The dependence of relaxation times on free volume in high polymers
Shift of mechanical and dielectric relaxation maxima of polyvinyl chloride over wide range of frequency, temperature, and pressure, and extension of Eyring theory
POLYVINYL CHLORIDE↗
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A model for the scattering of high-frequency electromagnetic fields from dielectrics exhibiting thermally-activated electrical losses
An equivalent circuit model (ECM) approach is used to predict the scattering behavior of temperature-activated, electrically lossy dielectric layers. The total electrical response of the dielectric (relaxation + conductive) is given by the ECM and used in combination with transmission line theory to compute reflectance spectra for a Dallenbach layer configuration. The effects of thermally-activated relaxation processes on the scattering properties is discussed. Also, the effect of relaxation and conduction activation energy on the electrical properties of the dielectric is described.
Hann, Raiford E.↗
High Entropy Oxide Relaxor Ferroelectrics
Relaxor ferroelectrics are important in technological applications due to strong electromechanical response, energy storage capacity, electrocaloric effect, and pyroelectric energy conversion properties. Current efforts to discover and design materials in this class generally rely on substitutional doping as slight changes to local compositional order can significantly affect the Curie temperature, morphotropic phase boundary, and electromechanical responses. In this work, we demonstrate that moving to the strong limit of compositional complexity in an ABO 3 perovskite allows stabilization of relaxor responses that do not rely on a single narrow phase transition region. Entropy-assisted synthesis approaches are utilized to synthesize single-crystal Ba(Ti 0.2 Sn 0.2 Zr 0.2 Hf 0.2 Nb 0.2 )O 3 [Ba(5B)O] films. The high levels of configurational disorder present in this system are found to influence dielectric relaxation, phase transitions, nanopolar domain formation, and Curie temperature. Temperature-dependent dielectric, Raman spectroscopy, and second-harmonic generation measurements reveal multiple phase transitions, a high Curie temperature of 570 K, and the relaxor ferroelectric nature of Ba(5B)O films. The first-principles theory calculations are used to predict possible combinations of cations to design relaxor ferroelectrics and quantify the relative feasibility of synthesizing these highly disordered single-phase perovskite systems. Further, the ability to stabilize single-phase perovskites with various cations on the B-sites offers possibilities for designing high-performance relaxor ferroelectric materials for piezoelectric, pyroelectric, and electrocaloric applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Dielectric behavior of semiconductors at microwave frequencies
A cylindrical microwave resonant cavity in TE(011) (Transverse Electric) mode is used to study the dielectric relaxation in germanium and silicon. The samples of these semiconductors are used to perturb the electric field in the cavity, and Slater's perturbation equations are used to calculate the real and imaginary parts of the dielectric constant. The dielectric loss of germanium and silicon is studied at different temperatures, and Debye's equations are used to calculate the relaxation time at these temperatures.
Dahiya, Jai N.↗
Interfacial Effects on the Dielectric Properties of Elastomer Composites and Nanocomposites
Elastomer-based composites and nanocomposites are discussed, with the emphasis on the filler and interfacial effects on their dynamics, and the resulting manifestation in their macroscopic dielectric or mechanical response. Specifically, selected polydimethylsiloxane (PDMS)/barium-titanate and styrene-butadiene rubber (SBR)/graphene oxide nanocomposites are discussed, as examples where controlled spatial distribution of filler (structured composites) gives rise to significantly different dielectric and thermomechanical behaviors. Also, ethylene–propylene–diene (EPDM)/carbon black (CB) composites are presented, as examples of systems that exhibit an abnormal temperature dependence of dielectric relaxation; and this response is discussed in the context of CB cluster polarization and quantified through a simple scaling model of the same. Finally, multi-filler EPDM/CB/ceramic elastomer nanocomposites are discussed, as examples of systems with antagonistic interfacial effects between conductive and dielectric fillers, as well as with strong interphase responses that can overwhelm the dielectric contributions from the fillers; in these systems, interphasial responses result in counter-intuitive dielectric behaviors and in strong deviations from standard design principles typically employed in the design of dielectric composite systems.
Li, Bo↗
Characterization of the relationship of the cure cycle chemistry to cure cycle processing properties
Dynamic Dielectric measurements made over a wide range of frequency provide a sensitive and convenient means for monitoring the cure process in thermosets and thermoplastics. The measurement of dielectric relaxation is one of only a few instrumental techniques available for studying molecular properties in both the liquid and solid states. Furthermore, it is probably the only convenient experimental technique for studying the polymerization process of going from a monomeric liquid of varying viscosity to a crosslinked, insoluble, high temperature solid. The objective of the research is to develop on-line dielectric instrumentation for quantitative nondestructive material evaluation and closed loop smart cure cycle control. The key is to relate the chemistry of the cure cycle process to the dielectric properties of the polymer system by correlating the time, temperature, and frequency dependent dielectric measurements with chemical characterization measurements. Measurement of the wide variation in magnitude of the complex permittivity with both frequency and state of cure, coupled with chemical characterization work, have been shown in the laboratory to have the potential to determine: resin quality, composition and age; cure cycle window boundaries; onset of flow and point of maximum flow; extent of and completion of reaction; evolution of volatiles; T sub g; and, crosslinking and molecular weight buildup.
Kranbuehl, D. E.↗
Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism
Abstract The properties of the water network in concentrated HCl acid pools in nanometer‐sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W 0 =9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H + and Cl − ions to adsorb to the micelle interface, together with an acid concentration effect that causes a “traffic jam” in which the short‐circuiting of the hydrogen‐bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.
Adams, Ellen M.↗
Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism
Abstract The properties of the water network in concentrated HCl acid pools in nanometer‐sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W 0 =9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H + and Cl − ions to adsorb to the micelle interface, together with an acid concentration effect that causes a “traffic jam” in which the short‐circuiting of the hydrogen‐bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Jacobian-free Newton–Krylov method for the simulation of non-thermal plasma discharges with high-order time integration and physics-based preconditioning
A preconditioning framework for the numerical simulation of non-thermal streamer discharges is developed using the Jacobian-free Newton-Krylov (JFNK) method. A reduced plasma fluid model is considered, consisting of electrons, one positive ion, one negative ion, and the electrostatic potential. Here, the plasma kinetics model includes ionization, electron-ion recombination, electron attachment, electron detachment, and ion-ion recombination. The governing equations are made dimensionless, discretized in space with finite differences, and integrated in time with a fully implicit method based on high-order backward differentiation formulas. The preconditioning framework is based on a linearized form of the governing equations and physics-based operator splitting. The efficiency of the preconditioning strategy is assessed through two test cases: streamer propagation between parallel plates and an axisymmetric pin-to-pin discharge. The fully implicit approach overcomes traditional restrictions in the time step size due to processes such as electron drift, electron diffusion, and dielectric relaxation. Excellent performance is observed through relevant statistics of the JFNK solver, although the number of linear iterations increases for the pin-to-pin discharge when nonlinear numerical boundary conditions are imposed at the electrodes. Performance studies show scalability with O(100-1000) processors for O(10M) unknowns with ample room for optimization.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Accessing One-Dimensional Chains of Halogenoindates(III) in Organic–Inorganic Hybrids
Organic-inorganic hybrids of halogenoindates(III) are typically represented by one of the zero-dimensional units: InX 4 – , InX 5 2– , InX 6 3– , or In 2 X 11 5– . Higher dimensional anionic forms, although not forbidden, have remained almost elusive. Here, in this study, we report for the first time In 3+ -based organic–inorganic hybrids, (C 4 H 5 N 2 S) 2 InCl 5 and (C 4 H 5 N 2 S) 2 InBr 5 , with 1D anionic chains of trans-halide-bridged InX 6 octahedra whose formation is guided by 2-mercaptopyrimidinium cations (C 4 H 5 N 2 S + ). The chains are characterized by the significant ease of deformation, which is reflected in the elongation of the bridging bonds or the displacement of In 3+ ions. The materials show a robust band gap predominantly governed by C 4 H 5 N 2 S + cations. Dielectric relaxation processes in (C 4 H 5 N 2 S) 2 InBr 5 arise from the cations’ dynamics and suggest the ability of the brominated system to accommodate even larger cations. Our work represents a successful attempt to expand the structural diversity of halogenoindates(III) and opens a pathway to reach multifunctional 1D In 3+ -based hybrids.
36 MATERIALS SCIENCE↗
Quantifying Species Populations in Multivalent Borohydride Electrolytes
Multivalent batteries represent an important beyond Li-ion energy storage concept. The prospect of calcium batteries, in particular, has emerged recently due to novel electrolyte demonstrations, especially that of a ground-breaking combination of the borohydride salt Ca(BH 4 ) 2 dissolved in tetrahydrofuran. Recent analysis of magnesium and calcium versions of this electrolyte led to the identification of divergent speciation pathways for Mg 2+ and Ca 2+ despite identical anions and solvents, owing to differences in cation size and attendant flexibility of coordination. To test these proposed speciation equilibria and develop a more quantitative understanding thereof, we have applied pulsed-field-gradient nuclear magnetic resonance and dielectric relaxation spectroscopy to study these electrolytes. Additionally, concentration-dependent variation in anion diffusivities and solution dipole relaxations, interpreted with the aid of molecular dynamics simulations, confirms these divergent Mg 2+ and Ca 2+ speciation pathways. These results provide a more quantitative description of the electroactive species populations. We find that these species are present in relatively small quantities, even in the highly active Ca(BH 4 ) 2 /tetrahydrofuran electrolyte. This finding helps interpret previous characterizations of metal deposition efficiency and morphology control and thus provides important fundamental insight into the dynamic properties of multivalent electrolytes for next-generation batteries.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ion Pairing and Redissociaton in Low-Permittivity Electrolytes for Multivalent Battery Applications
Detailed speciation of electrolytes as a function of chemical system and concentration provides the foundation for understanding bulk transport as well as possible decomposition mechanisms. In particular, multivalent electrolytes have shown a strong coupling between anodic stability and solvation structure. Furthermore, solvents that are found to exhibit reasonable stability against alkaline-earth metals generally exhibit low permittivity, which typically increases the complexity of the electrolyte species. To improve our understanding of ionic population and associated transport in these important classes of electrolytes, the speciation of Mg(TFSI)2 in monoglyme and diglyme systems is studied via a multiscale thermodynamic model using first-principles calculations for ion association and molecular dynamics simulations for dielectric properties. The results are then compared to Raman and dielectric relaxation spectroscopies, which independently confirm the modeling insights. We find that the significant presence of free ions in the low-permittivity glymes in the concentration range from 0.02 to 0.6 M is well-explained by the low-permittivity redissociation hypothesis. Here, salt speciation is largely dictated by long-range electrostatics, which includes permittivity increases due to polar contact ion pairs. The present results suggest that other low-permittivity multivalent electrolytes may also reach high conductivities as a result of redissociation.
25 ENERGY STORAGE↗
Nanoscale Ion Transport Enhances Conductivity in Solid Polymer-Ceramic Lithium Electrolytes
The predictive design of flexible and solvent-free polymer electrolytes for solid-state batteries requires an understanding of the fundamental principles governing the ion transport. In this work, we establish a correlation among the composite structures, polymer segmental dynamics, and lithium ion (Li + ) transport in a ceramic-polymer composite. Elucidating this structure–property relationship will allow tailoring of the Li + conductivity by optimizing the macroscopic electrochemical stability of the electrolyte. The ion dissociation from the slow polymer segmental dynamics was found to be enhanced by controlling the morphology and functionality of the polymer/ceramic interface. The chemical structure of the Li + salt in the composite electrolyte was correlated with the size of the ionic cluster domains, the conductivity mechanism, and the electrochemical stability of the electrolyte. Polyethylene oxide (PEO) filled with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium bis(fluorosulfonyl) imide (LiFSI) salts was used as a matrix. A garnet electrolyte, aluminum substituted lithium lanthanum zirconium oxide (Al-LLZO) with a planar geometry, was used for the ceramic nanoparticle moieties. Further, the dynamics of the strongly bound and highly mobile Li + were investigated using dielectric relaxation spectroscopy. The incorporation of the Al-LLZO platelets increased the number density of more mobile Li + . The structure of the nanoscale ion-agglomeration was investigated by small-angle X-ray scattering, while molecular dynamics (MD) simulation studies were conducted to obtain the fundamental mechanism of the decorrelation of the Li + in the LiTFSI and LiFSI salts from the long PEO chain.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Highly Altered State of Proton Transport in Acid Pools in Charged Reverse Micelles
Transport mechanisms of solvated protons of 1 M HCl acid pools, confined within reverse micelles (RMs) containing the negatively charged surfactant sodium bis(2-ethylhexyl) sulfosuccinate (NaAOT) or the positively charged cetyltrimethylammonium bromide (CTABr), are analyzed with reactive force field simulations to interpret dynamical signatures from TeraHertz absorption and dielectric relaxation spectroscopy. We find that the forward proton hopping events for NaAOT are further suppressed compared to a nonionic RM, while the Grotthuss mechanism ceases altogether for CTABr. We attribute the sluggish proton dynamics for both charged RMs as due to headgroup and counterion charges that expel hydronium and chloride ions from the interface and into the bulk interior, thereby increasing the pH of the acid pools relative to the nonionic RM. For charged NaAOT and CTABr RMs, the localization of hydronium near a counterion or conjugate base reduces the Eigen and Zundel configurations that enable forward hopping. Thus, localized oscillatory hopping dominates, an effect that is most extreme for CTABr in which the proton residence time increases dramatically such that even oscillatory hopping is slow.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Anion chemical composition of poly(ethylene oxide)-based sulfonylimide and sulfonate lithium ionomers controls ion aggregation and conduction
Maximizing ion conduction in single-ion-conducting ionomers is essential for their application in energy-related technologies such as Li-ion batteries. Understanding the anion chemical composition impacts on ion conduction offers new perspectives to maximize ion transport, since the current approach of lowering T g has apparently reached a limit (lowest T g ~ 190 K, highest conductivity ~10 -5 –10 -4 S cm -1 ). Here, a series of random ionomers are synthesized by copolymerizing poly(ethylene glycol)methacrylate with either sulfonylimide lithium methacrylate (MTLi) or sulfonate lithium methacrylate (MSLi) using reversible addition–fragmentation chain transfer (RAFT) polymerization. Li-Ion conduction and self-diffusion coefficients (DLi+) of the ionomers are characterized with dielectric relaxation spectroscopy (DRS) and pulsed-field-gradient (PFG) NMR diffusometry, respectively. Increasing ion content decreases the Li-ion conductivity and D Li+ , as expected from the increased T g . Moreover, a considerably lower ionic conductivity and D Li+ are observed for MSLi compared to MTLi at constant ion content and T g /T. As revealed from X-ray scattering, strong ion aggregation in MSLi results in much lower conductivity and DLi+ compared with less aggregated MTLi based on the more delocalized sulfonylimide anion. These results emphasize the detrimental and molecularly specific role of ion aggregation in Li-ion conductivity, and highlight the necessity for minimizing ion aggregation via the rational choice of anion chemical composition.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Floating zone crystal growth, structure, and properties of a cubic Li 5.5 La 3 Nb 1.5 Zr 0.5 O 12 garnet-type lithium-ion conductor
As a promising candidate for solid-state electrolytes in Li-ion batteries, the garnet-type Li-ion conductor series Li 5+x La 3 Nb 2-x Zr x O 12 (LLNZO) (0 ≤ x ≤ 2) exhibits high ionic conductivity at room temperature. However, no previous single-crystal growth or characterization has been reported for LLNZO compositions 0 ≤ x ≤ 1. To obtain a complete understanding of the trend in the structure–property relationship in this class of materials, we used the floating zone (FZ) method to grow a single crystal of Li 5.5 La 3 Nb 1.5 Zr 0.5 O 12 that was 4 mm in diameter and 10 mm in length. Using Laue neutron single-crystal diffraction, two distinct Li sites were observed: tetrahedral 24d and octahedral 96h sites. The maximum entropy method (MEM) based on neutron single-crystal diffraction data was used to map Li nuclear density and estimate that the bottleneck of Li transport exists between neighboring tetrahedral and octahedral sites, and that Li is delocalized between split octahedral sites. Room-temperature Li-ion conductivity in Li 5.5 La 3 Nb 1.5 Zr 0.5 O 12 measured with electrochemical impedance spectroscopy (EIS) was 1.37 × 10 -4 S cm -1 . The Li migration activation energy was estimated to be 0.50 eV from EIS and 0.47 eV from dielectric relaxation measurements. The Li-ion jump attempt rate was estimated to be 1.47 × 10 12 Hz while the time scale of successful migration is 10 -7 to 10 -6 s.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
First-Order Individual Gas Sensors as Next Generation Reliable Analytical Instruments
It is conventionally expected that the performance of existing gas sensors may degrade in the field compared to laboratory conditions because (i) a sensor may lose its accuracy in the presence of chemical interferences and (ii) variations of ambient conditions over time may induce sensor-response fluctuations (i.e., drift). Breaking this status quo in poor sensor performance requires understanding the origins of design principles of existing sensors and bringing new principles to sensor designs. Existing gas sensors are single-output (e.g., resistance, electrical current, light intensity, etc.) sensors, also known as zero-order sensors (Karl Booksh and Bruce R. Kowalski, Analytical Chemistry, DOI: 10.1021/ac00087a718). Any zero-order sensor is undesirably affected by variable chemical background and sensor drift that cannot be distinguished from the response to an analyte. To address these limitations, we are developing multivariable gas sensors with independent responses, which are first-order analytical instruments. Here, we demonstrate self-correction against drift in two types of first-order gas sensors that operate in different portions of the electromagnetic spectrum. Our radiofrequency sensors utilize dielectric excitation of semiconducting metal oxide materials on the shoulder of their dielectric relaxation peak and achieve self-correction of the baseline drift by operation at several frequencies. Our photonic sensors utilize nanostructured sensing materials inspired by Morpho butterflies and achieve self-correction of the baseline drift by operation at several wavelengths. These principles of self-correction for drift effects in first-order sensors open opportunities for diverse emerging monitoring applications that cannot afford frequent periodic maintenance that is typical of traditional analytical instruments.
Potyrailo, Radislav A.↗
Roles of temperature, materials, and domain inversion in high-performance, low-bias-drift thin film lithium niobate blue light modulators
We demonstrate a thin film lithium niobate electro-optic modulator operating at 456 nm with an RF voltage-length product of 0.38 V-cm and a bandwidth of 6.9 GHz. We test the dielectric relaxation of the modulator with sweeps of temperature and optical input power, and compare equivalent modulators with electrode materials of Cr-Au, Ti-Au and Al in terms of bias stability and current-voltage characteristics. We demonstrate bias stability over at least 8 hours with Al devices, and show relationships between drift, I-V characteristics and ferroelectric domain switching.
Celik, Oguz Tolga (ORCID:0000000264542306)↗