PEO Molecules Research Articles

Hydrogen Bonding-Induced Crystal Orientation Changes in Confined Microdomains Constructed by Block Copolymer Blends

This study examined crystal orientation confined within a lamellar microdomain morphology formed by the blends of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and polystyrene-block-poly(acrylic acid) (PS-b-PAA) through wide-angle X-ray diffraction. The hydrogen-bonding interaction between PEO and PAA molecules enabled block copolymers to co-organize into a microphase-separated morphology without inducing macrophase separation, but it hampered PEO crystallization. PEO crystallization that occurred at −20 °C resulted in the nucleation mechanism to be dominant, thus leading to the formation of small crystals. Small crystals allowed them to be free from spatial confinement, and they tended to be oriented with their c-axis parallel to the microdomain interface. By contrast, when PEO was crystallized at 40 °C, the high temperature facilitated PEO crystals to exhibit large crystallite sizes, which aligned perpendicularly to the microdomain interface. An increase in the PS-b-PAA concentration considerably reduced the crystallizability of PEO. The presence of a low amount of crystals and additional lateral confinement formed by hydrogen-bonded PEO/PAA reduced the degree of orientation regardless of the crystallization temperature.

Hydrogen bonding induced microphase and macrophase separations in binary block copolymer blends

This study investigated the macrophase and microphase transitions of blends comprising polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and polystyrene-block-poly(acrylic acid) (PS-b-PAA). PEO and PAA molecules formed hydrogen bonds that enabled the two block copolymers to organize into a single microphase-separated morphology composed of two PS block chains in a common PS microdomain and PEO and PAA block chains in a coexisting PEO/PAA microdomain. Increasing temperature weakened the hydrogen-bonding interaction through the formation of PAA monomers and anhydride, causing the blends to macrophase separate into PS-b-PEO-rich and PS-b-PAA-rich phases. Further increasing the temperature weakened the repulsive interactions between both the PS and PEO segments and the PS and PAA segments, inducing order-to-disorder transitions in the PS-b-PEO-rich and PS-b-PAA-rich phases. However, the increasing repulsive interaction between the PEO and PAA segments with increasing temperature prevented the blends from forming an isotropic phase. The unique phase transformation of each block copolymer in the blend with an upper critical ordering transition (UCOT)-type interaction parameter, which caused the formation of a lower-critical-solution-temperature-type phase diagram, was attributed to the hydrogen-bonding interaction between PEO and PAA, which outweighed the UCOT behaviors of PS-b-PEO and PS-b-PAA and reversed the phase behaviors of their blends.

Optical, electrical and chemical properties of PEO:I2 complex composite films

Synthesized PEO:I2 complex composite films with different I2 concentrations were deposited onto fused silica substrates using a dip-coating method. Incorporation of PEO films with I2 increases the electrical conductivity of the composite, reaching a maximum of 46 mS/cm for 7 wt% I2. The optical and optoelectronic properties of the complex composite films were studied using the transmittance and reflectance spectra in the UV-Vis region. The transmittance of PEO decreases with increasing I2 content. From this study, the optical bandgap energy decreases from 4.42 to 3.28 eV as I2 content increases from 0 to 7 wt%. In addition, the refractive index for PEO films are in the range of 1.66 and 2.00.1H NMR spectra of pure PEO film shows two major peaks at 3.224 ppm and 1.038 ppm, with different widths assigned to the mobile polymer chains in the amorphous phase, whereas the broad component is assigned to the more rigid molecules in the crystalline phase, respectively. By adding I2 to the PEO, both peaks (amorphous and crystal) are shifted to lower NMR frequencies indicating that I2 is acting as a Lewis acid, and PEO is acting as Lewis base. Hence, molecular iodine reacts favorably with PEO molecules through a charge transfer mechanism, and the formation of triiodide ({mathrm{I}}_{3}^{-}), the iodite ({mathrm{IO}}_{2}^{-}) anion, {mathrm{I}}_{2} cdot cdot cdot mathrm{ PEO} and {mathrm{I}}_{2}^{+} cdot cdot cdot mathrm{ PEO} complexes. PEO:I2 complex composite films are expected to be suitable for optical, electrical, and optoelectronic applications.

Interplay between Interparticle Potential and Adsorption Structure in Nanoparticle Dispersions with Polymer Addition as Displayed by Small-Angle Scattering.

The effect of polymer adsorption on the dispersion stability of particles is an important subject applicable to various manufacturing processes. In this study, small-angle scattering was used to examine the relationship between interparticle potential and polymer adsorption in dispersions of nanoparticles with an 81 Å radius containing two types of polymers. Small-angle X-ray scattering (SAXS) measurements in a silica/polyacrylamide (PAAm) system showed an increase in interparticle attractive interactions as PAAm concentration was increased. In a silica/poly(ethylene oxide) (PEO) system, the correlation between PEO concentration and interparticle potential strength became negligible at higher concentrations. Hence, the contrast variation small-angle neutron scattering (CV-SANS) method was employed to evaluate the interparticle potential and polymer adsorption simultaneously. CV-SANS revealed that PAAm was adsorbed to silica particles with a polymer shell layer thickness of 186 Å. The attractive potential observed in the absorbed layer region can be attributed to bridging PAAm molecules between the silica particles. By contrast, CV-SANS of the silica/PEO system indicated a low-polymer-concentration layer with a thickness of 34 Å around silica particles, indicating weak adsorption of PEO molecules. Negligible interaction between PEO and silica particles was assumed to be the origin of the depletion stabilization from excess polymer addition. Thus, quantitative analyses conducted using SAXS and CV-SANS measurements for the first time clearly demonstrated a difference in the adsorption structure of the polymer, which induces changes in the interaction potential between nanoparticles.

Flow-Induced Formation of Thin PEO Fibers in Water and Their Stability After the Strain Release

Recently, we have shown that a tensile stress applied to chains of poly(ethylene oxide) (PEO) in water reduces the solubility and leads to phase separation of PEO chains from water with the formation of a two-phase region. In this work, we further elucidate the generic mechanism behind strain-induced phase transitions in aqueous PEO solutions with concentrations of 50-60 wt % by performing all-atom molecular dynamics simulations. In particular, we study the stability of oriented PEO fibers after removing stretching forces. We found that the size of the PEO bundle increased with time, which is associated with the dissolution of PEO chains on the fiber surface due to the reformation of hydrogen bonds between the outer PEO molecules and water. For precise characterization of the fibers, the scattering patterns (small- and wide-angle X-ray spectra) for configurations taken at different relaxation times are calculated. The tendency of the oligomer chains to be peeled off from the surface of the bundle eventually might lead to a complete dissolution of the PEO fiber. We conclude that either entanglement constraints or a quick drying process are necessary to conserve the fiber structure in a quiescent state. The scattering results show that external strain induced a liquid-liquid phase separation first. On long time scales, this can be a precursor for crystallization of the fiber.

Highly accelerated crystallization kinetics of poly(ethylene oxide)/ionic liquid mixtures by phase separation: The coupling effect of hydrogen bonds breaking

The combination of polymers with ionic liquids (ILs) is of significant interest for a variety of possible applications e.g., polymer electrolytes, nanoencapsulations and actuators. Knowledge of phase separation, crystallization and their interplay in polymer/IL mixtures is of crucial importance for realizing these applications. In this work, the effect of phase separation on crystallization behavior for poly(ethylene oxide)/1-ethyl-3-methylimidazolium tetrofluoroborate (PEO/[EMIM][BF4]) mixtures with a lower critical solution temperature (LCST) was investigated for the first time. It is demonstrated that the crystallization of PEO/ILs mixtures could be highly accelerated by phase separation as the blended samples are quenched from two-phase region compared to those quenched from homogenous state. This phenomenon can be on one hand ascribed to the disruption of hydrogen bonds between PEO and IL molecules as evidenced by FTIR results, which causes an increase of chain mobility and diffusivity for developing a spherulite embryo, and on the other hand due to fluctuation concentration where local PEO-rich domains with higher crystallizable PEO concentration will exist, even though the interfacial area has disappeared upon quenching to the crystallization. The facilitating effect of phase separation on crystallization becomes more prominent as driven by spinodal decomposition (50 wt% PEO) than that driven by nucleation & growth (70 wt% PEO). This work will provide a new possibility to optimize the performance of polymer electrolytes by regulating the phase morphologies of polymer/IL blends.

Conformational and Dynamic Properties of Poly(ethylene oxide) in BMIM+BF4–: A Microsecond Computer Simulation Study Using ab Initio Force Fields

The behavior of polymers in complex solvents is interesting from a fundamental perspective and of practical importance from the standpoint of polymer processing. There has been recent interest in the conformational and dynamic properties of polymer in room temperature ionic liquids, with conflicting predictions from computations using models with different resolutions and conflicting results of experiments from different groups. In this work, we develop a first-principles, nonpolarizable united atom (UA) force field for a mixture of poly(ethylene oxide) (PEO) in the ionic liquid BMIM+BF4–. The UA force field is benchmarked against ab initio calculations, and the PEO atomic charges are parametrized to implicitly capture the polarization contribution to the solvation energy of a single PEO molecule in BMIM+BF4–. The UA model allows one to perform multi-microsecond molecular dynamics simulations. This is necessary because the conformational relaxation correlation times are of the order of 100 ns. The simulations predict that the radius of gyration, Rg, scales with molecular weight, Rg ∼ Mwν with ν ≈ 0.56 in the temperature range 300–600 K, consistent with experiment, seemingly in between a self-avoiding walk and an ideal chain. An examination of the snapshots of the polymer demonstrates, however, that the polymer conformations are composed of ringlike and linear segments, with ringlike parts of the chain wrapped around cations of the ionic liquid. The slow dynamics arises from the barrier to unwrapping the ringlike segments of the polymer. The mean-square displacement shows three regimes which we interpret as confinement, Zimm, and diffusive. The simulations emphasize the importance of accurate force fields and microsecond simulations in obtaining reliable results for polymers and elucidate important correlation effects for polymers in strongly interacting solvents.

Mesoscopic Diffusion of Poly(ethylene oxide) in Pure and Mixed Solvents.

We present results from an experimental dynamic light-scattering study of poly(ethylene oxide) (PEO) in both a pure solvent (water) and a mixed solvent (tert-butanol + water). The concentration dependence of the diffusive relaxation of the PEO molecules is found to be typical of polymers in a good solvent. However, the mesoscopic diffusive behavior of PEO in the mixed solvent is very different, indicating an initial collapse and subsequent reswelling of PEO caused by co-nonsolvency. Furthermore, in the solutions of PEO with very large molecular weights, we found additional hydrodynamic modes indicating the presence of PEO clusters and aggregates similar to those found by some other investigators.

Thermodynamics of aggregation of imidazolium-based surface active ionic liquids in aqueous poly(ethylene oxide) media

The aggregation behaviour of two imidazolium-based surface active ionic liquids (SAILs), e.g., 1-decyl-3-methylimidazolium chloride (C10MeImCl) and 1-hexadecyl- 3-methylimidazolium chloride (C16MeImCl) in aqueous solutions was investigated in presence of varying amount of poly(ethylene oxide) (PEO) to explore the possible SAIL-PEO interactions. Electrical conductivity measurements were performed in aqueous solutions of PEO having two different molar mass over a selected temperature range. The critical micellization concentrations of the investigated SAILs in PEO-water media were always found to be higher than those in pure water. PEO was found to play a dual role in the SAIL-PEO-water ternaries. It has been concluded that the PEO molecules added to water modify the property of the medium besides binding a very small fraction of the surfactant ions prior to the commencement of the micellization of SAILs. The thermodynamic parameters of micellization such as Gibbs free energy (ΔGm0), standard enthalpy (ΔHm0), and standard entropy (ΔSm0) of aggregation were estimated from the temperature dependence of the critical micellization concentration values. The effects of concentrations of PEO, and molar mass of PEO on the self-aggregation of the C10MeImCl and C16MeImCl have been discussed in terms of the phenomena prevailing in these solutions. The observed enthalpy-entropy compensation effect in these SAIL-PEO-water ternaries provided important information as to the behaviour of the PEO-water media with respect to the ions present in solution.

Size-Dependent Particle Dynamics in Entangled Polymer Nanocomposites.

Polymer-grafted nanoparticles with diameter d homogeneously dispersed in entangled polymer melts with varying random coil radius R0, but fixed entanglement mesh size a(e), are used to study particle motions in entangled polymers. We focus on materials in the transition region between the continuum regime (d > R0), where the classical Stokes-Einstein (S-E) equation is known to describe polymer drag on particles, and the noncontinuum regime (d < a(e)), in which several recent studies report faster diffusion of particles than expected from continuum S-E analysis, based on the bulk polymer viscosity. Specifically, we consider dynamics of particles with sizes d ≥ a(e) in entangled polymers with varying molecular weight M(w) in order to investigate how the transition from noncontinuum to continuum dynamics occur. We take advantage of favorable enthalpic interactions between SiO2 nanoparticles tethered with PEO molecules and entangled PMMA host polymers to create model nanoparticle-polymer composites, in which spherical nanoparticles are uniformly dispersed in entangled polymers. Investigation of the particle dynamics via X-ray photon correlation spectroscopy measurements reveals a transition from fast to slow particle motion as the PMMA molecular weight is increased beyond the entanglement threshold, with a much weaker M(w) dependence for M(w) > M(e) than expected from S-E analysis based on bulk viscosity of entangled PMMA melts. We rationalize these observations using a simple force balance analysis around particles and find that nanoparticle motion in entangled melts can be described using a variant of the S-E analysis in which motion of particles is assumed to only disturb subchain entangled host segments with sizes comparable to the particle diameter.

Poly(vinylalcohol)-borate hydrogels with improved features for the cleaning of cultural heritage surfaces

Poly(vinylacohol) (PVA) is a versatile polymer capable of forming hydrogels useful in a wide range of applications. Hydrogels based on cross-linking of PVA with borax, and able to incorporate organic solvents, have been used in the field of cultural heritage as tool for cleaning the surfaces. Poly(ethylenoxide) (PEO) has been introduced in the formulations of PVA-borax, with the aim of increasing the gel compatibility with organic solvents and of improving the mechanical properties of the materials. The formulations were investigated with rheological characterization, solvent loss measurements and study of the free water through the determination of the Free Water Index. The PEO molecules do not participate in the formation of the network but have been found to be responsible for a decrement of the storage moduli, explained by a spacing between crosslinks and the partial disentanglement of the PVA chains. At the same time PEO produces in the gel an increase of the apparent relaxation time, thus stabilizing the dispersions and enhancing their ability to maintain the shape. Cleaning tests for removal of an acrylic coating on limestone have been also successfully performed.

Tribo-surface charge and polar lubricant molecules on friction and lubrication under multiple 3D asperity contacts

Lubricant is usually a mixture of polar and non-polar molecules, and tribo-metal surfaces can be oxidised and have surface atoms with charges. A molecular dynamics simulation of bcc iron with additional charge as rough tribo-surface and polarisable PEO polymer as lubricant was proposed to investigate the tribo-surface charge and polar molecules on friction and lubrication during the compression and sliding. Tribo-surface roughness is crucial for asperity interaction because it affects real contact area, friction, wear and lubrication. Random Midpoint Displacement algorithm was introduced to generate 3D multiple asperities with irregular shape at upper and lower wall surfaces. The results show that compared to non-charged tribo-surfaces where the amount of lubricant and surface roughness determine the friction and lubrication, the charged tribo-surface attracts the polar PEO molecules to form a coated like layer; thereby resulting in a different tribology behaviour. The polar PEO polymers separate the positive charged sliding tribo-surfaces and reduce the direct asperity contact; hence significantly lowering the friction force.

In vitro toxicity and bioimaging studies of gold nanorods formulations coated with biofunctional thiol-PEG molecules and Pluronic block copolymers.

In this work, we investigated the cytotoxicity, colloidal stability and optical property of gold nanorods before and after functionalizing them with thiolated PEG and Pluronic triblock copolymer (PEO–PPO–PEO) molecules. The morphology of functionalized gold nanorods was characterized by UV–visible absorption spectroscopy, transmission electron microscopy, and dynamic light scattering. Solution phase synthesis of gold nanorods has remained the method of choice for obtaining varying shapes and aspect ratios of rod nanoparticles. This method typically involves the use of cetyltrimethylammonium bromide (CTAB) surfactants as directing agents to grow gold nanorods in the solution phase. The as-synthesized gold nanorods surfaces are terminated with CTAB molecules and this formulation gives rise to adverse toxicity in vitro and in vivo. To employ the gold nanorods for biological studies, it is important to eliminate or minimize the exposure of CTAB molecules from the gold nanorods surface to the local environment such as cells or tissues. Complete removal of CTAB molecules from the gold nanorods surface is unfeasible as this will render the gold nanorods structurally unstable, causing the aggregation of particles. Here, we investigate the individual use of thiolated PEG and PEO–PPO–PEO as capping agents to reduce the cytotoxicity of gold nanorods formulation, while maintaining the optical, colloidal, and structural properties of gold nanorods. We found that encapsulating gold nanorods with the thiolated PEG or PEO–PPO–PEO molecules guarantees the stability and biocompatibility of the nanoformulation. However, excessive use of these molecules during the passivation process leads to a reduction in the overall cell viability. We also demonstrate the use of the functionalized gold nanorods as scattering probes for dark-field imaging of cancer cells thereby demonstrating their biocompatibility. Our results offer a unique solution for the future development of safe scattering color probes for clinical applications such as the long term imaging of cells and tissues.

New insight into PEO modified inner surface of HNTs and its nano-confinement within nanotube

In this study, we demonstrate the use of poly (ethylene oxide) (PEO) for in-situ modification of the inner surface of halloysite nanotubes (HNTs) with water molecules as the hydrogen bond forming medium, as well as the nano-confinement of PEO molecular chains within the nanotube. Before testing, the Soxhlet experiment of PEO/HNTs powder is applied in order to remove the physical adsorption of PEO molecules onto the outmost surface of HNTs. The crystal temperature of PEO changes sharply from 36.9 °C of neat PEO to −25 °C of PEO in the PEO/HNTs powder and the decomposed temperature of PEO in the PEO/HNTs powder is about 13.1 °C higher than that of neat PEO, which is mainly owing to the nano-confinement effect of PEO within the HNTs with a diameter of about 10 nm. From thermo-gravimetric (TG) analysis, about 7.71 % by weight of PEO has been chemically bonded to HNTs. The hydrogen bonds among PEO, HNTs, and water molecules are evidenced by FTIR and XPS performances. Meanwhile, the binding energy of Al2p in the innermost surface of HNTs shifts from 74.7 eV in the neat HNTs to 74.5 eV in the PEO/HNTs powder, while that of Si2p on the outmost surface of HNTs keeps almost constant, indicating that the hydrogen bonds only exists inner the nanotube and PEO molecular chains have been trapped in nano-scale within HNTs, which is in accordance with the DSC and TG observation.

Effect of Linear Nonionic Polymer Additives on the Kinetic Stability of Dispersions of Poly(diallyldimethylammonium chloride)/Sodium Dodecylsulfate Nanoparticles

In this article, the impact of different neutral polymers on the kinetic stability of charge-stabilized poly(diallyldimethylammonium chloride) (PDADMAC)/sodium dodecylsulfate (SDS) colloidal dispersions is analyzed using dynamic light scattering, electrophoretic mobility, turbidity, and coagulation kinetics measurements. Poly(ethyleneoxide) (PEO), poly(vinylpyrrolidone) (PVP), and dextran of comparable molecular masses as well as a higher-molecular-weight dextran sample were tested as nonionic additives. The light scattering and mobility data indicate that the PEO and PVP molecules may adsorb on the surface of the PDADMAC/SDS nanoparticles formed in the presence of excess surfactant. The primary effect of these additives is manifested in enhanced coagulation of the PDADMAC/SDS nanoparticles due to bridging at lower polymer concentrations and depletion flocculation at higher polymer concentrations. These findings are in sharp contrast to the earlier published effect of the same nonionic polymers on the poly(ethyleneimine) (PEI)/SDS colloidal dispersions, which can be sterically stabilized at appropriate PEO or PVP concentrations. However, the adsorption of the investigated dextran samples is negligible on the PDADMAC/SDS nanoparticles. Therefore, dextran molecules may cause only depletion flocculation in the PDADMAC/SDS system in the vicinity of the critical overlap concentration.

Preparation and characterization of electrospun polycaprolactone/polyethylene oxide membranes

In this study, we prepared electrospun polycaprolactone/polyethylene oxide (PCL/PEO) membranes fabricated by electrospinning. We designed the membranes for the application of medical patch. In order to understand the drug-released behavior when the membranes were used in medical patch, ketoprofen was used as a model drug. The results show that ketoprofen-loaded electrospun membranes that comprised PCL/PEO released all ketoprofen in 30 min. The mebranes had potential application in medical patch. In additions, the viscosity of the PCL/PEO solution increased with the proportion of PEO. The low conductivities of the all PCL/PEO solutions were caused by the lack of electric charge on both PCL and PEO molecules. A higher PEO percentage was associated with high enthalpy of fusion of the electrospun PCL/PEO membrane. The crystallinity of PEO in the PCL/PEO composite decreased as the PEO content declined.

Enhanced sensitivity azimuthally controlled grating-coupled surface plasmon resonance applied to the calibration of thiol-poly(ethylene oxide) grafting

Azimuthally controlled grating-coupling surface plasmon resonance (φ≠0° GC-SPR) is known to exhibit refractive index sensitivity (SRI) up to one order of magnitude higher with respect to classic φ=0° GC-SPR. Here, grated gold surfaces (period of 500nm and amplitude of 40nm) were covered with different amounts of thiol-poly(ethylene oxide) (PEO, Mw 5kDa) through a 24h functionalization process using polymer solutions at increasing concentration (from 500nM to 2.5mM). The GC-SPR output signal generated by each PEO layer was measured in both null and rotated configuration. The number of PEO molecules adsorbed onto each surface (cm−2) and the corresponding molecular surface densities (σ [ng/cm2]) were calculated from the angle shifts collected after PEO film formation, by combining the model shown by Jung and the theory of PEO layer formation. In the end, we obtained a calibration curve that correlates the amount of PEO tethered onto the surface with the SPR measurement output signal, that will be useful for future reference. At the PEO surface saturation condition (PEO σ=592ng/cm2, obtained using PEO concentration ≥2mM), a SRI of 603°/RIU was reached (φ=45°), which is ≈10-fold higher than what obtained through the classic GC-SPR (φ=0°). This enhanced instrumental sensitivity allowed detecting tiny amounts of molecules adsorbed onto the surface (3.1ng vs 59.7ng of classic φ=0° GC-SPR), a property that is extremely valuable for the application of SPR sensing to quantitative determinations.

Dielectric properties and structural dynamics of melt compounded hot-pressed poly(ethylene oxide)–organophilic montmorillonite clay nanocomposite films

The dielectric properties of melt compounded hot-pressed nanocomposite films consisting of a poly(ethylene oxide) (PEO) and organophilic montmorillonite (OMMT) clay surface modified with trimethyl stearyl ammonium as filler with increasing amount up to 20 wt.% OMMT were investigated in a frequency range of 20 Hz–1 MHz at 30 °C. The predominance of OMMT exfoliated structures in PEO–OMMT nanocomposites were recognized by a decrease of the real part of complex dielectric function. OMMT concentration dependent dielectric and electric modulus relaxation times have revealed that the interactions compatibility between PEO molecules and dispersed OMMT nano-platelets in PEO matrix governs the PEO segmental dynamics. A.C. conductivity of these nanocomposites increases by two orders of magnitude in the experimental frequency range.

Effect of blend composition on crystallization behavior of polyoxymethylene/poly(ethylene oxide) crystalline/crystalline blends

The influence of blend composition on crystallization behavior of a typical crystalline/crystalline blend, polyoxymethylene (POM)/poly(ethylene oxide) (PEO), during slow non-isothermal crystallization was investigated by polarized light microscope (PLM) connected with a THMS600 hot-stage, scanning electron microscope (SEM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The experimental results indicated that with increasing PEO content in the blend, the crystallization temperature of POM of the blends reduced and the multiple crystalline morphologies or structures including two kinds of interfibrillar or interlamellar structures were produced. The melting point of each component decreased with raising the content of the other constituent due to the inclusion and entanglement between POM and PEO molecules. The shoulder melting peak of POM appeared in DSC heating traces of the PEO-rich blend because the stronger inclusion and entanglement induced the imperfect crystallization of POM.

Dielectric properties and structures of melt‐compounded poly(ethylene oxide)–montmorillonite nanocomposites

AbstractThe dielectric dispersion and relaxation process in melt‐compounded hot‐pressed poly(ethylene oxide) (PEO)–montmorillonite (MMT) clay nanocomposite films of 0–20 wt % MMT concentration were investigated over the frequency range 20 Hz to 1 MHz at ambient temperature. X‐ray diffraction study of the nanocomposites evidences that the PEO has been intercalated into the MMT interlayer galleries with a helical‐type multilayer structures, which results the formation of unique parallel plane PEO–MMT layered structures. The relaxation times corresponding to PEO chain segmental motion were determined from the loss peak frequencies of different dielectric formalisms and the same is used to explore the interactions compatibility between PEO molecules and the MMT nano platelets. It is revealed that the loading of only 1 wt % MMT in PEO matrix significantly increases the PEO chain segmental motion due to intercalation, which further varies anomalously with increase of MMT concentration. The real part of dielectric function at 1 MHz, relaxation time, and dc conductivity of these melt‐compounded nanocomposites were compared with the aqueous solution‐cast PEO–MMT films. Considering the comparative changes in the values of various dielectric parameters, the effect of synthesization route on the intercalated/exfoliated‐MMT structures and the PEO chain dynamics were discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011