PEO Nanocomposites Research Articles

Improving the optical, dielectric properties and antimicrobial activity of Chitosan–PEO by GO/MWCNTs: Nanocomposites for energy storage and food packaging applications

This work is an attempt to improve the multifunctionality of chitosan–polyethylene oxide (Ch.–PEO) blend for different industrial applications including energy storage and food packaging applications. Graphene oxide (GO)/blend and multi-walled carbon nanotubes (MWCNTs)/GO/blend films were prepared by the solution casting method. FTIR analysis indicated the existence of Ch. and PEO functional groups and the positive interaction between the added nanofillers and the blend chains. XRD data confirmed interfacial compatibility between PEO and Ch. and showed that the semicrystalline nature of the blend was decreased after the incorporation of the filler. SEM analysis displayed that the blend surface is homogenous and crack-free, and the MWCNTs/GO were well-dispersed and uniformly distributed on the surface. The blend showed transmittance in the visible and NIR regions in the range of 76–91%. Loading MWCNTs/GO reduced this range and significantly increased the extinction coefficient of the blend. The indirect/direct band gap decreased from 4.3/5.2 eV to 3.0/3.8 eV with increasing fillers content. Moreover, the optical constants of the blend and nanocomposite films were determined. The dielectric measurements revealed that MWCNTs/GO doping increases the defects and results in a larger number of dipoles inside the blend and hence increases the dielectric constant of the blend. In addition, tan (δ) for all films is very small (˂ 0.05) and MWCNTs/GO/blend exhibits conductivity four times greater compared with the pure blend. The conduction mechanism, dielectric modulus, and Cole-Cole plots in the temperature range of 30–110 °C and frequencies in the range of 10−2 Hz–10 MHz were reported. The thermal analyses (TGA and DSC) for the blend and nanocomposite films were performed in the temperature range of 25–550 °C. TGA and DTG revealed three distinct weight-loss events for the samples; 25–122 °C, 229–360 °C, and 365–440 °C. The doped samples were more thermally stable where the blend lost 20% of its weight at 180.9 °C, while after doping with GO and codoping with MWCNTs, this temperature increased to 190.5 and 210.2 °C, respectively. The blend and nanocomposite solutions showed a wide antimicrobial activity against gram-positive and gram-negative bacteria, yeast, and fungi. Specifically, both GO/Ch.–PEO and 0.004%MWCNTs/GO/Ch.–PEO represented the highest antimicrobial against all tested microbes. Staphylococcus aureus ATCC 8095 was founded to be the most sensitive among the examined microbes. Additionally, the least sensitivity to studied solutions was recorded by Penicillium roqueforti. The improvements in the optical and dielectric properties make the prepared nanocomposites suitable for energy storage devices, while the antimicrobial activity suggests the use of GO/Ch.–PEO and MWCNTs/GO/Ch.–PEO nanocomposites for food packaging applications.

Unique structure and new thermophysical properties of poly(ethylene oxide) in nanocomposites based on nanoporous polypropylene matrices

AbstractPolypropylene (PP)−poly(ethylene oxide) (PEO) nanocomposites were prepared by tensile drawing of PP films in water–ethanol solutions containing PEO with molecular masses of 4, 20, and 200 kDa via environmental crazing (EC). EC of PP films is accompanied by the development of nanoporous structure, which is loaded with the PEO component. The content of PEO in the PP − PEO nanocomposites can achieve 40%. Crystallization of PEO within the nanoporous PP matrix proceeds under the conditions of the confined space: as a result, the degree of crystallinity and melting temperature of PEO are markedly reduced. This effect appears to be more pronounced as the molecular mass of PEO increases. The direction of orientation of the PEO crystalline lamellae also depends on the molecular mass of PEO. The prepared PP‐PEO composites with new thermophysical properties of PEO can be used as gas‐separation membranes as well as in microelectronics and electrochemical devices.

Isothermal Crystallization Kinetics of Poly(ethylene oxide)/Poly(ethylene glycol)-g-silica Nanocomposites.

In this work, the crystallization kinetics of poly(ethylene oxide) (PEO) matrix included with poly(ethylene glycol) (PEG) grafted silica (PEG-g-SiO2) nanoparticles and bare SiO2 were systematically investigated by differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM) method. PEG-g-SiO2 can significantly increase the crystallinity and crystallization temperature of PEO matrix under the non-isothermal crystallization process. Pronounced effects of PEG-g-SiO2 on the crystalline morphology and crystallization rate of PEO were further characterized by employing spherulitic morphological observation and isothermal crystallization kinetics analysis. In contrast to the bare SiO2, PEG-g-SiO2 can be well dispersed in PEO matrix at low P/N (P: Molecular weight of matrix chains, N: Molecular weight of grafted chains), which is a key factor to enhance the primary nucleation rate. In particular, we found that the addition of PEG-g-SiO2 slows the spherulitic growth fronts compared to the neat PEO. It is speculated that the interfacial structure of the grafted PEG plays a key role in the formation of nuclei sites, thus ultimately determines the crystallization behavior of PEO PNCs and enhances the overall crystallization rate of the PEO nanocomposites.

Functional Group Analysis of CdS:PEO Nanocomposite Solid Films

Cadmium Sulphide nanoparticles were reinforced in PEO matrix and their functional group was analysed. FTIR-ATR spectroscopic studies were carried out for different concentrations of CdS: PEO nanocomposites. The results revealed the complexion of CdS with PEO in the matrix. The nature of bonding between CdS and PEO was analysed with the help of relative intensity ratio of prominent peaks from FTIR. Also the strongest C-O-C stretching ether group absorption of PEO with composites was analysed to ensure the bonding nature of PEO with CdS.

Studies on optical, structural and thermal properties of CdS:PEO nanocomposite solid films having different molar concentration

Cadmium Sulphide (CdS) nanoparticles were incorporated in PEO matrix. No capping agent was used other than the polymer to reduce the size of the CdS particles. The optical properties of the CdS:PEO nanocomposites were analysed and the transmittance of the solid films was found to be above 80%. The structural analysis of the nanocomposites was carried out using Transmission Electron microscope (TEM) and Atomic force microscope (AFM) and the particle size variation for different concentrations of CdS:PEO nanocomposites and the size distribution of CdS particles incorporated in the polymer matrix was analysed. The thermal properties of CdS:PEO nanocomposites were analysed using Differential scanning Calorimetry (DSC). The melting point shift of PEO matrix and the thermal stability of the matrix after incorporating CdS were found.

Effect of the GO Reduction Method on the Dielectric Properties, Electrical Conductivity and Crystalline Behavior of PEO/rGO Nanocomposites.

The effect of the reduction method to prepare reduced graphene oxide (rGO) on the melt linear viscoelastic properties, electrical conductivity, polymer matrix crystalline behavior and dielectric properties of PEO-rGO nanocomposites was investigated. Reduction was performed chemically with either sodium borohydride (NaBH4) or hydrazine monohydrate (N2H4·H2O) or both reduction agents consecutively as well as thermally at 1000 °C. The different reduction methods resulted in exfoliated rGO sheets with different types and amounts of remaining functional groups, as indicated by FT-IR, Raman, TGA and XRD characterization. Moreover, their electrical conductivity ranged between 10−4 and 10−1 S/cm, with the consecutive use of both chemical reduction agents being far superior. PEO nanocomposites with filler loadings of 0.5 wt %, 1 wt % and 2 wt % were prepared by solvent mixing. The rGO fillers affected the melt linear viscoelastic and crystalline behavior of the PEO matrix and resulted in nanocomposites with a substantially increased electrical conductivity. Despite the wide variability in filler conductivity, the effects on the polymer nanocomposite properties were less distinctive. A correlation was obtained between the reduction of the mobility of the polymer chains (evaluated by the glass transition temperature) and the dielectric strength of the interfacial polarisation originating from the effective entrapment of GO/rGO filler charges at the interface with the less conductive PEO. Thus, favorable interactions of the polar PEO with the filler led to reduced mobility of the PEO chains and thereby a more effective entrapment of the filler charges at the PEO interface.

Enhancing sodium-ion battery performance with interlayer-expanded MoS2–PEO nanocomposites

The larger ionic radius of Na ion (1.06Å) compared with that of Li ion (0.76Å) is a fundamental reason for the inferior diffusion kinetics of Na ion in intercalation hosts. Here we report interlayer expansion of intercalation hosts as a general strategy to facilitate the solid-state diffusion of Na ions. Based on this strategy, poly(ethylene oxide)–intercalated MoS2 composites (PEO–MoS2) were synthesized via a facile exfoliation-restacking method and tested as anode materials for Na-ion batteries (NIBs). The interlayer spacing of MoS2 was increased from 0.615nm to 1.45nm by insertion of controlled amounts of PEO. The bilayer PEO–intercalated MoS2 composite (PEO2L–MoS2) exhibits a specific capacity of 225mAhg−1 under a current density of 50mAg−1, twice as high as that of commercial MoS2 (com-MoS2), and shows improved rate performance due to enhanced Na-ion diffusivity. The improvement in the electrochemical performance demonstrates that interlayer expansion is an effective strategy for the development of high performance electrode materials for battery technologies based on the storage of large ions.

Surface modification of sepiolite nanofibers with PEG based compounds to prepare polymer electrolytes

The controlled surface modification of the fibrous clay mineral, sepiolite (Sep), with poly(ethylene glycol) (PEG) and Vitamin E tocopherol polyethylene glycol succinate (TPGS) is presented in this work. Sep, which has a rich surface reactivity because of the presence of silanol groups on its surface, is employed as nanofiller in clay polymer nanocomposites (CPN). It organizes itself into bundles of nanofibers which are difficult to separate from one another unless aqueous gels are prepared under very specific conditions. In the form of an aqueous gel, however, separation of the nanofibers and chemical modification of their surface can be easily done. Sets of very different organosepiolites (OSep) can be obtained in this way. In this work the resulting OSep are characterized in terms of mass incorporation and yields of reaction, specific surface, surface texture, surface water content and thermal stability. As the final purpose of these OSep is the mechanical reinforcement of poly(ethylene oxide) (PEO) based electrolytes highly loaded with ethylene carbonate (EC), blends with PEG or PEO and lithium triflate, with or without EC are prepared and the properties of the final materials are found to be strongly dependent on the type of OSep employed. In particular, examples on the fillers dispersion in the PEO nanocomposites and on their stability in dispersion of PEG/EC blends are described.

Prediction of thermal stability, crystallinity and thermomechanical properties of poly(ethylene oxide)/clay nanocomposites with artificial neural networks

The artificial neural network (ANN) technique with a feed-forward back propagation algorithm was used to examine the effect of clay composition and temperature on thermal stability, crystallinity and thermomechanical properties of poly(ethylene oxide)/clay nanocomposites. Based on dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) experiments, values of decomposition temperature, char yield, enthalpy of melting, storage modulus (E′) and tanδ were successfully calculated by well-trained ANNs. The simulated data is in very good agreement with the experimental data. ANN results confirm that thermal stability of PEO nanocomposites increases with the decrease of enthalpy of melting and relative crystallinity, and there is a directly proportional relationship between the modulus (stiffness) and thermal stability. The ANN technique is confirmed to be a useful mathematical tool in the thermal analysis of polymer/clay nanocomposites.

Morphology and chemical properties of silver-triblock copolymer nanocomposite thin films

The triblock copolymer PEO–PPO–PEO is thermoresponsive and have demonstrated excellent properties to act as a reducing as well as capping agent for synthesis of metal nanoparticles. Effect of reaction temperature in growth, morphology and chemical properties of self-assembled structures of silver PEO–PPO–PEO nanocomposites on silicon substrates is described here. The polymer–metal composites are deposited on hydrophilic and hydrophobic silicon substrates through adsorption from solution at different temperatures. Morphologies of the nanocomposite films observed by SEM are strongly dependent on reaction temperature as well as on philicity/phobicity of silicon substrates. Detailed investigations of the chemical properties of nanocomposite materials are performed using XPS and NEXAFS. At lower reaction temperatures, mainly thermoresponsive behavior of the copolymer controls nanocomposite formation and their organization on the substrates. Whereas at higher reaction temperatures, chemical nature of the copolymer that directly take part in the reaction is changed drastically and alters the nanocomposite formation process as well as the nature of self-assembly. The resemblance in spectroscopic data of this modified/degraded copolymer with that of fatty acid molecules indicate formation of fatty acid-like molecules at higher temperature.

Physically Crosslinked Nanocomposites from Silicate‐Crosslinked PEO: Mechanical Properties and Osteogenic Differentiation of Human Mesenchymal Stem Cells

The mechanical and biological properties of silicate-crosslinked PEO nanocomposites are studied. A strong correlation is observed between silicate concentration and mechanical properties. In vitro cell culture studies reveal that an increase in silicate concentration enhances the attachment and proliferation of human mesenchymal stem cells significantly. An upregulation in the expression of osteocalcin on nanocomposites compared to the tissue culture polystyrene control is observed. Together, these results suggest that silicate-based nanocomposites are bioactive and have the potential to be used in a range of biotechnological and biomedical applications such as injectable matrices, biomedical coatings, drug delivery, and regenerative medicine.

Assessment of using Laponite® cross-linked poly(ethylene oxide) for controlled cell adhesion and mineralization

The in vitro cytocompatibility of silicate (Laponite® clay) cross-linked poly(ethylene oxide) (PEO) nanocomposite films using MC3T3-E1 mouse preosteoblast cells was investigated while cell adhesion, spreading, proliferation and mineralization were assessed as a function of film composition. By combining the advantageous characteristics of PEO polymer (hydrophilic, prevents protein and cell adhesion) with those of a synthetic and layered silicate (charged, degradable and potentially bioactive) some of the physical and chemical properties of the resulting polymer nanocomposites could be controlled. Hydration, dissolution and mechanical properties were examined and related to cell adhesion. Overall, this feasibility study demonstrates the ability of using model Laponite cross-linked PEO nanocomposites to create bioactive scaffolds.

Residual Stress and Rheological Behavior of Polymeric Nanocomposites

AbstractRheological and mechanical characterizations were carried out for carbon nanotubes/poly(ethylene oxide) (PEO) nanocomposites to examine the effect of surface modification of carbon nanotubes on the CNT dispersion state. Residual stress in the gap-wise direction of the nanocomposites was measured using the layer removal method. It was found that the different chemical treatments for CNT surface make a big difference in the dispersion state of the CNTs and that the nanocomposites filled with better dispersed CNTs possess higher storage and elastic moduli. From the rheological observations, rheological percolation structure was found to exist in the nanocomposites, which was confirmed by morphological experiments. The residual stress data showed that stronger residual stress is developed in the PEO nanocomposites by non-isothermal cooling than in pure PEO.

Bioengineering Bacterial Cellulose/Poly(ethylene oxide) Nanocomposites

By adding poly(ethylene oxide) (PEO) to the growth medium of Acetobacter xylinum, finely dispersed bacterial cellulose (BC)/PEO nanocomposites were produced in a wide range of compositions and morphologies. As the BC/PEO w/w ratio increased from 15:85 to 59:41, the cellulose nanofibers aggregated in larger bundles, indicating that PEO mixed with the cellulose on the nanometer scale [corrected]. Fourier transform infrared spectroscopy suggested intermolecular hydrogen bonding and also preferred crystallization into cellulose Ibeta in the BC/PEO nanocomposites. The fine dispersion of cellulose nanofibers hindered the crystallization of PEO, lowering its melting point and crystallinity in the nanocomposites although remaining bacterial cell debris also contributed to the melting point depression. The decomposition temperature of PEO also increased by approximately 15 degrees C, and the tensile storage modulus of PEO improved significantly especially above 50 degrees C in the nanocomposites. It is argued that this integrated manufacturing approach to fiber-reinforced thermoplastic nanocomposites affords a good flexibility for tailoring morphology and properties. These results further pose the question of the necessity to remove bacterial cells to achieve desirable materials properties in biologically derived products.

Multiscale fiber‐reinforced composites prepared by vacuum‐assisted resin transfer molding

AbstractCarbon nanotube (CNT)/aramid fiber epoxy composites were produced using a new manufacturing method proposed in this study. The rheological and morphological experiments of the CNT/PEO nanocomposites indicates that the PEO nanocomposites have a good dispersion state of the CNTs. The flexural mechanical properties of the aramid fiber/CNT epoxy composites were measured. The CNTs dispersed in the epoxy resin between the aramid fibers were observed using field emission scanning electron miscroscope (FESEM). It was found that the flexural properties of the multiscale fiber‐reinforced composites were higher than those of aramid fiber/epoxy composites. POLYM. COMPOS., 28:458–461, 2007. © 2007 Society of Plastics Engineers.

Structure and dynamics in PEO nanocomposites

In this work, the effect of confinement on the local, the segmental and the ionic processes of poly(ethylene oxide)/montmorillonite (PEO/MMT) intercalates is investigated. X-ray diffraction and DSC data show that the intercalated PEO chains remain amorphous and it is only the excess PEO chains outside the galleries that crystallize. This is also evident in the behavior of the elastic intensity of quasi-elastic neutron scattering (QENS) experiments on the same hybrids. Dielectric relaxation spectroscopy reveals that confinement results in an acceleration of the PEO segmental dynamics that display an Arrhenius temperature dependence with low activation energy, whereas the local beta-process remains unaffected.

Molecular relaxation in cross-linked poly(ethylene glycol) and poly(propylene glycol) diacrylate networks by dielectric spectroscopy

The molecular relaxation characteristics of rubbery amorphous crosslinked networks based on poly(ethylene glycol) diacrylate [PEGDA] and poly(propylene glycol) diacrylate [PPGDA] have been investigated using broadband dielectric spectroscopy. Dielectric spectra measured across the sub-glass transition region indicate the emergence of an intermediate “fast” relaxation in the highly crosslinked networks that appears to correspond to a subset of segmental motions that are more local and less cooperative as compared to those associated with the glass transition. This process, which is similar to a distinct sub- T g relaxation detected in poly(ethylene oxide) [PEO], may be a general feature in systems with a sufficient level of chemical or physical constraint, as it is observed in the crosslinked networks, crystalline PEO, and PEO-based nanocomposites.

Montmorillonite−Poly(ethylene oxide) Nanocomposites: Interlayer Alkali Metal Behavior

Clay-PEO nanocomposites can have large electrical conductivities that make them potential electrolyte materials for rechargeable lithium batteries, but the origin of these large conductivities, especially for Li-containing materials, is poorly understood. This paper presents X-ray diffraction (XRD), TGA-DTA, and (7)Li and (23)Na NMR data for PEO nanocomposites made with natural (SWy-1) and synthetic (MNTS) montmorillonite clays that provide new insight into interlayer structure. An increase in basal d(001)-spacings demonstrates successful intercalation of PEO in all samples, and X-ray line narrowing shows that this intercalation improves the layer stacking order. The basal spacings of 17.9-19.4 A are consistent with a helical or bilayer structure of PEO in the interlayer. TGA-DTA provides quantitative results for the hydration state of the nanocomposites, demonstrates PEO intercalation, and shows that the composites prepared from the synthetic montmorillonite are less stable than those made with SWy-1. (7)Li NMR shows that the nearest neighbor hydration state of Li(+) is unaffected by PEO intercalation and suggests weak interaction of Li(+) with PEO. (23)Na NMR shows that PEO intercalation results in the conversion of the multiple Na(+) hydration states observed for the pristine clay into inner sphere sites most likely formed through coordination with the basal oxygens of the clay. These differences between lithium and sodium suggested that tighter binding of the Na to the clay may be the origin of the conductivity of Li-montmorillonite-PEO nanocomposites being as much as 2 orders of magnitude larger than those of Na-montmorillonite-PEO nanocomposites. The results confirm the idea that polymer oxygen atoms do not participate in sequestering the exchangeable cations and agree with the jump process for cation migration advanced by Kuppa and Manias (Kuppa, V.; Manias, E. Chem. Mater. 2002, 14, 2171).

Effect of clay modifier and matrix molar mass on the structure and properties of poly(ethylene oxide)/Cloisite nanocomposites via melt-compounding

The present study is concerned with the preparation and characterisation of PEO/clay nanocomposites via melt-extrusion. Two different matrix molar masses of PEO were investigated as well as various types of the Cloisite clay range. PEO/Cloisite Na+ nanocomposites give rise to intercalated structures displaying only a moderate improvement of the mechanical properties at higher clay concentrations, regardless of the matrix molar mass. The chemical nature of the organic modifier was proven to be detrimental for the final nanocomposite structure and resulting mechanical properties. PEO nanocomposites based on the Cloisite 30B clay, incorporating a polar modifier, give rise to exfoliated structures. They display a strongly increased storage modulus, regardless of the matrix molar mass. The structural organisation of the nanocomposites based on Cloisite 20A, containing an apolar modifier, is very dependent on the matrix molar mass. An exfoliated structure can only be achieved upon melt mixing with a high molar mass PEO. In general, the mechanical properties of the nanocomposites based on the high molar mass PEO matrix are slightly superior. The thermal properties are also distinctly influenced by the addition of clay, although the actual structural organisation of the nanocomposite is proven to be less important. The melt temperature, as well as the crystallinity, decreases upon the addition of clay, especially for the low molar mass PEO matrix. The decomposition temperature shows a slight increase upon the addition of clay, especially for the Cloisite 30B nanocomposites.