Search Results (27)

During long-term storage, polymer-bonded explosives (PBXs) undergo thermal-oxidative aging due to environmental factors such as moisture and oxygen, which leads to a critical determinant of explosive performance. This study employed molecular dynamics simulations to investigate the impact of thermal-oxidative aging of butadiene rubber and paraffin wax composites used in the RDX-based polymer-bonded explosives. The interfacial binding energy between the binder system and RDX crystalline surfaces was evaluated. The cohesive energy density (CED), fractional free volume (FFV), mean square displacement (MSD), and mechanical properties were analysed to probe the mechanism of aging for butadiene rubber (BR) and paraffin wax (PW). The results demonstrate that, with progressive aging, the oxidation-induced chain scission of BR molecules leads to an increase in both the CED and solubility parameter of the BR/PW system. Initial oxidation reduces the FFV of the BR/PW system from 0.183 to 0.166, while subsequent chain scission causes the FFV to rise to 0.175. In terms of mechanical properties, the BR/PW system exhibits ductile behavior, with reductions in both Young’s modulus and shear modulus as aging progresses, leading to decreased material stiffness. For the RDX/binder system, oxidation enhances the interfacial binding energy, whereas chain scission in BR leads to a slight decline in the binding energy. Overall, oxidation exerts a more pronounced influence on the interfacial binding energy compared to chain scission. Full article

Biomethane is one of the controllable Renewable Energy Sources. It may be derived from biogas, a multicomponent gas mixture, using, among others, membrane processes. The proper optimization of such a process requires the knowledge of the phenomena accompanying each specific biogas–membrane separation system. Therefore, the solubility, permeance and diffusion of CO₂, CH₄, O₂ and N₂ in a polyimide-based sample were described and analyzed using the Dual Mode Sorption and partial immobilization models. The parameters of the models were determined based on pure gas sorption isotherms measured gravimetrically and experimental permeances of the four gases. The membrane swelling caused by CO₂ was observed at temperatures of 293 and 303 K and for pressures higher than 3 bar. The adsorption of CH₄, O₂ and N₂ in the fractional free volume (FFV) has a dominant (>50%) share in their total solubility in the entire pressure range. This makes them sensitive to the presence of CO₂, whose affinity is the strongest towards the tested polyimide-based sample. The diffusion of O₂ is the fastest which makes it competitive with CO₂ in permeation through the membrane, despite its low solubility. The ideal CO₂/O₂ selectivity is thus relatively low (2.3–5.1). Methane, which is competitive in solubility compared to CO₂, was found to diffuse the slowest and as a result, it is also the slowest permeating gas. This translates into the very high CO₂/CH₄ ideal selectivity (33–95.7), which is, however, strongly dependent on temperature and pressure. Full article

The purpose of this study is to evaluate the strength of polyamide utilized in high pressure hydrogen transmission, exemplified by reinforced plastic hoses. The research encompasses a comprehensive investigation of materials employed in hydrogen infrastructure, focusing on their barrier and mechanical properties. It addresses challenges associated with hydrogen storage and transport, presenting various types of tanks and hoses commonly used in the industry and detailing the materials used in their construction, such as metals and polymers. Two materials were analyzed in the study; one new material and one material exposed to hydrogen. Key mechanisms and factors affecting gas permeation in materials are discussed, including an analysis of parameters such as fractional free volume (FFV), solubility coefficient (S), diffusion coefficient, and permeability coefficient. Methods for evaluating material permeation were outlined, as they are essential for assessing suitability in hydrogen infrastructure. Experimental analyses included Fourier Transform Infrared Spectroscopy (ATR), differential thermal analysis (DTA), scanning electron microscopy (SEM), and Energy dispersive X-ray spectroscopy (EDS). These techniques provided detailed insights into the structure and properties of polyamide, allowing for an assessment of its performance under high pressure hydrogen conditions. Pressure was identified as a critical factor influencing both the material’s mechanical strength and its hydrogen transport capability, as it affects the quantity of adsorbed particles. According to the DTA investigation, the polyamide demonstrates minimal mass loss at lower temperatures, indicating a low risk of material degradation. However, its performance declines significantly at higher temperatures (above 350 °C). Up to 250 °C, the material shows no notable decomposition occurred, suggesting its suitability for certain applications. The presence of functional groups was found to play a significant role in gas permeation, highlighting the importance of detailed physicochemical analysis. XRD studies revealed that hydrogen exposure did not significantly alter the internal structure of polyamide. These findings suggest that the structure of polyamide is well-suited for operation under specific conditions, making it a promising candidate for use in hydrogen infrastructure. However, the study also highlights areas where further research and optimization are needed. Overall, this work provides valuable insights into the properties of polyamide and its potential applications in hydrogen systems. Full article

Biogas, one of the important controllable renewable energy sources, may be split into two streams: bio-CH₄ and bio-CO₂ using, among others, membrane processes. The proper optimization of such processes requires the knowledge of phenomena accompanying each specific CH₄–CO₂–membrane system (e.g., competitive sorption or swelling). The phenomena were analyzed for the polysulfone-based membrane used in a developed adsorptive–membrane system for biogas separation. The Dual Mode Sorption and partial immobilization models were used to describe the solubility and diffusion of CO₂, CH₄ and their mixtures in this material. The parameters of the models were determined based on pure-gas sorption isotherms measured gravimetrically and permeances of CO₂/CH₄ mixture components from our previous studies. It was found, among other things, that the membrane swelling caused by CO₂ was observed for pressures higher than 5 bar. The real selectivity (permselectivity) of CO₂ vs. CH₄ is significantly lower than the selectivity of pure gases (ideal selectivity), while the solubility selectivity of CO₂ vs. CH₄ in the mixture is higher than that of pure gases. This is due to the better affinity of CO₂ towards the tested polysulfone membrane, making CO₂ the dominant component in competitive sorption. The reduction in the permselectivity is mainly due to an approximately two-fold decrease in the CO₂ diffusion rate in the presence of CH₄. It was also found that the fraction of solubility in the fractional free volume (FFV) is dominant for both gases, pure and mixed, reaching 65–73% of the total solubility. Moreover, in CO₂/CH₄ mixtures, the mobility of methane in FFV disappears, which additionally confirms the displacement of methane by CO₂ from FFV. Full article

The incorporation of reinforcing fillers into natural rubber latex (NR) to achieve superior elasticity and mechanical properties has been widely applied across various fields. However, the tendency of reinforcing fillers to agglomerate within NR limits their potential applications. In this study, multi-walled carbon nanotube (MWCNT)–silica (SiO₂)/NR composites were prepared using a solution blending method, aiming to enhance the performance of NR composites through the synergistic effects of dual-component fillers. The mechanical properties, dispersion behavior, and Payne effect of three types of composites—SiO₂/NR (SNR), MWCNT/NR (MNR), and MWCNT-SiO₂/NR (MSNR)—were investigated. In addition, the mean square displacement (MSD), fractional free volume (FFV), and binding energy of the three composites were simulated using molecular dynamics (MD) models. The results showed that the addition of a two-component filler increased the tensile strength, elongation at break, and Young’s modulus of NR composites by 56.4%, 72.41%, and 34.44%, respectively. The Payne effect of MSNR was reduced by 4.5% compared to MNR and SNR. In addition, the MD simulation results showed that the MSD and FFV of MSNR were reduced by 21% and 17.44%, respectively, and the binding energy was increased by 69 times, which was in agreement with the experimental results. The underlying mechanisms between the dual-component fillers were elucidated through dynamic mechanical analysis (DMA), a rubber process analyzer (RPA), and field emission scanning electron microscopy (SEM). This study provides an effective reference for broadening the application fields of NR. Full article

The polymer liner of the hydrogen storage cylinder was studied to investigate better hydrogen storage capacity in Type-IV cylinders. Molecular dynamics methods were used to simulate the adsorption and diffusion processes of hydrogen in a graphene-filled polyamide 6 (PA6) system. The solubility and diffusion characteristics of hydrogen in PA6 systems filled with different filler ratios (3 wt%, 4 wt%, 5 wt%, 6 wt%, and 7 wt%) were studied under working pressures (0.1 MPa, 35 MPa, 52 MPa, and 70 MPa). The effects of filler ratio, temperature, and pressure on hydrogen diffusion were analyzed. The results show that at atmospheric pressure when the graphene content reaches 5 wt%, its permeability coefficient is as low as 2.44 × 10⁻¹³ cm³·cm/(cm²·s·Pa), which is a 54.6% reduction compared to PA6. At 358 K and 70 MPa, the diffusion coefficient of the 5 wt% graphene/PA6 composite system is 138% higher than that at 298 K and 70 MPa. With increasing pressure, the diffusion coefficients of all materials generally decrease linearly. Among them, pure PA6 has the largest diffusion coefficient, while the 4 wt% graphene/PA6 composite system has the smallest diffusion coefficient. Additionally, the impact of FFV (free volume fraction) on the barrier properties of the material was studied, and the movement trajectory of H₂ in the composite system was analyzed. Full article

This work aims to expand the structure–property relationships of bromo-containing polyimides and the influence of bromine atoms on the gas separation properties of such materials. A series of intrinsically microporous polyimides were synthesized from 2,2′-dibromo-4,4′,5,5′-bipohenyltetracarboxylic dianhydride (Br-BPDA) and five bulky diamines, (7,7′-(mesitylmethylene)bis(8-methyldibenzo[b,e][1,4]dioxin-2-amine) (MMBMA), 7,7′-(Mesitylmethylene)bis(1,8-dimethyldibenzo[b,e][1,4] dioxin-2-amine) (MMBDA), 4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diamine (TBDA1), 4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-3,9-diamine (TBDA2), and (9R,10R)-9,10-dihydro-9,10-[1,2]benzenoanthracene-2,6-diamine (DAT). The Br-BPDA-derived polyimides exhibited excellent solubility, high thermal stability, and good mechanical properties, with their tensile strength and modulus being 59.2–109.3 MPa and 1.8–2.2 GPa, respectively. The fractional free volumes (FFVs) and surface areas (S_BET) of the Br-BPDA-derived polyimides were in the range of 0.169–0.216 and 211–342 m² g⁻¹, following the order of MMBDA > MMBMA > TBDA2 > DAT > TBDA1, wherein the Br-BPDA-MMBDA exhibited the highest S_BET and FFV and thus highest CO₂ permeability of 724.5 Barrer. Moreover, Br-BPDA-DAT displayed the best gas separation performance, with CO₂, H₂, O₂, N₂, and CH₄ permeabilities of 349.8, 384.4, 69.8, 16.3, and 19.7 Barrer, and H₂/N₂ selectivity of 21.4. This can be ascribed to the ultra-micropores (<0.7 nm) caused by the high rigidity of Br-BPDA-DAT. In addition, all the bromo-containing polymers of intrinsic microporosity membranes exhibited excellent resistance to physical ageing. Full article

Triamine-based HBPI membranes are known for high gas separation selectivity and physical stability, but their permeabilities are still very low. In this study, we utilized a tetramine monomer called TPDA (N,N,N′,N′-tetrakis(4-aminophenyl)-1,4-benzenediamine) as a crosslinking center and incorporated an additional diamine comonomer called DAM (2,4,6-trimethyl-1,3-diaminobenzene) to enhance gas separation performance, especially gas permeability. The findings demonstrated that the resultant 6FDA−DAM/TPDA membranes based on tetramine TPDA exhibited a greater amount of free volume compared to the triamine-based HBPI membranes, resulting in significantly higher gas permeabilities. Furthermore, the higher concentration of DAM component led to the generation of more fractional free volumes (FFV). Consequently, the gas permeabilities of the 6FDA−DAM/TPDA membranes increased with an increase in DAM content, with a minimal compromise on selectivity. The enhanced gas permeabilities of the 6FDA−DAM/TPDA membranes enabled them to minimize the footprint required for membrane installations in real-world applications. Moreover, the 6FDA−DAM/TPDA membranes exhibited remarkable durability against physical aging and plasticization, thanks to the incorporation of a hyperbranched network structure. Full article

Herein, we report for the first time a study dedicated to acidic gases’ solubility in ionic liquids with sterically hindered bulky anion, namely bis(2-ethylhexyl) sulfosuccinate ([doc]), experimentally evaluated at low pressures. The effect of cation change (imidazolium, pyridinium, and pyrrolidinium) on the thermophysical properties and sorption capacities was also discussed. The densities and the activation energies of the tested ILs exhibited minor differences. Furthermore, the COSMO-RS model was used to predict the free volumes of ILs aiming to investigate its influence on gas solubilities. The conducted calculations have revealed an antibate correlation between the fractional free volume (FFV) and Henry’s law constant. In particular, the lowest FFV in 1-methylimidazolium [doc] corresponded to the minimal sorption and vice versa. In addition, it was shown that the presence of protic cation results in a significant reduction in CO₂ and H₂S solubilities. In general, the solubility measurement results of the synthesized ILs have shown their superiority compared to fluorinated ILs based on the physical absorption mechanism. Full article

In the context of the global pandemic of COVID-19, the use and disposal of medical masks have created a series of ethical and environmental issues. The purpose of this paper is to study and evaluate the high temperature properties and thermal storage stability of discarded-mask (DM)-modified asphalt from a multi-scale perspective using molecular dynamics (MD) simulation and experimental methods. A series of tests was conducted to evaluate the physical, rheological, thermal storage stability and microscopic properties of the samples. These tests include softening point, rotational viscosity, dynamic shear rheology (DSR), Fourier transform infrared (FT-IR) spectroscopy and molecular dynamics simulation. The results showed that the DM modifier could improve the softening point, rotational viscosity and rutting factor of the asphalt. After thermal storage, the DM-modified asphalt produced segregation. The difference in the softening point between the top and bottom of the sample increased from 2.2 °C to 17.1 °C when the DM modifier admixture was increased from 1% to 4%. FT-IR test results showed that the main component of the DM modifier was polypropylene, and the DM-modified asphalt was mainly a physical co-blending process. MD simulation results show that the DM modifier can increase the cohesive energy density (CED) and reduce the fractional free volume (FFV) of asphalt and reduce the binding energy between base asphalt and DM modifier. Multi-scale characterization reveals that DM modifiers can improve the high temperature performance and reduce the thermal storage stability of asphalt. It is noteworthy that both macroscopic tests and microscopic simulations show that 1% is an acceptable dosage level. Full article

Herein, the curing kinetics and the glass transition temperature (T_g) of MXene/phenolic epoxy composites with two curing agents, i.e., 4,4-diaminodiphenyl sulfone (DDS) and dicyandiamine (DICY), are systematically investigated using experimental characterization, mathematical modeling and molecular dynamics simulations. The effect of MXene content on an epoxy resin/amine curing agent system is also studied. These results reveal that the MXene/epoxy composites with both curing agent systems conform to the SB(m,n) two-parameter autocatalytic model. The addition of MXene accelerated the curing of the epoxy composite and increased the T_g by about 20 K. In addition, molecular dynamics were used to simulate the T_g of the cross-linked MXene/epoxy composites and to analyze microstructural features such as the free volume fraction (FFV). The simulation results show that the introduction of MXene improves the T_g and FFV of the simulated system. This is because the introduction of MXene restricts the movement of the epoxy/curing agent system. The conclusions are in good agreement with the experimental results. Full article

The influences of thermal-oxidative aging on the diffusion behaviors of oxygen and cyclohexane in nitrile-butadiene rubber (NBR) at the micro-scale were investigated by molecular dynamics (MD) simulation. The two types of aged rubber models were established on the basis of rubber oxidative chains modified by the introduction of hydroxyl groups and carbonyl groups in rubber chains. The diffusion behaviors of oxygen and cyclohexane in NBR under different conditions were characterized by the fractional free volume (FFV), mean square displacement (MSD), diffusion coefficients, and diffusion trajectory. It turns out that the elevated temperature contributed to the increase in the free volume and diffusion range of oxygen and cyclohexane, while the compressive stress showed the reverse influence. Additionally, the introduction of oxidative polar functional groups (hydroxyl groups and carbonyl groups) in rubber chains lowered the flexibility of the rubber chains and promoted the formation of strong polar interaction, which further inhibits the diffusion of oxygen and cyclohexane. Full article

Volatile organic compounds (VOCs) are important sources of atmospheric pollutants on account of their high recycling value. The membrane of dense silicone rubber polydimethylsiloxane (PDMS) has wide-ranging prospects for the separation and recovery of VOCs. In this study, PDMS membrane body models were established in BIOVIA Materials Studio (MS) to simulate VOCs with C₃/N₂ gases, and to study the structure of PDMS membranes and the dissolution and diffusion process of gas in the membranes. The free volume fraction (FFV), cohesive energy density (CED), radial distribution function (RDF), diffusion coefficient and solubility coefficient of C₃H₈, C₃H₆ and N₂ in PDMS membranes were calculated, and the permeability coefficients were calculated according to these values. At the same time, the effects of temperature and mixed gas on the dissolution and diffusion of C₃/N₂ in PDMS membranes were investigated. The results show that the mass transfer process of C₃ in PDMS membranes is mainly controlled by the dissolution process, while that of N₂ is mainly controlled by the diffusion process. In a C₃/N₂ mixed gas system, there is a synergistic relationship between gases in the diffusion process, while there is competitive adsorption in the dissolution process. With an increase in temperature, the diffusion coefficients of the three gases in PDMS gradually increase, the solubility coefficients gradually decrease, and the overall permeability selectivity coefficients of the gases gradually decrease. Therefore, low-temperature conditions are more conducive to the separation of C₃/N₂ in PDMS membranes. The simulation results of the permeability selectivity coefficients of pure C₃ and N₂ in PDMS are similar to the experimental results, and the relationship between the micro- and macro-transport properties of PDMS membranes can be better understood through molecular simulation. Full article

A comprehensive study on the mechanical properties of a pure carbon nanotube (PCNT)/nitrile butadiene rubber (NBR) composite and an amide-functionalized carbon nanotube (CONH₂–CNT)/nitrile butadiene rubber (NBR) composite was carried out using molecular dynamics (MDs) simulations at different temperatures. The effects of temperature on the mechanical properties, fractional free volume (FFV), MSD, dipole autocorrelation function, number of hydrogen bonds of PCNT composites, and functionalized CNT composites were analyzed and compared, and the pull-out behavior of the composites under different condition temperatures was simulated. The enhancement mechanism of the interface interaction between the functionalized carbon nanotubes and the NBR matrix was explained from an atomic point of view. The results show that, due to the existence of hydrogen bonds, higher interfacial binding energies were formed between PCNT and NBR, and FFVs and MSDs were restricted at each temperature, with the mechanical properties of the composites being improved by 5.02–25.93%. Full article

The diffusion between the virgin and aged asphalt binder in the recycled asphalt mixture is a crucial factor affecting its macro-mechanical performance. In this study, a combined model of the virgin-aged layered asphalt structure was assembled based on the molecular dynamics (MD) method. A four-component and twelve-category molecule were used to model the asphalt. The diffusion behaviors of the virgin and aged asphalt were characterized by mean square displacement (MSD), diffusion coefficient, relative concentration and cohesive energy density (CED). Results indicated that at the same temperature, the diffusion coefficient of the virgin asphalt was the largest, followed by the virgin-aged asphalt and the aged asphalt. As the temperature increased, the relative concentration on both sides of the virgin-aged asphalt overlapped to a certain extent. The covered lengths of the virgin asphalt were larger than those of the aged asphalt, indicating the diffusion between the virgin asphalt and aged asphalt was mainly manifested as the diffusion from the virgin asphalt to the aged asphalt. The development of CED and the fraction of free volume (FFV) indicated the mutual attractive interactions among the molecules in virgin and aged asphalt layers became strong and the cohesion properties inside the model became better. Full article