Influence of surface modified TiO2 nanoparticles on dielectric properties of PVdF–HFP nanocomposites

Polyvinylidene fluoride-co-hexaflouropropylene (PVdF–HFP)/TiO₂ hybrid nanocomposites membranes for electrical applications have been prepared using a solvent casting technique. The interface between PVdF–HFP and TiO₂ was modified using aminopropyltrimethoxysilane (APS) coupling agent. The silane linkages on the TiO₂ surface have been confirmed using Fourier transform infra red spectroscopy. WAXD and DSC analysis has been employed to estimate the variation in crystallinity within the membrane as a function of the incorporation of both untreated and APS treated TiO₂. The dispersion of both nanoparticles in the PVdF–HFP matrix were characterized by atomic force microscopy and differences were observed in the images of APS treated and untreated. Variation in electrical properties such as conductivity, dielectric constant, dielectric loss and electric modulus of the hybrid composite films were studied employing AC impedance spectroscopy over a range of frequency from 1 kHz to 1 MHz at room temperature. Theoretical models like Maxwell, Faruka, Rayleigh and Lichtenecker were employed to calculate the effective dielectric constant of hybrid nanocomposite membranes and the estimated values were compared with the experimental data. Further, the variation in thermal stability of PVdF–HFP membrane as a function of untreated and silane treated TiO₂ reinforcement has been estimated using thermogravimetric analysis.     

Preparation and dielectric properties of surface modified TiO2/PEN composite films with high thermal stability and flexibility

A series of surface modified titanium dioxide (TiO₂)/polyarylene ether nitriles (PEN) composite films with different modified TiO₂ contents were prepared by solution casting method combined with ultrasonic dispersion technology. TiO₂ particles were successfully surface modified by PEN–COOH polymer previously, which was confirmed by transmission electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. Besides, SEM images of composite films revealed that the interfacial adhesion between surface modified TiO₂ particles and the PEN matrix was effectively improved because of their common cyano groups and similar structure units. Furthermore, thermal, mechanical and dielectric characterizations showed that the composite films possess excellent thermal properties and flexibility as well as good dielectric properties, their glass transition temperatures were as high as 223?°C and the initial decomposition temperatures were all above 480?°C. In addition, it was found that the tensile strength of modified TiO₂/PEN composites was better than raw TiO₂/PEN composites. More importantly, the dielectric constant of composite films increases linearly with increment of the surface modified TiO₂ particles content. When the mass fraction of modified TiO₂ particles reached 40?%, the dielectric constant of the composite film increased to 7.9 (1?kHz), while the dielectric loss is just 0.028 (1?kHz).     

Adjusting the properties of silicone rubber filled with nanosilica by changing the surface organic groups of nanosilica

A series of nanosilica (denoted as nano-SiO₂) surface-capped with organic modifiers hexamethyldisilazane (denoted as HMDS; molecular formula: C₆H₁₉NSi₂) and KH570 (molecular formula: C₁₀H₂₀O₅Si) containing CC double bond were prepared by in situ surface-modification method. As-obtained nano-SiO₂ particles were characterized by Fourier transform infrared spectrometry and transmission electron microscopy, and they were also used to reinforce silicone rubber (denoted as SR) in order to improve the mechanical properties. Moreover, a universal material testing machine was performed to determine the mechanical properties of the SR-matrix nanocomposites. Results showed that the surface properties of nano-SiO₂ can be adjusted by changing the ratio of these modifiers. The tensile strength, tear strength and elongation at break of nano-SiO₂/SR nanocomposites are comparable to or even better than those of R-106/SR nanocomposite (R-106 refers to commercially obtained fumed SiO₂ nanoparticles that was modified with silane coupling agent). The mechanical strength of nano-SiO₂/SR nanocomposites especially for tear strength largely improve with adding a small amount of CC content of the surface-capped nano-SiO₂. More importantly, it could be feasible to manipulate the mechanical properties of silicone rubber by properly adjusting the dosages of surface-modifiers HMDS and KH570 during the preparation of in situ surface-capped nanosilica, which could be of special significance to developing high performance SR-matrix nanocomposites.     

Improvement of epoxy resin properties by incorporation of TiO2 nanoparticles surface modified with gallic acid esters

Epoxy resin/titanium dioxide (epoxy/TiO₂) nanocomposites were obtained by incorporation of TiO₂ nanoparticles surface modified with gallic acid esters in epoxy resin. TiO₂ nanoparticles were obtained by acid catalyzed hydrolysis of titanium isopropoxide and their structural characterization was performed by X-ray diffraction and transmission electron microscopy. Three gallic acid esters, having different hydrophobic part, were used for surface modification of the synthesized TiO₂ nanoparticles: propyl, hexyl and lauryl gallate. The gallate chemisorption onto surface of TiO₂ nanoparticles was confirmed by Fourier transform infrared and ultraviolet–visible spectroscopy, while the amount of surface-bonded gallates was determined using thermogravimetric analysis. The influence of the surface modified TiO₂ nanoparticles, as well as the length of hydrophobic part of the gallate used for surface modification of TiO₂ nanoparticles, on glass transition temperature, barrier, dielectric and anticorrosive properties of epoxy resin was investigated by differential scanning calorimetry, water vapor transmission test, dielectric spectroscopy, electrochemical impedance spectroscopy and polarization measurements. Incorporation of surface modified TiO₂ nanoparticles in epoxy resin caused increase of glass transition temperature and decrease of the water vapor permeability of epoxy resin. The water vapor transmission rate of epoxy/TiO₂ nanocomposites was reduced with increasing hydrophobic part chain length of gallate ligand. Dielectric constant of examined nanocomposites was influenced by gallate used for the modification of TiO₂ nanoparticles. The nanocomposites have better anticorrosive properties than pure epoxy resin, because the surface modified TiO₂ nanoparticles react as oxygen scavengers, which inhibit steel corrosion by cathodic mechanism.     

Synergistic effect of organic and inorganic nano fillers on the dielectric and mechanical properties of epoxy composites

Titanium oxide TiO₂/epoxy and TiO₂ with detonation nano-diamond (DND)/epoxy nanocomposites were prepared by using ultrasonication method. TiO₂ and DND particles as reinforcement species and epoxy as matrix were used to produce nanocomposites. The addition of DND particles into TiO₂/epoxy composite improved the dielectric and mechanical properties of nanocomposites in significant amount. The dielectric properties of TiO₂-DND/epoxy nanocomposite demonstrated increase in permittivity and conductivity after addition of the DND particles. The maximum and minimum reflection losses of TiO₂-DND/epoxy nanocomposite for 0.6 and 0.2 wt% DND loading were detected at ?14.5 and ?1.3 dB, respectively. The flexural and tensile strength of TiO₂-DND/epoxy nanocomposites with the addition of 0.4 wt% DNDs were enhanced to 220% and 223%, respectively. Additionally, the energy to break and percent break strain were 3.9 J and 3.86, respectively for 0.4 wt% DND loading in TiO₂-DND/epoxy nanocomposite. Therefore, the present work findings claim that DND particles are well suitable to enrich the dispersion of TiO₂ nanoparticles in epoxy matrix, which develops a strong load transfer interface between the nanoparticles and epoxy matrix and consequently leads to superior properties.     

Fabrication and properties of meso-macroporous electrodes screen-printed from mesoporous titania nanoparticles for dye-sensitized solar cells

A meso-macroporous TiO₂ film electrode was fabricated by using mesoporous TiO₂ (m-TiO₂) nanoparticles through a screen-printing technique in order to efficiently control the main fabrication step of dye-sensitized solar cells (DSSCs). The qualities of the screen-printed m-TiO₂ films were characterized by means of spectroscopy, electron microscopy, nitrogen adsorption–desorption and photoelectrochemical measurements. Under the optimal paste composition and printing conditions, the DSSC based on the meso-macroporous m-TiO₂ film electrode exhibits an energy conversion efficiency of 4.14%, which is improved by 1.70% in comparison with DSSC made with commercially available nonporous TiO₂ nanoparticles (P25, Degussa) electrode printed with a similar paste composition. The meso-macroporous structure within the m-TiO₂ film is of great benefit to the dye adsorption, light absorption and the electrolyte transportation, and then to the improvement of the overall energy conversion efficiency of DSSC.     

Enhanced dielectric and ferroelectric properties induced by TiO2@MWCNTs nanoparticles in flexible poly(vinylidene fluoride) composites

Flexible polymer based composites containing multi-walled carbon nanotubes (MWCNTs) have been reported to present high dielectric constant. However, the composites generally exhibit high dielectric loss and low dielectric breakdown strength, which prohibits their practical use in electronic and electric industry. MWCNTs were coated with a continuous layer of TiO₂ nanoparticles (TiO₂@MWCNTs) by a simple hydrothermal process and TiO₂@MWCNTs/poly(vinylidene fluoride) (PVDF) composites were prepared by a solution casting method. Compared to the pristine MWCNTs/PVDF composites, the TiO₂@MWCNTs/PVDF composites presented enhanced dielectric constant and lower dielectric loss. Additionally, the breakdown strength of the TiO₂@MWCNTs/PVDF composites was also improved, which is favorable for enhanced ferroelectric properties in the composites.     

Band gap tuning and nonlinear optical characterization of TiO2–SiO2 nanocomposites with respect to composition and phase

We report on the linear and nonlinear optical studies on TiO₂–SiO₂ nanocomposites with varying percentage ratio. It is found that optical band gap of the material varies with respect to the amount of the SiO₂ in the composite. Nonlinear optical characterization of these samples was studied by using open as well as closed aperture Z-scan technique using an Nd:YAG laser (532 nm, 7 ns, 10 Hz). The nanocomposites showed enhanced nonlinear optical properties than pure TiO₂ and this can be attributed to the surface states and weak dielectric confinement of TiO₂ nanoparticles by SiO₂ matrix. The nanocomposites were thermally treated and similar studies were performed. The anatase form of TiO₂ in the nanocomposites showed superior properties relative to the amorphous and rutile phase of the composite. The involved mechanism is explained by taking into account the dominant role played by the excitons in the TiO₂ nanoparticles.     

Effect of coupling agent on the thermal and dielectric properties of PTFE/Sm2Si2O7 composites

The present study investigates the dielectric and thermal properties of PTFE/Sm₂Si₂O₇ composites. The composites were prepared by powder processing technique followed by hot pressing. The variation of the dielectric properties with filler content (0–0.5 V_f) was studied at 1 MHz and 9 GHz. The filler surface was chemically modified using phenyl trimethoxy silane (PTMS) as a coupling agent. The microstructural study using scanning electron microscopy (SEM) showed that the particles were well dispersed in the matrix when coupled with PTMS. The surface modification led to an improvement in the dielectric properties. The PTFE filled with 0.4 V_f silane treated Sm₂Si₂O₇ composite showed a low dielectric loss of 0.0054 and slightly higher relative permittivity of 3.92 when compared with the untreated composite of the same composition. The experimental values of relative permittivities were compared with the theoretical predictions and the Effective Medium Theory was found to agree well even for higher content of silane treated filler. It was found that the addition of silane coupling agent is very effective in improving the thermal properties of the PTFE/Sm₂Si₂O₇ composites.     

Effects of coupling agent on the preparation and dielectric properties of novel polymer–ceramic composites for embedded passive applications

The study was carried out to investigate the effects of silane coupling agent, γ-aminopropyl triethoxy silane (KH-550), on the preparation and dielectric properties of Barium titanate (BaTiO₃)/Bisphenol-A dicyanate (2,2′-bis (4-cyanatophenyl) isopropylidene)(BADCy) composites for embedded passive implications. It was found that KH-550 accelerated the polymerization of BADCy and was beneficial to improve the compatibility between BaTiO₃ particles and BADCy matrix. The dielectric constant (ε) and dielectric loss (tanδ) both increased at first and then decreased with the increase of the KH-550 content. With the increase of the frequency, the variation ranges of the dielectric constant and dielectric loss of these composites were not obvious since the dielectric properties of cyanate ester were stable at various frequencies.     

Study on thermal and mechanical properties of nano-calcium carbonate/epoxy composites

A study on evaluating the effect of nano-CaCO₃ particles on thermal and mechanical properties of epoxy resin cast was performed by TGA and mechanical tests. A silane coupling agent KH550 as an interfacial modifier was introduced into nanocomposites through preparing KH550/nano-CaCO₃ master batch. It is revealed that epoxy resin cast filled with nano-CaCO₃ particles represents higher thermal stability and mechanical strength. The improvement of thermal and mechanical properties is attributed to the surface modification of nano-particles, which can enhance the interfacial properties between nano-CaCO₃ fillers and epoxy resin. The mechanical properties of nano-CaCO₃/epoxy/carbon fibres composites based on the modified epoxy matrix are also enhanced.     

Facile fabrication of hierarchical BiVO<Subscript>4</Subscript>/TiO<Subscript>2</Subscript> heterostructures for enhanced photocatalytic activities under visible-light irradiation

BiVO₄/TiO₂ nanocomposites were fabricated by a facile wet-chemical process, followed by the synthesis of TiO₂ hierarchical spheres via hydrothermal method. The BiVO₄/TiO₂ nanocomposites were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV–Vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The results showed that prepared TiO₂ presented hierarchical spherical morphology self-assembled by nanoparticles and an anatase–brookite mixed crystal phase. The introduction of monoclinic BiVO₄ components retained the hierarchical structures and expanded the light response to around 510 nm. Type II BiVO₄/TiO₂ heterostructured nanocomposites exhibited improved photocatalytic degradation towards methylene blue under visible-light irradiation, especially for the composite photocatalysts with atomic Ti/Bi?=?10, which showed double degradation rate than that of pure BiVO₄. The enhanced photocatalytic mechanism of the heterostructured BiVO₄/TiO₂ nanocomposites was discussed as well.     

TiO2-MWCNT rice grain-shaped nanocomposites—Synthesis, characterization and photocatalysis

Titanium dioxide (TiO₂)-multiwalled carbon nanotube (MWCNT) nanocomposites with a novel morphology of rice-grains are prepared by electrospinning method. Anatase-MWCNT composites (with a negligibly small percentage of rutile and brookite) are obtained by high temperature sintering of the as-spun (polymer-TiO₂-MWCNT) composite fibers. The nanocomposites are characterized using spectroscopy and microscopy. The results show that the functionalized MWCNTs are integrated into the TiO₂ rice grain structures. The enhanced photocatalysis of the nanocomposites in comparison to TiO₂ rice grains and commercially available P-25 is demonstrated in photodegradation of Alizarin Red dye.     

Studies on morphological and optoelectronic properties of MEH-CN-PPV:TiO2 nanocomposites

Nanosized TiO₂ has been synthesized solvothermally using an autoclave. X-ray diffraction and electron microscopy studies elucidate that the synthesized nanoparticles are strongly crystalline and are dominantly in anatase phase. UV–vis and photoluminescence (PL) spectroscopy studies show a blue shift phenomenon in the synthesized nanoparticle in contrast to the bulk anatase TiO₂ which furnish evidence in support of quantum size effect. The nanocomposites of TiO₂ and MEH-CN-PPV have been prepared and characterized structurally (AFM, TEM) and optically (absorbance and photoluminescence). The nanocomposites have been used in light emitting diodes and electroluminescence (EL) and current density (J–V) of the device has been evaluated. The enhanced EL at elevated voltages for MEH-CN-PPV:5% TiO₂ hybrid device suggests influence of the reduced particle size and modified surface morphology.     

Dielectric response and energy storage efficiency of low content TiO2-polymer matrix nanocomposites

TiO₂/epoxy nanocomposites were prepared at different filler concentrations varying from 3 to 12 phr (parts per hundred resin per weight). The dispersion of TiO₂ was examined by Scanning Electron Microscopy and proved to be adequate. Differential Scanning Calorimetry was implemented to determine the glass to rubber transition temperature of the polymer matrix. The dielectric analysis was performed via Broadband Dielectric Spectroscopy in a wide frequency and temperature range. Five different mechanisms were observed in the spectra of the examined composites which are identified, in terms of increasing temperature at constant frequency, as γ, β, Intermediate Dipolar Effect (IDE), α and Interfacial Polarization (IP) relaxation modes. The activation energies of all relaxation modes were calculated. Finally, the dielectric response of the TiO₂ nanocomposites compared to that of the TiO₂ microcomposites reveals that the former exhibit significantly higher energy storage efficiency even at lower TiO₂ concentration than the corresponding of the microcomposites.     

Fabrication of quantum dot-sensitized solar cells with multilayer TiO2/PbS(X)/CdS/CdSe/ZnS/SiO2 photoanode and optimization of the PbS nanocrystalline layer

In this work, two multilayer photoanode structures of TiO₂/PbS(X)/CdS/ZnS/SiO₂ and TiO₂/PbS(X)/CdS/CdSe/ZnS/SiO₂ were fabricated and applied in quantum dot-sensitized solar cells (QDSCs). Then, the effect of PbS QDs layer on the photovoltaic performance of corresponding cells was investigated. The sensitization was carried out by PbS and CdS QDs layers deposited on TiO₂ scaffold through successive ionic layer adsorption and reaction (SILAR) method. The CdSe QDs film was also formed by a fast, modified chemical bath deposition (CBD) approach. Two passivating ZnS and SiO₂ layers were finally deposited by SILAR and CBD methods, respectively. It was shown that the reference cell with TiO₂/CdS/ZnS/SiO₂ photoanode demonstrated a power conversion efficiency (PCE) of 3.0%. This efficiency was increased to 4.0% for the QDSC with TiO₂/PbS(2)/CdS/ZnS/SiO₂ photoelectrode. This was due to the co-absorption of incident light by low-bandgap PbS nanocrystalline film and also the CdS QDs layer and well transport of the charge carriers. For the CdSe included QDSCs, the PbS-free reference cell represented a PCE of 4.1%. This efficiency was improved to 5.1% for the optimized cell with TiO₂/PbS(2)/CdS/CdSe/ZnS/SiO₂ photoelectrode. The maximized efficiency was enhanced about 25% and 70% compared to the PbS-free reference cells with and without the CdSe QDs layer.

     

Preparation and characteristics of polyimide/CaMoO<Subscript>4</Subscript> nanocomposites with enhanced dielectric performance and thermal stability

The polyimide/CaMoO₄ nanocomposites were successfully prepared by ex-situ polymerization. (3-Aminopropyl) triethoxysilane (KH550) was used as coupling agent to disperse the CaMoO₄ nanoparticles in polyimide matrix homogeneously. To characterize the structure and properties of the obtained nanocomposites, Scanning electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction, dielectric properties and thermal stability were studied. It was observed that the CaMoO₄ nanoparticles were dispersed homogeneously in the polyimide matrix without obvious aggregation. The results show that nano-sized CaMoO₄ will improve dielectric constant and decrease dielectric loss of the nanocomposites in the relatively high-frequency region (>10 kHz). And the nanocomposite with excellent dielectric properties of ε?=?3.04, δ?=?8.0?×?10^?3 was obtained after doping 2.5 wt% nano-sized CaMoO₄ into polyimides. Dielectric loss of the nanocomposites is reduced in low frequency domain (<10 kHz) and enhanced in high frequency domain (>10 kHz). In addition, the thermal stability of the nanocomposites was enhanced from 544 to 651?°C compared to pure polyimide.     

Mechanical and photocatalytic properties of hydroxyapatite/titania nanocomposites prepared by combined high gravity and hydrothermal process

Hydroxyapatite/titania nanocomposites of different ratios have been successfully synthesized by combined high gravity and hydrothermal methods. SEM and TEM observations showed that small spheres of TiO₂, identified as anatase crystals of 10–15 nm, were deposited on HAp rod-like crystals. EDAX analysis confirmed the presence of Ca, P, Ti and O. X-ray diffraction patterns indicated the presence of hydroxyapatite and anatase phase. More number of anatase peaks appeared in the XRD patterns with higher colloidal concentration of TiO₂ in the HAp/TiO₂ compound. Mechanical stability of the HAp/TiO₂ nanocomposites was determined by reinforcing them with high molecular weight polyethylene (HMWPE) and the tensile strength of the samples was analyzed. Photocatalytic activity of the HAp/TiO₂ particles was examined by decomposition of methyl orange (MO). The results showed that photocatalytic properties of HAp/TiO₂ composites are more effective than that of individual HAp and TiO₂ which implied that the HAp improved the photocatalytic activity of well known photocatalyst TiO₂.     

硅烷化多壁碳纳米管/硅橡胶复合材料的制备和介电性能

采用三种不同官能度的硅烷偶联剂(甲基三乙氧基硅烷(MTES）、二甲基二乙氧基硅烷(DMDES)及三甲基乙氧基硅烷(TMES))在有水条件下对多壁碳纳米管(MWCNTs)进行表面改性,通过FTIR、XPS、TG及SEM表征了MWCNTs改性前和改性后的化学结构。采用机械共混法制备了MWCNTs/硅橡胶(SR)复合材料。SEM结果表明,将不同质量分数的MWCNTs、MWCNTs-MTES、MWCNTs-DMDES和MWCNTs-TMES填充到SR中,硅烷改性可以降低MWCNTs间的相互作用,改善其在SR中的分散性。拉伸试验结果表明,改性MWCNTs与SR之间的相互作用增强,二者的相容性得到改善。当改性MWCNTs含量≤2wt%时,MWCNTs/SR复合材料的弹性模量无明显变化。介电性能测试结果表明,当MWCNTs-MTES质量分数为2wt% 时,MWCNTs-MTES/SR复合材料在104 Hz时介电常数达到5.02,较纯硅橡胶提高了57%,而介电损耗仍低于0.01,保持在极低水平。      

The role of epoxy matrix occlusions within BaTiO3 nanoparticles on the dielectric properties of functionalized BaTiO3/epoxy nanocomposites

In this work, the effects of controlled nanoparticles aggregations of barium titanate (BaTiO₃) on the dielectric properties of epoxy nanocomposites are investigated in detail with respect to different experimental parameters like frequency, ceramic content and temperature. Dispersing silanized BaTiO₃ nanopowder under ultrasonic and stir, nanocomposites of epoxy-amine matrix with different morphologies are obtained. The nanoparticles silane functionalization containing amine end groups effectively improve the compatibility of the nano-BaTiO₃ and the epoxy matrix. Storage modulus, glass transition temperature, tensile and flexural properties of nanocomposites and dielectric properties are increased until 10% by weight of nano-BaTiO₃ loading, well dispersed in the matrix. Above 10 wt.% of nano-BaTiO₃, scanning electronic microscopy and thermal analysis showed that agglomeration of nanoparticles occurs. Rheological and mechanical nanocomposites properties were evaluated and matrix occlusion behaviors were identified. In light of the specific behavior of the occluded polymer, the dielectric properties, especially dielectric loss are discussed.