Monte Carlo Dynamics Simulations Research Articles

Sodium titanate (Na2Ti4O9) nanoribbons for effective removal of organic dyes from water: Experimental and computational studies

In this work, Na2Ti4O9 nanoribbons (NTRs) were synthesized using the hydrothermal method for its potential application in water treatment. The NTRs were characterized by X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, zeta potential, Fourier Transform infrared spectroscopy, and surface area analyzer. The adsorption of organic dyes, including cationic methyl green (MeG) and methylene blue (MB) model pollutants, onto the NTRs was explored for the first time. Various parameters such as pH, adsorbent dose, initial dye concentration, regeneration, contact time, the effect of temperature, and thermodynamics were studied to determine the efficiency of NTRs for removing both dyes from water. A variety of isotherm and kinetic models were applied to fit the dye adsorption data at pH 7.0, providing insights into the adsorption mechanism and process kinetics. Kinetic data for both dyes fit well with pseudo-second-order and mixed 1,2-order models. The isotherm data agreed well with Langmuir-Freundlich and Sips models. At the studied temperatures of 298.2, 318.2, and 328.2 K, the maximum adsorption capacities for MeG (353.2, 367.7, and 443.2 mg·g−1) are significantly higher than for MB (29.3, 52.6, and 67.2 mg·g−1), indicating a stronger affinity for MeG, with adsorption efficiency improving as temperature increases. The MeG samples at 328.2 K exhibited interesting behavior. After adsorption, the samples became colorless, with a final pH near 7.0, indicating effective dye removal. However, the color faintly reappeared at pH 4.0, suggesting pH-dependent behavior and incomplete dye removal. The adsorption mechanism on the NTRs surface was investigated using Monte Carlo and molecular dynamics simulations.

Dynamic CO2 separation performance of nano-sized CHA zeolites under multi-component gas mixtures

To identify and evaluate promising adsorbents for CO2 separation, we synthesized CHA zeolites with different cations (Na+, K+, Cs+) and crystal sizes (45 nm – CHA45 and 500 nm – CHA500), and evaluated their explored CO2 adsorption performance from CO2/N2/He and CO2/CH4/He mixtures. Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations predicted CO2, N2, and CH4 adsorption isotherms and CO2 mobilities, respectively, which were compared to experimental data. Breakthrough curve analysis was used to assess the CO2 dynamic adsorption performance. The breakthrough curve analysis shows the smaller crystal sizes (45 nm) enhance the CO2 separation due to shorter interacrystalline diffusion pathways. Notably, Cs-CHA45 removed 2.2 times more CO2 from CO2/N2/He than Cs-CHA500. K-CHA45 showed the highest CO2/N2 selectivity (108) and achieved 841mmol g−1 for CO2 capture from N2 and 721mmol g−1 for CO2 from CH4. These findings underscore the potential of CHA nanocrystals for effective CO2 separation in various applications.

Experimental and computational analysis of poly(4-vinyl pyridine) and polyvinylpyrrolidone as effective corrosion inhibitors for low carbon steel in sulfuric acid

This study investigates the inhibitory effects of poly(4-vinyl pyridine) (P4VP) and polyvinylpyrrolidone (PVP) on the corrosion of low carbon steel (LCSt) in 1 M H2SO4. Protection efficacy (%PE) was measured using mass loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS). Results showed %PE values increased with higher polymer concentration and lower temperature. At 450 mg/L, %PE reached 93.13% and 94.19% for P4VP and PVP, respectively. These polymers function as mixed inhibitors, adsorbing onto the LCSt surface per Langmuir’s model as a mode of physical adsorption. EIS indicated that higher polymer concentration increased charge transfer resistance and decreased effective double-layer capacitance. Both P4VP and PVP also reduced pitting corrosion in chloride-containing solutions. Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) optimized the molecular structures of the inhibitors, evaluating electronic parameters such as frontier molecular orbital (FMO) energies, energy gap, softness, hardness, electron transfer fraction, dipole moment, and hyperpolarizability ( β ° ). Monte Carlo (MC) and molecular dynamics (MD) simulations provided insights into adsorption mechanisms, corroborating experimental findings and highlighting the effect of protonation. This comprehensive study enhances our understanding of the relationship between molecular structure and function in polymer inhibitors, improving their application in corrosion protection.

Molecular simulations of increased thermal energy storage in metal–organic heat carriers with R1234ze(E)/R32 mixtures combined with IRMOF-1

Metal-organic heat carrier (MOHC) nanofluids offer a promising solution to enhance the efficiency of Organic Rankine Cycle systems. In this study, we developed a computational model to assess the thermal energy storage capacity of MOHC nanofluids using a base fluid mixture of R1234ze(E) and R32 refrigerants. Through Grand Canonical Monte Carlo and molecular dynamics simulations, we examined the adsorption characteristics, desorption heat, and thermodynamic properties of MOHCs. Our findings reveal that R32 molecules are preferentially adsorbed in IRMOF-1 compared to R1234ze(E), with adsorption selectivity of R32 over R1234ze(E) increasing under higher adsorption pressures. When the temperature during the endothermic process surpasses the phase transition point of the base fluid, the latent heat of phase transition can be fully exploited to enhance energy storage. Moreover, the inclusion of IRMOF-1 nanoparticles significantly improves the energy storage properties of both R32 and R1234ze(E), as well as their mixtures. The energy storage enhancement provided by IRMOF-1 is particularly pronounced under high working pressures and low temperature differences. These insights offer valuable guidance for selecting appropriate base fluids in MOHC systems, thereby optimizing the utilization of low-grade energy sources.

Topological comparison of flexible and semiflexible chains in polymer melts with θ-chains.

A central paradigm of polymer physics states that chains in melts behave like random walks as intra- and interchain interactions effectively cancel each other out. Likewise, θ-chains, i.e., chains at the transition from a swollen coil to a globular phase, are also thought to behave like ideal chains, as attractive forces are counterbalanced by repulsive entropic contributions. While the simple mapping to an equivalent Kuhn chain works rather well in most scenarios with corrections to scaling, random walks do not accurately capture the topology and knots, particularly for flexible chains. In this paper, we demonstrate with Monte Carlo and molecular dynamics simulations that chains in polymer melts and θ-chains not only agree on a structural level for a range of stiffnesses but also topologically. They exhibit similar knotting probabilities and knot sizes, both of which are not captured by ideal chain representations. This discrepancy comes from the suppression of small knots in real chains, which is strongest for very flexible chains because excluded volume effects are still active locally and become weaker with increasing semiflexibility. Our findings suggest that corrections to ideal behavior are indeed similar for the two scenarios of real chains and that the structure and topology of a chain in a melt can be approximately reproduced by a corresponding θ-chain.

Cost-Benefit Analysis using Modular Dynamic Fault Tree Analysis and Monte Carlo Simulations for Condition-based Maintenance of Unmanned Systems

Recent developments in condition-based maintenance (CBM) have helped make it a promising approach to maintenance cost avoidance in engineering systems. By performing maintenance based on conditions of the component with regards to failure or time, there is potential to avoid the large costs of system shutdown and maintenance delays. However, CBM requires a large investment cost compared to other available maintenance strategies. The investment cost is required for research, development, and implementation. Despite the potential to avoid significant maintenance costs, the large investment cost of CBM makes decision makers hesitant to implement. This study is the first in the literature that attempts to address the problem of conducting a cost-benefit analysis (CBA) for implementing CBM concepts for unmanned systems. This paper proposes a method for conducting a CBA to determine the return on investment (ROI) of potential CBM strategies. The CBA seeks to compare different CBM strategies based on the differences in the various maintenance requirements associated with maintaining a multi-component, unmanned system. The proposed method uses modular dynamic fault tree analysis (MDFTA) with Monte Carlo simulations (MCS) to assess the various maintenance requirements. The proposed method is demonstrated on an unmanned surface vessel (USV) example taken from the literature that consists of 5 subsystems and 71 components. Following this USV example, it is found that selecting different combinations of components for a CBM strategy can have a significant impact on maintenance requirements and ROI by impacting cost avoidances and investment costs.

Synthesis, structural characterization, thermal analysis and anticorrosion properties of novel AZO-based imidazo[1,2-a]pyridine derivatives: Experimental study and theoretical approaches

In this study, innovative AZO-based imidazo[1,2-a]pyridine derivatives were synthesized using simple and efficient synthetic approach enabling large-scale production. Thermal analysis highlights their suitability for potential applications requiring resistance to moderate temperatures. These compounds were investigated as corrosion inhibitors for MS in a 1 M HCl-medium. Corrosion inhibition studies, including weight loss, PotentioDynamic polarization and electrochemical impedance spectroscopy methods, revealed that AZOs exhibited maximum corrosion inhibition efficiencies reaching 96.13 % and 94.07 %, respectively, at a concentration of 10−3 M and a temperature of 298 K, with both compounds acting as mixed-type inhibitors. The study also delved into the influence of temperature and immersion time on inhibitory performance, revealing stable inhibition within the temperature range of 298–328 K. The calculated standard free energy of adsorption was −42.06 and −40.62 kJ/mol for AZO 1 and AZO 2, respectively, suggesting mixed-type adsorption, with adsorption behavior following the Langmuir isotherm. Morphological analysis through SEM and AFM, showed a reduction in surface roughness in the presence of the inhibitors, while water contact angle measurements indicated a significant increase in surface hydrophobicity. UV–visible and FT-IR analyses confirmed the interaction of AZOs with the MS surface, suggesting the formation of a protective layer composed of adsorbed AZO molecules. Furthermore, computational investigations employing DFT, Monte Carlo, and Molecular Dynamic simulation revealed the formation of coordinate bonds between the studied inhibitors and the metal surface, confirming adsorption on the metallic surface. These findings align well with experimental outcomes, and a possible corrosion inhibition mechanism process was discussed.

Dissipative Self-Assembly of Patchy Particles under Nonequilibrium Drive: A Computational Study.

Inspired by biology and implemented using nanotechnology, the self-assembly of patchy particles has emerged as a pivotal mechanism for constructing complex structures that mimic natural systems with diverse functionalities. Here, we explore the dissipative self-assembly of patchy particles under nonequilibrium conditions, with the aim of overcoming the constraints imposed by equilibrium assembly. Utilizing extensive Monte Carlo (MC) and Molecular Dynamics (MD) simulations, we provide insight into the effects of external forces that mirror natural and chemical processes on the assembly rates and the stability of the resulting assemblies comprising 8, 10, and 13 patchy particles. Implemented by a favorable bond-promoting drive in MC or a pulsed square wave potential in MD, our simulations reveal the role these external drives play in accelerating assembly kinetics and enhancing structural stability, evidenced by a decrease in the time to first assembly and an increase in the duration the system remains in an assembled state. Through the analysis of an order parameter, entropy production, bond dynamics, and interparticle forces, we unravel the underlying mechanisms driving these advancements. We also validated our key findings by simulating a larger system of 100 patchy particles. Our comprehensive results not only shed light on the impact of external stimuli on self-assembly processes but also open a promising pathway for expanding the application by leveraging patchy particles for novel nanostructures.

Anticorrosion and rheological properties of Calyptocarpus vialis extract as a green coating for mild steel in 2MH2SO4

This study assesses the rheological properties and corrosion inhibition efficacy of Calyptocarpus vialis (CV) extract, a wild plant in Asteraceae family. Shear and dynamic rheology studies show that CV extract has shear-thinning behaviour, with viscosity changes occurring at higher shear rates, most likely owing to aggregate formation. These aggregates may develop due to certain solvent characteristics and a jamming tendency is due to the presence of extract phytochemicals. Dynamic rheology confirms its viscoelastic nature. Corrosion inhibition effectiveness was investigated using Mild Steel (MS) in 2 M H2SO4, resulting in an 82.69 % inhibition with an extract concentration of 1 g/L. Adsorption isotherm indicates phytochemical adsorption on MS surface. Contact angles of polished MS (87.30°), with extract (80.10°), and without extract (51.25°) show decrease in wetting and increase in hydrophobicity which indicates that a thin protective layer is formed at MS surface. FE-SEM (Field Emission Scanning Electron Microscopy) images reveal that the CV extract forms a protective barrier on the MS surface, significantly reducing corrosion as compared to the unprotected surface exposed to the mild acid solution. Theoretical calculations, including Density Functional Theory (DFT) simulations, Monte Carlo (MC), and Molecular Dynamics (MD) simulations, support the experimental findings, elucidating phytochemicals adsorption on the MS surface. Further research is required to examine the scalability of CV extracts for industrial applications, as well as their long-term stability and efficacy in various corrosive conditions.

Stability and dynamics of magnetic skyrmions in FM/AFM heterostructures

Magnetic skyrmions have garnered attention for their potential roles in spintronic applications, such as information carriers in computation, data storage, and nano-oscillators due to their small size, topological stability, and the requirement of small electric currents to manipulate them. Two key challenges in harnessing skyrmions are the stabilization requirement through a strong out-of-plane field, and the skyrmion Hall effect (SkHE). Here, we present a systematic model study of skyrmions in ferromagnetic/antiferromagnetic (FM/AFM) multilayer structures by employing both atomistic Monte Carlo and atomistic spin dynamics simulations. We demonstrate that skyrmions stabilized by exchange bias have superior stability to field-stabilized skyrmions due to the formation of a magnetic imprint within the AFM layer. Additionally, stacking two skyrmion hosting FM layers between two AFM layers suppresses the SkHE and enables the transport of AFM-coupled skyrmions with high velocity in the order of a few km/s. This proposed multilayer configuration could serve as a pathway to overcome existing limitations in the development of skyrmion-based devices, and the insights obtained through this study contribute significantly to the broader understanding of topological spin textures in magnetic materials. Published by the American Physical Society 2024

Measuring Oxygen Solubility in Amorphous and Semicrystalline Polyolefins Using Test Particle Insertion: A Comparative Study of Polyethylene and Isotactic Polypropylene.

The test particle insertion method is used to study the solubility of oxygen in two commonly used polymers: polyethylene (PE) and isotactic polypropylene (iPP). Amorphous samples for both polymers were prepared by means of Monte Carlo and molecular dynamics simulations, and the oxygen solubility was measured across different temperatures. The solubility-temperature dependence for iPP proved to be nonmonotonic due to the interplay between binding and reorganizational enthalpy, while for PE, it appeared to be monotonic based on the available data in the studied temperature range. A broad comparison to experiments and simulations is included. Further oxygen insertions were also performed in semicrystalline PE and iPP samples at ambient temperature, and the obtained values were compared to a linear relationship which correlates the solubility in the purely amorphous phase with the solubility in the crystalline phase. The solubility of PE closely follows the linear relationship, while iPP exhibits some divergence. All the semicrystalline samples were previously annealed at elevated temperatures for long periods (a few μs), and a strong effect of annealing was observed on the structure and the solubility of iPP. A well-developed iPP lamellar structure emerged at longer annealing times, while PE develops that structure already in the early crystallization stages. The solubility of semicrystalline iPP samples with lamellar morphology exhibited better agreement with extrapolated solubility values of the amorphous state─the extrapolation was made using a linear relationship connecting solubility in the purely amorphous phase and solubility in mixed phases (amorphous and crystalline). Results on the correlation of the solubility with the local structural ordering are also present.

Removal of tricyclazole residues from water by sorption on metal organic frameworks (MOFs): A theoretical insight of the experimental data

All over the world, there are stringent regulations in place concerning the acceptable amount of pesticide residues in various food commodities, including cereals. The majority of the water tainted with pesticides comes from agricultural drainage, making it imperative that this water be cleansed of any lingering traces of the chemicals. The presence of unacceptable levels of pesticides residues is another issue hindering India's ability to export Basmati rice and other commodities. Tricyclazole, a fungicide has been found in rice in recent years, leading to the rejection of a number of bulk consignments. Therefore, three metal organic frameworks (MOFs) viz., MIL-53(Al), Fe-BTC, and ZIF-8, based on three different metal ions (aluminium, iron, and zinc) and three different organic "struts" were investigated for the removal of TRCZ from water. Interestingly, TRCZ was found to be selective towards both metal ions and linkers. The maximum adsorption capacities of TRCZ onto MIL-53(Al), Fe-BTC and ZIF-8 were 980.0, 896.7 and 904.6 μg g−1 (@1 ppm aqueous solution), respectively. Adsorption followed pseudo-second-order kinetics and best fit the Sips isotherm. The adsorption of TRCZ molecules onto the surface of the MOFs were confirmed using Fourier Transform infrared (FTIR) and X-Ray Diffraction (XRD) spectroscopy. MIL-53(Al) showed the best regeneration capacity (> 90 % efficiency after the 4th cycle). The adsorption of pesticide molecules onto MOF surfaces was studied (in vacuo and in aqueous) circumstances using Grand Canonical Monte Carlo (GCMC) and Molecular Dynamics (MD) simulations revealing the prime competitive role of water molecules aided by π-π stacking and π-lone pair interactions during adsorption. Metal organic frameworks have the potential to replace costly commercial activated carbons in the future to treat pesticide-contaminated water.

Driven Self-Assembly of Patchy Particles Overcoming Equilibrium Limitations.

Bridging biological complexity and synthetic material design, we investigate dissipative self-assembly in patchy particle systems. Utilizing Monte Carlo and Molecular Dynamics simulations, we demonstrate how external driving forces mitigate equilibrium trade-offs between assembly time and structural stability, traditionally encountered in self-assembly processes. Our findings also extend to biological-mimicking environments, where we explore the dynamics of patchy particles under crowded conditions. This comprehensive analysis offers insights into advanced material design, opening avenues for innovations in nanotechnology applications.

Adsorption of cytochrome c on different self-assembled monolayers: The role of surface chemistry and charge density.

In this work, the adsorption behavior of cytochrome c (Cyt-c) on five different self-assembled monolayers (SAMs) (i.e., CH3-SAM, OH-SAM, NH2-SAM, COOH-SAM, and OSO3--SAM) was studied by combined parallel tempering Monte Carlo and molecular dynamics simulations. The results show that Cyt-c binds to the CH3-SAM through a hydrophobic patch (especially Ile81) and undergoes a slight reorientation, while the adsorption on the OH-SAM is relatively weak. Cyt-c cannot stably bind to the lower surface charge density (SCD, 7% protonation) NH2-SAM even under a relatively high ionic strength condition, while a higher SCD of 25% protonation promotes Cyt-c adsorption on the NH2-SAM. The preferred adsorption orientations of Cyt-c on the negatively-charged surfaces are very similar, regardless of the surface chemistry and the SCD. As the SCD increases, more counterions are attracted to the charged surfaces, forming distinct counterion layers. The secondary structure of Cyt-c is well kept when adsorbed on these SAMs except the OSO3--SAM surface. The deactivation of redox properties for Cyt-c adsorbed on the highly negatively-charged surface is due to the confinement of heme reorientation and the farther position of the central iron to the surfaces, as well as the relatively larger conformation change of Cyt-c adsorbed on the OSO3--SAM surface. This work may provide insightful guidance for the design of Cyt-c-based bioelectronic devices and controlled enzyme immobilization.

Impact of aminopropyl units on physisorption in mesostructured silica is larger for CH4 than CO2 and depends on pore curvature

Mesoporous silica-based materials attract great interest for diverse applications, including capture, storage, and catalysis due to their large surface area, uniform pore size distribution, and customizable surface. The regular 2D hexagonal pore symmetry of MCM-41 makes it an ideal model. Amine groups are introduced to enhance CO2 adsorption, but the interplay of factors influencing overall performance, including pore size, remains unclear. This computational study explores the physisorption of CO2 and CH4, shedding light on the microscopic details underlying adsorption capacity and selectivity. Three aminopropyl-functionalized MCM-41 models with different pore size are compared through Grand Canonical Monte Carlo and Molecular Dynamics simulations. Aminopropyl chains affect CO2 adsorption, but its affinity for the preserved silanol groups is larger. In addition, the competitive interaction between amine and silanol groups emerged, and it is pore curvature dependent. Surprisingly, CH4 physisorption is influenced even more by surface functionalization. Results show a non-monotonic trend as a function of pore size. Local density of the alkyl chains plays the major role. Overall, the intermediate pore size demonstrates the best performance, thanks to the balance among the various effects. The study emphasizes the importance of understanding the interplay between material texture and gas interactions to optimize adsorption performance.

Effect of surface roughness on methane adsorption in shale organic nanopores from the perspective of molecular simulations

Understanding the shale gas adsorption behavior within organic nanopores is crucial for its development. The pore surfaces commonly exhibit random inherent roughness, which can significantly impact gas adsorption, while it’s still in debate about whether the roughness could enhance the gas adsorption or not. To clarify the underlying mechanisms of the effect of surface roughness, in this study, the Grand Canonical Monte Carlo and Molecular Dynamic simulations are used to investigate the methane adsorption in wrinkled graphene nanochannels with various roughness. The heterogeneity of the adsorption layer along the rough topology is described in detail. The adsorption is enhanced near the concave region and weakened near the convex region. Additionally, increased surface roughness shifts the gas molecules’ aggregation modes in the concave region from a gradual gradient to oscillatory “adsorption points”. We observe that wall roughness due to the wrinkle can enhance the adsorption amount overall, attributed to the increased surface area and the increased unit adsorption capacity due to potential energy overlap. However, the contributions of both factors differ under various pressure and roughness conditions. Then a new mathematical method to estimate the gas adsorption amounts is provided and aligns well with molecular simulation results for a wide range of pressure and roughness conditions. And a potential answer the current debate about the positive or negative impact of adsorption due to roughness is promoted. The key may lie in the dominant role of the co-existed roughness caused by the fragment basal or edge surface. Our work could shed light on the underlying effect of surface roughness on the gas adsorption in shale, and have significant implications for the reserve estimation of shale gas formations.

In-depth study of a newly synthesized imidazole derivative as an eco-friendly corrosion inhibitor for mild steel in 1 M HCl: Theoretical, electrochemical, and surface analysis perspectives

The present study is concerned with the corrosion inhibition and adsorption behaviour of a series of novel imidazole derivatives. The compounds under investigation are 5,5-diphenyl-3-propyl-2-(propylthio)-3,5-dihydro-4 H-imidazol-4-one (AM3) and 3-allyl-2-(allylthio)-5,5-diphenyl-3,5-dihydro-4 H-imidazol-4-one (AM6). The objective of this study is to evaluate the efficacy of 5,5-diphenyl-3,5-dihydro-4 H-imidazol-4-one (AM6) as a corrosion inhibitor on mild steel immersed in a 1.0 M hydrochloric acid medium. This comprehensive study assesses the efficacy of these derivatives through a range of electrochemical and spectroscopic analysis techniques. Additionally, polarisation curves, electrochemical impedance spectroscopy and advanced computer simulations were employed to evaluate the efficacy and inhibition mechanism of imidazole derivatives, thereby facilitating a more profound understanding of their anticorrosive capacity. The results obtained from potentiodynamic polarisation (PDP), electrochemical frequency modulation (EFM) and electrochemical impedance spectroscopy (EIS) measurements demonstrate that the inhibition efficiency increases with increasing imidazole derivative concentration. Conversely, an inverse relationship is observed between inhibition efficiency and temperature. The thermodynamic parameters ΔG°_ads and ΔH°_ads corroborate the conclusion that the adsorption process is predominantly chemical in nature. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) were employed to characterise the surface morphology. The maximum protection afforded by imidazole derivatives was 95.2 % and 93 % for compounds AM3 and AM6, respectively. Polarisation curves indicated that imidazole derivatives exhibited mixed inhibition behaviour. Surface analysis demonstrated that imidazole derivatives were effectively adsorbed onto the carbon surface, thereby significantly reducing acid damage. This finding was corroborated by DFT calculations, as well as Monte Carlo (MC) and molecular dynamics (MD) simulations. These simulations provided a comprehensive insight into the adsorption of imidazole and its protonated form onto the carbon surface, offering valuable insight into the corrosion inhibition mechanism.

Damage kinetics in high-temperature irradiated Ni crystals

High-temperature (∼800 K) ion irradiation with 380 keV Ar ions was used to modify the surface of Ni single crystals in order to generate radiation defects and mimic the effect of neutrons avoiding sample activation. The modified 800 nm thick layer was analyzed regarding structural and mechanical properties utilizing a combination of experimental and simulation techniques. The ion implantation fluence ranged from 1 × 1014 cm−2 up to 1 × 1016 cm−2, which corresponds to values of displacements per atom from 0.25 to 25, respectively. The structural characterization was performed by Rutherford Spectroscopy in Channeling mode (RBS/C) associated with scanning (SEM) and transmission electron microscopy (TEM). The experimental results were supported by Monte Carlo (McChasy) and Molecular Dynamics (MD-LAMMPS) simulations. The simulations performed using the second generation of the McChasy code show that the influence of bubbles formed inside the material is not negligible and affects the quantitative analysis of defects in the simulated spectra. A second step in damage kinetics was revealed for the highest dose (i.e., 25 dpa) as a consequence of the entanglement of dislocations and agglomeration of noble gas bubbles, which was confirmed by TEM analysis. Moreover, nanomechanical results confirm that Ar bubbles deteriorate mechanical properties such as hardness.

Thermophysical Properties and Phase Behavior of CO2 with Impurities: Insight from Molecular Simulations.

Experimentally determining thermophysical properties for various compositions commonly found in CO2 transportation systems is extremely challenging. To overcome this challenge, we performed Monte Carlo (MC) and Molecular Dynamics (MD) simulations of CO2 rich mixtures to compute thermophysical properties such as densities, thermal expansion coefficients, isothermal compressibilities, heat capacities, Joule-Thomson coefficients, speed of sound, and viscosities at temperatures of (235-313) K and pressures of (20-200) bar. We computed thermophysical properties of pure CO2 and CO2 rich mixtures with N2, Ar, H2, and CH4 as impurities of (1-10) mol % and showed good agreement with available Equations of State (EoS). We showed that impurities decrease the values of thermal expansion coefficients, isothermal compressibilities, heat capacities, and Joule-Thomson coefficients in the gas phase, while these values increase in the liquid and supercritical phases. In contrast, impurities increase the value of speed of sound in the gas phase and decrease it in the liquid and supercritical phases. We present an extensive data set of thermophysical properties for CO2 rich mixtures with various impurities, which will help to design the safe and efficient operation of CO2 transportation systems.

Alkaloid extract of seed Citrullus colocynthis as novel green inhibitor for mild steel corrosion in one molar HCl acid solution: DFT and MC/MD approaches

The study was designed to explore the corrosion prevention capabilities of Citrullus colocynthis seeds alkaloid-rich extract (CSEA) on MS in a 1 M HCl environment by use of electrochemical and theoretical methods. Notably, Electrochemical Impedance Spectroscopy (EIS) and potentiodynamic polarization were used to probe the impact of immersion time and temperature. Energy-dispersive X-ray spectroscopy (EDX) and spanning electron microscopy (SEM) were used to confirm the presence of a protective layer on the substrate surface. Density functional theory (DFT) method was used to optimize the investigated species by use of B3LYP/6–31 + G(d, p) level of theory. The global and local quantum chemical reactivity descriptors were calculated to explore the inhibition corrosion efficiency and to identify the most favorable sites for electrophilic and nucleophilic attacks. Monte Carlo (MC) and molecular dynamics simulation (MDS) methods were used to study the interactions between corrosion inhibitor and metal surface. Noteworthy, results showed that CSEA exhibited an impressive inhibition efficiency, which reached 94.3% with a concentration of 2 g/L at 298 K. Potentiodynamic polarization revealed that the extract acted as a mixed-type inhibitor. Nyquist graphs showed that charge-transfer resistance and dæouble-layer capacitance both rised with increasing CSEA concentration, suggesting better inhibition efficiency. Notably, the Langmuir adsorption isotherm is well-aligned with the adsorption of inhibitor compounds. Importantly, all aforementioned theoretical methods were in agreement with the experimental findings. The outcome of the present work supported using Citrullus colocynthis seeds alkaloid-rich extract as ecofriendly agents to prevent corrosion.