Structural Evolution Research Articles

Unveiling the Electrostatically Driven Collapsing and Relaxation of Polyelectrolyte-Colloid Complexes: A Tunable Pathway to Colloidal Assembly.

Polyelectrolyte-colloid (PEC) complexes, ubiquitous across diverse fields, exhibit remarkable phase transitions, mimicking intricate biological assemblies. While the role of electrostatic forces in the PEC complex assembly is undeniable, achieving a holistic comprehension remains an elusive goal. This study unveils a fascinating phenomenon: the formation of highly collapsed coacervate structures in PEC complexes at elevated polyelectrolyte concentrations, followed by the swelling of complexes at even higher concentrations. Employing anionic silica colloids and cationic chitosan as a model system, small-angle X-ray/neutron (SAXS/SANS) elucidates the transition from a bead-on-a-necklace-like phase to a dense packed coacervate state (with volume fraction ∼0.62) until 3 wt % concentration of the polyelectrolyte. However, beyond 3 wt %, swelling of the dense collapsed assembly is observed. This structural evolution of PEC complexes as a function of chitosan concentration is attributed to the interplay of electrostatically driven interactions and the Donnan effect. Notably, the critical concentration for coacervation, Cs*, demonstrates a linear dependence on the initial colloid concentration. Interestingly, a complete expansion of the coacervate is observed at a high polyelectrolyte concentration, particularly for dilute colloid solutions (2 wt %). Furthermore, the addition of an electrolyte sheds light on the delicate interplay of forces. While a low electrolyte concentration partially screens charges, leading to a shift in phase diagram, higher concentrations trigger complete coacervate dissolution beyond the critical electrolyte concentration of 0.2 M, due to the complete screening of electrostatic charges.

Optical transmission, dielectric constants, and gamma shielding performance of Se95-xIn5Prx metallic alloys: Radiation protection applications

Due to the high density of metals, metallic materials such as alloys have the potential to have high gamma-radiation-absorbing abilities. This would make them relevant in a radiation environment as either a shielding material or a radiation sensor. These would, however, depend on their gamma radiation responses. Research aimed at evaluating the gamma response parameters of different glassy alloys that have technical applications is scarce compared to the traditional characterization with respect to optical features, structural evolution, and mechanical strength. In this paper, the optical and radiation shielding abilities of Se95-xIn5Prx (x = 2, 4, and 6) glassy alloys were investigated using standard theoretical techniques. The mass attenuation coefficient (MAC) of the materials was computed using the XCOM software. Reflection loss values are 0.20218, 0.22634, and 0.22908 for SIPr1, SIPr2, and SIPr3, respectively, while the optical transmittance values are 0.66365, 0.63087, and 0.62723 in the same order. The metallization criterion declined when Pr increased in the alloy. The values of MAC ranged from 0.0317 cm2/g to 98.2099 cm2/g for SIPr1, 0.0319 cm2/g to 97.3798 cm2/g for SIPr2 and 0.0322 cm2/g to 96.5372 cm2/g for SIPr3. The Higher attenuation and absorption coefficients were found for Pr-rich alloys. Pr therefore increase the ability of the SIPr-alloy to attenuate and absorb photon energy. The optical parameters of the investigated alloys could be used to identify their optical applications. SIPr3 had comparatively higher shielding ability compared to some known shields and could thus be used for radiation control and protection purposes.

Low Temperature and Rapid Synthesis of Li‐Rich Li(Li0.17Mn0.83)2O4 Spinel Cathodes Derived from Metal‐Organic Frameworks for Lithium‐Ion Batteries

Li‐rich spinel materials are a kind of promising cathode for lithium‐ion batteries because of their low cost and excellent rate performances. Nevertheless, their synthesis always involves high temperature and long time calcination, leading to low synthesis efficiency and high energy consumption. Herein, a low temperature and rapid synthesis strategy was developed to prepare Li‐rich Li(Li0.17Mn0.83)2O4 (LMO‐F) spinel cathodes in 8 minutes at 500 oC benefited from LiMn‐MOF precursor. The composition and structural evolution during pyrolysis process was systematically investigated to clarify the relationship between precursors and derivative. The results showed that short distances and uniform distributions of elements at atomic‐level in the MOF precursor promote cations diffusion result in ultrafast homogeneous nucleation of derivative. Notably, the LMO‐F achieved good electrochemical performance with 100.4 mAh g‐1 at 50 mA g‐1 after 100 cycles.

Structural Evolution and Tribological Properties of WC Particles-Strengthened Nickel-Based Cladding Layers

Structural Evolution and Tribological Properties of WC Particles-Strengthened Nickel-Based Cladding Layers

Using In situ Transmission Electron Microscopy to Study Strong Metal-Support Interactions in Heterogeneous Catalysis.

Precisely controlling the microstructure of supported metal catalysts and regulating metal-support interactions at the atomic level are essential for achieving highly efficient heterogeneous catalysts. Strong metal-support interaction (SMSI) not only stabilizes metal nanoparticles and improves their resistance to sintering but also modulates the electrical interaction between metal species and the support, optimizing the catalytic activity and selectivity. Therefore, understating the formation mechanism of SMSI and its dynamic evolution during the chemical reaction at the atomic scale is crucial for guiding the structural design and performance optimization of supported metal catalysts. Recent advancements in in situ transmission electron microscopy (TEM) have shed new light on these complex phenomena, providing deeper insights into the SMSI dynamics. Here, the research progress of in situ TEM investigation on SMSI in heterogeneous catalysis is systematically reviewed, focusing on the formation dynamics, structural evolution during the catalytic reactions, and regulation methods of SMSI. The significant advantages of in situ TEM technologies for SMSI research are also highlighted. Moreover, the challenges and probable development paths of in situ TEM studies on the SMSI are also provided.

Unconventional structural evolution of an oxide surface in water unveiled by in situ sum-frequency spectroscopy.

Oxide-water interfaces host a wide range of important reactions in nature and modern industrial applications; however, accurate knowledge about these interfaces is still lacking at the molecular level owing to difficulties in accessing buried oxide surfaces. Here we report an experimental scheme enabling in situ sum-frequency vibrational spectroscopy of oxide surfaces in liquid water. Application to the silica-water interface revealed the emergence of unexpected surface reaction pathways with water. With ab initio molecular dynamics and metadynamics simulations, we uncovered a surface reconstruction, triggered by deprotonation of surface hydroxylated groups, that led to unconventional five-coordinated silicon species. The results help demystify the multimodal chemistry of aqueous silica discovered decades ago, bringing in fresh information that modifies the current understanding. Our study will provide new opportunities for future in-depth physical and chemical characterizations of other oxide-water interfaces.

An early cladoxylopsid with complex vascular architecture: Paracladoxylon kespekianum gen. et sp. nov. from the Lower Devonian (Emsian) of Quebec, Canada.

Cladoxylopsids, one of the first lineages with complex organization to rise from the plexus of structurally simple plants that comprised the earliest euphyllophyte floras, are moniliformopsid euphyllophytes. They formed Earth's earliest forests by the Middle Devonian and are thought to have given rise to the equisetopsids and probably some fern lineages. The Lower Devonian (Emsian) Battery Point Formation (Quebec, Canada) contains previously unrecognized cladoxylopsids preserved anatomically. One of these provides new data on structural evolution among euphyllophytes and is described here. The anatomy and morphology of permineralized axes of the new plant were studied with light and electron microscopy on sections produced using the cellulose acetate peel technique. Morphological comparisons and phylogenetic analysis were used for taxonomic placement of the plant. The plant represents a new species, Paracladoxylon kespekianum Chu et Tomescu, gen. et sp. nov., that has tracheids with modern-looking bordered pits and the complex cauline vascular architecture characteristic of the genus Cladoxylon. Its dissected ultimate appendages have complex regular taxis and a pattern of vascularization that suggests bilateral symmetry. Paracladoxylon kespekianum is one of the largest Early Devonian euphyllophytes, among the oldest representatives of the cladoxylopsid group, and older than any species of the closely related Cladoxylon by at least 35 million years. It is also one of the oldest anatomically preserved representatives of the cladoxylopsid group. Its anatomical organization pushes the rise of complex vascular architecture among moniliformopsid euphyllophytes deeper in time than previously recognized.

Analysis of Controlling Factors of Pore Structure in Different Lithofacies Types of Continental Shale—Taking the Daqingzi Area in the Southern Songliao Basin as an Example

Due to the influence of terrigenous debris, the internal pore structure of continental shale is highly heterogeneous, and the controlling factors are complex. This paper studies the structure and controlling factors of shale reservoirs in the first member of the Qingshankou Formation in the Southern Songliao Basin using core data and various analytical test data. The results show that the original deposition and subsequent diagenesis comprehensively determine the shale reservoirs’ pore structure characteristics and evolution law. According to the severity of terrigenous debris, the shale reservoirs in the study area are divided into four categories and six subcategories of lithofacies. By comparing the characteristics of different shale lithofacies reservoirs, the results show that the lithofacies with a high brittle mineral content have more substantial anti-compaction effects, more primary pores to promote retention and a relatively high proportion of mesopores/macropores. Controlling the organic matter content when forming high-quality reservoirs leads to two possibilities. An excessive organic matter content will fill pores and reduce the pore pressure resistance. A moderate organic matter content will make the inorganic diagenesis and organic hydrocarbon generation processes interact, and the development of organic matter mainly affects the development of dissolution pores. The comprehensive results show that A3 (silty laminated felsic shale) reservoirs underwent the pore evolution process of “two drops and two rises” of compaction, cementation and pore reduction, dissolution and pore increase, and organic matter cracking and pore increase, and they are the most favourable lithofacies of the shale reservoirs in the study area.

Experimental and numerical investigation of the damage propagation in regularly arrayed short fiber reinforced composite laminates under low‐velocity impact

AbstractThe outstanding mechanical performance and flowability of unidirectionally arrayed chopped strands (UACSs) give them an advantage in the manufacture of engineering structures with complex geometry. For the application of practical structures, the impact responses and damage evolution of material under low‐velocity impact must be investigated in advance. In this study, UACS laminates and continuous carbon fiber laminates with a stacking sequence of [0/90]4s and a thickness of 2 mm were fabricated for low‐velocity impact tests at 7, 11, 15, and 20 J. The impact responses and postimpact intralaminar damage area were analyzed according to the experimental results, including impact load responses and ultrasound C‐scan inspections. Moreover, to predict the damage evolution of the internal structure, the 3D finite element models were constructed in ABAQUS using a progressive damage model (PDM) through a user‐material subroutine VUMAT. Compared with continuous carbon fiber laminates, the dissipated energy of UACS laminates increases by approximately 10.64% and 57.37% for the 15 and 20 J, respectively. However, the intralaminar damage area of UACS laminates decreased by 29.96% and 28.16% at 15 and 20 J, respectively, since the discontinuous slits in UACS laminates can guide damage paths and suppress damage propagation.Highlights The regularly arrayed short fiber reinforced composite was studied. Revealed the low‐velocity impact responses and predicted the damage evolution. UACS and CFRP laminates have comparable impact performance. Illustrated the slits design can suppress the damage to a relatively small area.

Correlation between sewage sludge pore structure evolution and water filtration performance: Effect of thermal hydrolysis with or without carbonaceous skeleton-assisted

Municipal sewage sludge contains a high water content and strong hydrophilicity, making mechanical dewatering a critical step in sludge treatment and disposal. To clarify the collapse of filtration channels within the sludge cake under high pressure and to develop more precise targeted conditioning methods, this study focused on the direct correlation between pore structure evolution and sludge dewatering performance. A self-designed online system was used to compare the dewatering processes of raw sludge, thermal hydrolyzed (TH) sludge, and carbonaceous skeleton-assisted thermal hydrolyzed (CSkel-TH) sludge. In-depth analysis was conducted on the structure scanning data of the filter cake at different time intervals and the corresponding filtrate mass data. The results showed that during the press filtration process, the raw sludge gradually transformed into a filter cake, with larger pores trapping the water. In the upper and bottom layers, regions with a porosity higher than 10 % appeared, forming a “water-locking layer” even with continued pressure, it became impossible to remove additional water. After separate hydrolysis, the porosity and pore connectivity of the sludge decreased, and the thickness of the “water-locking layer” increased as press filtration progressed, inhibiting water discharge and making cake formation difficult. Following CSkel-TH treatment, the number of pores with diameters ranging from tens to over a hundred micrometers increased, and the connectivity between pores was enhanced. In this case, the channels formed by interconnected small pores continuously transported the water trapped in the large pores outward, facilitating water discharge. This work provided a basis for further targeted regulation of pore structures to enhance the effectiveness of high-pressure dewatering of sludge.

Trance Amount of Ir Decorated NiFe Phosphide In-Situ Grown on Carbon Cloth as Cost-Effective Electrocatalyst for Oxygen Evolution Reaction.

Cost-effective electrocatalysts is a key constituent to establish the balance of cost and catalytic efficiency for oxygen evolution reaction (OER) via water electrolysis in the area of energy conversion and storage. NiFe phosphide decorated with trace amount of iridium (Ir) species in-situ grown on carbon cloth was prepared by a facile wet chemistry approach followed by a phosphorization post-treatment at a relative low temperature. The optimal electrocatalyst, Ir2-NiFePx/CC, exhibits excellent OER activity, with an low overpotential of 190 mV at 10 mA cm-2 for alkaline OER, and a desirable long-term durability over 90 h. The outstanding OER performance stems from the structural evolution via phosphorization process, Ir decoration with more high-valence stated Ir4+ species, and tight connection between individual components of the electrode, which gives rise to the strong activity to the active sites and faster reaction kinetics in the alkaline OER process. Mover, the Ir loading was as low as approximately ~1.7 wt% (0.29 mg cm-2), showing promissing propective in cost-effective OER.

A multilocus perspective on the evolutionary dynamics of multistrain pathogens

Many human pathogens, including malaria, dengue, influenza, Streptococcus pneumoniae , and cytomegalovirus, coexist as multiple genetically distinct strains. Understanding how these multistrain pathogens evolve is of critical importance for forecasting epidemics and predicting the consequences of vaccination. One factor believed to play an important role is naturally acquired immunity. Consequently, a large body of research has sought to predict how acquired immunity molds the genomics of pathogen populations (i.e., what shapes pathogen strain structure). The diversity of existing models has resulted in conflicting evolutionary predictions and has sparked an ongoing debate about which predictions are most broadly applicable. Here, we adopt a multilocus population genetics perspective that unifies the predictions of existing models. We identify three key factors that determine the role of naturally acquired immunity in the evolution of pathogen strain structure: i) the strength and specificity of immune protections, ii) the dynamic immunological landscape, and iii) the number of loci coding for the antigens of the pathogen. Isolating and discussing these three factors clarifies the relationship among previous models of multistrain dynamics, and establishes a solid theoretical foundation for the study of the evolutionary epidemiology of multistrain pathogens.

Fe(II)-Catalyzed Recrystallization Drives Phosphorus and Aluminum Release from Goethite.

Goethite often harbors impurities, such as phosphorus (P) and aluminum (Al), which are incorporated into its structure through direct substitution or coprecipitation with nanocrystalline phases. Understanding the processes that drive the release of P and Al from goethite is of paramount importance for the iron ore industry and for managing nutrient and pollutant behavior in the environment. This study investigates the impact of Fe(II)-catalyzed recrystallization on the release of P and Al from goethite. We evaluated the solubility and extractability of P and Al in suspensions of Al- and P-coprecipitated goethite, treated with 57Fe-enriched Fe(II)aq under oxygen-free conditions for 30 days at neutral pH and room temperatures. The addition of Fe(II)aq induced the recrystallization of goethite dominant initial synthetic phases (i.e., low P- and Al-containing phases) and the transformation of higher P- and/or Al-bearing starting material that was actually a mixture of goethite and minor amounts of lepidocrocite and feroxyhyte. Our results reveal that Fe(II)-catalyzed mineral and structural evolution led to the repartitioning of P and, to a lesser extent, Al throughout the crystal structure, mineral surface, and aqueous solution. Following a 30 day reaction with Fe(II)aq, we extracted approximately 80, 68.8, 73.9, and 83.2% of P from P-only, low, medium, and high P + Al goethite, respectively. Additionally, we observed total Al removals of approximately 17, 27, and 25% from low, medium, and high P + Al goethite, respectively. The results demonstrate that treating both P-only and P + Al goethite with Fe(II) at room temperature, followed by a 24 h extraction using 1 M NaOH, significantly enhances the overall extractability of P and Al, including both aqueous and surface-adsorbed fractions, compared to Fe(II)-free controls. These findings advance our understanding of the recrystallization process and impurity substitution in goethite, offering promising avenues for developing new environmentally friendly methods to extract P and other impurities from goethitic iron ores at lower temperatures.

Structural, electronic and dielectric properties of carbon nanotubes interacting with Co nanoclusters

A new frontier in tuning the electromagnetic response of carbon-based materials, particularly carbon nanotubes, consists in adding metallic clusters or nanoparticles at their external surface. This allows to change optical, dielectric and magnetic properties with potential applications in electronics and telecommunications for aeronautics. By resorting to first principles dynamical simulations, we provide a microscopic picture of the interaction at finite temperature between a carbon nanotube and Co aggregates mimicking the experimental coverage. The electronic structure evolution provides the absorption spectrum and the dielectric function for comparison with experiments and guidelines for tuning these composite systems.

Boosting the Structural Reversibility of Layered Oxide Cathode for Realizing Long-Term Cycle Life Through Electronic Structure Regulation.

O3-type layered oxide cathode exhibits great application potential for practical sodium-ion batteries, due to its cost-effectiveness, abundant sodium and manganese resources, and high theoretical capacity. However, the irreversible phase transition, coupled with rapid capacity decay, which is primarily attributed to the Jahn-Teller effect of Mn3+, remains a significant bottleneck for commercial application. Additionally, the sluggish kinetics during the (de)sodiation process require urgent improvement. Herein, an electronic structure regulation strategy is proposed by low-valence Li/Cu co-substitution to address these issues. The roles of Li/Cu on the electronic structure, structural evolution, and electrochemical properties in the Na0.96Ni0.22Fe0.2Mn0.5Li0.04Cu0.04O2 (NFMLC) cathode are comprehensively explored through systematic in situ/ex situ characterization techniques and theoretical calculations. The results reveal that this strategy effectively activates more Ni2+/3+ and Fe3+/4+ redox reactions above 2.5V, while suppressing Mn3+/4+ redox activity below 2.5V, thereby achieving highly structural reversibility. Therefore, the NFMLC electrode displays excellent long-term cycling stability (81.5% capacity retention after 2000 cycles at 5 C), and significantly enhanced rate performance (from 45.5% to 80.4% under a ratio of 5 C to 0.5 C). This work provides a valuable perspective on the design of low-cost, long-life, and high-performance layered oxide cathodes for practical sodium-ion batteries.

Spatiotemporal Evolution of Land Use Structure and Function in Rapid Urbanization: The Case of the Beijing–Tianjin–Hebei Region

Spatiotemporal Evolution of Land Use Structure and Function in Rapid Urbanization: The Case of the Beijing–Tianjin–Hebei Region

Study on the evolution of the spatial structure and driving force of traditional village tourism in South Anhui province

Study on the evolution of the spatial structure and driving force of traditional village tourism in South Anhui province

Architecture of the post-obductional Sunub Structure, northeastern Sultanate of Oman: Based on mapping, 3D gravity inversion and shale migration

We examined the structural evolution of the poorly understood Sunub Structure, which is associated with the northern margin of the Saih Hatat Dome and the extensional Frontal Range Fault (northeastern Oman). The Sunub Structure is located at a dextral transtensional segment and on the hanging wall of the NNE-striking Frontal Range Fault. The fault was active during the Campanian(?)/Maastrichtian to early Eocene (Interval I) and mid-/late Eocene to early Miocene (Interval II). Gravitational inversion using 175 stations and mapping shows: (1) The Sunub Structure is possibly >1200–1350 m deep and filled mostly with the >900-m-thick Campanian(?)/Maastrichtian siliciclastic Al-Khod Formation, including shale, and some overlying Paleogene limestones. (2) The bottom of the basin cannot be depicted. (3) The lower part of the structure is a basin (Sunub Sedimentary Basin), bounded by sub-vertical to steep contacts. (4) The upper part of the Sunub Structure is a basin fold displaying a bowl-shape down to ∼300 m below the surface, referred to as the Sunub Bowl. (5) The bowl is cut by radial faults and five ∼E/W-striking transverse faults. The Sunub Structure formed during Interval I as a deep transtensional, syn-depositional basin. Gentle post-depositional tectonics during Interval II and visco-plastic shale movements produced the present-day bowl-shape that is visible at the surface. Gravitational inversion depict possible evidence for shale migration within the Al-Khod Formation. Although no hydrocarbons are present, the Sunub Structure can serve as an analogue for hydrocarbon migration and storage in similar structures.

Synergistic effects of waste coral powder and metakaolin in cement pastes: Hydration, pore structure, rheology, and strength

Coral reefs are abundant in waste coral powder, and how to utilize coral powder efficiently to construct far-sea projects has become a major focus of research and engineering field, which is conducive to the development of green economy. However, existing research lacks a comprehensive and systematic investigation of the cement-coral powder-metakaolin ternary system. In this study, the hydration and rheological behavior, micromechanical and mechanical properties, and pore structure evolution of the ternary system are systematically investigated to uncover the synergistic mechanism between metakaolin and coral powder. The results indicated that, based on hydration, rheology, and mechanical properties, the recommended proportions of cement, coral powder, and metakaolin are 75 %, 10 %, and 15 %, respectively. The combination of coral powder and metakaolin effectively promotes hydration. Furthermore, it accelerates the aluminate reaction, resulting in a stronger aluminate exothermic peak immediately. In addition, metakaolin reacts with coral powder to form carboaluminate, activating the activity of the coral powder, which in turn improves the mechanical properties and pore structure of the ternary system. Moreover, metakaolin undergoes a pozzolanic reaction with calcium hydroxide, which contributes to optimizing the pore structure of the ternary system and enhancing its mechanical properties. Additionally, coral powder promotes the conversion of monosulfate to carboaluminate while inhibiting the transformation of ettringite into monosulfate. The Herschel-Bulkley model accurately simulates the dynamic rheological behavior of the ternary system. This study is highly significant and practically valuable for transforming waste coral powder into a supplementary cementitious material for the construction of the far-sea projects, providing a scientific basis for future related studies.

Defect-Driven Evolution of Oxo-Coordinated Cobalt Active Sites with Rapid Structural Transformation for Efficient Water Oxidation.

Reconstructing the surface nature of metal-organic frameworks (MOFs) as precatalytic structures is a promising methodology for improving electrocatalytic performance. However, regulating the structural evolution of MOFs during electrolysis remains highly uncontrollable and lacks an in-depth understanding of the role of in situ-derived active sites. Here, we suggest a simple approach to fine-tune the symmetry of Co-MOFs with an oxo-coordinated asymmetric coordination that acts as a prototypical structure motif for the oxygen evolution reaction (OER). Through a facile thermal treatment, the Co-N4 configuration of Co-MOFs transforms to the distorted Co-N3-oxo configuration of defective Co-ligand nanoclusters. By operando spectroscopic characterization, the reconstructed Co-N3-oxo structure enables a rapid structural transition toward homogeneous oxyhydroxides. Moreover, the defective nature of the precatalytic structure regulates the surface Co-O bonding environment with abundant μ2-O-Co3+ sites, thereby exhibiting highly enhanced OER activity with an overpotential of 256 mV at 10 mA cm-2 and excellent durability for 100 h, compared with the pristine Co-MOFs. Atomistic simulations reveal that the effect of OER intermediates on the oxyhydroxides gets distributed among neighboring Co ions, promoting balanced binding of the intermediates. This work highlights an effective strategy to design the MOF-based structure for optimizing the surface nature, thus enhancing the electrocatalytic activity.