X-ray Diffraction Measurements Research Articles

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.

Sintering of Platinum-Containing Conjugated Polymers: Gas Adsorption and Catalysis of the Formed Pt-Carbon Composites.

Pt-containing meta- and para-linked poly(phenyleneethynylene)s were synthesized by the dehydrochlorination coupling polymerization of PtCl2(PBu3)2 with m- and p-diethynylbenzenes. The formed polymers were sintered at 900 °C to obtain Pt-graphene hybrids, whose structures were examined by Raman scattering spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) measurements. Shapes─facets, terraces, and steps─with average diameters of 2.0-3.4 μm were observed by field emission scanning electron microscopy (FE-SEM). The Pt-graphene hybrids moderately adsorbed CO2 and O2 and slightly adsorbed ethylene and methane. Epoxidation of stilbene was carried out using Pt-graphene hybrids as catalysts to obtain stilbene oxide.

Laboratory investigation on inhibition of polyvinyl alcohol used for wireline coring drilling

AbstractTo address the problems of wall collapse, cuttings slurrying, and scaling on the inner wall of the drill pipe, which often occur in small-diameter diamond wireline core drilling, the inhibition properties of polyvinyl alcohol (PVA) was investigated, and the formulation of solids-free drilling fluid with PVA as the inhibitor were completed. PVA has the advantages of fast adsorption and easy regulation of rheological properties Firstly the inhibition effect of PVA was compared with that of common inorganic salts (sodium chloride, NaCl, potassium chloride, KCl) by bentonite dispersion test, linear swelling test, shale rolling recovery test and mud ball immersion test in this study. Then, the inhibition mechanism of PVA was analyzed with potentiometric particle size tests, Fourier transform infrared (FT-IR) and X-ray Diffraction (XRD) measurements. Based on the outstanding inhibition performance of PVA, tackifiers and filtration reducers were preferred through the compatibility test. And finally, the effects of various contaminants on the comprehensive performance of the formulated solids-free drilling fluids were evaluated. The results showed that PVA exhibited better inhibition of clay hydration and dispersion in shale recovery and linear swelling compared to NaCl and KCl, which was particularly evident in the mud ball immersion test. FT-IR and XRD tests revealed that the inorganic salts were used to replace the cations with larger radius and high degree of hydration in the clay layer by ion exchange ti achieve the effect of clay de-watering by reducing the spacing of the clay interlayer and the electrostatic repulsion between the particles. However, PVA is strongly adsorbed on the clay surface in the form of hydrogen bonds due to its unique multi-hydroxyl chain structure, forming a hydrophobic barrier to prevent water molecules from entering the clay layer, thus inhibiting the hydration and swelling of the clay. Using PVA as an inhibitor, compounded with xanthan gum, sulfonated lignite resin and sulfonated gilsonite (FT-1), the solids-free drilling fluid is promising for use in diamond wireline core drilling in complex formations.

Coevolution of superconductivity and Hall coefficient with anisotropic lattice shrinkage in compressed KCa2Fe4As4F2

Abstract It is well known that the stability of superconductivity in superconductors is widely recognized to be determined by various factors, including charge, spin, orbit, lattice, and other related degrees of freedom. Here, we report our findings on the pressure-induced coevolution of superconductivity and Hall coefficient in KCa2Fe4As4F2, an iron-based superconductor possessing a hybrid crystal structure combining KFe2As2 and CaFeAsF. Our investigation, involving high-pressure resistance, Hall effect and X-ray diffraction (XRD) measurements, allows us to observe the connection of the superconductivity and Hall coefficient with the anisotropic lattice shrinkage. We find that its ambient-pressure tetragonal (T) phase presents a collapse staring at around 18 GPa, where the sign of the Hall coefficient (R H ) changes from positive to negative. Upon further compression, both superconducting transition temperature (Tc) and R H exhibit a monotonous decrease. At around 41 GPa, the superconductivity is completely suppressed (T c =0), where the parameter a begins to decline again and the Hall coefficient remain nearly unchanged. Our experiment results clearly demonstrate that the pressure-induced anisotropic lattice collapse plays a curial role in tuning the interplay among multiple degrees of freedom in the superconducting system and, correspondingly, the stability of the superconductivity.

C54-TiSi2 formation using nanosecond laser annealing of A-Si/Ti/A-Si stacks

Low resistive Ti-based contacts are required to reach the targeted performances of 3D imaging devices. To fulfill this request, the C54-TiSi2 phase appears to be the most efficient. However, in view of monolithic integration, the temperature needed to form C54-TiSi2 must be drastically reduced by at least 100 °C in order to avoid damage in other parts of the device. Indeed, as these 3D imaging devices require the co-integration of Ti and Ni based silicides, it is crucial to develop a thermal treatment which allows to form the C54-TiSi2 phase without agglomerating the NiSi layer (i.e. at temperatures lower than 600 °C). In this work, a three-layer stack made of a Ti layer in between two amorphous Si thin films deposited on (100) Si substrate has been studied. Nanosecond laser annealing (NLA) followed by rapid thermal annealing (RTA) from 500 to 800 °C were performed on those stacks. Sheet resistance and X-Ray Diffraction measurements showed that the C54-TiSi2 phase could be formed with a RTA treatment at a temperature as low as 600 °C in this case. In line with some previous work, this was due to another phase sequence involving the C40-TiSi2 during the laser annealing. The most favorable microstructure to form C54-TiSi2 by a subsequent RTA treatment seemed to be a matrix made of amorphous titanium silicide containing grains of the C40-TiSi2 template phase. This hypothetical microstructure was formed by laser annealing at a lower energy density when layers of amorphous Si were used.

An approach for identifying the deformation-induced strain from tensile tests and x-ray diffraction measurements

ABSTRACT Non-uniform plastic deformation and phase transformation introduce residual stress (RS) in a material. The present study focuses on the influence of tensile strain on RS development in 304L austenitic stainless steel, wherein strain-induced martensite (SIM) transformation influences deformation behaviour. Room temperature tensile tests were interrupted at various tensile strains between the material yield and ultimate tensile strength at 5.21 × 10−4 and 1.3 × 10−2 s−1 strain rates. Microstructural characterisation of as-received and deformed samples by electron backscatter diffraction provides evidence of SIM formation and shear bands. Analysis of tensile flow and work hardening behaviour is discussed in correlation to the microstructural and dislocation density variations. In addition, RS in the austenite and martensite phases was measured using the x-ray diffraction method, and the RS balance that occurs between the longitudinal and transverse components and the two phases after tensile deformation is presented. It is shown that a combined analysis of RS and x-ray diffraction peak width could be utilised to find the deformation level in tensile fractured, press brake bent, and roll bent samples.

Intermolecular Correlations in Liquid Lactic Acid Based on ab initio Molecular Dynamics Simulations Combined with High-Energy X-ray Diffraction Measurements

Intermolecular Correlations in Liquid Lactic Acid Based on ab initio Molecular Dynamics Simulations Combined with High-Energy X-ray Diffraction Measurements

Simultaneous Li-Doping and Formation of SnO2-Based Composites with TiO2: Applications for Perovskite Solar Cells.

Tin oxide (SnO2) has been recognized as one of the beneficial components in the electron transport layer (ETL) of lead-halide perovskite solar cells (PSCs) due to its high electron mobility. The SnO2-based thin film serves for electron extraction and transport in the device, induced by light absorption at the perovskite layer. The focus of this paper is on the heat treatment of a nanoaggregate layer of single-nanometer-scale SnO2 particles in combination with another metal-dopant precursor to develop a new process for ETL in PSCs. The combined precursor solution of Li chloride and titanium(IV) isopropoxide (TTIP) was deposited onto the SnO2 layer. We varied the heat treatment conditions of the spin-coated films comprising double layers, i.e., an Li/TTIP precursor layer and SnO2 nanoparticle layer, to understand the effects of nanoparticle interconnection via sintering and the mixing ratio of the Li-dopant on the photovoltaic performance. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) measurements of the sintered nanoparticles suggested that an Li-doped solid solution of SnO2 with a small amount of TiO2 nanoparticles formed via heating. Interestingly, the bandgap of the Li-doped ETL samples was estimated to be 3.45 eV, indicating a narrower bandgap as compared to that of pure SnO2. This observation also supported the formation of an SnO2/TiO2 solid solution in the ETL. The utilization of such a nanoparticulate SnO2 film in combination with an Li/TTIP precursor could offer a new approach as an alternative to conventional SnO2 electron transport layers for optimizing the performance of lead-halide perovskite solar cells.

High-Pressure Polymorphism in Silver Ferrite Delafossite, AgFeO2.

The delafossites are a class of layered metal oxides that are notable for being able to exhibit optical transparency alongside an in-plane electrical conductivity, making them promising platforms for the development of transparent conductive oxides. Pressure-induced polymorphism offers a direct method for altering the electrical and optical properties in this class, and although the copper delafossites have been studied extensively under pressure, the silver delafossites remain only partially studied. We report two new high-pressure polymorphs of silver ferrite delafossite, AgFeO2, that are stabilized above ∼6 and ∼14 GPa. In situ X-ray diffraction and vibrational spectroscopy measurements are used to examine the structural changes across the two phase transitions. The high-pressure structure between 6 and 14 GPa is assigned as a monoclinic C2/c structure that is analogous to the high-pressure phase reported for AgGaO2. Nuclear resonant forward scattering reveals no change in the spin state or valence state at the Fe3+ site up to 15.3(5) GPa.

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

Abstract Here we report the successful synthesis of large single crystals of triangular frustrated PrMgAl11O19 using the optical floating zone technique. Single crystal Xray diffraction 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.

Residual Stress Evaluation in L-PBF-Produced SS 316L Specimens.

The identification of residual stresses (RS) in components made by selective laser melting (SLM) is necessary for subsequent technological optimization. The presented research is devoted to evaluating the influence of the combination of laser power (P), scanning velocity (v) and the rarely considered number of layers (nL) on surface residual stresses in SLM stainless steel SS 316L. Experimental parameters were set based on the Design of Experiment (DoE) method, with follow-up X-ray diffraction (XRD) measurements and data processing using analysis of variance (ANOVA) and regression analysis. The obtained data are a valuable stepping-stone for the subsequent design of research focused on the application of sustainable eco-friendly Abrasive Water Jet (AWJ) peening for RS modification in the evaluated material.

Superconductivity above 105 K in Nonclathrate Ternary Lanthanum Borohydride below Megabar Pressure.

Hydrides are promising candidates for achieving room-temperature superconductivity, but a formidable challenge remains in reducing the stabilization pressure below a megabar. In this study, we successfully synthesized a ternary lanthanum borohydride by introducing the nonmetallic element B into the La-H system, forming robust B-H covalent bonds that lower the pressure required to stabilize the superconducting phase. Electrical transport measurements confirm the presence of superconductivity with a critical temperature (Tc) of up to 106 K at 90 GPa, as evidenced by zero resistance and Tc shift under an external magnetic field. X-ray diffraction and transport measurements identify the superconducting compound as LaB2H8, a nonclathrate hydride, whose crystal structure remains stable at pressures as low as ∼ half megabar (59 GPa). Stabilizing superconductive stoichiometric LaB2H8 in a submegabar pressure regime marks a substantial advancement in the quest for high-Tc superconductivity in polynary hydrides, bringing us closer to the ambient pressure conditions.

Temperature Evolution of Composition, Thermal, Electrical and Magnetic Properties of Ti3C2Tx-MXene.

MXenes are a family of two-dimensional nanomaterials. Titanium carbide MXene (Ti3C2Tx-MXene), reported in 2011, is the first inorganic compound reported among the MXene family. In the present work, we report on the study of the composition and various physical properties of Ti3C2Tx-MXene nanomaterial, as well as their temperature evolution, to consider MXenes for space applications. X-ray diffraction, thermal analysis and mass spectroscopy measurements confirmed the structure and terminating groups of the MXene surface, revealing a predominant single OH layer character. The temperature dependence of the specific heat shows a Debye-like character in the measured range of 2 K-300 K with a linear part below 10 K, characteristic of conduction electrons of metallic materials. The electron density of states (DOS) calculations for Ti3C2OH-MXene reveal a significant DOS value at the Fermi level, with a large slope, confirming its metallic character, which is consistent with the experimental findings. The temperature dependence of electrical resistivity of the MXene samples was tested for a wide temperature range (3 K-350 K) and shows a decrease on lowering temperature with an upturn at low temperatures, where negative magnetoresistance is observed. The magnetoresistance versus field is approximately linear and increases its magnitude with decreasing temperature. The magnetization curves are straight lines with temperature-independent positive slopes, indicating Pauli paramagnetism due to conduction electrons.

Mixed Tin Valence in the Tin(II/IV)-Nitridophosphate Sn3P8N16.

Sn3P8N16 combines the structural versatility of nitridophosphates and Sn within one compound. It was synthesized as dark gray powder in a high-pressure high-temperature reaction at 800°C and 6GPa from Sn3N4 and P3N5. The crystal structure was elucidated from single-crystal diffraction data (space group C2/m (no. 12), a=12.9664(4), b=10.7886(4), c=4.8238(2)Å, β=109.624(1)°) and shows a 3D-network of PN4 tetrahedra, incorporating Sn in oxidation states +II and +IV. The Sn cations are located within eight-membered rings of vertex-sharing PN4 tetrahedra, stacked along the [001] direction. A combination of solid-state nuclear magnetic resonance spectroscopy, 119Sn Mössbauer spectroscopy and density functional theory calculations was used to confirm the mixed oxidation of Sn. Temperature-dependent powder X-ray diffraction measurements reveal a low thermal expansion of 3.6ppm/K up to 750°C, beyond which Sn3P8N16 starts to decompose.

Catalytic Reduction of 4-Nitrophenol and Methylene Blue with Silver Nanoparticles Decorated with Drymoglossum piloselloides Extract

Drymoglossum piloselloides is one of the epiphytic plants that is commonly found in Southeast Asia region. In this study, the ethanol extract of D. piloselloides plant has been used in the green synthesis of silver nanoparticles. The synthesized silver nanoparticles were characterized by ultraviolet-visible (UV-Vis) spectrophotometry, X-ray diffraction (XRD),Fourier-transform infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM) measurements. The UV-Vis spectrum of silver nanoparticles showed a maximum wavelength at 453 nm. The XRD measurement showed the silver nanoparticles peaks at 38.38°, 44.60°, 64.76°, and 77.62°. The FTIR spectra provided evidence of the interaction between silver and chemicals in the plant extract as a weak signal at 682 cm-1. Meanwhile, TEM revealed an average size of 12.63nm. The synthesised silver nanoparticles were utilised for the reduction of 4-nitrophenol with a conversion percentage of up to 100% with a reduction reaction rate constant of 7.104 s-1. In addition, methylene blue was also successfully reduced with the synthesised silver nanoparticles as the catalyst with a reduction reaction rate constant (k) of 21.150 s-1. This study highlights the superior advantage of utilizing ethanolic extract of D. piloselloides to prepare silver nanoparticles with promising catalytic reduction purposes.

Structural and superconducting properties in the Te-doped spinel CuRh2Se4

In this paper, we discuss the impact of tellurium (Te) doping on the spinel superconductor CuRh2Se4. We conducted a comprehensive evaluation of the structural and superconducting properties of the system using various techniques, including X-ray diffraction (XRD), resistivity, magnetization, and specific heat measurements. Based on our XRD analysis, we found that the spinel superconductor CuRh2Se4-xTex (0 ≤ x ≤ 0.28) crystallizes in the space group Fd3̅m (227), while the layered compound CuRh2Se4-xTex (2.8 ≤ x ≤ 4.0) crystallizes in the space group P3̅m1 (164). The upper critical magnetic field can be increased from 0.95(2) T for CuRh2Se4 to 3.44(1) T for CuRh2Se3.72Te0.28 by doping with elemental Te. However, the layered compound CuRh2Se4-xTex (2.8 ≤ x ≤ 4.0) did not exhibit superconducting properties. Besides, the specific heat measurements of CuRh2Se4-xTex (x = 0, 0.1, 0.28) indicate that the Te element doping affects the electronic structure and interactions of the material and breaks the stability of the superconducting pairing, which leads to a decrease in the Tc. Finally, we show the electronic phase diagram of Tc with Te doping to summarise our findings.

Effect of Boron-Doping on Gate-Opening CO2 Adsorption in Zinc-Benzimidazolate Coordination Networks.

Flexible metal-organic frameworks (MOFs) have attracted much attention as selective gas adsorption and storage. This report describes boron doping in zeolitic imidazolate framework-7 (B-ZIF-7), which exhibits reversible phase transition during CO2 adsorption/desorption. We have successfully prepared B-ZIF-7 coordination networks using boron-bridged benzimidazolate (B(bim)4-) as organic ligands. Powder X-ray diffraction (PXRD) measurements and infrared spectroscopy revealed that B-ZIF-7 has a crystal structure similar to that of ZIF-7 while containing boron bridging in the coordination network. Since B-ZIF-7 forms a cationic coordination network, the guest anions are encapsulated within the pore. CO2 adsorption/desorption measurements at 300 K showed that B-ZIF-7(NO3), which contains nitrate ions (NO3-) as guest anions in its pores, exhibits a S-shaped CO2 adsorption/desorption isotherm, which is characteristic of gate-opening type MOFs. Compared with ZIF-7, B-ZIF-7(NO3) has superior CO2 adsorption capacity in the low-pressure and superior CO2 storage capacity. The CO2 adsorption and desorption behavior of B-ZIF-7(NO3) was analyzed by in situ temperature-controlled PXRD measurements and thermogravimetric analysis under a CO2 atmosphere, and a reversible phase transition was observed. We have also successfully prepared B-ZIF-7(Cl) and B-ZIF-7(OTf) (OTf = CF3SO3-) with different guest anions. The CO2 adsorption/desorption behaviors of B-ZIF-7(Cl) and B-ZIF-7(OTf) were significantly different from those of B-ZIF-7(NO3) and ZIF-7. B-ZIF-7(Cl) showed gate opening at a higher pressure than ZIF-7, and B-ZIF-7(OTf) did not show S-shaped CO2 adsorption isotherm and showed adsorption behavior in micropores. These results indicate that the CO2 adsorption behavior of B-ZIF-7 depends on the interaction between the guest anions and CO2 molecules or the cationic framework and the bulkiness of the guest anions. Boron doping in a coordination network with boron-bridged imidazolate ligands is a promising strategy to increase the gas adsorption capability of porous materials.

Crystal growth, physical and optical properties of TlSr2Cl5 and TlSr2Br5

Small diameter (Ø 16 mm) TlSr2Cl5 and TlSr2Br5 crystals were grown by the Vertical Bridgman method. X-ray diffraction measurements show that both have the monoclinic crystal structure with space group P21/c. TlSr2Cl5 and TlSr2Br5 have a density of 4.14 g/cm3 and 5.03 g/cm3, respectively. The effective Z of TlSr2Cl5 and TlSr2Br5 is 63.7 and 58.6, respectively. Radioluminescence spectra of TlSr2Cl5 and TlSr2Br5 feature a broad emission band peaking at 440 and 445 nm, respectively. The light yield of TlSr2Cl5 and TlSr2Br5 was estimated to be 17,000 and 45,000 ph/MeV, respectively.