Electric field-induced clustering in nanocomposite films of highly polarizable inclusions.

A nanocomposite film containing highly polarizable inclusions in a fluid background is explored when an external electric field is applied perpendicular to the planar film. For small electric fields, the induced dipole moments of the inclusions are all polarized in field direction, resulting in a mutual repulsion between the inclusions. Here we show that this becomes qualitatively different for high fields: the total system self-organizes into a state which contains both polarizations, parallel and antiparallel to the external field such that a fraction of the inclusions is counter-polarized to the electric field direction. We attribute this unexpected counter-polarization to the presence of neighboring dipoles which are highly polarized and locally revert the direction of the total electric field. Since dipoles with opposite moments are attractive, the system shows a wealth of novel equilibrium structures for varied inclusion density and electric field strength. These include fluids and solids with homogeneous polarizations as well as equilibrium clusters and demixed states with two different polarization signatures. Based on computer simulations of an linearized polarization model, our results can guide the control of nanocomposites for various applications, including sensing external fields, directing light within plasmonic materials, and controlling the functionality of biological membranes.

Nonlinear ferroelectric characteristics of barium titanate nanocrystals determined via a polymer nanocomposite approach.

The growing demand for high energy storage materials has garnered substantial attention towards lead-free ferroelectric nanocrystals (NCs), such as BaTiO3 (BTO), for next-generation multilayer ceramic capacitors. Notably, it remains challenging to accurately measure the dielectric constant and polarization-electric field (P-E) hysteresis loop for BTO NCs. Herein, we report on nonlinear ferroelectric characteristics of BTO NCs via a polymer nanocomposite approach. Specifically, poly(vinyl pyrrolidone) (PVP)/BTO nanocomposite films of 3-10 µm thickness, containing 380 nm tetragonal-phased and 60 nm cubic-phased BTO NCs with uniform particle dispersion, were prepared. Theoretical deconvolution of the broad experimental P-E loops of the PVP/BTO NC composite films revealed three contributions, that is, the linear deformational polarization of the nanocomposites, the polarization of BTO NCs (Pp), and the polarization from strong particle-particle interactions. Using different mixing rules and nonlinear dielectric analysis, the overall dielectric constants of BTO NCs were obtained, from which the internal field in the BTO NCs (Ep) was estimated. Consequently, the Pp-Ep hysteresis loops were obtained for the BTO380 and BTO60 NCs. Interestingly, BTO380 exhibited square-shaped ferroelectric loops, whereas BTO60 displayed slim paraelectric loops. This work presents a robust and versatile route to extract the Pp-Ep loops of ferroelectric NCs from polymer/ceramic nanocomposites.

Structural correlations and phase separation in binary mixtures of charged and neutral colloids.

Structural correlations between colloids in a binary mixture of charged and neutral spheres are calculated using computer simulations of the primitive model with explicit microions. For aqueous suspensions in a solvent of large dielectric constant, the traditional Derjaguin-Landau-Vervey-Overbeek (DLVO) theory of linear screening, supplemented with hard core interactions, reproduces the structural correlations obtained in the full primitive model quantitatively. However, for lower dielectric contrast, the increasing Coulomb coupling between the counterions and charged colloids results in strong deviations. We find a fluid-fluid phase separation into two regions either rich in charged or rich in neutral colloids, which is not reproduced by DLVO theory. Our results are verifiable in scattering or real-space experiments on charged-neutral mixtures of colloids or nanoparticles.

Structural correlations in highly asymmetric binary charged colloidal mixtures.

We explore structural correlations of strongly asymmetric mixtures of binary charged colloids within the primitive model of electrolytes considering large charge and size ratios of 10 and higher. Using computer simulations with explicit microions, we obtain the partial pair correlation functions between the like-charged colloidal macroions. Interestingly the big-small correlation peak amplitude is smaller than that of the big-big and small-small macroion correlation peaks, which is unfamiliar for additive repulsive interactions. Extracting optimal effective microion-averaged pair interactions between the macroions, we find that on top of non-additive Yukawa-like repulsions an additional shifted Gaussian attractive potential between the small macroions is needed to accurately reproduce their correct pair correlations. For small Coulomb couplings, the behavior is reproduced in a coarse-grained theory with microion-averaged effective interactions between the macroions. However, the accuracy of the theory deteriorates with increasing Coulomb coupling. We emphasize the relevance of entropic interactions exerted by the microions on the macroions. Our results are experimentally verifiable in binary mixtures of micron-sized colloids and like-charge nanoparticles.

Hard-to-soft transition-enhanced piezoelectricity in poly(vinylidene fluoride) via relaxor-like secondary crystals activated by high-power ultrasonication.

Although high piezoelectric coefficients have recently been observed in poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] random copolymers, they have low Curie temperatures, which makes their piezoelectricity thermally unstable. It has been challenging to achieve high piezoelectric performance from the more thermally stable PVDF homopolymer. In this report, we describe how high-power ultrasonic processing was used to induce a hard-to-soft piezoelectric transition and improve the piezoelectric coefficient d31 in neat PVDF. After high-power ultrasonication for 20 min, a uniaxially stretched and poled PVDF film exhibited a high d31 of 50.2 ± 1.7 pm V-1 at room temperature. Upon heating to 65 °C, the d31 increased to a maximum value of 76.2 ± 1.2 pm V-1, and the high piezoelectric performance persisted up to 110 °C. The enhanced piezoelectricity was attributed to the relaxor-like secondary crystals in the oriented amorphous fraction, broken off from the primary crystals by ultrasonication, as suggested by differential scanning calorimetry and broadband dielectric spectroscopy studies.

Challenges and Opportunities of Polymer Nanodielectrics for Capacitive Energy Storage.

With the modern development of power electrification, polymer nanocomposite dielectrics (or nanodielectrics) have attracted significant research attention. The idea is to combine the high dielectric constant of inorganic nanofillers and the high breakdown strength/low loss of a polymer matrix for higher energy density polymer film capacitors. Although impressively high energy density has been achieved at the laboratory scale, there is still a large gap from the eventual goal of polymer nanodielectric capacitors. In this review, we focus on essential material issues for two types of polymer nanodielectrics, polymer/conductive nanoparticle and polymer/ceramic nanoparticle composites. Various material design parameters, including dielectric constant, dielectric loss, breakdown strength, high temperature rating, and discharged energy density will be discussed from both fundamental science and high-voltage capacitor application points of view. The objective is to identify advantages and disadvantages of the polymer nanodielectric approach against other approaches utilizing neat dielectric polymers and ceramics. Given the state-of-the-art understanding, future research directions are outlined for the continued development of polymer nanodielectrics for electric energy storage applications.

Enhanced piezoelectricity from highly polarizable oriented amorphous fractions in biaxially oriented poly(vinylidene fluoride) with pure ß crystals.

Piezoelectric polymers hold great potential for various electromechanical applications, but only show low performance, with |d33 | < 30 pC/N. We prepare a highly piezoelectric polymer (d33 = -62 pC/N) based on a biaxially oriented poly(vinylidene fluoride) (BOPVDF, crystallinity = 0.52). After unidirectional poling, macroscopically aligned samples with pure ß crystals are achieved, which show a high spontaneous polarization (Ps) of 140 mC/m2. Given the theoretical limit of Ps,ß = 188 mC/m2 for the neat ß crystal, the high Ps cannot be explained by the crystalline-amorphous two-phase model (i.e., Ps,ß = 270 mC/m2). Instead, we deduce that a significant amount (at least 0.25) of an oriented amorphous fraction (OAF) must be present between these two phases. Experimental data suggest that the mobile OAF resulted in the negative and high d33 for the poled BOPVDF. The plausibility of this conclusion is supported by molecular dynamics simulations.

Length segregation in mixtures of spherocylinders induced by imposed topological defects.

We explore length segregation in binary mixtures of spherocylinders of lengths L1 and L2 which are tangentially confined on a spherical surface of radius R. The orientation of the spherocylinders is constrained along an externally imposed direction field on the sphere which is either along the longitude or the latitude lines of the sphere. In both situations, integer orientational defects at the poles are imposed. Using computer simulations we show that these topological defects induce a complex segregation picture also depending on the length ratio factor γ = L2/L1 and the total packing fraction η of the spherocylinders. When the binary mixture is aligned along the longitude lines of the sphere, shorter rods tend to accumulate at the topological defects of the polar caps whereas longer rods occupy the central equatorial area of the spherical surface. In the reverse case of latitude ordering, a new state can emerge where longer rods are predominantly both in the cap and in the equatorial areas and shorter rods are localized in between. As a reference situation, we consider a defect-free situation in the flat plane and do not find any length segregation there at similar γ and η; hence, the segregation is purely induced by the imposed topological defects. We also develop an Onsager-like density functional theory which is capable of predicting length segregation in ordered mixtures. At low density, the results of this theory are in good agreement with the simulation data.

Smectic monolayer confined on a sphere: topology at the particle scale.

The impact of topology on the structure of a smectic monolayer confined to a sphere is explored by particle-resolved computer simulations of hard rods. The orientations of the particles are tangential to the sphere and either free or restricted to a prescribed director field with a latitude or longitude orderings. Depending on the imprinted topology, a wealth of different states are found including equatorial smectic with isotropic poles, equatorial smectic with empty poles, a broken egg-shell like modulated smectic, a capped nematic with equatorial bald patches, equatorial nematic with empty poles, and a situation with 4 or 8 half-strength topological defects. Potentially these states could be verified in experiments with Pickering emulsions of droplets with colloidal rods. The unique nature of dipolar structures consisting of positive and negative half-strength disclinations is revealed. These structures, classified by their density and interaction with other defects in the system, relieve the strain of the poles by separating closely positioned half-strength defects. The proximity of these structures to the half-strength defects might enhance the structural diffusion of the defects across the system.

Dipole correlation effects on the local field and the effective dielectric constant in composite dielectrics containing high-k inclusions.

Mixing dielectric polymers with high permittivity (high-k) inclusions can affect their electrical properties. In actuation applications of dielectric elastomers, the polarized inclusions generate additional volume polarization-related electrostriction. In energy storage applications, it is possible to store more energy in dielectric composites because of additional polarization of the inclusions and interfaces. However, mixing an electroactive polymer with high-k inclusions also brings several disadvantages. The expulsion of the field from the interior of high-k fillers and the presence of two poles on the filler surface along the applied field direction result in higher local fields EL near the inclusion poles. The resulting field enhancement lowers the breakdown field (Eb) threshold for the material and therefore compromises the actuation and energy storage capabilities of dielectric composites. To mitigate this issue, the dependence of EL on the morphology of inclusion distribution, the field localization effect in chained configurations, and the role of the dipole-dipole correlation effects in the enhancement of the dipolar field of inclusions are analyzed. We show that the dipolar correlation effects are strong in large inclusion composites and their contribution to the inclusion dipole moment µ and to the local fields EL can reach 30-50%. A new method for deriving the composite permittivity from the field EL distribution, based on a caged probe technique, is also presented.

A simulation study of the electrostriction effects in dielectric elastomer composites containing polarizable inclusions with different spatial distributions.

Controlled actuation of electroactive polymers with embedded high dielectric nanoparticles is theoretically analyzed. If the inclusions are placed randomly in the elastomer body, the composite always contracts along the direction of the applied field. For a simple cubic distribution of inclusions, contraction occurs if the applied field is directed along the [001] direction of the lattice. For inclusions occupying the sites of other lattice structures such as body-centered or face-centered cubic crystals, the composite elongates along the field direction if it is applied along the [001] direction. The stability of the elongation against the imperfectness of the lattice site positions and the distortion ratio of the initial structures are examined. Finite elongation windows show up for the initially distorted body-centered cubic and face-centered cubic crystals as a function of the distortion ratio of the initial structure. The existence of these elongation windows are also predicted from the analysis of the electrostatic energy of the distorted body-centered cubic and face-centered cubic lattice structures. Our results indicate that the electrostriction effect, which is the main contribution to the actuation of low aspect-ratio composites, strongly depends on the geometry of the spatial distribution of nanoparticles, and can thereby largely be tuned.

Semicrystalline Structure-Dielectric Property Relationship and Electrical Conduction in a Biaxially Oriented Poly(vinylidene fluoride) Film under High Electric Fields and High Temperatures.

Poly(vinylidene fluoride) (PVDF)-based homopolymers and copolymers are attractive for a broad range of electroactive applications because of their high dielectric constants. Especially, biaxially oriented PVDF (BOPVDF) films exhibit a DC breakdown strength as high as that for biaxially oriented polypropylene films. In this work, we revealed the molecular origin of the high dielectric constant via study of a commercial BOPVDF film. By determination of the dielectric constant for the amorphous phase in BOPVDF, a high value of ca. 21-22 at 25 °C was obtained, and a three-phase (i.e., lamellar crystal/oriented interphase/amorphous region) semicrystalline model was proposed to explain this result. Meanwhile, electronic conduction mechanisms in BOPVDF under high electric fields and elevated temperatures were investigated by thermally stimulated depolarization current (TSDC) spectroscopy and leakage current studies. Space charge injection from metal electrodes was identified as a major factor for electronic conduction when BOPVDF was poled above 75 °C and 20 MV/m. In addition, when silver or aluminum were used as electrodes, new ions were generated from electrochemical reactions under high fields. Due to the electrochemical reactions between PVDF and the metal electrode, a question is raised for practical electrical applications using PVDF and its copolymers under high-field and high-temperature conditions. A potential method to prevent electrochemical degradation of PVDF is proposed in this study.

Enhanced ionic diffusion in ionomer-filled nanopores.

Coarse-grained simulations in the united-atom-model approximation are used to investigate confinement-induced morphological changes in Nafion-like ionomers. The system we study models a cylindrical pore in a hydrophobic matrix of supporting material with pore diameters that vary from 0.7 to 3.96 nm. Simulation results indicate a strong dependence of the equilibrium ionomer structures both on the pore diameter and on the sulfonate concentration in the pore. In the case of larger pores, the ionic clustering has the shape of a branched wire-like network oriented parallel to the pore axis. In the case of narrow pores, the ionic clusters occupy the pore center and exhibit strong density modulations both along the pore axis and across the pore diameter. The calculated diffusion coefficients for the ions indicate a sharp increase within the narrow pores. This finding is explained by ballistic-type ionic motion at shorter times and by the collective motion of ions in hydrophilic clusters. The influence of the hydrophobic walls on the distribution of ions and solvent molecules is discussed.

Highly asymmetric electrolytes in the primitive model: hypernetted chain solution in arbitrary spatial dimensions.

The pair-correlation functions for fluid ionic mixtures in arbitrary spatial dimensions are computed in hypernetted chain (HNC) approximation. In the primitive model (PM), all ions are approximated as nonoverlapping hyperspheres with Coulomb interactions. Our spectral HNC solver is based on a Fourier-Bessel transform introduced by Talman (J. Comput. Phys. 1978, 29, 35), with logarithmically spaced computational grids. Numeric efficiency for arbitrary spatial dimensions is a commonly exploited virtue of this transform method. Here, we highlight another advantage of logarithmic grids, consisting in efficient sampling of pair-correlation functions for highly asymmetric ionic mixtures. For three-dimensional fluids, ion size and charge-ratios larger than 1000 can be treated, corresponding to hitherto computationally not accessed micrometer-sized colloidal spheres in 1-1 electrolyte. Effective colloidal charge numbers are extracted from our PM results. For moderately large ion size and charge-asymmetries, we present molecular dynamics simulation results that agree well with the approximate HNC pair correlations.

Simulation study of poled low-water ionomers with different architectures.

The role of the ionomer architecture in the formation of ordered structures in poled membranes is investigated by molecular dynamics computer simulations. It is shown that the length of the sidechain L(s) controls both the areal density of cylindrical aggregates N(c) and the diameter of these cylinders in the poled membrane. The backbone segment length L(b) tunes the average diameter D(s) of cylindrical clusters and the average number of sulfonates N(s) in each cluster. A simple empirical formula is noted for the dependence of the number density of induced rod-like aggregates on the sidechain length L(s) within the parameter range considered in this study.

Doubled heterogeneous crystal nucleation in sediments of hard sphere binary-mass mixtures.

Crystallization during the sedimentation process of a binary colloidal hard spheres mixture is explored by Brownian dynamics computer simulations. The two species are different in buoyant mass but have the same interaction diameter. Starting from a completely mixed system in a finite container, gravity is suddenly turned on, and the crystallization process in the sample is monitored. If the Peclet numbers of the two species are both not too large, crystalline layers are formed at the bottom of the cell. The composition of lighter particles in the sedimented crystal is non-monotonic in the altitude: it is first increasing, then decreasing, and then increasing again. If one Peclet number is large and the other is small, we observe the occurrence of a doubled heterogeneous crystal nucleation process. First, crystalline layers are formed at the bottom container wall which are separated from an amorphous sediment. At the amorphous-fluid interface, a secondary crystal nucleation of layers is identified. This doubled heterogeneous nucleation can be verified in real-space experiments on colloidal mixtures.

A simulation study of field-induced proton-conduction pathways in dry ionomers.

The morphological changes that can be induced in a dry ionomer by application of a strong electric field have been studied by means of computer simulation. The internal energy of the membrane at first slowly decreases with increasing field, but then rapidly increases after a certain threshold field is reached. This effect is interpreted as the reorganization of interacting head group dipoles in response to the external perturbation. The resulting morphology contains continuous channels of hydrophilic material capable of facilitating proton conduction. Upon removal of the poling field, the system does not return to its original morphology, but retains the anisotropic structure of the poled material. The poled structure appears to be thermodynamically stable, as confirmed by calculations of the Helmholtz energy of the original and poled samples.

Simulation study of field-induced morphological changes in a proton-conducting ionomer.

A simulation study was made of the effects of strong electric fields on the morphology of a Nafion-like ionomer at various levels of hydration. The results of united-atom molecular-dynamics computations showed a self-organization of the side chain terminal groups into cylindrical clusters. The walls of these clusters contain the sulfonate dipoles, while the interior holds the majority of the water molecules. These cylindrical structures then align to form an hexatic array aligned along the direction of the applied electric field. The hexatic morphology persists after the removal of the field. A calculation by means of the Kirkwood coupling parameter method shows the Helmholtz free energy of the hexatic morphology of the poled membrane to be lower than that of the initial isotropic material, even in the absence of the applied field.

Predicted electric-field-induced hexatic structure in an ionomer membrane.

Coarse-grained molecular-dynamics simulations were used to study the morphological changes induced in a Nafion-like ionomer by the imposition of a strong electric field. We observe the formation of structures aligned along the direction of the applied field. The polar head groups of the ionomer sidechains aggregate into clusters, which then form rodlike formations which assemble into a hexatic array aligned with the direction of the field. Occasionally these lines of sulfonates and protons form a helical structure. Upon removal of the electric field, the hexatic array of rodlike structures persists and has a lower calculated free energy than the original isotropic morphology.

Simulation study of the correlation between structure and conductivity in stretched nafion.

We have used coarse-grained simulation methods to investigate the effect of stretching-induced structure orientation on the proton conductivity of Nafion-like polymer electrolyte membranes. Our simulations show that uniaxial stretching causes the hydrophilic regions to become elongated in the stretching direction. This change has a strong effect on the proton conductivity, which is enhanced along the stretching direction, while the conductivity perpendicular to the stretched polymer backbone is reduced. In a humidified membrane, stretching also causes the perfluorinated side chains to tend to orient perpendicular to the stretching axis. This in turn affects the distribution of water at low water contents. The water forms a continuous network with narrow bridges between small water clusters absorbed in head group multiplets. In a dry membrane the side chains orient along the stretching direction.