Broadband Dielectric Measurements Research Articles

A method for extracting the 1-60 GHz dielectric spectrum of trace liquids using standard design coplanar waveguide sensing devices

Abstract This paper introduces a sensor designed for measuring the dielectric constant of small amounts of liquid. The sensor consists of a coplanar waveguide transmission line and an open container for the liquid, enabling broadband dielectric spectroscopy measurements for milliliter-scale liquids in the 1-60 GHz range. To improve the accuracy of dielectric spectroscopy testing, the sensor is calibrated using air and deionized water to obtain a coefficient matrix relating the sensor’s distributed parameters to the sample’s dielectric constant. This matrix is then used to calculate the dielectric spectroscopy of subsequent test samples. Tests on the dielectric spectroscopy of deionized water with this sensor and algorithm indicate that over the 1-60 GHz band, the error compared to previous literature results is within 5%, demonstrating the reliability of the proposed sensor and dielectric spectroscopy extraction algorithm.

Dynamics of polylactic acid under ultrafine nanoconfinement: The collective interface effect and the spatial gradient.

Polymers under nanoconfinement can exhibit large alterations in dynamics from their bulk values due to an interface effect. However, understanding the interface effect remains a challenge, especially in the ultrafine nanoconfinement region. In this work, we prepare new geometries with ultrafine nanoconfinement ∼10nm through controlled distributions of the crystalline phases and the amorphous phases of a model semi-crystalline polymer, i.e., the polylactic acid. The broadband dielectric spectroscopy measurements show that ultrafine nanoconfinement leads to a large elevation in the glass transition temperature and a strong increment in the polymer fragility index. Moreover, new relaxation time profile analyses demonstrate a spatial gradient that can be well described by either a single-exponential decay or a double-exponential decay functional form near the middle of the film with a collective interface effect. However, the dynamics at the 1-2nm vicinity of the interface exhibit a power-law decay that is different from the single-exponential decay or double-exponential decay functional forms as predicted by theories. Thus, these results call for further investigations of the interface effect on polymer dynamics, especially for interfaces with perturbed chain packing.

Structural characterization of LLDPE/MgO insulation composites in terms of space charge accumulation in an HVDC field

This study addresses the critical role of insulation materials in high-voltage direct current (HVDC) transmission systems, emphasizing the challenges associated with space charge accumulation and slow polarization effects. The primary objective of this study is to investigate the utilization of linear low-density polyethylene (LLDPE) in High Voltage Direct Current (HVDC) applications, with a focus on enhancing its performance through the incorporation of magnesium oxide (MgO) nanoparticles. The research employs various techniques, including X-ray diffraction, nuclear magnetic resonance, broadband dielectric spectroscopy, conductivity measurements and pulse electroacoustic measurements, to analyse the internal structure, crystallinity, and space charge dynamics of LLDPE/MgO nanocomposites. The results demonstrate that controlled MgO incorporation optimizes the internal electric field, improving the electrical properties without significantly altering the charge decay rate. The multidimensional approach of the study provides valuable insights into tailored modification of insulation materials for enhanced HVDC transmission performance, considering both electrical and structural aspects.

Effect of Hot Pressing on the Optical, Thermal, and Dielectric Properties of Solution Cast Prepared Nanocomposite Films Based on a Poly(Vinylidene Fluoride-co-Hexafluoropropylene) and Poly(Ethylene Oxide) Blend Matrix with Dispersed Zinc Oxide Nanoparticles

In our research described herein, the hot pressing treatment at 90 °C under 2 tons of pressure on solution cast polymer nanocomposite (PNC) films based on a host matrix of poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) and poly(ethylene oxide) (PEO) with varying polymer blend compositions (20, 50, and 80 wt% P(VDF-HFP) or PEO) and 2 wt% zinc oxide (ZnO) nanofiller, was performed; the effects of this treatment and the composition variations on the optical, thermal, and dielectric properties was explored. The ultraviolet-visible wavelength range study revealed slightly reduced absorbance and a little increased energy band gap after the hot pressing of the nanocomposite films. Differential scanning calorimetry of the solution cast-hot pressed (SC-HP) PNC films explained the reduced thermal stability of the poly(ethylene oxide) crystallites and also the degree of crystallinity. The broadband dielectric measurements of these materials, at 27 °C, confirmed significant changes in various dielectric polarization processes, demonstrating a large redistribution of constituent interfaces by the hot press treatment. Additionally, the 90 °C hot pressed PNC film of equal polymer compositional ratio was further hot pressed at 130 °C and 160 °C, step by step, and characterized to examine the variations in dielectric properties. The properties of these thermally treated composite films are discussed concerning their use for flexible device applications.

Dynamics of poly(methyl acrylate)/poly(methyl methacrylate)-grafted-Fe3O4 nanocomposites.

We investigated the dynamics of nanocomposites prepared through mixing poly(methyl methacrylate) grafted Fe3O4 nanoparticles (PMMA-g-Fe3O4) with poly(methyl acrylate) (PMA). A key feature here different from previous dynamics measurements of polymer nanocomposites is the different chemistry between the matrix polymer and the polymer grafts, which introduces chemical heterogeneity. Transmission electron microscopy shows clear evidence of nanoparticle clustering due to the poor miscibility between the bulk PMA and the bulk PMMA. At the same time, broadband dielectric spectroscopy measurements detect two leading relaxations, i.e. the α and α* processes, where the α process is associated with the bulk PMA and the α* process from the PMA interacting with the grafted PMMA in the nanoparticle clustering region. Interestingly, the characteristic time of α*, τα*, is slightly slower than that of the α, τα, at high temperatures, and exhibits near Arrhenius temperature dependence at low temperatures. As a result, τα* and τα cross each other in the activation plot upon cooling and τα* ≪ τα is observed at temperatures approaching the glass transition temperature of PMA. These observations suggest the presence of component dynamics and the dynamics confinement effect between PMA and PMMA in the nanoparticle clustering region, highlighting an active interaction between PMA and PMMA at the interface despite their poor miscibility. These results thus suggest new routes to control interface dynamics through immiscible polymer pairs.

Close-packing effect of water clusters within metal-organic framework pores on proton conductivity: a dielectric relaxation phenomenon in loose space and colossal dielectric permittivity.

Proton-conducting metal-organic frameworks (MOFs) have attracted tremendous attention for their promising application in proton-exchange membrane fuel cells. Water clusters play an extremely important role in the proton-conduction process and affect the proton conductivity of host materials. To date, the close-packing effect of water clusters within pores on proton conductivity due to the amorphous structure of commercial proton-exchange membranes is unclear. Herein, we prepared two crystalline MOFs containing different water clusters, namely, [Sm2(fum)3(H2O)4]·3H2O (Sm-fum-7H2O) and [Er2(fum)3(H2O)4]·8H2O (Er-fum-12H2O) (H2fum = fumaric acid), and regulated their proton conductivities by changing the water clusters. As expected, Sm-fum-7H2O showed a high proton conductivity of 6.89 × 10-4 S cm-1 at 333 K and ∼97% RH because of the close packing of the water clusters within the pores triggered by a lanthanide contraction effect, outperforming that of Er-fum-12H2O and some previously reported MOFs. Additionally, Sm-fum-7H2O and Er-fum-12H2O demonstrated high dielectric functions, reaching 2.22 × 103 and 1.42 × 105 at 102.5 Hz, respectively, making Er-fum-12H2O a highly dielectric material. More importantly, broadband dielectric spectroscopy measurements indicated that there was a dielectric relaxation process in Er-fum-12H2O with an activation energy of 0.59 eV. The present findings provide a better understanding of the crucial role of confined water clusters in proton conductivity and the novel phenomenon of the coexistence of proton conduction and dielectric relaxation in crystalline MOF materials.

Effect of Ion Mass on Dynamic Correlations in Ionic Liquids.

Ionic liquids (ILs) are a class of liquid salts with distinct properties such as high ionic conductivity, low volatility, and a broad electrochemical window, making them appealing for use in energy storage applications. The ion-ion correlations are some of the key factors that play a critical role in the ionic conductivity of ILs. In this work, we present the study of the impact of ion mass on ion-ion correlations in ILs, applying a combination of broadband dielectric spectroscopy measurements and molecular dynamics simulations. We examined three ILs with the same cation but different anions to consider three different cases of cation-anion masses: M+ > M-, M+ ≈ M-, and M+ < M-. We applied the momentum conservation approach to estimate the contribution of distinct ion-ion correlations from experimental data and obtained good agreement with direct calculations of distinct ion-ion correlations from molecular dynamics simulations. Our findings reveal that relative ion mass has a strong effect on the distinct ion-ion correlations, leading to swapping of the relative amplitude of distinct cation-cation and anion-anion correlations.

Magnetic and Electrical Characteristics of Nd3+ and Mn2+-Co-doped Calcium Molybdato-Tungstates Single Crystals.

Single crystals of Ca1-3x-yMny□xNd2x(MoO4)1-3x(WO4)3x molybdato-tungstates (□ denotes vacant sites) with a scheelite-type structure have been successfully grown by the Czochralski technique in an inert atmosphere. This paper presents the results of structural, optical, magnetic, and electrical properties, as well as the broadband dielectric spectroscopy measurements of single crystals with different Nd3+ ion concentrations, i.e., when x = 0.0050 or x = 0.0098, and with constant content of Mn2+ ions, i.e., when y = 0.0050. Our magnetic studies have shown that substitution of diamagnetic Ca2+ ions in the CaMoO4 matrix with paramagnetic Nd3+ ones with a content not exceeding 0.02 and having a screened 4f-shell revealed a significant effect of orbital diamagnetism and Van Vleck's paramagnetism. Both single crystals have revealed residual electrical conductivity without an intrinsic region and a change of sign of the Seebeck coefficient at ca. 230 K. Dielectric spectroscopy measurements have shown constant values of relative permittivity (εr ∼ 8) and loss tangent (tan δ ∼ 0.01) both up to 400 K and up to 1 MHz, as well as the Fermi energy (∼0.04 eV) and the Fermi temperature (∼500 K) determined for both crystals from the diffusion component of thermopower. These results suggest the presence of shallow acceptor and donor levels in the studied crystals.

Testing the Performance of the Azo-Polyimide Supramolecular Systems as Substrate for Sensors Based on Platinum Electrodes.

Azo-polyimide films with supramolecular structure were obtained by casting onto glass plates a mixture based on polyamidic acid and different quantities of azochromophore, followed by thermal treatment to realize the final azo-polyimide structure. The dielectric characteristics of the supramolecular structure of polymer films were investigated by broad-band dielectric spectroscopy measurements at different temperatures and frequencies. The free-standing films proved to be flexible and tough and maintained their integrity after repeated bending. The work of adhesion at the polymer/platinum interface was calculated after the evaluation of the surface energy parameters before and after plasma treatment. Atomic force microscopy was used to image the surface morphology, the evolution of the roughness parameters, and the adhesion force between the platinum-covered tip and the polymer surface, registered at the nanoscale with the quantity of the azo dye introduced in the system. The simulation of the columnar growth of a platinum layer was made to provide information about the deposition parameters that should be used for optimal results in the deposition of platinum electrodes for sensors.

Computationally driven design of low dielectric-loss epoxy resin for medium-frequency transformers

The design of low dielectric-loss epoxy resin (EP) systems plays an important role in the insulation optimization of medium-frequency transformers (MFTs). Due to the diversity of EP and curing agents, the traditional design method inspired by dielectric-loss measurements cannot complete low dielectric-loss EP systems design in plentiful candidate EP systems. In this study, molecular dynamics (MD) computation was introduced to drive the design of a low dielectric-loss EP system for MFTs. By analyzing the relationship between the dielectric loss and molecular motion of the EP systems, two MD results were selected as descriptors to indicate the dielectric loss of EP systems, including mean square displacement and α-transition temperature. Eventually, the low dielectric-loss EP system blending EP, methyl tetrahydrophthalic anhydride, and dodecenyl succinic anhydride was effectively designed according to the descriptors. The rationality of the computationally driven design was verified by broadband dielectric spectroscopy measurement and the finite element method. Compared with previous EP systems, MFT insulated with the designed EP system had not only a 40% lower dielectric loss (9.79 W) but a higher overload capacity. This study provides an effective method for the design of low dielectric-loss EP systems.

Magnetic and Electrical Characteristics of Nd3+-Doped Lead Molybdato-Tungstate Single Crystals.

Single crystals of Pb1-3x▯xNd2x(MoO4)1-3x(WO4)3x (PNMWO) with scheelite-type structure, where ▯ denotes cationic vacancies, have been successfully grown by the Czochralski method in air and under 1 MPa. This paper presents the results of structural, optical, magnetic and electrical, as well as the broadband dielectric spectroscopy measurements of PNMWO single crystals. Research has shown that replacing diamagnetic Pb2+ ions with paramagnetic Nd3+ ones, with a content not exceeding 0.01 and possessing a screened 4f-shell, revealed a significant effect of orbital diamagnetism and Van Vleck's paramagnetism, n-type electrical conductivity with an activation energy of 0.7 eV in the intrinsic area, a strong increase of the power factor above room temperature for a crystal with x = 0.005, constant dielectric value (~30) and loss tangent (~0.01) up to room temperature. The Fermi energy (~0.04 eV) and the Fermi temperature (~500 K) determined from the diffusion component of thermopower showed shallow donor levels.

Tailoring Thermal and Electrical Properties of Jeffamine Segmented Polyetherimide Composite Films Containing BaTiO3 particles.

The continuous advancement of materials science has highlighted the ongoing need for additional studies on the main composite materials topics, particularly in the field of multifunctional nano-composites, towards improving their capability to meet multifaceted requirements in order to stimulate both scientific and technological development. In this study, we report the preparation and characterization of polyetherimides (PEIs) derived from 4,4'-(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride) following a two-step polycondensation reaction using either 4,4'-(1,3-phenylenedioxy) dianiline, or Jeffamine ED-600 as comonomers, or a mixture of the two diamines. Based on the PEI containing flexible Jeffamine segments, polymer composite films were developed by incorporating BaTiO3 particles. The chemical structure and morphology of the composite films were investigated by FTIR spectroscopy and scanning electron microscopy. Thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry. The influence of Jeffamine segments on the thermal decomposition process was investigated by TG/MS/FTIR measurements under air and nitrogen atmospheres. Based on the obtained data, the thermal decomposition mechanism was established and is discussed in accordance with the chemical structures of the polymers. The surface properties of the PEI and PEI-composite films were characterized by performing contact angle measurements. The addition of BaTiO3 increased the wettability of the surfaces. The dielectric characteristics of polymer composite films were investigated by broad band dielectric spectroscopy measurements. It was noticed that the addition of BaTiO3 nanoparticles to the copolymer matrix gradually enhanced the dielectric constant of the composites.

Effect of Dielectric Relaxation of Epoxy Resin on Dielectric Loss of Medium-Frequency Transformer

Epoxy resin (EP) is a typical and widely used insulating material for medium-frequency transformers (MFTs). The dielectric loss of EP is one of the key variables in the design and operation of MFT. In this article, six types of epoxy/anhydride systems are prepared, and the dielectric loss of MFT is calculated by finite element method (FEM) analysis based on broadband dielectric spectroscopy measurements. The material dependence of the dielectric loss of MFT is investigated using dielectric spectroscopy and molecular dynamics simulations over a wide temperature and frequency range. The results show that the variation of dielectric loss with output power is attributed to the temperature characteristics of the imaginary part ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\varepsilon ^{\prime \prime }$ </tex-math></inline-formula> ) of complex permittivity. Compared to the dielectric loss at no-load state, the one at rated power is reduced by 5–10 W. The anhydride hardener containing benzene ring or a methyl substituent has an inhibitory effect on dielectric loss, and the EP cured by methyl nadic anhydride (MeNA) has the lowest dielectric loss (16.2 W) at rated power. The dielectric loss and overload characteristics of MFT are closely related to the <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\beta $ </tex-math></inline-formula> -relaxation and <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\alpha $ </tex-math></inline-formula> -relaxation of EP, respectively. The acid anhydride curing agent containing benzene ring or a methyl substituent reduces the temperature corresponding to the <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\beta $ </tex-math></inline-formula> -relaxation peak by more than 50 °C compared to the one without. The increased rigidity of the chain segment of EP makes the <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\beta $ </tex-math></inline-formula> -relaxation move to the low-temperature side, which is beneficial to suppress the dielectric loss. This article not only serves as a bridge among dielectric loss of MFT, dielectric spectroscopy, and molecular structure of EP but also lays a solid foundation for the selection of insulating materials for MFT.

Gold Nanoparticles as Effective ion Traps in Poly(dimethylsiloxane) Cross-Linked by Metal-Ligand Coordination.

At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl2-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl− counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl− counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems.

Evaluation of water structures in cotton cloth by fractal analysis with broadband dielectric spectroscopy

Broadband dielectric spectroscopy measurements were performed on naturally dried cotton cloth, and a recently developed analytical technique for fractal analysis of water structures was applied to obtain existential states and locations of water molecules in the material. Three relaxation processes observed in GHz, MHz, and kHz frequency regions were attributed to dynamic behaviors of hydrogen bonding networks (HBNs) of water and interacting molecules, polymer chains with interacting ion and water molecules, and ions restricted on the interfaces of larger structures, respectively. Water molecules were heterogeneously distributed in the cotton cloth, and the HBNs remained as a broad GHz frequency process. Fractal analysis suggested that water molecules distributed in the material were characterized by a small value (0.55) of the Cole–Cole relaxation time distribution parameter, indicating spatial distribution of HBN fragments with various sizes in cotton cloth. This result was also supported by the T2 relaxation time obtained from nuclear magnetic resonance for naturally dried cotton yarn. Comparing previous results of dielectric relaxation measurements and fractal analysis with the τ–β diagram for various aqueous systems, the results determined that water molecules cannot exist inside cellulose microfibrils. The fractal analysis employed in this work can be applied to dynamic water structures in any material. The presented analytical technique with a universal τ–β diagram is expected to be an effective tool to clarify water structure detail even for heterogeneous hydrations of the low water content substances.Graphical abstract

Effect of Gd3+ Substitution on Thermoelectric Power Factor of Paramagnetic Co2+-Doped Calcium Molybdato-Tungstates.

A series of Co2+-doped and Gd3+-co-doped calcium molybdato-tungstates, i.e., Ca1−3x−yCoy xGd2x(MoO4)1−3x(WO4)3x (CCGMWO), where 0 < x ≤ 0.2, y = 0.02 and represents vacancy, were successfully synthesized by high-temperature solid-state reaction method. XRD studies and diffuse reflectance UV–vis spectral analysis confirmed the formation of single, tetragonal scheelite-type phases with space group I41/a and a direct optical band gap above 3.5 eV. Magnetic and electrical measurements showed insulating behavior with n-type residual electrical conductivity, an almost perfect paramagnetic state with weak short-range ferromagnetic interactions, as well as an increase of spin contribution to the magnetic moment and an increase in the power factor with increasing gadolinium ions in the sample. Broadband dielectric spectroscopy measurements and dielectric analysis in the frequency representation showed a relatively high value of dielectric permittivity at low frequencies, characteristic of a space charge polarization and small values of both permittivity and loss tangent at higher frequencies.

Numerical modeling of multifrequency complex dielectric permittivity dispersion of sedimentary rocks

The dielectric response of rocks results from electric double layer (EDL), Maxwell-Wagner (MW), and dipolar polarizations. The EDL polarization is a function of solid-fluid interfaces, pore water, and pore geometry. MW and dipolar polarizations are functions of charge accumulation at the interface between materials with contrasting impedances and the volumetric concentration of its constituents, respectively. However, conventional interpretation of dielectric measurements only accounts for volumetric concentrations of rock components and their permittivities, not interfacial properties such as wettability. Numerical simulations of the dielectric response of rocks provide an ideal framework to quantify the impact of wettability and water saturation ([Formula: see text]) on electric polarization mechanisms. Therefore, we have developed a numerical simulation method to compute pore-scale dielectric dispersion effects in the interval from 100 Hz to 1 GHz including effects of pore structure, [Formula: see text], and wettability on permittivity measurements. We solve the quasielectrostatic Maxwell’s equations in 3D pore-scale rock images in the frequency domain using the finite-volume method. Then, we verify simulation results for a spherical material by comparing to the corresponding analytical solution. Additionally, we introduce a technique to incorporate [Formula: see text]-polarization to the simulation and we verify it by comparing pore-scale simulation results to experimental measurements on a Berea sandstone sample. Finally, we quantify the impact of [Formula: see text] and wettability on broadband dielectric permittivity measurements through pore-scale numerical simulations. The numerical simulation results show that mixed-wet rocks are more sensitive than water-wet rocks to changes in [Formula: see text] at sub-MHz frequencies. Furthermore, permittivity and conductivity of mixed-wet rocks have weaker and stronger dispersive behaviors, respectively, when compared to water-wet rocks. Finally, numerical simulations indicate that conductivity of mixed-wet rocks can vary by three orders of magnitude from 100 Hz to 1 GHz. Therefore, Archie’s equation calibrated at the wrong frequency could lead to water saturation errors of up to 73%.

Dielectric Responses of Polyurethane/Zinc Oxide Blends for Dry-Type Cast Cold-Curing Resin Transformers.

The influence of different concentrations (0.5, 1.0, and 2.0 wt.%) of Zinc Oxide (ZnO) filler on the dielectric properties of the cold-curing polyurethane (PU) resin is presented in this study. For this purpose, the direct DC conductivity and the broadband dielectric spectroscopy measurements were used to describe the changes in dielectric responses of PU/ZnO nanocomposites over the frequency and temperature range, respectively. It can be stated that, the 1.0 wt.% nanoparticles and lower caused a decrease in the real relative permittivity compared to the pure PU resin, while the higher concentration of nanoparticles for frequencies above 1 Hz had the opposite effect. The presence of nanoparticles in the polyurethane resin affected the segmental dynamics of the polymer chain and changed a charge distribution in the given system. These changes caused a shift of local relaxation peaks in the spectra of imaginary permittivity and dissipation factor of nanocomposites. It is suggested that the temperature-dependent transition of the electric properties in the nano-composite is closely associated with the -relaxation and intermediate dipolar effects (IDE).

Interfacial Dynamics in Supported Ultrathin Polymer Films-From the Solid to the Free Interface.

Molecular dynamics in ultrathin layers is investigated using nanostructured electrodes to perform broadband dielectric spectroscopy measurements, and by atomistic molecular dynamics simulations. Using poly(vinyl acetate) as the model system and taking advantage of access to the distribution of relaxation times in an extended temperature range above the glass transition temperature, Tg, we demonstrate that while the mean rates of the segmental relaxation remain bulklike down to 12 nm film thickness, modified molecular mobilities arise in the interfacial zones. Combining results from simulations and experiments, we show unambiguously that both the slow relaxations arising from adsorbed polymer segments and the faster modes attributed to segments in the vicinity of the free interface have non-Arrhenius temperature activation. These interfacial regions span thicknesses of ∼1.5 nm each just above the calorimetric Tg independent of molecular weight and film thickness. These deviations at interfaces are relevant for applications of polymers in adhesion, coatings, and polymer nanocomposites.

Electrical and magnetic properties of ZnCr2S4 – nanoparticles

The results of magnetic and electrical measurements of ZnCr2S4 – nanoparticles (NPs) synthesized by mechanical alloying method showed an almost ideal paramagnetic state with the weak ferromagnetic short-range interactions derived from a small positive paramagnetic Curie-Weiss temperature of θ = 0.9 K and the presence of magnetic NPs confirmed by the significantly lower value of the effective magnetic moment (μeff = 2.089 μB/f.u.) compared to the μeff = 5.215 μB/f.u. for bulk spinel as well as n-type semiconducting behavior with an extrinsic region not thermally activated and with an intrinsic region with an activation energy of 0.253 eV. Broadband dielectric spectroscopy measurements showed the relaxation processes only in the intrinsic region of the electrical conductivity, i.e. above 170 K, in which the dipole relaxation becomes faster as temperature rise. These results are interpreted in the framework of the Cole-Cole function and a hopping variable range model including structural defects.