Watching (De)Intercalation of 2D Metals in Epitaxial Graphene: Insight into the Role of Defects.

Intercalation forms heterostructures, and over 25 elements and compounds are intercalated into graphene, but the mechanism for this process is not well understood. Here, the de-intercalation of 2D Ag and Ga metals sandwiched between bilayer graphene and SiC are followed using photoemission electron microscopy (PEEM) and atomistic-scale reactive molecular dynamics simulations. By PEEM, de-intercalation "windows" (or defects) are observed in both systems, but the processes follow distinctly different dynamics. Reversible de- and re-intercalation of Ag is observed through a circular defect where the intercalation velocity front is 0.5 nm s-1 ± 0.2 nm s.-1 In contrast, the de-intercalation of Ga is irreversible with faster kinetics that are influenced by the non-circular shape of the defect. Molecular dynamics simulations support these pronounced differences and complexities between the two Ag and Ga systems. In the de-intercalating Ga model, Ga atoms first pile up between graphene layers until ultimately moving to the graphene surface. The simulations, supported by density functional theory, indicate that the Ga atoms exhibit larger binding strength to graphene, which agrees with the faster and irreversible diffusion kinetics observed. Thus, both the thermophysical properties of the metal intercalant and its interaction with defective graphene play a key role in intercalation.

Joint Theoretical and Experimental Study of Stress Graphitization in Aligned Carbon Nanotube/Carbon Matrix Composites.

Stress graphitization is a unique phenomenon at the carbon nanotube (CNT)-matrix interfaces in CNT/carbon matrix (CNT/C) composites. A lack of fundamental atomistic understanding of its evolution mechanisms and a gap between the theoretical and experimental research have hindered the pursuit of utilizing this phenomenon for producing ultrahigh-performance CNT/C composites. Here, we performed reactive molecular dynamics simulations along with an experimental study to explore stress graphitization mechanisms of a CNT/polyacrylonitrile (PAN)-based carbon matrix composite. Different CNT contents in the composite were considered, while the nanotube alignment was controlled in one direction in the simulations. We observe that the system with a higher CNT content exhibits higher localized stress concentration in the periphery of CNTs, causing alignment of the nitrile groups in the PAN matrix along the CNTs, which subsequently results in preferential dehydrogenation and clustering of carbon rings and eventually graphitization of the PAN matrix when carbonized at 1500 K. These simulation results have been validated by experimentally produced CNT/PAN-based carbon matrix composite films, with transmission electron microscopy images showing the formation of additional graphitic layers converted by the PAN matrix around CNTs, where 82 and 144% improvements of the tensile strength and Young's modulus are achieved, respectively. The presented atomistic details of stress graphitization can provide guidance for further optimizing CNT-matrix interfaces in a more predictive and controllable way for the development of novel CNT/C composites with high performance.

Role of Bilayer Graphene Microstructure on the Nucleation of WSe2 Overlayers.

Over the past few years, graphene grown by chemical vapor deposition (CVD) has gained prominence as a template to grow transition metal dichalcogenide (TMD) overlayers. The resulting two-dimensional (2D) TMD/graphene vertical heterostructures are attractive for optoelectronic and energy applications. However, the effects of the microstructural heterogeneities of graphene grown by CVD on the growth of the TMD overlayers are relatively unknown. Here, we present a detailed investigation of how the stacking order and twist angle of CVD graphene influence the nucleation of WSe2 triangular crystals. Through the combination of experiments and theory, we correlate the presence of interlayer dislocations in bilayer graphene with how WSe2 nucleates, in agreement with the observation of a higher nucleation density of WSe2 on top of Bernal-stacked bilayer graphene versus twisted bilayer graphene. Scanning/transmission electron microscopy (S/TEM) data show that interlayer dislocations are present only in Bernal-stacked bilayer graphene but not in twisted bilayer graphene. Atomistic ReaxFF reactive force field molecular dynamics simulations reveal that strain relaxation promotes the formation of these interlayer dislocations with localized buckling in Bernal-stacked bilayer graphene, whereas the strain becomes distributed in twisted bilayer graphene. Furthermore, these localized buckles in graphene are predicted to serve as thermodynamically favorable sites for binding WSex molecules, leading to the higher nucleation density of WSe2 on Bernal-stacked graphene. Overall, this study explores synthesis-structure correlations in the WSe2/graphene vertical heterostructure system toward the site-selective synthesis of TMDs by controlling the structural attributes of the graphene substrate.

Computational study of effect of radiation induced crosslinking on the properties of flattened carbon nanotubes.

Flattened carbon nanotubes (flCNTs) are a primary component of many carbon nanotube (CNT) yarn and sheet materials, which are promising reinforcements for the next generation of ultra-strong composites for aerospace applications. Significant improvements in the performance of CNT materials can be realized with improvements in the load transfer between flCNTs, which are generally oriented at different angles with respect to each other. An intriguing approach to improving the load transfer is via irradiation-induced chemical crosslinking between adjacent flCNTs. The objective of this research is to use molecular dynamics (MD) simulations to predict the behavior of flCNT junctions with 0- and 90-degree orientations and varying levels of crosslinking. The results indicate that crosslinking improves the flCNT interfacial load transfer for both orientations, but degrades the flCNT tensile response. The primary toughening mechanism at the flCNT/flCNT interface is the formation of carbon chains that provide load transfer up to the point of total rupture. Based on these results, it is clear that irradiation-induced crosslinking is beneficial in CNT-based composite systems in which interfacial load transfer between flCNTs is of primary importance, even though individual flCNTs may lose some mechanical integrity with crosslinking.

Cost-effective carbon fiber precursor selections of polyacrylonitrile-derived blend polymers: carbonization chemistry and structural characterizations.

Blending polyacrylonitrile (PAN) with plastic wastes and bio-based polymers provides a convenient and inexpensive method to realize cost-effective carbon fiber (CF) precursors. In this work, PAN-based blend precursors are investigated using ReaxFF reactive molecular dynamics simulations with respect to the formation of all-carbon rings, the evolutions of oxygen-containing and nitrogen-containing species, and the migration of carbon atoms to form turbostratic graphene. From these simulations, we identify that PAN/cellulose (CL) blend manifests the highest carbon yield and the most substantial all-carbon ring formation. This ReaxFF-based finding is confirmed by Raman and TEM experiments indicating high crystallinity for PAN/CL-derived blend CFs. We trace the pathway of gasification and carbonization of PAN/CL to elaborate the mechanism of the formation of all-carbon ring networks. We discover that the acetals of CL can catalyze the cyclization of the blend precursor, allowing for the search for CL derivatives or the other kinds of bio-based polymers with similar functionalities as alternative blends. In addition, we examine the structural characteristics using the carbon-carbon (C-C) radial distribution functions, C-C bond length distributions, and sp2 C atom ratios for the four representative precursors, i.e., PAN, oxidized PAN, PAN/nylon 6,6, and PAN/CL. Our simulation results show the most extensive all-carbon ring cluster and graphitic structure growths for PAN/CL. Therefore, we propose PAN/CL as a cost-effective alternative CF precursor, since (a) CL is naturally abundant and eco-friendly for production, (b) the blend precursor PAN/CL does not require oxidation treatment, (c) PAN/CL has a high carbon yield with substantial all-carbon ring formation, and (d) PAN/CL based CFs potentially provide a mechanical property enhancement.

Atomistic Mechanisms of Thermal Transformation in a Zr-Metal Organic Framework, MIL-140C.

To understand the mechanisms responsible for thermal decomposition of a Zr-MOF (MIL-140C), we perform atomistic-scale molecular dynamics (MD) simulations and discuss the simulation data in comparison with the TEM images obtained for the decomposed Zr-MOF. First, we introduce the ReaxFF parameters suitable for the Zr/C/H/O chemistry and then apply them to investigate the thermal stability and morphological changes in the MIL-140C during heating. Based on the performed simulations we propose an atomic mechanism for the collapse of the MIL-140C and the molecular pathways for carbon monoxide formation, the main product of the MIL-140C thermal degradation. We also determine that the oxidation state of the ZrOx clusters, evolved due to the thermal degradation, approximates the tetragonal phase of ZrO2. Both simulations and experiments show a distribution of very small ZrOx clusters embedded in the disrupted organic sheet that could contribute to the unusual high catalytic activity of the decomposed MIL-140C.

Graphene reinforced carbon fibers.

The superlative strength-to-weight ratio of carbon fibers (CFs) can substantially reduce vehicle weight and improve energy efficiency. However, most CFs are derived from costly polyacrylonitrile (PAN), which limits their widespread adoption in the automotive industry. Extensive efforts to produce CFs from low cost, alternative precursor materials have failed to yield a commercially viable product. Here, we revisit PAN to study its conversion chemistry and microstructure evolution, which might provide clues for the design of low-cost CFs. We demonstrate that a small amount of graphene can minimize porosity/defects and reinforce PAN-based CFs. Our experimental results show that 0.075 weight % graphene-reinforced PAN/graphene composite CFs exhibits 225% increase in strength and 184% enhancement in Young's modulus compared to PAN CFs. Atomistic ReaxFF and large-scale molecular dynamics simulations jointly elucidate the ability of graphene to modify the microstructure by promoting favorable edge chemistry and polymer chain alignment.

Unveiling Carbon Ring Structure Formation Mechanisms in Polyacrylonitrile-Derived Carbon Fibers.

As the demand for electric vehicles (EVs) and autonomous vehicles (AVs) rapidly grows, lower-cost, lighter, and stronger carbon fibers (CFs) are urgently needed to respond to consumers' call for greater EV traveling range and stronger safety structures for AVs. Converting polymeric precursors to CFs requires a complex set of thermochemical processes; a systematic understanding of each parameter in fiber conversion is still, to a large extent, lacking. Here, we demonstrate the effect of carbonization temperature on carbon ring structure formation by combining atomistic/microscale simulations and experimental validation. Experimental testing, as predicted by simulations, exhibited that the strength and ductility of PAN CFs decreased, whereas the Young's modulus increased with increasing carbonization temperature. Our simulations unveiled that high carbonization temperature accelerated the kinetics of graphitic phase nucleation and growth, leading to the decrease in strength and ductility but increase in modulus. The methodology presented herein using combined atomistic/microscale simulations and experimental validation lays a firm foundation for further innovation in CF manufacturing and low-cost alternative precursor development.

Atomistic Scale Analysis of the Carbonization Process for C/H/O/N-Based Polymers with the ReaxFF Reactive Force Field.

During the carbonization process of raw polymer precursors, graphitic structures can evolve. The presence of these graphitic structures affects mechanical properties of the carbonized carbon fibers. To gain a better understanding of the chemistry behind the evolution of these structures, we performed atomistic-scale simulations using the ReaxFF reactive force field. Three different polymers were considered as a precursor: idealized ladder PAN (polyacrylonitrile), a proposed oxidized PAN, and poly( p-phenylene-2,6-benzobisoxazole). We determined the underlying molecular details of polymer conversion into a carbon fiber structure. Because these are C/H/O/N-based polymers, we first developed an improved force field for C/H/O/N chemistry based on the density functional theory data with a particular focus on N2 formation kinetics and its interactions with polymer-associated radicals formed during the carbonization process. Then, using this improved force field, we performed atomistic-scale simulations of the initial stage of the carbonization process for the considered polymers. On the basis of our simulation data, the molecular pathways for the formation of low-molecular-weight gas species and all-carbon ring formation were determined. We also examined the possible alignment of the developed all-carbon 6-membered ring clusters, which is crucial for the further graphitic structure evolution.

[Secrets of the red-headed]. / Tajemnice rudowlosych.

Only 1-2% of people is red-headed but in the Russian Udmurt Republic or United Kingdom they can be met more often. A specific variant of MC1R gene (R allele) is responsible for the red hair. The gene encodes a receptor for melanocortins. These substances stimulate melanocytes to product melanin- a dye of the skin which is transported to keratinocytes. It protects a cellular nucleus from ultraviolet radiation. Melanin has two types: eumelanin which is dark brown or even black and red/orange pheomelanin. The second one is mostly observed in red-headed which is caused by R allele. The DNA damage occurs more easily because of worse protecting ability of pheomelanin. Moreover this allele is connected with inefficient DNA repair. People with R allele have not only flaming red hairstyle but also very fair skin (often with freckles) and blue eyes. Unfortunately this phenotype is more exposed to harmful effects of UV rays. It means that too extensive exposition to solar light leads to sunburn and development of cancerous skin diseases with melanoma as the worst. R allele is a recessive variant of the gene so only in homozygous persons this characteristic phenotype is observed. Nevertheless blond- or auburn-haired carriers of this allele are also more prone to develop carcinomas. The red-headed also differ from the others in sensitivity to anaesthetics, what is shown by increased MAC. On the other hand these persons less often suffer from vitamin D deficiency. The aim of the article is to present facts and myths of red-headed.

[Asymptomatic HBsAg antigenemia in children referred to hospital treatment for various reasons]. / Bezobjawowe nosicielstwo antygenu HBs u dzieci kierowanych na leczenie szpitalne z róznych przyczyn.

HBsAg antigenemia still constitutes a serious clinical problem. In 852 children at the age of 3 months to 17 years (54.2% boys and 45.8 girls) referred in 2001 to J. Korczak hospital in Lódz, antigen HBsAg was determined with the Axsym (V2) test, MEIA (Abbott) method. Asymptomatic HBsAg antigenemia was recognized in 2.35% (20/852) children. The children were from 9 to 17 years old (0 girls and 10 boys); they came mainly from Lódz. Among HBsAg antigenemic children, 95% (19/20) had not been vaccinated against Hepatitis B. The Children were hospitalized mainly on the surgical wards (because of accidents and injuries) as well as the neurological ward. Hospitalization was shown to be the mainly cause of HBV infection.

[Frequency of asymptomatic C viral infections in children referred to hospital treatment for various reasons]. / Czestosc wystepowania bezobjawowych zakazen wirusem zapalenia watroby typu C u dzieci kierowanych na leczenie szpitalne z róznych przyczyn.

In 2221 children aged 0.468-17.580 (56% boys and 44% girls) referred to hospital treatment for various reasons, antibodies anti HCV were determined with 3rd Generation Axsym (Abbott) test. In 3% (66/221) children the result was positive. Significant increase in the frequency of anti HCV occurrence was observed in children over 6, especially in 9, 10 and 11 years old--54% (36/66). Children anti HCV positive came mainly from large cities: 83% (55/66). Risk factors are presumed to be firstly blood sampling in out-patient clinics 34.8% (23/66) and hospitalization 22.7% (15/66), then dental procedures 18.2 (12/66), hairdressing and cosmetic procedures (tattoo and ear pricking) 12.1% (8/66). The authors point at the necessity of control in institutions performing such procedures as well as the need of sanitary education among medical personnel and school children in the period of hepatotropic viral infections.

Oscillations and dynamics in a two-dimensional prey-predator system.

Using Monte Carlo simulations we study two-dimensional prey-predator systems. Measuring the variance of densities of prey and predators on the triangular lattice and on the lattice with eight neighbors, we conclude that temporal oscillations of these densities vanish in the thermodynamic limit. This result suggests that such oscillations do not exist in two-dimensional models, at least when driven by local dynamics. Depending on the control parameter, the model could be either in an active or in an absorbing phase, which are separated by the critical point. The critical behavior of this model is studied using the dynamical Monte Carlo method. This model has two dynamically nonsymmetric absorbing states. In principle both absorbing states can be used for the analysis of the critical point. However, dynamical simulations which start from the unstable absorbing state suffer from metastablelike effects, which sometimes renders the method inefficient.