Cu(i) substituted wurtzite ZnO: a novel room temperature lead free ferroelectric and high-κ giant dielectric

Semiconducting wurtzite ZnO, with the highest incipient piezoelectricity is an attractive alternative choice with doping transition metal ions in the host lattice to develop novel binary ferroelectric materials that can be easily fabricated in any device architecture. Up to 8% Cu⁺ ion substitution on Zn²⁺ sites in the ZnO lattice was achieved by careful selection of raw material and adaptation of a low temperature sol–gel synthesis route for the preparation of bulk material. Phase purity and substitution of Cu⁺ ions in the ZnO lattice along with oxide-ion vacancy formation was confirmed using Powder X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray analysis (EDX), X-ray Photoelectron Spectroscopy (XPS) and Magnetic property measurement system (MPMS) studies. A giant dielectric constant (∼6300) was observed at 600 °C for Zn_0.95Cu_0.05O_1−δ pellets at 100 kHz frequency. Bulk Zn_0.95Cu_0.05O_1−δ also exhibits ferroelectricity at room temperature with remnant polarization P_r and V_c equal to 9.60 × 10⁻³ μC cm⁻² and 3.83 × 10² V cm⁻¹ respectively.

Cu⁺ ion substituted ZnO, Zn_1−xCu_xO_1−δ have shown high dielectric constant (∼6300) at 600 °C at 100 kHz frequency and ferroelectricity at room temperature than for bulk Zn_0.95Cu_0.05O_1−δ samples.     

Thermally-stable high energy storage performances and large electrocaloric effect over a broad temperature span in lead-free BCZT ceramic

Ba_0.85Ca_0.15Zr_0.10Ti_0.90O₃ (BCZT) relaxor ferroelectric ceramics exhibit enhanced energy storage and electrocaloric performances due to their excellent dielectric and ferroelectric properties. In this study, the temperature-dependence of the structural and dielectric properties, as well as the field and temperature-dependence of the energy storage and the electrocaloric properties in BCZT ceramics elaborated at low-temperature hydrothermal processing are investigated. X-ray diffraction and Raman spectroscopy results confirmed the ferroelectric–paraelectric phase transition in the BCZT ceramic. At room temperature and 1 kHz, the dielectric constant and dielectric loss reached 5000 and 0.029, respectively. The BCZT ceramic showed a large recovered energy density (W_rec) of 414.1 mJ cm⁻³ at 380 K, with an energy efficiency of 78.6%, and high thermal-stability of W_rec of 3.9% in the temperature range of 340–400 K. The electrocaloric effect in BCZT was explored via an indirect approach following the Maxwell relation at 60 kV cm⁻¹. The significant electrocaloric temperature change of 1.479 K at 367 K, a broad temperature span of 87 K, an enhanced refrigerant capacity of 140.33 J kg⁻¹, and a high coefficient of performance of 6.12 obtained at 60 kV cm⁻¹ make BCZT ceramics potentially useful coolant materials in the development of future eco-friendly solid-state refrigeration technology.

Thermally-stable recovered energy density and significant electrocaloric temperature change over a broad temperature span in BCZT ceramic elaborated by low-temperature hydrothermal processing.     

Effects of electrical-hydrothermal aging degradation on dielectric and trap properties of high temperature vulcanized silicone rubber materials

In this paper, a new aging platform combined the high voltage electric field and the hydrothermal environment was built. To investigate the aging mechanism, physicochemical, dielectric and trap properties of HTV SR before and after electrical-hydrothermal aging for 24 days were discussed. The results indicated that, compared with hydrothermal aging, more cracks and holes appeared on the surface of HTV SR after electrical-hydrothermal aging, and the content of flame retardant decreased significantly. Due to the main chain and side chain scission of PDMS, lots of low weight molecular (LWM) substances and free radicals were produced. And the tensile strength and elongation at break significantly decreased. Various physical and chemical defects appeared in the HTV SR specimen in the process of electrical-hydrothermal degradation, as a result of which, the dielectric constant significantly increased and the peak trap density increased by about 2.5 times compared to the virgin sample. The increase in trap density in turn accelerated the charge accumulation and enhanced the breakdown probability, resulting in the electric field strength decrease from 21.8 kV mm⁻¹ to 16.1 kV mm⁻¹ and severe degradation of HTV SR.

In this paper, a new aging platform combined the high voltage electric field and the hydrothermal environment was built.     

Controlling high blood pressure: a simple and effective approach

Fixed-dose combination tablets, such as diuretic plus β-adrenergic blocking drug or ACE inhibitor are more effective than is any monotherapy. Other advantages include simple titration, low toxicity and reduced expense which encourage better compliance required for optimal blood pressure control.     

On the relationship between spectroscopic constants of diatomic molecules: a machine learning approach

Through a machine learning approach, we show that the equilibrium distance, harmonic vibrational frequency and binding energy of diatomic molecules are related, independently of the nature of the bond of a molecule; they depend solely on the group and period of the constituent atoms. As a result, we show that by employing the group and period of the atoms that form a molecule, the spectroscopic constants are predicted with an accuracy of <5%, whereas for the A-excited electronic state it is needed to include other atomic properties leading to an accuracy of <11%.

Through a machine learning approach, we show that the equilibrium distance, harmonic vibrational frequency and the binding energy of diatomic molecules are universally related, independently of the nature of the bond of a molecule.     

Terahertz dielectric spectroscopy of human brain gliomas and intact tissues ex vivo: double-Debye and double-overdamped-oscillator models of dielectric response

Terahertz (THz) technology offers novel opportunities in the intraoperative neurodiagnosis. Recently, the significant progress was achieved in the study of brain gliomas and intact tissues, highlighting a potential for THz technology in the intraoperative delineation of tumor margins. However, a lack of physical models describing the THz dielectric permittivity of healthy and pathological brain tissues restrains the further progress in this field. In the present work, the ex vivo THz dielectric response of human brain tissues was analyzed using relaxation models of complex dielectric permittivity. Dielectric response of tissues was parametrized by a pair of the Debye relaxators and a pair of the overdamped-oscillators – namely, the double-Debye (DD) and double-overdamped-oscillator (DO) models. Both models accurately reproduce the experimental curves for the intact tissues and the WHO Grades I–IV gliomas. While the DD model is more common for THz biophotonics, the DO model is more physically rigorous, since it satisfies the sum rule. In this way, the DO model and the sum rule were, then, applied to estimate the content of water in intact tissues and gliomas ex vivo. The observed results agreed well with the earlier-reported data, justifying water as a main endogenous label of brain tumors in the THz range. The developed models can be used to describe completely the THz-wave – human brain tissues interactions in the frameworks of classical electrodynamics, being quite important for further research and developments in THz neurodiagnosis of tumors.     

Preparation of graphene/polypropylene composites with high dielectric constant and low dielectric loss via constructing a segregated graphene network

In this paper, a reduced graphene oxide/polypropylene (rGO/PP) dielectric composite with high dielectric constant and low dielectric loss at a low filler content was prepared via constructing a segregated moderately-reduced graphene network by encapsulation of GO on PP latex particles and subsequent in situ reduction of GO by hydrazine hydrate. GO/PP latex was prepared through artificial PP latex preparation in the presence of GO based on the solution-emulsification technique. As the emulsification proceeded, GO could self-assemble to become encapsulated on the surface of PP latex particles composed of PP and maleic-anhydride-grafted-PP because of the hydrogen bonding interaction between maleic-anhydride-grafted-PP and GO nanosheets. After reduction, the rGO encapsulated PP latex particles were obtained, and after coagulation and hot pressing, a segregated graphene network was achieved at a low content of rGO, demonstrated by TEM images. The dielectric constant at 1 kHz obviously increased from 3.28 for PP to 55.8 for the composite with 1.5 wt% rGO. The dielectric loss of the composite was retained at a low value (1.04). This study provides a new simple and effective strategy for preparing high-performance dielectric composites with high dielectric constant and low dielectric loss, facilitating the wide application of dielectric materials.

The rGO/PP composites with high dielectric constant and low dielectric loss at a low filler content were prepared via constructing a segregated graphene network by encapsulating of GO on PP latex particles and the in situ reduction in GO.     

Influence of surface coating on the microstructures and dielectric properties of BaTiO3 ceramic via a cold sintering process

We present herein a modified cold sintering process (CSP) for BaTiO₃ ceramics using a surface coating at the particle surface which could enhance the relative density of BaTiO₃ up to ∼93.5% at 220 °C and 500 MPa. The surface coating greatly enhances the ceramic density, mainly because it facilitates the dissolution–precipitation process during CSP. Ba vacancies form at the surface of the coated powders, so Ba(OH)₂ solution is used to compensate Ba ions in the as-cold-sintered ceramics, which increases the dielectric permittivity. Post-annealing at 700 and 900 °C increases the relative density to 97%, and the resulting relative dielectric permittivities are 810 and 1550, respectively, at room temperature and 1 kHz. This technique may also be extended to materials with very small, incongruent solubility in water or volatile solutions that use the cold sintering process.

Surface coating facilitates to dissolution–precipitation process and improves the dielectric properties of barium titanate ceramics during cold sintering process.     

Modified halloysite nanotube filled polyimide composites for film capacitors: high dielectric constant,low dielectric loss and excellent heat resistance

In this work, halloysite nanotubes (HNTs) were chosen as the fillers and high performance polyimide (PI) as the matrix to form a series of dielectric composite materials with high dielectric constant, low dielectric loss and excellent heat resistance. Firstly, KH550 was used to modify the surface of HNTs to make sure of a good dispersion of HNTs into the polymer. The results showed that the addition of KH550 modified HNTs (K-HNTs) can improve the dielectric constant of the composite films while maintaining their excellent dielectric loss properties. To further increase the dielectric constant of the HNTs/PI composites, conductive polyaniline (PANI) was used to coat the surface of HNTs to obtain PANI modified HNTs (PANI-HNTs). Compared with the K-HNTs filled systems, the dielectric constant of the PANI-HNTs/PI nanocomposite films is greatly enhanced. The highest dielectric constant of the PANI-HNTs/PI films can achieve 17.3 (100 Hz) with a low dielectric loss of 0.2 (100 Hz). More importantly, the as-prepared composite films have high breakdown strengths (>110.4 kV mm⁻¹) and low coefficients of thermal expansion, as low as 7 ppm per °C, and a maximum discharge energy density of 0.93 J cm⁻³. Also, such properties are maintained stably up to 300 °C, which is critical for manufacturing heat-resisting film capacitors.

Halloysite nanotubes (HNTs) were chosen as the fillers and polyimide (PI) as the matrix to form a series of composites with excellent dielectric properties and thermostabilities.     

A selective detection approach for copper(ii) ions using a hydrazone-based colorimetric sensor: spectroscopic and DFT study

The development of an efficient and miniaturized analytical approach to determine trace levels of toxic ions in aqueous fluids presents a current research challenge. Hydrazone-based chemosensors are considered potential candidates due to their high sensitivity and selectivity towards heavy metal ions. Computational techniques can be properly implemented to elucidate possible modes of ligand–metal interaction and provide an in-depth understanding of the chemistry involved. The present study reports the use of 3-hydroxy-5-nitrobenzaldehyde-4-hydroxybenzoylhydrazone (3-HNHBH) ligand for highly sensitive, quick and re-usable colorimetric sensing of copper(ii) ions in aqueous media. DFT calculations suggest that the complexation of 3-HNHBH with copper(ii) ions adopts a seesaw coordination geometry and results in the largest HOMO–LUMO gap and most effective coulombic interaction compared to Zn and Ni counterparts. It demonstrated a high selectivity towards copper ions with a detection limit of 0.34 μg L⁻¹. The ligand was readily regenerated using a 0.5 M HCl solution, indicating its feasibility to be used as a re-usable sensor for the convenient detection of copper ions in aqueous media. The influence of metal interference, pH and solvents on the selectivity and regeneration of the ligand was also investigated.

The development of an efficient and miniaturized analytical approach to determine trace levels of toxic ions in aqueous fluids presents a current research challenge.     

Redox chemistry in the pigment eumelanin as a function of temperature using broadband dielectric spectroscopy

Conductive biomolecular systems are investigated for their promise of new technologies. One biomolecular material that has garnered interest for device applications is eumelanin. Its unusual properties have led to its incorporation in a wide set of platforms including transistor devices and batteries. Much of eumelanin''s conductive properties are due to a solid state redox comproportionation reaction. However, most of the work that has been done to demonstrate the role of the redox chemistry in eumelanin has been via control of eumelanin''s hydration content with scant attention given to temperature dependent behavior. Here we demonstrate for the first time consistency between hydration and temperature effects for the comproportionation conductivity model utilizing dielectric spectroscopy, heat capacity measurements, frequency scaling phenomena and recognizing that activation energies in the range of ∼0.5 eV correspond to proton dissociation events. Our results demonstrate that biomolecular conductivity models should account for temperature and hydration effects coherently.

We demonstrate on synthetic eumelanin that biomolecular conductivity models should account for temperature and hydration effects coherently.     

Structure properties and dielectric relaxation of Ca0.1Na0.9Ti0.1Nb0.9O3 ceramic

In this paper, the synthesis of Ca_0.1Na_0.9Ti_0.1Nb_0.9O₃ (CNTN) ceramic by a solid-state reaction method is reported. The results of Rietveld refinement of X-ray diffraction (XRD) patterns at room temperature showed a pure tetragonal perovskite (P4mm space group). Raman spectroscopy analysis, ranging from of 50 to 1000 cm⁻¹, at room temperature, validates the results of XRD. The dielectric properties was studied by complex impedance spectroscopy examined in broad frequency range, 100 Hz to 200 kHz, at different temperatures. The dielectric permittivity for our CNTN compound confirms the typical relaxor behavior. The investigation of the diffuseness of the transition was conducted by fitting the experimental data with modified Curie–Weiss law; Gaussian distribution and Power law confirm the presence of a short-range association between the polar nanoregions (PNRs). The obtained values of the diffuseness coefficient are of the order 1.6, which corresponds to the diffuse phase transition (DPT) ascribed to the existence of various states of polarization, thus various relaxation times in different regions. The value of diffuseness is of the order 85 and the degree of relaxor (ΔT_cm = 65 K) is interesting as far as microelectric applications are concerned. Moreover, based on the frequency dependence of temperature at dielectric maxima using Vogel–Fulcher relationship, a strong evidence for a static freezing temperature with regards to thermally-activated polarization fluctuations was found.

In this paper, the synthesis of Ca_0.1Na_0.9Ti_0.1Nb_0.9O₃ (CNTN) ceramic by a solid-state reaction is reported. The results of Rietveld refinement of X-ray diffraction patterns at room temperature showed a pure tetragonal perovskite (P4mm space group).     

Stability of fMRI striatal response to alcohol cues: a hierarchical linear modeling approach

In functional magnetic resonance imaging (fMRI) studies of alcohol-dependent individuals, alcohol cues elicit activation of the ventral and dorsal aspects of the striatum (VS and DS), which are believed to underlie aspects of reward learning critical to the initiation and maintenance of alcohol dependence. Cue-elicited striatal activation may represent a biological substrate through which treatment efficacy may be measured. However, to be useful for this purpose, VS or DS activation must first demonstrate stability across time. Using hierarchical linear modeling (HLM), this study tested the stability of cue-elicited activation in anatomically and functionally defined regions of interest in bilateral VS and DS. Nine non-treatment-seeking alcohol-dependent participants twice completed an alcohol cue reactivity task during two fMRI scans separated by 14 days. HLM analyses demonstrated that, across all participants, alcohol cues elicited significant activation in each of the regions of interest. At the group level, these activations attenuated slightly between scans, but session-wise differences were not significant. Within-participants stability was best in the anatomically defined right VS and DS and in a functionally defined region that encompassed right caudate and putamen (intraclass correlation coefficients of .75, .81, and .76, respectively). Thus, within this small sample, alcohol cue-elicited fMRI activation had good reliability in the right striatum, though a larger sample is necessary to ensure generalizability and further evaluate stability. This study also demonstrates the utility of HLM analytic techniques for serial fMRI studies, in which separating within-participants variance (individual changes in activation) from between-participants factors (time or treatment) is critical.     

Magnetic response of chlorophyll self-assembly within hydrogel: a mechanistic approach towards enhanced photoharvesting

Self-assembly of chlorophyll-a (Chl-a) molecules within a protein environment serves as the key factor behind controlled and efficient light energy harvesting in natural photosystems. Long-range ordering among supramolecular structures in terms of spin–orbit coupling and edge effect helps in untrapping of excitons in the disordered energy landscape. Mimicking the photosynthetic machinery would give a new paradigm for organic photovoltaic material design where a large amount of disorder exists. In this paper, we report the experimental evidence of room temperature magnetic domain wall formation and edge effect along with spin flop canting in self-assembled Chl-a within hydrogel matrix via SQUID magnetometry. This was further correlated with intermolecular coupling and exciton delocalization through specific arrangements of self-assembly as evident from NMR spectral and photophysical characteristics. The data cumulatively suggest electronic backscattering protection which is also substantiated by the ferroelectric behavior coming from coexisting symmetry lowering. Here the polarization evolves through primary distribution of π electronic density along with a photoresponsive IV loop, similar to the photoprotection of photosynthesis. This work thus proposes a promising design principle for room temperature Chl-a based biomimetic systems efficient in photoharnessing.

Chlorophyll molecular-arrangement, geometry and coupling result in magnetic domain wall as well as edge effect. These facilitate topologically protected ultrafast energy migration, where back scattering of exciton is restricted.     

Preparation and mechanism analysis of high performance ceramic membrane by spray coating

A spray coating method was proposed to fabricate an α-Al₂O₃ micro-filtration membrane with excellent performance. It was observed that air gaps could form inside the support during the coating stage that effectively prevent membrane forming particles from penetrating into the support without an intermediate layer. Thus the pure water permeability of the membrane with average pore size of 0.13 μm and thickness of 25.46 μm could reach 2893 Lm⁻² h⁻¹ bar⁻¹. The effects of firing conditions, membrane thickness and backwash or backpulse conditions on the pore size distribution of the membrane were investigated. Meanwhile the prepared membrane could sustain good filtration performance and mechanical integrity during backpulsing and backwashing processes under the transmembrane pressure (TMP) of 8 bar, which also exhibited a rejection rate of 98.8% for the carbon ink with an average particle size of 164 nm.

We have fabricated a high performance ceramic membrane. We find and explain the effect of reducing particle penetration by spray coating.     

Doping effect and oxygen defects boost room temperature ferromagnetism of Co-doped ZnO nanoparticles: experimental and theoretical studies

Co-doped ZnO nanoparticles with different dosage concentrations were fabricated by a thermal decomposition method. The nanoparticles show a pure wurtzite structure without the formation of a secondary phase or Co clusters, in which Co ions present as Co²⁺ and occupy Zn²⁺ tetrahedral sites within the ZnO matrix. All the samples show ferromagnetic properties at room temperature with nonzero coercivity and remanence magnetization. Besides, the magnetic data is also fitted by the model of bound magnetic polarons (BMP). By increasing the Co²⁺ doping concentration, the saturation magnetization values of Co-doped ZnO nanoparticles increase first and then decreases, which is related to the variation tendency of oxygen defects on the surface and the number of BMPs. This phenomenon can be ascribed to the formation of defect-induced BMPs, in which ferromagnetic coupling occurs at lower Co²⁺ concentration and Co²⁺–O²⁻–Co²⁺ antiferromagnetic coupling arises at higher Co²⁺ concentration. Air annealing experiments further demonstrate this result, in which the saturation magnetization of Co-doped ZnO nanoparticles is reduced after annealing in Air. The doping effect and oxygen defects on the magnetic ordering of Co-doped ZnO were calculated using density functional theory. The calculation results reveal that stable long-range magnetic ordering in Co-doped ZnO nanoparticles is mainly attributed to the localized spin moments from 3d electrons of Co²⁺ ions. Both the experimental and theoretical studies demonstrate that the ferromagnetism in Co-doped ZnO nanoparticles is originated from the combined effects of Co doping and oxygen vacancies. These results provide an experimental and theoretical view to understand the magnetic origination and tune the magnetic properties of diluted magnetic semiconductors, which is of great significance for spintronics.

Co-doped ZnO nanoparticles with different dosage concentrations were fabricated by a thermal decomposition method.     

Quinic acid and hypervalent chromium: a spectroscopic and kinetic study

The redox reaction between an excess of quinic acid (QA) and Cr^VI involves the formation of intermediates, namely, Cr^IV and Cr^V species, which in turn react with the organic substrates. As observed with other substrates that have already been studied, Cr^IV does not accumulate during this reaction because of the rate of the reaction. Its rate of disappearance is several times higher than that of the reaction of Cr^VI or Cr^V with QA. Kinetic studies indicate that the redox reaction proceeds via a combined mechanism that involves the pathways Cr^VI → Cr^IV → Cr^II and Cr^VI → Cr^IV → Cr^III, which is supported by the observation of superoxo-Cr^III (CrO₂²⁺) ions, free radicals, and oxo-Cr^V species as intermediates and the detection of Cr^VI ester species. The present study reports the complete rate laws for the QA/chromium redox reaction.

The redox reaction between an excess of quinic acid (QA) and Cr^VI involves the formation of intermediates, namely, Cr^IV and Cr^V species, which in turn react with the organic substrates.