Exploring supercapacitance of solvothermally synthesized N-rGO sheet: role of N-doping and the insight mechanism.

We demonstrate the method of achieving excellent supercapacitance in nitrogen-doped reduced graphene oxide (N-rGO) sheets by controlling the amount of N-content through the use of different ratios of GO and urea during solvothermal synthesis. Here, urea plays a dual role in reducing GO and simultaneously doping nitrogen into the GO flakes forming exfoliated N-rGO sheets. The nitrogen content in N-rGO samples rises with an increase in the amounts of urea and saturates at a value of ∼14% for the GO : urea ratios beyond 1 : 8. The obtained N-rGO sheets with ∼ 5% N-content (obtained for GO : urea ratio of 1 : 3) were demonstrated as excellent supercapacitor materials. Using a 3-electrode setup, the maximum specific capacitance obtained for this sample was 514 F g-1 at a current density of 0.5 A g-1 (mass normalized current). The insights into the origin of this excellent supercapacitive behavior are explained through our results on optimum N-content, the relative amount of different N-environments, defects/disorders, and the degree of reduction of GO. Importantly, a proper stacking of rGO sheets with moderate N-content (∼5-6%) and a moderate amount of defects is the key to achieve high specific-capacitance. Furthermore, our 2-electrode device demonstrates the excellence of our samples with a Csp of 237 F g-1, a power density of 225 W kg-1, and an energy density of 6.7 W h kg-1 at 0.5 A g-1, exhibiting a high cyclic constancy with high capacitive retention of ∼ 82% even after 8000 cycles. Hence, our work provides a way to control the properties of N-rGO in achieving excellent supercapacitive performance.

Mechanistic insights into the optical limiting performance of carbonaceous nanomaterials embedded with core-shell type graphite encapsulated Co nanoparticles.

Globular amorphous carbonaceous materials embedded with graphite encapsulated metallic Co-nanoparticles with a high degree of crystallinity are synthesized by pyrolysis and demonstrated as excellent candidates for optical limiters. The amount of metal precursor (Co-acetylacetonate) used with toluene for pyrolysis is chosen as a strategy to control the degree of graphitization of graphene-like shells around the embedded Co-nanoparticles and also the crystallinity of these Co nanoparticles in the samples. The graphitic shell with an optimum amount of defects tunes the electronic properties of these nanomaterials, providing the electronic states required for the enhancement of nonlinear optical absorption (NLA) through an excited state absorption (ESA) process. Simultaneously, the increase in the crystallinity of the Co nanoparticle enhances its metallic nature, which helps in increasing NLA performance through the free carrier absorption (FCA) process. The importance of highly metallic Co is to involve both the Co nanoparticle and its graphitic encapsulation in facilitating the FCA process, which substantially enhances NLA. In comparison with many similar samples (e.g., Fe3C@C at 100 µJ of laser energy), our present samples show superior NLA performance even at the much lower laser pulse energy of ∼15 µJ. This performance is much better than many of the present-day NLA materials too. The simple, low-cost and one-step pyrolysis synthesis process makes our materials even more attractive.

Low temperature dielectric properties and NTCR behavior of the BaFe0.5Nb0.5O3 double perovskite ceramic.

The double perovskite-structured barium iron niobate (BaFe0.5Nb0.5O3, BFN), a lead-free ferroelectric, shows a very high dielectric constant value. We report here the temperature dependent dielectric permittivity, impedance and electric modulus behavior of the BFN ceramic studied between 300 K and 20 K. The phase-pure BFN powder sample was synthesized using a conventional solid state reaction route. The microstructure and the temperature dependent dielectric behavior of the sample are correlated. The dipolar and Maxwell-Wagner (M-W) polarizations of the sample show distinctly different relaxation behaviors at the grain and grain boundary (GB) regions. With a decrease in temperature from 300 K to 20 K, the M-W polarization contribution decreases monotonously. Furthermore, due to the ion-blocking effect originating from the atomic disorder at the GB regions, the impedance of the GB is found to be higher than that of the grains. The grains and GB regions were found to have characteristically very different dipolar relaxation times. Interestingly, the dipolar relaxation time distribution is the broadest at 120 K due to the temperature dependent shift of the dipolar relaxation times at the grain and GB regions. Furthermore, our results confirm that the dipolar polarization mechanism in BFN is associated only with short-range movement of the cations. Our systematic investigation provides a detailed understanding of the low temperature dielectric properties of the BaFe0.5Nb0.5O3 ceramic and makes it potentially attractive for low temperature thermistor applications.

Enhancing absorption dominated microwave shielding in Co@C-PVDF nanocomposites through improved magnetization and graphitization of the Co@C-nanoparticles.

Using composites of polyvinylidene fluoride (PVDF) and carbon nanostructures embedded with Co-nanoparticles we demonstrate that electromagnetic shielding effectiveness depends strongly on the graphitic carbon concentration and the magnetic properties of Co-particles. Cobalt nanoparticles encapsulated by graphitic carbon embedded in an amorphous carbon-matrix were synthesized by a one-pot pyrolysis method at two different synthesis temperatures, TS = 800 °C (Co-800) and 1000 °C (Co-1000). We demonstrate that TS plays an important role in determining the structure, morphology and magnetic properties of the carbonaceous matrix, the graphite layer and the Co nanoparticles. Higher amounts of graphitic carbon and high saturation magnetization were observed for the Co-1000 sample than that for the Co-800 sample. We observed that the electromagnetic interference (EMI) shielding behavior of the PVDF-Co-1000 nanocomposite shows higher shielding effectiveness than that of the PVDF-Co-800 specimen. A more inhomogeneous dielectric medium in the PVDF-Co-1000 composite results in higher dielectric loss and impedance mismatch. A direct correlation between the shielding effectiveness with dielectric permittivity and magnetic permeability is demonstrated. The synergy between the multiple reflections at the interfaces and absorption of the microwave radiation in the conducting species confirms that a higher degree of graphitization and highly magnetic particles in nanocomposites are effectively superior for EMI shielding of microwave radiation.

Structural transformations and physical properties of (1 - x) Na0.5Bi0.5TiO3 - x BaTiO3 solid solutions near a morphotropic phase boundary.

Piezoelectric and other physical properties are significantly enhanced at (or near) a morphotropic phase boundary (MPB) in ferroelectrics. MPB materials have attracted significant attention owing to both fundamental physics as well as the possibility of well-regulated energy and information storage devices which are dominated by lead (Pb)-based materials. Here, we report the crystal structure, Raman spectra, dielectric constant and polarization near the MPB of lead free (1 - x) Na0.5Bi0.5TiO3 - x BaTiO3 (0.00 ⩽ x ⩽ 0.10) solid-solution, prepared by sol-gel auto combustion technique and sintered by microwave sintering technique. With the addition of BaTiO3 into Na0.5Bi0.5TiO3, it induces a structural phase transition from R3c (a single phase) to R3c + P4mm (a dual phase) close to x = 0.06 and 0.07 and transform to a high symmetry tetragonal phase P4mm at higher compositions (x = 0.08 to 0.10) as evident from our x-ray Rietveld refinement and Raman spectroscopic results. We perform first-principles calculations based on density functional theory that confirm a structural transition from a rhombohedral to a tetragonal phase under increasing x. In the prepared solid solution, an anomalous enhancement of remnant polarization ([Formula: see text]) was observed for x = 0.06 and 0.07, which has been explained based on the existence of the MPB. On the other hand, the value of coercive field [Formula: see text] was found to be decreased linearly from x = 0.00 to 0.06; it is constant for higher compositions. Further details of the ferroelectric properties on the electric field poled samples have been studied and compared with the as-grown (unpoled) samples.

Carbon encapsulated nanoscale iron/iron-carbide/graphite particles for EMI shielding and microwave absorption.

Homogenously dispersed nanoparticles having a magnetic core and graphitic-carbon shells in amorphous carbon globules are prepared using a low-cost pyrolysis technique. Synergetic microwave absorption in carbon globules embedded with nanoscale iron/iron-carbide graphite (FeC) particles via dielectric, magnetic and Ohmic losses is emphasized in this work. The electromagnetic interference (EMI) shielding properties of the FeC nanoparticles dispersed in polyvinylidene fluoride (PVDF) are studied in the 8-18 GHz frequency range and compared with those of PVDF composites containing similar weight fractions of conducting/magnetic phase micro-particles such as carbonyl iron (CI) or electrolytic iron (EI) or a similar amount of amorphous carbon phase such as amorphous carbon (a-C) globules. The PVDF/FeC composite shows a maximum SET value of -23.9 dB at 18 GHz, as compared to the SET for the other composites. The enhanced EMI shielding in the PVDF/FeC composite is attributed to the increased interfaces of the nanoscale particles, which facilitate enhanced Maxwell-Wagner interfacial polarization. The homogenous dispersion of iron and iron-carbide phases in the carbon matrix of the FeC sample enhances the interfacial polarization and multiple internal scattering of the penetrated EM waves, which get synergistically attenuated by the Ohmic, magnetic and dielectric losses. Based on complex permittivity and permeability results we have calculated the Reflection Loss (RL) of the PVDF/FeC composite. The PVDF-FeC composite shows a RL peak of -40.5 dB for a 4.3 mm thick specimen positioned at 5 GHz frequency. The RL peak is explained using the quarter-wave cancellation model. Our work demonstrates that incorporating carbon globules containing nanoscale magnetic and conducting particles in a polymer matrix, provides an effective way to enhance EMI shielding via absorption of the EM wave in a lightweight thin composite coating.

Electromagnetically induced transparency with resonant nuclei in a cavity.

The manipulation of light-matter interactions by quantum control of atomic levels has had a profound impact on optical sciences. Such manipulation has many applications, including nonlinear optics at the few-photon level, slow light, lasing without inversion and optical quantum information processing. The critical underlying technique is electromagnetically induced transparency, in which quantum interference between transitions in multilevel atoms renders an opaque medium transparent near an atomic resonance. With the advent of high-brilliance, accelerator-driven light sources such as storage rings or X-ray lasers, it has become attractive to extend the techniques of optical quantum control to the X-ray regime. Here we demonstrate electromagnetically induced transparency in the regime of hard X-rays, using the 14.4-kiloelectronvolt nuclear resonance of the Mössbauer isotope iron-57 (a two-level system). We exploit cooperative emission from ensembles of the nuclei, which are embedded in a low-finesse cavity and excited by synchrotron radiation. The spatial modulation of the photonic density of states in a cavity mode leads to the coexistence of superradiant and subradiant states of nuclei, respectively located at an antinode and a node of the cavity field. This scheme causes the nuclei to behave as effective three-level systems, with two degenerate levels in the excited state (one of which can be considered metastable). The radiative coupling of the nuclear ensembles by the cavity field establishes the atomic coherence necessary for the cancellation of resonant absorption. Because this technique does not require atomic systems with a metastable level, electromagnetically induced transparency and its applications can be transferred to the regime of nuclear resonances, establishing the field of nuclear quantum optics.

Collective Lamb shift in single-photon superradiance.

Superradiance, the cooperative spontaneous emission of photons from an ensemble of identical atoms, provides valuable insights into the many-body physics of photons and atoms. We show that an ensemble of resonant atoms embedded in the center of a planar cavity can be collectively excited by synchrotron radiation into a purely superradiant state. The collective coupling of the atoms via the radiation field leads to a substantial radiative shift of the transition energy, the collective Lamb shift. We simultaneously measured the temporal evolution of the superradiant decay and the collective Lamb shift of resonant 57Fe nuclei excited with 14.4-kilo-electron volt synchrotron radiation. Our experimental technique provides a simple method for spectroscopic analysis of the superradiant emission.