Search Results (47)

Metal–Organic Frameworks (MOFs) have diverse applications due to their tunable porosity, large surface area, and diverse chemical functionalities. Among them, one of the most researched MOFs is MIL-101(Cr), which, in addition, is very stable in water. We have used a commercially available substance with approximately 300 nm large crystals for the preparation of a sensing nano-thin layer for the emerging water contaminant PFOS, due to its high selectivity towards this compound. Here, we have synthesized 20 nm sized crystals of MIL-101(Cr), which are among the smallest reported, and compared them to the same material with 300 nm sized crystals. The material was characterized by TEM and XPS. It was possible to prepare insoluble monolayers at the air–water interface (Langmuir films), which were characterized with film compression isotherms, Brewster angle microscopy, and surface potential measurements. The Langmuir–Blodgett (LB) method was used to deposit monolayers on Si wafers and 434 MHz Surface Acoustic Wave resonator simultaneously. The LB layers were very stable over time. The smaller-sized MIL-101 (Cr) crystals exhibit denser, more homogeneous water coverage and packing upon compression, with no observable 10–100 µm aggregates. LB monolayers from the 20 nm particles have approximately six times lower surface roughness. The LB monolayer is far from being smooth, but this will allow excellent access to the MOF pores by the tested analyte in a chemical sensing application. The lack of research on depositing presynthesized MOFs using probably the best method for nanoarchitectonics—the LB method—is addressed. The 20 nm sized MOF crystals are the smallest deposited by this method so far. Full article

Since methanol has a significant health hazard due to its inherent toxicity, it is urgent to develop a method capable of rapid, sensitive, and continuous monitoring of methanol. The present study successfully synthesized a NiCo₂O₄/MIL-Ti₁₂₅ composite material and conducted a comprehensive analysis of its effectiveness for the detection of methanol employing cataluminescence (CTL) technology. The findings demonstrated that the composite material displays marked CTL in response to methanol, showcasing notable sensitivity, selectivity, and stability. The composite’s heterogeneous structure significantly improves the adsorption and reaction efficiency of methanol and further reduces the sensor’s working temperature. Under the optimal conditions of 215 °C and a flow rate of 300 mL/min, the CTL signal intensity is governed by the equation Y = 10.388X − 4.473 (R² = 0.982), with a detection limit as low as 0.431 ppm. The NiCo₂O₄/MIL-Ti₁₂₅ sensor exhibits high selectivity towards methanol. In addition, a relative standard deviation (RSD) of 4.95% demonstrates its excellent stability. Utilizing X-ray photoelectron spectroscopy (XPS), the study investigated the impact of elemental valence changes on the CTL process. We believe that the NiCo₂O₄/MIL-Ti₁₂₅ composite material, as a high-performance low-temperature CTL methanol sensor, is promising for applications. Full article

The paradigm of molecular-network conformations in Se-rich glassy arsenoselenides As_xSe_100−x compositionally approaching pure Se (x < 10) is considered, employing comprehensive XRD analysis of diffuse peak-halos and nanocrystalline reflections from the known Se polymorphs in their XRD patterns. Within a modified microcrystalline model, the changes with growing Se content in these alloys are interpreted in terms of suppression in intermediate range ordering due to shifting to high diffraction angles and a narrowed FSDP (first sharp diffraction peak)-related diffuse peak-halo, accompanied by enhancement in extended range ordering due to a shift to low diffraction angles and a broadened SSDP (second sharp diffraction peak)-related peak-halo. Overlapping of these peak-halos is enhanced in Se-rich alloys, tending towards unified FSDP-SSDP-related halos with characteristic doublet asymmetry due to the remnants of nanocrystalline trigonal t-Se. Drastic enhancement of the crystallization processes related to the trigonal t-Se phase is a principal feature of nanostructurization effects in Se-rich glassy arsenoselenides driven by nanomilling. The nanostructurization response in these alloys is revealed as a fragmentation impact on the correlation length of the FSDP-responsible entities, accompanied by an agglomeration impact on the correlation length of the SSDP-responsible entities. The FSDP- and SSDP-related diffuse peak-halos become more distinguishable in the XRD patterning of nanostructured arsenoselenides, being associated with other contributions from crystalline remnants, such as those expected in transition to glassy arsenoselenides with higher Se content. An irregular sequence of randomly distributed cis- and trans-configurated multiatomic Se linkages is visualized by ab initio quantum-chemical modeling of Se_n chain- and ring-like conformations. The most critical point of molecular-network disproportionality analysis in the examined arsenoselenide As_xSe_100−x glassy alloys obeying the chain-crossing model corresponds to x = 7 (equivalent to 93 at. % of Se in the binary As-Se system), as an equilibrium point between mixed cis-trans-configurated Se₇ chains and exceptionally cis-configurated molecular Se₈ rings. At the basis of developed models, the paradigm of thermodynamically stable molecular-network conformations in the nanostructured Se-rich arsenoselenides As_xSe_100−x (x < 10) is surely resolved in favor of chain-like network-forming conformations composed of mixed cis-trans-configurated network-forming multiatomic Se fragments. Full article

Silicon carbide (SiC) half-bridge power modules are widely utilized in new energy power generation, electric vehicles, and industrial power supplies. To address the research gap in collaborative validation between electro-thermal coupling models and process reliability, this paper proposes a closed-loop methodology of “design-simulation-process-validation”. This approach integrates in-depth electro-thermal simulation (LTspice XVII/COMSOL Multiphysics 6.3) with micro/nano-packaging processes (sintering/bonding). Firstly, a multifunctional double-pulse test board was designed for the dynamic characterization of SiC devices. LTspice simulations revealed the switching characteristics under an 800 V operating condition. Subsequently, a thermal simulation model was constructed in COMSOL to quantify the module junction temperature gradient (25 °C → 80 °C). Key process parameters affecting reliability were then quantified, including conductive adhesive sintering (S820-F680, 39.3 W/m·K), high-temperature baking at 175 °C, and aluminum wire bonding (15 mil wire diameter and 500 mW ultrasonic power/500 g bonding force). Finally, a double-pulse dynamic test platform was established to capture switching transient characteristics. Experimental results demonstrated the following: (1) The packaged module successfully passed the 800 V high-voltage validation. Measured drain current (4.62 A) exhibited an error of <0.65% compared to the simulated value (4.65 A). (2) The simulated junction temperature (80 °C) was significantly below the safety threshold (175 °C). (3) Microscopic examination using a Leica IVesta 3 microscope (55× magnification) confirmed the absence of voids at the sintering and bonding interfaces. (4) Frequency-dependent dynamic characterization revealed a 6 nH parasitic inductance via Ansys Q3D 2025 R1 simulation, with experimental validation at 8.3 nH through double-pulse testing. Thermal evaluations up to 200 kHz indicated 109 °C peak temperature (below 175 °C datasheet limit) and low switching losses. This work provides a critical process benchmark for the micro/nano-manufacturing of high-density SiC modules. Full article

Nanomilling-driven effects on polyamorphic transitions are examined in tetra-arsenic biselenide As₄Se₂ alloy, which is at the boundary of the glass-forming region in the As-Se system, using multifrequency temperature-modulated DSC-TOPEM^® technique, supported by X-ray powder diffraction (XRPD) and micro-Raman spectroscopy analysis. As shown by XRPD analysis, this alloy reveals a glassy–crystalline nature due to rhombohedral As and cubic As₂O₃ (arsenolite) inclusions, which especially grew after milling in a PVP (polyvinylpyrrolidone) water solution. At the medium-range structure level, nanomilling-driven changes are revealed as the disruption of intermediate-range ordering and enhancement of extended-range ordering. The generalized molecular-to-network amorphization trend in this alloy is confirmed by the microstructure response revealed in the broadened and obscured features in micro-Raman scattering spectra collected for nanomilled specimens. Thermophysical heat-transfer phenomena are defined by molecular-to-network polyamorphic transformations activated under nanomilling. The domination of thioarsenide-type As₄Se_n entities in this alloy results in an abnormous nanomilling-driven network-enhanced glass transition temperature increase. The nanomilled alloys become notably stressed owing to the destruction of molecular thioarsenide and incorporation of their remnants into the newly polymerized arsenoselenide network. This effect is more pronounced in As₄Se₂ alloy subjected to dry nanomilling, while it is partly counterbalanced when this alloy is additionally subjected to wet milling in a PVP water solution, accompanied by the stabilization of the As₄Se₂/PVP nanocomposite. Full article

Molecular network conformations in the over-stoichiometric arsenoselenides of canonical As_xSe_100−x system (40 ≤ x ≤ 100) covering a full row of thioarsenide-type As₄Se_n entities (0 ≤ n ≤ 6) are analyzed with ab initio quantum-chemical modeling employing cluster-simulation code CINCA. Native (melt-quenching-derived) and nanostructurization-driven (activated by nanomilling) polymorphic and polyamorphic transitions initiated by decomposition of the thioarsenide-type As₄Se_n cage molecules and incorporation of their remnants into a newly polymerized arsenoselenide network are identified on the developed map of molecular network clustering in a binary As-Se system. Within this map, compositional counter lines corresponding to preferential molecular or network-forming tendencies in the examined arsenoselenides are determined, explaining that network-crystalline conformations prevail in the boundary compositions corresponding to n = 6 and n = 0, while molecular-crystalline ones dominate inside the rows corresponding to n = 4 and n = 3. A set of primary and secondary equilibrium lines is introduced in the developed clustering map to account for inter-phase equilibria between the most favorable (regular) and competitive (irregular) thioarsenide phases. Straightforward interpretation of decomposition reactions accompanying induced crystallization and amorphization (reamorphization) in the arsenoselenides is achieved, employing disproportionality analysis of thioarsenide-type molecular network conformations within the reconstructed clustering map. The preference of network clustering at the boundaries of the As₄Se_n row (at n = 6 and n = 0) disturbs inter-phase equilibria inside this row, leading to unexpected anomalies, such as absence of stable tetra-arsenic triselenide As₄Se₅ molecular-crystalline species; polyamorphism in mechanoactivated As₄Se_n alloys (2 ≤ n ≤ 6); breakdown in the glass-forming ability of melt-quenching-derived arsenoselenides in the vicinity of tetra-arsenic biselenide As₄Se₂ composition; plastically and normally crystalline polymorphism in tetra-arsenic triselenide As₄Se₃-based thioarsenides, and so on. Full article

Polyamorphic transitions driven by high-energy mechanical milling (nanomilling) are studied in thioarsenide As₄Se_n-type glassy alloys obtained by melt quenching deviated from arsenic triselenide As₂Se₃ stoichiometry towards tetraarsenic pentaselenide (g-As₄Se₅) and tetraarsenic tetraselenide (g-As₄Se₄). This employs a multiexperimental approach based on powder X-ray diffraction (XRD) analysis complemented by thermophysical heat transfer, micro-Raman scattering (micro-RS) spectroscopy, and revised positron annihilation lifetime (PAL) analysis. Microstructure scenarios of these nanomilling-driven transformations in arsenoselenides are identified by quantum-chemical modeling using the authorized modeling code CINCA (the Cation Interlinked Network Cluster Approach). A straightforward interpretation of a medium-range structure response of a nanomilling-driven polyamorphism in the arsenoselenides is developed within the modified microcrystalline model. Within this model, the diffuse peak-halos arrangement in the XRD patterning is treated as a superposition of the Bragg-diffraction contribution from inter-planar correlations supplemented by the Ehrenfest-diffraction contribution from inter-atomic (inter-molecular) correlations related to derivatives of network As₂Se₃-type and molecular As₄Se₄-type conformations. Changes in the medium-range structure of examined glassy arsenoselenides subjected to nanomilling occur as an interplay between disrupted intermediate-range ordering and enhanced extended-range ordering. The domination of network-forming conformations in arsenoselenides deviated from As₂Se₃ stoichiometry (such as g-As₄Se₅) results in rather slight changes in their calorimetric heat-transfer and micro-RS responses. At the atomic-deficient level probed by PAL spectroscopy, these changes are accompanied by reduced positron trapping rate of agglomerated multiatomic vacancies and vacancy-type clusters in an amorphous As-Se network. Under an increase in As content beyond the g-As₄Se₅ composition approaching g-As₄Se₄, nanomilling-driven polyamorphic transitions, which can be classified as reamorphization (amorphous I-to-amorphous II) phase transitions, are essentially enhanced due to the higher molecularity of these glassy alloys enriched in thioarsenide-type As₄Se₄ cage-like molecular entities and their low-order network-forming derivatives. Full article

Binary As_xSe_100−x alloys from the border of a glass-forming region (65 < x < 70) subjected to nanomilling in dry and dry–wet modes are characterized by the XRPD, micro-Raman scattering (micro-RS) and revised positron annihilation lifetime (PAL) methods complemented by a disproportionality analysis using the quantum–chemical cluster modeling approach. These alloys are examined with respect to tetra-arsenic biselenide As₄Se₂ stoichiometry, realized in glassy g-As₆₅Se₃₅, glassy–crystalline g/c-As₆₇Se₃₃ and glassy–crystalline g/c-As₇₀Se₃₀. From the XRPD results, the number of rhombohedral As and cubic arsenolite As₂O₃ phases in As-Se alloys increases after nanomilling, especially in the wet mode realized in a PVP water solution. Nanomilling-driven amorphization and reamorphization transformations in these alloys are identified by an analysis of diffuse peak halos in their XRPD patterning, showing the interplay between the levels of a medium-range structure (disruption of the intermediate-range ordering at the cost of an extended-range one). From the micro-RS spectroscopy results, these alloys are stabilized by molecular thioarsenides As₄Se_n (n = 3, 4), regardless of their phase composition, remnants of thioarsenide molecules destructed under nanomilling being reincorporated into a glass network undergoing a polyamorphic transition. From the PAL spectroscopy results, volumetric changes in the wet-milled alloys with respect to the dry-milled ones are identified as resulting from a direct conversion of the bound positron–electron (Ps, positronium) states in the positron traps. Ps-hosting holes in the PVP medium appear instead of positron traps, with ~0.36–0.38 ns lifetimes ascribed to multivacancies in the As-Se matrix. The superposition of PAL spectrum peaks and tails for pelletized PVP, unmilled, dry-milled, and dry–wet-milled As-Se samples shows a spectacular smoothly decaying trend. The microstructure scenarios of the spontaneous (under quenching) and activated (under nanomilling) decomposition of principal network clusters in As₄Se₂-bearing arsenoselenides are recognized. Over-constrained As_6·(2/3) ring-like network clusters acting as pre-cursors of the rhombohedral As phase are the main products of this decomposition. Two spontaneous processes for creating thioarsenides with crystalline counterparts explain the location of the glass-forming border in an As-Se system near the As₄Se₂ composition, while an activated decomposition process for creating layered As₂Se₃ structures is responsible for the nanomilling-driven molecular-to-network transition. Full article

Polyamorphic transformations driven by high-energy mechanical ball milling (nanomilling) are recognized in a melt-quenched glassy alloy of tetra-arsenic triselenide (As₄Se₃). We employed XRPD analysis complemented by thermophysical heat-transfer and micro-Raman spectroscopy studies. A straightforward interpretation of the medium-range structural response to milling-driven reamorphization is developed within a modified microcrystalline model by treating diffuse peak-halos in the XRPD patterns of this alloy as a superposition of the Bragg-diffraction contribution from inter-planar correlations, which are supplemented by the Ehrenfest-diffraction contribution from inter-atomic and/or inter-molecular correlations related to derivatives of thioarsenide As₄Se_n molecules, mainly dimorphite-type As₄Se₃ ones. These cage molecules are merely destroyed under milling, facilitating the formation of a polymerized network with enhanced calorimetric heat-transfer responses. Disruption of intermediate-range ordering, due to weakening of the FSDP (the first sharp diffraction peak), accompanied by an enhancement of extended-range ordering, due to fragmentation of structural entities responsible for the SSDP (the second sharp diffraction peak), occurs as an interplay between medium-range structural levels in the reamorphized As₄Se₃ glass alloy. Nanomilling-driven destruction of thioarsenide As₄Se_n molecules followed by incorporation of their remnants into a glassy network is proved by micro-Raman spectroscopy. Microstructure scenarios of the molecular-to-network polyamorphic transformations caused by the decomposition of the As₄Se₃ molecules and their direct destruction under grinding are recognized by an ab initio quantum-chemical cluster-modeling algorithm. Full article

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are pollutants of concern due to their long-term persistence in the environment and human health effects. Among them, perfluorooctane sulfonic acid (PFOS) is very ubiquitous and dangerous for health. Currently, the detection levels required by the legislation can be achieved only with expensive laboratory equipment. Hence, there is a need for portable, in-field, and possibly real-time detection. Optical and electrochemical transduction mechanisms are mainly used for the chemical sensors. Here, we report the first gravimetric detection of small-sized molecules like PFOS (MW 500) dissolved in water. A 100 MHz quartz crystal microbalance (QCM) measured at the third harmonic and an even more sensitive 434 MHz two-port surface acoustic wave (SAW) resonator with gold electrodes were used as transducers. The PFOS selective sensing layer was prepared from the metal organic framework (MOF) MIL-101(Cr). Its nano-sized thickness and structure were optimized using the discreet Langmuir–Blodgett (LB) film deposition method. This is the first time that LB multilayers from bulk MOFs have been prepared. The measured frequency downshifts of around 220 kHz per 1 µmol/L of PFOS, a SAW resonator-loaded Q_L-factor above 2000, and reaction times in the minutes’ range are highly promising for an in-field sensor reaching the water safety directives. Additionally, we use the micrometer-sized interdigitated electrodes of the SAW resonator to strongly enhance the electrochemical impedance spectroscopy (EIS) of the PFOS contamination. Thus, for the first time, we combine the ultra-sensitive gravimetry of small molecules in a water environment with electrical measurements on a single device. This combination provides additional sensor selectivity. Control tests against a bare resonator and two similar compounds prove the concept’s viability. All measurements were performed with pocket-sized tablet-powered devices, thus making the system highly portable and field-deployable. While here we focus on one of the emerging water contaminants, this concept with a different selective coating can be used for other new contaminants. Full article

Multifunctional nanocomposites from an equimolar As₄S₄/Fe₃O₄ cut section have been successfully fabricated from coarse-grained bulky counterparts, employing two-step mechanochemical processing in a high-energy mill operational in dry- and wet-milling modes (in an aqueous solution of Poloxamer 407 acting as a surfactant). As was inferred from the X-ray diffraction analysis, these surfactant-free and surfactant-capped nanocomposites are β-As₄S₄-bearing nanocrystalline–amorphous substances supplemented by an iso-compositional amorphous phase (a-AsS), both principal constituents (monoclinic β-As₄S₄ and cubic Fe₃O₄) being core–shell structured and enriched after wet milling by contamination products (such as nanocrystalline–amorphous zirconia), suppressing their nanocrystalline behavior. The fluorescence and magnetic properties of these nanocomposites are intricate, being tuned by the sizes of the nanoparticles and their interfaces, dependent on storage after nanocomposite fabrication. A specific core–shell arrangement consisted of inner and outer shell interfaces around quantum-confined nm-sized β-As₄S₄ crystallites hosting a-AsS, and the capping agent is responsible for the blue-cyan fluorescence in as-fabricated Poloxamer capped nanocomposites peaking at ~417 nm and ~442 nm, while fluorescence quenching in one-year-aged nanocomposites is explained in terms of their destroyed core–shell architectures. The magnetic co-functionalization of these nanocomposites is defined by size-extended heterogeneous shells around homogeneous nanocrystalline Fe₃O₄ cores, composed by an admixture of amorphous phase (a-AsS), nanocrystalline–amorphous zirconia as products of contamination in the wet-milling mode, and surfactant. Full article

We examined the evolution of fenofibrate (FNB, drug) particle size distribution (PSD) during the production of nanosuspensions via wet stirred media milling (WSMM) with a cell-based population balance model (PBM). Our objective was to elucidate the potential impacts of batch size, suspension volumetric flow rate, and imperfect mixing in a recirculating WSMM. Various specific breakage rate functions were fitted to experimental PSD data at baseline conditions assuming perfect mixing. Then, the best function was used to simulate the PSD evolution at various batch sizes and flow rates to validate the model. A novel function, which is a product of power–law and logistic functions, fitted the evolution the best, signifying the existence of a transition particle size commensurate with a grinding limit. Although larger batches yielded coarser and wider PSDs, the suspensions had identical PSDs when milled for the same effective milling time. The flow rate had an insignificant influence on the PSD. Furthermore, the imperfect mixing in the mill chamber was simulated by considering more than one cell and different back-mixing flow ratios. The effects were weak and restricted to the first few turnovers. These insights contribute to our understanding of recirculating WSMM, providing valuable guidance for process development. Full article

Dual centrifugation (DC) is an innovative in-vial homogenization and in-vial nanomilling technique that has been in use for the preparation of liposomes for more than one decade. Since then, DC has continuously been developed for preparing various liposomes and other lipid nanoparticles including emulsions and solid lipid nanoparticles (SLNs) as well as polymersomes and nanocrystals. Improvements in equipment technology have been achieved over the past decade, so that DC is now on its way to becoming the quasi-standard for the simple, fast, and aseptic production of lipid nanoparticles and nanocrystals in small and medium batch sizes, including the possibility of simple and fast formulation screening or bedside preparations of therapeutic nanoparticles. More than 68 publications in which DC was used to produce nanoparticles have appeared since then, justifying an initial review of the use of DC for pharmaceutical nanotechnology. Full article

The PAO/MgO nanofluids-based dielectric fluid DF(MgO-20) has significantly increased corrosion resistance as a coating. Electrochemical studies show that the DF(MgO-20) coating has protection efficiency of up to 99% for steel, copper, and aluminum. This coating is capable of providing corrosion protection for steel samples for up to 120 h in salt spray tests, and printed circuit boards (PCBs) for more than 20 days in salt spray tests in accordance with the ASTM B117 standard. The DF(MgO-20) coating fully meets the moisture resistance and fungal resistance standards required by the MIL-1-46058 C standard. The coating also demonstrates water displacement, meeting the requirements of the MIL-PRF-81309G standard. The DF(MgO-20) coating is able to protect electronic equipment working in underwater environment for up to 20 days. The aforementioned outstanding protection properties are achieved thanks to the nanofluid effect of the DF(MgO-20) dielectric fluid with the presence of MgO nano-additives that increase its overflow ability. The coating penetrates deeply and adheres tightly to the metal substrates, helping to separate them from moisturizing agents and corrosive agents. The research results aim to apply this coating to protect electronic equipment working in the tropical marine climate of Vietnam. Full article

A superhydrophobic wood surface was produced by employing the solvothermal method to form shuttle-like, well-crystallized MIL-88(Fe) on the surface of wood and assembling a Octadecylphosphonic acid (OPA) reagent. The nanosized MIL-88(Fe) molecule caused the wood’s surface to take on a nano mastoid shape. In addition, MIL-88(Fe) provides metal sites to capture OPA molecules, preventing the long-chain alkane hydrophobic group from contacting the surface of the wood. They both make a considerable difference in the growth of a hydrophobic wood surface. The results of the experiment indicate that the water contact angle (WCA) increases with reactant concentration. The WCA of the samples prepared with 5.0 × 10⁻² M FeCl₃ was 140.57°. When the reactant concentration was 10.0 × 10⁻² M, the greatest WCA = 153.69° reading was obtained. The research’s findings present a novel technique for producing superhydrophobic wood surfaces. Full article