Search Results (214)

The compound 3-((benzyloxy)carbonyl)bicyclo[1.1.1]pentane-1-carboxylic acid was successfully synthesized. High-quality crystals were obtained, and its X-ray structure was solved and refined by Hirshfeld atom refinement using custom aspherical scattering factors with the Olex2/NoSphereA2 package. Hydrogen bonding interactions lead to head-to-head carboxylic acid dimer formation. A positional disorder for the bridging H-atom was detected and modeled to two parts in a 0.85:0.15 ratio. Detailed comparison with a neutron diffraction study of benzoic acid at the same temperature (100 K) demonstrates that the E–H-bond distances in the title compound are in excellent agreement (differing less than 1%) and the displacement ellipsoids volumes to the model are also in excellent agreement to the neutron diffraction structure. Moreover, both the variation in refined disorder occupancy and differences in C=O and C–O lengths of the disordered carboxylic acids in the two structures track well with their dimer O···O separations. This is longer by 0.023 Å in the structure of the title compound than in that of benzoic acid. A database search was conducted and used for comparison of the title compound to other high-quality structures of bicyclo[1.1.1]pentane-containing species. Full article

Mesoporous silica nanoparticles have been synthesized through sol–gel synthesis in basic conditions. Gemini surfactants having urea in the headgroups were used as pore-forming agents. The effect of the spacer length of the surfactant on the particle morphology was studied on the sub-micrometer and nanometer scales using nitrogen porosimetry, small-angle X-ray scattering (SAXS), ultra-small-angle neutron scattering, and scanning and transmission electron microscopy (SEM, TEM). Depending on the spacer, spherical and/or cylindrical nanoparticles formed in different proportions, as revealed by statistical analysis of SEM micrographs. All prepared materials showed the hexagonal pore structure characteristic of the MCM-41 molecular sieves, with the exception of the sample prepared using the gemini surfactant with the shortest spacer length. The influence of the spacer length on the lattice parameter of the pore network, as well as the average size of the ordered domains, has been assessed by SAXS and TEM. Detailed analysis of the TEM images revealed a spread of the lattice parameter in a range of 10–20%. The broadening of the diffraction peaks was shown to be due to the combination of the effects of the finite domain size and the variance of the lattice parameter across the crystalline domains. The structural differences between the silica gels synthesized with the different surfactants were related to the variation of the micelle morphologies, reported in previous light scattering and small-angle scattering experiments. No connection could be revealed between the micelle shape and size and the pore sizes, showing that surfactants with a broad range of spacer lengths can equally well be used for the preparation of MCM-41 materials. Full article

Among the many nanomaterials studied for biomedical uses, silica and gold nanoparticles have gained significant attention because of their unique physical and chemical properties and their compatibility with living tissues. Mesoporous silica nanoparticles (MSNs) have great stability and a large surface area, while gold nanoparticles (AuNPs) display remarkable optical features. Both types of nanoparticles have been widely researched for their individual roles in drug delivery, imaging, biosensing, and therapy. When combined with gadolinium (Gd), a common contrast agent, these nanostructures provide improved imaging due to gadolinium’s strong paramagnetic properties. This study focuses on incorporating gold nanoparticles and gadolinium into a silica matrix to develop a theranostic system. Various analytical techniques were used to characterize the nanocomposites, including infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-Vis), thermogravimetric analysis (TGA), nitrogen adsorption, scanning electron microscopy (SEM), dynamic light scattering (DLS), X-ray fluorescence (XRF), X-ray diffraction (XRD), vibrating sample magnetometry (VSM), and neutron activation analysis (NAA). Techniques like XRF mapping, XANES, nitrogen adsorption, SEM, and VSM were crucial in confirming the presence of gadolinium and gold within the silica network. VSM and EPR analyses confirmed the attenuation of the saturation magnetization for all nanocomposites. This validates their potential for biomedical applications in diagnostics. Moreover, activating gold nanoparticles in a nuclear reactor generated a promising radioisotope for cancer treatment. These results indicate the potential of using a theranostic nanoplatform that employs mesoporous silica as a carrier, gold nanoparticles for radioisotopes, and gadolinium for imaging purposes. Full article

In this study, we developed and characterized novel scintillators with Ce: LiCaAlF₆–CaF₂–Li₃AlF₆ and Ce: CaF₂–LiF–Li₃AlF₆ ternary systems for thermal neutron detectors. The eutectics were grown by the vertical Stochbarger-Bridgman (VB) technique, and their constituent phases were identified using powder X-ray diffraction and scanning electron microscopy. Radioluminescence spectra irradiated under an Ag-target X-ray tube and confirmed the 5d-4f and self-trapped exciton luminescence derived from Ce³⁺. Scintillation decay and pulse height measurements were performed using ²⁵²Cf and ⁶⁰Co sources. The Ce: CaF₂–LiF–Li₃AlF₆ sample exhibited approximately 5.6 times higher effective neutron sensitivity compared with a Ce: LiCaAlF₆ single crystal. A favorable decrease in the neutron discrimination threshold level (Q_th) due to reduced γ-ray emission was observed. ⁶Li-enriched Ce: CaF-based scintillators hold potential for nuclear decommissioning applications. Full article

Spinels like Co₃O₄ have acquired relevance because of their photocatalytic, electrocatalytic, optical and magnetic properties. In this context, we investigated the defect structure evolution of compounds synthetized using the nitrate precursor method and after annealing cycles at temperatures ranging from 260 to 650 °C by means of thermogravimetric analysis (TGA), neutron powder diffraction (NPD), X-ray powder diffraction (XRPD) coupled to Pair Distribution Function (PDF) analysis, and Density Functional Theory (DFT) calculations. Deuterated and hydrogenated precursors were adopted to produce the samples for NPD and XRPD experiments, respectively. TGA measurements displayed weight losses, the extent of which increased on lowering the preparation annealing temperature, suggesting that the adopted wet synthesis introduces structural water in the sample. Both XRPD and NPD revealed the presence of vacancies in tetrahedral cobalt sites ($V_{Co1}^{″}$) whose concentration at RT decreases on raising the annealing temperatures, while octahedral cobalt and oxygen sites were fully occupied in all the samples. In addition, the $V_{Co1}^{″}$ presence induces a shrinking of the volume of the CoO₄ tetrahedra. The combination of DFT calculation and diffraction revealed that deuterium/hydrogen ions ($D_i^{•}$/$H_i^{•}$), introduced during the synthesis by the nitrate precursor balanced the $V_{Co1}^{″}$. Finally, DFT calculations revealed that ($D_i^{•}$/$H_i^{•}$) in Co₃O₄ forms hydroxyl groups. Full article

Shallow gas reservoirs exhibit low formation pressure and gas injection levels, leading to low-resistivity contrast between gas-bearing reservoirs and fully water-saturated layers. Gas-bearing formation identification and water saturation estimation face great challenges. To improve the accuracy of shallow gas reservoir identification and logging evaluation, it is essential to analyze the genesis mechanisms underlying the low-resistivity contrast. This study used the HJ Formation, a typical shallow gas reservoir located in the BY Sag of the eastern South China Sea Basin as an example. Combining the results of nuclear magnetic resonance (NMR), full rock mineral analysis and X-ray diffraction of clay minerals in the laboratory, it was determined that the genesis mechanism for the low-resistivity contrast in the gas-bearing reservoir was due to the high irreducible water saturation (S_wi) and the cation-induced supplementary conductivity. Afterwards, we integrated three methods, density–neutron correlation, calculation of the apparent formation water resistivity, and cross-plots of conventional and gas-logging curves, to identify shallow gas reservoirs. In addition, we also established a Waxman–Smits-based model to estimate water saturation. Compared with the typical Archie’s equation, the predicted water saturation curve using the Waxman–Smits-based model was more reasonable. The established methods and models can be used in target shallow gas reservoir evaluations, and it also has reference value for other types of oilfields with similar physical characteristics. Full article

Recently, we have described SrMo_1-xMg_xO_3-δ perovskites (x = 0.1, 0.2) as excellent anode materials for solid oxide fuel cells (SOFCs), with mixed ionic and electronic conduction (MIEC) properties. After depositing on the solid electrolyte, they were annealed for sintering at high temperatures (typically 1000 °C), giving rise to oxidized scheelite-type phases, with SrMo_1-xMg_xO_4-δ (x = 0.1, 0.2) stoichiometry. To obtain the active perovskite phases, they were reduced again in the working anode conditions, under H₂ atmosphere. Therefore, there must be an excellent reversibility between the oxidized Sr(Mo, Mg)O_4-δ scheelite and the reduced Sr(Mo, Mg)O_3-δ perovskite phases. This work describes the topotactical oxidation, by annealing at 400 °C in air, of the SrMo_0.9Mg_0.1O_3-δ perovskite oxide. The characterization by X-ray diffraction (XRD) and neutron powder diffraction (NPD) was carried out in order to determine the crystal structure features. The scheelite oxides are tetragonal, space group I4₁/a (No. 88), whereas the perovskites are cubic, s.g. Pm-3m (No. 221). The Rietveld refinement of the scheelite phase from NPD data after annealing the perovskite at 400 °C and cooling it down slowly to RT evidences the absence of intermediate phases between perovskite and scheelite oxides, as well as the presence of oxygen vacancies in both oxidized and reduced phases, essential for their performance as MIEC oxides. The topotactical relationship between both crystal structures is discussed. Full article

In this study, we propose a self-adaptive weighted multi-mineral inversion model (SQP_AW) based on Sequential Quadratic Programming (SQP) and the Adam optimization algorithm for the accurate evaluation of mineral content in carbonate reservoir rocks, addressing the high costs of traditional experimental methods and the strong parameter dependence in geophysical inversion. The model integrates porosity curves (compensated density, compensated neutron, and acoustic time difference), elastic modulus parameters (shear and bulk moduli), and nuclear magnetic porosity data for the construction of a multi-dimensional linear equation system, with calibration coefficients derived from core X-ray diffraction (XRD) data. The Adam algorithm dynamically optimizes the weights, solving the overdetermined equation system. We applied the method to the Asmari Formation in the M oilfield in the Middle East with 40 core samples for calibration, achieving a 0.91 fit with the XRD data. For eight additional uncalibrated samples from Well A, the fit reaches 0.87. With the introduction of the elastic modulus and nuclear magnetic porosity, the average relative error in mineral content decreases from 9.45% to 6.59%, and that in porosity estimation decreases from 8.1% to 7.1%. The approach is also scalable to elemental logging data, yielding inversion precision comparable to that of commercial software. Although the method requires a complete set of logging data and further validation of regional applicability for weight parameters, in future research, transfer learning and missing curve prediction could be incorporated to enhance its practical utility. Full article

The lattice parameters of both the product phase and the matrix phase have determined using in situ X-ray and neutron diffraction measurements during forward and reverse transformations in steels. The lattice parameters are well known to be influenced by various factors, including temperature, internal stresses induced by transformation strains, partitioning of alloying elements, crystal defects, and magnetic strains. Therefore, it is crucial to accurately disentangle the contributions of these factors to the observed changes in lattice parameters. This review examines the evaluation of internal strain (stress) associated with ferrite, pearlite, bainite, martensite, and reverse austenite transformations, with a particular emphasis on the distinction between diffusional and displacive transformations. Additionally, the effects of plastic deformation of austenite on the bainite or martensite transformation are discussed. In this context, the roles of dislocations and vacancies are highlighted as key areas for further investigation. Full article

A common route for the synthesis of molybdenum nitrides is through the temperature-programmed reaction of molybdenum oxides with NH₃, or ammonolysis. In this work, the role of precursor phase, gas phase chemistry (impact of H₂O), and temperature profile on the reaction outcome (700 °C) was examined, which resulted in varying amounts of MoO₂, H₂MoO₅, and the nitride phases—cubic γ (nominally Mo₂N) and hexagonal δ (nominally MoN). The phase fraction of the δ phase increased with precursor in the sequence MoO₂ > MoO₃ > H₂MoO₅. Steam in the reaction gas also favored the production of δ over γ, but with too much steam, MoO₂ was obtained in the product. Synthesis conditions for obtaining nearly phase-pure δ were identified: MoO₂ as the precursor, 2% H₂O in the gas stream, and a moderate heating rate (3 °C/min). In situ X-ray diffraction provided insights into the reaction pathway. Extensive physico-chemical analysis of the δ phase, including synchrotron X-ray and neutron diffraction, electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and prompt gamma activation analysis, revealed its stoichiometry to be MoO_0.108(8)N_0.892(8)H_0.012(5), indicating non-trivial oxygen incorporation. The presence of N/O ordering and an impurity phase Mo₅N₆ were also revealed, detectable only by neutron diffraction. Notably, a computationally predicted MoON phase (doi: 10.1103/PhysRevLett.123.236402), of interest due to its potential to display a metal-insulator transition, did not appear under any reaction condition examined. Full article

The application of oxygen-deficient perovskites (ODPs) has attracted interest as anode materials for lithium-ion batteries for their unique properties. One such material, CaSrFe_0.75Co_0.75Mn_0.5O_6-δ, has been studied extensively. The structure of CaSrFe_0.75Co_0.75Mn_0.5O_6-δ was investigated using various techniques, including Rietveld refinements with X-ray diffraction and neutron diffraction. Additionally, iodometric titration and X-ray photoelectron spectroscopy were employed to study the oxygen-deficiency amount and the transition metal’s oxidation states in the material. As an anode material, CaSrFe_0.75Co_0.75Mn_0.5O_6-δ exhibits promising performance. It delivers 393 mAhg⁻¹ of discharge capacity at a current density of 25 mAg⁻¹ after 100 cycles. Notably, this capacity surpasses both the theoretical graphite anode capacity (372 mAhg⁻¹) and that of the calcium analog reported previously. Furthermore, the electrochemical performance of CaSrFe_0.75Co_0.75Mn_0.5O_6-δ remains highly reversible across various current densities ranging from 25 to 500 mAg⁻¹. This suggests the material’s excellent stability and reversibility during charge–discharge cycles, showing its probable application as an anode for lithium-ion batteries. The mechanism of lithium intercalation and deintercalation within CaSrFe_0.75Co_0.75Mn_0.5O_6-δ has also been discussed. Understanding this mechanism is crucial for optimizing the battery’s performance and ensuring long-term stability. Overall, this study highlights the significant potential of oxygen-deficient perovskites, particularly CaSrFe_0.75Co_0.75Mn_0.5O_6-δ, for applications as an anode material for lithium-ion batteries, offering enhanced capacity and stability compared with traditional graphite-based anodes. Full article

Cracks due to stress corrosion cracking in stainless steels are becoming a problem not only in boiling water reactors but also in pressurized water reactor nuclear plants. Stress improvement measures have been implemented mainly for large-bore welded piping, but in the case of small-bore welded piping, post-welding stress improvement measures are often not possible due to dimensional restrictions, etc. Therefore, knowing the actual welding residual stresses of small-bore welded piping regardless of reactor type is essential for the safe and stable operation of nuclear power stations, but there are only a limited number of examples of measuring the residual stresses. In this study, austenitic stainless steel pipes with an outer diameter of 100 mm and a wall thickness of 11.1 mm were butt-welded. The residual stresses were measured by the strain scanning method using neutrons. Furthermore, to obtain detailed residual stresses near the penetration bead where the maximum stress is generated, the residual stresses near the inner surface of the weld were measured using the double-exposure method (DEM) with hard X-rays of synchrotron radiation. A method using a cross-correlation algorithm was proposed to determine the accurate diffraction angle from the complex diffraction patterns from the coarse grains, dendritic structures, and plastic zones. A quantum beam hybrid method (QBHM) was proposed that uses the circumferential residual stresses obtained by neutrons and the residual stresses obtained by the double-exposure method in a complementary use. The residual stress map of welded piping measured using the QBHM showed an area where the axial tensile residual stress exists from the neighborhood of the penetration bead toward the inside of the welded metal. This result could explain the occurrence of stress corrosion cracking in the butt-welded piping. A finite element analysis of the same butt-welded piping was performed and its results were compared. There is also a difference between the simulation results of residual stress using the finite element method and the measurement results using the QBHM. This difference is because the measured residual stress map also includes the effect of the stress of each crystal grain based on elastic anisotropy, that is, residual micro-stress. Full article

Boron Neutron Capture Therapy is a re-emerging therapy for the treatment of cancer, and the development of new neutron-reactive nuclei carriers with enhanced efficiency is of great importance. In this work we propose three new boron-based solid compounds, of formulas [Ca(H₂O)₆](C₁₄H₈O₆B)₂ (CaSB), [Cu(C₁₄H₈O₆B)] (CuSB), and [Li(C₁₄H₈O₆B)(H₂O)] (LiSB), usable as nanoparticles for the carriage of the ¹⁰B isotope. The copper atom in CuSB was introduced because it is known that its presence magnifies the effect of the radiation on cells. Furthermore, the lithium atom in LiSB also allows us to include the ⁶Li isotope, which can take part in the nuclear reactions, enhancing the efficiency of the anti-cancer treatment. The compounds were characterized with single-crystal X-ray diffraction to compare the densities of the reactive isotopes in the materials, a key parameter related to the efficiency of the materials. In this work, we used a computational method to calculate the dose absorbed by a tumor mass treated with nanoparticles of the compounds in order to select the most efficient one for the therapy. The results reported in this work are encouraging. Full article

In an earlier report, we conjectured that oligo-phenylenevinylene (OPV) molecules bearing terminal OH groups may form molecular complexes in organogels prepared in benzyl alcohol. This assumption was based on circumstantial evidence only. In this paper, we report on new experimental evidence by means of neutron diffraction that unambiguously demonstrates this conjecture. After ascertaining that the thermodynamic properties of OPV gels are not altered by the use of a solvent isotope (hydrogenous vs. deuterated benzyl alcohol), we show that the neutron diffraction pattern in hydrogenous benzyl alcohol differs from that in deuterated benzyl alcohol. These patterns also exhibit additional peaks with respect to those obtained by X-ray. Comparison is further achieved with an OPV molecule without hydrogen bond terminal groups. In the latter case, no molecular complex is formed. These molecular structures may have a direct bearing on the differences observed in the gel morphologies. Full article

Defect recovery and recrystallization studies of neutron-irradiated tungsten (W) addressing the microstructural evolution in relation to the mechanical properties, provide valuable insight into defect interactions and annihilation processes. Understanding these mechanisms can aid in the development of effective healing processes, potentially extending the lifespan of fusion reactor components. Additionally, this research helps to elucidate how neutron exposure alters the behaviour of materials used in fusion reactor components, contributing to improved design and durability. Within this framework, an ITER grade forged W bar was neutron irradiated to a damage of 0.21 displacements per atom at 600 °C and subsequently isochronally annealed from 700 up to 1550 °C in 50 °C steps. Irradiation causes the formation of dislocation loops and vacancy clusters as well as the formation of Re and Os transmutation products, leading to a 35% increase in hardness and a 23% increase in resistivity. The evolution of the microstructure after isochronal annealing is investigated through positron annihilation lifetime spectroscopy, X-ray diffraction, resistivity, and Vickers hardness measurements. The total dislocation line density as well as the number density and size of voids are determined as a function of annealing temperature. Specifically, the critical resolved stresses of dislocations and voids are correlated with their densities and distinct recovery stages are identified. The kinetics of defect annihilation are discussed in relation to the annealing temperature. Nearly complete dislocation annihilation occurs after annealing at 1300 °C, followed by complete void dissolution and recrystallization at 1450 °C. Full article