Pendant Group Functionalization of Cyclic Olefin for High Temperature and High-Density Energy Storage.

High-temperature flexible polymer dielectrics are critical for high-power-density energy storage and conversion under harsh operating conditions. These types of dielectrics will need to simultaneously possess a high bandgap, dielectric constant and glass transition temperature - a substantial challenge when designing novel dielectric polymers. In this work, by varying halogen substituents of an aromatic pendant hanging off a bicyclic mainchain polymer, a class of high-temperature olefins with adjustable thermal stability are obtained, all with uncompromised large bandgaps. Halogens substitution of the pendant groups at para or ortho position of polyoxanorborneneimides (PONB) imparts it with tunable high glass transition temperature from ∼220 to 245 °C, while with also moderate dielectric constant of ∼ 2.8-3.0 and high breakdown strength of ∼625-800 MV/m. A high energy density of 7.1 J/cc at 200 °C is achieved with p-POClNB, representing the highest reported energy density among all-organic homo-polymer dielectrics. Molecular dynamic simulations and ultrafast infrared spectroscopy were used to probe the free volume element distribution and chain relaxations of the polymers to provide insights to the dielectric thermal properties. An increase in free volume element is observed with the change in the pendant group from fluorine to bromine at the para position; however, a decrease in free volume element is observed as we change the pendant group from fluorine to chlorine at the ortho position because of the steric hindrance. Overall, the dielectric constant and band gap remain stable while the glass transition temperature changes more obviously. Consequently, by proper designing the pendant groups, the thermal stability of PONB can be improved for harsh condition electrification. This article is protected by copyright. All rights reserved.

Dynamics of Water Clusters Confined in Ionic Liquid at an Elevated Pressure.

Over the years, numerous experimental and theoretical efforts have been dedicated to investigating the mysteries of water and determining its new unexplored physical properties. Despite this, high-pressure studies of water and aqueous mixtures close to the glass transition still represent an unknown area of research. Herein, we address a fundamental issue: the validity of the density scaling concept for fast water dynamics. For this purpose, we performed ambient and high-pressure dielectric measurements of a supercooled equimolar aqueous mixture of an acidic ionic liquid. All isothermal and isobaric relaxation data describing the time scale of charge transport (τσ) and fast dynamics within the water clusters (τν) reveal visual evidence of a liquid-glass transition. Furthermore, both relaxation processes satisfy the ργ/T scaling concept with a single exponent γ = 0.58. Thus, the scaling exponent is a state-point-independent parameter for the dynamics of water clusters confined in ionic liquid investigated in the pressure range up to 300 MPa.

Combined description of pressure-volume-temperature and dielectric relaxation of several polymeric and low-molecular-weight organic glass-formers using SL-TS2 approach.

We apply our recently-developed mean-field "SL-TS2" (two-state Sanchez-Lacombe) model to simultaneously describe dielectric α-relaxation time, τα, and pressure-volume-temperature (PVT) data in four polymers (polystyrene, poly(methylmethacrylate), poly(vinyl acetate) and poly(cyclohexane methyl acrylate)) and four organic molecular glass formers (ortho-terphenyl, glycerol, PCB-62, and PDE). Previously, it has been shown that for all eight materials, the Casalini-Roland thermodynamical scaling, τα = f(Tvγsp) (where T is temperature and vsp is specific volume) is satisfied (R. Casalini and C. M. Roland, Phys. Rev. E, 2004, 69(6), 62501). It has also been previously shown that the same scaling emerges naturally (for sufficiently low pressures) within the "SL-TS2" framework (V. V. Ginzburg, Soft Matter, 2021, 17, 9094-9106). Here, we fit the ambient pressure curves for the relaxation time and the specific volume as functions of temperature for the eight materials and observe a good agreement between theory and experiment. We then use the Casalini-Roland scaling to convert those results into "master curves", thus enabling predictions of relaxation times and specific volumes at elevated pressures. The proposed approach can be used to describe other glass-forming materials, both low-molecular-weight and polymeric.

Flexible cyclic-olefin with enhanced dipolar relaxation for harsh condition electrification.

Flexible large bandgap dielectric materials exhibiting ultra-fast charging-discharging rates are key components for electrification under extremely high electric fields. A polyoxafluoronorbornene (m-POFNB) with fused five-membered rings separated by alkenes and flexible single bonds as the backbone, rather than conjugated aromatic structure typically for conventional high-temperature polymers, is designed to achieve simultaneously high thermal stability and large bandgap. In addition, an asymmetrically fluorinated aromatic pendant group extended from the fused bicyclic structure of the backbone imparts m-POFNB with enhanced dipolar relaxation and thus high dielectric constant without sacrificing the bandgap. m-POFNB thereby exhibits an unprecedentedly high discharged energy density of 7.44 J/cm3 and high efficiency at 150 °C. This work points to a strategy to break the paradox of mutually exclusive constraints between bandgap, dielectric constant, and thermal stability in the design of all-organic polymer dielectrics for harsh condition electrifications.

Surfactant Modulated Phase Transitions of Liquid Crystals Confined in Electrospun Coaxial Fibers.

Confinement of liquid crystals (LCs) in polymeric fibers offers a promising strategy to control liquid crystal response to external stimuli. Here, the confinement of 4-cyano-4'-pentylbiphenyl (5CB), a nematic liquid crystal, within the core of coaxially electrospun fibers composed of poly(vinylpyrrolidone) (PVP) containing different surfactants is discussed. The effects of surfactant type, surfactant concentration, and core flow rate (confinement) on the LC behavior were demonstrated using polarized optical microscopy, scanning electron microscopy, differential scanning calorimetry, Raman, and dielectric spectroscopy. Introduction of surfactant dopants of varying hydrophilic and hydrophobic components into the sheath altered the interfacial interaction between the PVP sheath and the 5CB core of the fibers. Significant effects on the LC nematic to isotropic phase transition were attributed to changes in surface anchoring between the sheath and core. Confinement of nematic LCs in surfactant doped polymeric fibers demonstrates a facile method for tuning LC phase behavior.

Underwater sound transmission through arrays of disk cavities in a soft elastic medium.

Scattering from a cavity in a soft elastic medium, such as silicone rubber, resembles scattering from an underwater bubble in that low-frequency monopole resonance is obtainable in both cases. Arrays of cavities can therefore be used to reduce underwater sound transmission using thin layers and low void fractions. This article examines the role of cavity shape by microfabricating arrays of disk-shaped air cavities into single and multiple layers of polydimethylsiloxane. Comparison is made with the case of equivalent volume cylinders which approximate spheres. Measurements of ultrasonic underwater sound transmission are compared with finite element modeling predictions. The disks provide a deeper transmission minimum at a lower frequency owing to the drum-type breathing resonance. The resonance of a single disk cavity in an unbounded medium is also calculated and compared with a derived estimate of the natural frequency of the drum mode. Variation of transmission is determined as a function of disk tilt angle, lattice constant, and layer thickness. A modeled transmission loss of 18 dB can be obtained at a wavelength about 20 times the three-layer thickness, and thinner results (wavelength/thickness ∼ 240) are possible for the same loss with a single layer depending on allowable hydrostatic pressure.

Effect of physical aging on Johari-Goldstein relaxation in La-based bulk metallic glass.

The influence of physical aging on the ß relaxation in La60Ni15Al25 bulk metallic glass has been investigated by mechanical spectroscopy. The amplitude of the ß relaxation (ΔG″) decreases while its relaxation time (τ(ß)) increases during aging. We find that, as in organic glasses, the changes of ln (τ(ß)) and ln (ΔG(max) ) are linearly correlated with ln (τ(ß)) = b - a ln (G(max)″). This behavior is discussed in term of the asymmetric double-well potential (ADWP) model, with U and Δ the energies characterizing the ADWP. It is suggested that during aging the ratio U/Δ remains approximately constant, with a value close to the coefficient describing the linear correlation between ln (τ(ß)) and ln (G(max)″)(U/Δ ~ a). Moreover, the evolution versus aging time of ΔG(max) can be described by a simple stretched exponential equation giving values of τ(aging) consistent with tan(δ) measurements during aging. The very similar behavior of the ß relaxation during aging in metallic glasses and organic material strongly suggests a common nature for this relaxation.

Characteristics of the structural and Johari-Goldstein relaxations in Pd-based metallic glass-forming liquids.

The dynamics of Pd-based metallic glass-forming liquids (Pd(40)Ni(10)Cu(30)P(20), Pd(42.5)Ni(7.5)Cu(30)P(20), Pd(40)Ni(40)P(20), and Pd(30)Ni(50)P(20)) was studied by mechanical spectroscopy and modulated differential scanning calorimetry (MDSC). We found that the change in composition has a significant effect on the α relaxation dynamics; the largest difference corresponds to an increase of the glass transition temperature Tg of ∼ 15 K, for materials in which 30% Ni was substituted by 30% Cu (i.e., from Pd(40)Ni(40)P(20) to Pd(40)Ni(10)Cu(30)P(20)). We also found that all Pd-based metallic glasses have very similar fragilities, 59 < m < 67, and Kohlrausch stretched exponents, 0.59 < ßKWW < 0.60. It is interesting that the values of m and ßKWW correlate well with the general relation proposed by Böhmer et al. for nonmetallic glass formers (Böhmer, R.; et al. J. Chem. Phys. 1993, 99, 4201-4209), which for the observed ßKWW values predicts 58 < m < 61. From a linear deconvolution of the α and ß relaxations, we find that the substitution of the Ni with Cu induced a large change in the time constant of the Johari-Goldstein relaxation, τß. The activation energy, Uß, of the ß relaxation was largely independent of chemical composition. In all cases, 25 < Uß/RT < 28, a range in agreement with results for other glass formers (Kudlik, A.; et al. Europhys. Lett. 1997, 40, 649-654 and Ngai, K. L.; et al. Phys. Rev. E 2004, 69, 031501). From the heat capacity and mechanical loss, estimates were obtained for the number of dynamically correlated units, Nc; we find significantly larger values for these metallic glass-forming liquids than Nc for other glass-forming materials.

Relaxation of bulk metallic glasses studied by mechanical spectroscopy.

The relaxational dynamics in metallic glasses (MGs) is investigated by using mechanical spectroscopy. The spectra show that in MGs there are two relaxations: (i) the α relaxation, linked to the glass transition, as observed in other classes of amorphous materials; and (ii) the ß relaxation, well observed below the glass transition, with an intensity strongly dependent on the MG composition, the nature of which has been linked to the local microstructure of MGs. For the investigated MGs we find that the intensity and relaxation time of the ß relaxation depends, in a reproducible fashion, on the thermal history of the samples. During aging experiments, the intensity decreases (as well as the τß) with a time dependence described well by a stretched exponential, with an exponent ß(aging) independent of the driving frequency. Moreover, we find that the activation energy Uß and the peak temperature Tßp of the ß relaxation follow the approximate relationship: Uß ≈ 31.5RTßp (for driving frequency 1 Hz), indicating that the high temperature limit of the peak frequency is approximately the same for all the MGs investigated. Finally, the frequency separation of the α and ß processes in the mechanical loss spectra for La-and Pd-based metallic glasses is tested against the prediction of the Coupling Model.

Pressure evolution of the excess wing in a type-B glass former.

Glass formers are defined as "type B" when they exhibit a distinct Johari-Goldstein (JG) relaxation, but lack an excess loss ("excess wing," EW) in their structural relaxation peak. By studying the dielectric spectra of a well-known type-B glass former under high pressure, we unequivocally show the existence of an EW, simultaneously with the JG relaxation. Moreover, at very high pressures (0.6 GPa), the EW becomes a distinct relaxation peak, although correlated with the structural relaxation. The implication is that the EW, rather than the higher frequency relaxation ascribed to the JG process, is perhaps a universal feature of glass formers, albeit not always discernible at ambient pressure. Our findings may reconcile all opposing points of view present in the literature, as well as indicate that the type-A or type-B classification of glass formers should be modified or even discontinued.

Influence of molecular structure on the dynamics of supercooled van der Waals liquids.

Dielectric spectroscopy was carried out on the van der Waals liquid, 1,1(')-di(4-methoxy-5-methylphenyl)cyclohexane (BMMPC) in the supercooled state at pressures up to 218 MPa. The excess wing in this type-A glass former exhibits a response to pressure and temperature changes that is identical to that of the primary structural relaxation peak, indicating that the two processes reflect correlated molecular motions. Under no conditions was a distinct secondary peak observed in BMMPC, unlike the structurally very similar BMPC [1,1(')-bis(p-methoxyphenyl)cyclohexane]. However, the pressure dependences of both the glass temperature and fragility for the two materials are very close. The fragility is a decreasing function of pressure, although there is no concomitant narrowing of the relaxation peak. The pressure dependence of the relaxation times could be described as a simple volume-activated process, with the activation volume at the glass transition having the same magnitude as the molar volume.