Camphor sulfonic acid doped polyaniline-tin oxide hybrid nanocomposites: Synthesis,structural, morphological,optical and electrical transport properties

Camphor sulfonic acid (CSA) doped PANi–SnO₂ hybrid nanocomposites were synthesized by solid-state synthesis route with varying amounts (10–50%) of CSA. X-ray diffraction studies have proven the successful incorporation of CSA into the polyaniline–SnO₂ hybrid nanocomposites and the results are also supported by microstructural analysis. UV–visible and Fourier infrared spectroscopy studies have provided insight into the electronic interaction between the CSA, polyaniline, and SnO₂. The room temperature dc electrical conductivity of CSA-doped PANi–SnO₂ hybrid nanocomposite films were observed to depend on the amount of CSA doping and the morphology.     

Spark plasma sintering technique for reaction sintering of Al2O3/Ni nanocomposite and its mechanical properties

Al₂O₃/Ni nanocomposites were prepared by spark plasma sintering (SPS) using reaction sintering method and the mechanical properties of the obtained nanocomposites are reported. The starting materials of Al₂O₃–NiO solid solution were synthesized from aluminum sulfate and nickel sulfate. These Al₂O₃–NiO powders were changed into Al₂O₃ and Ni phases during sintering process. The obtained nanocomposites showed high relative densities (>98%). SEM micrographs showed homogeneously dispersed Ni grains in the matrix. The 3-point strength and the fracture toughness of the composites significantly improved from 450 MPa in the monolithic α-Al₂O₃ to 766 MPa in the 10 mol% (2.8 vol.%) Ni nanocomposite and from 3.7 to 5.6 MPa m^1/2 in 13 mol% (3.7 vol.%) Ni nanocomposite. On the other hand, Young's modulus and Vickers hardness of the nanocomposites were mostly same as those of the monolithic α-Al₂O₃.     

Experimental and theoretical dielectric studies of PVDF/PZT nanocomposite thin films

Poly(vinylidene fluoride)/lead zirconate titanate nanocomposite thin films (PVDF/PZT-NPs) were successfully prepared by mixing fine Pb(Zr_0.52,Ti_0.48)O₃ nanoparticles (PZT-NPs) into a PVDF solution under ultrasonication. The mixture was spin coated onto glass substrate and then cured at 110 °C. X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) were used to characterize the structure and properties of the obtained thin-film nanocomposites. The dielectric properties of the PVDF/PZT-NPs were analyzed in detail with respect to frequency. In comparison with pure poly (vinylidene fluoride), the dielectric constant of the nanocomposite (15 vol.% PZT-NPs) was significantly increased, whereas the loss tangent was unchanged in the frequency range of 100 Hz to 30 MHz. The nanocomposites exhibited good dielectric stability over a wide frequency range. Different theoretical approaches were employed to predict the effective dielectric constants of the thin film nanocomposite systems, and the estimated results were compared with the experimental data.     

Densification and microwave dielectric properties of CaO–B2O3–SiO2 system glass–ceramics

In order to relieve the narrow processing window and poor material compatibility in practical applications as well as understand the microwave dielectric properties, investigation on the formulations of CaO/B₂O₃/SiO₂ glasses on their structure, thermal properties, and microwave properties were performed in this study. Six glasses with different molar ratios of CaO/B₂O₃/SiO₂ (designed as CBS-3, CBS-5, CBS-7, CBS-8, CBS-9, and CBS-10) were prepared and pulverized. Results indicate that most softening points of glasses are ranging from 680 to 710 °C. They were sintered at different temperatures to reach maximum densification. Among various glass formulations, CBS-9 glass–ceramic containing the largest amount of SiO₂ has the lowest CTE. The dielectric constants can be divided into two groups including around 4–5 and 7–8, and the dielectric losses (tan δ) are all below 0.005 in the frequency of ≈10 GHz. The dielectric constants and dielectric losses are generally frequency dependent. For CBS-9 glass–ceramic, the dielectric constant and dielectric loss at 4.7 and 18.6 GHz are 4.13 and 0.0018, and 4.20 and 0.0063, respectively.     

Efficient preparation of hybrid nanocomposite coatings based on poly(vinyl alcohol) and silane coupling agent modified TiO2 nanoparticles

In the present investigation, at first, the surface of titanium dioxide (TiO₂) nanoparticles was modified with γ-aminopropyltriethoxy silane as a coupling agent. Then a new kind of poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposites coating with different modified TiO₂ loading were prepared under ultrasonic irradiation process. Finally, these nanocomposites coating were used for fabrication of PVA/TiO₂ films via solution casting method. The resulting nanocomposites were fully characterized by Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), thermogravimetric analysis/derivative thermal gravimetric (TGA/DTG), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The TEM and SEM results indicated that the surface modified nanoparticles were dispersed homogeneously in PVA matrix on nanoscale and based on obtained results a possible mechanism was proposed for ultrasonic induced nanocomposite fabrication. TGA confirmed that the heat stability of the nanocomposite was improved. UV–vis spectroscopy was employed to evaluate the absorbance and transmittance behavior of the PVA/TiO₂ nanocomposite films in the wavelength range of 200–800 nm. The results showed that this type of films could be used as a coating to shield against UV light.     

Visible light photocatalytic degradation of thiophene using Ag–TiO2/multi-walled carbon nanotubes nanocomposite

Ag–TiO₂ nanocatalyst, supported on multi-walled carbon nanotubes, was synthesized successfully via a modified sol–gel method, and the prepared photocatalyst was used to remediate aqueous thiophene environmentally by photocatalytic oxidation under visible light. The prepared Ag–TiO₂/multi-walled carbon nanotubes nanocomposite photocatalyst was characterized through X-ray diffraction, Brunauer–Emmett–Teller (BET), transmission electron microscopy, and UV–vis spectra (UV–vis). The results showed that both Ag and TiO₂ nanoparticles were well-dispersed over the MWCNTs and formed a uniform nanocomposite. Ag doping can eliminate the recombination of electron–hole pairs in the catalyst, and the presence of MWCNTs in the TiO₂ composite can change surface properties to achieve sensitivity to visible light. The optimum mass ratio of MWCNT:TiO₂:Ag was 0.02:1.0:0.05, which resulted in the photocatalyst's experimental performance in oxidizing about 100% of the thiophene in a 600 mg/L solution within 30 min and with 1.4 g L⁻¹ amount of catalyst used.     

Effect of Ta2O5 in (Ca,Si, Ta)-doped TiO2 ceramic varistors

TiO₂ varistors doped with 0.2 mol% Ca, 0.4 mol% Si and different concentrations of Ta were obtained by ceramic sintering processing at 1350 °C. The effect of Ta on the microstructures, nonlinear electrical behavior and dielectric properties of the (Ca, Si, Ta)-doped TiO₂ ceramics were investigated. The ceramics have nonlinear coefficients of α = 3.0–5.0 and ultrahigh relative dielectric constants which is up to 10⁴. Experimental evidence shows that small quantities of Ta₂O₅ improve the nonlinear properties of the samples significantly. It was found that an optimal doping composition of 0.8 mol% Ta₂O₅ leads to a low breakdown voltage of 14.7 V/mm, a high nonlinear constant of 4.8 and an ultrahigh electrical permittivity of 5.0 × 10⁴ and tg δ = 0.66 (measured at 1 kHz), which is consistent with the highest and narrowest grain boundary barriers of the ceramics. In view of these electrical characteristics, the TiO₂–0.8 mol% Ta₂O₅ ceramic is a viable candidate for capacitor–varistor functional devices. The characteristics of the ceramics can be explained by the effect and the maximum of the substitution of Ta⁵⁺ for Ti⁴⁺.     

Preparation and characterizations of highly transparent UV-curable ZnO-acrylic nanocomposites

A sol–gel chemical route was adopted to prepare the zinc oxide (ZnO) nanoparticles as small as 4 nm. UV-curable ZnO-acrylic nanocomposites were then prepared by employing 3-(trimethoxysilyl)propyl methacrylate (TPMA) as the surface modification agent of ZnO particles. UV–vis analysis revealed a high optical transparency (>95%) in visible light region for nanocomposite thin films with ZnO contents up to 20 wt.%. The addition of ZnO nanoparticles also enhanced the dielectric constants of nanocomposites and the dielectric constants greater than 4 in frequencies ranging from 1 to 600 MHz was obtained in the samples containing 10 wt.% of ZnO nanoparticles. A comparison of experimental results and theoretical calculation indicated that the interfacial polarizations in between ZnO nanoparticles and polymer matrix may play an important role in the enhancement of dielectric properties of nanocomposites.     

A kinetic study on the electrophoretic deposition of hydroxyapatite–titania nanocomposite based on a statistical approach

In the present study, the electrophoretic deposition (EPD) process of hydroxyapatite–titania nanocomposite was kinetically described by the use of response surface methodology (RSM). The electrostatic interaction between particles in ethanol based suspensions was determined by Zeta potential and particle size analyses. After successful electrophoretic deposition from hydroxyapatite–titania suspensions with 0, 10 and 20 wt% of titania nanoparticles, it was shown that Baldisserri model can well reproduce the experimental data among the other semi-empirical kinetic equations. The as-deposited hydroxyapatite–titania nanocomposites were characterized employing SEM, AFM, XRD, and FT-IR analyses. Then, the effects of deposition voltage, deposition time and wt% TiO₂ on the kinetic of EPD at two time intervals (10–60 s and 60–300 s) were identified and quantified via RSM based on a central composite design (CCD). According to the results obtained from the statistical analysis, it was found that the deposition rate decreases by an increase in wt% TiO₂ and time. Also, a transition in deposition mechanism from linear to parabolic mode was observed and two second order polynomial equations were fitted to the response (deposit weight) at each time intervals.     

Sintering of glass-added BaZn1/3Nb2/3O3 ceramics

The complex perovskite oxide Ba(Zn_1/3Nb_2/3)O₃ (BZN) has been studied for its attractive dielectric properties which place this material interesting for applications as multilayer ceramics capacitors or hyperfrequency resonators. This material is sinterable at low temperature with combined glass phase–lithium salt additions, and exhibits, at 1 MHz very low dielectric losses combined with relatively high dielectric constant and a good stability of this later versus temperature. The 2 wt.% of ZnO–SiO₂–B₂O₃ glass phase and 1 wt.% of LiF-added BZN sample sintered at 900 °C exhibits a relative density higher than 95% and attractive dielectric properties: a dielectric constant ?_r of 39, low dielectrics losses (tan(δ) < 10⁻³) and a temperature coefficient of permittivity τ_? of 45 ppm/°C⁻¹. The 2 wt.% ZnO–SiO₂–B₂O₃ glass phase and 1 wt.% of B₂O₃-added BZN sintered at 930 °C exhibits also attractive dielectric properties (?_r = 38, tan(δ) < 10⁻³) and it is more interesting in terms of temperature coefficient of the permittivity (τ_? = −5 ppm/°C). Their good dielectric properties and their compatibility with Ag electrodes, make these ceramics suitable for L.T.C.C applications.     

Structure and electrical properties of Nd2O3-doped 0.82Bi0.5Na0.5TiO3–0.18Bi0.5K0.5TiO3 ceramics

Nd₂O₃ doped 0.82Bi_0.5Na_0.5TiO₃–0.18Bi_0.5K_0.5TiO₃ (abbreviated to BNKT) binary lead-free piezoelectric ceramics were synthesized by the conventional mixed-oxide method. The results show that the BNKT ceramics with 0–0.15 wt.% Nd₂O₃ doping possesses a single perovskite phase with rhombohedral structure. The grain size of BNKT decreased with the addition of Nd₂O₃ dopant. The temperature dependence of the dielectric constant ?_r revealed that there were two-phase transitions from ferroelectric to anti-ferroelectric and anti-ferroelectric to paraelectric. A diffuse character was proved by linear fitting of the modified Curie–Weiss law. At room temperature, the specimens containing 0.0125 wt.% Nd₂O₃ with homogeneous microstructure presented excellent electrical properties: the piezoelectric constant d₃₃ = 134 pC/N, the electromechanical coupling factor K_p = 0.27, and the dielectric constant ?_r = 925 (1 kHz).     

Enhanced dielectric constant and suppressed electrical conductivity in polymer nanocomposite films via loading MXene/TiO2/MoS2 nanosheets

Conductor/polymer nanocomposites can achieve high dielectric constant with low filler loading, but conductive fillers come into contact with each other easily, resulting in the formation of conductive paths. In this work, MXene/TiO₂/MoS₂ nanosheets were prepared by one-step hydrothermal method, and MXene/TiO₂/MoS₂/poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite films were prepared by solution casting method. At 1 kHz, with an optimized MXene/TiO₂/MoS₂ nanosheets loading of 8.0 wt%, MXene/TiO₂/MoS₂/P(VDF-HFP) nanocomposite films achieve a high dielectric constant of 944 and maintain a low dielectric loss of 0.19. TiO₂ and MoS₂ semiconductive layers on the surface of MXene nanosheets can prevent the formation of conductive paths, and therefore, nanocomposite films possess suppressed electrical conductivity. Moreover, MXene/TiO₂/MoS₂ nanosheets can build more microcapacitor structures in nanocomposite films with higher filler loading, which further improves the dielectric constant of nanocomposite films. Finite element simulation shows that TiO₂ and MoS₂ semiconductive layers can lower the electric field intensity and polarization intensity at the interface between conductive fillers and polymer matrix. Herein, MXene/TiO₂/MoS₂/P(VDF-HFP) nanocomposite films possess not only excellent dielectric properties, but also excellent mechanical properties, which can be used as flexible dielectric materials in electronic packaging technology.     

Thermal conductivity and dielectric property of hot-pressing sintered AlN–BN ceramic composites

A study was conducted of the effects of sintering temperature and CaF₂ additives on densification, microstructure, dielectric property and thermal conductivity of AlN–BN composites. Increasing sintering temperature and CaF₂ contents help to improve the densification, thermal conductivity, and purification of the grain boundaries. Thermal conductivity value reached 110 W m⁻¹ K⁻¹ for AlN–BN composites with 3 wt.% CaF₂ and sintered at 1850 °C. Increasing sintering temperature decreases relative dielectric constant and tan δ. The increase in CaF₂ content increases relative dielectric constant and decreases tan δ. Relative dielectric constants values were between 7.29 and 7.64 and dielectric loss tangent values ranged from 6.36 to 7.83 × 10⁻⁴ at 1 MHz.     

Microwave dielectric properties of SnO2-doped CaSiO3 ceramics

SnO₂-doped CaSiO₃ ceramics were successfully synthesized by a solid-state method. Effects of different SnO₂ additions on the sintering behavior, microstructure and dielectric properties of Ca(Sn_1−xSi_x)O₃ (x=0.5–1.0) ceramics have been investigated. SnO₂ improved the densification process and expanded the sintering temperature range effectively. Moreover, Sn⁴⁺ substituting for Si⁴⁺ sites leads to the emergence of Ca₃SnSi₂O₉ phase, which has a positive effect on the dielectric properties of CaO–SiO₂–SnO₂ materials, especially the Qf value. The Ca(Sn_0.1Si_0.9)O₃ ceramics sintered at 1375 °C possessed good microwave dielectric properties: ε_r =7.92, Qf =58,000 GHz and τ_f=−42 ppm/°C. The Ca(Sn_0.4Si_0.6)O₃ ceramics sintered at 1450 °C also exhibited good microwave dielectric properties of ε_r=9.27, Qf=63,000 GHz, and τ_f=−52 ppm/°C. Thus, they are promising candidate materials for millimeter-wave devices.     

Photocatalytic properties of TiO2 sol-gel modified nanocomposite films

TiO₂ nanocomposite films with different concentrations of TiO₂ MT-150A nanoparticles were immobilized on glass substrates using a dip coating process. The crystalline structure and surface chemical state of nanocomposite film properties were examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The specific surface area and morphology of TiO₂ MT-150A nanoparticles were evaluated by the BET method and Field Emission Scanning Electron Microscopy (FE-SEM). The photocatalytic activities of films were evaluated by the methyl orange decoloring rate. XPS measurements showed that the oxygen amount (%) was related to the film composition. The composite film with 10 g/L MT-150A loading yielded the highest amount of surface oxygen (26.82%) and TiO₂ rutile showed the lowest amount of surface oxygen (13.67%) in the form of surface hydroxyl groups. The remaining oxygen was identified as lattice oxygen. In addition, the nanocomposite film with 10 g/L MT-150A loading yielded the highest photocatalytic activity.     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.     

Synthesis and film performances of SiO2/P(MMA-BA) core–shell structural latex

In this study, we have successfully synthesized silica/poly(methyl methacrylate-butyl acrylate) (SiO₂/P(MMA-BA)) core–shell nanocomposite colloids via in situ emulsion copolymerization using cationic 2,2′-azobis(2-amidinopropane)dihydrochloride (AIBA) as the initiator and the 3-Glycidoxypropyl-trimethoxysilane (GPTMS)-modified SiO₂ nanoparticles as the seeds. The SiO₂ nanoparticles embedded can reach as high as 60 wt%. The nanocomposite film presents almost the same high transparency as the pure polymer film (>90% transmittance in visible range), and displays significantly improved mechanical and UV weathering resistant properties over its pure polymer film.     

Effects of compressive stress on the dielectric properties of PIN–PT ceramics

Lead indium niobate, Pb(In_1/2Nb_1/2)O₃ (PIN), is an interesting ferroelectric due to a transition from a disordered to an ordered state by long-time thermal annealing. However, the temperature related to the maximum dielectric constant (T_max) of PIN in relaxor phase is low (at 1 kHz, T_max = 66 °C). In this study, lead titanate PbTiO₃ (PT) was added to PIN with compositions (1 − x)PIN–xPT (for x = 0.1–0.5) to increase their T_max. The influence of stress on dielectric properties of (1 − x)PIN–PT ceramics was then investigated. The dielectric properties were measured under various uniaxial compressive stresses up to 400 MPa. The results showed the reduction of dielectric constant in 0.9PIN–0.1PT with superimposed compression load. For other compositions, dielectric constants first increased with compressive stress, then decreased when the stress was further increased up to 400 MPa. The loss tangent of all composition was found to decrease with increasing compressive stress.     

Preparation,characterization, and dynamic adsorption–desorption studies on polypyrrole encapsulated TiO2 nanoparticles

Binary doped polypyrrole (PPy) encapsulated Titania (TiO₂) nanoparticles were prepared by oxidative polymerization using FeCl₃ as oxidant in presence of camphorsulfonic acid (CSA) as surfactant. Both FeCl₃ (oxidant) and camphorsulfonic acid (surfactant) also act as dopant and hence thus prepared polypyrrole/Titania (TiO₂@PPy) is termed as binary doped nanocomposite i.e. FeCl₃ dopes polypyrrole by oxidation mechanism while camphorsulfonic acid dopes polypyrrole by protonic doping mechanism. The TiO₂@PPy coreshell nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), thermogravimetry, differential scanning calorimetry (DSC), field emission‐scanning electron microscopy (FE‐SEM), and inductance‐capacitance‐resistance (LCR) measurements. The results indicated that the structural and electrical properties of the TiO₂@PPy coreshell nanocomposites were significantly influenced by the extent of TiO₂ nanoparticles loading of polypyrrole. The direct current (DC) electrical conductivity of the as‐prepared TiO₂@PPy coreshell nanocomposites was higher than that of PPy. As‐prepared TiO₂@PPy coreshell nanocomposites were also studied for their dielectric losses for alternating current (AC) which is useful characteristic for their application in the fabrication of charge storing devices. TiO₂@PPy coreshell nanocomposites showed synergistic effect of combining components in improving their alcohol sensing properties. This improvement may be attributed to the adsorption on and desorption from alcohols TiO₂@PPy interface of the nanocomposites and alcohol vapors causing decrease in depletion region. The TiO₂@PPy coreshell nanocomposites were observed to show better reproducibility of electrical conductivity and fast self‐recovery during the alcohol vapor sensing process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43411.     

Enhanced photocatalytic activity of Ag doped TiO2 nanoparticles synthesized by a microwave assisted method

Pure anatase TiO₂ photocatalyst with different Ag contents was prepared via a controlled and energy efficient microwave assisted method. The prepared material was further characterized by several analytical techniques like X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), surface area measurement (BET), Fourier transform-infrared spectroscopy (FT-IR), diffused reflectance spectroscopy (DRS), and thermogravimetric–differential thermal analysis (TGA–DTA). A 10 nm average crystallite size with nano-crystals of pseudo-cube like morphology was obtained for optimal (0.25 mol%) Ag doped TiO₂. The present research work is mainly focused on the enhancement of degradation efficiency of methyl orange (MO) by doping of Ag in TiO₂ matrix using UV light (365 nm). A 99.5% photodegradation efficiency of methyl orange was achieved by utilizing 0.25 mol% Ag doped TiO₂ (1 g/dm³) at pH=3 within 70 min. Recyclability of photocatalyst was also studied, with the material being found to be stable up to five runs.