Effect of chemisorption structure on the interfacial bonding characteristics of graphene-polymer composites

The influence of the chemical functionalization of graphene on the interfacial bonding characteristics between graphene and polymer was investigated using molecular mechanics and molecular dynamics simulations. In this study, three chemical functionalization, (a) phenyl groups, (b) -C₆H₁₃ and(c) -C₂H₄(C₂H₅)₂, which have the same number of carbon atoms, were chosen to investigate the influence of the structure of functionalized groups on the bonding energy and shear stress in the graphene-polyethylene (PE) composites. Our simulations indicated that, the interfacial bonding energy between the graphene modified by -C₆H₁₃ groups and PE matrix has the strongest enhancement, but the shear force between the graphene modified by -C₂H₄(C₂H₅)₂ groups and PE matrix is the strongest in the graphene-polymer composites. Therefore, the suitable structure of chemical groups to the graphene surface may be an effective way to significantly improve the load transfer between the graphene and polymer when graphene is used to produce nanocomposites.     

Effects of different parameters on thermal and mechanical properties of aminated graphene/epoxy nanocomposites connected by covalent: A molecular dynamics study

This paper is devoted to studying the thermal and mechanical properties of aminated graphene (AG)/epoxy nanocomposites connected by covalent bond using molecular dynamics (MD) simulation. The effects of crosslinking degree, mass fraction and functionalized graphene (FG) type on AG/epoxy nanocomposites are considered. The elasticity modulus (E), the glass transition temperature (T_g), the coefficient of thermal expansion (CTE) and the interfacial energy (E_int) are also investigated. The MD simulation results indicate that, when the mass fraction of AG is between 1.2% and 3.1% and crosslinking degree reaches about 70%, the E, T_g, E_int and CTE of AG/epoxy nanocomposites are significantly improved compared with those of pure epoxy and graphene/epoxy nanocomposites. The reason is that AG not only possesses some excellent thermodynamic properties of graphene, but also has the function of curing agent to crosslink with epoxy monomer to form the carbon-nitrogen (C–N) covalent bond. A better interfacial interaction between nanoparticles and epoxy is essential in enhancing the thermal and mechanical properties of nanocomposite materials, which will provide a microscopic theoretical basis for the study of epoxy nanocomposites.     

Enhanced dielectric properties and energy storage density of interface controlled ferroelectric BCZT-epoxy nanocomposites

Polymer nanocomposites with ferroelectric fillers are promising materials for modern power electronics that include energy storage devices. Ferroelectric filler, Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃ (BCZT) nanopowder, was synthesized by sol-gel method. X-ray diffraction (XRD) studies confirmed the phase purity and the particle size distribution was determined by transmission electron microscopy (TEM). Extended aromatic ligand in the form of naphthyl phosphate (NPh) was chosen for surface passivation of BCZT nanoparticles. Surface functionalization was validated by thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and impedance spectroscopy using slurry technique. The dielectric constant of surface-passivated BCZT nanopowder was ~155, whereas pristine BCZT nanopowder dielectric constant could not be assessed due to high innate surface conductivity. Furthermore, BCZT–epoxy nanocomposite films were prepared and analyzed by differential scanning calorimetry (DSC), dielectric spectroscopy, dielectric breakdown strength (DBS), and scanning electron microscopy (SEM). Owning to stronger polymer–particle interface, dielectric measurements of 5 vol.% NPh surface functionalized BCZT–epoxy nanocomposites indicated improved DBS and glass transition temperature (T_g), reduced dielectric loss, and enhanced energy storage density compared to untreated BCZT–epoxy composites and pure epoxy. The energy storage density of 30 vol.% NPh surface functionalized BCZT–epoxy nanocomposite of 20 μm film thickness was almost three times that of pure epoxy polymer of identical film thickness.     

A versatile method for the preparation of end-functional polymers onto SiO2 nanoparticles by a combination of surface-initiated ATRP and Huisgen [3 + 2] cycloaddition

A versatile method was developed for the chain-end functionalization of the grafted polymer chains for surface modification of nanoparticles with functionalized groups through a combination of surface-initiated atom-transfer radical polymerization (ATRP) and Huisgen [3 + 2] cycloaddition. First, the surface of SiO₂ nanoparticles was modified with poly(methyl methacrylate) (PMMA) brushes via the “grafting from” approach. The terminal bromides of PMMA-grafted SiO₂ nanoparticles were then transformed into an azide function by nucleophilic substitution. These azido-terminated PMMA brushes on the nanoparticle surface were reacted with alkyne-terminated functional end group via Huisgen [3 + 2] cycloaddition. FTIR and ¹H NMR spectra indicated quantitative transformation of the chain ends of PMMA brushes onto SiO₂ nanoparticles into the desired functional group. And, the dispersibility of the end-functional polymer-grafted SiO₂ nanoparticles was investigated with a transmission electron microscope (TEM).     

Computational analysis of effect of modification on the interfacial characteristics of a carbon nanotube-polyethylene composite system

In this study, the non-covalent association of single-walled nanotube (SWNT) with polyethylene (PE) molecule and the influence of sidewall modification on the interfacial bonding between the SWNTs and polymer were investigated using molecular mechanics (MM) and molecular dynamics (MD) simulations. The model of interaction between the initially separated PE and SWNT fragments, which can be either wrapping or filling, was computed. The possible extension of polymers wrapping or filling SWNTs can be used to structurally bridge the SWNTs and polymers to significantly improve the load transfer between them when SWNTs are used to produce nanocomposites. The interfacial bonding characteristics between the single-walled nanotubes, on which -COOH, -CONH₂, -C₆H₁₁, or -C₆H₅ groups have been chemically attached, and the polymer matrix were also investigated by performing pullout simulations. The results show that appropriate functionalization of nanotubes at low densities of functionalized carbon atoms drastically increase their interfacial bonding and shear stress between the nanotubes and the polymer matrix, where chemisorption with -C₆H₅ groups to as little as 5.0% of the nanotube carbon atoms increases the shear stress by about 1700%. Furthermore, this suggests the possibility to use functionalized nanotubes to effectively reinforce other kinds of polymer-based materials as well.     

HLDPE/organic functionalized SiO2 nanocomposites with improved thermal stability and mechanical properties

High-pressure low-density polyethylene (HLDPE)/organic functionalized SiO₂ nanocomposites were synthesized using melt-blending technique in a sigma internal mixer. The properties of the nanocomposites were studied using two different organic functional modifiers: diglycidyl ether of bisphenol-A (DGEBA) and triacetoxyvinylsilane. Reinforcing, thermal stability and toughening effects of organic functionalized nanosilica on the polymer matrix were found at loading of 2.5% nanosilica functionalized with 2.8% of DGEBA and silane coupling agent respectively. Organic functionalization on the nanosilica particle surface led to different microstructures when compared with that of the pure polymer. Organic functionalization on the nanosilica particle surface produced good interfacial adhesion and homogeneous dispersion in the polymer matrix, while the use of nanosilica resulted in aggregated silica particles in the polymer matrix. There was no significant improvement in thermal stability and mechanical properties when only nanosilica was added to the pure polymer. On the contrary, the addition of pretreated nanosilica with organic functional modifiers led to an increase of thermal stability from 313–363°C, elastic modulus and toughness from 0.12–0.18 GPa and 3.23–9.81 MJ/m³ respectively.     

多价态高分子链在受体平面上的超选择性吸附

利用三维朗之万动力学模拟研究了多价态高分子链在受体平面上的吸附行为。其在受体平面上的吸附具有超选择性,随着高分子链上配体浓度的增大,发生超选择性吸附时的平面受体浓度范围变窄;而超选择性吸附最显著时的平面受体浓度,即最佳平面受体浓度随着链上配体浓度的增大而减小。对处于吸附态的多价态高分子链的构象性质进行了系统地研究,发现链的平衡回转半径R_g及其水平分量R_g},随着平面受体浓度的增大都存在极大值。其平衡回转半径R_g与其链长N间的标度指数表明当平面受体浓度的增大时,处于吸附态的链构象介于二维链构象和三维链构象之间;随着平面受体浓度的进一步增大,吸附在平面上的多价态高分子链发生轻微的塌缩     

Influence of hydrophilic properties on capacitive behavior of functionalized graphene

Super-hydrophobic graphene was treated with 4-benzenediazoniumsulfonate to obtain a series of functionalized graphene (FG) with enhanced hydrophilic properties. The results from Fourier transform infrared (FT-IR) spectra and thermogravimetric (TG) analyses demonstrate that ?SO₃H groups are covalently anchored to functionalized graphene and alter the thermal stability of graphene-based materials. In comparison to pristine graphene (PG), functionalized graphene as prepared exhibits enhanced hydrophilic properties which can be conducted by varying the diazotization-coupling reaction time. Cyclic voltammetry (CV) curves indicate that enhanced hydrophilic properties improve the capacitance of functionalized graphene up to twice than that of pristine graphene in Na₂SO₄ electrolytes. Moreover, electrochemical impedance spectroscopy (EIS) reveals that the high level of functionalization will cause the decrease of the electric conductivity and capacitive performance, suggesting that functionalization of graphene provides the competitive relationship between the positive hydrophilicity increase and the negative conductivity decrease to capacitive performance.     

Monolayer characteristics of stereoregular PMMA at the air/water interface

Behaviors of isotactic, atactic and syndiotactic poly(methyl methacrylate) (PMMA) monolayers at the air/water interface were investigated. The monolayer characteristics of the three stereoisomers were studied and compared in terms of surface pressure-area per molecule (π-A) isotherm, hysteresis and relaxation phenomena, and the phase images observed from Brewster angle microscopy (BAM). The results show that iPMMA monolayer has a more extended and compressible property, and exhibits pronounced hysteresis and relaxation phenomena among the three tactic PMMAs. Such characteristics can reasonably be attributed to the higher flexibility of chains segments of iPMMA as estimated from its lower T_g. On the other hand, sPMMA, the one with the highest T_g, forms a more condensed monolayer due to the high cohesive interaction among polymer chains. The BAM images show that PMMA molecules are not well extended on the subphase and thus, aggregative phases were observed even in a state corresponding to the gas phase. The aggregative structures are especially significant on sPMMA monolayer, which is consistent with the results estimated from the π-A isotherms. When the temperature is elevated from 25 to 40 °C, all the monolayers of the three stereoisomers become more expanded and compressible due to the increase in chain flexibility.     

A new function of graphene oxide emerges: inactivating phytopathogenic bacterium Xanthomonas oryzae pv. Oryzae

The main goal of the present work is to examine the effect of graphene layers on the structural and dynamical properties of polymer systems. We study hybrid poly(methyl methacrylate) (PMMA)/graphene interfacial systems, through detailed atomistic molecular dynamics simulations. In order to characterize the interface, various properties related to density, structure and dynamics of polymer chains are calculated, as a function of the distance from the substrate. A series of different hybrid systems, with width ranging between 2.60 and 13.35 nm, are being modeled. In addition, we compare the properties of the macromolecular chains to the properties of the corresponding bulk system at the same temperature. We observe a strong effect of graphene layers on both structure and dynamics of the PMMA chains. Furthermore, the PMMA/graphene interface is characterized by different length scales, depending on the actual property we probe: density of PMMA polymer chains is larger than the bulk value, for polymer chains close to graphene layers up to distances of about 1.0–1.5 nm. Chain conformations are perturbed for distances up to about 2–3 radius of gyration from graphene. Segmental dynamics of PMMA is much slower close to the solid layers up to about 2–3 nm. Finally, terminal-chain dynamics is slower, compared to the bulk one, up to distances of about 5–7 radius of gyration.     

Thermodynamic approach to enhance the dispersion of graphene in epoxy matrix and its effect on mechanical and thermal properties of epoxy nanocomposites

Graphene-reinforced polymer nanocomposites are under intense investigation in recent years. In this work, graphene nanosheets have been prepared using chemical reduction method of graphene oxide. Graphene-reinforced epoxy nanocomposites show an enhancement in mechanical and thermal properties at 0.05 wt.% of graphene in epoxy matrix. Modification of graphene with polyvinylpyrrolidone (PVP) shows the significant enhancement in mechanical and thermal properties of epoxy nanocomposites. PVP-modified graphene nanosheets reduces the gap of enthalpic and entropic penalties and facilitates improved dispersion of graphene in epoxy matrix. In addition, enhanced dispersion of PVP-modified graphene in epoxy matrix results in better load transfer across graphene–epoxy interface. Glass transition temperature (T_g) of PVP-modified graphene epoxy nanocomposites increases as compared to pure epoxy because there exist an interaction between epoxy and PVP. Fractography study reveals the localized ductile fracture.     

氢及其同位素在聚苯乙烯与Cu界面的扩散

为了探索气体在固体表面高分子链中的扩散,使用分子动力学（MD）的方法,对H2,D2,T2在聚苯乙烯与金属铜（PS-Cu）界面的扩散进行了计算模拟,通过所得到气体的均方位移计算了气体在不同金属表面与聚苯乙烯界面中的扩散系数。结果显示:气体在界面的扩散系数比在聚苯乙烯本体中的扩散系数小,气体在PS-Cu(110)界面的扩散系数最大,在PS-Cu(111)界面的扩散系数最小。计算和分析了PS与金属表面的相互作用,发现其相互作用能越大,气体在此界面的扩散系数越小。同时,金属表面的晶面密度对气体在界面中的扩散也有一定的影响。     

Morphology and thermal properties of clay/PMMA nanocomposites obtained by miniemulsion polymerization

Miniemulsion polymerization was used as the synthetic method to produce clay/poly(methyl methacrylate) nanocomposites. Two kinds of interfacial interactions clay–polymer particle were observed by electron microscopy, one where the polymer particles are adhered on the surface of the larger fragments of clay, and another where nanometric fragments of clay are encapsulated by polymer particles. Variations in the glass transition temperature (T_g) and thermomechanical properties of the matrix, as function of clay content, were observed. In particular, at the highest clay loading (1.0 wt%) depression of T_g and thermomechanical properties were observed. The increased clay–polymer matrix interfacial area appears to be the conditioning factor that determines such behavior.     

Molecular responses of cells to 2-mercapto-1-methylimidazole gold nanoparticles (AuNPs)-mmi: investigations of histone methylation changes

Reduced graphene oxide (RGO) sheet was functionalized with nanocrystalline cellulose (NCC) via click coupling between azide-functionalized graphene oxide (GO-N₃) and terminal propargyl-functionalized nanocrystalline cellulose (PG-NCC). First, the reactive azide groups were introduced on the surface of GO with azidation of 2-chloroethyl isocyanate-treated graphene oxide (GO-Cl). Then, the resulted compounds were reacted with PG-NCC utilizing copper-catalyzed azide-alkyne cycloaddition. During the click reaction, GO was simultaneously reduced to graphene. The coupling was confirmed by Fourier transform infrared, Raman, DEPT135, and ¹³C NMR spectroscopy, and the complete exfoliation of graphene in the NCC matrix was confirmed with X-ray diffraction measurement. The degree of functionalization from the gradual mass loss of RGO-NCC suggests that around 23 mass % has been functionalized covalently. The size of both NCC and GO was found to be in nanometric range, which decreased after click reaction.     

Functionalization of thermally reduced graphene by in situ atom transfer radical polymerization

In this report, functionalization of functionalized graphene sheets (FGS) was carried out by atom transfer radical polymerization (ATRP). Poly(methyl methacrylate) (PMMA) or polystyrene (PS) was successfully grafted from FGS. Thermogravimetric analysis (TGA) was used to estimate the content of linked organic compound. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) were used to observe the morphologies of the hybrid materials obtained. This approach was proved to be an effective way for functionalizing the graphene and tailoring the polymer structures.     

Depletion effect on partial organization of atactic polymer chain segments in microcells

Glass transition for atactic poly(methyl methacrylate) (a-PMMA) prepared in nano-cells by microemulsion polymerization was measured at a faster heating rate after slow cooling of the sample from a temperature above T_g. An additional enthalpy relaxation and glass transition were observed at higher temperatures for the a-PMMA sample due to the partial organization of the chain segments which occurred during microemulsion polymerization. The re-precipitated a-PMMA did not show any self-organization under the same thermal conditions, although there are no changes in molecular weight or tacticity of the polymer chains. A depletion-interaction phenomenon was understood to provide entropic force for the self-organization of polymer chains inside the walls of the microemulsion cells.     

Surface glass transition in bimodal polystyrene mixtures

Using the cluster-embedding method of V. Zaporojchenko et al. (Macromolecules 34, 1125 (2000)), we measured the glass transition temperature T _g at the polystyrene/vacuum interface of bimodal mixtures of monodisperse polystyrenes of 3.5k and 1000k. Embedding of ≈ 1 nm Au clusters was monitored in situ by X-ray photoelectron spectroscopy (XPS). The clusters were formed by evaporation of Au onto the polymer surface. Only one glass transition was observed in the mixtures. The surface glass transition temperatures are correlated to but are below the bulk values of the mixtures and obey the Gordon-Taylor equation. The results suggest that the earlier reported molecular-weight dependence of the surface glass transition is not due to segregation of short chains to the surface.     

Surface states and adsorption energy of carbon in the interface of the two-dimensional graphene/Al2O3(0001) system

This paper reports on the results of density functional theory investigations of the band structure of the graphene/Al₂O₃(0001) interface as a possible element base of graphene field-effect transistors. The regularities of the changes in the band structure in the series graphene → 2D-Al₂O₃(0001) → 2D-graphene/Al₂O₃(0001) have been analyzed. The specific features of the energy distribution of the surface states in the 2D-graphene/Al₂O₃(0001) interface have been discussed. The nature of the bonding between graphene and sapphire has been investigated using the density functional theory calculations.     

Polymer Surface Functionalization Using Plasma,Ultraviolet and Synchrotron Radiation

Polyurethane (PU) and polystyrene (PS) films were functionalized by ultraviolet (UV) or selective synchrotron radiations (SR) in the presence of reactive gases. The UV-PU results were compared with lowpressure plasma treatments of the same films. Oxygen or acrylic acid vapours (AA) were used as reactive gases. X-ray photoelectron spectroscopy measurements of UV modified films in the presence of oxygen or AA matched the RF-plasma treatments results. It is shown that COO and C=O functional groups were incorporated at the polymer surface efficiently with both methodologies. In addition, near-edge X-ray absorption fine structure showed that a thin film of poly(acrylic acid) is formed over the PU and PS films during the UV irradiation in the presence of AA vapours. These results resemble previous AA low-power plasma treatments. PU and PS films were also selectively functionalized by SR using oxygen as reactive gas. Surface concentrations of COO and C=O functional groups were enhanced by C_1s → σ* _C–C excitation after irradiation and oxygen introduction. This efficient surface functionalization was clearly observed in PS films which do not have CO and COO groups in their molecular structure. Excitations involving transitions to π* orbital (π*_C=C, π*_C=O) led to much lower functionalization efficiency. The SR results can be explained by taking into account previous photon stimulated ion desorption studies of polymers. SR results may open new ways to functionalize polymer surfaces selectively and efficiently.     

Glass transition of the two distinct single-chain particles of poly(N-isopropylacrylamide)

Two distinct single-chain particles of poly(N-isopropylacrylamide) (PNIPAM) in the state of loose coil and compact globule, have been prepared successfully below and above the lower critical solution temperature (LCST) in extreme dilute aqueous solution by the freeze-drying method, respectively. During the preparation of the compact globular single-chain sample, the surfactant of sodium n-dodecyl sulfate (SDS) was added into the system to prevent aggregation of globular single chains formed at a temperature above the LCST. After all the coil has been transformed into the compact globular particle, the SDS molecules were removed by dialysis. The glass transition temperature (T_g) of the two single-chain samples has been measured by differential scanning calorimetery (DSC) in comparison with that of bulk polymer. It was found that the T_g of the single-chain sample in compact-globule state was very near to that of the bulk polymer, whereas the T_g of the single-chain sample in loose-coil state was approximately 6 K lower than that of the bulk polymer. After treating the sample with repeated DSC cycles, the T_g of the single-chain sample in loose-coil state rose up successively near to that of the bulk polymer. These results have been explained in terms of the effect of entanglement on the mobility of the polymer segments in the two distinct single-chain samples.