Synthesis,structural and ferroelectric properties of barium titanate based glass-ceramic nano-composites

Novel glass-ceramic nano-composites based on BaTiO₃–V₂O₅–Bi₂O₃ glasses were prepared via heat-treatment at crystallization temperature (T_cr). The nanostructural and ferroelectric properties were investigated by differential scanning calorimeter (DSC), transmission electron microscope (TEM), X-ray diffraction (XRD) and dielectric measurements, respectively. It was shown by XRD and TEM studies that appropriate heat-treatment glasses can turn into glass-ceramic nano-composites consisting of crystallites smaller than 30 nm embedded in the glassy matrix. The observed dielectric constant of heat‐treated samples, showed average broad peak around 324 K. The average Curie temperature (T_c) observed around 324 K in the present system. This observation of these glass-ceramic nano-composites can be utilized to control T_c by proper adjustment of BaTiO₃ content. This result, therefore, supports dipolar orientation and phase transition in the glass-ceramic samples dispersed with nanocrystalline BaTiO₃. Such a feature can be used for industrial applications where the shape of the application article is a necessary requirement such as integrated capacitor.     

Dielectric relaxation of (N(C2H5)4)2CoCl2Br2 nanocrystallites incorporated into the PMMA matrix

The dielectric properties of tetraethylammonium dibromo-dichloro-cobaltate (N(C₂H₅)₄)₂CoCl₂Br₂ (TEA-CBC) nanocrystallites incorporated into the polymethylmethacrylate (PMMA) matrix were investigated within the spectral range of 3 × 10⁵–3 × 10⁹ Hz in the temperature range of 90–300 K. The considerable difference of the dielectric spectra of the nanocomposite compared to the TEA-CBC crystal and to the pure PMMA matrix was observed. The phenomenon of the ‘negative capacity’ has been found in the considered material. Its dependence on the NC content was investigated. Temperature investigations of the dielectric permittivity for the TEA-CBC NC incorporated into the polymer PMMA matrices have shown the sharp-like resonance dependences of the imaginary part of the dielectric permittivity near 1.2 GHz. The intensity of the corresponding resonance peaks increase sub-linearly with increasing NC content. Taking into account the substantial growth of the imaginary part of the permittivity with increasing NC concentration, one can assume that the main contribution to the effect is given by the interface NC-PMMA regions. Additional experiments were performed to eliminate the influence of ‘geometry factor’.     

Dielectric properties of polystyrene–CCTO composite

The control of the dielectric properties of polymer composites is a relevant tool to synthesize a material to a specific industrial application. Polystyrene (PS) is a suitable host because it is readily available, and is easy to cast into desired shapes, maintaining the mechanical integrity of the matrix. CaCu₃Ti₄O₁₂ (CCTO) is a well-known high dielectric constant material, very useful for capacitors and memory devices. In this work, we studied the dielectric properties of the composite PS–CCTO, in the frequency range 10 Hz to 100 kHz, for CaCu₃Ti₄O₁₂ grains concentrations up to 64% by volume. Different mixture laws were used to fit the data: Hanai, Wiener, Maxwell–Wagner, Kraszewsky, Looyenga and Generalized Looyenga. The last one presents the best results. The calculated exponent of this law was then correlated with the shape particles observed by scanning electron microscopy. Finally, using Generalized Looyenga law, we can carefully select the adequate CCTO concentration in order to tailor the desired behavior, producing interesting composites for potential applications.     

Exploration on nano-composite fumed silica-based composite polymer electrolytes with doping of ionic liquid

Fumed silica (SiO₂)-based composite polymer electrolytes were prepared by means of solution casing technique. Horizontal attenuated total reflectance-Fourier Transform Infrared (HATR-FTIR) study shows the complexation between polymer matrix and SiO₂. The highest ionic conductivity of (4.11 ± 0.01) × 10^? 3 Scm^? 1 is achieved upon inclusion of 8 wt.% of SiO₂. Three different regions have been observed in the frequency dependence–ionic conductivity study. The conductivity rises sharply with frequency at low frequency regime. It is followed by a frequency independent plateau region and sharp decrease in the conductivity at high frequency range. The dielectric permittivity (ε^') and dielectric loss (ε^") are decreased with increasing the frequency. This phenomenon is mainly attributed to the electrode polarization effect. The formation of electrical double layer has been proven in these dielectric permittivity studies. This indicates the non-Debye properties of the nano-composite polymer electrolytes.     

Enhancement of ferroelectricity in the compositionally graded (Pb,Sr)TiO3 thin films derived by a sol–gel process

The compositionally graded Pb_1−xSr_xTiO₃ (PST) films with a fine compositional gradient from Pb_0.6Sr_0.4TiO₃ to Pb_0.3Sr_0.7TiO₃ were fabricated on LNO-buffered Pt/Ti/SiO₂/Si substrates by a sol–gel deposition method. The graded films crystallized into a pure perovskite structure and exhibited highly (1 0 0) preferred orientation after post-deposition annealing. Dielectric and ferroelectric properties were investigated as a function of temperature, frequency and direct current bias field. Dielectric constant peaks, common to a ferroelectric transition, were not observed in the temperature range of 25–250 °C within which the dielectric constant showed weak temperature dependence. This compositionally graded thin film can result in a dielectric constant more than double and a remanent polarization at least two and a half times larger than conventional PST thin films.     

Glass transition and segmental dynamics in poly(dimethylsiloxane)/silica nanocomposites studied by various techniques

We report new results on segmental dynamics and glass transition in a series of poly(dimethylsiloxane) networks filled with silica nanoparticles prepared by sol-gel techniques, obtained by differential scanning calorimetry (DSC), thermally stimulated depolarization currents (TSDC), broadband dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA). The nanocomposites are characterized by a fine dispersion of 10 nm silica particles and hydrogen bonding polymer/filler interactions. The first three techniques indicate, in agreement with each other, that a fraction of polymer in an interfacial layer around the silica particles with a thickness of 2–3 nm shows modified dynamics. The DSC data, in particular measurements of heat capacity jump at T_g, are analyzed in terms of immobilized polymer in the interfacial layer. The dielectric TSDC and DRS data are analyzed in terms of slower dynamics in the interfacial layer as compared to bulk dynamics. We employ a special version of TSDC, the so-called thermal sampling (TS) technique, and provide experimental evidence for a continuous distribution of glass transition temperatures (T_g) and molecular mobility of the polymer in the interfacial layer, which is consistent with the DRS data. Finally, DMA results show a moderate slowing down of segmental dynamics of the whole polymer matrix (increase of glass transition temperature by about 10 K as compared to the pure matrix).     

Continuous silica fiber reinforced silica composites densified by polymer-derived silicon nitride: Mechanical properties and microstructures

Continuous silica glass fiber reinforced silica composites were prepared via silica sol suspension infiltration/sintering method followed by densification treatment by preceramic polymer infiltration/pyrolysis process, and the mechanical properties and microstructures of the composites were investigated. Pyrolyzed at 873 K in ammonia atmosphere, the preceramic polymer polyhydridomethylsilazane resulted in a low-carbon near-stoichiometric ceramic with an empirical formula of Si_1.0N_1.38C_0.01O_0.04H_0.78. After the densification treatment, the density of the composites increased a little from 1.64 g/cm³ to 1.79 g/cm³, and the flexural strength increased greatly from 69.4 MPa to 95.9 MPa. However, the densified composites exhibited a tendency to brittle failure due to the relatively strong interfacial bonding between the glass fibers and polymer-derived silicon nitride, and also the degradation of glass fibers during post-treatment.     

Dielectric and optical properties of surface crystallized TeO2– LiNbO3 glasses

Glasses with composition (100 − x) TeO₂–x LiNbO₃ (10⩽x⩽50) were prepared by conventional melt-quenching. The glass-formation ability, dielectric and optical properties of these glasses were studied. LiNbO₃ microcrystallites were directly precipitated on the surface of the glass, with the composition 50 TeO₂ – 50 LiNbO₃, by a single step heat treatment. The polar nature and second-order optical non-linearity of the transparent surface crystallized glasses are manifested in their strong pyroelectric response, ferroelectric hysteresis and intense second harmonic generation of 1064 nm wavelength radiation.     

Preparation and characterization of SrTiO3/BaTiO3 thin multilayer films deposited on Pt/Ti/SiO2/Si substrate by radio frequency magnetron sputtering

SrTiO₃/BaTiO₃ thin films with multilayer structure were deposited on Pt/Ti/SiO₂/Si substrates by a double target radio frequency (RF) magnetron sputtering at 500 °C. The structure and properties of the SrTiO₃/BaTiO₃ thin multilayers have been evaluated by X-ray diffraction (XRD), Auger electron spectrometry (AES), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), electron diffraction (ED) and polarization-electric field hysteresis loop. The XRD result reveals that the SrTiO₃/BaTiO₃ thin multilayers with the designed modulation have been accomplished. The lattice strain increases with layer number. According to AES analysis and morphology observation, a discrete interlayer exists at a position between the interface of Pt electrode and SrTiO₃. The remanent polarization (P_r) and coercive field (E_c) of SrTiO₃/BaTiO₃ thin multilayer are 3.0 μC/cm² and 20.0 kV/cm, respectively. In comparison with BaTiO₃, the device containing dual layers of SrTiO₃/BaTiO₃ possesses higher E_c but lower P_r.     

Influence of manganese ions on spectroscopic and dielectric properties of LiF-SrO-B2O3 glasses

Transparent glasses, obtained through melt quenching technique, with composition 30LiF-10SrO-(60-x)B₂O₃-xMnO, with 0 ≤ x ≤ 3 mol% (x = 0, 1, 1.5, 2, 2.5 and 3), were characterized by X-ray diffraction (XRD) and then they were analyzed for physical, spectroscopic studies (optical absorption, electron spin resonance (ESR) and FTIR) and dielectric properties (dielectric constant ε′, loss tanδ ?and conductivity σ_ac etc.). The results were analyzed and correlated with each other in the light of local environment and oxidation states of manganese ion in the glass network. The increase in the area of optical absorption peak and ESR signal intensity indicate that both Mn²⁺ and Mn³⁺ ions exist in octahedral symmetry are increased with increasing MnO dopant in the glass matrix. The semi conducting nature of the glass network is found to increase due to the considerable increase in BO₃, MnO₆ structural units whenever B₂O₃ in the host glass is gradually replaced by MnO.     

Dielectric relaxation and electro-optical switching behavior of nematic liquid crystal dispersed in poly(methyl methacrylate)

Polymer dispersed liquid crystal composite films were prepared from poly(methyl methacrylate) and nematic liquid crystal E44 by solvent induced phase separation method. In the present investigation we report effect of liquid crystal concentration on the electro-optical and dielectric properties of the composite films. The results were interpreted in terms of phase separation of liquid crystal and polymer, shape and size of liquid crystal droplet, interfacial charge layer effect, liquid crystal loading and miscibility of liquid crystal in the polymer matrix. The miscibility between two phases at interface was investigated by employing Fourier‐Transform Infrared Spectroscopy and differential scanning calorimetry. Morphological study showed that liquid crystal phase is embedded in a spongy poly(methyl methacrylate) matrix and homogeneous distribution increased with increasing E44 content. Electro optical behavior of these composite films under the condition of an externally applied AC electric field (0–200 Vp-p, 50–1000 Hz) and wide range of temperature was determined using He–Ne laser (wave length 632.8 nm) as a light source. It was found that Poly(methyl methacrylate)/E44 (30/70) wt.% composite has more significant properties than the other concentrations. The performance of all composites showed variations with respect to applied voltage as well as temperatures. Dielectric measurement of polymer dispersed liquid crystals has been carried out in the frequency range from 20 Hz to 20 MHz and over the temperature range from 24 °C to 100 °C. The Maxwell–Wagner effect due to interfacial charge accumulation between boundaries of liquid crystal droplets and surrounding of polymer matrix has been observed.     

Electroactive influence of ferroelectric nanofillers on polyamide 11 matrix properties

Barium titanate ceramic powders have been incorporated in polyamide 11 to form homogeneous dispersion of particles in the matrix. Barium titanate/polyamide 11 nanocomposites have been synthesized using a solvent casting method with ultrasonic stirring to homogeneously disperse inclusions in the matrix. Composites with volume fraction of barium titanate ϕ ranging from 0.01 to 0.4 were elaborated. Films were fabricated using a hot press method. Only the inclusions were poled in the matrix to form a ferroelectric particles/unpoled matrix composite. Interactions between the particles and the matrix, pyroelectric and piezoelectric response were studied as a function of ϕ by dynamic dielectric spectroscopy. Composites show interesting pyro-piezoelectric activity. Pyroelectric merit factor increases linearly and it reaches a limit value of 0.3 for a volume fraction ϕ = 0.1.     

Hydrothermal synthesis of BaTiO3 thin films on nanoporous TiO2 covered Ti substrates

It is well known that there is an upper limit (<0.25 μm) for the thickness of hydrothermal thin films grown on Ti substrate in the 100–200 °C temperature range, even the reaction time is extended to several weeks. In this paper, BaTiO₃ thin films have been firstly hydrothermally synthesized on titanium substrates covered with a nanoporous TiO₂ layer. By using TiO₂ covered substrates, the thickness of BaTiO₃ films can easily reach ∼1.0 μm at 110 °C after only 2 h hydrothermal treatment. It is found that the large quantity of pores with size at the tens of nanometer range in the oxide layer served as easy paths for the diffusion of Ba²⁺ and OH⁻ and enabled the film grow thicker. SEM and XRD results show that the films are crack-free and in polycrystalline phase.     

Multiferroic behavior in silicate glass nanocomposite having a core–shell microstructure

Nanosized iron core and barium titanate shell microstructure was generated within a silicate glass of composition 23.1 Na₂O, 23.1 BaO, 23.0 TiO₂, 7.6 B₂O₃, 5.8 Fe₂O₃, 17.4 SiO₂ by first reducing it at 893 K for ½ h and then subjecting it to heat treatment at 759 K for 4 h. Transmission electron microscopy showed the composite particles to have a mean diameter of 3.9 nm. The nanocomposite exhibited both ferroelectric and ferromagnetic behavior. The dielectric constant peak was not prominent because of a small thickness of the barium titanate phase. The magnetic hysteresis loop showed an asymmetric behavior giving rise to a small exchange bias field. This is believed to arise due to exchange interaction between the ferromagnetic iron core and the thin layer of Fe₃O₄ on the core surface with a spin glass-like behavior. The magnetization under zero-field cooled (ZFC) and field cooled (FC) conditions indicated superparamagnetic behavior at temperatures higher than 300 K. The optical absorption spectra exhibited a peak at around 325 nm. This was analyzed satisfactorily on the basis of a metal core–oxide shell nanoconfiguration. The extracted values of metal core conductivity showed a metal insulator transition for iron core diameters less than 2.4 nm. The present synthesis approach will lead to newer multiferroic nanocomposites and glasses with multifunctionalities.     

Dielectric low-k composite films based on PMMA,PVC and methylsiloxane-silica: Synthesis,characterization and electrical properties

This report describes the preparation of low-k inorganic–organic hybrid dielectric films, based on a polymethylmethacrylate–polyvinylchloride (PMMA–PVC) blend and a silica powder functionalized on the surface with methylsiloxane groups (m-SiO₂). By dispersing m-SiO₂ into a [(PMMA)_x(PVC)_y] 50/50 (x/y) wt% polymer blend, six [(PMMA)_x(PVC)_y]/(m-SiO₂)_z hybrid inorganic–organic materials were obtained, with z ranging from 0 to 38.3 wt% and x = y = (100 − z)/2. The transparent, homogeneous, crack-free films were obtained by a solvent casting process from a THF solution. The morphology, thermal stability and transitions of hybrid materials were studied by environmental scanning electron microscopy (ESEM), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). ESEM revealed that hybrid dielectric films are very homogeneous materials. The electrical response of the dielectric films was studied by detailed broadband dielectric spectroscopy (BDS). BDS measurements were performed at frequencies of 40 Hz to 10 MHz and a temperature range of 0–130°C. In these temperature and frequency ranges the proposed materials have a dielectric constant of <3.5 and a tan δ of <0.05. BDS also revealed molecular relaxation events in [(PMMA)_x(PVC)_y]/(m-SiO₂)_z materials as a function of temperature and sample composition. Results showed that these films with z in the range 25–35 wt% are very promising low-k dielectrics for applications in organic thin film transistor (OTFT) devices.     

Evolution of nanocrystalline BaBi2Nb2O9 in Li2B4O7–BaO–Bi2O3–Nb2O5 glass system

Transparent glasses and glass nano crystal composites (GNCs) of various compositions in the system (100 − x)Li₂B₄O₇–x(BaO–Bi₂O₃–Nb₂O₅) (where x = 10, 20, and 30 in molar ratio) were fabricated via splat-quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses. X-ray powder diffraction and transmission electron microscopic (TEM) studies confirmed the formation of layered perovskite BBN via a fluorite like phase. TEM studies revealed the presence of 10 nm sized spherical crystallites of fluorite like BaBi₂Nb₂O₉ phase in the glassy matrix of Li₂B₄O₇ (LBO). The influence of composition on the dielectric and the optical properties (transmission, optical band gap) of these samples has been investigated.     

Structural impact of iron ions on BaBiBO4 glasses: Spectroscopic and dielectric investigations

Transparent glasses of composition 10BaO.20Bi₂O₃.(70 ? x)B₂O₃.xFe₂O₃ (wt.%) where 0 ≤ x ≤ 2.0, were characterized by XRD and SEM. Physical, spectroscopic and dielectric properties were investigated. At higher dopant of Fe₂O₃, EPR results revealed that, the number of Fe³⁺ ions participate in the resonance is decreased by forming a new signal at g ≈ 3.015 due to increase of antiferromagnetic interaction of Fe³⁺ ions and/or formation of low spin Fe³⁺ ions in the glass matrix. With initial 0.5 wt.% doping of Fe₂O₃, less dense glass is formed with colloids of metallic Bi⁰ atoms. The absorption bands at 604 and 712 nm in F5 glass are ascribed to Bi⁰ and Bi⁺ radicals respectively. No characteristic Fe³⁺ absorption bands (spin-forbidden) are found. Fe²⁺ ions are increased at higher concentration of Fe₂O₃. Higher concentration of Fe₂O₃ is favorable for BO₂O^?, BO₃, BiO₆ and FeO₆ symmetry unit leads to low band gap and high Urbach energy. By doping of Fe₂O₃ the dielectric parameters like dielectric constant (ε′), loss (tanδ and ac electrical conductivity (σ_ac) are found to increase.     

Polarons in boron doped iron phosphate glasses

The electrical conductivity and dielectric properties of xB₂O₃–(40 ? x)Fe₂O₃–60P₂O₅ (x = 6–20, mol%) glasses were investigated in the frequency range from 0.01 Hz to 1 MHz and the temperature range from 303 K to 523 K. At temperatures below 523 K an ac conductivity and the dielectric constant follow the universal dielectric response (UDR), being typical for hopping or tunneling of localized charge carriers. A detailed analysis of the temperature dependence of the UDR parameter s in terms of the theoretical model for tunneling of small polarons revealed that below 523 K this mechanism governs the charge transport in these glasses. The comparison of the values of characteristic coefficients W_∞ and α determined by two different methods confirms the polaronic behavior of boron doped iron phosphate glasses.     

Thermal,vibrational and Ac impedance studies on proton conducting polymer electrolytes based on poly(vinyl acetate)

Proton conducting polymer electrolytes based on poly(vinyl acetate) (PVAc) and perchloric acid (HClO₄) have been prepared by solution casting technique with various compositions. The X-ray diffraction analysis confirms the polymer–HClO₄ complex formation. FTIR spectra analysis reveals the interaction between proton and ester oxygen of poly(vinyl acetate) (PVAc). The shift in T_g towards the lower temperature indicates that the polymer salt interaction takes places in the amorphous phase of the polymer matrix. Ac impedance spectroscopy reveals that 75 mol% PVAc:25 mol% HClO₄ exhibits maximum conductivity, 3.75 × 10^? 3 S cm^? 1 at room temperature (303 K). The increase in conductivity with increase in dopant concentration and temperature may be attributed to the enhanced mobility of the polymer chains, number of charge carriers and rotations of side chains. The temperature dependence of conductivity shows non-Arrhenius behavior at higher temperatures.     

Electromechanical and electro-optic properties of xBiScO3–yBiGaO3–(1−x−y)PbTiO3 single crystals

Single crystals in the xBiScO₃–yBiGaO₃–(1−x−y)PbTiO₃ (BS–BG–PT) system were grown by the high temperature solution method using Pb₃O₄ and Bi₂O₃ as the flux. The dielectric permittivity (ε_r) at room temperature for unpoled tetragonal crystals was determined to be 500–600 with dielectric loss tangents less than 0.3%. The Curie temperature was found to be around ∼420–450°C, with a dielectric maximum, exhibiting relaxor behavior. The longitudinal piezoelectric coefficient (d₃₃) was found to be ∼300 pC/N for 〈0 0 1〉 oriented tetragonal crystals with electromechanical coupling factor (k₃₃) of 75%, with a shear mode, d₁₅∼290 pC/N and k₁₅∼45%, lateral mode, d₃₁∼−55 pC/N and k₃₁∼−37%. The remnant polarization (P_r) was 46 μC/cm² with a coercive field (E_c) of 43 kV/cm at 1 Hz and DC field of 60 kV/cm. The linear electro-optic (E-O) coefficients of poled crystals determined using an automated scanning Mach–Zehnder interferometer method at room temperature and wavelength of 632.8 nm were r₃₃=36 and r₁₃=4 pm/V, respectively.