted the surface analytical potential of ¹³C, ¹⁹F and ²⁹Si solid-state NMR (SS-NMR) as compared to Fourier transformed infrared spectroscopy (FTIR) in the characterization of functionalized PSi particles (PSiPs). The reduced invasiveness of the organosilanization regarding the PSiPs morphology was confirmed using transmission electron microscopy (TEM) and FESEM. Relevantly, the results obtained on PSiPs complemented those obtained on PSiFs. SS-NMR suggests a number of siloxane bonds between the organosilane and the PSiPs, which does not reach levels of maximum heterogeneous condensation, while ToF-SIMS suggested a certain degree of organosilane polymerization. Additionally, differences among the carbons in the organic (non-hydrolyzable) functionalizing groups are identified, especially in the case of the perfluorodecyl group. The spectroscopic characterization was used to propose a mechanism for the visible light activation of the organosilane assembly, which is based on the initial photoactivated oxidation of the PSi matrix. Full article

Polyurethane acrylate (PUA) from vegetable oil has been synthesized and prepared for solid polymer electrolyte. Polyol has been end-capped with Toluene 2,4-Diisocyanate (TDI) followed by hydroxylethylmethylacrylate (HEMA) in a urethanation process to produce PUA. The mixtures were cured to make thin polymeric films under UV radiation to produce excellent cured films which exhibit good thermal stability and obtain high ionic conductivity value. 3 to 15 wt. % of ethylene carbonate (EC) mixed with 25 wt. % LiClO₄ was added to PUA to obtain PUA electrolyte systems. PUA modified with plasticizer EC 9 wt. % achieved the highest conductivity of 7.86 × 10⁻⁴ S/cm, and relatively improved the linear sweep voltammetry, transference number and dielectric properties. Fourier Transform Infrared Spectroscopy (FTIR) and dielectric analysis were presented. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), followed by X-ray Diffraction (XRD) and morphology have been studied. The addition of plasticizer to the polyurethane acrylate shows significant improvement in terms of the conductivity and performance of the polymer electrolyte. Full article

Molecular dynamics (MD) simulation has been employed to study the wetting transitions of liquid gallium droplet on the graphene surfaces, which are decorated with three types of carbon nanopillars, and to explore the effect of the surface roughness and morphology on the wettability of liquid Ga. The simulation results showed that, at the beginning, the Ga film looks like an upside-down dish on the rough surface, different from that on the smooth graphene surface, and its size is crucial to the final state of liquid. Ga droplets exhibit a Cassie–Baxter (CB) state, a Wenzel state, a Mixed Wetting state, and a dewetting state on the patterned surfaces by changing distribution and the morphology of nanopillars. Top morphology of nanopillars has a direct impact on the wetting transition of liquid Ga. There are three transition states for the two types of carbon nanotube (CNT) substrates and two for the carbon nanocone (CNC) one. Furthermore, we have found that the substrates show high or low adhesion to the Ga droplet with the variation of their roughness and top morphology. With the roughness decreasing, the adhesion energy of the substrate decreases. With the same roughness, the CNC/graphene surface has the lowest adhesion energy, followed by CNT/graphene and capped CNT/graphene surfaces. Our findings provide not only valid support to previous works but also reveal new theories on the wetting model of the metal droplet on the rough substrates. Full article

The influence of heating conditions, heating temperature, and heating time on the formation of a thin carbonate-containing hydroxyapatite (CA) film onto partially stabilized zirconia using a molecular precursor method was evaluated. The molecular precursor solution was prepared from a mixture of calcium-ethylenediaminetetraacetic acid complex and phosphate compounds at Ca/P ratio of 1.67. After the application of molecular precursor solution onto zirconia, four different heating conditions—namely, 600 °C-2 h, 800 °C-2 h, 1000 °C-2 h, and 600 °C-4 h—were applied. No distinct difference of surface appearance of CA coating was observed between 600 and 800 °C-2 h. Fusion of apatite crystals was observed at 1000 °C-2 h. Surface roughness of CA film at 1000 °C-2 h was significantly higher than those under other heating conditions. Heating at 800 °C produced a significantly more hydrophilic surface and higher degree of crystallization. No significant differences were recognized in the critical load at the first crack in the coating among the four samples by scratch tests. After 30 days’ immersion in phosphate buffered saline, the four different CA coating films were still present. Simulated body fluid immersion experiments were performed as in vitro biocompatibility tests. After 48 h immersion, the CA film at 800 °C-2 h showed a greater amount of spherical crystal precipitation. It was suggested that properties of CA coating on partially stabilized zirconia using a molecular precursor method were influenced by the heating temperature and time. Full article