Microstructure,dielectric and piezoelectric properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>-Ba(Ti<Subscript>0.95</Subscript>Zr<Subscript>0.05</Subscript>)O<Subscript>3</Subscript> lead-free ceramics with CuO sintering aid

Using an ordinary ceramic fabrication technique, we fabricated lead-free (1-x)(K_0.5Na_0.5)NbO₃-xBa(Ti_0.95Zr_0.05)O₃ ceramics with CuO sintering aid . Ba(Ti_0.95Zr_0.05)O₃ diffuses into (K_0.5Na_0.5)NbO₃ to form a new solid solution. The ceramics with perovskite structure possess orthorhombic phase at x≤0.04 and become tetragonal phase at x≥0.06. Both the paraelectric cubic–ferroelectric tetragonal and the ferroelectric tetragonal–ferroelectric orthorhombic phase transition temperatures decrease with increasing the concentration of Ba(Ti_0.95Zr_0.05)O₃. The doping of CuO effectively promotes the densification of the ceramics. The coexistence of the orthorhombic and tetragonal phases at 0.04<x<0.06 and the improvement in sintering performances of the ceramics significantly enhance the piezoelectric and dielectric properties at room temperature. The ceramics with x=0.04–0.06 and y=0.75–1.50 possess excellent properties: d₃₃=119–185 pC/N, k_P=37–44%, k_t=35–49%, ε=341–1129, cosδ=0.7–4.4% and T_c=312–346 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s     

Controlling the physical properties of PbIn<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> ferroelectric ceramics by intense mechanical action with shear

PbIn_0.5Nb_0.5O₃ (PIN) ferroelectric relaxer ceramics obtained by the solid-phase method is studied. Prior to sintering, the synthesized charge is subjected to mechanical action in Bridgman anvils at room temperature. The electrophysical properties of the reference sample and test samples are compared. It is concluded that mechanical treatment of the material at the stage of preparation allows one to control the physical properties of ferroelectric ceramics. Starting from a certain amount of the action, the electrophysical properties of PIN ceramics vary nonmonotonically.     

Preparation and dielectric properties of the lead-free BaFe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> ceramics obtained from mechanically triggered powder

In the paper the influence of mechanical activation of the powder on the final dielectric properties lead-free Ba(Fe_1/2Nb_1/2)O₃ (BFN) ceramic was examined. The BFN ceramics were obtained by 3-steps route. Firstly, the substrates were pre-homogenized in a planetary ball mill. Than, the powder was activated in vibratory mill (the shaker type SPEX 8000 Mixer Mill) for different duration between 25 h and 100 h. The influence of the milling time on the BFN powder was monitored by X-ray diffraction. The diffraction data confirmed that the milling process of the starting components is accompanied by partial synthesis of the BFN materials. The longer of the high-energy milling duration the powders results in increasing the amount of amorphous/nanocrystalline content. The mechanically activated materials were sintered in order to obtain the ceramic samples. During this temperature treatment the final crystallisation of the powder appeared what was confirmed by XRD studies. The performed dielectric measurements have revealed the reduction of the dielectric loss of the BFN ceramics compared to materials obtained by classic methods.     

Synthesis of submicron CaZrO<Subscript>3</Subscript> in combustion reactions

Submicron CaZrO₃ powder is obtained in combustion reactions (solution combustion synthesis—SCS) with glycine. It is found that SCS reduces the sintering temperature of CaZrO₃ powders. The dielectric properties of calcium zirconate ceramics are studied by the electrochemical impedance method. It is shown that a ceramics of powders obtained by the SCS method has high dielectric characteristics.     

Effect of Ba-substitution on the structure and properties of Pb<Subscript>0.8</Subscript>Ba<Subscript>0.2</Subscript>[(In<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)<Subscript>1-x</Subscript>Ti<Subscript>x</Subscript>]O<Subscript>3</Subscript> ceramics

Ferroelectric ceramics with formula Pb_0.8Ba_0.2[(In_1/2Nb_1/2)_1-xTi_x]O₃ (PBINT) (x=0.0,0.1,0.2,0.3,0.4 and 0.5) were prepared via a two-step solid state reaction method. It was found that ceramics with compositions in the range of x=0.0∼0.3 showed a pseudo-cubic structure, whereas the ceramic with x=0.5 displayed a tetragonal structure. All compositions showed significant frequency dispersion in their dielectric properties. The remanent polarization P_r as well as the coercive field E_c, measured at room temperature, increases with the Ti content. The experimental results obtained in this system are summarized into a phase diagram, with the morphotropic phase boundary (MPB) located at x=0.4. Compared with the Pb[(In_1/2Nb_1/2)_1-xTi_x]O₃ solid solution system, incorporating Ba in the A-site leads to a significant decrease in the dielectric maximum temperature T_max, a suppression of the dielectric relaxation parameter γ, and a shift of the MPB composition to a higher Ti content. PACS 77.84.Dy; 77.80.Bh; 77.22.Ch     

Phase transition and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)(Nb<Subscript>1-x</Subscript>Ta<Subscript>x</Subscript>)O<Subscript>3</Subscript> lead-free piezoelectric ceramics

(K_0.5Na_0.5)(Nb_1-xTa_x)O₃ lead-free piezoelectric ceramics have been prepared by an ordinary sintering technique. The results of X-ray diffraction reveal that Ta⁵⁺ diffuses into the K_0.5Na_0.5NbO₃ lattices to form a solid solution with an orthorhombic perovskite structure. Because of the high melting temperature of KTaO₃, the (K_0.5Na_0.5)(Nb_1-xTa_x)O₃ ceramics can be sintered at higher temperatures. The partial substitution of Ta⁵⁺ for the B-site ion Nb⁵⁺ decreases both paraelectric/cubic–ferroelectric/tetragonal and ferroelectric/tetragonal–ferroelectric/orthorhombic phase transition temperatures, T_C and T_O-T. It also induces a relaxor phase transition and weakens the ferroelectricity of the ceramics. The ceramics become ‘softened’, leading to improvements in d₃₃, k_p, k_t and ε_r and a decease in E_c, Q_m and N_p. The ceramics with x=0.075–0.15 become optimum, having d₃₃=127–151 pC/N, k_p=0.43–0.44, k_t=0.43–0.44, ε_r=541–712, tanδ=1.75–2.48% and T_C=378–329 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s     

Nanostructured multiferroic PbFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> and its physical properties

Polycrystalline multiferroic PbFe_0.5Nb_0.5O3 (PFN) fabricated by a solid-phase method is studied. Before sintering, a synthesized PFN powder is processed in Bridgman anvils via a force action in combination with shear deformation (FASD) at room temperature. The electrophysical properties and structural parameters of processed samples and a reference sample are compared. Point defects are shown to play a key role in the formation of the physical properties beginning from an FASD of 200 MPa.     

Investigations of dielectric enhancement in (Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>)<Subscript>1-x</Subscript>(TiO<Subscript>2</Subscript>)<Subscript>x</Subscript> ceramics prepared by laser-sintering technique

The maximum dielectric permittivity of Ti-doped Ta₂O₅ ceramics may reach 450 by a laser-sintering technique. The aim of this study is to investigate the mechanisms of the dielectric enhancement based on the unique structural and morphological properties of the laser-sintered ceramics. The reason for the dielectric enhancement is due to the crystal structure distortion in the high-temperature phase, the oriented grain growth taking place in a direction deviating from [001] in the laser-sintered ceramics. The concurrent nature of quenching effects, a sharp temperature gradient and mass transfer in liquid phase originated from laser high energy irradiation with strict directivity leads to the structural and morphological properties. PACS 81.40.Tv; 61.80.Ba; 77.22.-d; 77.22.Ch     

Electrical properties of a lead-free perovskite ceramic: (Na<Subscript>0.5</Subscript>Sb<Subscript>0.5</Subscript>)TiO<Subscript>3</Subscript>

Polycrystalline (Na_0.5Sb_0.5)TiO₃ was prepared using a high-temperature solid-state reaction method. An XRD analysis indicated the formation of a single-phase monoclinic structure. Complex impedance studies revealed the presence of grain boundary effects from 300 °C onwards. Also, the dielectric relaxation in the system was found to be of a non-Debye type. The ac conductivity data were used to evaluate the density of states at the Fermi level, the minimum hopping length and activation energy of the compound. The dc electrical and thermal conductivities of grain and grain boundary have been assessed. The correlated barrier hopping model was found to successfully explain the mechanism of charge transport in (Na_0.5Sb_0.5)TiO₃. PACS 72.20.Ee; 77.22.Ch; 77.22.Gm; 77.84.Dy; 81.05.Je     

Phase transition behavior of highly (100) textured sol-gel-derived Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> thin films

We have investigated the relations between microstructure and dielectric properties in order to fabricate sol-gel-derived highly (100) oriented Ba_0.5Sr_0.5TiO₃ (BST 50/50) thin films with properties comparable to those of the bulk material. For the first time, we were able to fabricate BST thin films which exhibited the orthorhombic-to-tetragonal transition in addition to the commonly observed tetragonal-to-cubic transition. We were successful in explaining the commonly observed degradation of the dielectric behavior of BST thin films, when compared to that of the bulk material, in terms of grain size, compositional inhomogeneity (measured in terms of Sr/Ba ratio) between the grain bulk and grain boundary, and mechanical stresses. PACS 77.55.+f; 77.22Gm; 77.80.Bh; 77.80.Dj     

Structure,the lattice dynamic,and the dielectric characteristics of Sr<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films

Solid solution Sr_0.5Ba_0.5Nb₂O₆ films have been synthesized on a (111)Pt/(001)Si substrate by rf deposition in an oxygen atmosphere. The depolarized Raman spectra, the structure, and the dielectric characteristics of the films have been studied over a wide temperature range. It is found that the films were singlephase, had the tetragonal tungsten bronze structure, and had a pronounced axial texture with axis 001 directed perpendicular to the substrate surface. It is shown that the film material undergoes a diffuse phase transition to the state of a relaxor ferroelectric in the temperature range 300–425 K. Possible reasons of the regularities observed are discussed.     

Pressure induced antiferromagnet-ferromagnet transition in La<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>CoO<Subscript>2.8</Subscript> cobaltite

The anion deficient cobaltite La_0.5Ba_0.5CoO_2.8 with theformal cobalt valence state close to 3+ has been studied as function of pressure up to6.5 GPa at different temperatures by neutron powder diffraction. At ambient pressure thecrystal structure of this compound has cubic symmetry (space group Pm3?m) and is found to become antiferromagnetic withT _N close to 250 K. Applied pressure inducesa gradual transition from the antiferromagnetic into a ferromagnetic state through a mixedmagnetic state. The transition is not accompanied by obvious changes in the macroscopiccrystal symmetry. It is suggested that the magnetic ground state strongly depends on theunit cell volume and that the transition is associated with a spin state crossover of thecobalt ions whereas the formal Co³⁺/Co⁴⁺ ratio is less importantthan expected following the double exchange scenario for the appearance offerromagnetism.     

Polarization processes in BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> and SrBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics in infralow-frequency fields

The dielectric nonlinearity in BaBi₂Nb₂O₉ and SrBi₂Ta₂O₉ layered ceramics was studied by measuring their polarization loops and reverse dependences of permittivity. It was shown that the features of the dielectric response of BaBi₂Nb₂O₉ and SrBi₂Ta₂O₉ in strong fields can be explained by glass-like properties and the contribution of the domain structure of the ferroelectric material to repolarization processes, respectively.     

Dielectric properties,ionic conductivity and phase transitions in La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

The dspersion dielectric permeability and ion conductivity of La₂Mo₂O₉ ceramics was studied. It was established that the observed low-frequency dielectric dispersion is due to relaxation effects related to high ion conductivity. It is shown that the phase transition in La₂Mo₂O₉ has characteristic features of a superionic phase transition.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

Dielectric and polar order behaviors of BaTiO<Subscript>3</Subscript>-Bi(Mg<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics

New perovskite solid solution ceramics of (1−x)BaTiO₃-xBi(Mg_1/2Ti_1/2)O₃ ((1−x)BT-xBMT, x≤0.09) were synthesized by the solid-state reaction technique. X-ray diffraction studies have revealed a stable single perovskite structure for all samples. Dielectric measurements were carried out at different frequencies and temperatures. The polarization evolutions with temperatures were measured to investigate the ferroelectric properties. All the compositions show features of ferroelectrics with diffuse phase transition, though the temperature T _m of their dielectric constant maximum ε _m is frequency dependent. The dielectric constant peak ε(T) of (1−x)BT-xBMT ceramics become broad with increasing BMT content. During the temperature range of ε(T) peak summit, (1−x)BT-xBMT ceramics present quasi-linear dielectric phenomenon under high electric field with very high dielectric constant.     

Fabrication and dielectric properties of modified calcium (Pb<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>)(Zr<Subscript>0.7</Subscript>Ti<Subscript>0.3</Subscript>)O<Subscript>3</Subscript> ceramics

The aim of the present work is to report investigations concerning the influence of homovalent modificators on relaxor properties of PBZT 25/70/30 ceramics. The selection of the proper homovalent additive was very important. Literature reports as well as data taken from the periodic table indicated, that calcium ions substitute themselves for lead ions with high likelihood of occurrence. The investigations showed that the substitution significantly changed the microstructure of ceramics – with grains of calcium modified ceramics decreasing and density increasing. The XRD measurements indicate that the pure PBZT ceramics as well as calcium dopant were characterised by tetragonal structure with space group I4 /mmm. Addition of calcium leads to a slight decrease in the lattice constant and crystal structure. The calcium modification also changes the dielectric properties. The temperature characteristic of the dielectric constant achieved a broadened maximum at temperature T_m, which decreases with increasing Ca content. The properties typical for ferroelectric relaxors weaken with increasing calcium dopant.     

Short-Range Order in Amorphous and Crystalline Ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The microstructures of amorphous and polycrystalline ferroelectric Hf_0.5Zr_0.5O₂ films are studied by X-ray spectroscopy and ellipsometry. EXAFS spectra demonstrate that the amorphous film consists of an “incompletely mixed” solid solution of metallic oxides HfO₂ and ZrO₂. After rapid thermal annealing, the mixed Hf_0.5Zr_0.5O₂ oxide films have a more ordered polycrystalline structure, and individual Hf and Zr monoxide islands are formed in the films. These islands are several nanometers in size and have a structure that is similar to the monoclinic structure of HfO₂ and ZrO₂. The presence of the HfO₂ and ZrO₂ phases in the Hf_0.5Zr_0.5O₂ films is also detected by ellipsometry.     

AlF<Subscript>3</Subscript> coating of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> for high-performance Li-ion batteries

AlF₃-coating is attempted to improve the performance of LiNi_0.5Mn_1.5O₄ cathode materials for Li-ion batteries. The prepared powders are characterized by scanning electron microscope, powder X-ray diffraction, charge/discharge, and impedance. The coated LiNi_0.5Mn_1.5O₄ samples show higher discharge capacity, better rate capability, and higher capacity retention than the uncoated samples. Among the coated samples, 1.0 mol% AlF₃-coated sample shows highest capacity after charge–discharged at 30 mA/g for 3 cycles, but 4.0 mol% coated sample exhibits the highest capacity and cycling stability when cycled at high rate of 150 and 300 mA/g. The 40th cycle discharge capacity at 300 mA/g current still remains 114.8 mAh/g for 4.0 mol% AlF₃-coated LiNi_0.5Mn_1.5O₄, while only 84.3 mAh/g for the uncoated sample.     

Effect of carbon coating process on the structure and electrochemical performance of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>O<Subscript>2</Subscript> used as cathode in Li-ion batteries

LiNi_0.5Mn_0.5O₂ powder was synthesized by a coprecipitation method. LiOH.H₂O and coprecipitated [(Ni_0.5Mn_0.5)C₂O₄] precursors were mixed carefully together and then calcined at 900°C. Surface modified cathode materials were obtained by coating LiNi_0.5Mn_0.5O₂ with a thin layer of amorphous carbon using table sugar and starch as carbon source. Both parent and carbon-coated samples have the characteristic layered structure of LiNi_0.5Mn_0.5O₂ as estimated from X-ray diffractometry measurements. Transmission electron microscope showed the presence of C layer around the prepared particles. TGA analysis emphasized and confirmed the presence of C coating around LiNi_0.5Mn_0.5O₂. It is obvious that the carbon coating appears to be beneficial for the electrochemical performance of the LiNi_0.5Mn_0.5O₂. A capacity of about 150 mAh/g is delivered in the voltage range 2.5–4.5 V at current density C/15 for carbon coated LiNi_0.5Mn_0.5O₂ in comparison with about 165 mAh/g obtained for carbon free LiNi_0.5Mn_0.5O₂ at the same current density and voltage window. About 92% and 82% capacity retention was obtained at 50th cycle for coated LiNi_0.5Mn_0.5O₂ using sucrose and starch, respectively; whereas, 75% was retained after only 30th cycle for carbon free LiNi_0.5Mn_0.5O₂. This improvement is mainly attributed to the presence of thin layer of carbon layer that encapsulate the nanoparticles and improve the conductivity and the electrochemical performance of LiNi_0.5Mn_0.5O₂.