Search Results (321)

This study examines the impact of varying the content of lanthanum oxide and lanthanum fluoride on the formation of glass-ceramics and their effect on the thermal stability of Na-aluminosilicate glasses, depending on the type and concentration of the raw material used. The aim of this study is to obtain a fluoride crystalline phase in the glassy matrix. Such a phase, due to its low phonon energy, increases the probability of radiative transitions (decay) of optically active lanthanide dopants, thereby enhancing luminescence. The scope of the work included the preparation of two glass series with varying amounts of La₂O₃ and LaF₃ to determine the glass-forming range and to identify the characteristic temperatures of the glasses using Differential Thermal Analysis. It was found that increasing the La₂O₃ content above 10 mol% in this glass leads to exceeding the target melting temperature (1400 °C) of the glass batch. In contrast, the introduction of 10 mol% LaF₃ prevents the formation of homogeneous glass. Based on these results, a controlled crystallization process was designed, and the resulting crystalline phases were identified using X-ray diffraction (XRD). In the base glass, two crystalline phases were identified: Na₂O·Al₂O₃·SiO₂ and Na₂SiO₃. For the La-oxide series, the crystallization of NaAlSiO₄ and La₂SiO₅ was confirmed. In the case of the La-fluoride series, the formation of LaF₃ was observed. It was found that by introducing an appropriate amount of LaF₃ (7.5 mol%) into the aluminosilicate network, it is possible to obtain a glass suitable for controlled crystallization, leading to the formation of a low-phonon LaF₃ phase. Full article

In recent years, apatite-based materials have garnered significant interest, particularly for applications in tissue engineering. Apatite is most commonly employed as a coating for metallic implants, as a component in composite materials, and as scaffolds for bone and dental tissue regeneration. Among its various forms, hydroxyapatite (HAP) is the most widely used, owing to its natural occurrence in human and animal hard tissues. An emerging area of research involves the use of fluoride-substituted apatite, particularly fluorapatite (FAP), which can serve as a direct fluoride source at the implant site, potentially offering several biological and therapeutic advantages. However, substituting HAP with FAP may lead to unforeseen changes in material behavior due to the differing physicochemical properties of these two calcium phosphate phases. This study investigates the effects of replacing hydroxyapatite with fluorapatite in ceramic–polymer composite materials incorporating β-1,3-glucan as a bioactive polymeric binder. The β-1,3-glucan polysaccharide was selected for its proven biocompatibility, biodegradability, and ability to form stable hydrogels that promote cellular interactions. Nitrogen adsorption analysis revealed that FAP/glucan composites had a significantly lower specific surface area (0.5 m²/g) and total pore volume (0.002 cm³/g) compared to HAP/glucan composites (14.15 m²/g and 0.03 cm³/g, respectively), indicating enhanced ceramic–polymer interactions in fluoride-containing systems. Optical profilometry measurements showed statistically significant differences in profile parameters (e.g., Rp: 134 μm for HAP/glucan vs. 352 μm for FAP/glucan), although average roughness (Ra) remained similar (34.1 vs. 27.6 μm, respectively). Microscopic evaluation showed that FAP/glucan composites had smaller particle sizes (1 μm) than their HAP counterparts (2 μm), despite larger primary crystal sizes in FAP, as confirmed by TEM. XRD analysis indicated structural differences between the apatites, with FAP exhibiting a reduced unit cell volume (524.6 ų) compared to HAP (528.2 ų), due to substitution of hydroxyl groups with fluoride ions. Spectroscopic analyses (FTIR, Raman, ³¹P NMR) confirmed chemical shifts associated with fluorine incorporation and revealed distinct ceramic–polymer interfacial behaviors, including an upfield shift of PO₄³⁻ bands (964 cm⁻¹ in FAP vs. 961 cm⁻¹ in HAP) and OH vibration shifts (3537 cm⁻¹ in FAP vs. 3573 cm⁻¹ in HAP). The glucan polymer showed different hydrogen bonding patterns when combined with FAP versus HAP, as evidenced by shifts in polymer-specific bands at 888 cm⁻¹ and 1157 cm⁻¹, demonstrating that fluoride substitution significantly influences ceramic–polymer interactions in these bioactive composite systems. Full article

Lithium fluoride (LiF) crystals are widely employed both as optical windows transparent in the ultraviolet spectral region and as efficient personal dosimeters, with their application scope recently expanding into lithium-ion technologies. Moreover, as an alkali halide crystal (AHC), LiF serves as a model system for studying and simulating radiation effects in solids. This work identifies radiation-induced defects formed in lithium fluoride upon irradiation with swift heavy ion beams (N, O, Kr, U) and intense pulsed electron beams, investigates their thermal stability, and performs computer modeling of annealing processes. The theoretical analysis of existing experimental kinetics for $F$-centers induced by electron and heavy ion irradiation reveals considerable differences in the activation energies for interstitial migration. A strong correlation between the activation energy $E_a$ and the pre-exponential factor $X$($E_a$) is observed; notably, $X$($E_a$) is no longer constant but closely matches the potential function Ea. Indeed, with increasing irradiation dose, both the migration energy $E_a$ and pre-exponential factor $X$ decrease simultaneously, leading to an effective increase in the defect diffusion rate. Full article

All-solid-state lithium batteries (ASSLBs) employing Li-rich layered oxide (LLO) cathodes are regarded as promising next-generation energy storage systems owing to their outstanding energy density and intrinsic safety. Polymer-in-salt solid electrolytes (PISSEs) offer advantages such as high room-temperature ionic conductivity, enhanced Li anode interfacial compatibility, and low processing costs; however, their practical deployment is hindered by poor oxidative stability especially under high-voltage conditions. In this study, we report the rational design of a bilayer electrolyte architecture featuring an in situ solidified LiClO₄-doped succinonitrile (LiClO₄–SN) plastic–crystal interlayer between a Li_1.2Mn_0.6Ni_0.2O₂ (LMNO) cathode and a poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based PISSE. This PISSE/SN–LiClO₄ configuration exhibits a wide electrochemical stability window up to 4.7 V vs. Li⁺/Li and delivers a high ionic conductivity of 5.68 × 10⁻⁴ S cm⁻¹ at 25 °C. The solidified LiClO₄-SN layer serves as an effective physical barrier, shielding the PVDF-HFP matrix from direct interfacial contact with LMNO and thereby suppressing its oxidative decomposition at elevated potentials. As a result, the bilayer polymer-based cells with the LMNO cathode demonstrate an initial discharge capacity of ∼206 mAh g⁻¹ at 0.05 C and exhibit good cycling stability with 85.7% capacity retention after 100 cycles at 0.5 C under a high cut-off voltage of 4.6 V. This work not only provides a promising strategy to enhance the compatibility of PVDF-HFP-based electrolytes with high-voltage cathodes through the facile in situ solidification of plastic interlayers but also promotes the application of LMNO cathode material in high-energy ASSLBs. Full article

It was demonstrated that various defects can be induced in halide crystals by irradiation with swift heavy ions. Here, we irradiated barium fluoride (BaF₂) single crystals with 220 MeV xenon ions at room temperature and performed stepwise thermal annealing up to the temperature of 825 K to study the kinetics of ion-induced defects at different temperatures. Optical spectroscopy was utilized for the measurement of the wide range of absorption spectra from NIR to VUV. A sharp decrease in the F₂ absorption peak was observed for the samples annealed in the temperature range of 400–450 K. This result can be explained by their recombination with anion interstitials during thermal decay of the complex hole centers. The mobile interstitials, those did not recombine with the F₂ centers, increase the absorption peaks in the 9–10 eV region, which can be associated with interstitial aggregates. Full article

Thickness-controlled, easily patterned upconversion (UC) nanofilms are essential for high-precision optoelectronic devices, but challenges such as imprecise thickness control and low fluorescence intensity hinder their application. High-performance lanthanide-doped sodium yttrium fluoride UC materials are typically available in powder form, making direct integration into advanced devices difficult. Although physical vapor deposition (PVD) enables precise film formation, it often produces poor crystalline structures and weak fluorescence. To overcome these limitations, integrating non-noble plasmonic Ni with surface plasmon resonance to enhance fluorescence intensity is a promising yet understudied strategy, likely due to Ni’s ultraviolet resonant wavelength and oxidation susceptibility. This study introduces an integrated Ni-UC nanofilm design, combining an ultrathin Ni layer with a NaYF₄:Tm, Yb UC layer via PVD, followed by post-annealing. Annealing at 500 °C transforms the UC layer into a hexagonal-phase crystal structure while protecting the Ni layer from oxidation. The unannealed UC nanofilm showed no fluorescence, whereas the annealed UC nanofilm displayed clear peaks at 476, 648, and 699 nm. Notably, the integrated Ni-UC nanofilm exhibited fluorescence intensities 5.29, 4.43, and 4.29 times higher at these wavelengths, respectively. Additionally, the integrated design exhibited high transparency and stability, highlighting its protective benefits. These results underscore the potential of the integrated Ni-UC nanofilm for advanced optoelectronics and sensing technologies, offering enhanced fluorescence, micro-processing compatibility, and robust performance in a cost-effective, non-noble plasmonic system. Full article

Commercial hydrophobic membranes encounter severe problems such as membrane wetting and membrane fouling under extreme conditions, which affect membrane separation performance. To enhance the anti-fouling abilities of hydrophobic membranes, a composite membrane with omniphobic characteristics was fabricated successfully in this paper. Titanium dioxide (TiO₂) nanoparticles were in-situ grown via the hydrothermal synthesis method, and then fluorosilane with low surface energy was grafted on polyvinylidene fluoride (PVDF) membranes. Subsequently, the morphologies, chemical compositions, wetting properties and structural parameters of composite membranes were characterized systematically. Various contaminants were added to the feed to investigate the anti-fouling and anti-wetting performances of the composite membrane in membrane distillation tests. The results showed that butyl titanate was first hydrolyzed to form titanium hydroxide (Ti(OH)₄) and then it was dehydrated to form TiO₂ in the hydrothermal environment. TiO₂ crystals continued to grow and formed rough morphology with micro-nano synergistic distribution, which is similar to a “sunflower” disk composed of cubic clusters and nanopillars. Meanwhile, fluorosilane successfully was grafted onto TiO₂. The contact angles of deionized water, 0.4 mM sodium dodecyl sulfate (SDS) solution and 0.2% v/v mineral oil emulsion on the composite membrane surface were 167.3°, 162.0° and 158.5°, respectively, endowing the composite membrane with excellent omniphobic features. In direct contact membrane distillation (DCMD) tests, the composite membrane exhibited a relatively stable membrane permeate flux, and the salt rejection rate almost reached 100%. The mixture, consisting of inorganic salts, organic substances, surfactants and oil emulsions, was used as feed. In contrast, the commercial PVDF membrane flux decreased drastically and even dropped to 0 due to the membrane fouling and wetting. As for the pristine PVDF membrane, the membrane surface was covered with pollutants and membrane pores were blocked. Therefore, it was proved that the omniphobic composite membrane possesses outstanding anti-fouling and anti-wetting performance. Full article

Crystal twinning, a common growth phenomenon, can substantially affect material performance in fields such as semiconductors, nonlinear optics, and drug development, yet its elimination during crystallization is challenging. This study presents a method for the controlled synthesis of ZSM-5 zeolite as either single crystals or twinned crystals using kaolin as the primary raw material. The method leverages the etching effect of ammonium fluoride (NH${⁠}_4$F) on the aluminosilicate structure derived from pre-treated kaolin. By adjusting the concentrations of NH${⁠}_4$F and the structure-directing agent tetrapropylammonium bromide (TPABr), pure ZSM-5 single crystals and twinned crystals were selectively synthesized. Conventionally, NH${⁠}_4$F is employed to introduce defects into zeolite structures. In contrast, this work demonstrates its utility in controlling crystal habit. The synthesis utilizes kaolin, an abundant and low-cost aluminosilicate mineral, to provide the entire aluminum source and a portion of the silicon source, offering an economical alternative to expensive precursors like aluminum isopropoxide. The resulting single and twinned crystals exhibited high crystallinity, demonstrating the viability of using natural minerals to produce high-quality zeolites. The physical and chemical properties of the kaolin-derived ZSM-5 were characterized and compared to those of ZSM-5 synthesized from conventional chemical reagents. A growth mechanism for the formation of single and twinned crystals is also proposed. Full article

Hydrothermal scheelite from three Romanian occurrences was analyzed in order to ascertain its structural, physical, vibrational, paragenetic, and crystal-chemical peculiarities as an important tool for characterizing the metallogenetic behavior and facilitating the ore-processing. All three occurrences, i.e., Ciclova and Oravița in Banat and Băița Bihor in the Bihor Mountains, are related to skarn deposits developed at the contact of Upper Cretaceous granodioritic bodies with Mesozoic calcareous deposits. Typical crystals show {001}, {111}, and {101} forms and are up to 15 mm across. The structure was successfully refined as tetragonal, space group I4₁/a, with R₁ = 0.0165 (Ciclova), 0.0204 (Oravița), and 0.0237 (Băița Bihor), respectively. The cell parameters refined for the same samples are a = 5.2459(10) Å and c = 11.3777(5) Å at Ciclova, a = 5.2380(2) Å and c = 11.3679(8) Å at Oravița, and a = 5.2409(2) Å and c = 11.3705(6) Å at Băița Bihor. The multiplicity of bands in both infrared absorption and Raman spectra is consistent with the S₄ punctual symmetry of the tungstate anion, agreeing with the structural data. In all cases, the analyzed scheelite is close to the CaWO₄ end-member. Cathodoluminescence peculiarities at the level of single crystals suggest that they crystallized in a slightly oxidizing to reducing environment from late hydrothermal solutions. Textural and paragenetic peculiarities suggest that scheelite from the three occurrences crystallized from epithermal, low-temperature, fluoride- and boron-bearing aqueous solutions. Full article

Background: Due to limitations of fluoride (F) treatment as a main caries preventive measure, it is important to consider the use of other dental caries preventive measures to reduce caries prevalence, especially in its early stages. Recently, new remineralizing agents appeared on the market, with their commercial availability in a variety of oral care products. Objectives: The purposes include providing a scoping review that represents caries remineralizing efficacies of only commercially available products and their existing adverse effects (if it is presented) and ensuring that only evidence-based approved products are included. Methods: The following databases were used in searching scientific literature on 28 October 2024: PubMed, PubMed Advanced Search, MeSH database, and PubMed Clinical Queries. The study selection criteria were as follows: for laboratory, in vitro, and/or in situ—remineralization of enamel-scanning electron microscopy, spectroscopy, microhardness test, light microscopy, profilometry, transverse microhardness microradiography, integrated mineral loss, light microscopy, photothermal radiometry; if it was a randomized controlled trial—CONSORT protocol, ICDAS system (to detect dental caries), diagnostic additional devices; antibacterial ability-colony forming units, DNA-based sequencing, scanning electron microscopy, crystal violet staining, and confocal laser scanning microscopy. Results: This review includes 98 papers: 14 of them describing the current status of caries patterns in the world, 60 studies (45 laboratory studies and 15 RCTs), and 24 systematic reviews were analyzed in order to detect whether new remineralizing agents can replace fluoride in further caries prevention. Conclusions: All reviewed new remineralization agents could be used without additives to treat early caries lesions, but the combination with F promotes better remineralization. Only HAP demonstrated its potential to serve as an alternative to fluoride in oral care products. However, further clinical studies are needed to prove its role in the remineralizing process of initial caries lesions. One also needs to ensure that both the clinical trials and in vitro lab studies use the best gold standards to validate any changes in the tooth structure, both remineralization and demineralization. Full article

Y₅F₃[AsO₃]₄ crystallizes needle-shaped in the tetragonal space group P4/ncc with the lattice parameters a = 1143.80(8) pm, c = 1078.41(7) pm and c/a = 0.9428 for Z = 4. The yttrium-fluoride substructure linked via secondary contacts forms a three-dimensional network $\begin{array}{c}3\\ \infty \end{array}${[Y₅F₃]¹²⁺} and the remaining part consists of ψ¹-tetrahedral [AsO₃]³⁻ units, which leave lone-pair channels along [001]. In contrast, platelet-shaped Y₅Cl₃[AsO₃]₄ crystals adopt the monoclinic space group C2/c with the lattice parameters a = 1860.56(9) pm, b = 536.27(3) pm, c = 1639.04(8) pm and β = 105.739(3)° for Z = 4. Condensation of [(Y1,2)O₈]¹³⁻ polyhedra via four common edges each leads to fluorite-like $\begin{array}{c}2\\ \infty \end{array}$ {[(Y1,2)O $\begin{array}{c}e\\ 8/2\end{array}$ ]⁵⁻} layers spreading out parallel to the (100) plane. Their three-dimensional linkage occurs via the (Y3)³⁺ cations with their Cl⁻ ligands on the one hand and the As³⁺ cations with their lone-pairs of electrons on the other, which also form within [AsO₃]³⁻ anions lone-pair channels along [010]. Both colorless compounds can be obtained by solid-state reactions from corresponding mixtures of the binaries (Y₂O₃, As₂O₃ and YX₃ with X = F and Cl) at elevated temperatures of 825 °C, most advantageously under halide-flux assistance (CsBr for Y₅F₃[AsO₃]₄ and ZnCl₂ for Y₅Cl₃[AsO₃]₄). By replacing a few percent of YX₃ with EuX₃ or TbX₃, Eu³⁺- or Tb³⁺-doped samples are accessible, which show red or green luminescence upon excitation with ultraviolet radiation. Full article

Piezoelectric polymer composites, particularly polyvinylidene fluoride (PVDF) blended with barium titanate (BT), show promise for wearable technologies as both energy harvesters and haptic actuators. However, these composites typically exhibit limited electromechanical coupling and insufficient β-phase formation. This study presents a novel approach using ionic liquids (ILs) to enhance PVDF-based piezoelectric composite performance. Through solution-casting methods, we examined the effect of IL concentration on the structural, mechanical, and piezoelectric properties of PVDF/BT composites. Results demonstrate that the use of IL significantly improves β-phase crystallization in PVDF while enhancing electrical properties and mechanical flexibility, which are key requirements for effective energy harvesting and haptic feedback applications. The optimized composites show a 25% increase in β-phase content, enhanced flexibility, and a 100% improvement in piezoelectric voltage output compared to other more conventional PVDF/BT systems. The IL-modified composite exhibits superior piezoelectric response, generating an output voltage of 9 V and an output power of 40.1 µW under mechanical excitation and a displacement of 138 nm when subjected to 13 V peak-to-peak voltage, making it particularly suitable for haptic interfaces. These findings establish a pathway toward high-performance, flexible piezoelectric materials for multifunctional wearable applications in human–machine interfaces. Full article

Calcium fluoride (CaF₂) crystals are widely utilized in deep-ultraviolet (DUV) lithography due to their excellent optical properties. The laser-induced degradation and damage of CaF₂ crystals is a critical concern that restricts its extended application. Impurities of CaF₂ crystal are considered a key factor affecting its laser resistance. Establishing the quantitative relationship and mechanism of impurity content impacting the degradation and damage characteristics of CaF₂ crystal is essential. This study investigated the characteristics of different impurity contents affecting the degradation and laser-induced damage thresholds (LIDTs) of CaF₂ crystals under X-ray and 193 nm pulsed laser irradiations, and quantitatively analyzed the degradation process and mechanism. Our findings demonstrate that impurities at ppm levels significantly diminish the transmittance of CaF₂ crystals across various wavelengths following X-ray irradiation. In contrast, these impurities have a negligible effect on the LIDT test results, suggesting distinct damage mechanisms between X-ray and laser irradiation. This study provides valuable insights for optimizing the CaF₂ crystal fabrication process and enhancing irradiation resistance. Full article

A macrocyclic receptor based on azopyrrole and polyether was synthesized, and its structure was characterized by NMR (¹H and ¹³C), HRMS and X-ray crystallography. In the solid state, the macrocyclic molecules could bind methanol through a pair of N-H…O hydrogen bonds and further self-assembled into tubular structures through C-H…N hydrogen bonds. This revealed that the crystal could still keep its porous properties after the included molecules were removed. The UV–Vis titration indicates that the macrocylic receptor can chromogenically and selectively sense fluoride ion in DMSO solution, and the sensing mechanism was rationalized by ¹H NMR. Full article

Bridges play a key and controlling role in transportation systems. Steel bridges are favored for their high strength, good seismic performance, and convenient construction. As important node connectors of steel bridges, high-strength bolts are extremely susceptible to damage such as corrosion and loosening. Therefore, accurate identification of bolt loosening is crucial. First, a new type of adhesive piezoelectric sensor is designed and prepared using PMN-PT piezoelectric single-crystal materials. The PMN-PT sensor and polyvinylidene fluoride (PVDF) sensor are subjected to steel plate fixed frequency load and swept frequency load tests to test the performance of the two sensors. Then, a steel plate component connected by high-strength bolts is designed. By applying exciter square wave load to the structure, the vibration response characteristics of the structure are analyzed to identify the loosening of the bolts. In addition, a piezoelectric smart washer sensor is designed to make up for the shortcomings of the adhesive piezoelectric sensor, and the effectiveness of the piezoelectric smart washer sensor is verified. Finally, a bolt loosening index is proposed to quantitatively evaluate the looseness of the bolt. The results show that the sensitivity of the PMN-PT sensor is 21 times that of the PVDF sensor. Compared with the peak stress change, the natural frequency change is used to identify the bolt loosening more effectively. Piezoelectric smart washer sensor and bolt loosening indicator can be used for bolt loosening identification. Full article