Search Results (19)

Recently, it was shown that the nanocrystallization of $\mathrm{B}{\mathrm{i}}_2{\mathrm{O}}_3$ glasses with the addition of $\mathrm{S}\mathrm{i}{\mathrm{O}}_2$ and $\mathrm{A}{\mathrm{l}}_2{\mathrm{O}}_3$ leads to the stabilization of the $\delta$-like $\mathrm{B}{\mathrm{i}}_2{\mathrm{O}}_3$ phase at least down to room temperature, which is significantly below its stability range in bulk form. In this research, we investigated the properties of bismuthate glasses synthesized with various glass-forming agents such as $\mathrm{S}\mathrm{i}{\mathrm{O}}_2$, $\mathrm{G}\mathrm{e}{\mathrm{O}}_2$, ${\mathrm{B}}_2{\mathrm{O}}_3$, and $\mathrm{A}{\mathrm{l}}_2{\mathrm{O}}_3$. It was demonstrated that vitrification of all these systems is possible using a standard melt quenching route. Furthermore, we investigated the crystallization processes in pristine glasses upon increasing the temperature and the thermal stability of arising phases using thermal analysis and high-temperature XRD in situ experiments. It was shown that it is possible to stabilize crystallites’ isostructures with $\delta$-$\mathrm{B}{\mathrm{i}}_2{\mathrm{O}}_3$ embedded in a residual glassy matrix down to room temperature. The temperature range of the appearance of the $\delta$-like phase strongly depended on the nominal composition of the glasses. We postulate that the confinement effect depends on the local properties of the residual glassy matrix and its ability to introduce sufficient force to stretch the structure of the $\delta$-like $\mathrm{B}{\mathrm{i}}_2{\mathrm{O}}_3$ phase in the nanocrystallites. Full article

Laser-shock-peening technology is an international research hotspot in the surface-strengthening field, which utilizes the mechanical effects of laser-induced plasma shock waves to effectively improve the fatigue performance of metallic components by introducing the gradient microstructures and compressive residual stress into the surface layer of processed materials. The fatigue failure caused by high-frequency vibrations in aeroengines during service is the most important threat to flight safety, and this case is more prominent for military aeroengines because their service situation is harsher. The present paper focuses on components such as high-temperature components, fan/compressor blade, and thin-walled weldments, and it systematically introduces the researching findings about surface nanocrystallization and compressive residual stress formation mechanism in typical aeronautical metallic materials treated by laser shock peening. The contents mainly involve the characteristics, formation process, fatigue resistance mechanism, thermal stability of residual compressive stress, and nanocrystallization generated by laser shock peening. Full article

A fluorosilicate (FS) nano-crystallized glass ceramic (NGC) is one of the most commonly used gain materials for applications in optical devices due to its excellent thermal stability as well as high-efficiency luminescence. However, FS glass can hardly be used to prepare NGC fibers due to its high preparation temperature. Here, a series of low-temperature fluoro-borosilicate (FBS) glasses were designed for the fabrication of active NGC fibers. By modulating B₂O₃, the preparation temperature of FBS glass was reduced to 1050 °C, and the crystallization in FBS NGCs was more controllable than in FS NGC. The crystallization of the impure phase was inhibited, and single-phase rare earth (RE)-fluoride nanocrystals were controllably precipitated in the FBS NGCs. The 40Si-20B FBS NGC not only exhibited a higher optical transmittance, but the luminescence efficiency was also much higher than traditional FS NGCs. More importantly, NGC fibers were successfully fabricated by using the designed FBS glass as core glass. Nanocrystals were controllably precipitated and greatly enhanced, and upconversion luminescence was observed in NGC fibers. The designed FBS NGCs provided high-quality optical gain materials and offered opportunities for fabricating a wide range of NGC fibers for multiple future applications, including fiber lasers and sensors. Full article

Recently, an interest in NASICON-type materials revived, as they are considered potential cathode materials in sodium–ion batteries used in large-scale energy storage. We applied a facile technique of thermal nanocrystallization of glassy analogs of these compounds to enhance their electrical parameters. Six nanomaterials of the Na₃M₂(PO₄)₂F₃ (M = V, Ti, Fe) system were studied. Samples with nominal compositions of Na₃V₂(PO₄)₂F₃, Na₃Ti₂(PO₄)₂F₃, Na₃Fe₂(PO₄)₂F₃, Na₃TiV(PO₄)₂F₃, Na₃FeV(PO₄)₂F₃ and Na₃FeTi(PO₄)₂F₃ have been synthesized as glasses using the melt-quenching method. X-ray diffraction measurements were conducted for as-synthesized samples and after heating at elevated temperatures to investigate the structure. Extensive impedance measurements allowed us to optimize the nanocrystallization process to enhance the electrical conductivity of cathode nanomaterials. Such a procedure resulted in samples with the conductivity at room temperature ranging from $1\times {10}^{-9}$ up to $8\times {10}^{-5}$ S/cm. We carried out in situ impedance spectroscopy measurements (in an ultra-high-frequency range up to 10 GHz) and compared them with thermal events observed in differential thermal analysis studies. Full article

Understanding the processes occurring during the nanocrystallization of glass-forming liquids is important for creating artificial nanostructures for various applications. In this article, local thermal perturbations in supercooled glass-forming liquids and polymers during the nucleation of a crystalline phase are studied. To describe the thermal response of supercooled glass-forming liquids, an integro-differential heat equation with dynamic heat capacity is used. We have found that the effect of the dynamic heat capacity is significant for fast local thermal perturbations that arise in the early stages of crystal nucleation in glass-forming liquids and polymers. It has been established that local temperature perturbations during the nucleation of crystals in silicate glasses and polymers can change the nucleation rate by 2–5 orders of magnitude. The knowledge gained can be useful for the technology of artificial microstructures and advanced materials. Full article

Alluaudite-type materials are systematically attracting more attention as prospective cathode materials for sodium-ion batteries. It has been demonstrated that optimized thermal nanocrystallization of glassy analogs of various cathode materials may lead to a significant increase in their electrical conductivity. In this paper, three alluaudite-like glasses (Na${}_2$Fe${}_3$(PO${}_4$)${}_3$—FFF, Na${}_2$VFe${}_2$(PO${}_4$)${}_3$—VFF, and Na${}_2$VFeMn(PO${}_4$)${}_3$—VFM) were synthesized and subjected to an optimized thermal nanocrystallization. This procedure resulted in nanostructured samples with increased electrical conductivity at room temperature: $5\times {10}^{-7}$ S/cm (FFF), $7\times {10}^{-5}$ S/cm (VFM), and $6\times {10}^{-4}$ S/cm (VFF). The nanocrystalline microstructure was also evidenced by ultra-high-frequency impedance spectroscopy (up to 10 GHz) and proposed electrical equivalent circuits. Prototype electrochemical cells were assembled and characterized with voltage cutoffs of 1.5 and 4.5 V. The electrochemical performance was, however, modest. The gravimetric capacity varied between the studied materials, but did not exceed 35 mAh/g. Capacity retention after ca. 100 cycles was satisfactory. Further optimization of the residual-glass-to-nanocrystallite volume ratio would be desirable. Full article

Group IV quantum dots (QDs) in HfO₂ are attractive for non-volatile memories (NVMs) due to complementary metal-oxide semiconductor (CMOS) compatibility. Besides the role of charge storage centers, SiGeSn QDs have the advantage of a low thermal budget for formation, because Sn presence decreases crystallization temperature, while Si ensures higher thermal stability. In this paper, we prepare MOS capacitors based on 3-layer stacks of gate HfO₂/floating gate of SiGeSn QDs in HfO₂/tunnel HfO₂/p-Si obtained by magnetron sputtering deposition followed by rapid thermal annealing (RTA) for nanocrystallization. Crystalline structure, morphology, and composition studies by cross-section transmission electron microscopy and X-ray diffraction correlated with Raman spectroscopy and C–V measurements are carried out for understanding RTA temperature effects on charge storage behavior. 3-layer morphology and Sn content trends with RTA temperature are explained by the strongly temperature-dependent Sn segregation and diffusion processes. We show that the memory properties measured on Al/3-layer stack/p-Si/Al capacitors are controlled by SiGeSn-related trapping states (deep electronic levels) and low-ordering clusters for RTA at 325–450 °C, and by crystalline SiGeSn QDs for 520 and 530 °C RTA. Specific to the structures annealed at 520 and 530 °C is the formation of two kinds of crystalline SiGeSn QDs, i.e., QDs with low Sn content (2 at.%) that are positioned inside the floating gate, and QDs with high Sn content (up to 12.5 at.%) located at the interface of floating gate with adjacent HfO₂ layers. The presence of Sn in the SiGe intermediate layer decreases the SiGe crystallization temperature and induces the easier crystallization of the diamond structure in comparison with 3-layer stacks with Ge-HfO₂ intermediate layer. High frequency-independent memory windows of 3–4 V and stored electron densities of 1–2 × 10¹³ electrons/cm² are achieved. Full article

In our recent papers, it was shown that the thermal nanocrystallization of glassy analogs of selected cathode materials led to a substantial increase in electrical conductivity. The advantage of this technique is the lack of carbon additive during synthesis. In this paper, the electrochemical performance of nanocrystalline LiFePO₄ (LFP) and LiFe_0.88V_0.08PO₄ (LFVP) cathode materials was studied and compared with commercially purchased high-performance LiFePO₄ (C-LFP). The structure of the nanocrystalline materials was confirmed using X-ray diffractometry. The laboratory cells were tested at a wide variety of loads ranging from 0.1 to 3 C-rate. Their performance is discussed with reference to their microstructure and electrical conductivity. LFP exhibited a modest electrochemical performance, while the gravimetric capacity of LFVP reached ca. 100 mAh/g. This value is lower than the theoretical capacity, probably due to the residual glassy matrix in which the nanocrystallites are embedded, and thus does not play a significant role in the electrochemistry of the material. The relative capacity fade at high loads was, however, comparable to that of the commercially purchased high-performance LFP. Further optimization of the crystallites-to-matrix ratio could possibly result in further improvement of the electrochemical performance of nanocrystallized LFVP glasses. Full article

Group IV nanocrystals (NCs), in particular from the Si–Ge system, are of high interest for Si photonics applications. Ge-rich SiGe NCs embedded in nanocrystallized HfO₂ were obtained by magnetron sputtering deposition followed by rapid thermal annealing at 600 °C for nanostructuring. The complex characterization of morphology and crystalline structure by X-ray diffraction, μ-Raman spectroscopy, and cross-section transmission electron microscopy evidenced the formation of Ge-rich SiGe NCs (3–7 nm diameter) in a matrix of nanocrystallized HfO₂. For avoiding the fast diffusion of Ge, the layer containing SiGe NCs was cladded by very thin top and bottom pure HfO₂ layers. Nanocrystallized HfO₂ with tetragonal/orthorhombic structure was revealed beside the monoclinic phase in both buffer HfO₂ and SiGe NCs–HfO₂ layers. In the top part, the film is mainly crystallized in the monoclinic phase. High efficiency of the photocurrent was obtained in a broad spectral range of curves of 600–2000 nm at low temperatures. The high-quality SiGe NC/HfO₂ matrix interface together with the strain induced in SiGe NCs by nanocrystallization of both HfO₂ matrix and SiGe nanoparticles explain the unexpectedly extended photoelectric sensitivity in short-wave infrared up to about 2000 nm that is more than the sensitivity limit for Ge, in spite of the increase of bandgap by well-known quantum confinement effect in SiGe NCs. Full article

This study showed that thermal nanocrystallization of glassy analogs of LiFe${}_{1-x}$Mn${}_x$PO${}_4$ (with the addition of vanadium for improvement of glass forming properties) resulted in highly conducting materials that may be used as cathodes for Li-ion batteries. The glasses and nanomaterials were studied with differential thermal analysis, X-ray diffractometry, and impedance spectroscopy. The electrical conductivity of the nanocrystalline samples varied, depending on the composition. For $x=0.5$, it exceeded ${10}^{-3}$ S/cm at room temperature with an activation energy as low as 0.15 eV. The giant and irreversible increase in the conductivity was explained on the basis of Mott’s theory of electron hopping and a core-shell concept. Electrochemical performance of the active material with $x=0.5$ was also reported. Full article

The physical mechanism, reasons and conditions of nanocrystal formation in an amorphous NiTi metal film, stimulated by infrasonic action, are formulated. Nanostructural elements of an amorphous medium (relaxation centers) containing disordered nanoregions with two-level systems are considered to be responsible for this process. When exposed to infrasound, a large number of two-level systems are excited, significantly contributing to inelastic deformation and the formation of nanocrystals. The physical mechanism of the nanocrystallization of metallic glass under mechanical action includes both local thermal fluctuations and the additional quantum tunneling of atoms stimulated by shear deformation. A crystalline nanocluster appears as a result of local atomic rearrangement growing increasingly exposed to infrasound. It is possibly unstable in the absence of infrasound. When the radius of the nanocluster reaches a critical value, a potential well appears, in which a conducting electron is localized to form a phason (stable nanocrystal). Estimated values of the phason’s radius and the depth of the nanometer potential well is about 0.5 nm and 1 eV, respectively. It forms a condition of stable phason formation. The occurrence of the instability of the amorphous state and following transformation to the nanostructured state is based on the accumulation of the potential energy of inelastic deformation to a critical value equal to the latent heat of the transformation of the amorphous state into the nanostructured state. Full article

In the present work, we investigated in detail the thermal/crystallization behavior and magnetic properties of materials with Fe_84.5-xCo_xNb₅B_8.5P₂ (x = 0, 5, 10, 15 and 20 at.%) composition. The amorphous ribbons were manufactured on a semi-industrial scale by the melt-spinning technique. The subsequent nanocrystallization processes were carried out under different conditions (with/without magnetic field). The comprehensive studies have been carried out using differential scanning calorimetry, X-ray diffractometry, transmission electron microscopy, hysteresis loop analyses, vibrating sample magnetometry and Mössbauer spectroscopy. Moreover, the frequency (up to 300 kHz) dependence of power losses and permeability at a magnetic induction up to 0.9 T was investigated. On the basis of some of the results obtained, we calculated the values of the activation energies and the induced magnetic anisotropies. The X-ray diffraction results confirm the surface crystallization effect previously observed for phosphorous-containing alloys. The in situ microscopic observations of crystallization describe this process in detail in accordance with the calorimetry results. Furthermore, the effect of Co content on the phase composition and the influence of annealing in an external magnetic field on magnetic properties, including the orientation of the magnetic spins, have been studied using various magnetic techniques. Finally, nanocrystalline Fe_64.5Co₂₀Nb₅B_8.5P₂ cores were prepared after transverse thermo-magnetic heat treatment and installed in industrially available portable heating equipment. Full article

The temperature dependence thermal conductivity of the indium-gallium-zinc oxide (IGZO) thin films was investigated with the differential three-omega method for the clear demonstration of nanocrystallinity. The thin films were deposited on an alumina (α-Al₂O₃) substrate by direct current (DC) magnetron sputtering at different oxygen partial pressures ([PO₂] = 0%, 10%, and 65%). Their thermal conductivities at room temperature were measured to be 1.65, 1.76, and 2.58 Wm⁻¹K⁻¹, respectively. The thermal conductivities decreased with an increase in the ambient measurement temperature. This thermal property is similar to that of crystalline materials. Electron microscopy observations revealed the presence of nanocrystals embedded in the amorphous matrix of the IGZO films. The typical size of the nanocrystals was approximately 2–5 nm with the lattice distance of about 0.24–0.26 nm. These experimental results indicate that the nanocrystalline microstructure controls the heat conduction in the IGZO films. Full article

Nano-crystallization is a new emerging strategy to promote the saturation solubility, dissolution rate and subsequent bioavailability of Biopharmaceutical Class II drugs. Capsaicin belongs to BCS class-II drugs having low water solubility and dissolution rate. Nano-crystals (NC) of pure Capsaicin was developed and optimized in order to increase its water solubility, dissolution and further to promote its adhesiveness to skin epidermis layer. NC formulations were subjected to stability studies, droplet size, surface charge, poly-dispensability index, drug content, entrapment efficiency, thermal analysis, surface morphology, crystalline studies, solubility profile, in vitro release and ex vivo permeation studies. In vivo anti-inflammatory assay (Carrageenan-induced paw edema) was performed in Sprague Dawley rats. Nanocrystals loaded with capsaicin showed particle size 120 ± 3.0 nm with surface charge of −20.7 ± 3.5 and PDI was 0.48 ± 1.5. Drug content and entrapment efficiency of T3 was 85% and 90 ± 1.9% respectively. Thermal studies predicted that melting peak of capsaicin was present in the formulation suggested that there was no interaction between active moieties and excipients in NC formulation. Surface morphology confirmed the presence of Nano-size crystals having rough crystalline surface. XRD proved that the capsaicin NC are successfully developed by using high speed homogenization. The solubility of capsaicin was found to be 12.0 ± 0.013 μg/mL in water. In vitro study revealed that 89.94 ± 1.9% of drug was released within 24 h. Similarly, drug permeation was 68.32 ± 1.83%, drug retained in skin was 16.13 ± 1.11% while drug retained on skin was 9.12 ± 0.14% after 12 h. The nanocrystals showed higher anti-inflammatory activity as compared to marketed product (Dicloran^®). The study concluded that improvement in dissolution rate of capsaicin may potentially provide the opportunities in the development of a much cost-effective dosage forms that will produce improved pharmacological effects, but at low dose as compared to the already available products. Full article

This review article presents recent studies on nanostructured glass-ceramic materials with substantially improved electrical (ionic or electronic) conductivity or with an extended temperature stability range of highly conducting high-temperature crystalline phases. Such materials were synthesized by the thermal nanocrystallization of selected electrically conducting oxide glasses. Various nanostructured systems have been described, including glass-ceramics based on ion conductive glasses (silver iodate and bismuth oxide ones) and electronic conductive glasses (vanadate-phosphate and olivine-like ones). Most systems under consideration have been studied with the practical aim of using them as electrode or solid electrolyte materials for rechargeable Li-ion, Na-ion, all-solid batteries, or solid oxide fuel cells. It has been shown that the conductivity enhancement of glass-ceramics is closely correlated with their dual microstructure, consisting of nanocrystallites (5–100 nm) confined in the glassy matrix. The disordered interfacial regions in those materials form “easy conduction” paths. It has also been shown that the glassy matrices may be a suitable environment for phases, which in bulk form are stable at high temperatures, and may exist when confined in nanograins embedded in the glassy matrix even at room temperature. Many complementary experimental techniques probing the electrical conductivity, long- and short-range structure, microstructure at the nanometer scale, or thermal transitions have been used to characterize the glass-ceramic systems under consideration. Their results have helped to explain the correlations between the microstructure and the properties of these systems. Full article