Crystal Density Research Articles

Machine Learning Models for High Explosive Crystal Density and Performance

Machine Learning Models for High Explosive Crystal Density and Performance

Unveiling the Monoclinic Phase in CsPbBr3-xClx Perovskite Crystals, Phase Transition Suppression and High Energy Resolution γ-Ray Detection.

All-inorganic CsPbBr3 and CsPbCl3 perovskites are promising materials for high-performance solar cells and advanced radiation detection technologies with high stability. Here we report that CsPbBr3-xClx (x = 0-3) crystals exhibit eutectoid behavior for the melting points and phase transition temperatures. The well-known halide perovskite cubic phase transition temperature shifts near room temperature (∼37 °C for CsPbBr2Cl). We conducted an extensive crystallographic analysis on single crystals of 7 different compositions, including the end members CsPbBr3 and CsPbCl3. Contrary to previous beliefs, we discovered they exhibit a monoclinic structure with space group symmetry P21/m at room temperature, rather than the orthorhombic Pnma. This new structural model is more precise and features a unit cell volume that is four times larger than that of the orthorhombic model. From high-quality single crystals of CsPbBr2Cl, grown by the Bridgman method, we constructed γ-ray detectors achieving an energy resolution of 7.2% at 200 V for 57Co radiation. Thermally stimulated current spectroscopy of the CsPbBr2Cl samples revealed that the defect densities in crystals from different regions of the ingot were relatively uniform, with values of ∼4.72 × 1012 and ∼5.09 × 1012 cm-3. These findings indicate that low deep-level defect densities can be achieved that are consistent with the notable performance of the CsPbBr2Cl perovskite as a high-energy γ radiation detector.

Fabrication of interfacial crystallized oleogel emulsion for quercetin delivery with enhanced environmental stability and bioaccessibility.

Quercetin is a flavonoid compound with numerous bioactivities. However, the low solubility, easy degradation and low bioaccessibility limit its application. In this study, a novel interfacial crystallized oleogel emulsion was fabricated, where beeswax was used as the oleogelator, for quercetin encapsulation with enhanced stability and bioaccessibility. The process of interfacial crystallization was investigated using interfacial rheology and polarized microscopy, with a positive correlation between crystal density and beeswax content in the oil phase. Emulsion stability was directly linked to beeswax concentration in the oil phase, with 100 mg g-1 showing enhanced stability under storage, UVB light exposure and ionic conditions. Beeswax addition significantly increased the quercetin loading capacity of the emulsion; particularly, at a 200 mg g-1 beeswax concentration, the loading capacity was improved by 285.55%, and the environmental stability was enhanced against UV light and Ca2+. Ultimately, in vitro simulated digestion experiment indicated improved bioaccessibility of quercetin. This strategy significantly enriched the formulation of oleogel emulsion and its potential applications in delivering bioactive ingredients with high environmental vulnerability. © 2024 Society of Chemical Industry.

Towards improving the characteristics of high-energy pyrazines and their N-oxides.

Based on the methods of quantum chemistry and atom-atom potentials, the molecular and crystal structure of a number of high-energy pyrazines was modeled: unsubstituted diazines, as well as fully nitrated 1,4-diazabenzenes, their oxides and polymorphs. The enthalpies of formation, densities of molecular crystals, and some performance characteristics of these compounds were determined. The parameters of decomposition of substances were estimated. It has been established that tetranitropyrazine-1,4-dioxide has maximum energy content and excellent performance characteristics, which determine the prospects for using this compound as a high-energy one in the considered series of compounds. In this work, DFT calculations were conducted through the software Gaussian 09 using B3LYP functional with basis set aug-cc-PVDZ and the Grimme dispersion correction D2. For crystal structure optimization, the atom-atom potential methods with PMC program (Packing of Molecules in Crystal) were used. Charges for molecular electrostatic potential were fitted by FitMEP and enthalpies of formation in gas phase were assessed by G3B3.

Study of the effect of SMAW welding speed on the microstructure and crystal stability of X70 steel using X-ray diffraction

This study investigates the impact of manual electric arc welding (SMAW) speed on the microstructure of X70 steel. Welding was performed at two distinct speeds: S1 = 20 mm/min and S2 = 35 mm/min, at the COSIDER BISKRA workshop in Algeria. X-ray diffraction (XRD) analysis was conducted on the welded zones to examine crystal orientation, size, dislocation density, and structural stability across different welding areas, including the base metal (MB), heat-affected zones (HAZ1 and HAZ2), and weld zones (WZ1 and WZ2). The XRD results revealed that key crystal peaks, such as {110} and {200}, retained their positions at both welding speeds, though variations in {110} peak intensity were noted. The lower welding speed (S1) resulted in a higher heat input, which enhanced crystal stability, increased crystal size, and reduced dislocation density. On the other hand, the higher speed (S2) produced lower heat input, leading to smaller crystal sizes, increased residual stresses, and a greater number of defects due to rapid cooling. These findings underscore the critical influence of welding speed on heat input, cooling rates, and their consequent effects on microstructure. The study highlights the importance of optimizing welding parameters to balance microstructural integrity, mechanical performance, and production efficiency.

Deciphering Regulatory Role of Melatonin in Foliar Nastic Movements of Portulaca oleracea: Visual Insights from Histology and Anatomy

AbstractPlant nastic movements exhibit unique behavioural patterns that synchronize with external cues. Given that the foliar nastic motions of Portulaca species are solely circadian, it is intriguing to investigate whether and how melatonin governs these movements. Analysis of histological traits concurrent with anatomical traits such as stomatal behaviour provides visual data on the plant species' gnosophysiology, offering clues and validation of the influence of multiple external stimuli on hydraulic forces that in turn alter turgor pressure. The current study aims to elucidate how exogenous melatonin modulates foliar nastic movements in Portulaca oleracea. Our findings indicate that melatonin functions as an intracellular hydraulic flux controller, influencing idioblast and crystal densities, as well as stomatal behaviour. Timepoint studies at specific Zeitgebers reveal that abiotic variables such as light and temperature can influence the endogenous melatonin concentration of P. oleracea. Therefore, this hormone potentially serves as an additional internal regulator of turgor pressure, influenced by both light and temperature. Thus, melatonin plays a crucial role in shaping the characteristic foliar nastic movements observed in P. oleracea, inherently tied to the circadian rhythm. Further investigation into idioblast and crystal torques, along with their angular momentum, is warranted to calculate the hydraulic forces at work in the leaf lamina. Thus the study underscores the multifaceted role of melatonin in navigating nastic movement processes through turgor pressure alterations brought about by intracellular depositions. The study in future could unravel melatonin's pleiotropic actions and the underlying mechanisms of foliar idiosyncratic nastic motions in other plant species as well. Moreover, both histology and anatomy play vital roles in the present study as it has provided visual evidence of the underlying mechanisms of foliar nastic movements in P. oleracea. Graphical Abstract

Tyramine as a Prolific Coformer in Crystal Engineering: Insights from Classical Crystal Structure Analysis and Electron Density Studies

Tyramine as a Prolific Coformer in Crystal Engineering: Insights from Classical Crystal Structure Analysis and Electron Density Studies

Effects of polyunsaturated fatty acid and diacylglycerol on the crystallization behaviors of palm-based oil

Diacylglycerol (DAG) is a novel functional structural lipid, but its application in base oils remains underexplored. This research investigated the effect of three liquid oils (groundnut oil, corn oil, and flaxseed oil), with varying polyunsaturated fatty acid (PUFA) (39.60, 69.50, and 77.65 %) and DAG content (0.00, 40.00, 80.00 %), on the crystallization behaviors of palm-based oil. DAG (40.00 %), obtained through enzymatic glycerolysis and molecular distillation, was found to stabilize the binary system with good compatibility and fine crystal structure. “Liquid” DAG played a dual role: diluting solid lipids, and promoting crystallization. Increasing DAG content led to larger crystalline domain size, while higher PUFA content accelerated crystallization and increased crystal orderliness, though decreasing crystal density. These results demonstrated the clear influence of PUFA and DAG content on palm-based oil crystallization. This knowledge can guide the utilization of different unsaturated DAGs for tailored fat crystallization in food application.

Synthesis and Properties of N1, N3‐di (2,4‐dinitrophenyl) −2‐fluoro‐1,3‐diamino‐4,6‐ Dinitrobenzene and its Analogues

AbstractPolynitrobenzene compounds are a type of heat‐resistant explosives with excellent thermal stability. This study reported three novel energetic compounds, namely compounds N1, N3‐bis(2,4‐dinitrophenyl)‐2‐fluoro‐4,6‐dinitrobenzene‐1,3‐ diamine (3), 2‐fluoro‐4,6‐dinitro‐N1,N3‐bis(2,4,6‐trinitrophenyl)benzene‐1,3‐ diamine (4), and 2‐chloro‐4,6‐dinitro‐N1,N3‐bis(2,4,6‐trinitrophenyl)benzene‐1,3‐ diamine (6). The target compounds were prepared with commercially available 2,3,4‐trifluoronitrobenzene and 2,3,4‐trichloronitrobenzole. The crystalline structures of compounds 3, 4, and 6 were determined by single‐crystal X‐ray diffraction, and the crystal densities (ρ) were calculated to be 1.7585 g cm−3, 1.6651 g cm−3, and 1.7371 g cm−3, respectively. Based on the calculated standard molar enthalpy of formation and crystal densities, the Chapman–Jouguet detonation properties of 3, 4, and 6 were predicted. Their enthalpy of formation (ΔHf), detonation velocities (D), and detonation pressures (P) were in the ranges of 110.1 kJ mol−1 to 349.9 Kj mol−1, 7264 m s−1 to 7770 m s−1, and 21.8 GPa to 25.9 GPa, respectively. Notably, the density, thermal decomposition temperature, detonation velocity, detonation pressure, and impact sensitivity value of compound 3 were 1.76 g cm−3, 313°C, 7546 m s−1, 24.2 GPa, and 16 J, respectively, suggesting that compound 3 is a high‐performance heat‐resistant explosive.

Study on the enhancement of device performance by the action of carbonohydrazide at the buried bottom interface of inverted mesoporous perovskite solar cells

The interface of perovskite solar cells (PSCs) significantly influences their efficiency and stability. Researchers tend to pay more attention to the upper surface of the perovskite absorber layer and conduct relatively less research on the bottom buried interface, mainly because the bottom of the perovskite film is challenging to peel off, which increases the difficulty of the characterization of the observation and analysis. Defects at the bottom interface make it more challenging to optimize the treatment than the upper surface. For inverted PSCs, the interface located in direct contact between the light absorption layer of perovskite and the hole transport layer is the buried interface. The buried interface is the direct interface for transporting charge carriers of PSCs and is also the center of non-radiative compound enrichment. The defect density is higher than the defect density of perovskite film crystal. Due to the DMSO initially left in the commonly used perovskite precursor solution during the film formation process, evaporation during the annealing and crystallization process creates vacancy holes at the bottom of the perovskite layer film. These holes and crystal boundaries tend to produce many non-radiative recombinations. These holes are also the sites of photodecomposition, leading to reduced efficiency and stability in PSCs, ultimately impacting the overall performance of PSCs. The work adds an Al2O3 mesoporous layer on top of the hole transport layer (HTL), which reduces the direct contact area between PTAA and perovskite film. In the perovskite precursor solution, we incorporate a solid additive called Carbonohydrazide (CBH), this substance replaces some of the DMSO and fills in the voids at the bottom of the perovskite film that is left when the DMSO evaporates. This process helps to reduce non-radiative recombination and photodegradation caused by the voids at the bottom of the perovskite, leading to an improvement in the efficiency and stability of the cell. The optimization of the buried bottom interface has improved the cell’s average efficiency from 17.6 % to 19.7 %, an 11.9 % increase. The aperture area of the devices in this work is 0.048 cm2, and the photoelectric conversion efficiency of our device still reaches 80.64 % of the initial efficiency after 600 h of continuous heating in a glove box with a nitrogen atmosphere, maintaining a test temperature of 60 °C.

Recent Progress of Thin Crystal Engineering for Perovskite Solar Cells.

Metal halide perovskite single crystals hold promise for photovoltaics with high efficiency and stability due to their superior optoelectronic properties and weak bulk ion migration. The past several years have witnessed rapid development of single-crystal perovskite solar cells (PSCs) with efficiency rocketed from 6.5% to 24.3%, however, which still lags behind their polycrystalline counterparts. Moreover, the poor device stability under light illumination is contrary to the high ion migration barrier of perovskite single crystals. The key limiting factors should be the low crystalline quality and high surface defect density of solution-grown thin single crystals. Under this circumstance, a review paper summarizing the recent progress and challenges will be instructive for future development of this emerging field. In this manuscript, the crystal engineering used to enhance carrier transport and suppress carrier recombination in vertical single-crystal PSCs will be summarized initially, including crystal growth, component control, surface and interface modification. Subsequently, the application of perovskite single crystals in lateral single-crystal PSCs will be discussed and compared with the conventionally vertical structure. Finally, the challenges and proposed strategies for the development of single-crystal PSCs are provided.

Enhanced Emitting Dipole Orientation Based on Asymmetric Iridium(III) Complexes for Efficient Saturated-Blue Phosphorescent OLEDs.

Three novel asymmetric Ir(III) complexes have been rationally designed to optimize their emitting dipole orientations (EDO) and enhance light outcoupling in blue phosphorescent organic light-emitting diodes (OLEDs), thereby boosting their external quantum efficiency (EQE). Bulky electron-donating groups (EDGs), namely: carbazole (Cz), di-tert-butyl carbazole (tBuCz), and phenoxazine (Pxz) are incorporated into the tridentate dicarbene pincer chelate to induce high degree of packing anisotropy, simultaneously enhancing their photophysical properties. Angle-dependent photoluminescence (ADPL) measurements indicate increased horizontal transition dipole ratios of 0.89 and 0.90 for the Ir(III) complexes Cz-dfppy-CN and tBuCz-dfppy-CN, respectively. Analysis of the single crystal structure and density functional theory (DFT) calculation results revealed an inherent correlation between molecular aspect ratio and EDO. Utilizing the newly obtained emitters, the blue OLED devices demonstrated exceptional performance, achieving a maximum EQE of 30.7% at a Commission International de l'Eclairage (CIE) coordinate of (0.140, 0.148). Optical transfer matrix-based simulations confirmed a maximum outcoupling efficiency of 35% due to improved EDO. Finally, the tandem OLED and hyper-OLED devices exhibited a maximumEQE of 44.2% and 31.6%, respectively, together with good device stability. This rational molecular design provides straightforward guidelines to reach highly efficient and stable saturated blue emission.

Refractometry of β-modification LiNH4SO4 crystals with an admixture of Mn2+ and Cu2+

Crystals of β-LiNH4SO4 doped with 2 and 5 wt% of Cu2+ and Mn2+ were synthesized. The crystal structure was determined using X-ray diffraction, and the dispersion of refractive indices and birefringence was investigated. The study revealed that adding impurities increased the absolute values of the refractive indices for all crystal physical directions. As the concentration of Mn2+ and Cu2+ impurities increased to 5%, the average refractive index showed an almost linear increase, attributed to the increase in crystal density due to a decrease in the volume of the unit cell. Furthermore, the impurities of Mn2+ and Cu2+ ions significantly altered the absolute values of birefringence. The refractions, electronic polarizabilities, and dispersion parameters were calculated using the Sellmeier formula, showing that adding impurities increased the values of molar refractions and electronic polarizabilities. The study also found that introducing Mn2+ and Cu2+ impurities shifted the optical isotropic point to the long-wavelength part of the spectrum by approximately 26 and 31 nm, respectively.

Hardness and Corrosion Behavior of CrMnFeCoNi Alloy Fabricated by Ball Milling and Spark Plasma Sintering.

The mechanical properties and electrochemical stability of high-entropy alloys are substantially affected by their composition distribution and crystal structure. However, the details concerning the conditions of milling and sintering for sintered alloys have rarely been reported. In this work, a series of CrMnFeCoNi alloys were fabricated by ball milling and spark plasm sintering for different periods. Their crystal structure, density, hardness, and corrosion resistance were investigated. As a result, a partial alloying of Cr, Mn, Fe, Co, and Ni was achieved by ball milling. However, Cr-rich particles, including Mn, were formed in the milled powders. The sintered alloys inherited the Cr-rich particles to form Cr-rich zones. The formation and change of chromium carbide were also confirmed in sintered alloys. Extended milling or sintering to 12 h achieved high hardness and corrosion resistance for the sintered alloys. The Cr-rich zones showed high hardness and Kelvin potential, which affect both the hardness and the corrosion resistance.

First Alliance of Pyrazole and Furoxan Leading to High-Performance Energetic Materials.

Nitrogen heterocyclic scaffolds retain their leading position as valuable building blocks in material science, particularly for the design of small-molecule energetic materials. However, the search for more balanced combinations of directly linked heterocyclic cores is far from being exhausted and aims to reach ideally balanced high-energy substances. Herein, we present the synthetic route to novel pyrazole-furoxan framework enriched with nitro groups and demonstrate a promising set of properties, viz., good thermal stability, acceptable mechanical sensitivity, and high detonation performance. In-depth crystal analysis showed that the isomers having lower-impact sensitivity values in both types of regioisomeric pairs are those with the exocyclic furoxan oxygen atom being closer to the pyrazole ring. Owing to the favorable combination of high crystal densities (1.83-1.93 g cm-3), positive oxygen balance to CO (up to +13.9%), and high enthalpies of formation (322-435 kJ mol-1), the synthesized compounds show high calculated detonation velocities (8.4-9.1 km s-1) and excellent metal accelerating abilities. The incorporation of the 3-nitrofuroxan moiety increases the thermal stability (by ca. 20 °C) and decreases the mechanical sensitivity of target hybrid materials in both types of regioisomeric pairs. Simultaneously, the detonation performance of 3-nitrofuroxans is almost identical to that of 4-nitrofuroxans, highlighting the potential of the regioisomeric tunability in the future design of energetic materials.

Microstructure-induced anisotropic biocorrosion response of laser additive manufactured WE43 alloy

The microstructure and corrosion of laser-processed WE43 was studied. Results suggest that multi-factors like grain structure, crystallographic defect, and precipitate distribution result in an anisotropic corrosion response. XY plane with high crystal defect densities offers more sites for pitting corrosion. Filiform corrosion is detected on both XY plane and XZ plane, where Zr-rich and RE-rich precipitate distribution plays an essential role in corrosion initiation and propagation. The enrichment of Zr around filament corrosion promotes local micro-galvanic corrosion. Notably, the XY-plane, with continuous distribution and extended scanning trajectory edge, is particularly susceptible to filiform corrosion as compared with XZ-plane.

Oxygen Gas-Filled Metal-Organic Frameworks (MOFs) Delivery System: A Hypothetical Design for Injectable Oxygen

Oxygen delivery systems are crucial in critical care medicine, particularly for managing acute respiratory distress. This study presents a novel approach, exploring the potential of Metal-Organic Frameworks (MOFs) as oxygen delivery systems. We highlight their unique properties and potential for enhancing oxygenation in medical settings. Understanding their biocompatibility, oxygen-carrying capacity, and controlled release mechanisms is pivotal for successful implementation in clinical practice. Thanks to their exceptional porosity, structural diversity, lower crystal density, and tunability, MOFs offer a fresh perspective on developing innovative oxygen carriers. We propose that MOFs will demonstrate biocompatibility, stability, and the ability to deliver oxygen in a controlled and sustained manner when administered intravenously in living organisms. Gas adsorption and molecular simulation techniques will demonstrate reversible oxygen binding within MOFs and predict controlled release kinetics. The findings of the simulations and experiments should indicate the feasibility of utilising MOFs as intravenous oxygen carriers with controlled and reversible oxygen release behaviour.

Fabrication, Characterization, and Performance Evaluation of Thermally Stable [5,6]-Fused Bicyclic Energetic Materials.

In recent decades, there has been considerable interest in investigating advanced energetic materials characterized by high stability and favorable energetic properties. Nevertheless, reconciling the conflicting balance between high energy and the insensitivity of such materials through traditional approaches, which involve integrating fuel frameworks and oxidizing groups into an organic molecule, presents significant challenges. In this study, we employed a promising method to fabricate high-energy-density materials (HEDMs) through the intermolecular assembly of variously substituted purines with a high-energy oxidant. Purines are abundant in nature and are readily available. A series of advanced energetic materials with a good balance between energy and sensitivity were prepared by the simple and effective self-assembly of purines with high-energy oxidants. Notably, these compounds exhibit incredibly improved crystal densities (1.80-2.00 g·cm-3) and good detonation performance (D: 7072-8358 m·s-1; P: 19.82-34.56 GPa). In comparison to RDX, these self-assembled energetic materials exhibit reduced mechanical sensitivities and enhanced thermal stabilities. Compounds 1-5 demonstrate both high energy and low sensitivity, indicating that self-assembly represents a straightforward and effective approach for developing advanced energetic materials with a balanced combination of energy and safety. Moreover, this study offers an avenue for synthesizing energetic materials based on naturally occurring compounds assembled through intermolecular attractions, thereby achieving a balance between energy and sensitivity along with versatile functionality.

Hardness, VSM, cyclic voltammetric and DFT studies of Cesium Sulphate-doped TGS crystals

The creation of capacitors, transducers, sensors, and infrared detectors utilise the nonlinear, ferroelectric triglycine sulphate (TGS) crystal. Cesium sulphate is incorporated into the lattice of TGS crystal to change its characteristics. Cesium sulfate-doped triglycine sulphate (CSTGS) single crystals were produced using a solution approach and a slow evaporation process. The title crystal was studied by single crystal XRD, FTIR, hardness, VSM, cyclic voltammetric and density functional theoretical (DFT) studies and the results are discussed in this paper.

Synthesis of MoS2@MoO3/(Cu+/g-C3N4) ternary composites with double S-scheme heterojunction for peroxymonosulfate activation exposing to visible light

The construction of semiconductor heterojunction is an effective way for charge separation in photocatalytic degradation of pollutants. In this study, a novel MoS2@MoO3/(Cu+/g-C3N4) ternary composites (MMCCN) was prepared via a simple calcination method. The as-prepared composites exhibited exceptional performance in activating peroxymonosulfate (PMS) for the degradation of rhodamine B (RhB). The activity testing results indicated that 99.41 % of RhB (10 mg·L−1, 10 mL) was effectively removed by the synergistic effect of composites photocatalyst (0.1 g·L−1) and PMS (0.1 g·L−1) under visible light irradiation for 40 min. Its reaction rate constant exceeded that of Cu+/g-C3N4, MoO3 and MoS2 by a factor of 3.56, 17.30 and 11.73 times, respectively. The crystal structure, band gap and density of states (DOS) of the semiconductors were calculated according to the density functional theory (DFT). Free radical trapping tests and electron spin resonance spectroscopy validated that 1O2, O2− and h+ are primary reactive species participating in the decomposition of RhB. The ternary composites demonstrated good stability and maintained excellent degradation efficiency even across four reaction cycles. Furthermore, the activation mechanism and the intermediates produced during the decomposition course of RhB by MMCCN/PMS/vis system were analyzed and elucidated. A double S-scheme heterojunctions was responsible for efficient separation of photo-induced electron-hole pairs. This work presents a novel method in the construction of double S-scheme heterojunctions for PMS activation which is expected to find wide applications in wastewater treatment and environmental remediation.