High-temperature X-ray Diffraction Research Articles

Unveiling the Influence of Water Molecules on the Structural Dynamics of Prussian Blue Analogues.

3D-framework Prussian blue analogues (PBAs) are appealing as a cost-effective, sustainable cathodes for Na-ion batteries. However, the aqueous-based synthesis of PBAs inherently introduces three different forms of water molecules (surface, interstitial and crystal) into the structure. Removal of water molecules causes phase transformation from monoclinic (M) to rhombohedral (R). This work presents the effects of water molecules on the structure before the phase transformation temperature, employing two promising PBA cathodes, Na2Fe[Fe(CN)6]·1.69H2O and Na2Mn[Fe(CN)6]·1.76H2O. Specifically, the water molecules impact the molecular interactions at the local structure and the electrochemical properties. This work has performed calculations on low-vacancy Na2M[Fe(CN)6] PBAs (where M = Mn, Fe, Co, Ni and Cu) to understand the dehydration energy. Employing in situ high-temperature X-ray diffraction and Raman spectroscopy, this work observes that water removal induces negative thermal expansion and stronger interactions between C≡N and Na ions, resulting in biphasic reactions with sluggish kinetics. Additionally, water molecules play a role in maintaining the open 3D tunnels and facilitating a solid-solution like insertion of Na ions. Calculated phonon-Raman spectra provide insights into cyanide group deformations, revealing the interactions between water molecules, alkali-ions, and transition-metal ions. This study enhances the understanding of the relationship among electronic, vibrational, and electrochemical properties.

High-temperature behaviour of fluorcarletonite, KNa4Ca4Si8O18(CO3)4(F,OH)⋅H2O, from the Murun Alkaline Complex, Russia, appraised by experimental and theoretical methods

Abstract The thermal behaviour of fluorcarletonite, KNa4Ca4Si8O18(CO3)4(F,OH)⋅H2O, from the charoitites of the Severny district at the Malyy Murun massif, Murun complex, NW Aldan Shield, Siberia, Russia, has been investigated in order to understand the temperature-induced changes in the crystal structure of this rare silicate. The study has been carried out combining in situ high-temperature single-crystal X-ray diffraction (T range 25–550°C), ex situ high-temperature Fourier-transform infrared spectroscopy (25–700°C) and ab initio calculations. An increasing trend of lattice parameters and cell volume was observed in the 150–550°C temperature range, when the mineral underwent a progressive dehydration process. At 550°C ~40% water loss was detected. If compared with the fluorcarletonite structure at room temperature, the partially dehydrated fluorcarletonite shows: the same space group (P4/mbm); increased distances between the oxygens of the H2O molecules (O11w and O12w) and their Na-centred octahedral cations (Na1 and Na2, respectively); distortion of the four- and six-member tetrahedral rings of the double silicate layer. The dehydration process mainly involves the oxygen at the O11w site which has a different local environment with respect to the oxygen at the O12w site. At T > 600°C, the complete dehydration is accompanied by deprotonation of the OH groups substituting for the F atoms and by the collapse of the structure when the CO2 is released. The adopted approach allowed definition of the temperature thresholds at which modifications occur in the fluorcarletonite crystal structure when subjected to controlled heating conditions. Our findings contribute to assessment of stability, reactivity and, more generally, the thermal behaviour of sheet silicates with fluorcarletonite-like topology.

Influence of reduced graphene oxide layer on sensing characteristics of Co3O4/rGO nanocomposite towards Liquefied Petroleum Gas (LPG)

Liquefied petroleum gas (LPG), a mixture of different hydrocarbons, is a highly inflammable and explosive gas that is harmful to the environment and human health. Thus, it is imperative to fabricate LPG sensors with higher sensitivity, selectivity, stability, and minimal power consumption, functioning at low temperatures. The current study reports on the monitoring and detection of LPG at low functional temperatures using Co3O4-loaded on rGO (rGO-Co) prepared using the hydrothermal method. The microstructural properties of the materials were investigated in detail. The rGO-Co (80 wt%) sensor showed outstanding sensitivity (0.00364 ppm−1) and selectivity toward LPG, as well as a limit of detection of 1 ppm at a temperature of 125 °C. The sensing mechanism showed that an even distribution of Co3O4 throughout the rGO layers, serving as efficient sites for the adsorption and desorption of LPG molecules, was associated with enhanced gas-sensing capabilities. Furthermore, the response to LPG detection was significantly influenced by the combination of the finite spherical nanoparticles with increased pore sizes between them and reduced energy band gaps. Thus, the novel improvement of the sensor towards LPG detection was linked to the ohmic connection formed between rGO and Co3O4 forming a p-p heterojunction at the interface. Additionally, the coupling of Co-O-C bonds validated by high-temperature X-ray diffraction and X-ray photoelectron spectroscopy provided extra active sites from Co3+ for effective LPG adsorption. The sensing mechanism induced by the loading of Co3O4 on the rGO surface was also deliberated.

Properties of cement raw meals used as sorbents in a calcium looping process

Calcium looping (CaL) is a promising carbon capture and storage (CCS) technology that has the potential to significantly reduce CO2 emissions in cement production. Integrating CaL with cement production provides a viable solution to the high CO2 emissions generated during the calcination process. This study examines the behavior of two industrial cement raw meals from different sites (A-RM and B-RM) under CaL conditions, focusing on phase composition, particle size distribution, and clinker phase evolution up to 1450 °C. Calcination and CaL experiments were conducted in a CO2-rich atmosphere, with materials characterized using quantitative X-ray diffraction (Q-XRD) and high-temperature X-ray diffraction (HT-XRD). The results showed that both raw meals absorbed similar amounts of CO2 during the cyclic CaL experiments. A-RM formed C2S and other silicates, while B-RM retained more free CaO due to a less effective reaction with coarser quartz (SiO2) particles. HT-XRD revealed delayed clinker-phase evolution in the 1000–1400 °C range in CaL-treated raw meals. However, CaL-treated raw meals achieved low free CaO at 1450 °C, suggesting that optimal kiln conditions can produce the desired phase composition. These findings indicate that integrating CaL-treated raw meals into cement production requires careful optimization of operational parameters to maintain clinker quality and minimize energy consumption. Further research should focus on improving the efficiency and reactivity of CaL-treated raw meals to enhance their suitability for industrial cement production.

Conversion of CO2(g) to CO(g) via reverse water–gas shift cycle on mixed cerium/praseodymium oxides at 500 °C

Reactions of cerium/praseodymium oxides under hydrogen atmospheres, and subsequently, carbon dioxide, involved in chemical looping reverse water–gas shift cycles (RWGS) at 500 °C were investigated by in-situ high-temperature X-ray powder diffraction, FTIR and thermogravimetry. The RWGS cycle is a critical chemical process for converting carbon dioxide into useful products, such as carbon monoxide, which can be used to synthesize fuels and chemicals. The mixed oxides exploit the redox properties of Ce and Pr, which can switch between oxidation states, making them suitable for oxygen incorporation and release during the RWGS process allowing them to react with H2(g), and subsequently with CO2(g), promoting their interaction and conversion into H2O(g) and CO(g). Pure cerium and praseodymium oxides showed poor CO2(g) conversion efficiency. However, we found that nanometric Ce/Pr mixed oxides exhibit enhanced oxyreduction performance suitable for this application, particularly with a composition of 75 mol% Ce and 25 mol% Pr, significantly improved performance, achieving an average CO(g) yield of 0.6 mmol/(goxide.cycle) and a maximum rate of 0.26 mmol/(goxide.min). Pr enhances oxygen mobility in CeO2, which improves the dissociation of C═O bonds in CO2(g). This is because the remaining oxygen atoms are delivered more quickly to the support sink, thereby cleaning up the vacant sites generated during the reduction step. These findings suggest that Ce/Pr mixed oxides are highly effective for CO2(g) conversion to CO(g) via RWGS cycle, offering a potentially viable option for industrial application.

Enhancement of Thermoelectric Performance through Transport Properties Decorrelation in the Quaternary Pseudo-Hollandite Chalcogenide Rb0.2Ba0.4Cr5Se8.

The novel quaternary compound Rb0.2Ba0.4Cr5Se8 was synthesized and characterized in both single crystal and polycrystalline forms. Crystallizing in the monoclinic crystal system (space group C2/m, cell parameters a = 18.7071(4) Å, b = 3.6030(1) Å, c = 8.9637(3) Å, β = 104.494(2)°) and isostructural to pseudo-hollandite compounds, it features mixed Rb and Ba occupancy within its one-dimensional channels. High-temperature X-ray diffraction revealed no decomposition up to 973 K, and the thermal expansion coefficient at 300 K was determined to be 2.6(1)·10-5 K-1. Spin-polarized density functional theory (DFT) calculations showed that the density of states for Rb0.2Ba0.4Cr5Se8 is more polarized than that of Ba0.5Cr5Se8, resulting in a higher Seebeck coefficient, which was experimentally confirmed to reach a peak value of 400 μV·K-1 at 620 K. Resistivity measurements indicated a degenerate semiconducting behavior below 550 K, with a resistivity peak of 100 mΩ·cm at that temperature, leading to a maximum power factor of 0.21 mW·m-1·K-2. Thermal conductivity measurements indicated low values around 0.8 W·m-1·K-1 in the 300-900 K range, resulting in a thermoelectric figure of merit of 0.22 at 873 K. Decorrelated transport properties observed in this double-inserted pseudo-hollandite compound make Rb0.2Ba0.4Cr5Se8 a good example of beneficial synergistic effects for higher thermoelectric performance.

Transient liquid phase bonding of Hastelloy X to Ni3Al intermetallic compound: Microstructure and phase transformation study

The microstructure of dissimilar transient-liquid-phase (TLP) bonding of Hastelloy X nickel base super alloy to Ni3Al intermetallic by AWS BNi2 filler metal at different temperatures (1000–1150 °C) and time ranges (60–180 min) was investigated. A novel study was done to correlate the phase transformation during bonding with microstructure and phase transformation using field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HR-TEM), and high temperature X-ray diffraction (HTXRD). Efforts were performed to correlate the phase transformation stages during isothermal solidification (IS), formation of Cr-Mo precipitates in diffusion affected zone (DAZ) and dissolution of nickel silicides (eutectic morphology) in athermal solidification zone (ASZ) with their respective reaction temperatures. The high tendency of Hastelloy X to react intensely with filler metal generated Mo-Cr rich phase in DAZ. The ISZ was developed across the joint area after holding at 1100 °C for 180 min. High temperature XRD results on half joint of HX revealed new phases generated at above 1050 °C including BNi2,BNi3, and Ni2Si (Ni-Si eutectic phase) confirmed by FESEM. On the other half joint (Ni3Al), no BNi phases were generated nor nickel silicides by increasing temperature as high as 1150 °C.

Melting Curve of Black Phosphorus: Evidence for a Solid-Liquid-Liquid Triple Point.

Black phosphorus (bP) is a crystalline material that can be seen as an ordered stacking of two-dimensional layers, which results in outstanding anisotropic physical properties. The knowledge of its pressure (P)-temperature (T) phase diagram, and in particular, of its melting curve is fundamental for a better understanding of the synthesis and stability conditions of this element. Despite the numerous studies devoted to this subject, significant uncertainties remain regarding the determination of the position and slope of its melting curve. Here we measured the melting curve of bP in an extended P, T region from 0.10(3) to 5.05(40) GPa and from 914(25) to 1788(70) K, using in situ high-pressure and high-temperature synchrotron X-ray diffraction. We employed an original metrology based on the anisotropic thermoelastic properties of bP to accurately determine P and T. We observed a monotonic increase of the melting temperature with pressure and the existence of two distinct linear regimes below and above 1.35(15) GPa, with respective slopes of 348 ± 21 and of 105 ± 12 K·GPa-1. These correspond to the melting of bP toward the low-density liquid and the high-density liquid, respectively. The triple point at which solid bP and the two liquids meet is located at 1.35(15) GPa and 1350(25) K. In addition, we have characterized the solid phases after crystallization of the two liquids and found that, while the high-density liquid transforms back to solid bP, the low-density liquid crystallizes into a more complex, partly crystalline and partly amorphous solid. The X-ray diffraction pattern of the crystalline component could be indexed as a mixture of red and violet P.

In Situ High‐Temperature X‐ray Diffraction Study of the Thermal Stability of the Co0.22Cr0.23Fe0.29Ni0.20Ti0.06 High‐Entropy Alloy Produced by High‐Energy Ball Milling

In this report, the effect of Ti addition on the phase evolution of a near‐equiatomic CoCrFeNi‐based high‐entropy alloy (HEA) during annealing in a vacuum is described. The HEA Co0.22Cr0.23Fe0.29Ni0.20Ti0.06 is synthesized through mechanical alloying of constituent elements for a milling duration of 1 h. The as‐prepared HEA is a two‐phase alloy containing body centred cubic (BCC) precipitates in an face centred cubic (FCC) matrix. The thermal stability of the HEA is experimentally studied by subjecting it to 5 h of isothermal annealing at 600, 800, and 1000 °C, using high‐temperature X‐ray diffraction (HTXRD). The HTXRD analysis indicates a noteworthy reduction in the BCC phase content after isothermal annealing at 600 °C. The formation of intermetallic σ‐phases does not occur. At temperatures of 800 and 1000 °C, the alloy matrix exhibits a single‐phase FCC solid solution. At 800 and 1000 °C, HEA undergoes partial oxidation, resulting in the formation of oxide phases on the surface and within the particles of the powder in the form of nanoscale inclusions. This oxidation depletes the metal matrix with titanium, leading to a change in the composition of the HEA. The alloy transforms into a CoCrFeNi solid solution containing 3–4 at% Ti. Thus, the alloy matrix phase remains a stable FCC solid solution.

Stabilization of δ-like Bi2O3 Phase at Room Temperature in Binary and Ternary Bismuthate Glass Systems with Al2O3, SiO2, GeO2, and B2O3.

Recently, it was shown that the nanocrystallization of Bi2O3 glasses with the addition of SiO2 and Al2O3 leads to the stabilization of the δ-like Bi2O3 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 SiO2, GeO2, B2O3, and Al2O3. 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 δ-Bi2O3 embedded in a residual glassy matrix down to room temperature. The temperature range of the appearance of the δ-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 δ-like Bi2O3 phase in the nanocrystallites.

Structure and Stability of Charge-Coupled Lanthanide-Substituted Ca10(PO4)6F2 as a Potential Fluoride Bearing Nuclear Waste Form.

The structure and stability of charge-coupled lanthanide-substituted Ca10(PO4)6F2 as a potential fluoride-bearing nuclear waste form for the back-end fuel cycle of Gen-IV molten salt reactor have been studied in detail. Here, calcium fluorapatite (CaFAp) as a model structure was taken for incorporation of trivalent lanthanides (Lns, La-Lu except Pm) in a charge-coupled fashion, i.e., 2Ca2+ = Na+ + Ln3+. In these fluorapatite phases, Na+ is substituted exclusively at nine coordinated sites, Ca1, while Ln3+ is preferentially substituted at seven coordinated sites, Ca2. These compositions are further characterized for the local structure by Fourier transform infrared (FTIR) and Raman spectroscopy. Thermal expansion was measured by high-temperature X-ray diffraction (XRD) and the instantaneous thermal expansion coefficient correlates well with the unsubstituted CaFAp. The heat capacities of these solids were measured by differential scanning calorimetry and drop calorimetry, whereas enthalpies of formation were obtained by high-temperature oxide melt solution calorimetry. The thermodynamic analysis demonstrated that lanthanides having ionic radii closure to Ca2+ (Sm3+ and Gd3+) imparted higher thermodynamic stability to the substituted CaFAp as compared to that of other Ln3+. According to structural and thermodynamic investigations, entropy-stabilized fluorapatite waste from NaPr0.125Nd0.125Sm0.125Eu0.125Gd0.125Tb0.125Dy0.125Ho0.125Ca8(PO4)6F2 (WF-Ln) was successfully synthesized for the first time. Furthermore, electron beam irradiation studies probed by XRD, FTIR, Raman, and X-ray absorption (XAS) spectroscopy implied the radiation resistance nature of this substituted CaFAps up to 20 MGy.

Alkali cation stabilization of defects in 2D MXenes at ambient and elevated temperatures

Transition metal carbides have been adopted in energy storage, conversion, and extreme environment applications. Advancements in their 2D counterparts, known as MXenes, enable the design of unique structures at the ~1 nm thickness scale. Alkali cations have been essential in MXenes manufacturing processing, storage, and applications, however, exact interactions of these cations with MXenes are not fully understood. In this study, using Ti3C2Tx, Mo2TiC2Tx, and Mo2Ti2C3Tx MXenes, we present how transition metal vacancy sites are occupied by alkali cations, and their effect on MXene structure stabilization to control MXene’s phase transition. We examine this behavior using in situ high-temperature x-ray diffraction and scanning transmission electron microscopy, ex situ techniques such as atomic-layer resolution secondary ion mass spectrometry, and density functional theory simulations. In MXenes, this represents an advance in fundamentals of cation interactions on their 2D basal planes for MXenes stabilization and applications. Broadly, this study demonstrates a potential new tool for ideal phase-property relationships of ceramics at the atomic scale.

Evolution of the Pd0/PdO phase change on Pd-MCM-41 catalyst for efficient production of furfural from the fast pyrolysis of cellulose

Furfural (C5H4O2) is a high-value platform chemical that is traditionally derived from the solvolysis of hemicellulose. However, its production from pyrolysis is far from satisfactory. In particular, the abundant cellulose within lignocellulosic biomass has yet to be successfully upgraded into furfural. Consequently, the overall yield of furfural from a lignocellulosic biomass is extremely low. Herein, we report a facile heterogeneous catalyst prepared from a simple impregnation of palladium (Pd) onto MCM-41 mesoporous silica. The catalyst demonstrated a remarkably high selectivity of ∼58.5% and yield of ∼32.5 wt% for furfural from the fast pyrolysis of wet cellulose. It was also confirmed to reach a selectivity of 65.4% and yield of 44.5 wt% for furfural from wet xylan, as well as a furfural yield of 23.9 wt% from wet sugarcane bagasse. All these values are superior to the literature reports. Through advanced characterisation including in-situ synchrotron high-temperature XRD and DRIFTS measurement, the loading of Pd in a tiny quantity of 1 mol% was confirmed to be sufficient in enhancing the surface hydrophilicity of the MCM-41 support, promoting the adsorption of reactants especially the formaldehyde group (HCHO), as well as the desorption of the target product furfural. In addition, Pd oxide (i.e., Pd2+O) was confirmed to be the catalytic active site. However, it was partly reduced into metallic Pd0 during the cellulose pyrolysis, due to the preferred reduction by adsorbed formaldehyde group and other reductants including H2 and CO in the vicinity of the PdO sites on the Pd-O-Si interface. Nevertheless, the catalyst was proven to retain the memory of its initial state after combustive regeneration in air, having oxidation state of Pd, particle size, and dispersion degree being reversed to its original construction. Accordingly, its activity remained stable upon cyclic testing. All these results demonstrate a high practical viability of this heterogenous catalyst for the valorisation of cellulose-rich biomass, an otherwise abundant crop waste across the world.

Desorption of humic monomers from Y zeolite: A high-temperature X-ray diffraction and thermogravimetric study

In this work, the thermal behaviour and kinetic modelling of p-hydroxybenzaldehyde (HBA) desorption was studied using both isothermal and non-isothermal methods from Y zeolite, to obtain a detailed structural and kinetic interpretation of the process. Rietveld refinement of in situ powder XRD patterns and TG analysis highlighted that the HBA thermal degradation occurred in the temperature range ∼530–750 K. This process significantly affects the geometry of the zeolite framework, thus causing a cooperative tilting of the tetrahedra and resulting in the deformation of both 6MRs and 12MRs rings. The HBA desorption experiment was also carried out in isothermal conditions at four different temperatures (473, 523, 623 and 673 K) which are selected on the basis of the relevant features from DTG/DTA curves. The value for the reaction order is nearly the same for all isothermal rates, providing strong confirmation of the validity of the reported apparent activation energy of the p-HBA decomposition process. The corresponding activation energy value (60.92 kJ/mol) agrees with literature data reported for dealuminated HZY (58 kJ/mol) and NaY.

High-Temperature Oxidation and Phase Stability of AlCrCoFeNi High Entropy Alloy: Insights from In Situ HT-XRD and Thermodynamic Calculations.

The high-temperature oxidation behaviour and phase stability of equi-atomic high entropy AlCrCoFeNi alloy (HEA) were studied using in situ high-temperature X-ray diffraction (HTXRD) combined with ThermoCalc thermodynamic calculation. HTXRD analyses reveal the formation of B2, BCC, Sigma and FCC, phases at different temperatures, with significant phase transitions observed at intermediate temperatures from 600 °C-100 °C. ThermoCalc predicted phase diagram closely matched with in situ HTXRD findings highlighting minor differences in phase transformation temperature. ThermoCalc predictions of oxides provide insights into the formation of stable oxide phases, predominantly spinel-type oxides, at high p(O2), while a lower volume of halite was predicted, and minor increase observed with increasing temperature. The oxidation behaviour was strongly dependent on the environment, with the vacuum condition favouring the formation of a thin, Al2O3 protective layer, while in atmospheric conditions a thick, double-layered oxide scale of Al2O3 and Cr2O3 formed. The formation of oxide scale was determined by selective oxidation of Al and Cr, as further confirmed by EDX analysis. The formation of thick oxide in air environment resulted in a thick layer of Al-depleted FFC phase. This comprehensive study explains the high-temperature phase stability and time-temperature-dependent oxidation mechanisms of AlCrCoFeNi HEA. The interplay between surface phase transformation beneath oxide scale and oxides is also detailed herein, contributing to further development and optimisation of HEA for high temperature applications.

Thermally enhanced luminescence and photoluminescence properties of green-emitting Lu2(1-x)Tb2x(WO4)3 phosphors

A series of Lu2(1-x)Tb2x(WO4)3 (x = 0.00–1.00) white powder materials were prepared by a high-temperature solid-phase method. The crystal structure, microscopic morphology, elemental composition, bandgap energy, photoluminescence properties, and thermal stability of luminescence of the prepared materials were analyzed and studied through room and high temperature X-ray diffraction patterns, field emission scanning electron microscopy images, energy energy-dispersive spectra and X-ray photoelectron spectra, diffuse reflectance spectra, room and high temperature photoluminescence spectra. Under 260 nm excitation, the green emitting Lu2(1-x)Tb2x(WO4)3 samples exhibited an optimum Tb3+ doping concentration at x = 0.30. Calculated results illustrate that the concentration quenching was mainly caused by dipole-dipole interaction. Lu1.98Tb0.02(WO4)3 phosphor exhibited thermally enhanced luminescence at 120 °C, with a maximum luminescence intensity of 254 % of the initial room temperature intensity. Lu1.4Tb0.6(WO4)3 phosphor exhibited thermally enhanced luminescence at 150 °C, with a maximum luminescence intensity of 109 % of the initial room temperature intensity. The mechanism of the thermally enhanced luminescence phenomenon is further discussed to be the adsorbed crystal water and the negative thermal expansion of the material. Thermally enhanced luminescence is of great significance in overcoming luminescent thermal quenching phenomenon, improving the luminescence efficiency, optimizing the material design, and so forth. It has potential applications in high-temperature lighting, display technology, temperature sensing, and optical anti-counterfeiting.

Thermal Behavior of Clinoptilolite

Understanding the thermal properties of zeolites is crucial for their industrial applications. This study explores the thermal stability and dehydration process of clinoptilolite using high-temperature X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Clinoptilolite’s thermal decomposition was monitored from 25 °C to 1200 °C, with results analyzed based on its crystal structure. Principal components analysis (PCA) of the DRIFT spectra indicated progressive water removal and dehydration upon heating, leading to the formation of hydrogen bonds. Thermogravimetric analysis (TGA) revealed a two-step endothermic weight loss: initially, physically adsorbed water was lost up to 100 °C, followed by the removal of tightly bound water and hydroxyl groups until 800 °C. Clinoptilolite remained the dominant phase up to 800 °C, after which albite and cristobalite took over. Rietveld refinement showed that the sample initially contained 70% clinoptilolite, 24% albite, and 6% cristobalite. Above 800 °C, clinoptilolite disappeared, leaving 93% albite and 7% cristobalite. FT-IR spectra changes due to water loss were evident: drying of adsorbed water occurred up to 75 °C and minimal changes were observed from 75 °C to 135 °C, followed by further dehydration until 240 °C. Complete dehydration was confirmed by the disappearance of OH stretching vibration bands by 395 °C, consistent with TGA findings.

New solvothermal flow synthesis of strontium titanate nanoparticles based on the use of acetylacetonate precursors in water/ethanol mixture

In this study, strontium titanate (SrTiO3) nanoparticles were obtained utilizing a one-step supercritical continuous solvothermal synthesis process involving acetylacetonate precursors for both strontium and titanium cations instead of the historical alkoxide ones. These precursors are expensive, difficult to access (especially for strontium isopropoxyde) and inadequately stable, forcing the use of a glove box and controlled atmospheres, which is not the case for acetylacetonates. Pure SrTiO3 nanoparticles with a crystallite size of roughly 20 nm were successfully synthesized. In addition to the cubic structure of SrTiO3, FTIR revealed surface functions that are typical of "wet" processes, while Raman spectroscopy showed the activation of non-centrosymmetric modes brought on by non-linear contributions. The nanoparticles show a faceted shape and are stable at elevated temperatures (up to 800 °C), according to in-situ high temperature XRD measurements. However, due to a chemical deficiency in strontium, titanium dioxide (TiO2) phases are formed at higher temperatures. In-situ high temperature HRTEM investigations showed the existence of two populations of particles, with a better stability for the bigger-sized particles after thermal treatment as well as the sintering and restructuring of the smallest ones. Also, the microscopy results suggest the possibility of a chemical inhomogeneity within the crystallites. Overall, this study offers important new knowledge on the physicochemical characteristics of the synthesized SrTiO3 nanoparticles and their thermal stability using a novel supercritical continuous solvothermal approach based on the use of acetylacetonate precursors.

3D Confinement Stabilizes the Metastable Amorphous State of Antimony Nanoparticles - A New Material for Miniaturized Phase Change Memories?

The wet-chemical synthesis of 3D confined antimony nanoparticles (Sb-NP) at low and high temperatures is described. Using reaction conditions that are mild in temperature and strong in reducing power allows the synthesis of amorphous Sb-NP stabilized with organic ligands. Exchanging the organic ligand 1-octanethiol by iodide enabled to investigate the unusual strong stability of this metastable material through simultaneous thermal analysis combining differential scanning calorimetry and thermogravimetric analysis. Additionally, in situ high temperature powder x-ray diffraction (p-XRD) shows a significant increase in stabilization of the amorphous phase in comparison to thin layered, 1D confined Sb or bulk material. Further, it is shown with scattering-type scanning near-field optical microscopy (s-SNOM) experiments that the optical response of the different phases in Sb-NP make the distinctness of each phase possible. It is proposed that the Sb-NP introduced here can serve as a 3D-confined optically addressable nanomaterial of miniaturized phase change memory devices.

Identification of different WO3 modifications in thin films for photocatalytic applications by peak shape analysis in high temperature XRD diffractometry

Until now, the structural analysis of WO3 films has been insufficient. The similar peak positions of the possible crystalline phases make a precise differentiation difficult or even impossible. In particular, the presence of possible mixed phases is difficult to determine. However, the exact determination of the crystalline phases would be important for use as a photocatalyst, as these phases and also their mixtures may have an effect on the photocatalytic properties.The identification of the monoclinic (P21/n), orthorhombic (Pbcn) and triclinic (P1¯) components at room temperature seems to be of particular interest. By heating WO3 films before cooling them to room temperature, a broadening of the diffraction peaks was observed, which can be associated with phase transformations. By following these peak broadenings, individual phases of WO3 could be identified and the progression of mixed phases could be visualized. By avoiding a delamination process, which can occur at high temperatures, and an adapted heating strategy, it should be possible to identify different crystalline phases of WO3 films at room temperature after calcination.