The effects of sintered sample thickness on the dielectric properties of CaCu3Ti4O12 ceramics prepared at 1000–1100 °C in air

In this study, the relationship between dielectric properties and sintered sample thickness (d) (0.41–2.74 mm) of CaCu₃Ti₄O₁₂ (CCTO) ceramics prepared at 1000–1100 °C in air was investigated. Compacted green ceramic bodies in varying weights and sintered at different temperatures were prepared to obtain ceramics with varying thicknesses. The samples were evenly polished on either surface, electroded and measured by a precision LCR meter at 20 Hz–1 MHz. The results showed that the ε′ increased monotonically with increasing sintering temperature and indicated a linear relationship with d for samples sintered at ≥1040 °C, while the ε′ for samples sintered at ≤1030 °C was barely affected. Complex impedance analysis showed that the ρ_gb was nearly constant with the change of d. The inverse effect of ε′ and ρ_gb with d can also be observed for the gradual thickness reduction sample sintered at 1040 °C, confirming that the grain boundary plays a key role in the variation of dielectric properties for CCTO ceramics.     

Deficient or excessive CuO-TiO2 phase influence on dielectric properties of CaCu3Ti4O12 ceramics

The influence of the CuO–TiO₂ phase (CT) on dielectric properties of the CCTO ceramic was investigated. CaCu_XTi_YO₁₂ (CC_XT_YO) powders were prepared based on the coprecipitated method, where 2.70 ≤ x ≤ 3.30 and 3.25 ≤ y ≤ 4.75. XRD patterns confirmed the presence of CCTO and also the secondary phases as CuO, TiO₂, and CaTiO₃ for each sample and aided in its quantification. Scanning Electron Microscopy (SEM) shows secondary phases evolution in the grain boundaries, and its influence on size and morphology of the grains. Impedance spectroscopy measurements showed that the ceramics with lower amount of CuO and TiO₂ phases (CT/deficient ceramics) exhibited the highest ε′ values (2.1 × 10⁴ at 1 kHz for CC_2.9T_3.75O ceramic). Also, CT/deficient ceramics showed lower tanδ values (0.090 at 1 kHz for CC_2.9T_3.75O ceramic) than ceramics prepared with excessive CuO–TiO₂ phase (0.241 at 1 kHz for CC_3.1T_4.25O ceramics). The deficiency of CuO and TiO₂ phases associated with high percentage of CCTO and CaTiO₃ phases resulted in ceramics with the higher ε′ values.     

Optimize the dielectric properties of CaCu3Ti4O12 ceramics by adjusting the conductivities of grains and grain boundaries

Reduction of dielectric loss for CCTO ceramics is a prerequisite for their applications. Considering internal barrier layer capacitance effect, improving the capacitance and grain boundary resistance is an effective way to reduce dielectric loss. Therefore, more conductive Ti³⁺ and Cu⁺ ions were introduced to grains by adding carbon to ceramic bodies, improving the permittivity of CCTO ceramics. Annealing was performed to increase the grain boundary resistance. The dielectric loss of the CCTO ceramics thus prepared, which maintain a giant permittivity, is significantly reduced. Specifically, the CCTO ceramic with carbon addition, which was sintered at 1080 °C for 8 h and air annealed at 950 °C for 2 h, exhibits a giant permittivity of about 2.50(5)×10⁴ and a low dielectric loss of less than 0.050(2) from below 20 Hz to 50 kHz at room temperature. Meanwhile, its dielectric loss at 1–10 kHz is less than 0.050(2) from below room temperature to about 100 °C.     

Influence of atmospheres on the dielectric properties of calcium copper titanate ceramics

Calcium Copper Titanate Ceramics (CaCu₃Ti₄O₁₂; CCTO) are useful as capacitors because of the large dielectric constant. This study investigated the effect of testing atmospheres such as air and dry N₂ on the stability and reproducibility of the electrical properties displayed by CCTO ceramics. Solid-state reaction method is used to synthesize phase pure CCTO powders, which are used to fabricate dense samples by sintering. Samples with different microstructures are obtained by sintering at different temperatures of 1070 and 1100°C. AC impedance spectroscopy is used to study the effects of testing atmospheres, temperatures, microstructures, and frequency on the dielectric properties of the sintered samples. Highly irreproducible dielectric properties are observed upon testing in ambient conditions. Stable and reproducible dielectric properties are only obtained in dry N₂. Re-exposing the same CCTO samples back into ambient air after treating in dry N₂ restored irreproducibility. The results from this study suggested that the role of moisture/air in the ambient on the dielectric properties should not be over-looked and is expected to play a key role in controlling the stability of dielectric properties of CCTO. This new approach of characterizing the CCTO ceramics can be used as guidelines to eliminate hysteresis due to ambient atmosphere and to produce stable and reproducible dielectric properties useful as capacitors.     

Improved dielectric properties in A′‐site nickel‐doped CaCu3Ti4O12 ceramics

The improved dielectric properties and voltage‐current nonlinearity of nickel‐doped CaCu₃Ti₄O₁₂ (CCNTO) ceramics prepared by solid‐state reaction were investigated. The approach of A′‐site Ni doping resulted in improved dielectric properties in the CaCu₃Ti₄O₁₂ (CCTO) system, with a dielectric constant ε′≈1.51×10⁵ and dielectric loss tanδ≈0.051 found for the sample with a Ni doping of 20% (CCNTO20) at room temperature and 1 kHz. The X‐ray photoelectron spectroscopy (XPS) analysis of the CCTO and the specimen with a Ni doping of 25% (CCNTO25) verified the co‐existence of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺. A steady increase in ε′(f) and a slight increase in α observed upon initial Ni doping were ascribed to a more Cu‐rich phase in the intergranular phase caused by the Ni substitution in the grains. The low‐frequency relaxation leading to a distinct enhancement in ε′(f) beginning with CCNTO25 was confirmed to be a Maxwell‐Wagner‐type relaxation strongly affected by the Ni‐related phase with the formation of a core‐shell structure. The decrease of the dielectric loss was associated with the promoted densification of CCNTO and the increase of Cu vacancies, due to Ni doping on the Cu sites. In addition, the Ni dopant had a certain effect on tuning the current‐voltage characteristics of the CCTO ceramics. The present A′‐site Ni doping experiments demonstrate the extrinsic effect underlying the giant dielectric constant and provides a promising approach for developing practical applications.     

Dielectric relaxations of shellac/amino resin blends

The dielectric constant (ε′) and loss (ε″) of shellac/melamine resin blends have been determined at temperatures between 20° and 120°C and frequencies between 0.1 and 100 kHz. ε′ decreases with increase in the percentage of melamine resin in the blend. Two relaxations have been observed, of ΔH = 4.99 kcal/mole and 11.1 kcal/mole. The glass transition is observed between 60° and 70°C. The cole-cole parameter increases with temperature and becomes constant above T_g.     

Improved dielectric,nonlinear and magnetic properties of cobalt-doped CaCu3Ti4O12 ceramics

The dielectric properties and voltage–current nonlinearity of the pure and various cobalt-doped CaCu₃Ti₄O₁₂ (Co-doped CCTO) prepared by solid-state reactions were investigated. The improved dielectric properties in the Co-doped CCTO, with a dielectric constant $\text{ε'}$ ≈7.4?×?10⁴ and dielectric loss $\text{tan}\text{δ}$?≈?0.034, were observed in the sample with a Co doping of 5% (CCTO05) at room temperature and 1?kHz. The related multi-relaxations, RII (?20 to 40?°C) and RIII (100–150?°C), were demonstrated to be a Debye-like relaxation and a Maxwell–Wagner relaxation related to oxygen vacancies. The low dielectric loss of CCTO05 was associated with the high grain boundary resistance and the increase in cation vacancies. The improved nonlinear electrical properties (CCTO05, with nonlinear coefficients $\text{α}$?≈?5.22 and breakdown electric field ${\text{E}}_{\text{b}}$?≈?300.46?V/cm) and the ferromagnetism in Co-doped CCTO were also discussed.     

Direct and hybrid microwave solid state synthesis of CaCu3Ti4O12 ceramic: Microstructures and dielectric properties

CaCu₃Ti₄O₁₂ (CCTO) electroceramic possesses unusual giant dielectric permittivity up to ε?=?10⁴ at low frequency range and room temperature. CCTO dielectric properties strongly depend on its microstructure therefore it is essential to pay attention to the processing techniques which impact grain size and microstructure. In this work, direct and hybrid microwave solid state synthesis was specifically designed and used for the synthesis of CCTO. The microwave process was also compared to the conventional process which involves usual infrared heating. The structural (XRD) and microstructural (SEM) characterizations indicate that microwave synthesis is particularly efficient to get rapidly pure CCTO powder. The fully automated 915?MHz single-mode microwave cavity used for hybrid synthesis allows a perfect control of the temperature distribution and heating rate. Therefore hybrid microwave synthesis leads to a fine, mono-disperse and practically pure CCTO powder in the range of 300 – 500?nm. The advantages of the hybrid microwave heating method are discussed and compared to the conventional and direct microwave heating processes. From the powders synthesized by the different routes, dense compacts were sintered in air at 1050?°C in a conventional furnace. Microstructural characterizations reveal abnormal grain growth during sintering which levels dielectric properties. All exhibit a giant dielectric constant ε?>?10³ at room temperature which decreases drastically to ε?=?90 at 10?K. Those properties are discussed according to the well-established Internal Barrier Layer Capacitor (IBLC) model.     

Photocatalytic Activity of AgBr as an Environmental Catalyst

The photocatalytic activity of AgBr has been investigated. AgBr(N₂) was prepared by solid(AgNO₃)–solid(KBr) reaction at different temperatures in a stream of N₂. AgBr(N₂) prepared at 250 °C showed the highest H₂ generation activity although the larger crystallites of Ag were observed. When the preparation was carried out under air [AgBr(air)] at 250 °C, the photoactivity and the crystallization of Ag were lowered by the formation of silver oxides species in AgBr(air) probably during the natural cooling under air. It is pointed out however that the amount of hydrogen of both AgBr(N₂) and AgBr(air) increased linearly increasing with reaction time regardless of the formation of large Ag crystallites even after UV irradiation for 50 h. This suggests that the behavior of Ag formed might be different from that of the latent image in the photographic process.     

Epoxy resins based on aromatic glycidylamines. V. Shelf life of TGDDM-based epoxy resins

The effect of aging on resin composition was investigated as a part of a study concerned with the evaluation of epoxies containing N, N, N′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM). Long-term stability of three different epoxy resins based on TGDDM and their mixtures with 4,4′-diaminodiphenylsulfone (DDS) was followed at 23 ± 2°C at a relative humidity ranging from 45% to 55%, by means of GPC and HPLC; short-term stability of the resins was evaluated at 125°C.     

Microstructures and dielectric relaxation behaviors of pure and tellurium doped CaCu3Ti4O12 ceramics prepared via vibro-milling method

In this work, we have reported microstructures and the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics doped with different proportions of TeO₂ dopant (mol%, x=0, 0.5%, 1.0%, 2.0%). The pure and tellurium doping CCTO ceramics were prepared by a conventional solid-state reaction method and the effects of TeO₂ doping on the electrical properties and microstructures of these ceramics were investigated. XRD analysis confirmed the formation of single-phase material in samples. Scanning electron microscopy (SEM) is used in the micro structural studies of the specimens, which showed that TeO₂ doping can reduce the mean grain size and increasing size of an abnormal grain growth. Lattice parameter increases slightly with tellurium doping in CCTO, the dielectric constant reached a value as high as 18,000 (at 1 kHz) at a tellurium-doping concentration of 2.0 mol% and showed temperature stability at high frequency. The loss tangent of Te-doped CCTO ceramics was less than 0.05 at 1 kHz region below 105 °C. The loss tangent properties could be interpreted by the internal barrier layer capacitor model and the impedance measurement data.     

Photografting of N‐isopropylacrylamide and glycidyl methacrylate binary monomers on polyethylene film: Effect of mixed solvent consisting of water and organic solvent

Photografting (λ > 300 nm) of N‐isopropylacrylamide (NIPAAm) and glycidyl methacrylate (GMA) binary monomers (NIPAAm/GMA) on low‐density polyethylene film (thickness = 30 μm) was investigated at 60°C using mixed solvent consisting of water and an organic solvent such as acetone. Xanthone was used as a photoinitiator by coating it on the film surfaces. A maximum percentage of grafting was observed at a certain concentration of acetone in the mixed solvent, which was commonly observed for both ratios of NIPAAm/GMA, 8/2 and 7/3. Based on the photografting of NIPAAm/GMA on xanthone‐coated film, monomer reactivity ratios of NIPAAm (r₁) and GMA (r₂) were calculated using the Fineman–Ross method. The values were 0.31 ± 0.1 and 4.8 ± 0.2 for the water solvent system, while they were 0.96 ± 0.1 and 4.9 ± 0.1 for the mixed solvent system. NIPAAm/GMA‐grafted films with a homogeneous distribution of grafted chains were formed by photografting using water and mixed solvents. The NIPAAm/GMA‐grafted films exhibited temperature‐responsive characters, whereas the grafted films showed a reversible change in the degree of swelling between 0 and 50°C, respectively. Epoxy groups in the grafted poly(NIPAAm/GMA) chains could be aminated with ethylenediamine in N,N′‐dimethylformamide at 70°C for 3 h. Complexes of the aminated NIPAAm/GMA‐grafted chains with cupric ion exhibited catalytic activity for the decomposition of hydrogen peroxide at 20 to 50°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2469–2475, 2005     

A copolymer of poly[2,2′‐(m‐phenylene)‐5,5′‐ bibenzimidazole] and poly(2,5‐benzimidazole) for high‐temperature proton‐conducting membranes

A novel copolymer of polybenzimidazoles was prepared by copolymerization of 3,3′‐diaminobenzidine tetrahydrochloride, 3,4‐diaminobenzoic acid and isophthalic acid in polyphosphoric acid at 200 °C. The polymerization could be performed within 90–110 min with the assistance of microwave irradiation. The solubility of the copolymer obtained in N,N‐dimethylacetamide (DMAc) was improved compared with those of poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] and poly(2,5‐benzimidazole). Thus copolymer membranes could be readily prepared by dissolving the copolymer powders in DMAc with refluxing under ambient pressure. The decomposition temperature of the copolymer was about 520 °C in air according to thermogravimetric analysis data. The proton conductivity and mechanical strength of the phosphoric acid‐doped copolymer membranes were investigated at elevated temperatures. A conductivity of 0.09 S cm^?1 at 180 °C and a tensile stress at break of 5.9 MPa at 120 °C were achieved for the acid‐doped copolymer membranes by doping acids in a 75 wt% H₃PO₄ solution. Copyright © 2010 Society of Chemical Industry     

Dielectric stability in the relaxor: Na0.5Bi0.5TiO3-Ba0.8Ca0.2TiO3-Bi(Mg0.5Ti0.5)O3- NaNbO3 ceramic system

Ceramics with temperature-stable dielectric characteristics have been developed in the system: 0.6[0.85Na_0.5Bi_0.5TiO₃-(0.15-x)Ba_0.8Ca_0.2TiO₃-xBi(Mg_0.5Ti_0.5)O₃]?0.4NaNbO₃, x ≤ 0.15. Dielectric measurements exhibited relaxor ferroelectric characteristics with temperature-stable relative permittivity from ε_r~1330 ± 15% in the temperature range from ?70?°C to 215?°C and tanδ ≤ 0.02 from ?20?°C to 380?°C for x = 0 compositions. For the Bi(Mg_0.5Ti_0.5)O₃ modified compositions the temperature range of stable relative permittivity extended from ?70?°C to 400?°C, with ε_r ~ 950 ± 15% and tanδ ≤ 0.02 from ?70?°C to 260?°C. Values of dc resistivity were ~ 10⁸ Ω?m at a temperature of 300?°C and the corresponding RC constant values were in the range from 0.40 ? 0.78?s at 300?°C. All ceramic samples exhibited a linear polarisation-electric field response at maximum applied electric field of 5?kV/cm (1?kHz).     

Crystallization Mechanism of CVD Si3N4–SiCN Composite Ceramics Annealed in N2 Atmosphere and Their Excellent EMW Absorption Properties

To tailor a new electromagnetic wave (EMW) absorbing material with lower reflection coefficient (RC) and larger operating frequency band, the CVD Si₃N₄–SiCN composite ceramics were prepared from SiCl₄–NH₃–C₃H₆–H₂–Ar system and then annealed at the temperatures of 1400–1700°C in N₂ atmosphere. Effect of the annealing temperatures on the microstructure, phase composition, permittivity, and microwave‐absorbing properties of the ceramic were investigated. Results showed that the CVD Si₃N₄–SiCN ceramics gradually crystallized into nanosized SiC grains, Si₃N₄ grains and graphite (T ≤ 1600°C), and then the grains grew up at T = 1700°C. The permittivity, dielectric loss, and electrical conductivity of as‐annealed CVD Si₃N₄–SiCN ceramics (T ≤ 1600°C) increased firstly due to the formation of conductivity and polarity network and the increase in nanograin boundary, and then decreased at 1700°C because of the growth of nanograins and the disappearance of nanograin boundary. The minimal RC and effective absorption bandwidth of the as‐annealed CVD Si₃N₄–SiCN ceramic at 1600°C was ?41.67 dB at the thickness of 2.55 mm and 3.95 GHz at the thickness of 3.05 mm, respectively, demonstrating that the totally crystallized CVD Si₃N₄–SiCN ceramic (T = 1600°C) had the superior microwave‐absorbing ability.     

Polymerization of N,N′-bismaleimido-4,4′-diphenylmethane with arenedithiols. Synthesis of some new polyimidosulphides

Two new polyimidosulphides were prepared in 94% yield or higher and with inherent viscosities as high as 1.45 dl g^?1 (0.5 g polymer/100 ml dimethyl sulphoxide; 25°C) by the addition of 4,4′-dimercaptodiphenylether or 4,4′-dimercaptobiphenyl to N,N′-bismeleimido-4,4′-diphenylmethane. Formation of soluble species requires a solvent that is or contains a proton source, since crosslinked products results otherwise. The polymers are amorphous thermoplastics with rigid backbones, reflected by their high glass transition temperatures (T_g = 185°–212°C) as well as by their insolubility in all but highly polar media, such as dimethyl sulphoxide of N,N-dimethylformamide. Both polyimidosulphides, when heated under nitrogen or air (thermogravimetric analysis), show no weight loss up to about 350°C, but the polymers degrade catastrophically (apparently via base-catalysed thiol elimination) within minutes at room temperature when dissolved in aprotic solvents containing secondary or tertiary amines.     

Surfactant free green synthesis of GOSiMa hybrid nanocomposite for charge storage application

Present work reveals the synthesis of graphene oxide-silica@magnesium oxide (GO-SiO₂@MgO)/(GOSiMa) hybrid nanocomposite by using a green sol-gel technique from its constituent precursors GO sheets, tetraethyl orthosilicate (TEOS) and magnesium chloride (MgCl₂). Broad ranges of characterization techniques like TEM, FESEM, EDAX, FTIR, XRD, DLS and BET are followed to investigate the hybrid composite. The cyclic voltammetry (CV) behaviour is studied at N₂ and O₂ atmosphere with Ag/AgCl electrode as a reference. The surface area of nanocomposites is found to be 107.59 m²/g with an average porosity value of 97.8602 Å. From the dielectric study, it is found that, synthesized GOSiMa nanocomposite has dielectric constant ε′ from 10² up to 2.5 × 10⁴ with the minimal dielectric loss ε′′ of ≤10² at all range of temperature 22 °C–185 °C and frequency range of 10³–10⁶ Hz. The effect of polarization and atomic rearrangements are the prime factors for enhancement of dielectric constant. Conductivities (σac) of this hybrid nanocomposite are measured as 8 × 10⁻³ S/m in the low-frequency region at 1 kHz and 1 × 10⁻² S/m at a high-frequency region of 2 MHz at a temperature of 160 °C for justifying the as-synthesized nanocomposite is a potential power electronics candidate for application in the charge storage device. The current work highlights the dielectric and charge storage potential of the prepared hybrid nanocomposite in a cost-effective and eco-friendly method.     

Effect of isomerization on thermal behaviour of bisitaconimides

The effect of isomerization of N,N′‐bisitaconimido‐4,4′‐diphenyl ether to the corresponding biscitraconimide on the curing characteristics and thermal stability of cured resins is described. Resins having bisitaconimide:biscitraconimide ratios of 23:77–93:7 were prepared by reacting 4,4′‐diaminodiphenyl ether with itaconic anhydride in solvents of different polarities and under different reaction conditions. Resins containing a higher proportion of citraconimide had a lower melting point (191 vs 208 °C). The curing exotherm was observed immediately after melting in all the resins and exothermic peak temperature reduced with increase in citraconimide content. Resins having a higher proportion of citraconimide on isothermal curing (200 °C, 2 h) and subsequent heating in nitrogen atmosphere degraded at a slightly lower temperature. However, the char yield at 800 °C did not show any systematic dependence on citraconimide content. © 2002 Society of Chemical Industry     

Effect of glycol and filler types on some polymeric composite properties

Two unsaturated polyesters based on maleic anhydride, phthalic anhydride, and sebasic acid with each of linear 1,6‐hexanediol (PE_L) and cyclic 1,4‐cyclohexanediol (PE_C) were prepared. Their structures were characterized by IR and ¹H NMR spectra. Their composites were prepared by mixing different ratios (60, 70, and 80%) with talc and kaolin with polyester/styrene mixture. The effect of linear and cyclic glycols and the effect of filler type and concentration of these composites were studied in terms of their electrical properties and the hardness before and after aging. The thermal behavior of styrenated polyesters and their composites was studied using thermogravimetric analysis. It has been found that both fillers increase the thermal stability and decrease the weight loss. The permittivity ε′ and the dielectric loss ε″ were measured in the frequency range 100 Hz up to 100 kHz at room temperature 25°C ± 1. The polyester composite samples containing 70% filler lead to good electrical properties in addition to its resistance to thermal aging. The hardness value was increased by increasing the filler content before and after aging. The polyester composites based on cyclic glycol and loaded with 80% kaolin gave the highest hardness values. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Microstructure and EMW absorption properties of CVI Si3N4–SiCN ceramics with BN interface annealed in N2 atmosphere

A kind of chemical vapor infiltration (CVI) Si₃N₄–BN–SiCN composite ceramic with excellent electromagnetic wave (EMW) absorbing properties is obtained by CVI BN interface and SiCN matrix on porous Si₃N₄ ceramics, and then annealed at high temperatures (1200°C‐1500°C) in N₂ atmosphere. The crystallization behavior, EMW absorbing mechanism and mechanical properties of the composite ceramics have been investigated. Results showed CVI SiCN ceramics with BN interface were crystallized in the form of nanograins, and the crystallization temperature was lower. Moreover, both EMW absorbing properties and mechanical properties of CVI Si₃N₄–BN–SiCN composite ceramics firstly increased and then decreased with the increase in annealing temperature due to the influence of BN interface on the microstructure and phase composition of the composite ceramics. The minimum reflection coefficient (RC) and maximum effective absorption bandwidth (EAB) of the composite ceramics annealed at 1300°C were ?47.05 dB at the thickness of 4.05 mm and 3.70 GHz at the thickness of 3.65 mm, respectively. The flexural strength and fracture toughness of the composite ceramics annealed at 1300°C were 94 MPa and 1.78 MPa/m^1/2, respectively.