Internal Crystal Structure Research Articles

Oxygen vacancy-assisted construction of phosphorus-doped layers to improve the lithium storage performance of T-Nb2O5

T-Nb2O5 is a promising anode material for high power density lithium-ion batteries (LIBs) due to its fast lithium storage capacity and safe lithiation potential. However, its practical application is hindered by its low electronic conductivity. In this work, we improved the electrochemical performance of T-Nb2O5 by surface P-doping and the N-doped carbon substrate. Surface P-doping guided by defects enhances the electronic conductivity of the material, which can synergize with N-doped carbon substrates to form a conductive network and accelerate the lithiation/delithiation process. More importantly, surface P-doping does not destroy the internal crystal structure of the material, ensuring the stability of the Nb2O5 during the charge/discharge process. When used as the anode for LIBs, the Nb2O5-P/N-C exhibits great cycling stability and high-current charge/discharge performance. The specific capacity of Nb2O5-P/N-C exceeds 116 mAh g−1 after 1000 cycles at 1000 mA g−1. This work presents a novel approach to improve the electrochemical performance of T-Nb2O5.

Modification of Ceritinib Crystal Morphology via Spherical Crystallization

The formulation process for some drugs can be challenging, due to their unfavorable physical and mechanical properties and poor water solubility. Powder technology has made a significant impact in regard to the modification of the particles in active pharmaceutical ingredients (APIs) to produce high-quality granules. Spherical particles are preferred over other shapes, due to their high tap and bulk density, reduced dustiness, better flowability, strong anti-caking properties, and better mechanical performance during tableting. The present study investigates the possibility of obtaining spherical crystals of ceritinib, a drug used for the treatment of anaplastic lymphoma kinase (ALK)-positive advanced non-small cell lung cancer, which belongs to BCS class IV drugs and has a platy crystal structure. Ceritinib spheres were prepared by spherical agglomeration, in a ternary system, and quasi-emulsion solvent diffusion, with the addition of polyvinylpyrrolidone, as well as a combination of these two methods. With the combined method of spherical crystallization, crystals with the most favorable morphology and the narrowest distribution of particle sizes were obtained, which was the reason for further optimization. The influence of different impeller geometries and mixing rates on the morphology of the obtained crystals was examined and the optimal conditions for the process were selected. Using empirical correlations and a visual criterion, the process was scaled up from a 0.1 L to a 1 L batch crystallizer. The obtained crystals were characterized by light and scanning electron microscopy. The addition of a bridging liquid and/or a polymer additive did not change the internal structure of the ceritinib crystals, which was confirmed by X-ray powder diffraction.

Liquid Crystal Ordering in Densely Packed Colloidal Suspensions of Highly Anisotropic Monolayer Nanosheets

Monolayer nanosheets of zirconium phosphate in aqueous suspension exhibit short-range repulsion and long-range attraction, producing, at overall volume fractions larger than about half a percent, phase separation into higher-concentration liquid crystal and lower-concentration isotropic regions. At high concentrations, this phase separation takes the form of an emulsion of condensed, liquid-crystalline droplets, which anneal to form lens-shaped tactoids. These tactoids provide an opportunity to study the liquid crystal ordering of inorganic nanosheets in the limit of large shape anisotropy (diameter/thickness~400) and high packing fraction (volume fraction ≳ 70%). The internal liquid crystal structure of the tactoids remains nematic even under conditions that would usually favor ordering into lamellar smectics. Local lamellar ordering is suggested by short-range, smectic-like layer correlations, but a full transition into a smectic phase appears to be inhibited by the nanosheet edges, which act as a perturbative population of dislocation loops in the system of layers. Under conditions of thermal equilibrium, the nanoplates organize positionally to enable bend deformation of the director, a hallmark of the nematic phase and its principal distinction from the smectic, where bend must be expelled.

Influence of bottom supporting columns and cooling rate on the surface shape characteristics of sapphire substrates

The manufacturing process of sapphire substrates involves several key steps, including epitaxy, annealing, cutting, and processing. Among these, epitaxy and annealing are particularly crucial. The temperature variances along both the longitudinal and transverse axes within the furnace during the crystallization process play a significant role in determining the crystallization rate and internal structure of sapphire crystals. Furthermore, annealing sapphire serves to alleviate internal stress, enhance crystal structure, optimize physical properties, improve optoelectronic characteristics, enhance surface quality, and increase overall yield. This step is paramount in enhancing the performance and application value of sapphire materials. In order to investigate and optimize the effects of different thermal conductivities of support columns at the base and various annealing procedures on the surface characteristics of sapphire substrates, thereby improving product quality, this study conducted research by utilizing support columns made of different materials and carefully controlling the cooling rate parameters for sapphire. The findings revealed that using graphite as the base support column for the crystal furnace can reduce both the longitudinal and transverse temperature gradients within the furnace, consequently promoting crystal growth and enhancing the quality of sapphire ingots. Additionally, sapphire chips annealed using the rapid one-step annealing program exhibited the highest average warpage and bending rate variation, reaching 2.0 μm, and the average dislocation density was half that of conventionally produced chips, at 108.89 pits/cm2.

In-depth approach and establishment from a structural perspective of LiFePO4 cathodes for lithium-ion batteries by a two-step sintering

Most synthesis of olivine LiFePO4 (LFP) studies have emphasized the importance of a two-step sintering process for the formation of a uniform carbon coating. However, in this study, it is found that, as an advantage of the two-step sintering process, stable carbonization not only improves lithium-ion conductivity by forming a coating layer but also increases the uniformity of the internal crystal structure. In addition to basic crystallinity and structure analysis using X-ray diffraction (XRD), in-depth calculations are performed to explain the formation mechanism of crystal structure according to the two-step sintering process and the temperature of the first sintering step. In particular, lattice defects and structural uniformity are closely investigated from the crystal structure perspective by comparing lattice micro-strain and dislocation density. Improvement in lithium-ion conductivity from structural uniformity is also demonstrated through cyclic voltammetry (CV) analysis. As a result, it is confirmed that LFP, which undergoes a high-temperature two-step sintering, has high capacity and excellent cycle retention at high rates. Furthermore, ex-situ XRD analysis demonstrates the performance difference according to lithium-ion mobility by comparing the LiFePO4/FePO4 two-phase transformation reaction of two-step sintered LFP and the plateau stability during charging.

Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic-Inorganic Hybrid Materials with Controlled Internal Structures.

Efficient occlusion of particulate additives into a single crystal has garnered an ever-increasing attention in materials science because it offers a counter-intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization-induced self-assembly is employed to synthesize well-defined and highly anionic poly(3-sulfopropyl methacrylate potassium)41-block-poly(benzyl methacrylate)500 [PSPMA41-PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic‐Inorganic Hybrid Materials with Controlled Internal Structures

AbstractEfficient occlusion of particulate additives into a single crystal has garnered an ever‐increasing attention in materials science because it offers a counter‐intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization‐induced self‐assembly is employed to synthesize well‐defined and highly anionic poly(3‐sulfopropyl methacrylate potassium)41‐block‐poly(benzyl methacrylate)500 [PSPMA41‐PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Fire-resistant and mechanically-robust phosphorus-doped MoS2/epoxy composite as barrier of the thermal runaway propagation of lithium-ion batteries

Thermal runaway propagation (TRP) is an utmost safety issue in battery modules owing to its derivative accidents of fire or explosion. This study develops a novel flame-retardant epoxy resin (EP) board to prevent the battery TRP. The phosphorus doped MoS2 nanowires (PR-MoS2) is designed and incorporated into EP matrix to acquire EP/3.0 PR-MoS2 composite. The composite shows 159.4 % increase in char yield, 56.7 % decrease in peak heat release rate, 56.6 % reduction in peak CO production rate. By using EP/PR-MoS2-3 (EP/3.0 PR-MoS2 composite with thickness of 3 mm) between 103450-pouch cells, TRP can be effectively stopped. Meanwhile, the temperature of surviving battery remains below 100 °C. Of note, the minimum changes in internal crystal structure, chemical composition and electrochemical characteristics are discerned for the surviving battery. This research will offer inspirations for the design of TRP suppression materials, guaranteeing the safety the battery.

In situ X-ray diffraction and thermal simulation of material extrusion additive manufacturing of polymer

Material extrusion additive manufacturing (AM) has gradually become a dominant technology for the fabrication of complex-designed thermoplastic polymers that require a higher level of control over the morphological and mechanical properties. The polymer internal crystal structure formed during the AM process can present significant impacts on the mechanical properties of the individual filaments, as well as the whole structure. Currently, limited details are known about the crystal structure evolution during the material extrusion AM processes of polymers. A novel in situ synchrotron X-ray diffraction (XRD) experimental configuration was developed enabling us to capture the material evolution data throughout the extrusion AM process. The in situ time-resolved data was analysed to reveal nucleation and crystallization sequences during the continuous deposition, with the aid of both complimentary numerical simulations and post-process (ex situ) characterisations. The thermal simulations supported the prediction of the filament temperature profile over time and location during the AM process, while ex situ characterisations validated the correlation between polymer crystallinity (resulting from printing parameters) and corresponding mechanical properties. The results obtained from varied process parameters suggest that the processing temperature has a dominant influence on the crystal microstructure evolution compared to the deposition velocity. A lower processing temperature just above the melting temperature permitted favourable crystallization conditions. The overall analysis demonstrated prospects for enhancing polymer AM, to engineering mechanically hierarchical structures through correlative investigations.

Study on the effect of heat treatment on the structure, mechanical and electrical properties of alumina fiber insulation

In this paper, the heat treatment of alumina fiber was studied. The infiltration agent on the fiber surface was removed after heat treatment at 450 °C for 6 h. TG-DSC, scanning electron microscope, x-ray diffraction, Fourier infrared spectrometer, energy dispersive spectrometer, and patterning were used to analyze the thermal weight loss, fiber surface morphology, crystal structure, and composition of alumina fibers. The results show that the aluminum oxide fiber has excellent temperature resistance and does not undergo crystal phase transformation during thermal weight loss. After heat treatment, the fiber surface infiltration agent ablates and dissolves from the fiber surface, and the internal crystal structure of the fiber remains stable. The tensile testing machine was utilized to test the breaking strength of alumina fiber. The fiber still maintained high strength after heat treatment, and the retention rate of breaking strength was greater than 74%. ZC-90G high insulation resistance measuring instrument and WDY-Ⅱ automatic voltage tester were utilized to analyze the insulation resistivity and breakdown strength of alumina fiber before and after heat treatment. The results show that heat treatment can effectively improve the insulation performance and breakdown strength of alumina fiber.

Study on the soft magnetic properties, corrosion, and wear resistance of Ni–Co–W coatings deposited via laser-assisted electrochemical technique: Potential applications in advanced electromagnetic devices

Ni–Co–W alloy possesses several advantages, including exceptional hardness, outstanding wear resistance, and remarkable high-temperature resistance. The coating exhibits favorable soft magnetic performance when the Co content is high. This study combines the introduction of Co element and laser irradiation to explore the changing mechanisms in the soft magnetic properties, corrosion resistance, and wear resistance. Coatings are electrochemically deposited on copper substrates employing a pulsed current, and a Ni–Co–W coating is assisted-deposited utilizing a picosecond laser with a single pulse energy of 10μJ. The experimental results reveal that when 12 g/L of CoSO4·7 H2O is added to the electrolyte, the Co elements significantly improve the soft magnetic properties of the Ni–Co–W alloy. Meanwhile, the reduction of WO42− is also promoted and the W content is increased (nearly 2.6 times, 1.95 Wt%), thereby obtaining microhardness, corrosion resistance, and wear resistance superior to Ni–W. Laser irradiation effectively increases the W content (nearly 2.3 times, 4.52 Wt%) while reducing surface defect. The increased W content alters the internal crystal structure and refines the grain. Moreover, laser irradiation significantly improves the soft magnetic properties (a 33.17 % increase in Ms, a 12.97 % increase in Hc, and a 5.66 % increase in Mr). This study achieves soft magnetic coatings with excellent corrosion and wear resistance through a laser electrochemical deposition process. It provides new processing ideas and methods for preparing soft magnetic alloy coatings and has broad application prospects in magnetic thin film storage devices and high-frequency electromagnetic devices.

Evaluation of Ammonium Nitrate(V) Morphology and Porosity Obtained by SEM and Tomography Imaging.

This paper presents an evaluation of the morphology of fertilizer-grade and prill-grade ammonium nitrate(V). All samples were analyzed using X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and tomography techniques. The XRD results revealed that despite various provenances, all samples exhibited similar Pmmm symmetry and diffraction patterns. SEM images indicated that prill ammonium nitrate(V) showed a more complex external and internal crystal structure than fertilizer-grade counterparts. Furthermore, tomography analysis revealed that each prill ammonium nitrate(V) sample demonstrated distinct porosity characteristics, including varying pore sizes and distribution patterns. Both methods confirmed that fertilizer-grade ammonium nitrate(V) in the cross-section had a pumice structure, and porous prill ammonium nitrate(V) had a rather complex structure, with a central cavity observed only in the case of Sample 4. The appearance of a central cavity can be explained by the different conditions or manufacturing processes of porous prill ammonium nitrate(V). Moreover, the fertilizer-type ammonium nitrate(V) exhibited the lowest surface-to-volume ratio of ca. 21% compared to the porous-type ammonium nitrate(V). This, together with the lowest surface area of ca. 116 mm2, confirmed the lowest absorption capacity of the fertilizer-grade ammonium nitrate(V) disclosed by the ammonium nitrate(V) producer.

Visualizing the Internal Nanocrystallinity of Calcite Due to Nonclassical Crystallization by 3D Coherent X-Ray Diffraction Imaging.

The internal crystallinity of calcite is investigated for samples synthesized using two approaches: precipitation from solution and the ammonium carbonate diffusion method. Scanning electron microscopy (SEM) analyses reveal that the calcite products precipitated using both approaches have a well-defined rhombohedron shape, consistent with the euhedral crystal habit of the mineral. The internal structure of these calcite crystals is characterized using Bragg coherent diffraction imaging (BCDI) to determine the 3D electron density and the atomic displacement field. BCDI reconstructions for crystals synthesized using the ammonium carbonate diffusion approach have the expected euhedral shape, with internal strain fields and few internal defects. In contrast, the crystals synthesized by precipitation from solution have very complex external shapes and defective internal structures, presenting null electron density regions and pronounced displacement field distributions. These heterogeneities are interpreted as multiple crystalline domains, created by a nonclassical crystallization mechanism, where smaller nanoparticles coalescence into the final euhedral particles. The combined use of SEM, X-ray diffraction (XRD), and BCDI allows for structurally differentiating calcite crystals grown with different approaches, opening new opportunities to understand how grain boundaries and internal defects alter calcite reactivity.

Shish‐kebab structure evolution of HDPE/UHMWPE during hot drawing

AbstractUsing a solution‐mixing method, this research aimed to fabricate high‐density polyethylene (HDPE)/ultra‐high molecular weight polyethylene (UHMWPE) composite materials with uniform dispersion. By incorporating a small quantity of UHMWPE as a nucleating agent, additional contact points were introduced to enhance the crystallization rate of the HDPE matrix. Thermal stretching experiments were conducted on composite systems with varying UHMWPE contents and molecular weight additions at different temperatures. Elevating the stretching temperature was found to decrease the yield strain and yield strength, extend the stage of tensile plastic deformation, and diminish the overall mechanical properties of the composite material. Notably, stretching at temperatures ranging from 90 to 110°C accentuated the development of internal crystal orientation structures. Under low strain conditions, crystal slip was observed to be concentrated, with single crystals undergoing continuous stretching and breaking, resulting in a decrease in the long period. Conversely, at high strains, the induced formation of oriented lamellar structures was observed.Highlights Prepared HDPE/UHMWPE blends by UHMWPE with varying molecular weights. Analyzed the alterations in the HDPE/UHMWPE blends' internal crystal structure. Influence of UHMWPE addition, temperature on the evolution of crystal structure.

Featuring vertical channel structure through directional solidification method to endow GNP-aerogels with enhanced ultra-electromagnetic wave absorption

Three-dimensional (3D) carbon-based electromagnetic waves absorbing materials (EWAMs) have garnered significant attention due to high electrical conductivity, high dielectric loss, low density, and improved characterization of impedance matching. However, there is a paucity of research on the design of material structures. In this regard, we proposed the graphene nanoplates (GNPs) EWAMs featuring a vertically aligned channel structure through liquid nitrogen rapid directional solidification and freeze-drying techniques. By utilizing methyl cellulose (MC) as a binder to modify the internal ice crystal structure, an exceptional electromagnetic waves (EWs) absorption material exhibiting excellent impedance matching characteristics and demonstrating multiple polarization phenomena were created. Notably, the material showcased superior absorption performance with a minimal reflection loss (RLmin) of −57.20 dB. Furthermore, the pre-solidification slurry possesses remarkable plasticity, facilitating the fabrication of various complex structures for EWAMs during directional solidification. This method provides novel insights for future exploration and fabrication of tuneable frequency band EWAMs.

The multifunctional flexible conductive viscose fabric prepared by thiol modification followed by copper plating

Based on the current rapid development of electronic products, the development of light-weight, processable, environmentally friendly, long-life, durable, less corrosive, and tunable conductive composite materials with multiple applications may be the development direction of next-generation electronic devices. In this work, for the first time, we employed 3-Mercaptopropyltrimethoxysilane (3-MT) to modify viscose nonwovens and enhance the copper plating process. The prepared samples were characterized by Fourier transform infrared, Wide-angle X-ray diffraction (WAXD), scanning electron microscope + energy dispersive X-ray spectroscopy (SEM + EDS), thermogravimetric analysis (TGA), electrical resistivity, anti-corrosion, Joule heating, and electromagnetic interference (EMI) shielding. Results showed that 3-MT was covalently bound to the viscose surface through hydrolysis and condensation reactions and introduced SH groups. WAXD confirmed that the thiol modification did not change the internal crystal structure of viscose and copper ions. TGA and surface morphology analysis confirmed that the modified viscose promoted the deposition of metal particles in the copper plating process due to the affinity of thiol to metal so that copper particles almost completely wrapped the viscose fibers. In addition, 3MT@Cu@Viscose exhibits extremely low surface and volume resistivity (346.6 and 333.2 mΩ·m), improved corrosion resistance (corrosion rate reduced by 58% compared to the unmodified sample), fast Joule heating response (within 10 s) in low voltage (1 V) and excellent EMI shielding effectiveness (EMI SE > 50 dB). It showed great potential in future multi-functional electronic products such as electric heating sensors, smart clothing, and EMI shielding barrier.

Crystal structure and thermoelectric properties of bulk polycrystalline (SbxBi1-x)2Se3 alloys

Samples of (SbxBi1-x)2Se3 compounds were synthesized from pure elements via simple melting in evacuated quartz tubes. Internal crystal structure, distribution of constituent elements and surface morphology were examined by X-ray diffraction analysis, energy dispersive x-ray spectroscopy and scanning electron microscope, respectively. Over a temperature range of 300–480 K, electrical and thermoelectrical properties were investigated. The electrical conductivity showed semi-metallic behavior against temperature increasing till a certain point, thereafter, exhibited semiconducting trend. A significant increase was observed due to Sb-doping. Seebeck coefficient exhibited notable increase as temperature increases, reaching its maximum. However, a serious decrease was observed with further temperature increasing. The most Sb-doped compound (Sb0.1Bi0.9)2Se3 showed a maximum power factor of 13.29 μW cm−1 K−2 at 373 K. Temperature dependence of the thermoelectric figure of merit ZT was studied, showing that the values increase with temperature increasing and then decrease. For the pristine Bi2Se3 compound, at room temperature, ZT increased from 0.014 to 0.68 at 363 K and then decreased again to 0.13 at 473 K. Doping with Sb at x = 0.1 resulted in remarkable increase in the ZT values over the entire temperature range. The improvement in electrical conductivity and the power factor are responsible for the greatly enhanced ZT throughout the whole temperature range. The maximum ZT was found at 0.87 for (Sb0.1Bi0.9)2Se3 at 373 K.

Simulated HRTEM images of nanoparticles to train a neural network to classify nanoparticles for crystallinity.

Machine learning approaches for image analysis require extensive training datasets for an accurate analysis. This also applies to the automated analysis of electron microscopy data where training data are usually created by manual annotation. Besides nanoparticle shape and size distribution, their internal crystal structure is a major parameter to assess their nature and their physical properties. The automatic classification of ultrasmall gold nanoparticles (1-3 nm) by their crystallinity is possible after training a neural network with simulated HRTEM data. This avoids a human bias and the necessity to manually classify extensive particle sets as training data. The small size of these particles represents a significant challenge with respect to the question of internal crystallinity. The network was able to assign real particles imaged by HRTEM with high accuracy to the classes monocrystalline, polycrystalline, and amorphous after being trained with simulated datasets. The ability to adjust the simulation parameters opens the possibility to extend this procedure to other experimental setups and other types of nanoparticles.

Multifunctional ammonium salts synergizing etching and passivation capability enable efficient deep-blue CsPbBr3 nanoplates

2,6-Diaminopyridinium hydrobromide has dual functions of etching and passivation. It can peel off the outer layers and simultaneously passivate the internal crystal structure, ultimately achieving high-performance deep blue CsPbBr3 NPLs.

Theoretical investigation of the growth of GaAs on Si(001), Si(110), Si(111), Si(113) and Si(331)

The atomic structure of the first atomic layers of GaAs over Si(hhl) substrates were studied by ab initio calculations employing the density functional theory (DFT). Layered converged Si(hhl) supercells were used to investigate the interfacial interaction with the first Ga/GaAs and As/GaAs layers. Formation energies and volumetric charge densities differences confirms the stronger tendency of the As atoms, compared to Ga atoms, to form bonds with the different Si(hhl) surfaces. We confirm the reported experimental order sequence Si(111) > Si(001) > Si(110) in internal crystal structure quality of GaAs growth via the calculation of the interfacial energy, work of adhesion and total charge transfer. From this work, we expand the sequence in internal crystal structure quality as Si(111) > Si(331) ≥ Si(001) > Si(113) ≥ Si(110).