Colossal dielectric properties of Na1/3Ca1/3Sm1/3Cu3Ti4O12 ceramics: Computational and experimental investigations

A modified sol?gel technique was used to synthesize a high dielectric ceramic, Na_1/3Ca_1/3Sm_1/3Cu₃Ti₄O₁₂. The crystal structure of this sintered ceramic matches the standard pattern of a body?centered cubic (bcc) system within the Im3 space group (JCPDS No. 75–2188). No impurity phases were observed. Interestingly, a high dielectric permittivity of ～1.14–1.35 × 10⁴ and a low loss tangent of ～0.027–0.039 were achieved in this sintered Na_1/3Ca_1/3Sm_1/3Cu₃Ti₄O₁₂ ceramic. Our DFT calculations disclosed that substitution of Na⁺ ions at Cu²⁺ sites causes an observed excess Cu concentration. As a result, metastable insulating phases were formed at a relatively high sintering temperature. Additionally, our electron density calculations revealed that Na ions lose their electrons to Sm ions, whereas the oxidation states of Cu and Ti are unaltered. Our results show that Cu⁺ and Ti³⁺ were observed after introducing an oxygen vacancy into this lattice. Significantly different values of R_g, R_gb, and E_g, E_gb support an internal barrier layer capacitor as the most likely origin of the giant dielectric properties of this ceramic. XPS results show mixed Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ in all ceramics, suggesting that electron hopping between Cu⁺?Cu²⁺ and Ti³⁺?Ti⁴⁺ is the probable origin of the n?type semiconducting state inside the grains.     

Effect of naturally formed oxide films and other variables in the early stages of Mg-alloy corrosion in NaCl solution

The influence of initial surface conditions on the subsequent corrosion behaviour of AZ31 and AZ61 magnesium alloys in 0.6 M NaCl solution has been studied using electrochemical impedance spectroscopy. For obtaining the different surface conditions, some of the specimens were immersion tested with the surface in the as-received condition, while others were tested immediately after mechanical polishing, and part of the polished specimens after six months of exposure to the laboratory atmosphere. Considering the evolution of the high-frequency capacitive arc of the Nyquist diagram, whose diameter is related to the corrosion process, a clear effect of the initial surface conditions is observed only in the early stages of testing. This effect is especially significant for the freshly polished specimens.     

Electrical properties of Ag-doped ZnO nano-plates synthesized via wet chemical precipitation method

Ag-doped and pure zinc oxide (ZnO) nano-plates were successfully synthesized via low cost wet precipitation method. The crystalline phases and the morphological features of the synthesized samples were assessed by X-ray diffraction (XRD) and scanning electron microscopy. These techniques coupled with Energy-dispersive X-ray spectroscopy (EDS) measurements confirmed the incorporation of Ag element into the ZnO matrix. The dielectric loss and ac conductivity were studied as a function of frequency and composition. A detailed analysis of the dielectric loss and ac conductivity as a function of composition were done in a wide frequency range at room temperature. In addition, the charge transport mechanism through the grain and grain boundary regions were investigated using impedance spectroscopy analysis.     

Effect of Mn-doping on the structure and electrical properties of (Pb0.325Sr0.675)TiO3 ceramics

Pb_0.325Sr_0.675Ti_1-xMn_xO₃ ceramics (x?=?0, 0.001, 0.005, 0.01, and 0.05) were successfully prepared by traditional solid-state reaction method. It was found that the lattice constant calculated through Rietveld refinement initially increased and then decreased with increasing Mn content, which was attributed to the variation in valence state of Mn and Ti ions. The microstructure gradually varied from the coexistence of large grains and fine grains for x?=?0 to the uniform grain for x?=?0.05 by increasing the doping Mn ions. With increasing Mn content from x?=?0 to x?=?0.05, the Curie temperature (Tc) dramatically decreased from 25?°C to ??40?°C and dielectric maximum decreased from 27,100 to 13,200. Pb_0.325Sr_0.675Ti_1-xMn_xO₃ ceramics with x?=?0.001 showed the lowest dielectric loss of 0.006 with a relatively high dielectric peak value of ~ 21,000. The grain boundaries resistance obtained from the complex impedance decreased with the increase of Mn content. The decrease in resistance was ascribed to oxygen vacancies and electronics produced by the change of ionic valence state. X-ray photoemission spectroscopy revealed that Ti ions were Ti⁴⁺ and the valences of Mn ions were deduced to be mainly in the form of Mn²⁺ and/or Mn³⁺ for ceramics with low content of Mn, while the Ti ions were in the form of Ti³⁺ and Ti⁴⁺ and Mn ions were diverse valence states with the coexistence of Mn²⁺, Mn³⁺, and Mn⁴⁺ for ceramics with x?=?0.01 and 0.05.     

Dieletric and relaxation behaviors of (PbMg1/3Nb2/3O3)0.67(PbTiO3)0.33 single crystal

Dielectric permittivity along the [111] direction has been measured as a function of temperature for a relaxor ferroelectric single crystal (PbMg_1/3Nb_2/3O₃)_0.67(PbTiO₃)_0.33 (PMN-33%PT). A sharp ferroelectric phase transition was observed near 425 K and 429 K for cooling and heating processes, respectively. As temperature decreases, a diffuse phase transition (which begins near 330 K upon cooling) was detected. In addition, the nature of the thermal hysteresis for the dielectric permittivity confirms that these transitions (near 330 and 425 K upon cooling) are diffuse first-order and first-order, respectively. The frequency-dependent dielectric data ε'₁₁₁ (ƒ, T) prove the existence of an electric dipolar relaxation process between 350 and 400 K. The activation energy, the Vogel-Fulcher temperature and attempt frequency corresponding to this relaxation process are also calculated.     

Synthesis,characterization and corrosion protection properties of poly(N-vinyl carbazole-co-glycidyl methacrylate) coatings on low nickel stainless steel

Methacrylate based copolymers are considered as one of the best organic coating materials for anticorrosive application. Poly(N-vinyl carbazole-co-glycidyl methacrylate) have been synthesized by free radical solution polymerization technique from different mole ratios of N-vinyl carbazole (N-Vc) and glycidyl methacrylate (GMA) and characterized using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (¹H NMR and ¹³C NMR). Thermal analyses of the poly(N-Vc-co-GMA) were performed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The number average molecular weight (M_n) of different compositions of the same was determined by gel permeation chromatography (GPC). The corrosion performances of low nickel stainless steel specimens coated with different composition of copolymers were investigated in 1 M H₂SO₄ using potentiodynamic polarization, electrochemical impedance spectroscopic (EIS) method, scanning electron microscopic (SEM) and energy dispersive X-ray analysis (EDAX). Poly(N-Vc-co-GMA) have been provided in order to achieve adherent, low permeability to aggressive ions as well as environmentally favored good anticorrosive coating. Electrochemical corrosion test and surface analysis results clearly showed that poly(N-Vc-co-GMA) coatings served as a stable host matrix on low nickel stainless steel against corrosion. It was also observed that the coatings of poly(N-Vc-co-GMA) with equal mole ratio of N-Vc and GMA exhibited the best corrosion resistance among all combinations.     

Electrical transport properties of M2FeV3O11 (M=Mg,Zn, Pb,Co, Ni) ceramics

Multicomponent oxide systems have been widely studied in the last few decades and can be used as cathode materials in high-energy cells. However, the electrical characteristics have not yet been fully disclosed. We report the electrical conductivity, thermoelectric power, the I-V characteristics, conductance and dielectric spectroscopy measurements made for M₂FeV₃O₁₁ (M=Mg, Zn, Pb, Co, Ni) ceramics. This multicomponent oxide system was found to show semiconducting properties strongly thermally activated above room temperature, n-type conduction at higher temperatures, higher conductance for the ceramics containing Co²⁺, Ni²⁺ and Mg²⁺ ions as well as a strong dependence of relative dielectric constant and loss tangent on temperature and frequency. Moreover, the transition metal ions, which have unfilled 3d-shells strongly affected polarization and conductivity of the ceramics, while the effect of porosity could be neglected. These effects are discussed in terms of microstructure, thermal activation of charge carriers, small polarons as well as the Maxwell–Wagner polarization.     

Electropolymerization, characterization and corrosion performance of poly(N-ethylaniline) on copper

Poly(N-ethylaniline) (PNEA) coatings were grown by cyclic voltammetry technique on copper from 0.1 M N-ethylaniline (NEA) in 0.3 M oxalic acid solution. The optimum conditions (e.g. upper potential limit, scan rate and cycle number) effect on corrosion performance of synthesized PNEA films were determined in order to obtain best protection results against corrosion. The electrodeposited coatings were characterized by cyclic voltammetry (CV), Fourier Transform Infrared-Attenuated Total Reflectance (FTIR-ATR) spectroscopy and scanning electron microscopy (SEM). Redox parameters were found after electrochemical tests and results of stability tests of these films impart an electroactive behavior that is composed of both diffusion control and thin film behavior. In addition, corrosion performance of PNEA coatings were investigated in 0.1 M H₂SO₄ by Tafel extrapolation and electrochemical impedance spectroscopy (EIS) techniques.     

Synthesis, characterization and corrosion protection properties of poly(N-(methacryloyloxymethyl) benzotriazole-co-glycidylmethacrylate) coatings on mild steel

The synthesis of copolymers from different feed ratios of N-(methacryloyloxymethyl) benzotriazole (MMBT) and glycidyl methacrylate (GMA) was achieved by using free radical solution polymerization technique and characterized using FT-IR and ¹³C NMR spectroscopy. The thermal stability of the synthesized copolymers was studied using thermogravimetric analysis (TGA). The corrosion performances of mild steel specimens dip coated with different composition of copolymers were investigated in 0.1 M HCl using potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) method. The polarization and impedance measurements showed different corrosion protection efficiency with change in composition of the copolymers. It was found that the corrosion protection properties are owing to the barrier effect of the polymer layer covered on the mild steel surfaces. However, it was observed that the copolymer obtained from 1:1 mole ratio of MMBT and GMA exhibited better protection efficiency than other combinations.     

Dielectric spectroscopy of poly(butylene succinate) films

Dielectric properties of poly(butylene succinate) crystallized under different conditions have been reported in the temperature range of 163-383 K and in the frequency range of 0.01-10⁵ Hz. Both the dipolar α and β processes have been identified at low temperatures: the α process is associated with the amorphous fraction while the β with the relaxations in both the amorphous and crystalline fractions. The space charge effect dominates the high temperature dielectric spectra. These spectra have been analyzed in the light of an equivalent circuit model. The Maxwell-Wagner-Sillars polarization, electrode polarization and free charge motion are well resolved. At 383 K, near the melting temperature (387 K), massive melting and subsequent recrystallization have been observed. The peculiar evolution of the spectra is also analyzed using the same equivalent circuit model. The relationship between the fitting parameters and the evolved microstructures is discussed.     

Zinc substitution effect on the structural,spectroscopic and electrical properties of nanocrystalline MnFe2O4 spinel ferrite

This paper reports the structural, morphological, spectroscopic, dielectric, ac conductivity, and impedance properties of nanocrystalline Mn_1-xZn_xFe₂O₄. The nanocrystalline Mn–Zn ferrites were synthesized using a solvent-free combustion reaction method. The structural analysis using X-ray diffraction (XRD) pattern reveals the single-phase of all the samples and the Rietveld refined XRD patterns confirmed the cubic-spinel structure. The calculated crystallite size values increase from 8.5 nm to 19.6 nm with the Zn concentration. The surface morphological analysis using field emission scanning electron microscopy and the transmission electron microscopy confirms the nano size of the prepared ferrites. X-ray photoelectron spectroscopy was used to study the ionic state of the atoms present in the samples. Further, the high-resolution Mn 2p, Zn 2p, Fe 2p, and O 1s spectra of Mn_1-xZn_xFe₂O₄ does not result in the appearance of new peaks with Zn content, indicating that the Zn substitution does not change the ionic state of Mn, Zn, Fe, and O present in nanocrystalline Mn_1-xZn_xFe₂O₄. The investigated electrical properties show that the dielectric constant, tan δ and ac conductivity gradually decrease with increasing Zn substitution and the sample Mn_0·2Zn_0·8Fe₂O₄ has the lowest value of conductivity at 303 K. The ac conductivity measured at different temperatures shows the semiconducting nature of the ferrites. The impedance spectra analysis shows that the contribution of grain boundary is higher compared with the grain to the resistance. The obtained results suggest that the Zn substituted manganese ferrite nanoparticles can act as a promising candidate for high-frequency electronic devices applications.     

Electron transfer across anodic films formed on tin in carbonate-bicarbonate buffer solution

Impedance and steady-state data were recorded in order to study the kinetics of electron transfer between passive tin electrodes and an electrolytic solution containing the K₃Fe(CN)₆-K₄Fe(CN)₆ redox couple. Film thickness plays a key role in determining the type of electronic conduction of these oxide covered electrodes. Electron exchange with the oxide takes place with participation of the conduction band in the semiconducting film. A mechanism involving direct electron tunneling through the space charge barrier is the most suitable to interpret the experimental evidence.     

The growth kinetics and properties of potentiodynamically formed thin oxide films on aluminium in citric acid solutions

The growth kinetics and properties of potentiodynamically formed thin oxide films on Al were investigated in 0.05 M citric acid solutions of different pH (5, 6 and 7) by means of potentiodynamic polarization and a.c. electrochemical impedance spectroscopy (EIS) measurements. Al showed passive behaviour within the pH range that was examined. The potentiodynamic growth of the oxide film on Al takes place due to ionic conductivity under the influence of the high electric field. Characteristic kinetic oxide film growth parameters such as the high-field growth exponential law constants (A and B), ionic conductivity through the oxide film, field strength and half barrier width have been calculated. Impedance measurements were used to determine the parameters related to the characteristic sizes and properties of oxide film. The capacitive response of the impedance spectrum was related to the thickness and dielectric properties of the barrier oxide film. The oxide film resistance values were very high, indicating that the oxide films formed under potentiodynamic conditions are highly uniform in thickness and very resistant. The anodic behaviour of Al in the citric solutions under potentiodynamic conditions were characterized by the rapid growth of the oxide film which diminished the influence of relaxation processes on the growth kinetics and structural characteristics of the aluminium/anodic oxide film/electrolyte system.     

Defect-curing function of self-limiting Al2O3 thin films in graphene materials

Impedance spectroscopy was applied to 2-dimensional graphene materials that were thermally grown on copper substrates to quantitatively monitor the quality of the as-grown graphene materials without the subsequent transfer process. The presence of the graphene layer prevents the dissolution of the metallic copper elements in the corrosive electrolyte and provides an interface between the ionic electrolyte and electronic graphene/copper materials. The highest impedance appears at the graphene/electrolyte to be associated with electrochemically robust graphene materials, i.e., the as-grown graphene materials subjected to atomic layer deposition of Al₂O₃. Such an effect is attributed to the anti-corrosive protection of graphene materials and the defect-curing function of Al₂O₃ in graphene materials. The impedance-based information can be exploited in-situ without the use of any destructive approaches to evaluate the electrical perfectness vulnerable to preparation environments.     

Impedance measurements of a chalcogenide membrane iron(III)-selective electrode in contact with aqueous electrolytes

The electrochemical characterization of a chalcogenide-based iron(III)-selective electrode [Fe(III) ISE] [i.e., Fe_2.5(Se₆₀Ge₂₈Sb₁₂)_97.5] was achieved using impedance spectroscopy. The influence of electrolyte composition (i.e., NO₃⁻, Cl⁻, and pH) on the membrane oxidation reaction has been examined, and a mechanism for its action is proposed. Equivalent circuit analysis was undertaken to determine the interfacial charge transfer resistance and corresponding double layer capacitance as a function of electrolyte composition and immersion time. Variations were detected in the charge transfer time constant, and this was attributed to changes in the dielectric/conduction properties of the surface layer. It was found that the Fe_2.5(Se₆₀Ge₂₈Sb₁₂)_97.5 oxidation kinetics depend on the pH, and the interfacial reaction is dictated by sluggish charge transfer. By contrast, chloride was shown to accelerate the rate of membrane oxidation presumably via the formation of soluble metal-chloride complexes. Electrochemical impedance spectroscopy (EIS) aging studies of the Fe_2.5(Se₆₀Ge₂₈Sb₁₂)_97.5 membrane in chloride electrolyte under alkaline conditions showed that the charge transfer resistance decreases with exposure time. However, extended aging revealed a change in the rate of oxidation, which was attributed to a combined diffusion/passivation effect. It is proposed that the development of a modified surface layer (MSL) and passive surface layer (PSL) are partly responsible for the electrochemical stability of the chalcogenide membrane. This paper attempts to clarify and address some of the misconceptions/issues reported previously in the literature on the chalcogenide iron(III)-selective electrode.     

Hybrid inorganic-organic polymer electrolytes: synthesis, FT-Raman studies and conductivity of {Zr[(CH2CH2O)8.7]ρ/(LiClO4)z}n network complexes

This paper describes the synthesis and characterization of three-dimensional hybrid inorganic-organic networks prepared by a polycondensation reaction between Zr(O(CH₂)₃CH₃)₄ and polyethylene glycol 400 (PEG400). Eleven hybrid networks doped with varying concentrations of LiClO₄ salt were prepared. On the basis of analytical data and FT-Raman studies it was concluded that these polymer electrolytes consist of inorganic-organic networks with zirconium atoms bonded together by PEG400 bridges. These polymers are transparent with a solid rubber consistency and are very stable under inert atmosphere. Scanning electron microscopy revealed a smooth glassy surface. X-ray fluorescence microanalysis with energy dispersive spectroscopy demonstrated that all the constituent elements are homogeneously distributed in the materials. Thermogravimetric measurements revealed that these materials are thermally stable up to 262 °C. Differential Scanning Calorimetry measurements indicated that the glass transition temperature T_g of these inorganic-organic hybrids varies from −43 to −15 °C with increasing LiClO₄ concentration. FT-Raman investigations revealed the TGT (T=trans, G=gauche) conformation of polyether chains and allowed characterization of the types of ion-ion and ion-polymer host interactions in the bulk materials. The conductivity of the materials at different temperatures was determined by impedance spectroscopy over the 20 Hz-1 MHz frequency range. Results indicated that the materials conduct ionically and that their ionic conductivity is strongly influenced by the segmental motion of the polymer network and the type of ionic species distributed in the bulk material. Finally, it is to be highlighted that the hybrid network with a n_Li/n_O molar ratio of 0.0223 shows a conductivity of ca. 1×10⁻⁵ S cm⁻¹ at 40 °C.     

Enhanced dielectric characteristics of Ba0.94Bi0.04(Fe0.5Nb0.5)O3 coated with SiO2 and SiO2/Al2O3 over a broad frequency and temperature range

Pure phase of Ba_0.94Bi_0.04(Fe_0.5Nb_0.5)O₃ (BBFN) nano-particles were obtained by chemical co-precipitation method. The core-shell structure of BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ particles and the target ceramics were successfully prepared by aqueous chemical coating approach. The microstructures and dielectric properties of BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ were studied. Both the BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ samples show significantly decreased dielectric loss and good frequency and temperature stability on relative permittivity. Compared to the rapid decline of relative permittivity of BBFN@SiO₂, the synergistic effect of SiO₂ and Al₂O₃ in BBFN@SiO₂/Al₂O₃ ceramics made the relative permittivity of which remains a relatively high level with very low dielectric loss, making it more suitable in colossal permittivity applications. Based on the impedance analysis, the grain boundary effect and IBLC models play the important role for the improvement of dielectric properties of BBFN@SiO₂/Al₂O₃ samples.     

Electrochemical formation and characterization of porous titania (TiO2) films on Ti

Galvanostatically and potentiostatically formed surface oxide films on titanium in H₂O₂ free and H₂O₂ containing H₂SO₄ solutions were investigated. Conventional electrochemical techniques, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy, were used. In the absence of H₂O₂, the impedance response indicated a stable thin oxide film which depends on the mode of anodization of the metal. However, in the presence of H₂O₂ the film characteristics were changed. A significant decrease in the corrosion resistance of the surface film was recorded. The film characteristics were also found to be affected by the mode of oxide film growth and polarization time. The EIS results and the impedance data fitting to equivalent circuit models have shown that the oxide film consists of two layers. The electrochemical characteristics of the anodic films formed under different conditions have been discussed.     

Electrochemical performance of quaternary (1-x)ZnMn2O4/(x)MgFe2O4 solid solution as supercapacitor electrode

Novel nano quaternary metals solid solutions from MgFe₂O₄ and ZnMn₂O₄ were synthesized using a sol-gel procedure. The development of a solid solution and the formed phase were examined by phase analysis utilizing the X'Pert High Score Plus program and Fourier transform infrared (FTIR) spectroscopy technique. Rietveld analysis of X-ray diffraction data (XRD), scanning electron microscope (SEM/EDS) and transmission electron microscope (TEM) were applied to determine the lattice parameters, crystallite size, different cations distribution and elemental analysis of the formed solid solutions. The measured dielectric properties of obtained solid solutions are found to be affected by the composition ratio (x). The solid solution (1-x)ZnMn₂O₄/(x)MgFe₂O₄ samples exhibited a ferroelectric–paraelectric transition at ferroelectric Curie temperature (T_c). The different hopping mechanisms in the different samples were also examined. The electrochemical performance was tested and influence of composition ratio (x) on the cathodic and anodic potential was investigated. The specific capacitance (C_s) value of electrodes depended on the composition ratio (x) beside the type of cations forming oxides. The (0.9)MgFe₂O₄/(0.1)ZnMn₂O₄ sample showed the best performance as a supercapacitor material. The outstanding electrochemical property of the (0.9)MgFe₂O₄/(0.1)ZnMn₂O₄ electrode was further confirmed by EIS inspection. The super stability of MgFe₂O₄/ZnMn₂O₄ solid solution could be attributed to the activation of the solid solution materials during the CV cycling and the synergistic effects.     

Enhanced electric and magnetic properties of (BiLi)1/2(Fe2/3W1/3)O3 multiferroic as compared to BiFeO3

Very low electric and magnetic moments are the two major disadvantages which restrict the practical applications of BiFeO₃. We have doped Li⁺ and W⁶⁺ in Bi³⁺ and Fe³⁺ site respectively to overcome the limitations of BiFeO₃. Pure BiFeO₃ and (BiLi)_1/2(Fe_2/3W_1/3)O₃ (BLFWO) are synthesized by a solid-state reaction technique. The samples are characterized by X-ray diffractometer, LCR meter, P–E loop tracer, vibrating sample magnetometer and dc resistivity setup to understand their different properties. Dielectric and impedance studies of the samples are measured at different frequency (10²–10⁶ Hz) in a wide temperature range (30–375 °C). Due to co-doping in pure BFO the remnant polarization and remnant magnetization are enhanced and thus BLFWO may show large industrial utility.