Broadband Dielectric Spectroscopy Research Articles

In situ monitoring of CO2$$ {}_2 $$ sorption on polyethylenimine dynamics through broadband dielectric spectroscopy

AbstractChemical reactions between carbon dioxide (CO) and amine have been extensively characterized, however, their influence on the dynamics of polyamines remains largely unexplored. In this work, we compare the dynamics of polyethylenimine (PEI) before and after CO absorption through broadband dielectric spectroscopy (BDS). The molecular processes of bulk PEI are very different from those of thin film PEI, highlighting an interesting interface and nano‐confinement effect. Detailed analyses show CO absorption slows down the PEI dynamics, which is consistent with an elevated glass transition temperature of PEI upon CO absorption from differential scanning calorimetry measurements. Further in situ kinetic measurements demonstrate nonmonotonic changes in relaxation times or dielectric amplitudes of some relaxation processes during CO sorption or desorption, suggesting an intriguing interplay between CO chemisorption and the dynamics of PEI. These results demonstrate that BDS is a powerful platform to resolve the temporal dynamics changes of polyamines for CO capture.

Synthesis and characterization of ceramic refractories based on industrial wastes

The possibility of reusing ceramic roller waste to produce cordierite and mullite refractories was investigated. Five batches were designed using wastes representing ceramic roller waste, magnesite, and silica sand, shaped and fired at 1300 °C/2 h, and one batch was selected at 1200 °C. The chemical composition and precipitated phases of the used raw materials and the fired batches were analyzed using XRF and XRD techniques, respectively. Densification parameters, morphology, microstructure and electrical properties were also studied to evaluate the effect of the formed phases on the properties of fired materials. Bulk density increases with an increase in mullite and a decrease in cordierite, and it also increases with increasing temperature, whereas porosity and water absorption show a opposite behavior to density (it decreases with an increase in mullite and temperature). The main phases developed after firing at 1300 °C/2 h were cordierite, mullite, corundum, baddeleyite, and spinel. Bending strength increases with increasing mullite percentage and density, and decreasing grain size and porosity. The microstructure develops and becomes finer with increasing mullite percentage and density. The grain size of the crystals was very fine at 1200 °C/2 h and increased at 1300 °C/2 h. Broadband dielectric spectroscopy was employed to study the electrical and dielectric behavior of the investigated samples. The increase in mullite concentration shows a remarkable increase in ε’, especially at lower frequencies, as it is three times higher than that of M10. At f > 103 Hz ε’, frequency independence is accompanied by an increase in mullite concentrations due to the lag of dynamics fluctuations after the alteration of the electric field. The generation of new free ions leads to the enhancement of conductivity as the mullite concentration increases.

The role of lignin as interfacial compatibilizer in designing lignocellulosic-polyester composite films

Advancing nanocomposites requires a deep understanding and careful design of nanoscale interfaces, as interfacial interactions and adhesion significantly influence the physical and mechanical properties of these materials. This study demonstrates the effectiveness of lignin nanoparticles (LNPs) as interfacial compatibilizer between hydrophilic cellulose nanofibrils (CNF) and a hydrophobic polyester, polycaprolactone (PCL). In this context, we conducted a detailed analysis of surface-to-bulk interactions in both wet and dry conditions using advanced techniques such as quartz crystal microbalance with dissipation (QCM-D), atomic force microscopy (AFM), water contact angle (WCA) measurements, broadband dielectric spectroscopy (BDS), and inverse gas chromatography (IGC).QCM-D was employed to quantify the adsorption behavior of LNPs on CNF and PCL surfaces, demonstrating LNPs’ capability to interact with both hydrophilic and hydrophobic phases, thereby enhancing composite material properties. LNPs showed extensive adsorption on a CNF model film (1186 ± 178 ng.cm−2) and a lower but still significant adsorption on a PCL model film (270 ± 64 ng.cm−2). In contrast, CNF adsorption on a PCL model film was the lowest, with a sensed mass of only 136 ± 35 ng.cm−2. These findings were further supported by comparing the morphology and wettability of the films before and after adsorption, using AFM and WCA analyses. Then, to gain insights into the molecular-level interactions and molecular mobility within the composite in dry state, BDS was employed. The BDS results showed that LNPs improved the dispersion of PCL within the CNF network. To further investigate the impact of LNPs on the composites’ interfacial properties, IGC was employed. This analysis showed that the composite films containing LNPs exhibited lower surface energy compared to those composed of only CNF and PCL. The presence of LNPs likely reduced the availability of surface hydroxyl groups, thus modifying the physicochemical properties of the interface. These changes were particularly evident in the heterogeneity of the surface energy profile, indicating that LNPs significantly altered the interfacial characteristics of the composite materials.Overall, these findings emphasize the necessity to control the interfaces between components for next-generation nanocomposite materials across diverse applications.

New Ceramic Material Y2‐xVxO3+x ‐ Mechanochemical Synthesis and Some Physicochemical Properties

AbstractPotential applications of known compounds from the V2O‐Y2O3 system, i. e. YVO4, Y8V2O17 and Y10V2O20, were the inspiration to undertake research, the main goal of which was to determine whether unknown phases of the solid solution type are formed in this system. Solid solutions are still sought‐after phases because their properties depend on their chemical composition. In this work it was experimentally demonstrated that a new substitute solid solution with the formula Y2‐xVxO3+x (0.00<×<0.60) is formed from mixtures of V2O5 with Y2O3 as a result of mechanochemical synthesis. Its properties were examined by using, i.a. XRD (X‐ray diffraction) and UV‐Vis‐DRS (ultraviolet‐visible light spectroscopy with diffusion reflectance) methods. It was found among other things, that it crystallizes in a regular system, exhibits a Y2O3 structure and is thermally stable up to at least 800 °C (for x=0.40). Moreover, the estimated value of the band gap width indicated that the solid solution Y2‐xVxO3+x belongs to the class of semiconductors. The study of dielectric properties of new phase was performed by means of broadband dielectric spectroscopy. The obtained measurement data showed the presence of relaxation type dielectric mechanisms. The thermally activation energies of the relaxation processes related to the electric conductivity were calculated.

Emergent Research Trends on the Structural Relaxation Dynamics of Molecular Clusters: From Structure-Property Relationship to New Function Prediction.

ConspectusMolecular clusters (MCs) are monodispersed, precisely defined ensembles of atom collections featured with shape-persistent architectures that can deliver certain functions independently. Their molecular compositions and surface functionalities can be tailored feasibly in a predefined manner, and they can be applied as basic structural units to be engineered into materials with desirable hierarchical structures and enriched functions. The chemical systems also offer great opportunities for the design and fabrication of soft structural materials without the chain topologies of polymers. The bulks of MC assemblies demonstrate viscoelasticity that is used to be considered as the unique feature of polymers, while the MC systems are distinct from polymers since their elasticities are resilient even at temperatures 100 K above their glass transition temperatures. The understanding of their anomalous viscoelasticity and the extended studies of general structure-property relationships are desired for the development of new chemical systems for emergent functions and the possibilities to resolve the intrinsic trade-offs of traditional materials.Meanwhile, general macroscopic functions or properties of materials are related to the transportation of mass, momentum, and/or energy, and they are basically realized or directed by the motions of structural units at different length scales. Structural relaxation dynamics research is critical in quantifying motions ranging from fast bond deformation, bond break/formation, and diffusion of ions and particles to the cooperative motions of structure units. Due to the advancement of measurement technology for relaxation dynamics (e.g., quasi-elastic scattering and broadband dielectric spectroscopy), the structural relaxation dynamics of MC materials have been probed for the first time, and their multiple relaxation modes across several temporal scales were systematically studied to bridge the correlation between molecular structures and macroscopic functions. The fingerprint information from dynamics studies, e.g., the temperature dependence of relaxation time and certain property, e.g., ion conductivity, was proposed to quantify the structure-property relationship, and the microscopic mechanism on the mechanical properties, ion conduction, and gas absorption and separation of MC materials can be fully understood.In this Account, to elucidate the uniqueness of MC materials, especially in comparison with polymers, four topics are mainly summarized: structural features, relaxation dynamics characterization techniques, relaxation dynamics characteristics, and quantified understanding of the structure-property relationship. The capability for new function prediction from relaxation dynamics studies is also introduced, and the typical example in impact resistant materials is provided. The Account aims to prove the significance of relaxation dynamics characterization for material innovation, while it also confirms the potential of MCs for functional material fabrications.

DYNAMICS IN ELASTOMERS WITH HYDROGEN BOND INTERACTIONS

ABSTRACT The dynamics of low molecular weight polybutadiene (PB) functionalized with side chains able to form hydrogen-bonded networks is investigated by a combination of calorimetry, rheology, and broadband dielectric spectroscopy (BDS). The modified PBs are found to have extremely different macroscopic viscosities with respect to the starting polymer; however, rather unexpectedly, when investigated using these three techniques, we find that the changes to the segmental motion responsible for the glass transition temperature remain unchanged. This is attributed to the high flexibility of the side chain, which does not restrict the motions of the highly flexible segments in the PB chain. In the presence of the hydrogen-bonded network we observe in both the rheological and dielectric spectra an additional relaxation, orders of magnitude slower than the segmental relaxation. We find that the temperature dependence and its dynamics are well explained in terms of the lifetime of the hydrogen bond, with a binding energy of about 100 kJ/mol.

Mechanisms of enhanced performance in Zr4+/Ta5+ codoped rutile-TiO2 ceramics via broadband dielectric spectroscopy.

Aliovalent dopant codoped rutile-TiO2 materials have garnered attention due to their excellent performance properties, characterized by low loss tangent (tanδ), high dielectric permittivity (ε'), and stable ε' over a broad temperature range. This performance is primarily due to the electron-pinned defect-dipoles (EPDDs) of the complex defects [Formula: see text]Ti3+-[Formula: see text]Ti3+BTi. Notably, the excellent dielectric properties in ZrxTa2.5%Ti0.975-xO2 (Zr-TTO) ceramics can be achieved using the traditional mixed oxide method without the EPDDs, due to the absence of A3+ (acceptor doping ions). Instead, the existence of localized free electrons and oxygen vacancies ([Formula: see text]) in Zr-TTO structures, due to doping ions and the sintering process, was confirmed by X-ray photoelectron and Raman spectroscopies. These ceramics exhibited ε'~ 2 × 104 and tanδ < 0.03 at 1kHz and 25°C in the 2.5-10%Zr-TTO samples. Moreover, all ceramics demonstrated a maximum ε' change (∆ε') of less than ±15% over the temperature range suitable for X7R and X8R type ceramic capacitors. Significantly, the change in ε' related to relative humility was calculated to be less than ±0.5% over the range of 50-95% RH, indicating the environmental stability of the dielectric properties, which is essential for capacitor applications. Investigations suggested that at least four mechanisms contributed to this system: the intrinsic effect of ionic polarization, Ti4+ · e- -[Formula: see text]- Ti4+ · e- and Ti4+ · e- - [Formula: see text] defects, interfacial polarization at insulating grain boundaries, and non-Ohmic contact between the surface sample and the metal electrode.

Probing the influence of composition and cross-linking degree on single-chain nanoparticles from poly(tetrahydrofuran-ran-epichlorohydrin) copolymers: Insights from neutron scattering, calorimetry, and dielectric spectroscopy

The industrial sector has made significant strides in the development of multicomponent and multiphasic polymer materials, including polymer blends, composites (such as nanocomposites), and various copolymers. Random copolymers, characterized by their statistical arrangement of repeating units, are particularly noteworthy due to their tunability from amorphous to semicrystalline states. In this study, we focus on poly(tetrahydrofuran-ran-epichlorohydrin) (P(THF-ran-ECH)) copolymers, which serve as precursors for single-chain nanoparticles (SCNPs). These SCNP-based materials are of particular interest as they bridge the gap between traditional polymers and colloids. This research comprehensively investigates how the type and degree of internal cross-linking influence the structure and dynamics of P(THF-ran-ECH) copolymers and their SCNPs. Techniques such as quasielastic neutron scattering (QENS), differential scanning calorimetry (DSC), and broadband dielectric spectroscopy (BDS) were employed to study copolymers with varying compositions and levels of cross-linking. By analyzing two samples with different epichlorohydrin (ECH) contents (13 mol% and 27 mol%), we aim to control crystallization and explore its effects on dynamic behavior. Our results show that both the composition and the degree of cross-linking significantly impact the dynamics of the SCNPs, with SCNPs exhibiting slower dynamics compared to their precursor copolymers. Furthermore, semicrystalline samples display faster dynamics in SCNPs than amorphous samples. These findings provide valuable insights for the design and optimization of advanced multicomponent polymer systems.

Ion Association and Hydration of Some Heavy-Metal Nitrate Salts in Aqueous Solution.

Aqueous solutions of four heavy-metal nitrate salts (AgNO3, TlNO3, Cd(NO3)2 and Pb(NO3)2) have been studied at 25 °C using broadband dielectric relaxation spectroscopy (DRS) at frequencies 0.27 ≤ ν/GHz ≤ 115 over the approximate concentration range 0.2 ≲ c/mol L-1 ≲ 2.0 (0.08 ≲ c/mol L-1 ≲ 0.4 for the less-soluble TlNO3). The spectra for AgNO3, TlNO3, and Pb(NO3)2 were best described by assuming the presence of three relaxation processes. These consisted of one solute-related Debye mode centered at ∼2 GHz and two higher-frequency solvent-related modes: one an intense Cole-Cole mode centered at ∼18 GHz and the other a small-amplitude Debye mode at ∼500 GHz. These modes can be assigned, respectively, to the rotational diffusion of contact ion pairs (CIPs), the cooperative relaxation of solvent water molecules, and its preceding fast H-bond flip. For Cd(NO3)2 solutions an additional solute-related Debye mode of small-amplitude, centered at ∼0.5 GHz, was required to adequately fit the spectra. This mode was consistent with the presence of small amounts of solvent-shared ion pairs. Detailed analysis of the solvent modes indicated that all the cations are strongly solvated with, at infinite dilution, effective total hydration numbers (Zt0 values) of irrotationally bound water molecules of ∼5 for both Ag+ and Tl+, ∼10 for Pb2+, and ∼20 for Cd2+. These results clearly indicate the presence of a partial second hydration shell for Pb2+(aq) and an almost complete second shell for Cd2+(aq). However, the hydration numbers decline considerably with increasing solute concentration due to ion-ion interactions. Association constants for the formation of contact ion pairs indicated weak complexation that varies in the order: Tl+ < Ag+ < Pb2+ < Cd2+, consistent with the charge/radius ratios of the cations and their Gibbs energies of hydration. Where comparisons were possible the present constants mostly agreed well with the rather uncertain literature values.

Complexity of confined water vitrification and its glass transition temperature

The ability of vitrification when crossing the glass transition temperature (Tg) of confined and bulk water is crucial for myriad phenomena in diverse fields, ranging from the cryopreservation of organs and food to the development of cryoenzymatic reactions, frost damage to buildings, and atmospheric water. However, determining water's Tg remains a major challenge. Here, we elucidate the glass transition of water by analyzing the calorimetric behavior of nano-confined water across various pore topologies (diameters: 0.3 to 2.5 nm). Our approach involves subjecting confined water to annealing protocols to identify the temperature and time evolution of nonequilibrium glass kinetics. Furthermore, we complement this calorimetric approach with the dynamics of confined water, as seen by broadband dielectric spectroscopy and linear calorimetric measurements, including the fast scanning technique. This study demonstrated that confined water undergoes a glass transition in the temperature range of 170 to 200 K, depending on the confinement size and the interaction with the confinement walls. Moreover, we also show that the thermal event observed at ~136 K must be interpreted as an annealing prepeak, also referred to as the "shadow glass transition." Calorimetric measurements also allow the detection of a specific heat step above 200 K, which is insensitive to annealing and, thereby, interpreted as a true thermodynamic transition. Finally, by connecting our results to bulk water behavior, we offer a comprehensive understanding of confined water vitrification with potential implications for numerous applications.

UV- blocking and dielectric properties of polyethersulfone/ nanolignin composites

Agricultural wastes contain many recyclable constituents of versatile properties that enable their utilization in many technological applications. Among these renewable materials, lignin appears as an abundant and affordable biodegradable polymer. In this work, nanolignin (NL) is blended in different ratios with polyethersulphone (PES) namely 0.25, 0.5, 1, and 3%. Casted films prepared from PES/NL composites were thoroughly characterized by FTIR and UV spectroscopy. The films demonstrated high UV absorbance that increases by rising amount of NL in the composite film. Moreover samples PES-NL1.00 and PES-NL3.00 showed ≈0.20 % transmittance at 380 nm. Thermal gravimetric analysis revealed enhanced thermal stability of nanocomposite films compared to pure PES. The electric conductivity and dielectric properties are evaluated using the Broadband Dielectric Spectroscopy (BDS) technique. The measurements showed that the prepared films have low permittivity accompanied by a very low dielectric loss. Addition of NL at concentration varied between 0 and 3 wt% to the PES decreases ε′ unsystematically from 4.4 to 3.5 and tan δ from 0.008 to 0.005. On the other hand, the increase of temperature by 100 °C, increases the permittivity by about 1% indicating the thermal stability against dielectric properties. These UV-blocking and dielectric features make this nanocomposite very promising as high-performance interlayer dielectrics for fabricating semiconductor devices.

Broadband dielectric spectroscopy studies of Co3O4 and Co2TiO4 two-phase spinel composites

Broadband dielectric spectroscopy studies of the two-phase composites, (1 – x) Co3O4 + x Co2TiO4, have been reported over a wide range of compositions (0 ≤ x ≤ 1) and temperatures (80 K ≤ T ≤ 573 K). Normal spinel Co3O4 and inverse spinel Co2TiO4 phases are well distinguishable with ∼4.6 % variation in the lattice parameter of the Co3O4 phase with an increase of x from 0 to x = 1. The ac-conductivity (σ) of this composite follows Johnscher's power law (∼Aωs) variation with frequency exponent factor ‘s’ both greater than as well as less than unity. The temperature dependence of ‘σ’ reveals the Arrhenius-like behavior instead of variable range hopping of charge carriers with activation energy in the 2–1800 meV range. Systematic analysis of such conductivity mechanisms for all the compositions is compared with the pristine Co3O4 system.

Investigation of thermal, optical properties, AC conductivity and broadband dielectric spectroscopy of poly(ethyl methacrylate)/poly(vinyl chloride) polymer blend

This work reports the structural, thermal, optical and electrical properties of PEMA, PVC and their polyblends. These properties are investigated by FTIR, TGA, UV/Vis and broadband dielectric spectroscopy. FTIR spectra showed that the characteristic bands of PEMA and PVC are affected by blending and displayed red and blue shifts confirming that an intermolecular interaction between PEMA and PVC is occurred. Thermal degradation kinetics of PEMA, PVC and its polyblend samples is investigated in details and the thermal properties of each decomposition stage are estimated. UV measurements analysis revealed that Urbach energy (EU) is increased while optical bandgap decreased upon increasing the PVC content. The indirect and direct band gap (Eig/Edg) values are decreased from (3.95/4.21) to (3.10/3.92) eV. Also, upon increasing the content of PVC, the lattice dielectric constant (εL) is increased from 2.71 to 7.83. Wemple-DiDomenico model is applied for investigating the refractive index dispersion and to calculate the oscillator and dispersion energies. It is observed that the linear/nonlinear parameters are increased nonlinearly with increasing the PVC content. χ(1), χ(3) and n2 values are found to increase from 0.104, 0.213 × 10−13 and 4.01 × 10−12 to 0.363, 31.26 × 10−13 and 5.33 × 10−12. These results make PEMA/PVC polyblend strong candidates for use in the development and design of advanced optoelectronic devices. AC conductivity (σac) and dielectric measurements are carried out at various temperatures in wide frequency range. Jonscher power law is applied and showed that the predominant conduction mechanism in our samples is overlapping large-polaron tunneling (OLPT). The dielectric constant and electrical impedance are found to be frequency and temperature dependent. The investigation of the electric modulus (M*) revealed that M′ is increased non-linearly with increasing the frequency, while M″ spectra displayed two different modes of relaxation. The interfacial polarization (IP) is observed in low frequency region, while, dipolar relaxation is detected in high frequency region.

Structure-Glass Transition Relationships in Non-Isocyanate Polyhydroxyurethanes.

The molecular dynamics, with an emphasis on the calorimetric and dynamic glass transitions, of non-isocyanate polyhydroxyurethanes (PHUs) produced by the equimolar polyaddition of polyether-based dicyclic carbonates (P-CCs) and various short diamines was studied. The diamine component consisted of a short aliphatic diamine (1,4-diaminobutane, DAB) and a more complex 'characteristic' diamine. The study was conducted to investigate (i) the chemical structure of the characteristic amine, (ii) its molar ratio, and (iii) the structure and molar mass of the P-CC. Infrared spectroscopy, differential scanning calorimetry, and broadband dielectric spectroscopy were employed. The P-CC, constituting the bulk of the systems, was the most crucial component for the glass transition. The characteristic amine influenced the glass transition as a result of its bulky structure, but also presumably as a result of the introduction of free volume and the formation of hydrogen bonds. The dynamic glass transition (α relaxation) trace in the Arrhenius plots showed a subtle change at a certain temperature that merits further study in the future. The charge mobility was fully coupled with the molecular mobility, as evidenced by dc conductivity being directly proportional to the characteristic frequency of α relaxation. The fluctuation in carbonyl units (β relaxation) was mildly affected by changes in their immediate environment.

Controllable Design and Synthesis of Polyurethane Elastomers Containing Polar Dangling Chains with High Mechanical Properties and Wide Damping Temperature Range.

Vibration and noise severely affect the operation of mechanical equipment and is also detrimental to human health. Therefore, the development of high performance damping materials is crucial. However, current methods to improve damping properties often come at the expense of mechanical properties, resulting in inferior mechanical performance of materials. In order to address the issue of imbalance between damping properties and mechanical properties in polyurethane damping elastomers. In this study, polyester dangling chains containing polar groups are synthesized and introduced into polyurethane. The obtained polyurethane exhibited an effective damping temperature range of 154 °C (-54 °C to 100 °C) and a tensile strength of 15.82 MPa. Furthermore, dynamic mechanical analysis and broadband dielectric relaxation spectroscopy are combined to investigate the influence of polar dangling chains on the structure and properties of polyurethane. The degree of microphase separation increases after the introduction of polar dangling chains, indicating enhances intermolecular interaction forces, facilitating the formation of hydrogen bond between the main chain and dangling chains, thereby increasing molecular chain friction and energy dissipation. This work overcomes the challenge of balancing the damping and mechanical properties of polyurethane, providing a new strategy for designing high performance polyurethane damping elastomers.

Combining linear and cyclic sulfones as a strategy for elaborating more efficient high-dielectric polymer materials: A second case of dipolar glass copolymers

Motivated by the excellent features exhibited by sulfone functional groups in the development of high-dielectric polymer materials, this work assesses the combination of linear and cyclic sulfone structures through copolymerization to prepare novel polymer materials exhibiting high dielectric constants (ԑr'), low dissipative behavior, and improved thermal properties. Five new polymethacrylate-based copolymers with varying compositions were synthesized through reversible addition-fragmentation chain transfer (RAFT) polymerization. The correct structure and macromolecular nature of the devised materials were confirmed by infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (1H/13C NMR), and gel permeation chromatography (GPC), while their thermal properties were evaluated using thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). All specimens exhibited adequate thermal properties for most capacitor applications in terms of onset degradation (Ti) and glass transition (Tg) temperatures. All materials degraded well above 250 °C, with increased Ti and Tg values depending on the final composition of the cyclic sulfone monomer in the material. The incorporation of cyclic sulfones not only increased the thermal robustness of the specimens but also raised their Tg values to as high as 189 °C, notably expanding the range of temperatures where these systems can operate without dissipative phenomena. More importantly, broadband dielectric spectroscopy (BDS) revealed that all samples exhibited dielectric properties notably superior to those of conventional polymer materials, with high ԑr' values between 6.0 and 8.9 (at 25 °C and 1 Hz) and low loss factors (Tan(δ) < 0.018). Overall, the present work successfully demonstrates the advantages of including cyclic structures with high dipole moments in polymeric backbones, offering a new strategy to enhance the thermal and dielectric properties of high-dielectric polymer materials.

Towards millimetre-wave spectroscopy of human blood using an open-ended waveguide

Broadband dielectric spectroscopy of blood above 50 GHz is scarce due to hardware limitations, affordability, and complexity. This study explores the use of a rectangular waveguide as a probe for analysing human blood in the 55 to 95 GHz range, at temperatures from 23 °C to 36 °C, and Haemoglobin levels between 0 and 16 g/dL, focusing on practical aspects such as sample preparation and the setup’s mechanical, thermal, and calibration requirements. The research highlights the effectiveness of the Short-Open-Load calibration method, evidenced by precise measurements of saline solutions. Furthermore, analysis of 84 human blood samples indicates that while Haemoglobin levels introduce some uncertainty in dielectric constant measurements, dielectric loss readings remain consistent across temperature and Haemoglobin variations, with a low uncertainty of under 2.65%, indicating the potential use of this parameter in future millimetre-wave techniques for non-invasive testing of blood analytes.

Thermoplastic Starch Processed under Various Manufacturing Conditions: Thermal and Electrical Properties.

Eco-friendly materials like carbohydrate-based polymers are important for a sustainable future. Starch is particularly promising because of its biodegradability and abundance but its processing to thermoplastic starch requires optimization. Here we developed thermoplastic maize starch materials based on three manufacturing protocols, namely: (1) starch/glycerol manual mixing and extrusion, (2) starch/glycerol manual mixing, extrusion, and kneading, (3) starch/glycerol/water manual mixing and kneading. The physical properties were investigated by differential scanning calorimetry, thermogravimetric analysis, and broadband dielectric spectroscopy. As expected from a partially miscible blend, the dielectric spectra revealed two distinct α-relaxations for the glycerol-rich and the starch-rich phases, respectively. By employing kneading after extrusion, the miscibility between the two phases was found to improve based on thermal and dielectric methods. Moreover, the addition of water during the premixing stage was observed to facilitate phase separation between starch and glycerol, with the α-relaxation dynamics of the latter being comparable to pure glycerol.

Dielectric Response of ZnO/PMMA Nanocomposites with Atmospheric Pressure Plasma-Modified Surfaces.

In this work, the effect of etching the surface of polymer matrix nanocomposites with atmospheric pressure plasma targeting to achieve enhanced dielectric properties was investigated. Polymer nanocomposites, with varying reinforcing phase content, were modified by atmospheric-pressure plasma resulting in an increase in the surface filler's concentration. Polymethyl methacrylate (PMMA) matrix nanocomposites reinforced with zinc oxide (ZnO) nanoparticles were prepared and dielectrically studied as a function of the nanoparticle content and the plasma modified surfaces. The electrical response of the composite systems was studied by means of Broadband Dielectric Spectroscopy (BDS) over a wide range of temperatures and frequencies. The dielectric permittivity increased with the embedded phase content and with plasma surface treatment. Energy density followed the same trend as dielectric permittivity, and the plasma-treated nanocomposite with the higher ZnO content exhibited approximately 27% higher energy density compared to the unreinforced matrix.

Nanocomposite polyphenyleneoxide with amino-functionalized silica: structural characterization based on thermal analysis

AbstractA polymer nanocomposite based on sulfonated polyphenylene oxide with amino-functionalized mesoporous silica was designed, synthesized, and tested as a new material for proton exchange membrane (PEM preparation. Characterization of the intermediate and final products of synthesis was realized by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and thermal analysis. Broadband Dielectric Spectroscopy (BDS) was used to determine dielectric properties including ionic conductivity. Thermogravimetric analysis has provided important information regarding the composition and thermal stability of the three compounds, subject to thermal degradation: 1) the amino-silica with cetyltrimethylammonium bromide (CTAB) template inside the pores (MS-NH2I), 2) the mesoporous amino-silica after removing the template (MS-NH2II) and 3) the polymer nanocomposite (sPPO-MS-NH2). The thermal decomposition of the composite samples occurs in three stages: in the first, up to 150 °C, water and organic solvents were lost; the second stage, between 200-300 °C, was due to breaking the organic functionalities (-NH2, amino and -SO3H, sulfonic acid), and the third stage, above 400 °C was due to polymer chain degradation. The final residue at 700 °C reflects the contribution of inorganic silica. The proton conductivity, for polymeric (sPPO) and composite (sPPO-MS-NH2) membranes was determined from BDS dates, both in dry and hydrated states. For dried samples, the higher values of proton conductivities were: 0.16 mS cm−1 (sPPO, 70 °C) and 0.03 mS cm−1 (sPPO-MS-NH2, 120 °C), and the higher values of proton conductivity increased for the hydrated samples with two orders of magnitude: 36.5 mS cm−1 (sPPO, 40 °C) and 22.4 mS cm−1 (sPPO-MS-NH2, 50 °C). However, the proton conductivity is still dependent on the hydration state, even for the composite membrane.