Molecular dynamics study on size-dependent elastic properties of silicon nanoplates

Using molecular dynamics simulations, the size-dependent Young's moduli of silicon nanoplates due to surface effects are investigated at intrinsic scale. The transformations of surface reconstructions are discussed in terms of the difference between the total strain energy densities (u_T) of the system from the MD and the specified strain energy densities (u_C). An analytical prediction for the effective Young's modulus is derived for the intrinsic scale specimens, and it agrees well with MD simulations.     

Molecular dynamics study on oscillation dynamics of a C60 fullerene encapsulated in a vibrating carbon-nanotube-resonator

We investigated the oscillation dynamics of a C₆₀ fullerene encapsulated in a single-walled carbon-nanotube-resonator via classical molecular dynamics simulations. The C₆₀ fullerene positions in a single-walled carbon-nanotube-resonator could be controlled by vibrating the resonator. The C₆₀-fullerene’s oscillations along the tube axis in a vibrating carbon-nanotube-resonator were originated by centrifugal forces exerted at the central position of the vibrating carbon-nanotube, and thus property was very different from its oscillation due to van der Waals forces in the fixed carbon-nanotube. These properties suggest that a carbon-nanotube-resonator encapsulating a C₆₀ fullerene has a potential application for programmable multiple-position devices controlled by the resonance frequency.     

Functionalized Fullerene for Inhibition of SARS-CoV-2 Variants

As virus outbreaks continue to pose a challenge, a nonspecific viral inhibitor can provide significant benefits, especially against respiratory viruses. Polyglycerol sulfates recently emerge as promising agents that mediate interactions between cells and viruses through electrostatics, leading to virus inhibition. Similarly, hydrophobic C₆₀ fullerene can prevent virus infection via interactions with hydrophobic cavities of surface proteins. Here, two strategies are combined to inhibit infection of SARS-CoV-2 variants in vitro. Effective inhibitory concentrations in the millimolar range highlight the significance of bare fullerene's hydrophobic moiety and electrostatic interactions of polysulfates with surface proteins of SARS-CoV-2. Furthermore, microscale thermophoresis measurements support that fullerene linear polyglycerol sulfates interact with the SARS-CoV-2 virus via its spike protein, and highlight importance of electrostatic interactions within it. All-atom molecular dynamics simulations reveal that the fullerene binding site is situated close to the receptor binding domain, within 4 nm of polyglycerol sulfate binding sites, feasibly allowing both portions of the material to interact simultaneously.     

Applications of fullerene beams in analysis of thin layers

Molecular dynamics computer simulations have been employed to model ejection of particles from Ag{1 1 1} metal substrate and thin benzene overlayer bombarded by fullerene cluster projectiles. The sputtering yields are analyzed depending on the size (from C₂₀ up to C₅₄₀) and the kinetic energy (5-20 keV) of a projectile. It has been found that for clean metal substrate bombarded by 15 keV projectiles the maximum ejection is stimulated by the impact of the C₆₀ cluster. However, the size of the cluster projectile maximizing the yield depends on the kinetic energy of the cluster, shifting towards larger clusters as the impact energy increases. For a thin benzene overlayer, the yield increases monotonically with the size of the cluster within investigated range of fullerene projectiles and kinetic energies.     

A new route to graphene starting from heavily ozonized fullerenes: Part 1—thermal reduction under inert atmosphere

It is shown that heavily ozonized C₆₀ or C₇₀ fullerenes (known also as “fullerene ozopolymers”) are suitable substrates for the preparation of graphene or nanographene in place of graphite oxide (GO) by thermal reduction in inert atmosphere. TGA-FTIR study shows that the release profile of CO₂ and CO from fullerene ozopolymers in the temperature range between 25°C and 900°C is comparable to that shown by GO. Furthermore, the FT-IR spectral evolution of fullerene ozopolymers from room temperature to 630°C under inert atmosphere is once again strikingly comparable to that observed on GO under the same conditions.     

Temperature-dependent Thermodynamic Behaviors of Carbon Fullerene Molecules at Atmospheric Pressure

The study aims at investigating the linear and volumetric thermal expansion coefficients (CTEs) at temperature below the Debye temperature and phase transformation behaviors at atmospheric pressure of carbon fullerenes, i.e., C₆₀, C₇₀ and C₈₀, through a modified Nosé-Hoover (NH) thermostat method incorporated with molecular dynamics (MD) simulation. The calculated results are compared with those obtained from the standard NH and "massive" NHC (MNHC) thermostats and also with the literature experimental and theoretical data. Results show that at temperature below the Debye temperature, the CTEs of the fullerene molecules would significantly decrease with a decreasing temperature and tend to become negative at temperature below 5K. The present results are much more consistent with the literature experimental and theoretical data, in contrast to the other two thermostat algorithms. Besides, it is found that C₆₀ fullerene directly undergoes a solid-vapor phase transformation, instead of a solid-liquid phase transition, implying that the molecule will sublimate when heated rather than melt under atmospheric pressure. This phenomenon is coincident with that of graphite at pressures below 10MPa. The sublimation point of C₆₀ fullerene is about 4350±20K, comparable to that of graphite in the range of about 4000-4500K at pressures below 10 MPa.     

Molecular dynamics investigations on the interfacial energy and adhesive strength between C60-filled carbon nanotubes and metallic surface

The mechanical and adhesive properties of C₆₀@(10,10) carbon nanopeapods (CNPs) adhering to gold surfaces are investigated by atomistic simulations. The effects of C₆₀ fill density, tube length, surrounding temperature, and peeling velocity on the adhesion behavior are studied. Results show that the interfacial binding energy of CNPs (which depends on the C₆₀ fill density and temperature) is 2.0∼4.4% higher than that of (10,10) single-walled CNTs and 3.4∼4.7% lower than that of (5,5)@(10,10) double-walled CNTs (DWCNTs). Despite their lower interfacial binding energy, CNPs have a higher adhesive strength than that of DWCNTs (1.53 nN vs. 1.4 nN). Distinct from the inner tubes of DWCNTs, which have continuum mechanical properties, the discrete C₆₀ molecules that fill CNPs exhibit unique composite mechanical properties, with high flexibility and bend-buckling resistance. The bend-buckling forces for CNPs filled with a low/medium fill density of C₆₀ are approximately constant. When the fill density is 1 C₆₀ molecule per nanometer length, the bend-buckling force dramatically increases.     

Design of composite materials with improved impact properties

Composites have been widely used in applications where there is a risk of impact, due to the excellent properties these materials display for absorbing impact energy. However, composites during impact situations typically generate an enormous number of small pieces, due to the energy absorption mechanism of these materials, a mechanism which does not include plastic deformation. This can prove dangerous in sports competitions, where the small fragments of the original structure may harm competitors.This study was designed to explore the possibility of incorporating a material which, whilst maintaining a high level of energy absorption without any plastic deformation mechanism, was able to maintain its original form, or at least significantly reduce the number of pieces generated after impact.The addition of a polyamide layer, NOMEX^®, to a monolithic fabric laminate was investigated in this paper. The process of fabrication is described and the different properties of the material under consideration: interlaminar fracture toughness energy (G_IC), indentation (id) and delamination after impact (A_i) and compression after impact (σ_CAI), were measured and compared with those of the original monolithic fabric.     

Effects of pores on shear bands in metallic glasses: A molecular dynamics study

The effects of nanoscale pores on the strength and ductility of porous Cu₄₆Zr₅₄ metallic glasses during nanoindentation and uniaxial compression tests are modelled and investigated using molecular dynamics (MD) simulations. In the MD simulations, atomistic amorphous samples were digitally prepared through fast quenching from the liquid states of copper and zirconium alloy. In both of the nanoindentation and uniaxial compression simulations, shear transformation zones and shear bands are observed through the local deviatoric shear strains in the samples. The results show that the existence of pores causes strain concentrations and greatly promotes the initialization and propagation of shear bands. Importantly, only pores reaching critical size can effectively facilitate the formation of multiple shear bands. It is also observed that hardening occurs through pore annihilation and the shear band stops in porous metallic glasses.     

Atomistic simulations of shearing friction and dynamic adhesion of double-walled carbon nanotubes on Au substrates

Functional gecko-mimetic adhesives have attracted a lot of research interest in recent years. In this paper, the physical adhesion behavior of (5, 5)@(10, 10) double-walled carbon nanotubes (DWCNTs) on an Au substrate is investigated by performing detailed, fully atomistic molecular dynamics (MD) simulations. The effects of adhesion temperature, tube length, and peeling velocity on the binding energy, normal adhesion force, lateral shearing friction, and adhesion time are thoroughly analyzed. The simulation results indicate that the binding energy (per unit length) of the DWCNT–Au adhesive system is −26.7 × 10⁻² eV/Å, which is 7.2% higher than that of single-walled counterparts. The tip-surface adhesion force for a single DWCNT is calculated to be 1.4 nN, and thus the adhesive strength of a DWCNT array is about 1.4 × 10¹–1.4 × 10³ N/cm² (corresponding to an aerial density of 10¹⁰–10¹² tubes/cm²). Two distinctive friction modes, namely (i) sliding friction (by the nanotube wall) and (ii) sticking friction (by the nanotube tip), are elucidated in term of the phase relationship of atomic friction forces. Moreover, the effective Young’s moduli of double- and single-walled CNTs are obtained using MD simulations combined with Euler–Bernoulli beam theory. The calculation results show good agreement with previously reported numerical and experimental results.     

The response of a multi-directional composite laminate to through-thickness loading

The through-thickness mechanical response of a carbon fibre/epoxy laminated composite of lay-up [0/45/−45]_ns is measured at low rates of strain. Uniaxial tension and compression experiments are carried out on dogbone specimens cut from a thick laminate along different directions, and failure mechanisms are observed via optical and electron microscopy. The effect of direct and shear stresses at the ply interfaces on the onset of failure is measured, and a failure envelope is constructed. The compressive response of specimens of different shape is investigated. Composite beams of different volume and aspect ratios are tested to failure in three-point bending and these tests reveal a strong dependence of the apparent out-of-plane tensile strength of the composite on the beam volume; this effect is modelled by Weibull theory.     

Fullerene C<Subscript>60</Subscript> diffusion in thin layers of amorphous polymers: Polystyrene and poly(α-methylstyrene)

The outdiffusion of fullerene C₆₀ from submicron films of polymer-fullerene blends has been studied by thermodesorption mass spectrometry (TDMS). The energy parameters of C₆₀ diffusion in polystyrene and poly(α-methylstyrene) were determined and compared to the parameters of desorption of C₆₀ molecules from a multilayer film of pure fullerene deposited onto a substrate from toluene solution.     

A new route to graphene starting from heavily ozonized fullerenes: Part 2—oxidation in air

Graphite oxide (GO) and heavily ozonized C₆₀ and C₇₀ fullerenes known as “fullerene ozopolymers” were studied by TGA-FTIR (Thermogravimetry coupled with FT-IR spectroscopy), DTG (Differential Thermogravimetry) and DTA (Differential Thermal Analysis) in air flow. It was found that GO burns at 70°C higher temperature than the fullerene ozopolymers. This different behavior toward the thermal oxidation of GO is due to the size of the oxidized and staked graphene layers which are expected to be significantly larger than those of the fullerene ozopolymers. Furthermore, the latter should necessarily have a buckybowl shaped structure which should favor their reactivity with oxygen.     

A STUDY ON THE THERMAL STABILITY TO 1000°C OF VARIOUS CARBON ALLOTROPES AND CARBONACEOUS MATTER BOTH UNDER NITROGEN AND IN AIR

ABSTRACT

The thermal behavior of graphite, C₆₀ fullerene, fullerene black (carbon soot containing fullerenes), extracted fullerene black and diamond has been analyzed to 1000°C by TGA–DTA (thermogravimetric analysis and differential thermal analysis) under a nitrogen flow at a heating rate of 20°C/min. Very small weight losses have been recorded in the case of graphite and diamond. Furthermore no diamond graphitization has been observed. The sublimation of pure C₆₀ and the fullerene fraction of fullerene black (both pristine and extracted) has been observed and discussed.

The combustion reaction in air flow of graphite, C₆₀ and C₇₀ fullerenes, fullerene black (both unextracted and extracted), carbon nanotubes and diamond has been studied by TGA–DTA at a heating rate of 20°C/min. C₇₀ fullerene and fullerene black have been found to be the most reactive carbon materials with O₂. The role played by C₇₀ in the degradation of fullerites has been discussed. Among the carbon materials examined, the best resistance to O₂ attack has been shown by diamond and carbon nanotubes. The behavior of graphite is intermediate between diamond and fullerene blacks. The behavior of C₆₀ fullerene appears closer to that of graphite although it appears to be more reactive with O₂. Samples of graphite and carbon blacks N375 and N234 have been studied by TGA–DTA in air flow before and after a radiation treatment with neutrons or γ radiation. The effect of the radiation damage in the combustion reaction of these carbon materials has been discussed.     

Mechanical properties and electronic structures of compressed C<Subscript>60</Subscript>, C<Subscript>180</Subscript> and C<Subscript>60</Subscript>@C<Subscript>180</Subscript> fullerene molecules

Molecular dynamics simulations were performed for compressed C₆₀, C₁₈₀ and C₆₀@C₁₈₀ fullerene molecules, and the semi-empirical PM3 calculations were carried out to obtain the electronic structure of the compressed fullerenes. According to the obtained results, the differences of mechanical properties between these compressed fullerenes, as well as the changes of their FMO (Frontier molecular orbital) energy-levels during compression, were discussed. It is shown that (1) the C₆₀ molecule has much higher load-support and energy-absorbing capability than the C₁₈₀ and C₆₀@C₁₈₀ molecules, and the C₆₀@C₁₈₀ is only slightly superior to the C₁₈₀, (2) of the three molecules, the C₆₀ molecule has the best chemical-stability, and the C₆₀@C₁₈₀ molecule has the worst one, (3) with the increase of compressive strain, both the C₆₀ and C₆₀@C₁₈₀ molecules become more chemically active, and (4) when the compressed C₁₈₀ molecule caves in at the loading position(s), its chemical-stability decreases abruptly.     

Isomers of the C84 fullerene: A theoretical consideration within energetic,structural, and topological approaches

Currently, there is no common conception on the stability and achievability of fullerene isomers under the arc-discharge synthesis conditions. Different approaches operate with energetic, structural, and topological parameters of the fullerene molecules to explain why some fullerene isomers are more preferable than the others. In the present work, we have selected the most appropriate approaches based on topological roundness, information entropy, nuclear volumes, and sphericities and compared their predictions with the relevant experimental data on the C₈₄ fullerene isomers (obeying the isolated pentagon rule) and density functional theory estimates of their stability. We have found that the molecules of most stable (and most abundant) C₈₄ isomers have the minimal extremal roundness, maximal sphericity, and largest volume and vice versa. In the case of the information entropy, no correlation is observed. Interestingly, the found correlation between the volume and the stability of the C₈₄ isomers is unexpectedly inverse, i.e. more stable C₈₄ isomers have larger inner cavities inside, though traditionally large volume is associated with instability of hollow framework molecules. We assume that the large volumes allows enhancing the sphericity of the fullerene cages as we found the last one favoring the stability and the unstable C₈₄ fullerene cages having low volumes are far from the spherical shape. We think that the results obtained may be extrapolated to other fullerene isomeric sets and contribute to the understanding the grounds of the interconnection in the triad “topology – structure – energy” underlying structural chemistry.     

XPS characterization of MWCNT and C60-based composites

X-ray photoelectron spectroscopy was used for characterization of MWNT-C₆₀ composites with assistance of scanning and transmission electron microscopy. The composites were received by immerison of nanotubes into fullerene solution in CS₂ with consequent processing with green laser irradiation at aproximately 10 W/cm². It was shown that C1s spectra of composites are different from simple addition of MWNT and C₆₀ features. It found that preliminary nanotube purification by oxidative treatment influences strongly the nature of fullerene-nanotube bonding. Hydrophilic surface of oxidized nanotube material has lower affinity to C₆₀ molecules and provides for concentration of C₆₀ molecules into clusters, which show differential charging effect in XPS spectra. The differential charging effect disappears after laser processing, which induces photopolymerization of fullerene clusters. The as-synthesized nanotubes form composites with more evenly distributed fullerene.     

Highly selective ethanol In2O3-based gas sensor

The sensitive composite material was prepared by loading Pt and La₂O₃ into ultrafine In₂O₃ matric material (8 nm) synthesized by microemulsion method. A highly selective ethanol gas sensor was developed based on hot-wire type gas sensor, which was sintered in a bead (0.8 mm in diameter) to cover a platinum wire coil (0.4 mm in diameter). The gas sensor was operated by a bridge electric circuit. The influences of La₂O₃ and Pt additives on C₂H₅OH sensing properties of In₂O₃-based gas sensor were discussed. The addition of La₂O₃ resulted in a prominent selectivity for C₂H₅OH, and the addition of Pt improved the response rate to C₂H₅OH without affecting the sensitivity. The temperature and humidity characteristics of the sensor output were also investigated. The selective sensor had low power consumption, significantly minor humidity and temperature dependence, high selectivity and prominent long-term stability.     

Two Alternative Ways for Formation of Mono‐atomic Carbon Layer on Ni(1 1 1): Organic‐Gas Cracking and Thermal Decomposition of Fullerenes in Thin Film

Abstract

Formation of graphite mono‐atomic layers (monolayer of graphite, MG) on Ni(1 1 1) single‐crystal surface by cracking of propylene C₃H₆ as well as by decomposition of fullerene molecules C₆₀ was investigated. Comparative analysis of carbon films was made in both cases by means of auger electron spectroscopy (AES), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM) techniques. It was shown with the LEED measurements, that quality of graphite mono‐atomic layer obtained in the two different ways is similar and high enough. For the system prepared by fullerene fragmentation some fullerene‐similar topography features were found in STM images. These observations are explained as a result of arrangement of single C₆₀ molecules underneath the MG on Ni(1 1 1).     

Controlling the Number of Arms of Polymer Stars with a Fullerene C60 Core

Abstract

Pure di‐ and tetra‐adducts can be obtained by grafting polystyrene (PS) chains onto C₆₀ via an atom transfer radical addition. Stars with a C₆₀ core and exactly six PS arms of molar mass ranging from 1000 to several 100,000 are easily produced by adding an excess of PSLi to the fullerene. Tri‐ to penta‐adducts can be prepared by controlling the stoichiometry PSLi/C₆₀. The number of grafts on the fullerene can be extended to seven or eight by initiation of the anionic polymerization of an adequate monomer with a “living” hexa‐adduct or by grafting onto this latter an halogen terminated polymer.