Preparation and characterization of transparent ZnO/epoxy nanocomposites with high-UV shielding efficiency

Transparent ZnO/epoxy nanocomposites with high-UV shielding efficiency were reported in this paper. First, zinc oxide (ZnO) precursor was synthesized via the homogeneous precipitation method and ZnO nanoparticles were then made by calcination of the precursor at different temperature. The structural properties of the as-prepared ZnO nanoparticles were studied in detail using thermogravimetry (TGA), differential thermal analysis (DTA), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR) and transmission electron microscopy (TEM), respectively. Transparent ZnO/epoxy nanocomposites were subsequently prepared from transparent epoxy (EP-400) and as-prepared ZnO nanoparticles via in situ polymerization. Optical properties of ZnO/epoxy nanocomposites, namely visible light transparency and UV light shielding efficiency, were studied using an ultraviolet-visible (UV-vis) spectrophotometer. The optical properties of the as-obtained nanocomposites were shown to depend on ZnO particle size and content. The nanocomposite containing a very low content (0.07% in weight) of ZnO nanoparticles with an average particle size of 26.7 nm after calcination at 350 °C possessed the most optimal optical properties, namely high-visible light transparency and high-UV light shielding efficiency, that are desirable for many important applications.     

Sol–gel derived undoped and boron-doped ZnO semiconductor thin films: Preparation and characterization

We report the influence of boron doping concentration on the microstructure, electrical and optical properties of solution-processed zinc oxide (ZnO) thin films. The B doping concentration in the resultant solutions was varied from 0 to 5 at%, and the pH value of each synthetic solution was adjusted to 7.0. XRD measurements, SEM observations, and SPM examinations revealed that boron doping produced ZnO thin films consisting of a fine grain structure with a flat surface morphology. Moreover, ZnO thin films doped with B raised the texture coefficient along the (002) plane. All B-doped ZnO (ZnO:B) thin films exhibited higher transparency than that of the undoped ZnO thin film in the wavelengths between 350 and 650 nm. The optical band gap and Urbach energy of the ZnO:B thin films were higher than those of the undoped thin film. According to electrical transport characteristics, the 1% B-doped ZnO thin film exhibited the highest Hall mobility of 17.9 cm²/V s, the highest electron concentration of 1.2×10¹⁵ cm⁻³, and the lowest electrical resistivity of 2.2×10² Ω cm among all of the ZnO:B thin films.     

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.     

Size‐dependent optical properties of transparent,spin‐coated polystyrene/ZnO nanocomposite films

Zinc oxide (ZnO) nanoparticles are synthesized using a simple chemical method at room temperature. A variation in molar concentration of the precursor, potassium hydroxide, from 0.25 to 0.01 mol L^?1 is accompanied by a decrease in the average size of the nanoparticles. These nanoparticles are used for the preparation of polystyrene/ZnO nanocomposite films using the spin‐coating technique. These films are found to be highly transparent throughout the visible region and absorb UV light in the region from 395 to190 nm, almost covering the near and middle UV ranges (400 to 200 nm). This observation highlights the possible prospects of these films in UV shielding applications. The wavelength corresponding to the onset of UV absorption is found to be blue shifted with a decrease in size of the ZnO particles in the composite films due to confinement effects. The photoluminescence spectra of the composite films also change as a function of particle size. The emissions at longer wavelength due to defects and impurity‐related states in ZnO are almost quenched as a result of surface modification by the polymer matrix. The observed band‐gap enlargement with a decrease in size of the ZnO particles in the composite films is significant for band‐gap engineering of nanoparticles for various applications. Copyright © 2011 Society of Chemical Industry     

Continuous synthesis of surface-modified zinc oxide nanoparticles in supercritical methanol

Continuous synthesis of surface-modified zinc oxide (ZnO) nanoparticles was examined using surface modifiers (oleic acid and decanoic acid) in supercritical methanol at 400 °C, 30 MPa and a residence time of ∼40 s. Wide angle X-ray diffraction (WAXD) analysis revealed that the surface-modified nanoparticles retained ZnO crystalline structure. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the surface modifiers changed drastically the size and morphology of the ZnO nanoparticles. When the molar ratio of oleic acid to Zn precursor ratio was 30, 10 nm size particles with low degree of aggregation were produced. The surface-modified ZnO nanoparticles had higher BET surface areas (29-36 m²/g) compared to unmodified ZnO particles synthesized in supercritical water (0.7 m²/g). Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA) indicated that aliphatic, carboxylate and hydroxyl groups were chemically attached on the surface of ZnO nanoparticles. Long-term (80 days) dispersion test using ultraviolet transmittance showed that the surface-modified ZnO particles had enhanced dispersion stability in ethylene glycol.     

Synthesis of polystyrene encapsulated nanosaponite composite latex via miniemulsion polymerization

The synthesis and characterization of polystyrene encapsulated nanosaponite composite suspension via miniemulsion polymerization are reported in this study. The particle size of nanoclay and its pre-modification are critical to successfully producing a stable complex suspension. The final products were characterized by X-ray diffraction spectra, transmission electron microscopy (TEM), scanning electron microscopy (SEM), thin window energy dispersive spectroscopy (EDS), and light scattering. The results show that ar-vinylbenzyltrimethylammonium chloride (VBTAC) modified nanosaponite could be fully exfoliated and encapsulated inside the polystyrene latex via in situ miniemulsion polymerization. When the concentration of hexadecane (a co-stabilizer used in the miniemulsion polymerization) was high, the final composite particles are composed mainly of spherical particles with size less than 100 nm, and a small number of hemispherical or bowl-structured particles of size ∼100 nm to 1000 nm. The phase separation due to the existence of large amounts of hexadecane accounted for the formation of a variety of morphologies.     

Rapid synthesis and dye-sensitized solar cell applications of hexagonal-shaped ZnO nanorods

This paper reports, for the first time, a very rapid and large-scale synthesis and dye-sensitized solar cells (DSSCs) application of well-crystallized hexagonal-shaped ZnO nanorods at very low temperature of about 70 °C in 20 min. The thin films of as-grown nanorods were used as photo-anode materials to fabricate the DSSCs which exhibited an overall light to electricity conversion efficiency (ECE) of 1.86% with a fill factor of 74.4%, short-circuit current of 3.41 mA/cm² and open-circuit voltage of 0.73 V.     

A novel high power symmetric ZnO/carbon aerogel composite electrode for electrochemical supercapacitor

We present, for the first time, a new material of symmetric electrochemical supercapacitor in which zinc oxide (ZnO) with carbon aerogel (CA) was used as active material. Physical properties of ZnO/CA composite were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that ZnO has single hexagonal structure and the grain size increases with increase of ZnO compository. The result of cyclic voltammetry indicates that the specific capacitance of ZnO/CA composite in 6 M KOH electrolyte was approximately 25 F/g at 10 mV/s for 2:1 composition. AC impedance analysis reveals that ZnO with carbon aerogel powder enhanced the conductivity by reducing the internal resistance. Galvanostatic charge/discharge measurements were done at various current densities, namely 25, 50, 75, and 100 mA/cm². It was found that the cells have excellent electrochemical reversibility and capacitive characteristics in KOH electrolyte. The maximum capacitance of the ZnO/CA supercapacitor was 500 F/g at 100 mA/cm². It has been observed that the specific capacitance is constant up to 500 cycles at all current densities, which implies that the dendrite formation was controlled.     

Preparation and characterization of UV-cured polyurethane acrylate/ZnO nanocomposite films based on surface modified ZnO

A series of polyurethane acrylate (PUA)/ZnO nanocomposite films with different ZnO contents were prepared via a UV-curing system. To ensure good dispersion in the PUA matrix, ZnO nanoparticles were modified with a silane coupling agent and confirmed by FT-IR analysis. The morphological structures, thermal properties, mechanical properties and water transfer properties of the prepared films were investigated as a function of their ZnO concentration. WAXD and SEM analyses showed that the surface-modified ZnO nanoparticles were homogeneously dispersed in the PUA matrix and the molecular ordering increased with increasing ZnO content. Compared with neat PUA, the hardness and elastic modulus in films increased from 0.03 to 0.056 GPa and from 2.75 to 3.55 GPa, respectively. Additionally, the water uptake and WVTR in the PUA/ZnO nanocomposite films decreased as the ZnO content nanoparticles increased, which may come from enhanced molecular ordering and hydrophobicity in films. UV light below approximately 450 nm can be efficiently absorbed by incorporating ZnO nanoparticles into a PUA matrix, indicating that these composite films exhibit good weather ability and UV-shielding effects. The enhanced physical properties achieved by incorporating modified ZnO nanoparticles can be advantageous in various applications, whereas the thermal stability of the composite films should be increased.     

Improvement of field emission performance on nitrogen ion implanted ultrananocrystalline diamond films through visualization of structure modifications

The relationship between the electron field emission properties and structure of ultra-nanocrystalline diamond (UNCD) films implanted by nitrogen ions or carbon ions was investigated. The electron field emission properties of nitrogen-implanted UNCD films and carbon-implanted UNCD films were pronouncedly improved with respect to those of as-grown UNCD films, that is, the turn-on field decreased from 23.2 V/μm to 12.5 V/μm and the electron field emission current density increased from 10E−5 mA/cm² to 1 × 10E−2 mA/cm². The formation of a graphitic phase in the nitrogen-implanted UNCD films was demonstrated by Raman microscopy and cross-sectional high-resolution transmission electron microscopy. The possible mechanism is presumed to be that the nitrogen ion irradiation induces the structure modification (converting sp³-bonded carbons into sp²-bonded ones) in UNCD films.     

Functionalized organic nanoparticles from core-crosslinked poly(4-vinylbenzocyclobutene-b-butadiene) diblock copolymer micelles

Surface-functionalized polymeric nanoparticles were prepared by: a) self-assembly of poly(4-vinylbenzocyclobutene-b-butadiene) diblock copolymer (PVBCB-b-PB) to form spherical micelles (diameter: 15-48 nm) in decane, a selective solvent for PB, b) crosslinking of the PVBCB core through thermal dimerization at 200-240 °C, and c) cleavage of the PB corona via ozonolysis and addition of dimethyl sulfide to afford aldehyde-functionalized nanoparticles (diameter: ∼16-20 nm), along with agglomerated nanoparticles ranging from ∼30 to ∼100 nm in diameter. The characterization of the diblock copolymer precursors, the intermediate micelles and the final surface-functionalized crosslinked nanoparticles was carried out by a combination of size exclusion chromatography, static and dynamic light scattering, viscometry, thermogravimetric analysis, ¹H NMR and FTIR spectroscopy and transmission electron microscopy.     

Synthesis of ZnO nanoparticles by an aerosol process

Spherical nano-sized zinc oxide (ZnO) particles were produced by a spray pyrolysis method using the aerosol technique described in this study. The effects of reaction temperatures of 600, 800 and 1000 °C and collection locations of the particles, such as the flask collector and the tube exit, on the morphology and crystal structure of the ZnO particles were investigated. X-ray diffraction (XRD) studies showed that the crystallinity of the particles was increased by increasing the reaction temperature from 600 °C to 1000 °C. Fourier transform infrared spectroscopy (FTIR) measurements revealed that the particles were pure and similar to each other. Scanning electron microscopy (SEM) revealed that the synthesized nanoparticles had sizes between 200 nm and 400 nm, with uniform morphologies. A computational fluid dynamics (CFD) model of the horizontally positioned tube reactor was developed. Simulation results provided information about the residence time and the temperature distribution along the tube, which were found to be correlated to the particle morphology.     

Electrodeposited Pt for cost-efficient and flexible dye-sensitized solar cells

Pt electrodes were prepared by direct and pulse current electrodeposition for use as counter electrodes in dye-sensitized solar cells. Scanning electron microscope and transmission electron microscope images confirmed the formation of uniform Pt nanoclusters of ∼40 nm composed of 3 nm nanoparticles, when the pulse current electrodeposition method was used, as opposed to the dendritic growth of Pt by the results from direct current electrodeposition. By applying pulse electrodeposited Pt which has a 1.86 times higher surface area compared to direct current electrodeposited Pt, short-circuit current and conversion efficiency were increased from 10.34 to 14.11 mA/cm² and from 3.68 to 5.03%, respectively. In addition, a flexible solar cell with a pulse current electrodeposited Pt counter electrode with a conversion efficiency of 0.86% was demonstrated.     

Synthesis of double-walled carbon nanotube films and their field emission properties

Continuous double-walled carbon nanotube (DWCNT) films were synthesized using an Fe-Mo catalyst by the arc discharge method. This new catalyst has dramatically improved the purity and selectivity of DWCNT product. High-resolution transmission electron microscopy indicates that the outer and inner diameter of DWCNT are 1.9-4.7 nm and 1.2-3.8 nm, respectively. The field emission properties of DWCNT films have been studied. The directly grown film was transferred onto quartz substrates and used as emission cathodes, and has demonstrated a quite good emission performance. Moreover, the emissions of DWCNT films have been further improved by heat treatment. The film after 400 °C oxidation shows excellent field emission property with a low turn-on (E_to = 0.6 V/μm) and threshold field (E_th = 0.9 V/μm) corresponding to the emission current density of 1 μA/cm² and 1 mA/cm², respectively.     

Controlled synthesis and methanol sensing capabilities of Pt-incorporated ZnO nanospheres

Platinum nanoparticles incorporated ZnO hybrid nanospheres (PtZONS) have been synthesized via electrodeposition which is easy to control over the size distribution range. The Pt nanoparticles in ZnO nanospheres have been identified with high-resolution transmission electron microscopy (HRTEM) and energy dispersive spectroscopy (EDS). Methanol sensing capabilities of the nanospheres have been investigated through electrochemical measurements. The electrochemical measurements prove that these nanospheres demonstrate the abilities to electrocatalyze the oxidation of methanol and substantially raise the response current. The sensitivity of the Nafion/PtZONS/glassy carbon modified electrode to methanol is 235.47 μA M⁻¹ cm⁻², which is much higher than that of a pure ZnO and Pt nanospheres modified electrodes. Furthermore, it has been revealed that the electrode exhibits a good anti-interference and long-term stability. Our investigation demonstrates that the Pt-ZnO nanospheres can be employed for various applications.     

Polyurethane nanoparticles from a natural polyol via miniemulsion technique

Original natural triol (castor oil) was used as a monomer for the synthesis of monodisperse polyurethane nanoparticles (size ranging from 200 to 400 nm) by miniemulsion technique in water. Various parameters such as the concentration of the reactants, the nature of stabilizers and the shear were tuned to control the particle size and its distribution. The polyaddition between the natural triol and isophorone diisocyanate (IPDI) was conducted at 60 °C, in the absence of catalyst and monitored by infrared spectroscopy. The characterization of these polyurethane latexes was carried out using light scattering measurements and transmission electron microscopy (TEM).     

Solvothermal synthesis of microsphere ZnO nanostructures in DEA media

Microsphere ZnO nanostructures (ZnO-MNs) were synthesized via solvothermal method in diethanolamine (DEA) media. DEA was utilized to terminate the growth of ZnO nanoparticles which forms the ZnO-MNs. The ZnO-MNs were characterized by a number of techniques, including X-ray diffraction analysis (XRD) and field emission scanning electron microscopy (SEM). The ZnO-MNs prepared by solvothermal process at the temperature of 150 °C for 6, 12, 18, and 24 h exhibited a hexagonal (wurtzite) structure with sizes ranging from 2 to 4 μm. The growth mechanism and morphology of the ZnO-MNs were also investigated, and it was found that the ZnO-MNs were formed by ZnO nanoparticles with average particle size of 25 ± 5 nm. To show role of DEA in the formation of Zn-MNs, effect of MEA (monoethanolamine) and TEA (triethanolamine) on morphology of the final product are also investigated. The results showed that DEA is a good polymerization agent that can be used as a stabilizer in the solvothermal technique for preparing fine ZnO powder.     

Electrochemical study of NiO nanoparticles electrode for application in rechargeable lithium-ion batteries

Nickel oxide nanoparticles were synthesized via a simple and inexpensive microwave-assisted synthesis method within a fast reaction time of less than 20 min. The calcination of as-prepared precursor at 600 °C produces single phase nickel oxide. The lattice structure and morphology of the sample were investigated by X-ray diffraction, field-emission scanning electron microscopy and field-emission transmission electron microscopy. The particle size range of the nickel oxide nanoparticles varied from 50 to 60 nm. Nickel oxide nanoparticles exhibited good electrochemical performances as an anode material for lithium-ion batteries. The prepared nickel oxide anode revealed a large initial discharge capacity of 1111.08 mAh g⁻¹ at 0.03 C rate and retained 80% of initial capacity (884.30 mAh g⁻¹) after 20 cycles. Furthermore, at elevated rate of 3.7 C, the charge capacity of the nickel oxide electrode was as high as 253.1 mAh g⁻¹, which was 35% greater than that of commercial bulk nickel oxide (188 mAh g⁻¹). The enhancement of the electrochemical performance was attributed to the high specific surface area, good electric contact among the particles and easier lithium ion diffusion.     

Electrodeposition of hard magnetic films and microstructures

Electrochemical deposition of materials with hard magnetic properties in the as-deposited state is essential for the efficient integration of micro-magnetic components into MEMS devices. Here we discuss the growth process and the microstructure-magnetic properties correlation for two Co-rich alloys, Co-Ni-P and Co-Pt. Under suitable synthesis conditions, these materials exhibit perpendicular anisotropy and hard magnetic properties in the as-deposited state; in addition, such properties are maintained up to several micrometer film thickness through close control of the film microstructure. In the case of Co-Ni-P films we achieved a saturation magnetization of 1.21 T (963 emu/cm³), perpendicular coercivity up to 188 kA/m (2.36 kOe) at a thickness of 10 μm, and energy products up to 4.2 kJ/m³. Co-rich Co-Pt films were grown on several substrates - Cr, Cu(0 0 1), Cu(1 1 1), and Ru(0 0 0 1) - in order to control magnetic anisotropy and achieve optimum hard magnetic properties. Cu(1 1 1) contributes to stabilize the hexagonal hcp phase at high current density yielding excellent hard magnetic properties, although only in films thicker than 100 nm; saturation magnetization in these films was about 1.04 T (828 emu/cm³). Perpendicular coercivities up to 485.6 kA/m (6.1 kOe) were obtained in 1 μm thick film deposited at 50 mA/cm². Ru(0 0 0 1) seed layers provide an appropriate interface structure to further facilitate the epitaxial growth of hcp films, yielding hard magnetic properties and perpendicular coercivity with a squareness ∼1 in films as thin as 10 nm. The hard magnetic properties were only marginally compromised at large film thickness. Deposition at higher current density (50 mA/cm²) favored markedly improved hard magnetic properties. The Co-Pt films on Ru exhibited perpendicular anisotropy with anisotropy constant up to 1.2 MJ/m³. The electrodeposition process was further extended to fill lithographically patterned hole arrays (850 nm diameter, center-to-center distance 2550 nm and about 700 nm thick resist), yielding arrays of micron-sized hard magnetic cylinders with perpendicular coercivity of 361 kA/m (4.54 kOe) and high squareness.     

Influence of ionic liquid on the photoelectrochemical properties of ZnO particles

ZnO particles synthesized by the microwave-assisted hydrothermal method were sensitized with different amounts of ionic liquid (IL) 1.3-dimethylimidazolium iodide (MMI.I). The structure of the modified and unmodified ZnO particles were characterized by X-ray diffraction, Raman spectroscopy, field emission gun-scanning electron microscopy (FEG-SEM), ultraviolet-visible (UV–vis) absorption spectroscopy, photoluminescence (PL), and photoelectrochemical measurements. While the sensitization of ZnO particles by the ionic liquid does not change the ZnO phase, it reduces the particle size and converts shallow defects to deep defects. These changes cause the photocurrent density of the ZnO/IL films to increase significantly from 0.05?mA?cm^?2 for pure ZnO to 0.52 and 1.24?mA?cm^?2 for the ZnO films containing 20% and 35% by mass of the IL, respectively, at 1.08?V vs. Ag/AgCl. This about 24-fold increase in the photocurrent density of the ZnO/IL35 sample may indicate that the MMI.I IL may be acting as a dye, since it is constituted by an organic part, MMI⁺. This good performance presented by this sample indicates that this is a promising material for photoanode in solar cells.