Dynamic Insights into the Growth Mechanisms of 2D Covalent Organic Frameworks on Graphene Surfaces.

Producing high-quality two-dimensional (2D) covalent organic frameworks (COFs) is crucial for industrial applications. However, this remains significantly challenging with current synthetic techniques. A deep understanding of the intermolecular interactions, reaction temperature, and oligomers is essential to facilitate the growth of highly crystalline COF films. Herein, molecular dynamics simulations were employed to explore the growth of 2D COFs from monomer assemblies on graphene. Our results showed that chain growth reactions dominated the COF surface growth and that van der Waals (vdW) interactions were important in enhancing the crystallinity through monomer preorganization. Moreover, appropriately tuning the reaction temperature improved the COF crystallinity and minimized the effects of amorphous oligomers. Additionally, the strength of the interface between the COF and the graphene substrate indicated that the adhesion force was proportional to the crystallinity of the COF. This work reveals the mechanisms for nucleation and growth of COFs on surfaces and provides theoretical guidance for fabricating high-quality 2D polymer-based crystalline nanomaterials.

High-Strength Polycrystalline Covalent Organic Framework with Abnormal Thermal Transport Insensitive to Grain Boundary.

Grain boundaries (GBs) in two-dimensional (2D) covalent organic frameworks (COFs) unavoidably form during the fabrication process, playing pivotal roles in the physical characteristics of COFs. Herein, molecular dynamics simulations were employed to elucidate the fracture failure and thermal transport mechanisms of polycrystalline COFs (p-COFs). The results revealed that the tilt angle of GBs significantly influences out-of-plane wrinkles and residual stress in monolayer p-COFs. The tensile strength of p-COFs can be enhanced and weakened with the tilt angle, which exhibits an inverse relationship with the defect density. The crack always originates from weaker heptagon rings during uniaxial tension. Notably, the thermal transport in p-COFs is insensitive to the GBs due to the variation of minor polymer chain length at defects, which is abnormal for other 2D crystalline materials. This study contributes insights into the impact of GBs in p-COFs and offers theoretical guidance for structural design and practical applications of advanced COFs.

Ultra-Strong Janus Covalent Organic Framework Membrane with Smart Response to Organic Vapor.

Vapor-driven smart Janus materials have made significant advancements in intelligent monitoring, control, and interaction, etc. Nevertheless, the development of ultrafast response single-layer Janus membrane, along with a deep exploration of the smart response mechanisms, remains a long-term endeavor. Here, the successful synthesis of a high-crystallinity single-layer Covalent organic framework (COF) Janus membrane is reported by morphology control. This kind of membrane displays superior mechanical properties and specific surface area, along with excellent responsiveness to CH2Cl2 vapor. The analysis of the underlying mechanisms reveals that the vapor-induced breathing effect of the COF and the stress mismatch of the Janus structure play a crucial role in its smart deformation performance. It is believed that this COF Janus membrane holds promise for complex tasks in various fields.

Ultrastretchable Helical Carbon Nanotube-Woven Film.

Helical carbon nanotube (HCNT) is regarded as one of the most promising nanomaterials due to its excellent tensile strength and superhigh stretchability. Here, a novel HCNT-woven film (HWF) is proposed, and its in-plane and out-of-plane mechanical properties are systematically investigated via molecular dynamics (MD) simulation. The MD results show that HWF possesses highly stretchable capability resulting from sliding and straightening of CNT segments, and the maximum tensile strain can reach 2113%. Furthermore, the HWF presents an obvious tensile mechanical anisotropy. The torsion failure is the main fracture mode when the HWF is stretched along the longitudinal direction. However, when the HWF is stretched along the transverse direction, the fracture is mainly caused by intertube compression. On the other hand, the HWF can dissipate large amount of kinetic energy of projectile via sliding and fracture of HCNTs, leading to high specific penetration energy. This work provides a theoretical guidance for designing and fabricating next-generation superstrong two-dimensional CNT-based nanomaterials.

A single carbon nanotube-entangled high-performance buckypaper with tunable fracture mode.

It is well known that the traditional buckypaper (BP) is composed of a certain number of short carbon nanotubes (CNTs) intertwined with each other and sliding always happens when the BP is under tensile and impact loading, which results in inferior mechanical properties compared to single CNTs. In this work, a highly-entangled single-wire BP (SWBP) structure is constructed by a modified self-avoiding random walk approach. The in-plane mechanical properties and impacting behaviors of the SWBPs with different entanglement degrees and interface frictions are systematically investigated via newly developed coarse-grained molecular dynamics (CGMD) simulation. A coarse-grained method can effectively reflect the inter-tube van der Waals (vdW) interactions and the mechanical behaviors of CNTs, including tension, bending and adhesion. In this work, from the tensile simulations of the SWBP, the results showed that the self-locking mechanism between entangled CNTs could significantly enhance the tensile resistance of the film. Besides, the mechanical properties of the SWBP are highly dependent on the entanglement degree and the interface friction between CNTs. Furthermore, two distinct fracture modes, ductile fracture and brittle fracture, are revealed, which can be efficiently controlled by changing the related friction between CNTs. From the impacting simulations, it is found that the impacting performance can be effectively tuned by adjusting the entanglement degree of the film. In addition, the kinetic energy of the projectile could be rapidly dissipated through the stretching and bending of CNTs in the SWBP. This work provides an in-depth understanding of the effect of interface friction and entanglement degree on the mechanical properties of the buckypaper and provides a reference for the preparation of strong CNT-based micromaterials.

High Impact Resistance of 2D MXene with Multiple Fracture Modes.

Two-dimensional (2D) transition metal carbides/nitrides (MXenes) are promising nanomaterials due to their remarkable mechanical and electrical properties. However, the out-of-plane mechanical properties of MXene under impact loading remain unclear. Here, particular impact-resistant fracture behaviors and energy dissipation mechanisms of MXene were systemically investigated via molecular dynamics (MD) simulation. Specifically, it was found that the specific penetration energy of MXene exceeds most conventional impact-resistant materials, such as aluminum and polycarbonate. Two kinds of novel energy dissipation mechanisms, including radial fracture and crushed fracture under different impact velocities, are revealed. In addition, the sandwiched atomic-layer structure of MXene can deflect cracks and restrain their propagation to some extent, enabling the cracked MXene to retain remarkable resistance. This work provides in-depth insights into the impact-resistance of MXene, laying a foundation for its future applications.

Improving the Hydrophobicity and Insulation Properties of Epoxy Resins by the Self-Assembly-Induced Coating of Fluorinated Graphene.

Moisture and insulation deterioration are important factors that cause the failure of epoxy packaging materials. Thus, improving the long-term stability of epoxy resins in a hot and humid environment is an important prerequisite for electronic components to adapt to complex working conditions and achieve high power densities. In this study, fluorinated graphene doped with hydroxy-terminated poly(dimethylsiloxane) was prepared and self-assembled into a micro/nanostructure on the surface of an epoxy resin, which effectively improved the surface hydrophobicity of the epoxy resin. In addition, the doping with hydroxy-terminated poly(dimethylsiloxane) modified the fluorinated graphene filler, thereby forming an arch bridge energy band structure inside the epoxy resin and thus regulating carrier migration. The water absorption of the epoxy resin decreased from 1.02 to 0.24%, and the surface water contact angle increased from 93.58 to 133.2°. Moreover, the electrical insulation performance of the modified epoxy resin was greatly improved when the surface resistivity and flashover voltage increased by 50.5 and 36.4%, respectively. Therefore, the proposed method realizes a simultaneous improvement in the hydrophobicity and insulation of epoxy resins.

Multiple Impact-Resistant 2D Covalent Organic Framework.

Exploring and designing two-dimensional (2D) nanomaterials for armor-piercing protection has become a research focus. Here, by molecular dynamics simulation, we revealed that the ultralight monolayer covalent organic framework (COF), one kind of novel 2D crystalline polymer, possesses superior impact-resistant capability under high-velocity impact. The calculated specific penetration energy is much higher than that of other traditional impact-resistant materials, such as steel, poly(methyl methacrylate), Kevlar, etc. It was found that the hexagonal nanopores integrated by polymer chains have large deformation compatibility resulting from flexible torsion and stretching, which can remarkably contribute to the energy dissipation. In addition, the deformable nanopores can effectively restrain the crack propagation, enable COF to resist multiple impacts. This work uncovers the extreme dynamic responses of COF under high-velocity impact and provides theoretical guidance for designing superstrong 2D polymer-based crystalline nanomaterials.

Levels, origins and probabilistic health risk appraisal for trace elements in drinking water from Lhasa, Tibet.

Due to the lack of monitoring systems and water purification facilities, residents in western China may face the risk of drinking water pollution. Therefore, 673 samples were collected from Lhasa's agricultural and pastoral areas to reveal the status quo of drinking water. We used inductively coupled plasma-mass spectrometry to determine trace elements concentrations for water quality appraisal, source apportionment, and health risk assessment. The results indicate that concentrations of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, and Pb are below the guidelines, while As concentrations in a few samples exceed the standard. All samples were classified into "excellent water" for drinking purpose based on Entropy-weighted water quality index. Thereafter by principal component analysis, three potential sources of trace elements were extracted, including natural, anthropogenic, and mining activities. It is worth noting that geotherm and mining exploitation does not threaten drinking water safety. Finally, health risks were assessed using Monte Carlo technique. We found that the 95th percentiles of hazard index are 1.80, 0.80, and 0.79 for children, teenagers, and adults, indicating a non-carcinogenic risk for children, but no risks for the latter two age groups. In contrast, the probabilities of unacceptable cautionary risk are 7.15, 2.95 and 0.69% through exposure to Cr, Ni, As, and Cd for adults, children, and teenagers. Sensitivity analyses reveal As concentration and ingestion rate are most influential factors to health risk. Hence, local governments should pay more attention to monitoring and removal of As in the drinking water.

Mechanical and thermal properties of carbon nanotubes in carbon nanotube fibers under tension-torsion loading.

In carbon nanotube fibers (CNFs) fabricated by spinning methods, it is well-known that the mechanical and thermal performances of CNFs are highly dependent on the mechanical and thermal properties of the inherent CNTs. Furthermore, long CNTs are usually preferred to assemble CNFs because the interaction and entanglement between long CNTs are effectively stronger than between short CNTs. However, in CNFs fabricated using long CNTs, the interior carbon nanotubes (CNTs) inevitably undergo both tension and torsion loading when they are stretched, which would influence the mechanical and thermal performances of CNFs. Here, molecular dynamics (MD) simulations were carried out to study the mechanical and thermal properties of individual CNTs under tension-torsion loading. As for mechanical properties, it was found that both the fracture strength and Young's modulus of CNTs decreased as the twist angle α increased. Besides, step-wise fracture happened due to stress concentration when the twisted CNTs are stretched. On the other hand, it could be seen that the thermal conductivity of CNTs decreased as α increased. This work presents the systematic investigation of the mechanical and thermal properties of CNTs under tension-torsion loading and provides a theoretical guideline for the design and fabrication of CNFs.

Multifunctional Ti3C2Tx MXene-Based Composite Coatings with Superhydrophobic Anti-icing and Photothermal Deicing Properties.

Although advances in industrial products have brought convenience to our lives, severe weather has increased the safety risks to industrial facilities. Considerable efforts have been made to develop high-performance superhydrophobic anti-icing coatings. Nevertheless, designing a functional coating with both anti-icing properties and self-deicing remains a major challenge. Here, we propose a design strategy to exploit a photothermal superhydrophobic multifunctional coating with excellent anti-icing and deicing properties based on MXene by high-temperature sintering and layer-by-layer coating. Specifically, poly(tetrafluoroethylene) (PTFE) particles provide low surface energy and binding effects. Room-temperature-vulcanized silicone rubber (RTV) enhances the dispersion of the composite particles and the adhesion of the functional coating to a glass substrate. Furthermore, the functional coatings constructed with MXene exhibit outstanding photothermal effects, imparting excellent superhydrophobicity (CA = 160.18°, SA = 1.8°) and efficient photothermal conversion (equilibrium temperature of 109.3 °C). An anti-icing/deicing test is simulated to confirm their efficient anti-icing/deicing performance in practical applications. Overall, the functional coatings designed in this work can be applied in real industrial facilities.

3D-printed silica with nanoscale resolution.

Fabricating inorganic materials with designed three-dimensional nanostructures is an exciting yet challenging area of research and industrial application. Here, we develop an approach to 3D print high-quality nanostructures of silica with sub-200 nm resolution and with the flexible capability of rare-earth element doping. The printed SiO2 can be either amorphous glass or polycrystalline cristobalite controlled by the sintering process. The 3D-printed nanostructures demonstrate attractive optical properties. For instance, the fabricated micro-toroid optical resonators can reach quality factors (Q) of over 104. Moreover, and importantly for optical applications, doping and codoping of rare-earth salts such as Er3+, Tm3+, Yb3+, Eu3+ and Nd3+ can be directly implemented in the printed SiO2 structures, showing strong photoluminescence at the desired wavelengths. This technique shows the potential for building integrated microphotonics with silica via 3D printing.

Enhancing Dielectric Strength of Epoxy Polymers by Constructing Interface Charge Traps.

Epoxy polymer-based dielectric materials play a crucial role in advanced electronic devices and power equipment. However, high voltage-stress applications impose stringent requirements, such as a high dielectric strength, on epoxy polymers. Previously reported studies have shown promising material architectures in the form of epoxy polymer-nanoparticle dielectrics, which can restrict the movement of high-energy electrons by the interface charge traps associated with the various interfacial regions. However, these high-energy electrons inevitably traverse the epoxy polymer matrix and destroy the molecular structure, thereby creating a weak link for dielectric breakdown. In this study, a general strategy is developed to improve the dielectric strength by constructing interface charge traps in the molecular structure of the epoxy polymer matrix, using the -CF3 group in partial replacement of the -CH3 group. The proposed strategy increases the dielectric strength (39.5 kV mm-1) and surface breakdown voltage (26.9 kV) of the epoxy polymer matrix by 22.08% and 13.3%, respectively, because the interface charge trap hinders the movement of high-energy electrons. At the same time, the strategy does not degrade the mechanical and thermal properties. The results hold potential for wide application in the manufacturing of advanced future electrical and electronic equipment requiring resilience to high-voltage stress.

Impact-resistant carbon nanotube woven films: a molecular dynamics study.

Fiber-based fabrics have great potential in impacting protection. Here, we propose a novel nanostructure, wherein single-walled CNTs (SWCNTs) were employed to weave plain 2D films. The in-plane mechanical properties and impacting properties of SWCNT woven films (SWFs) were investigated via fully atomic molecular dynamics (MD) simulation. It was found that their fracture strength and Young's modulus present obvious anisotropy, depending on the loading direction. When the loading is along the CNT axis, the mechanical performances are the best. From the impacting test, we found that this SWF synchronously possesses high impacting strength and a percentage of absorbed energy. This is mainly a result of high intrinsic strength, excellent flexibility and radial deformation capability of CNTs. In addition, it was observed that the high-speed impact of projectile can lead to the intricate entanglements of CNTs, which also could dissipate some energy by friction between the CNTs. This study provides an in-depth understanding on the mechanical properties of SWFs and broadens the applications of CNT-based nanomaterials.

Plateau river research: spatial-temporal variations of δ18O and δd in the water of the Yarlung Tsangpo River and their controlling factors.

Stable isotope technology has been widely used to trace sources and evolution of water bodies, relationships between different water bodies and pollution sources. Based on δ18O and δD data from the Yarlung Tsangpo River in 2017, this paper analyzes the composition characteristics of δ18O and δD in the river water during the low-flow, high-flow and normal-flow seasons of the entire Yarlung Tsangpo River and further reveals the spatial evolution and influencing factors. The results show that the values of δ18O, δD and d-excess were different in time and space. The δ18O, δD and d-excess values of the Yarlung Tsangpo River in the low-flow season were significantly higher than in the high-flow season. This was mainly due to weak evaporation enrichment and precipitation supply effects on the river water during the wet season. From the perspective of season change, the d-excess in the low-season is significantly higher than in the high-flow season and the normal-flow season; from the perspective of spatial change, the d-excess shows the same spatial variation trend as the δ18O, which first decreases and then increases. Based on the investigation of δ18O and δD in the main and Branch rivers of the Yarlung Tsangpo River Basin, it was found that the upper reaches of the basin were mainly supplied by snowmelt, the lower reaches were mainly supplied by rainfall.

The Effect of Fe3O4 Nanoparticle Size on Electrical Properties of Nanofluid Impregnated Paper and Trapping Analysis.

This paper systematically studies the effect of Fe3O4 nanoparticle size on the insulation performance of nanofluid impregnated paper. Three kinds of Fe3O4 nanoparticles with different sizes and their nanofluid impregnated papers were prepared. Environmental scanning electron microscopy (ESEM) and infrared spectroscopy were used to analyze the combination of Fe3O4 nanoparticles and nanofluid impregnated paper. The effect of nanoparticle size on breakdown voltage and several dielectric characteristics, e.g., permittivity, dielectric loss, of the nanofluid impregnated paper were comparatively investigated. Studies show that the Fe3O4 nanoparticles were bound to impregnated paper fibers by O-H bonds, while the relative permittivity and dielectric loss of the nanofluid impregnated papers were increased. Meanwhile, the increase of trap depth, caused by the nanoparticles, can trap the electric charge and improve the breakdown strength. The test results show that the direct current (DC) and alternating current (AC) breakdown voltages of nanofluid impregnated paper increased by 9.1% and 10.0% compared to FR3 nanofluid impregnated paper, respectively.

Spatiotemporal variability of heavy metals and identification of potential source tracers in the surface water of the Lhasa River basin.

The Lhasa River basin is the economic and population center of Tibet and has abundant resources. Due to its harsh weather condition, high elevation, and inconvenient accessibility, few studies have focused on heavy metal distributions in this region. In the present study, to investigate the dissolved trace metal pollution and its controlling factors, 57 water samples from the Lhasa River and its tributaries were collected during three water flow regimes in 2016. The data on the dissolved fraction revealed that the Lhasa River basin appeared to have no to low pollution levels. However, the Lhasa River water showed alkaline characteristics which may affect the presence of heavy metal elements in a dissolved fraction. The concentration of heavy metal elements in colloidal or particulate matter therefore needs attention. Multivariate analyses were performed to determine the significant relationship between the data and to identify controlling factors for dissolved heavy metals in the study area. The results suggested that Mn, Cd, Cu, and Zn originated from a natural geological background, whereas Pb originated from mining drainage and As was influenced by geothermal flows. The concentration of dissolved heavy metals in the Meldromarchu tributary was greatly affected by the mining drainage water, while that in the Tölungchu tributary was greatly influenced by the geothermal water sources. This paper provides the first comprehensive analysis of dissolved heavy metal pollution characteristics and the controlling factors of pollution during the three different water flow regimes of the Lhasa River basin.

Carbon nanotubes kirigami mechanical metamaterials.

Imparting elasticity and functionality to materials is one of the key objects of materials science research. Here, inspired by the art of kirigami, mechanical metamaterials comprising carbon nanotubes (CNTs) are hypothetically constructed. Using classical molecular dynamics (MD) simulations, a systematic study of the elastic limit, extensibility and yield stress of as-generated CNTs kirigami (CNT-k) is performed. Three designated kirigami patterns are employed to achieve high stretchability of CNTs. It is shown that CNT-k typically exhibits three distinct deformation stages, of which the first stage, which is referred to as geometric deformation, contributes quite a high proportion of the ductility. Various geometric parameters of CNT-k that influence the key mechanical properties of interest are respectively discussed. Three types of CNT-k with specifically identical geometric parameters exhibit distinct mechanical characteristics. This study provides an interesting example of interplay between the geometry, ductility, and mechanical characteristics of tubular materials.

Morphology-Controlled Tensile Mechanical Characteristics in Graphene Allotropes.

A number of graphene allotropes constructed by sp3, sp2, and sp hybrid orbitals have recently been proposed to provide the broad potential for practical applications. Here, using molecular dynamics simulation, the structural and tensile characteristics of nine distinct graphene allotropes have been investigated to understand their morphology-controlled mechanical properties. Results show that the averaged out-of-plane displacement is independent of nonhexagons while being dominated by the arrangement of carbon polygons on the sheets. Each sheet possesses unique surface morphology and in-plane tensile properties that significantly vary with morphology and anisotropic crystalline orientation. Brittle, semibrittle, or ductile failure is observed, depending on the evolution of their packed polygons in facilitating tension deformation and in dissipating energy. Particularly, pentagraphene exhibits superductility as a consequence of large-scale structural transformations, accommodating stress relaxation beyond initial failure. Two distinct plastic deformation patterns in overstretched pentagraphene are uncovered, depending on the tension directions: one is dominated by structural transition from sp3-carbon-contained penta-(C5) to mixed sp2-carbon polygons and the other is mainly controlled by a stepwise pentagon-to-hexagon transition. These findings provide physical insights into the structural evolvement of two-dimensional graphene allotropes and their effects on the mechanical properties.