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1.
Phys Chem Chem Phys ; 26(26): 17969-17978, 2024 Jul 03.
Article in English | MEDLINE | ID: mdl-38895835

ABSTRACT

The ground state and excited state resonance dipole-dipole interaction energy between two elongated conducting molecules is explored in this study. We review the current status for ground state interactions. This interaction is found to be of a much longer range than in the case when the molecules are pointlike and nonconducting. These are well known results found earlier by Davies, Ninham, and Richmond, and later, using a different formalism, by Rubio and co-workers. We show how the theory can be extended to excited state interactions. A characteristic property observed from our calculation is that the interaction energy dependence on separation (R) follows f(R)/R2 for both resonance and van der Waals cases in the long-range limit. Under some limits, f(R) has a logarithmic dependency, while under others, it has constant values. We predict an unusual slow decay rate for the energy transfer between conducting molecules.

2.
Phys Chem Chem Phys ; 25(9): 6636-6652, 2023 Mar 01.
Article in English | MEDLINE | ID: mdl-36790196

ABSTRACT

Gas hydrates (GHs) in water close to freezing temperatures can be stabilised via the formation of ice layers. In a recent work [Boström et al., Astron. Astrophys., A54, 650, 2021], it was found that a surface region with partial gas dilution could be essential for obtaining nano- to micron-sized anomalously stabilizing ice layers. In this paper, it is demonstrated that the Casimir-Lifshitz free energy in multi-layer systems could induce thinner, but more stable, ice layers in cavities than those found for gas hydrates in a large reservoir of cold water. The thickness and stability of such ice layers in a pore filled with cold water could influence the leakage of gas molecules. Additional contributions, e.g. from salt-induced stresses, can also be of importance, and are briefly discussed.

3.
Materials (Basel) ; 14(6)2021 Mar 23.
Article in English | MEDLINE | ID: mdl-33806999

ABSTRACT

In the current study, polymer nanocomposites (NCPs) based on poly (vinyl alcohol) (PVA) with altered refractive index and absorption edge were synthesized by means of a solution cast technique. The characterization techniques of UV-Vis spectroscopy and XRD were used to inspect the structural and optical properties of the prepared films. The XRD patterns of the doped samples have shown clear amendments in the structural properties of the PVA host polymer. Various optical parameters were studied to get more insights about the influence of CeO2 on optical properties of PVA. On the insertion of CeO2 nanoparticles (NPs) into the PVA matrix, the absorption edge was found to move to reduced photon energy sides. It was concluded that the CeO2 nanoparticles can be used to tune the refractive index (n) of the host polymer, and it reached up to 1.93 for 7 wt.% of CeO2 content. A detailed study of the bandgap (BG) was conducted using two approaches. The outcomes have confirmed the impact of the nanofiller on the BG reduction of the host polymer. The results of the optical BG study highlighted that it is crucial to address the ε" parameter during the BG analysis, and it is considered as a useful tool to specify the type of electronic transitions. Finally, the dispersion region of n is conferred in terms of the Wemple-DiDomenico single oscillator model.

4.
Materials (Basel) ; 14(3)2021 Jan 26.
Article in English | MEDLINE | ID: mdl-33530457

ABSTRACT

In this study, cobalt-based metal-organic framework (MOF) powder was prepared via the solvothermal method using 2,6-naphthalenedicarboxylic acid (NDC) as the organic linker and N,N-dimethylformamide (DMF) as the solvent. The thermal decomposition of the pristine cobalt-based MOF sample (CN-R) was identified using a thermogravimetric examination (TGA). The morphology and structure of the MOFs were modified during the pyrolysis process at three different temperatures: 300, 400, and 500 °C, which labeled as CN-300, CN-400, and CN-500, respectively. The results were evidenced via field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The crystallite size of all samples was calculated using Scherrer's equation. The smallest crystallite size of 7.77 nm was calculated for the CN-300 sample. Fourier transform infrared spectroscopy (FTIR) spectra were acquired for all the samples. The graphical study of the cyclic voltammogram (CV) gave the reduction and oxidation peaks. The charge transfer resistance and ionic conductivity were studied using electrical impedance spectroscopy (EIS). The galvanostatic charge-discharge (GCD) responses of all samples were analyzed. The relatively high specific capacitance of 229 F g-1 at 0.5 A g-1 was achieved in the sample CN-300, whereby 110% of capacitance was retained after 5000 cycles. These findings highlighted the durability of the electrode materials at high current densities over a long cycle.

5.
Polymers (Basel) ; 13(3)2021 Jan 26.
Article in English | MEDLINE | ID: mdl-33530553

ABSTRACT

The polymer electrolyte system of chitosan/dextran-NaTf with various glycerol concentrations is prepared in this study. The electrical impedance spectroscopy (EIS) study shows that the addition of glycerol increases the ionic conductivity of the electrolyte at room temperature. The highest conducting plasticized electrolyte shows the maximum DC ionic conductivity of 6.10 × 10-5 S/cm. Field emission scanning electron microscopy (FESEM) is used to investigate the effect of plasticizer on film morphology. The interaction between the electrolyte components is confirmed from the existence of the O-H, C-H, carboxamide, and amine groups. The XRD study is used to determine the degree of crystallinity. The transport parameters of number density (n), ionic mobility (µ), and diffusion coefficient (D) of ions are determined using the percentage of free ions, due to the asymmetric vibration (υas(SO3)) and symmetric vibration (υs(SO3)) bands. The dielectric property and relaxation time are proved the non-Debye behavior of the electrolyte system. This behavior model is further verified by the existence of the incomplete semicircle arc from the Argand plot. Transference numbers of ion (tion) and electron (te) for the highest conducting plasticized electrolyte are identified to be 0.988 and 0.012, respectively, confirming that the ions are the dominant charge carriers. The tion value are used to further examine the contribution of ions in the values of the diffusion coefficient and mobility of ions. Linear sweep voltammetry (LSV) shows the potential window for the electrolyte is 2.55 V, indicating it to be a promising electrolyte for application in electrochemical energy storage devices.

6.
Materials (Basel) ; 13(21)2020 Nov 07.
Article in English | MEDLINE | ID: mdl-33171877

ABSTRACT

In this study, structural characterization, electrical properties and energy storage performance of plasticized polymer electrolytes based on polyvinyl alcohol/methylcellulose/ammonium thiocyanate (PVA/MC-NH4SCN) were carried out. An X-ray diffraction (XRD) study displayed that the plasticized electrolyte system with the uppermost value of direct current (DC) ionic conductivity was the most amorphous system. The electrolyte in the present work realized an ionic conductivity of 2.903 × 10-3 Scm-1 at room temperature. The main charge carrier in the electrolyte was found to be the ions with the ionic transference number (tion) of 0.912, compared to only 0.088 for the electronic transference number (telec). The electrochemical stability potential window of the electrolyte is 2.1 V. The specific capacitance was found to reduce from 102.88 F/g to 28.58 F/g as the scan rate increased in cyclic voltammetry (CV) analysis. The fabricated electrochemical double layer capacitor (EDLC) was stable up to 200 cycles with high efficiency. The specific capacitance obtained for the EDLC by using charge-discharge analysis was 132.7 F/g at the first cycle, which is slightly higher compared to the CV plot. The equivalent series resistance (ESR) increased from 58 to 171 Ω throughout the cycles, which indicates a good electrolyte/electrode contact. Ions in the electrolyte were considered to have almost the same amount of energy during the conduction process as the energy density is approximately at 14.0 Wh/kg throughout the 200 cycles. The power density is stabilized at the range of 1444.3 to 467.6 W/kg as the EDLC completed the cycles.

7.
Polymers (Basel) ; 12(11)2020 Nov 17.
Article in English | MEDLINE | ID: mdl-33212879

ABSTRACT

In this work, plasticized polymer electrolyte films consisting of chitosan, ammonium nitrate (NH4NO3) and glycerol for utilization in energy storage devices was presented. Various microscopic, spectroscopic and electrochemical techniques were used to characterize the concerned electrolyte and the electrical double-layer capacitor (EDLC) assembly. The nature of complexation between the polymer electrolyte components was examined via X-ray diffraction analysis. In the morphological study, field emission scanning electron microscopy (FESEM) was used to investigate the impact of glycerol as a plasticizer on the morphology of films. The polymer electrolyte (conducting membrane) was found to have a conductivity of 3.21 × 10-3 S/cm. It is indicated that the number density (n), mobility (µ) and diffusion coefficient (D) of ions are increased with the glycerol amount. The mechanism of charge storing was clarified, which implies a non-Faradaic process. The voltage window of the polymer electrolyte is 2.32 V. It was proved that the ion is responsible for charge-carrying via measuring the transference number (TNM). It was also determined that the internal resistance of the EDLC assembly lay between 39 and 50 Ω. The parameters associated with the EDLC assembly are of great importance and the specific capacitance (Cspe) was determined to be almost constant over 1 to 1000 cycles with an average of 124 F/g. Other decisive parameters were found: energy density (18 Wh/kg) and power density (2700 W/kg).

8.
Polymers (Basel) ; 12(10)2020 Oct 01.
Article in English | MEDLINE | ID: mdl-33019543

ABSTRACT

Compatible green polymer electrolytes based on methyl cellulose (MC) were prepared for energy storage electrochemical double-layer capacitor (EDLC) application. X-ray diffraction (XRD) was conducted for structural investigation. The reduction in the intensity of crystalline peaks of MC upon the addition of sodium iodide (NaI) salt discloses the growth of the amorphous area in solid polymer electrolytes (SPEs). Impedance plots show that the uppermost conducting electrolyte had a smaller bulk resistance. The highest attained direct current DC conductivity was 3.01 × 10-3 S/cm for the sample integrated with 50 wt.% of NaI. The dielectric analysis suggests that samples in this study showed non-Debye behavior. The electron transference number was found to be lower than the ion transference number, thus it can be concluded that ions are the primary charge carriers in the MC-NaI system. The addition of a relatively high concentration of salt into the MC matrix changed the ion transfer number from 0.75 to 0.93. From linear sweep voltammetry (LSV), the green polymer electrolyte in this work was actually stable up to 1.7 V. The consequence of the cyclic voltammetry (CV) plot suggests that the nature of charge storage at the electrode-electrolyte interfaces is a non-Faradaic process and specific capacitance is subjective by scan rates. The relatively high capacitance of 94.7 F/g at a sweep rate of 10 mV/s was achieved for EDLC assembly containing a MC-NaI system.

9.
Polymers (Basel) ; 12(9)2020 Sep 16.
Article in English | MEDLINE | ID: mdl-32947829

ABSTRACT

This research paper investigates the electrochemical performance of chitosan (CS): dextran (DX) polymer-blend electrolytes (PBEs), which have been developed successfully with the incorporation of ammonium hexafluorophosphate (NH4PF6). X-ray diffraction (XRD) analysis indicates that the plasticized electrolyte system with the highest value of direct current (DC) ionic conductivity is the most amorphous system. The glycerol addition increased the amorphous phase and improved the ionic dissociation, which contributed to the enhancement of the fabricated device's performance. Transference number analysis (TNM) has shown that the charge transport process is mainly by ions rather than electrons, as tion = 0.957. The CS:DX:NH4PF6 system was found to decompose as the voltage goes beyond 1.5 V. Linear sweep voltammetry (LSV) revealed that the potential window for the most plasticized system is 1.5 V. The fabricated electrochemical double-layer capacitor (EDLC) was analyzed with cyclic voltammetry (CV) and charge-discharge analysis. The results from CV verify that the EDLC in this work holds the characteristics of a capacitor. The imperative parameters of the fabricated EDLC such as specific capacitance and internal resistance were found to be 102.9 F/g and 30 Ω, respectively. The energy stored and power delivered by the EDLC were 11.6 Wh/kg and 2741.2 W/kg, respectively.

10.
Membranes (Basel) ; 10(6)2020 Jun 25.
Article in English | MEDLINE | ID: mdl-32630546

ABSTRACT

This work indicates that glycerolized chitosan-NH4F polymer electrolytes incorporated with zinc metal complexes are crucial for EDLC application. The ionic conductivity of the plasticized system was improved drastically from 9.52 × 10-4 S/cm to 1.71 × 10-3 S/cm with the addition of a zinc metal complex. The XRD results demonstrated that the amorphous phase was enhanced for the system containing the zinc metal complex. The transference number of ions (tion) and electrons (te) were measured for two of the highest conducting electrolyte systems. It confirmed that the ions were the dominant charge carriers in both systems as tion values for CSNHG4 and CSNHG5 electrolytes were 0.976 and 0.966, respectively. From the examination of LSV, zinc improved the electrolyte electrochemical stability to 2.25 V. The achieved specific capacitance from the CV plot reveals the role of the metal complex on storage properties. The charge-discharge profile was obtained for the system incorporated with the metal complex. The obtained specific capacitance ranged from 69.7 to 77.6 F/g. The energy and power densities became stable from 7.8 to 8.5 Wh/kg and 1041.7 to 248.2 W/kg, respectively, as the EDLC finalized the cycles.

11.
Polymers (Basel) ; 12(6)2020 Jun 24.
Article in English | MEDLINE | ID: mdl-32599794

ABSTRACT

This report presents the preparation and characterizations of solid biopolymer blend electrolyte films of chitosan as cationic polysaccharide and anionic dextran (CS: Dextran) doped with ammonium iodide (NH4I) to be utilized as electrolyte and electrode separator in electrical double-layer capacitor (EDLC) devices. FTIR and XRD techniques were used to study the structural behavior of the films. From the FTIR band analysis, shifting and broadening of the bands were observed with increasing salt concentration. The XRD analysis indicates amorphousness of the blended electrolyte samples whereby the peaks underwent broadening. The analysis of the impedance spectra emphasized that incorporation of 40 wt.% of NH4I salt into polymer electrolyte exhibited a relatively high conductivity (5.16 × 10-3 S/cm). The transference number measurement (TNM) confirmed that ion (tion = 0.928) is the main charge carriers in the conduction process. The linear sweep voltammetry (LSV) revealed the extent of durability of the relatively high conducting film which was 1.8 V. The mechanism of charge storage within the fabricated EDLC has been explained to be fully capacitive behavior with no redox peaks appearance in the cyclic voltammogram (CV). From this findings, four important parameters of the EDLC; specific capacitance, equivalent series resistance, energy density and power density were calculated as 67.5 F/g, 160 ohm, 7.59 Wh/kg and 520.8 W/kg, respectively.

12.
J Phys Chem B ; 124(15): 3103-3113, 2020 Apr 16.
Article in English | MEDLINE | ID: mdl-32208624

ABSTRACT

In view of the vital role of water, exact knowledge of its dielectric function over a large frequency range is important. We report on currently available measurements of the dielectric function of water at room temperature (25 °C) across the full spectrum: microwave, IR, UV, and X-ray (up to 100 eV). We parameterize the complex dielectric function of water with two Debye (microwave) oscillators and high resolution of IR and UV/X-ray oscillators. We also report dielectric parameters for ice-cold water with a microwave/IR spectrum measured at 0.4 °C, while taking the UV spectrum at 25 °C (assuming negligible temperature dependence in UV). We employ van der Waals dispersion interactions to contrast our model of ice-cold water with earlier models. Air bubbles in water and dissolved gas molecules show attraction toward interfaces rather than repulsion. The van der Waals interaction promotes complete freezing rather than supporting a thin layer of water on ice. We infer that premelting is driven by charge and ion adsorption. Density-based extrapolation from warm to cold water of the dielectric function is satisfactory in microwave but poor (40% error) at IR frequencies.

13.
Phys Rev Lett ; 120(13): 131601, 2018 Mar 30.
Article in English | MEDLINE | ID: mdl-29694221

ABSTRACT

The Casimir-Lifshitz torque between two biaxially polarizable anisotropic planar slabs is shown to exhibit a nontrivial sign reversal in its rotational sense. The critical distance a_{c} between the slabs that marks this reversal is characterized by the frequency ω_{c}∼c/2a_{c} at which the in-planar polarizabilities along the two principal axes are equal. The two materials seek to align their principal axes of polarizabilities in one direction below a_{c}, while above a_{c} their axes try to align rotated perpendicular relative to their previous minimum energy orientation. The sign reversal disappears in the nonretarded limit. Our perturbative result, derived for the case when the differences in the relative polarizabilities are small, matches excellently with the exact theory for uniaxial materials. We illustrate our results for black phosphorus and phosphorene.

14.
J Phys Chem A ; 121(51): 9742-9751, 2017 Dec 28.
Article in English | MEDLINE | ID: mdl-29185741

ABSTRACT

Theories for the effective polarizability of a small particle in a medium are presented using different levels of approximation: we consider the virtual cavity, real cavity, and the hard-sphere models as well as a continuous interpolation of the latter two. We present the respective hard-sphere and cavity radii as obtained from density-functional simulations as well as the resulting effective polarizabilities at discrete Matsubara frequencies. This enables us to account for macroscopic media in van der Waals interactions between molecules in water and their Casimir-Polder interaction with an interface.

15.
Opt Lett ; 40(10): 2365, 2015 May 15.
Article in English | MEDLINE | ID: mdl-26393740

ABSTRACT

We elaborate on a recent paper by Hurwitz and Gbur [Opt. Lett.39, 6529 (2014)], dealing with null-field sources. After commenting on their theory in Minkowski space, we show how the theory can be conveniently generalized to the case of curvilinear space.

16.
J Phys Condens Matter ; 27(21): 214008, 2015 Jun 03.
Article in English | MEDLINE | ID: mdl-25965881

ABSTRACT

This paper extends our recent study on Casimir friction forces for dielectric plates moving parallel to each other (Høye and Brevik 2014 Eur. Phys. J. D 68 61), to a case where the plates are no longer restricted to rectilinear motion. Part of the mathematical formalism thereby becomes more cumbersome, but reduces in the end to the form that we expected to be the natural one in advance. As an example, we calculate the Casimir torque on a planar disc rotating with constant angular velocity around its vertical symmetry axis next to another plate.

17.
Phys Rev E Stat Nonlin Soft Matter Phys ; 80(2 Pt 1): 021125, 2009 Aug.
Article in English | MEDLINE | ID: mdl-19792095

ABSTRACT

We consider the Casimir energy in a geometry of an infinite magnetodielectric wedge closed by a circularly cylindrical, perfectly reflecting arc embedded in another magnetodielectric medium, under the condition that the speed of light be the same in both media. An expression for the Casimir energy corresponding to the arc is obtained and it is found that in the limit where the reflectivity of the wedge boundaries tends to unity the finite part of the Casimir energy of a perfectly conducting wedge-shaped sheet closed by a circular cylinder is regained. The energy of the latter geometry possesses divergences due to the presence of sharp corners. We argue how this is a pathology of the assumption of ideal conductor boundaries and that no analogous term enters in the present geometry.

18.
Phys Rev E Stat Nonlin Soft Matter Phys ; 80(1 Pt 1): 011104, 2009 Jul.
Article in English | MEDLINE | ID: mdl-19658650

ABSTRACT

The statistical mechanical approach to Casimir problems for dielectrics separated by a vacuum gap turns out to be compact and effective. A central ingredient of this method is the effect of interacting fluctuating dipole moments of the polarizable particles. At arbitrary temperature the path-integral formulation of quantized particles, developed by Høye-Stell and others, is needed. At high temperature-the limit considered in the present paper-the classical theory is, however, sufficient. Our present theory is related to an idea put forward earlier by Jancovici and Samaj (2004), namely, to evaluate the Casimir force between parallel plates invoking an electronic plasma model and the Debye-Hückel theory for electrolytes. Their result was recently recovered by Høye (2008), using a related statistical mechanical method. In the present paper we generalize this by including a constant permittivity in the description. The present paper generalizes our earlier theory for parallel plates (1998), as well as for spherical dielectrics (2001). We also consider the Casimir force between a polarizable particle and a conductor with a small density of charges, finding agreement with the result recently derived by Pitaevskii (2008).

19.
Phys Rev E Stat Nonlin Soft Matter Phys ; 79(4 Pt 1): 041120, 2009 Apr.
Article in English | MEDLINE | ID: mdl-19518186

ABSTRACT

We re-examine the electrodynamic Casimir effect in a wedge defined by two perfect conductors making dihedral angle alpha=pi/p. This system is analogous to the system defined by a cosmic string. We consider the wedge region as filled with an azimuthally symmetric material, with permittivity and permeability epsilon1, micro1 for distance from the axis ra. The results are closely related to those for a circular-cylindrical geometry, but with noninteger azimuthal quantum number mp. Apart from a zero-mode divergence, which may be removed by choosing periodic boundary conditions on the wedge, and may be made finite if dispersion is included, we obtain finite results for the free energy corresponding to changes in a for the case when the speed of light is the same inside and outside the radius a , and for weak coupling, |epsilon1-epsilon2|<<1, for purely dielectric media. We also consider the radiation produced by the sudden appearance of an infinite cosmic string, situated along the cusp line of the pre-existing wedge.

20.
Phys Rev Lett ; 103(21): 219301; author reply 219302, 2009 Nov 20.
Article in English | MEDLINE | ID: mdl-20366072
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