An isogeometric scaled boundary plate formulation for the analysis of ionic electroactive paper

In recent years, electroactive paper emerged as a new alternative in the field of smart actuators. It is based on a cellulose material which is able to bend under the influence of an external electric field similarly as ionic polymer metal composites. The bending mechanism is mainly attributed to the migration of ionic charges over the thickness of a thin sheet of paper. The present contribution proposes a numerical framework for the simulation of electroactive paper. It is based on a scaled boundary plate formulation for isogeometric analysis. In contrast to the standard scaled boundary plate approach, the scaling direction is solved numerically by a B-Spline approximation. This allows to render nonlinear effects over the plate thickness as well as displacement fields of higher continuity. The model is applicable to very thin structures such as electroactive paper, and it also captures the nonlinear ionic charge distribution which is coupled to the bending mechanism of the actuator.

Fischer–Tropsch Synthesis: Effect of the Promoter’s Ionic Charge and Valence Level Energy on Activity

In this contribution, we examine the effect of the promoter´s ionic charge and valence orbital energy on the catalytic activity of Fe-based catalysts, based on in situ synchrotron X-ray powder diffraction (SXRPD), temperature-programmed-based techniques (TPR, TPD, CO-TP carburization), and Fischer–Tropsch synthesis catalytic testing studies. We compared the promoting effects of K (a known promoter for longer-chained products) with Ba, which has a similar ionic radius but has double the ionic charge. Despite being partially “buried” in a crystalline BaCO3 phase, the carburization of the Ba-promoted catalyst was more effective than that of K; this was primarily due to its higher (2+) ionic charge. With Ba2+, higher selectivity to methane and lighter products were obtained compared to the K-promoted catalysts; this is likely due to Ba´s lesser capability of suppressing H adsorption on the catalyst surface. An explanation is provided in terms of a more limited mixing between electron-filled Ba2+ 5p and partially filled Fe 3d orbitals, which are expected to be important for the chemical promotion, as they are further apart in energy compared to the K+ 3p and Fe 3d orbitals.

Transient Current in Graphene Transistors Under Single- Proton Irradiation

Two-dimensional materials and their multilayers or heterostructures are promising candidates for optoelectronic devices. Their performance such as the transient current can be remarkably modified under irradiation since the atoms are extremely exposed. This effect, however, still lacks theoretical understanding. Using real-time time-dependent density functional theory extended to open systems for electrons and Ehrenfest dynamics for the moving ion, we explore the single-ion irradiation effects on graphene electronics. Perturbed electronic transport is identified in a field-effect transistor setup. The peak transient current is calculated as the key indicator to quantify the irradiation effects, the irradiation-energy dependence of which shows distinction from the stopping power that was well understood in recent studies. We find that the perturbation in transient current is driven by delocalized plasmonic excitation, in contrast to the localized electronic excitation that has a strong impact on the stopping power. The site dependence of transient current is determined by the local electron density and ionic charge, which highlights the roles of the lattice and electronic structures of materials. Following these understandings and the database developed for typical space-irradiation conditions, the device responses of graphene nanoelectronics can be modeled. These results and methods lay the ground for the material-informed design of nanoelectronics in, for example, space applications.

The Inhomogeneity of Composition Along the Magnetic Cloud Axis

Coronal mass ejections (CMEs) are one of the most energetic explosions in the solar system. It is generally accepted that CMEs result from eruptions of magnetic flux ropes, which are dubbed as magnetic clouds (MCs) in interplanetary space. The composition (including the ionic charge states and elemental abundances) is determined prior to and/or during CME eruptions in the solar atmosphere and does not alter during MC propagation to 1 AU and beyond. It has been known that the composition is not uniform within a cross section perpendicular to the MC axis, and the distribution of ionic charge states within a cross section provides us an important clue to investigate the formation and eruption processes of flux ropes due to the freeze-in effect. The flux rope is a three-dimensional magnetic structure intrinsically, and it remains unclear whether the composition is uniform along the flux rope axis as most MCs are only detected by one spacecraft. In this study, we report an MC that was observed by Advanced Composition Explorer at ∼1 AU during March 4–6, 1998, and Ulysses at ∼5.4 AU during March 24–28, 1998, sequentially. At these times, both spacecraft were located around the ecliptic plane, and the latitudinal and longitudinal separations between them were ∼2.2° and ∼5.5°, respectively. It provides us an excellent opportunity to explore the axial inhomogeneity of flux rope composition, as both spacecraft almost intersected the cloud center at different sites along its axis. Our study shows that the average values of ionic charge states exhibit significant difference along the axis for carbon, and the differences are relatively slight but still obvious for charge states of oxygen and iron as well as the elemental abundances of iron and helium. Besides the means, the composition profiles within the cloud measured by both spacecraft also exhibit some discrepancies. We conclude that the inhomogeneity of composition exists along the cloud axis.

Influence of LiCl and AgNO3 Doping on the Electrical Conductivity of PVA Flexible Electrolyte Polymer Film

Recently, the electrical conductive electrolyte based on flexible polymeric films have been attracted much attentions, due to their applications in batteries, thermoelectrics, temperature sensors and others. In this regard, two polymeric electrolytes (PVA/LiCl) and (PVA/AgNO3) films have been engineered and the influence of the dopants and the annealing temperature on the structural, morphology and ac and dc conductivities is extensively studied. It was found that the films crystallinity has the order PVA/AgNO3 (49.44%) > PVA (38.64%) > PVA/LiCl (26.82%). Additionally, the dc conductivity of the films is increased with embedding the dopants into the PVA as the order PVA/AgNO3 (13.7 × 10−4 S/cm) > PVA/LiCl (1.63 × 10−5 S/cm) > PVA (1.71 × 10−6 S/cm) at 110 °C. It is also found that there is a sharp increase for σac as the frequency increases up to 107 Hz and also as the temperature increases to 110 °C. However, the order of increasing the σac is PVA/LiCl (155 × 10−3 S/cm) > PVA/AgNO3 (2.5 × 10−5 S/cm) > PVA (2 × 10−6 S/cm) at f = 107 Hz and 110 °C. The values of exponent are 0.870, 0.405 and 0.750 for PVA, PVA/AgNO3 and PVA/LiCl, respectively, and it is increased as the temperature increases for PVA and PVA/LiCl, but it is decreased for PVA/AgNO3. The activation energies Ea are 0.84, 0.51 and 0.62 eV for PVA, PVA/AgNO3 and PVA/LiCl, respectively. Moreover, the values of activation energy for charge carrier migration Em are 0.60, 0.34 and 0.4 eV for PVA, PVA/AgNO3 and PVA/LiCl, respectively. By using a simple approximation, the carrier concentration, carrier mobility and carrier diffusivity are calculated, and their values are increased as the temperature increases for all samples, but they are higher for PVA/LiCl than that of PVA/AgNO3. These results are discussed in terms of some obtained parameters such as hopping frequency, free volume and chain mobility. Interestingly, the conduction mechanism was found to be the electronic charge hopping for PVA and PVA/LiCl films, however it was found to be the ionic charge diffusion (n < 0.5) for PVA/AgNO3 film. It has been predicted that these electrolytic films have a prospective applications in batteries design, temperature sensors, electronic and wearable apparatuses at an affordable cost.

Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds

Most of TM6-cluster compounds (TM = transition metal) are soluble in polar solvents, in which the cluster units commonly remain intact, preserving the same atomic arrangement as in solids. Consequently, the redox potential is often used to characterize structural and electronic features of respective solids. Although a high lability and variety of ligands allow for tuning of redox potential and of the related spectroscopic properties in wide ranges, the mechanism of this tuning is still unclear. Crystal chemistry approach was applied for the first time to clarify this mechanism. It was shown that there are two factors affecting redox potential of a given metal couple: Lever’s electrochemical parameters of the ligands and the effective ionic charge of TM, which in cluster compounds differs effectively from the formal value due to the bond strains around TM atoms. Calculations of the effective ionic charge of TMs were performed in the framework of bond valence model, which relates the valence of a bond to its length by simple Pauling relationship. It was also shown that due to the bond strains the charge depends mainly on the atomic size of the inner ligands.

The Casimir Interaction between Spheres Immersed in Electrolytes

We investigate the Casimir interaction between two dielectric spheres immersed in an electrolyte solution. Since ionized solutions typically correspond to a plasma frequency much smaller than kBT/ℏ at room temperature, only the contribution of the zeroth Matsubara frequency is affected by ionic screening. We follow the electrostatic fluctuational approach and derive the zero-frequency contribution from the linear Poisson-Boltzmann (Debye-Hückel) equation for the geometry of two spherical surfaces of arbitrary radii. We show that a contribution from monopole fluctuations, which is reminiscent of the Kirkwood-Shumaker interaction, arises from the exclusion of ionic charge in the volume occupied by the spheres. Alongside the contribution from dipole fluctuations, such monopolar term provides the leading-order Casimir energy for very small spheres. Finally, we also investigate the large sphere limit and the conditions for validity of the proximity force (Derjaguin) approximation. Altogether, our results represent the first step towards a full scattering approach to the screening of the Casimir interaction between spheres that takes into account the nonlocal response of the electrolyte solution.

Chemical-Physical Behaviour of Microgels Made of Interpenetrating Polymer Networks of PNIPAM and Poly(acrylic Acid)

Microgels composed of stimuli responsive polymers have attracted worthwhile interest as model colloids for theorethical and experimental studies and for nanotechnological applications. A deep knowledge of their behaviour is fundamental for the design of new materials. Here we report the current understanding of a dual responsive microgel composed of poly(N-isopropylacrylamide) (PNIPAM), a temperature sensitive polymer, and poly(acrylic acid) (PAAc), a pH sensitive polymer, at different temperatures, PAAc contents, concentrations, solvents and pH. The combination of multiple techniques as Dynamic Light Scattering (DLS), Raman spectroscopy, Small Angle Neutron Scattering (SANS), rheology and electrophoretic measurements allow to investigate the hydrodynamic radius behaviour across the typical Volume Phase Transition (VPT), the involved molecular mechanism and the internal particle structure together with the viscoelastic properties and the role of ionic charge in the aggregation phenomena.

Light-Modulated Cationic and Anionic Transport Across Protein Biopolymers

Light is a convenient source of energy and the heart of light-harvesting natural systems and devices. Here, we show light-modulation of both the chemical nature and ionic charge carrier concentration within a protein-based biopolymer that was covalently functionalized with photoacids or photobases. Using steady-state and time-resolved fluorescence, we explore the capability of the biopolymer-tethered photoacids and photobases to undergo excited-state proton transfer and capture (ESPT and ESPC), respectively. Various electrical measurements show that both the photoacid- and photobase-functionalized biopolymers exhibit an impressive increase in ionic conductivity upon light irradiation, which can be modulated by the light intensity. Whereas ESPT-induced cationic protons are the charge carriers for the photoacid-functionalized biopolymer, ESPC-induced water-derived anionic hydroxides are the suggested charge carriers for the photobase-functionalized biopolymer. Our work introduces a versatile toolbox to light?modulate charge carriers in polymers and taking together the attractive environmental nature of our new light-modulated ionic-conductive biopolymers, they can be considered for various photoelectrochemical applications. <br>