Formation Mechanism Of Structures Research Articles

Mechanism Studies in Electrochemical Depolymerization Processes of Alkali and Organosolv Lignin

AbstractTo better understand the process and mechanism of lignin structural changes and relative product formation during PbO2 anode electrolysis, a Ti/Sb−SnO2/PbO2 composite electrode has been prepared and utilized for the alkaline electrolytic oxidation of both alkali lignin (AL) and bagasse organosolv lignin (OL). By combining electrochemical measurements, in‐situ FTIR, 2D‐HSQC NMR, and product distribution analysis, we not only investigate the impact of influence factors on the process of lignin depolymerization, but also reveal the depolymerization mechanism from the whole process of lignin structural changes in details. Under certain electrolysis conditions, the highest vanillin yield, 10.1 mg g−1, has been obtained through the electrolysis of alkali lignin, whereas the highest syringaldehyde yield of 4.0 mg g−1 has been achieved during the electrolysis of organic solvent lignin. In particular, AL mainly performs depolymerization through the selective cleavage C−C bonds to produce a series of G unit monomer products of vanillin, acetovanillone, and vanillic acid. By contrast, the depolymerization of OL shows significant selectivity in H units. Particularly, the production of the major H unit monomer product of 4‐vinylphenol has been confirmed by IR spectroelectrochemical studies from the oxidation and decarboxylation of p‐coumaric acid unit.

Order–disorder–order mesophase transitions in self-assembled mesoporous alumina for enhanced CO2 adsorption

The addition of a hydrophobic micelle pore expander to self-assembling mesostructured hybrid materials enables access to new combinations with differently ordered mesophases and enhanced structural properties. Here we detail our investigations into the influence of 1,3,5-trimethylbenzene (TMB) on the self-assembly behaviors of an F127 Pluronic triblock copolymer with an aluminum oxide sol additive. By varying the chemical mixing sequence, the TMB-to-F127 mass ratio and the acid-to-metal molar ratio, we observe that TMB exhibits dual roles, functioning both as a hydrophobic swelling agent and as a low dielectric co-solvent. This induces a mesophase transition from an ordered p6mm lattice to a disordered state and subsequently back to the ordered p6mm phase. We propose a structure formation mechanism based on the DLVO theory to describe the thermodynamics and kinetic mobility of the hybrid micelles during the order-disorder and ensuing disorder-order mesophase transitions. The resulting ordered mesoporous alumina structures, with considerable pore sizes (up to 12 nm), high surface areas (up to 314 m2/g) and pore volumes (up to 0.74 cm3/g), organized pore geometry and variable inorganic wall thicknesses, have shown excellent CO2 adsorption capacities and are appealing for various applications, including stable high temperature catalyst supports, separation and sensing.

Athermal pulsational mode dynamics with negative ions

The stability dynamics of the pulsational mode of gravitational collapse (PMGC), excitable in athermal (nonthermal) spherical complex dust molecular clouds (DMCs) in the presence of active role of negative ions, is semi-analytically investigated. The adopted partially ionized DMC model consists of five constitutive plasma species, well-coupled via the gravito-electrostatic Poisson formalism, depicting the corresponding potential-density correlations. The nonthermal uncorrelated lighter (inertialess) species are electrons, positive ions, and negative ions. The thermal correlated heavier (inertial) species are neutral and charged dust grains. The application of a standard spherical wave analysis results in a generalized linear cubic dispersion equation involving a new set of multi-factorial dispersion coefficients dependent on diverse equilibrium plasma parameters. A numerical illustrative platform is broadly created to analyze the DMC stabilization and destabilization factors relative to the non-local inward Newtonian self-gravity. It is interestingly seen that the DMC stabilizing agents are the radial cloud size, dust charge, neutral dust viscoelastic relaxation time, Tribeche thermostatistical parameters, etc. In contrast, the dust mass and equilibrium neutral dust density show destabilizing effects, and so forth. The results systematically explored here are fairly consistent and reliably correlated with the previous results on structure formation mechanism in the DMCs as heretofore reported extensively in the literature.

Towards Understanding Formation Mechanism of Cellular Structures in Laser Powder Bed Fused AlSi10Mg.

A new approach is proposed that identifies three different zones of the Si-rich network structure (the cellular structure) in laser powder bed fused (LPBF) AlSi10Mg alloy, based on the variation in morphology, grain growth transition, and melt pool solidification conditions. The three identified zones are denoted in the present work as the liquid solidification zone (LSZ), the mushy solidification zone (MSZ), and the heat affected zone (HAZ). The LSZ is the result of liquid-solid transformation, showing small planar growth at the boundary and large cellular growth in the center, while the MSZ is related to a semisolid reaction, and the HAZ arises from a short-time aging process. The boundary between the LSZ and MSZ is identified by the change of grain growth direction and the Si-rich network advancing direction. The boundary between MSZ and HAZ is identified by the start of the breakdown of the Si-rich network. In addition, it is found that the fracture is generated in and propagates along the HAZ during tensile tests.

Polytropic spherical astrocosmic fluid stability in the EiBI gravity with strong collective correlative effects

We herein present a dynamical analysis of the Jeans (gravitational) instability in a viscoelastic polytropic astrocloud within the Eddington-inspired Born-Infeld (EiBI) gravity framework in spherical geometry. The zeroth-order material density curvature corrections to the effective self-gravitational potential are properly incorporated. The applied spherical normal mode analysis yields a unique form of monic cubic dispersion relation with multiparametric coefficients dependent on the diverse equilibrium astrofluidic conditions without invoking any kind of traditional quasi-classic approximation. It is seen that the positive EiBI gravity parameter (χ>0) acts as a stabilizing agent and a negative EiBI gravity parameter (χ<0) acts as a destabilizing agent against the inward non-local self-gravity action. Additionally, we find that larger astroclouds are more prone to gravitational collapse, irrespective of the χ-polarity, and vice-versa. It is further investigated that the cloud temperature plays a stabilizing role at larger wavenumbers and destabilizing at smaller wavenumbers for χ>0. However, for χ<0, the fluid temperature consistently exhibits a destabilizing effect. The viscoelastic relaxation time stabilizes the astrofluid against the self-gravity irrespective of the χ-polarity. The fluid density acts as a stabilizer for χ>0, destabilizer for χ<0, and so forth. This study could be potentially applicable in the EiBI-modified gravitational theory in exploring gravity-driven large-scale astrocosmic phenomena towards structure formation mechanism via the canonical Jeans condensation in diverse astrocosmic conditions.

Elucidating the intrinsic core-shell structure of carbon nanospheres from glucose hydrothermal carbonization

This study explores the core-shell structure formation mechanisms of primary carbon nanospheres (PCNs) through hydrothermal carbonization (HTC) of glucose at 200 °C, focusing on key phase-change polymerization reactions. Colloidal carbon nanoparticles in the aqueous phase filtrate self-assembled into secondary carbon nanospheres (SCNs) with intrinsic hollow structures during room temperature storage. FTIR results revealed similar functional groups on the surfaces of PCNs and SCNs due to esterification reactions during HTC cooling. XPS and 13 C NMR analyses identified HMF aldol condensation and etherification as dominant reactions for PCNs, while esterification and aldol condensation with levulinic acid were dominant for SCNs. The hypothesis suggests that PCNs initially formed hollow microframeworks but collapsed due to consumption of encapsulated organics, resulting in hydrophobic cores. These cores grew through aggregation (linear) and surface reactions (exponential), internalizing hydrophilic surfaces into hydrophobic cores, forming the final core-shell structure of PCNs.

Constructing structure-gradient silicone rubber/CNTs foam with desirable resilience and strength via green supercritical CO2 foaming of non-equilibrium gas concentration profiles

In comparison to uniform foams, structure-gradient foams can offer practical solutions that optimize their resilience and strength. However, controlling the gradient structure is a challenge, especially in silicone rubber (PMVS) based foams. Herein, a facile and eco-friendly one-step supercritical CO2 (scCO2) foaming technique is presented for fabricating structure-gradient PMVS/CNTs composite foams utilizing a non-equilibrium gas concentration profile. Compared with conventional scCO2 foaming, this method features a more energy-efficient process (lower saturation temperature and time) and results in lighter foam products (density as low as 0.11 g/cm3). Moreover, the formation mechanism of gradient cellular structures in PMVS/CNTs foams and the means of adjusting the cell gradient degree are further discussed. Finally, cyclic compression results demonstrate that PMVS/CNTs foams can be optimized to achieve desirable mechanical strength and resilience by adjusting cell gradient degree.

Mechanism of l-cysteine-induced fibrous structural changes of soybean protein at different high-moisture extrusion zones

In this study, the fibrous structure formation mechanism of soybean protein during high moisture extrusion processing was investigated using a dead-stop operation, and based on the interaction between soybean protein concentrate (SPC) and L-cysteine (CYS). The thermal properties, SDS-PAGE and particle size distribution of the samples from different extrusion zones were investigated. It was revealed that the addition of a moderate amount of CYS (0.1 %) promoted the fibrous structure formation in the SPC extrudates and optimised the textural properties of the SPC extrudates. In the extruder barrel, addition of CYS (0.1 %) promoted protein depolymerisation and unfolding in the mixing and cooking zones, and facilitated protein aggregation in the die and cooling zones. Protein solubility and raman spectroscopy revealed that disulfide bonds were principally responsible for fibrous structure formation; favoured when the intermolecular disulfide bonds (t-g-t mode) was increased. Finally, the transformation of protein conformation was revealed by secondary structure and surface hydrophobicity, which confirmed that the effect of CYS on protein conformation mainly occurred in the cooling zone. This study provides a theoretical basis for the application of CYS to regulate the fibrous structure of meat analogues.

Development and investigation of salt based composite phase change material containing diatomite as skeleton substance by cold sintering technology for medium and high temperature thermal energy storage

This work concerns the development of a nitrate salt based form-stable composite phase change material by cold sintering technology with the employment of diatomite as skeleton substance. Such fabrication strategy has never before been reported in the literature and we demonstrate for the first time the feasibility of salt-diatomite composite production through a cold sintering process by means of sodium hydroxide solution as sintering additive. The microstructural characteristics and development mechanism, chemical and physical compatibility, mechanical strength, phase change behaviour, thermal and shape stability of the composite are investigated to reveal the structure formation and densification mechanism of salt and diatomite. The results show that the composite could be sintered at a temperature of 180 °C, far lower than that required in the traditional hot sintering approach. Due to the congruent solubility of the salt and diatomite in aqueous alkali, a rigid and dense structure induced by a so-called dissolution-precipitation process could be generated in the composite, which provides solution to accommodate the salt, endowing the composite with splendid capacity to maintain the structure stability and restrain the liquid leakage over the phase change process. An excellent chemical and physical compatibility has been achieved between the salt and other components, and over 60 wt% salt could be encapsulated in the composite by which a melting temperature around 278 °C and an energy storage density over 650 kJ/kg at a temperature range of 50–600 °C are attained. The results also reveal that the composite exhibits preeminent mechanical strength and excellent thermal cycling performance. For a given cycling temperature range of 50–500 °C, a stable macroscopic shape with a compressive strength over 210 MPa could be achieved in the composite even after 100 times of thermal cycles.

Non-destructive method of blood serum composition analysis in forensic science

The article is devoted to consideration of non-destructive methods of blood serum composition analysis in forensics, problem solving and their improvement. At the current stage of creating materials and devices of a new generation, the task is not only to manage their properties, but also to effectively use them in various fields, in particular, in forensics. Analysis of the structural evolution of a heteroatomic liquid (in particular, blood) from the standpoint of theoretical and experimental approaches allows us to open new horizons in the practical plane, to determine the phenomenology of the process based on modern research methods. The authors of this work conducted a qualitative and quantitative analysis of experimental data related to the kinetics and mechanisms of structure formation of a multicomponent substance in the liquid state. It should be emphasized that the structural kinetics of a liquid such as blood serum, or blood itself, is a complex multistage process.

Identification of a Curtius Rearrangement Byproduct in LPA1 Antagonist (BMS-986020) Synthesis

BMS-986020 was developed as an antagonist of the LPA1 receptor for the treatment of lung fibrosis (Idiopathic Pulmonary Fibrosis (IPF)). During the development of BMS-986020, a high percentage byproduct was observed in the mother liquor of a Curtius rearrangement reaction. The structure identification and formation mechanism of this unknown byproduct was deemed necessary to understand for further the reaction optimization and knowledge generation for the project. The characterization process required a multifaceted approach utilizing LC-HRMS, VT-NMR, and HPLC isolation. The investigation’s final result implicated the reaction base as the root cause of the byproduct formation and indicated a nitrene-iminium reaction pathway to form the byproduct.

Preparation of Edible Colorant Lake Using Calcium Carbonate and β-Carotene: Structural Characterization and Formation Mechanism Study.

This study prepared a novel β-carotene colorant lake using calcium carbonate (CaCO3) and investigated the lake formation process and its basic characteristics. Kinetic adsorption analysis confirmed that medium pH (9.3) and medium temperature (40 °C) were more suitable for lake preparation, while desorption occurred, possibly due to crystalline transformation of CaCO3. The isothermal analysis and model fitting results suggested that the β-carotene and CaCO3 particles combined via a monolayer adsorption process driven by physical force. Electrostatic attraction likely participated in the process due to the net negative surface charges of β-carotene dispersion and positively charged groups on the CaCO3 particle surfaces. Ethanol, ultrasonic treatment, and drying method significantly influenced the immobilization efficiency (IE) of β-carotene in the lake and light stability of the lake, without affecting its crystal form. The thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) curves confirmed absorption of β-carotene onto CaCO3. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicated no obvious chemical bonds between β-carotene and CaCO3. Energy-dispersive spectroscopy (EDS) confirmed the presence of β-carotene on surfaces but not in the interior of the CaCO3 particles. The adsorption of β-carotene by calcium carbonate was further confirmed to be a physical adsorption on surface.

Microstructure and formation mechanism of the transition layer at the interface of Al–Cu EMPW joint

In the dissimilar metal welding field, electromagnetic pulse welding (EMPW) is a kind of potential technology. To further reveal the bonding mechanism of EMPW, this work carried out a Cu–Al sheet EMPW experiment with a discharge voltage of 15 kV and a gap of 1.5 mm. It analyzed the microstructure and formation mechanism of the Cu–Al EMPW joint bonding interface transition layer in detail by SEM, EDS, TEM, and FIB. The transition layer was found at the vortex zone, and there was an isolated long strip Cu particle separated from the main body of the Cu sheet. The tested results showed that the transition layer contained Al-rich intermetallic compound (IMC) Al2Cu, and some bulk particles in the transition layer were Cu-rich IMCs Al4Cu9 and AlCu4. There were Cu-rich IMCs Al4Cu9, AlCu4, and AlCu between the long strip Cu particle and the IMC transition layer. In the violent impact process between the Cu sheet and Al sheet, the Cu rapidly diffused in the Al matrix to form the Al-rich IMC (Al2Cu) as the primary transition layer, and the interface was high temperature and high pressure, forming a plastic flow and vortexes swirling. Some Cu particles separated from the Cu sheet and became the vortex piece during the plastic flow process, and continued to interact with the Al2Cu primary transition layer to form the secondary transition layer. This work could provide a basis for revealing the structure composition and formation mechanism of the Cu–Al EMPW joint interface transition layer.

Novel process for facile preparation of mesoporous silica-based materials with controllable pore structure from coal fly ash

Extraction of silica from fly ash to produce mesoporous silica materials is one of the most important utilization approaches. Mesoporous silica could not be synthesized on a large-scale by conventional sol-gel method. In this paper, facile preparation of mesoporous silica with controllable pore structure from fly ash by the template-free process via two steps of mineral phase transformation and selective acid etching was proposed. The influence of crystalline structure and acid etching degree on structure of as-synthesized mesoporous silica materials was revealed, as well as mechanism of crystalline structure transformation and pore structure formation. The results show that mullite and quartz could be transformed into acid-soluble kaliophilite when fly ash reacted with K2CO3 at temperature of 800–1100 °C. The hexagonal kaliophilite would be transformed into orthorhombic KAlSiO4–O1 phase when the temperature is controlled at 1100 °C. Mesoporous silica with specific surface area of 475.93 m2/g and 642.57 m2/g could be synthesized from activated fly ash with kaliophilite and KAlSiO4–O1 phase crystalline structure. By controlling the degree of acid etching, mesoporous silica materials with different pore structures can be obtained. This paper provides a cost-effective and large-scale process for the preparation of mesoporous silica materials with controllable pore structure from solid waste fly ash.

Grain boundary engineering using self-organized high-index twins produced by twin-twin reactions in β-Ti alloys: A phase field study

Introducing coherent twin boundaries is an effective way to develop submicron/nano-sized grains with improved thermal stability in polycrystals, which exhibit enhanced mechanical properties of metals, such as high strength, high hardness and high fracture toughness. However, crystalline defects, such as dislocations and disclinations, usually arise at twin boundary junctions, which lead to local stress concentration and property degradation. Here we show that a large number of high-index coherent twin boundaries (e.g., Σ11 and Σ19a) can be produced through a well-controlled deformation twinning process. By using metastable β-Ti alloys as an example and analyzing the broken symmetry associated with deformation twinning, we demonstrate that the abnormal high-index twins result from intercorrelated twinning pathways and twin-twin reactions. The formation mechanism of self-organized multi-twin structures has been analyzed systematically through phase field modeling and simulations. It has been found that, under well designed thermo-mechanical condition, regularly distributed high-index twin boundaries and geometrically-compatible twin boundary junctions (i.e., dislocation/disclination-free) can be produced. The stress/strain condition required to obtain self-organized twins has been quantitatively determined, which provides a theoretical guideline for the development of self-organized submicron/nano-twin metals for unprecedented properties.

Mechanisms of Structure Formation under Severe Plastic Deformation: A Review

Mechanisms of Structure Formation under Severe Plastic Deformation: A Review

The spatial correlation network structure and its formation mechanism of urban high-quality economic development: a comparative analysis from the Yangtze River Economic Belt and the Yellow River Basin in China.

In the context of regional integration, it is more than crucial to compare and analyze the spatial correlation network structure and formation mechanism of high-quality economic development in the Yangtze River Economic Belt and the Yellow River Basin urban cities as an attempt to strengthen collaborative work on high-quality economic development in both river basins. The paper measured high-quality economic development of the Yangtze River Economic Belt and the Yellow River Basin from 2010 to 2021. Then, it employed social network analysis and the QAP method to study the network structure's characteristics and formation mechanism. The conclusion of the research illustrates a few points clearly that first, the high-quality economic development of the two rivers presents a complex and multithreaded network structure. Although the network structure is hold at a comparatively stable state, the correlation degree needs improvement. Second, cities such as Chongqing, Wuhan, Hefei, Nanjing, Hangzhou, Shanghai, and Changsha and cities like Zhengzhou, Xi'an, Luoyang, Yulin, Hulunbuir, Ordos, and Nanyang are at the very central as well as central position of the network. The spatial correlation networks of the Yangtze River Economic Belt and the Yellow River Basin can be divided into four plates: "agent plate," "main outflow plate," "bidirectional spillover plate," and "main inflow plate." Third, reverse geographical distance and differences in the digital economy attach great significance to the spatial correlation networks of the two basins. The difference in urbanization level makes significant impacts only on the spatial correlation network of the Yangtze River Economic Belt, while the difference in environmental regulation and material capital accumulation only significantly influences the spatial correlation network of the Yellow River Basin.

Safe Explosion Works Promoted by 2D Graphene Structures Produced under the Condition of Self-Propagation High-Temperature Synthesis

The paper presents the results of a study on the effectiveness of few-layer graphene synthesized under SHS conditions from lignin as a modifying additive in creating composite pyrotechnic complexes based on porous silicon and calcium perchlorate. It was found that the addition of few-layer graphene (20–30 wt. %) could significantly increase the probability of the ignition of pyrotechnic compositions by laser diode (infrared) radiation (wavelength of 976 nm and power of 15 MW/m2) compared to the initial pyrotechnic compositions. Using few-layer graphene also leads to a sharp increase in sensitivity to infrared laser radiation and the initiation of explosive transformations in retrofitted pyrotechnic compositions compared to the initial pyrotechnic compositions. Due to the high productivity and low cost of the technique for synthesizing few-layer graphene, the use of composite pyrotechnic compositions modified with few-layer graphene is profitable in the actual industry. A phenomenological model of the formation mechanism of 2D graphene structures under the conditions of the SHS process is proposed.

SUPRAPLASTIC DEFORMATION OF ALUMINUM-LITHITHIUM ALLOYS 1450 AND 1460, ALLOYED WITH ZIRCONIUM AND SCANDIUM

The article presents the results of research directed to the determination of mechanisms of an ultrafine-grained structure formation in aluminum-lithium alloys 1450 and 1460, which include dispersed particles of zirconium and scandium aluminides, which are effective stabilizers of the microstructure, as well as for the determination of the features of structural changes during the course supraplastic deformation.

CeO2 -Based Frustrated Lewis Pairs via Defective Engineering: Formation Theory, Site Characterization, and Small Molecule Activation.

Activation of small molecules is considered to be a central concern in the theoretical investigation of environment- and energy-related catalytic conversions. Sub-nanostructured frustrated Lewis pairs (FLPs) have been an emerging research hotspot in recent years due to their advantages in small molecule activation. Although the progress of catalytic applications of FLPs is increasingly reported, the fundamental theories related to the structural formation, site regulation, and catalytic mechanism of FLPs have not yet been fully developed. Given this, it is attempted to demonstrate the underlying theory of FLPs formation, corresponding regulation methods, and its activation mechanism on small molecules using CeO2 as the representative metal oxide. Specifically, this paper presents three fundamental principles for constructing FLPs on CeO2 surfaces, and feasible engineering methods for the regulation of FLPs sites are presented. Furthermore, cases where typical small molecules (e.g., hydrogen, carbon dioxide, methane oxygen, etc.) are activated over FLPs are analyzed. Meanwhile, corresponding future challenges for the development of FLPs-centered theory are presented. The insights presented in this paper may contribute to the theories of FLPs, which can potentially provide inspiration for the development of broader environment- and energy-related catalysis involving small molecule activation.