Relaxation Studies Research Articles

Experimental studies of concrete relaxation in various modes

Introduction. At present, creep is the main parameter determined in the long-term loading tests of concrete samples. However, creep appears to be only one of the deformation properties of a concrete sample during operation under the action of long-term loading. Another important property involves stress relaxation. Moreover, in individual problems (temperature problems, force redistribution problems, etc.), stress relaxation plays a more important role than creep. The introduction of a new test procedure can improve the accuracy of the obtained results (in standard creep tests, concrete relaxation is determined only mathematically), which in turn will increase the accuracy of calculations.Aim. To develop a procedure for testing concrete samples with the determination of their stress relaxation.Materials and methods. The article describes a methodology for conducting an experiment to study the relaxation of concrete samples in compression and bending modes, as well as the parameters of test benches, samples and the principles of load transfer.Results. The main results of experimental studies are presented graphically. An analysis of the results obtained was carried out; the convenience of conducting tests was evaluated.Conclusion. The prospects of the proposed approach for testing concrete samples are demonstrated, and recommendations for amending GOST 24544 are prepared.

Molecular dynamics study of water rotational relaxation in saccharide solution for the development of bioprotective agent

Saccharides are often used as bio-protective agent owing to their unique interactions with the solvent water to change the water dynamics which dominate biomolecule deterioration. In this work, we present some basic laws for controlling water rotational relaxation time by performing molecular dynamics (MD) simulations of saccharide solutions. It is revealed that the water rotational relaxation time in saccharide solution is exponentially proportional to its residence time. Interestingly, the larger the solute dipole moment, the smaller the prerequisite residence time to obtain a tenfold retardation of the water relaxation time (the decuple-retarding period), which means the higher the increasing rate of the relaxation time vis-à-vis the residence time. We also find that water residence time exhibits a Gaussian distribution for various sugar solutions. This random walk of water within the solution further suggests that the larger ratio of the hydration layer volume to the overall water accessible space results in a longer residence time, thus a longer relaxation time distribution. We finally conclude that the protective agent with a large specific surface area and a large dipole moment is effective to retard the water rotational relaxation.

Synthesis and Dielectric Relaxation Studies of KxFeyTi8-yO16 (x = 1.4–1.8 and y = 1.4–1.6) Ceramics with Hollandite Structure

Some solid solutions with the chemical composition KxFeyTi8-yO16 (KFTO) and a hollandite-like structure were successfully synthesized by modified sol–gel method. The obtained powders were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The ceramic pellets based on KFTO powders were obtained by compressing and sintering at 1080 °C for 4 h. The sinters were characterized by X-ray and impedance spectroscopy. XRD results show that KFTO powders have a mono-phase tetragonal structure at x = 1.4–1.8 and y = 1.4–1.6. However, it was recognized that the hollandite-like phase could be broken during sintering to form TiO2 and Fe2TiO5 crystals distributed throughout the volume of the ceramics. A frequency dependency of dielectric properties for the sinters was studied by impedance spectroscopy. It was found that an increase in the TiO2 (rutile) phase during the sintering contributes to a decrease in dielectric losses. At the same time, the KFTO ceramics with reduced content of potassium had increased permittivity. The contribution of electron-pinned defect dipoles (EPDD) and internal barrier layer capacitance (IBLC) in the permittivity of the obtained ceramics was estimated using the Havriliak–Negami equation. It is shown that the KFTO ceramics have the polydisperse characteristic of dielectric relaxation. The observed grain and grain boundary dipole relaxation times were 1.03 × 10−6 to 5.51 × 10−6 s and 0.197 to 0.687 s, respectively.

Molecular Dynamics of Jelly Candies by Means of Nuclear Magnetic Resonance Relaxometry

1H spin-lattice Nuclear Magnetic Resonance relaxation studies have been performed for different kinds of Haribo jelly and Vidal jelly in a very broad frequency range from about 10 kHz to 10 MHz to obtain insight into the dynamic and structural properties of jelly candies on the molecular level. This extensive data set has been thoroughly analyzed revealing three dynamic processes, referred to as slow, intermediate and fast dynamics occurring on the timescale of 10-6 s, 10-7 s and 10-8 s, respectively. The parameters have been compared for different kinds of jelly for the purpose of revealing their characteristic dynamic and structural properties as well as to enquire into how increasing temperature affects these properties. It has been shown that dynamic processes in different kinds of Haribo jelly are similar (this can be treated as a sign of their quality and authenticity) and that the fraction of confined water molecules is reduced with increasing temperature. Two groups of Vidal jelly have been identified. For the first one, the parameters (dipolar relaxation constants and correlation times) match those for Haribo jelly. For the second group including cherry jelly, considerable differences in the parameters characterizing their dynamic properties have been revealed.

Graphene Oxide-Grafted Hybrid Diblock Copolymer Brush (GO-graft-PEG6k-block-P(MA-POSS)) as Nanofillers for Enhanced Lithium Ion Conductivity of PEO-Based Nanocomposite Solid Polymer Electrolytes.

Nanocomposite solid polymer electrolytes (NSPEs) with PEO as the matrix and (i) GO or (ii) GO-graft-PEG6k or (iii) GO-graft-PEG6k-block-P(MA-POSS) as nanofillers have been fabricated to elucidate the impact of the filler morphology on the lithium ion conductivity. GO-graft-PEG6k was obtained by grafting PEG6k onto GO via esterification. GO-graft-PEG6k-block-P(MA-POSS) was prepared via surface-initiated atom transfer radical polymerization. Fourier-transform infrared spectroscopy revealed enhanced salt dissociation and complexation between the filler and PEO host that could be attributed to Lewis acid-base interactions. Electrochemical impedance spectroscopy revealed the improved ion conductivity of the fabricated NSPEs as compared with the pristine PEO-LiClO4. As an example, at 50 °C, the ion conductivity increased to 4.01 × 10-5 and 6.31 × 10-5 S cm-1 with 0.3% GO and 0.3% GO-graft-PEG6k, respectively, from 2.36 × 10-5 S cm-1 of PEO-LiClO4, suggesting that the filler with brush-like architecture (GO-graft-PEG6k) is more efficient in enhancing the ion conductivity. Further increase in filler content resulted in lowering of the ion conductivity that could be ascribed to aggregation of the filler. The most dramatic impact on conductivity was observed with the incorporation of brush-like GO-graft-PEG6k-block-P(MA-POSS) as a nanofiller (3.0 × 10-4 S cm-1 at 50 °C with 1.0 wt % filler content). The increase in ion conductivity in the current systems, as opposed to the conventional view, could not be correlated with the content of the amorphous phase of the matrix. The conduction mechanism is still unclear; nevertheless, it could be assumed that in addition to the ion conduction through the PEO matrix, the filler forms additional low-energy ion conducting channels at its interface with the matrix. The pendent POSS nanocages of GO-graft-PEG6k-block-P(MAPOSS) might probably increase the free volume at the interface with the matrix that is associated with higher chain and ion mobility, thus further enhancing the ion conductivity as compared with GO and GO-graft-PEG6k. The faster ion dynamics in 1.0 wt % GO-graft-PEG6k-block-P(MAPOSS) NSPEs has also been verified by the dielectric relaxation studies. Thus, integration of both the PEG and POSS nanocages into GO-grafted brush-like architecture offers a new tool for tuning the lithium ion conductivity for potential Li ion battery applications.

Controlling quantum phases of electrons and excitons in moiré superlattices

Moiré lattices formed in twisted and lattice-mismatched van der Waals heterostructures have emerged as a platform to engineer the novel electronic and excitonic states at the nanoscale. This Perspective reviews the materials science of moiré heterostructures with a focus on the structural properties of the interface and its structural–property relationships. We first review the studies of the atomic relaxation and domain structures in moiré superlattices and how these structural studies provide critical insights into understanding the behaviors of quantum-confined electrons and excitons. We discuss the general frameworks to manipulate moiré structures and how such control can be harnessed for engineering new phases of matter and simulating various quantum phenomena. Finally, we discuss routes toward large-scale moiré heterostructures and give an outlook on their applications in quantum electronics and optoelectronics. Special emphasis will be placed on the challenges and opportunities of the reliable fabrication and dynamical manipulation of moiré heterostructures.

Study of Interactions between Saponin Biosurfactant and Model Biological Membranes: Phospholipid Monolayers and Liposomes

The aim of this study was to determine the effect of saponins-rich plant extract on two model biological membranes: phospholipid monolayers and liposomes. The Langmuir monolayer technique was used to study the interactions of model phospholipid membranes with saponins. The π-A isotherms were determined for DPPE (1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine) monolayer with the addition of various concentrations of licorice saponins extracts and subjected to qualitative as well as quantitative analysis. Additionally, relaxation studies of the obtained monolayers were carried out and morphological changes were examined using Brewster angle microscopy. Moreover, changes in the structure of phospholipid vesicles treated with solutions of saponins-rich plant extracts were assessed using the FTIR technique. The size and zeta potential of the liposomes were estimated based on DLS methods. The obtained results indicated that the saponins interact with the phospholipid membrane formed by DPPE molecules and that the stability of the mixed DPPE/saponins monolayer strongly depends on the presence of impurities in saponins. Furthermore, it was found that the plant extract rich in saponins biosurfactant interacts mainly with the hydrophilic part of liposomes.

Fast Motions Dominate Dynamics of Intrinsically Disordered Tau Protein at High Temperatures.

Reorientational dynamics of intrinsically disordered proteins (IDPs) contain multiple motions often clustered around three motional modes: ultrafast librational motions of amide groups, fast local backbone conformational fluctuations and slow chain segmental motions. This dynamic picture is mainly based on 15 N NMR relaxation studies of IDPs at relatively low temperatures where the amide-water proton exchange rates are sufficiently small. Less is known, however, about the dynamics of IDPs at more physiological temperatures. Here, we investigate protein dynamics in a 441-residue long IDP, tau protein, in the temperature range from 0-25 °C, using 15 N NMR relaxation rates and spectral density analysis. While at these temperatures relaxation rates are still better described in terms of amide group librational motions, local backbone dynamics and chain segmental motions, the temperature-dependent trend of spectral densities suggests that the timescales of fast backbone conformational fluctuations and slower chain segmental motions might become inseparable at higher temperatures. Our data demonstrate the remarkable dynamic plasticity of this prototypical IDP and highlight the need for dynamic studies of IDPs at multiple temperatures.

Dielectric Relaxation Studies on the Hydration Dynamics of Ionic, Non-Ionic and Zwitterionic Surfactants in Aqueous Acetate Buffer Solution

Dielectric relaxation studies of acetate buffer solutions of Sodium Dodecyl Sulphate (SDS- anionic), Cetyl Trimethyl Ammonium Bromide (CTAB- cationic), Tween 80 (TW-80-non-ionic), Betaine Anhydrous (BA- zwitterionic) surfactants have been examined in the frequency region between 1GHz and 25GHz for various concentrations of surfactants at the temperatures of 283, 288, 293 and 298K using time domain dielectric spectroscopy. The obtained corrected loss spectra of all the amphiphiles except betaine anhydrous in acetate buffer solution depicted peaks near 1-2GHz and 15GHz, respectively. For betaine anhydrous, expected peak was not observed in the 1-2GHz frequency region. The peak ascertained near 15GHz, and another peak about 1-2GHz was accorded to free water relaxation and bound water reorientation of the surfactant micelles, and has acquired the reliance of temperature with concentration in detail. Single Debye and Cole-Cole function was employed to compute the relaxation times of free water and bound water, respectively. The Arrhenius plot was used to calculate the enthalpy and entropy for the micelle forming surfactants.

Rosensweig Instability Study of Iron Oxide Nano Fluid Under Uniform Magnetic Field

We report the synthesis of magnetic nanofluids and the investigations on the formation of surface instabilities of ferrofluid when exposed to a normal uniform magnetic field. Ferrofluid of iron oxide particles with an average size of 9 nm, dispersed in a kerosene base is synthesized by a well-known chemical method. The structural analysis of the nanoparticles is carried out by employing X-ray diffraction technique. Fourier Transform Infrared Spectroscopy studies revealed the chemical binding with the surfactant. The Dynamic Light Scattering studies are performed to determine the hydrodynamic size of the suspended particles. The constancy in hydrodynamic size obtained for different particle concentrations is indicative of agglomeration-free suspension. The magnetic properties have been analyzed by the Superconducting Quantum Interference Device. The magnetization measurement signifies the superparamagnetic nature of particles. The temperature-dependent relaxation studies were carried out by field cooled (FC) and zero field cooled (ZFC) moment measurements at a constant applied field. We have demonstrated the Rosensweig instability experimentally and observed the pattern transition. The surface takes on a hexagonal pattern when the applied field surpasses the critical field, which shifts to a square pattern when the applied field reaches a second threshold. The surface tension of the fluid is measured by the pendant drop method and is correlated with the results obtained through instability measurement. The magnetic concentration of the sample is determined from the Thermo gravimetric analysis.

Ion Transport and Dielectric Studies on [PEO:TiO2]:NH4SCN Nanocomposite Polymer Electrolytes

AbstractAn improvement in ion transport behavior and dielectric properties of polyethylene oxide based polymer electrolytes have been investigated upon the dispersal of TiO2 nanoparticles. TiO2 nanoparticle is synthesized with the help of well‐known sol–gel technique. The different compositions of polymer electrolyte systems are prepared by the solution cast technique. Nanocomposite polymer electrolytes (NCPEs) films are synthesized by loading of nanoTiO2 particle in a pristine polymer electrolyte matrix. The structural and morphological behaviors of nanocomposite polymer electrolytes (NCPEs) have been subsequently characterized by XRD and SEM studies. The ionic behavior of synthesized NCPEs is ascertained by Wagner's polarization technique. AC and DC conductivity of polymer electrolyte films have been carried out using impedance spectroscopic techniques. Dielectric relaxation studies of polymer electrolytes are examined using impedance spectroscopic data. The conductivity relaxation mechanism of NCPEs has been concluded with the help of modulus formalism. DC conductivity of best ion‐conducting NCPEs at room temperature has been found to σ = 2.5 × 10−5 S cm−1. The electrode polarization effect has completely vanished in the dielectric and modulus formalism and the conductivity scaling data show a single master curve observed in ion dynamics. The change in ionic conductivity with frequency and temperature is studied by impedance spectroscopic investigations. The effect of salt on dielectric parameters of NCPEs is also extracted from impedance spectroscopic data to explore underlying ion dynamics.

Surface oxygen exchange kinetics of mixed conducting oxides: Dilatometric vs electrical conductivity relaxation study

The surface oxygen exchange kinetics of mixed ionic-electronic conducting (MIEC) oxides play a crucial role in a variety of applications, including solid oxide fuel/electrolysis cells (SOFCs/SOECs), permeation membranes and sensors. To date, a variety of methods, including isotope exchange, electrical conductivity, optical absorptivity and thermogravimetry relaxation, and impedance spectroscopy have been used to measure the oxygen exchange coefficient of MIEC oxides. Each of these methods have their advantages and limitations, depending on the physical and chemical properties of the investigated materials and their sample dimensions and densities. Here, we demonstrate the ability to precisely measure the surface oxygen exchange coefficient (kchem) of MIEC model material Pr0.1Ce0.9O2-δ (PCO) by use of dilatometric relaxation measurements, particularly of interest for materials that exhibit larger chemical expansion coefficients. This is achieved by use of porous bulk specimens to ensure that the contribution of oxygen exchange to the overall kinetics is dominant. We demonstrate that kchem values extracted from chemical expansion relaxation measurements on PCO are nearly identical to those derived from electrical conductivity relaxation measurements. This provides the opportunity to precisely investigate the oxygen exchange and chemical expansion kinetics of a wide range of materials used in high-temperature applications, particularly where more conventional methods are difficult or inappropriate to apply.

Dielectric relaxation studies of poly(ethylene oxide) with the addition of salt or nanofiller

AbstractPoly(ethylene oxide) (PEO)–lithium perchlorate (LiClO4) serves as the classical model of polymer–salt systems with good polymer–salt molecular interaction at low salt concentration, whereas titanium dioxide (TiO2) without any surface treatment when added to PEO serves as a classical model of polymer–filler systems with weak polymer–filler molecular interaction. The correlation of molecular interactions of polymer–salt or polymer–filler with thermal properties of the systems, which govern the formation of morphologies of the systems, was attempted in a previous study. Hence, this work focuses on the correlation of morphologies and dielectric relaxation properties of PEO with the addition of LiClO4 or TiO2 investigated using polarized optical microscopy and electrochemical impedance spectroscopy over the frequency range from 50 Hz to 1 MHz at 25 °C. The effects of the addition of LiClO4 or TiO2 on the dynamics and relaxations of the polymer chain of PEO are discussed empirically following the fluctuation–dissipation effects from the common electrochemical terms and equivalent circuit model. The PEO–LiClO4 system seems to be one of the promising polymer electrolytes for application in lithium rechargeable batteries where the charged entities may arise from the interaction of salt with the ether oxygen of PEO in the amorphous region. Meanwhile, the PEO–TiO2 system may be analogous to a polar polymer with longitudinal dipoles along the PEO backbone, ethylene oxide monomers (from PEO) of which may represent the molecular dipole or charged entity. The findings show that the transport of charged entities in the PEO systems after the addition of LiClO4 or TiO2 is dominated by short‐range motion at room temperature. © 2022 Society of Industrial Chemistry.

The Influence of Emulsifiers on the Physiochemical Behavior of Soy Wax/Rice Bran Oil-Based Oleogels and Their Application in Nutraceutical Delivery.

This research evaluated the influence of stearic acid, sunflower lecithin, and sorbitan monooleate on soy wax (SYW)/rice bran oil (RBO)-based oleogels. The physiochemical behavior of oleogel samples was evaluated using colorimetry, microscopy, FTIR, mechanical, crystallization kinetics, X-ray diffraction, and a drug release investigation. The prepared oleogels were light yellow, and adding emulsifiers did not change their appearance. All oleogels showed an oil binding capacity of >98%, independent of emulsifier treatment. The surface topography revealed that emulsifiers smoothed the surface of the oleogels. Bright-field and polarized micrographs showed the presence of wax grains and needles. FTIR spectra indicated that oleogel samples had the same functional group diversity as the raw materials. The oleogel samples lacked a hydrogen-bonding peak. Hence, we postulated that non-covalent interactions were involved in the oleogel preparation. According to stress relaxation studies, the firmness and elastic component of oleogels were unaffected by emulsifiers. However, EML3 (oleogel containing sorbitan monooleate) showed lower relaxing characteristics than the others. EML3 exhibited the slowest crystallization profile. Due to its low d-spacing, EML3 was found to have densely packed crystal molecules and the largest crystallite size. The in vitro drug release studies showed that emulsifier-containing oleogels dramatically affected curcumin release. These results may help customize oleogels properties to adjust bioactive component release in the food and pharmaceutical industries.

Effect of frequency on the classical and relaxor ferroelectric behavior of substituted titanate Ba0.7Er0.16Ca0.05Ti0.91Sn0.09O3.

In the present work, we synthesized the perovskite Ba0.70Er0.16Ca0.05Ti0.91Sn0.09O3 compound (BECTSO) by a solid-state reaction and sintering at 1200 °C. The effects of doping on the structural, electrical, dielectric, and ferroelectric characteristics of the material are examined in this work. X-ray powder diffraction analysis shows that BECTSO crystallizes in a tetragonal structure with space group P4mm. A detailed study of the dielectric relaxation of the BECTSO compound has been reported for the first time. Classical low-frequency ferroelectric and high-frequency relaxor ferroelectric behaviors have been studied. The study of the real part of the permittivity (ε') as a function of temperature demonstrated a high dielectric constant and identified a phase transition from the ferroelectric phase to the paraelectric phase at Tc = 360 K. The analysis of conductivity curves shows two behaviors: semiconductor behavior for f < 106 Hz and metallic behavior for f >106 Hz. The relaxation phenomenon is dominated by the short-range motion of the charge carriers. The BECTSO sample could be considered as a potential lead-free material for next-generation non-volatile memory devices and wide-temperature range capacitor applications.

Influence of stabilisers on the catalytic activity of supported Au colloidal nanoparticles for the liquid phase oxidation of glucose to glucaric acid: understanding the catalyst performance from NMR relaxation and computational studies

Impact of stabilisers on the catalytic performance of supported Au colloidal nanoparticles for the liquid phase oxidation of glucose to glucaric acid.

Tuning proton kinetics in BaCo0.4Fe0.4Zr0.2–XYXO3–δ triple ionic-electronic conductors via aliovalent substitution

Complementary permeation and conductivity relaxation studies reveal the optimal 10% yttrium B-site doping in BaCo0.4Fe0.4Zr0.2−XYXO3−δ (BCFZYX) triple ionic-electronic conductors for improved proton conductivity and surface exchange.

Dielectric relaxation studies in WO3 mixed lead vanadate glasses

Dielectric relaxation studies in WO3 mixed lead vanadate glasses

The extracellular chaperone clusterin prevents primary and secondary nucleation of an amyloidogenic variant of β2-microglobulin

Amyloid fibril formation by the extracellular protein β2-microglobulin (β2m) and its subsequent accumulation in periarticular tissues have been linked to dialysis-related amyloidosis. A natural variant of human β2m responsible for aggressive systemic amyloidosis contains an aspartate to asparagine mutation at residue 76 (i.e. D76N β2m), which readily forms amyloid fibrils in vitro under physiological conditions. In this study, we examined the role of the extracellular molecular chaperone clusterin in modulating D76N β2m fibril formation in vitro under physiological conditions. The presence of extrinsic charged amino acids modulated D76N β2m fibril formation, implying that electrostatic interactions are involved in the protein’s aggregation. Thioflavin T (ThT) and 1-anilinonaphthalene-8-sulfonate fluorescence assays indicated that clusterin interacts via hydrophobic and electrostatic forces with the monomeric, prefibrillar and fibrillar species of D76N β2m. As a result, clusterin was incorporated into D76N β2m aggregates during the latter’s fibril formation, as indicated by SDS-PAGE of depolymerised fibrils. SYPRO Orange and ThT fluorescence assays suggested that, compared to pure D76N β2m fibrils, those formed in the presence of clusterin are chemically more stable with a reduced ability to act as nucleation seeds. Detailed 15N NMR relaxation studies of mixtures of 15N-labelled β2m with clusterin confirmed that the chaperone interacts transiently and non-specifically with monomeric β2m. Clusterin inhibits both primary and secondary nucleation of D76N β2m fibril formation. In doing so, clusterin binds to D76N β2m fibrils and stabilises them to prevent possible fragmentation. In vivo, the multifaceted chaperone action of clusterin may delay, if not prevent, β2m amyloid proliferation and deposition in tissues.

Liquid crystalline phase behavior and hydration of hydroxypropyl cellulose in water: A liquid and solid NMR investigation

AbstractHydroxypropyl cellulose (HPC) is a functional material with numerous applications as a drug solubilizer, thickener, and stabilizer. Herein, the mobile and rigid regions of HPC are investigated using liquid‐ and solid‐state NMR, respectively, in the high‐viscosity regime of concentrated aqueous samples, below and above the formation of an ordered chiral liquid‐crystalline (LC) mesophase. Liquid NMR 13C relaxation and hydration studies reveal that hydroxypropyl pendant chains remain more fluid than the pyranose sugar rings at concentrations below the formation of the LC phase. The inner part of the pendant chains close to the cellulose backbone exhibits a higher water structuration and a lower water renewal than the outer part and the pyranoses, which likely compensates for their higher hydrophobicity. When the LC phase is formed, the sample viscosity increases and the differences in flexibility and hydration of the pendant chains are reduced with respect to the pyranoses, while the whole system is rigidified. The system is not completely rigid even at concentrations above the formation of LC, as the interaction of water with the pyranoses considerably enhances their fluidity. In contrast, the pendant chains are much less affected.