X-ray Diffraction Measurements Research Articles

Mechanochemical Synthesis of Resveratrol-Piperazine Cocrystals.

The 1:1 resveratrol-piperazine cocrystal was successfully synthesized and scaled-up to 300 g scale with the mechanochemical method, as a result of investigating key process parameters, namely the solvent and the grinding time. The use of water, ethanol or ethanol-water mixtures and reaction times up to 50 min were evaluated relative to the dry grinding process. Cocrystal formation and purity were monitored through X-ray diffraction and calorimetry measurements. The dry grinding resulted in an incomplete cocrystal formation, while the use of water or water-ethanol mixture yielded a monohydrate solid phase. Pure ethanol was found to be the optimal solvent for large-scale cocrystallization, as it delivered cocrystals with high crystallinity and purity after 10-30 min grinding time at the laboratory scale. Notably, a relatively fast reaction time (30-60 min) was sufficient for the completion of cocrystallization at larger scales, using a planetary ball mill and a plant reactor. Also, the obtained cocrystal increases the aqueous solubility of resveratrol by 6%-16% at pH = 6.8. Overall, this study highlights the potential of solvent-assisted mechanochemical synthesis as a promising new approach for the efficient production of pure resveratrol-piperazine cocrystals.

Synthesis and Properties of the Helium Clathrate and Defect Perovskite [He2-x □ x ][CaNb]F6.

The defect double perovskite [He2-x □ x ][CaNb]F6, with helium on its A-site, can be prepared by the insertion of helium into ReO3-type CaNbF6 at high pressure. Upon cooling from 300 to 100 K under 0.4 GPa helium, ∼60% of the A-sites become occupied. Helium uptake was quantified by both neutron powder diffraction and gas insertion and release measurements. After the conversion of gauge pressure to fugacity, the uptake of helium by CaNbF6 can be described by a Langmuir isotherm. The enthalpy of absorption for helium in [He2-x □ x ][CaNb]F6 is estimated to be ∼+3(1) kJ mol-1, implying that its formation is entropically favored. Helium is able to diffuse through the material on a time scale of minutes at temperatures down to ∼150 K but is trapped at 100 K and below. The insertion of helium into CaNbF6 reduces the magnitude of its negative thermal expansion, increases the bulk modulus, and modifies its phase behavior. On compressing pristine CaNbF6, at 50 and 100 K, a cubic (Fm3̅m) to rhombohedral (R3̅) phase transition was observed at <0.20 GPa. However, a helium-containing sample remained cubic at 0.4 GPa and 50 K. CaNbF6, compressed in helium at room temperature, remained cubic to >3.7 GPa, the limit of our X-ray diffraction measurements, in contrast to prior reports that upon compression in a nonpenetrating medium, a phase transition is detected at ∼0.4 GPa.

Annealing-Tunable Charge Density Wave in the Magnetic Kagome Material FeGe.

The unprecedented phenomenon that a charge density wave (CDW) emerges inside the antiferromagnetic (AFM) phase indicates an unusual CDW mechanism associated with magnetism in FeGe. Here, we demonstrate that both the CDW and magnetism of FeGe can be effectively tuned through postgrowth annealing treatments. Instead of the short-range CDW reported earlier, a long-range CDW order is realized below 110K in single crystals annealed at 320 °C for over 48h. The CDW and AFM transition temperatures appear to be inversely correlated with each other. The onset of the CDW phase significantly reduces the critical field of the spin-flop transition, whereas the CDW transition remains stable against minor variations in magnetic orders such as annealing-induced magnetic clusters and spin-canting transitions. Single-crystal x-ray diffraction measurements reveal substantial disorder on the Ge1 site, which is characterized by displacement of the Ge1 atom from the Fe_{3}Ge layer along the c axis and can be reversibly modified by the annealing process. The observed annealing-tunable CDW and magnetic orders can be well understood in terms of disorder on the Ge1 site. Our study provides a vital starting point for the exploration of the unconventional CDW mechanism in FeGe and of kagome materials in general.

Growth of high quality polycrystalline InGaO thin films by spray pyrolysis for coplanar thin-film transistors on polyimide substrate

The current mobile devices are moving towards flexible electronics. Introducing crystalline oxide semiconductors on flexible substrates is important to satisfy the requirements of high-resolution displays on flexible substrates. This study investigates the low-cost, as-grown polycrystalline (Poly) InGaO thin film transistor by spray pyrolysis on polyimide (PI) substrate. Grazing Incidence X-ray Diffraction (GI-XRD) measurements demonstrate that In0.8Ga0.2O, In0.7Ga0.3O, and In0.5Ga0.5O compositions exhibit crystallization on-set temperatures of ∼330, ∼350, and ∼415°C, respectively. Poly-In0.7Ga0.3O thin film with lower oxygen-vacancy (∼15 %) and less than 5 % O-H group could be achieved at the substrate temperature of 370°C. The hysteresis-free device performance with an average saturation mobility of 43.73 cm2V−1s−1 has been obtained using the poly-In0.7Ga0.3O with optimized N2O plasma treatment on the poly-oxide thin film. The TFTs show remarkable stability under humid environments and various stress conditions such as positive bias temperature, negative bias temperature, and mechanical stresses. In addition, the 96-stage gate shift register made of poly-In0.7Ga0.3O TFTs by spray pyrolysis exhibits the rising and falling times of less than 820 ns. Therefore, the poly-In0.7Ga0.3O TFTs by spray pyrolysis could be used for high-resolution, cost-effective, flexible active-matrix light-emitting displays.

Growth of AlGaN alloys with ∼ 90 % AlN mole fraction by plasma-assisted molecular beam epitaxy: Indication of phase-segregation effects

AlGaN alloys with very high AlN mole fraction (∼90 %) were grown by plasma-assisted molecular beam epitaxy (PA-MBE) and their alloy properties were investigated by high-resolution X-ray diffraction (HR-XRD) measurements. Growth was carried out employing a series of group III/V ratios and for samples grown under a high group-III regime, phase-segregation in the alloy was evident from a characteristic splitting of the AlGaN (0002) peak in the HR-XRD pattern. With decreasing excess group-III conditions the separation of peak positions continuously reduced, till a single peak was observed. However, for samples where such splitting was absent, spontaneous superlattice peaks were seen at lower incident angles of the XRD patterns indicating the presence of long-range atomic ordering (LRAO). Thus, for AlGaN alloys with extremely high Al content, effects of phase-segregation, or of LRAO were observed, depending on the kinetics of growth. These results on phase-segregation effects are expected to promote the development of high-efficiency deep ultraviolet emitters for skin-safe germicidal action by mitigating the detrimental effect of dislocations and related non-radiative recombination centers through carrier localization processes at potential minima.

Radiation-Induced Synthesis and Superparamagnetic Properties of Ferrite Fe3O4 Nanoparticles.

Ultra-small magnetic Fe3O4 nanoparticles are successfully synthesized in basic solutions by using the radiolytic method of the partial reduction in FeIII in the presence of poly-acrylate (PA), or by using the coprecipitation method of FeIII and FeII salts in the presence of PA. The optical, structural, and magnetic properties of the nanoparticles were examined using UV-Vis absorption spectroscopy, high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and SQUID magnetization measurements. The HRTEM and XRD analysis confirmed the formation of ultra-small magnetite nanoparticles in a spinel structure, with a smaller size for radiation-induced particles coated by PA (5.2 nm) than for coprecipitated PA-coated nanoparticles (11 nm). From magnetization measurements, it is shown that the nanoparticles are superparamagnetic at room temperature. The magnetization saturation value Ms = 50.1 A m2 kg-1 of radiation-induced nanoparticles at 60 kGy is higher than Ms = 18.2 A m2 kg-1 for coprecipitated nanoparticles. Both values are compared with nanoparticles coated with other stabilizers in the literature.

Unraveling the Irreversible Storage of Dimethyl Carbonate-Solvated Hexafluorophosphate Anions in Graphite Electrode.

LiPF6 dissolved in dimethyl carbonate (DMC) is one of the cheapest groups of electrolyte solutions in dual-ion batteries. Generally, the discharge capacity of anion storage delivered by the graphite cathode grows with increasing LiPF6 concentration. This fact is consistent with the irreversible storage of DMC-solvated PF6-, and then, the underlying mechanism is clarified by the electrochemical tests and ex situ X-ray diffraction (XRD) measurements of graphite cathodes as well as infrared (IR) and Raman spectroscopy characterizations of solutions. Moreover, quaternary ammonium salts have facile dissociation, which can effectively regulate the solvation state of the anion and the interaction between ion pairs in the electrolyte. A small amount of tetrabutylammonium hexafluorophosphate (TBAPF6) is introduced into the highly concentrated LiPF6-DMC solution to improve the performance of the graphite cathode. The discharge capacity of the Li/graphite cell has increased by approximately 50%. This effect is also correlated with the solvation state of the anion. This study provides an insightful clue for the choice of electrolyte solution in dual-ion batteries.

Impact of Temperature Optimization of ITO Thin Film on Tandem Solar Cell Efficiency.

This study examined the impact of temperature optimization on indium tin oxide (ITO) films in monolithic HJT/perovskite tandem solar cells. ITO films were deposited using magnetron sputtering at temperatures ranging from room temperature (25 °C) to 250 °C. The sputtering target was ITO, with a mass ratio of In2O3 to SnO2 of 90% to 10%. The effects of temperature on the ITO film were analyzed using X-ray diffraction (XRD), spectroscopic ellipsometry, and sheet resistance measurements. Results showed that all ITO films exhibited a polycrystalline morphology, with diffraction peaks corresponding to planes (211), (222), (400), (440), and (622), indicating a cubic bixbyite crystal structure. The light transmittance exceeded 80%, and the sheet resistance was 75.1 Ω/sq for ITO deposited at 200 °C. The optical bandgap of deposited ITO films ranged between 3.90 eV and 3.93 eV. Structural and morphological characterization of the perovskite solar cell was performed using XRD and FE-SEM. Tandem solar cell performance was evaluated by analyzing current density-voltage characteristics under simulated sunlight. By optimizing the ITO deposition temperature, the tandem cell achieved a power conversion efficiency (PCE) of 16.74%, resulting in enhanced tandem cell efficiency.

Growth of Size-Tunable Ag2O Polyhedra and Revelation of Their Bulk and Surface Lattices.

By primarily adjusting the reagent amounts, particularly the volume of AgNO3 solution introduced, Ag2O cubes with decreasing sizes from 440 to 79 nm, octahedra from 714 to 106 nm, and rhombic dodecahedra from 644 to 168 nm are synthesized. 733 nm cuboctahedra are also prepared for structural analysis. With in-house X-ray diffraction (XRD) peak calibration, shape-related peak shifts are recognizable. Synchrotron XRD measurements at 100 K reveal the presence of bulk and surface layer lattices. Bulk cell constants also deviate slightly. They show a negative thermal expansion behavior with shrinking cell constants at higher temperatures. The Ag2O crystals exhibit size- and facet-dependent optical properties. Bandgaps red-shift continuously with increasing particle sizes. Optical facet effect is also observable. Moreover, synchrotron XRD peaks of a mixture of Cu2O rhombicuboctahedra and edge- and corner-truncated cubes exposing all three crystal faces can be deconvoluted into three components with the bulk and the [111] microstrain phase as the major component. Interestingly, while the unheated Cu2O sample shows clear diffraction peak asymmetry, annealing the sample to 450 K yields nearly symmetric peaks even when returning the sample to room temperature, meaning even moderately high temperatures can permanently change the crystal lattice.

Analysis of high temperature phase transformation behavior of ultra-low-carbon steel using X-ray topography, diffraction, and synchronized temperature measurement

Despite the technical importance of δ/γ phase transition in steel alloys, conventional thermal analysis techniques like calorimetry lack precise kinetics measurement. This study introduces an integrated approach combining X-ray topographic imaging, diffraction, and precise temperature measurement to overcome these limitations. This methodology allows for the accurate quantification of recalescence due to release of latent heats from solidification and solid-state phase transformation. It also enables tracking of the fractional volume changes of the δ phase during continuous cooling. We demonstrate that in Ultra-Low Carbon steels, the δ to γ transformation occurs rapidly in the single γ phase region far below the solidus temperature in the phase diagram, and this transformation accelerates further in the higher cooling rate. Furthermore, it can be inferred that in phase transformation, its rate becomes a critical factor in the temperature increase resulting from the released latent heat, overshadowing the influence of undercooling during continuous cooling.

Synchrotron radiation excited luminescence of Eu, Er, and Tm codoped β-Ga2O3 thin film

Ga2O3 thin film with Eu, Er, and Tm codoping was prepared on Si substrate by pulsed laser deposition. The obtained codoping film has a monoclinic Ga2O3 structure identified by X-ray diffraction and Raman measurements. The excitation wavelength-dependent photoluminescence measurements were performed using synchrotron radiation sources with photon energies both below and above bandgap. Moreover, temperature-dependent PL measurements were carried out from 30 to 300 K to systematically investigate the PL characteristics of codoped Eu3+, Er3+, Tm3+ ions in the Ga2O3 film. Typical luminescent bands originating from Eu3+, Er3+, and Tm3+ dopants were concurrently observed in the PL spectra. The codoping film emits a near purple light when it was excited at 30 K, which gradually shifts to the orange region as the temperature rises to 300 K. This color evolution results from different quenching rates of Eu3+, Er3+, and Tm3+ dopants with the increase of temperature. These findings provide a solid foundation for Si-compatible full-color displays using RE doped Ga2O3.

Development of a laser-driven shock compression platform for time-resolved XRD experiments at the ID09 beamline of the European Synchrotron Radiation Facility

ABSTRACT We present a newly developed laser-driven shock compression platform at the ID09 beamline of the European Synchrotron Radiation Facility (ESRF). This platform combines a custom high-power EKSPLA laser with ESRF's high-energy X-ray pulses to perform in situ, time-resolved X-ray diffraction (XRD) measurements in materials under well characterized, moderate pressure (up to 1 Mbar) and short-duration shock waves. Its purpose is to serve as a shock driver to study materials under dynamic pressure, focusing on phase transitions in condensed matter. We provide a detailed description of this platform's design and functionalities, along with preliminary experimental results obtained from iron and tin samples subjected to shock compression. These results not only demonstrate the platform's ability to acquire high-quality X-ray diffraction data but also highlight its potential for advancing research in material science and high-energy-density physics.

Synthesis, disorder and Ising anisotropy in a new spin liquid candidate PrMgAl11O19

Here we report the successful synthesis of large single crystals of triangular frustrated PrMgAl11O19 using the optical floating zone technique. Single crystal x-ray diffraction (XRD) measurements unveiled the presence of quenched disorder within the mirror plane, specifically ~7% of Pr ions deviating from the ideal 2d site towards the 6h site. Magnetic susceptibility measurements revealed an Ising anisotropy with the c-axis being the easy axis. Despite a large spin–spin interaction that develops below ~10 K and considerable site disorder, the spins do not order or freeze down to at least 50 mK. The availability of large single crystals offers a distinct opportunity to investigate the exotic magnetic state on a triangular lattice with an easy axis out of the plane.

STRUCTURAL, MAGNETIC AND MAGNETOCALORIC PROPERTIES OF La0.7Sr0.2Ba0.1MnO3 MANGANITE

In this present work, the structural, magnetocaloric and magnetic properties of La0.7Sr0.2Ba0.1MnO3 (LSBM) manganite were investigated. The material was synthesized using the sol-gel method and X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM) devices were used to analyze structural properties such as crystal structure and surface morphology. XRD measurement revealed that the crystal structure of LSBM manganite is hexagonal. Based on the magnetic measurements, the TC value of La0.7Sr0.2Ba0.1MnO3 manganite compounds was calculated as 362 K. The ∆SM value of sample is established as 2.79 Jkg-1K-1 in an applied magnetic field of 5T. Arrott curves revealed that the phase transition was second order.

Intelligent double-layer film based on gellan gum/modified anthocyanin/curcumin/sodium alginate/zinc oxide for monitoring shrimp freshness

In this study, intelligent double-layer films were prepared using modified black rice anthocyanin (MBRA)-curcumin (CUR)-gellan gum (GG) as the inner indicator layer and sodium alginate (ALG)‑zinc oxide (ZnO) as the outer antimicrobial layer. The bilayer films were successfully prepared, as revealed by scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction measurements. The mechanical characteristics, moisture content, and water vapor resistance of GG-MBRA/CUR1@ALG-ZnO, GG-MBRA/CUR2@ALG-ZnO, and GG-MBRA/CUR3@ALG-ZnO films showed significant enhancement compared to GG-MBRA/CUR3 and ALG-ZnO films. The bilayer films exhibited excellent pH responsiveness and reacted effectively to ammonia. The outer layer significantly improved the antioxidant and antibacterial properties of the inner layer. When the films were applied to shrimp, it was found that the double-layer films not only monitored the freshness of the shrimp in real-time but also were influential in extending the shelf life of the shrimp by about 1 d. Therefore, the double-layer film demonstrated potential as a smart packaging material for real-time monitoring of meat product freshness.

A new concept of ternary aqueous electrolytes based on lithium 4,5-dicyanoimidazolate hydrates

A new concept of aqueous electrolytes based on heterocyclic anions (hydrated anionic triplet electrolyte, HATE) has been presented. Structural studies showed that dimeric lithium 4,5-dicyanoimidazolate (LiTDI) dihydrate molecules, in the presence of acetonitrile, form an ionic system preserved in high concentrations and solid states. X-ray diffraction measurements show that electroneutral dihydrate units can coordinate additional lithium cations acting as charge carriers. The crystalline ionic phase was characterized using spectroscopic, thermal, and electrochemical methods and was used to prepare model electrolytes based on LiTDI hydrates. Linear sweep voltammetry and impedance spectroscopy measurements show, in this system, the depletion of water activity, high conductivity, and reversible cycling of full cells comprising examined electrolytes. We will prove that a concentrated triplet solution acts similarly to the anhydrous electrolyte; regardless of the concentration, it reaches high ionic conductivity values (12–16 mS/cm at room temperature) and is electrochemically stable.

Synthesis and dual sensing of vanadium and copper ions using protein capped selenium nanoparticles

Highly homogenous and spherical shaped Selenium nanoparticles with an average size of 20 nm were synthesized from an eco-friendly and environmentally safe approach using bovine milk protein casein as stabilizing agent (named as CasSeNPs). Protein functionalization provided excellent stability at variable temperatures (25–60 °C), pH (8–10), ionic strength (0.05–2 M), and storage period for more than five months. Synthesized CasSeNPs were extensively characterized using various spectroscopic (UV–visible, Fourier transform infrared (FTIR), circular dichroism (CD), intrinsic fluorescence spectroscopy), particle sizing (dynamic light scattering (DLS) and zeta potential), microscopic (scanning electron microscopy, energy dispersive X-ray spectroscopy (SEM/EDS), atomic force microscopy (AFM)), and X-ray diffraction (XRD) measurements. Moreover, CasSeNPs was established as highly sensitive and selective sensor for the simultaneous detection of vanadium (V+2) and copper (Cu+2) ions with significant linearity (0.5–10 and 0.1–1.0 µM, respectively), detection limits (LOD = 0.03 and 0.067 µM, respectively), and percent recoveries (94–105 %) in real environmental (tap water) and biological (human plasma and urine) samples with adequate test performance. Cumulatively, obtained results revealed that the established very simple, biocompatible and economical nanosensor has great potential for applications in analytical chemistry as well as for biological investigations.

Oxidized Graphite Nanocrystals for White Light Emission

We investigated the formation of graphite nanocrystals covered with graphite oxide for white light generation. The nanoparticles were formed using cost-efficient oxidation of a carbon-based dye pigment at different temperatures and verified using X-ray diffraction and Raman measurements. Formation of the graphite nanoparticles via thermal annealing was observed, while their light emission increased at higher oxidation temperatures. This was associated with a higher amount of oxygen defect groups. The time-resolved photoluminescence measurements showed linearly faster decays at shorter wavelengths and similar decays at different annealing temperatures. Broadband and linear vs. excitation emission spectra of the particles were found to be suitable for white-light-emitting devices and phosphor markers. The fast photoluminescence decay opens the possibility for the application of nanoparticles in optical wireless communication technology.

Catalytic activity of TiO2 nanoparticles in cyclization reactions for pyrazolone formation: DNA binding analysis via spectroscopy, X-ray crystallography, and molecular docking

This method of sustainable synthesis utilizes a range of aromatic/heterocyclic aldehydes, phenylhydrazine, and ethyl acetoacetates. The TiO2 nanoparticle catalyst facilitates cyclization reactions, yielding pyrazolone derivatives with exceptional efficiency (95–97 %) under reflux conditions at 80 °C. The current method achieves high yields of the corresponding cyclo-products in a short reaction time. A variety of physicochemical methods were employed to ascertain the chemical characteristics and structure of the synthesized heterocycles, and the geometrical structure of the well-crystallized compound (Z)-4-((5-bromofuran-2-yl)methylene)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one was characterized by the use of single-crystal X-ray diffraction measurement. The morphology and elemental composition of TiO2 nanoparticles were examined using SEM/EDX before and after the model reaction. A drop in the Ti (titanium) signal following the reaction indicates surface alterations. The present process provides a new and improved synthesis process for the formation of pyrazolones that is more convenient, well organized in terms of good yields, a simple handling procedure, a short reaction time, and user-friendliness compared to other surviving procedures. One of the synthesized compounds, (Z)-4-((5-bromofuran-2-yl)methylene)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (2), exhibited significant DNA binding activity. This was further confirmed by a molecular docking study, which revealed a binding energy of −7.2 kcal/mol, and by analyzing the mode of interaction.

Lanthanide-Containing Polyoxometalate Crystallized with Bolaamphiphile Surfactants as Inorganic–Organic Hybrid Phosphors

Lanthanide elements such as europium exhibit distinctive emissions due to the transitions of inner-shell 4f electrons. Inorganic materials containing lanthanide elements have been widely used as phosphors in conventional displays. The hybridization of lanthanide ions with organic components enables to control of the material’s shapes and properties and broadens the possibility of lanthanide compounds as inorganic–organic materials. Lanthanide ion-containing polyoxometalate anions (Ln-POM) are a promising category as an inorganic component to design and synthesize inorganic–organic hybrids. Several inorganic–organic Ln-POM systems have been reported by hybridizing with cationic surfactants as luminescent materials. However, single-crystalline ordering has not been achieved in most cases. Here, we report syntheses and structures of inorganic–organic hybrid crystals of lanthanide-based POM and bolaamphiphile surfactants with two hydrophilic heads in one molecule. An emissive decatungstoeuropate ([EuW10O36]9−, EuW10) anion was employed as a lanthanide source. The bolaamphiphile counterparts are 1,8-octamethylenediammonium ([H3N(CH2)8NH3]2+, C8N2) and 1,10-decamethylenediammonium ([H3N(CH2)10NH3]2+, C10N2). Both hybrid crystals of C8N2-EuW10 and C10N2-EuW10 were successfully obtained as single crystals, and their crystal structures were unambiguously determined using X-ray diffraction measurements. The photoluminescence properties of C8N2-EuW10 and C10N2-EuW10 were investigated by means of steady-state and time-resolved spectroscopy. The characteristic emission derived from the EuW10 anion was retained after the hybridization process.