Annealing of PrF3 nanoparticles by microwave irradiation

The influence of microwave irradiation on the recovery of nanocrystalline PrF₃ powders has been experimentally analyzed by nuclear magnetic resonance (NMR) at T = 1.5 K. It is established that the relaxation times of ¹⁴¹Pr and ¹⁹F nuclei rise significantly with an increase in the hydrothermal-treatment time, whereas the ¹⁴¹Pr NMR spectra narrow, which indicates a decrease in the number of defects in the lattices of nanosamples.     

Rapid synthesize of gold nanoparticles by microwave irradiation method and its application as an optical limiting material

We present rapid synthesis of gold nanoparticles by microwave irradiation method. Sample with average particle size 7.7 nm is obtained from TEM. Linear and nonlinear optical studies of the prepared samples are discussed. Reverse saturable absorption (RSA) at longitudinal surface plasmon resonance (SPR) in gold nanoparticles (Au NPs) have been observed using Z-scan and transient absorption techniques with 532 nm laser pulses. Such RSA behavior makes Au NPs an ideal candidate for optical limiting applications.     

Ultrasound irradiation as an effective tool in synthesis of the slag-based catalysts for carboxymethylation

Waste minimization strategy was applied in the current work for synthesis of the catalysts from industrial solid waste, namely desulfurization slag. The starting slag material comprising CaCO₃, Ca(OH)₂, SiO₂, Al₂O₃, Fe₂O₃, and TiO₂ was processed by various treating agents systematically varying the synthesis parameters. A novel efficient technique – ultrasound irradiation, was applied as an additional synthesis step for intensification of the slag dissolution and crystallization of the new phases. Physico-chemical properties of the starting materials and synthesized catalysts were evaluated by several analytical techniques. Treatment of the industrial slag possessing initially poor crystal morphology and a low surface area (6 m²/g) resulted in formation of highly-crystalline catalysts with well-developed structural properties. Surface area was increased up to 49 m²/g. High basicity of the neat slag as well as materials synthesized on its basis makes possible application of these materials in the reactions requiring basic active sites. Catalytic performance of the synthesized catalysts was elucidated in the synthesis of carbonate esters by carboxymethylation of cinnamyl alcohol with dimethyl carbonate carried out at 150 °C in a batch mode. Ultrasonication of the slag had a positive effect on the catalytic activity. Synthesized catalysts while exhibiting similar selectivity to the desired product (ca. 84%), demonstrated a trend of activity increase for materials prepared using ultrasonication pretreatment. The choice of the treating agent also played an important role in the catalytic performance. The highest selectivity to the desired cinnamyl methyl carbonate (88%) together with the highest activity (TOF₃₅ = 3.89*10⁻⁷ (mol/g*s)) was achieved over the material synthesized using 0.6 M NaOH solution as the treating agent with the ultrasound pre-treatment at 80 W for 4 h.     

FePt nanoparticles as heterogeneous Fenton-like catalysts for hydrogen peroxide decomposition and the decolorization of methylene blue

The potential effects of oxidized multi-walled carbon nanotubes (o-MWCNTs) with a length ranging from 50 to 630?nm on the development and physiology of wheat plants were evaluated by examining their effects on seed germination, root elongation, stem length, and vegetative biomass at a concentration ranging from 10 to 160???g/mL in the plant. Results indicated that after 7?days of exposure to the o-MWCNTs medium, faster root growth and higher vegetative biomass were observed, but seed germination and stem length did not show any difference as compared with controls. Moreover, a physiological study was conducted at cellular level using a traditional physiological approach to evidence the possible alterations in morphology, the cell length of root zone, and the dehydrogenase activity of seedlings. Transmission electron microscopy images revealed that o-MWCNTs could penetrate the cell wall and enter the cytoplasm after being taken up by roots. The cell length of root zone for the seedlings germinated and grown in the o-MWCNTs (80???g/mL) medium increased by 1.4-fold and a significant concentration-dependent increase in the dehydrogenase activity for the o-MWCNT-treated wheat seedlings was detected. These findings suggest that o-MWCNTs can significantly promote cell elongation in the root system and increase the dehydrogenase activity, resulting in faster root growth and higher biomass production.     

Catalytic generation of hydrogen by applying fluorinated-metal hydrides as catalysts

Metal–hydrogen complexes such as NaAlH₄, KBH₄, and NaBH₄ are known as high H-content materials. The highly reactive natures of these materials against moist air and water can be easily stabilized in aqueous KOH and NaOH solutions. Accordingly, it is required to develop catalysts suitable for generating hydrogen from the stabilized metal–hydrogen complexes in alkaline solutions. This work is aimed at developing catalysts that can generate hydrogen from such solutions with considerably high kinetics under moderate temperature and pressure conditions. We have found that Mg₂Ni, a typical high-temperature hydriding alloy, exhibits excellent functions as a catalyst for the hydrolysis of BH₄ ^--ion-containing solutions. The fluorination-treatment (F-treatment) effects on granular particles of Mg₂Ni and Mg₂NiH₄ are reported in this paper. Received: 13 November 2000 / Accepted: 14 November 2000 / Published online: 9 February 2001     

Synthesis of nanocrystalline ZnTiO3 perovskite thin films by sol-gel process assisted by microwave irradiation

Nanocrystalline ZnTiO₃ thin films have been grown on Si (1 0 0) at room temperature by using simple, cost effective sol-gel process assisted by microwave irradiation for thermal treatment. For comparison purpose the deposited films have subjected to two kinds of annealing treatments: first set by using conventional annealing and second set by irradiating the deposited films at different microwave powers for 10 min. In both treated films, formation of cubic phase ZnTiO₃ structure has been observed. It is evident that there is a dramatic structural modification when the deposited films are exposed to microwave. It is evident that there is a dramatic change in the morphological properties of the films irradiated in microwave compared to the conventional annealing temperature. Microwave exposed films have shown 19% of Zn, 19% of Ti and 62% of O in the films close to the stiochiometry of the ZnTiO₃, where as annealed films have shown 18% of Zn, 17.5% of Ti, and 64.5% of O in the films of ZnTiO₃. Plausible mechanism for the formation of cubic phase of ZnTiO₃ at low microwave powers has also been discussed. This new innovative microwave heating could open a door for the advanced technologies to cut down the process cost in post treatment of the materials.     

Rapid synthesis and size control of CuInS2 semi-conductor nanoparticles using microwave irradiation

The properties of CuInS₂ semi-conductor nanoparticles make them attractive materials for use in next-generation photovoltaics. We have prepared CuInS₂ nanoparticles from single source precursors via microwave irradiation. Microwave irradiation methods have allowed us to increase the efficiency of preparation of these materials by providing uniform heating and rapid reaction times. The synergistic effect of varying thiol capping ligand concentrations as well as reaction temperatures and times resulted in fine control of nanoparticle growth in the 3–5 nm size range. Investigation of the photophysical properties of the colloidal nanoparticles were performed using electronic absorption and luminescence emission spectroscopy. Qualitative nanoparticles sizes were determined from the photoluminescence (PLE) data and compared to HRTEM images.

Microwave assisted IMDAF# reaction: microwave irradiation applied with success to cycloaddition reaction of N-propargyl-N-p-tolyl-N-2-furfurylamines

The new tertiary furfurylamine with triple bond as a dienophylic part i.e. N-(5-methyl-2-furfuryl)-N-prop-2-ynyl-p-toluidine (1) was prepared and the intramolecular Diels-Alder reaction of the amine (1) was performed under microwave irradiation conditions and by heating a benzene solution of the amine under nitrogen. Comparing the results of the usual thermal and the MAOS reaction, we confirmed our expectations that MAOS could promote the outcome of IMDA reaction of the suitably N-substituted tertiary 2-furfuryl-amines. In the present example, N-p-tolyl-5-methyl-5,7a-dihydro-5,7a-epoxyisoindoline was obtained in much better yield and of higher purity.     

Development of high sensitivity ethanol gas sensor based on Co-doped SnO2 nanoparticles by microwave irradiation technique

We have successfully synthesized Co doped SnO₂ nanoparticles by a simple microwave irradiation technique. Powder X-ray diffraction results reveal that the SnO₂ doped with cobalt concentration from 0 to 5 wt % crystallizes in tetragonal rutile-type structure. The products were annealed at 600 °C for 5 h in ambient atmosphere in order to improve crystallinity and structural perfection. Transmission electron microscopy (TEM) studies illustrate that both the undoped and Co doped SnO₂ crystallites form in spherical shapes with an average diameter of 30–15 nm, which is in good agreement with the average crystallite sizes calculated by Scherrer's formula. A considerable red shift in the absorbing band edge was observed with increasing of Co content (0–5 wt %) by using UV–Vis diffuse reflectance spectroscopy (DRS). Oxygen-vacancies, tin interstitial and structural defects were analyzed using photoluminescence (PL) spectroscopy. Electron paramagnetic resonance (EPR) spectroscopic studies clearly showed that the Co²⁺ was incorporated into the SnO₂ host lattice. Ethanol gas sensitivity of pure and Co-doped (5 wt %) SnO₂ nanoparticles were experimented at ambient temperature using optical fiber based on clad-modified method. By modifying the clad exposure to ethanol vapor, the sensitivities were estimated to be 18 and 30 counts/100 ppm for undoped and Co-doped SnO₂ nanoparticles, respectively. These results show that the Co doping into SnO₂ enhances its ethanol gas sensitivity significantly.     

Properties of SBA-15 modified by iron nanoparticles as potential hydrogen adsorbents and sensors

SBA-15-Fe was synthesized via the incorporation of Fe⁰ nanoparticles (Fe(0)-Nps) in the mesoporous channels. Electron microscopy and X-ray diffraction showed that dispersion of fine iron NPs occurs mainly inside the channels of SBA-15, producing a slight structure compaction. This was accompanied by a significant improvement of both the affinity towards hydrogen and electrical conductivity, as supported by hydrogen adsorption tests and impedance measurements. CO₂ thermal programmed desorption measurements revealed an attenuation of the acid character of the solid surface. This was explained in terms of strong iron interaction with the lattice oxygen atoms that reduces the SiO–H bond polarity. The close vicinity of fine Fe(0)-Nps combined with the large pore size of SBA-15 appear to contribute to a synergistic improvement of the electrical conductivity. The results reported herein open new prospects for SBA-15 as potential adsorbents for hydrogen storage and carriers for hydrogen sensors. The use of iron in lieu of noble metals for designing such materials is a novelty, because such applications of iron-loaded silica have not been envisaged so far due to the high reactivity of iron towards air and water. The development of such technologies, if any, should address this issue.     

Blue luminescence of nanocrystalline PbWO4 phosphor synthesized via a citrate complex route assisted by microwave irradiation

Nanocrystalline PbWO₄ phosphor powders, which have scheelite structure, were successfully synthesized at low temperatures via a modified citrate complex route assisted by microwave irradiation. Crystallization of the PbWO₄ precursor were detected at 400 °C, and entirely completed at 500 °C. Prepared PbWO₄ nanocrystallites showed primarily spherical and disperse morphology. The average crystallite sizes were between 18 and 29 nm, showing an ordinary tendency to increase with temperature. The nanocrytalline PbWO₄ phosphor powders exhibited spread-eagle shape of blue luminescence. Especially the PbWO₄ phosphor powders prepared at 600 °C showed the strongest luminescent intensity, which was due to the higher crystallinity and homogeneous particle morphology.     

Scattering by inhomogeneous particles: microwave analog experiments and comparison to effective medium theories

It is common practice to use effective medium theories (EMT) to estimate average, “effective” optical constants of inhomogeneous materials. A variety of EMTs were developed for different internal structures of the medium and for a variety of shapes, size distributions and physical properties of the inhomogeneities. The most popular EMTs (Maxwell Garnett, Bruggeman, Looyenga, etc.) consider inhomogeneities that are much smaller than the wavelength. The so-called extended EMTs were developed to find effective optical constants in the case of inhomogeneities comparable and slightly larger than the wavelength. This paper compares angular distribution and wavelength dependence of intensity and polarization of scattered light obtained from calculations using the most popular EMTs and extended EMTs with the results of microwave analog measurements at the microwave facilities of the University of Florida. We simulated the light scattering by organic grains with silicate inclusions of size parameter x=0.075 (≈0.01 μm), 0.60 (≈0.1 μm), and 1.24 (≈0.2 μm). The conclusion is that for inclusions of a small size and for a small volume fraction of them in the mixture all EMTs yield similar results and show reasonable agreement with experimental results. The accuracy is better for the angular dependencies of the intensity and of the polarization of the scattered light than for their wavelength dependencies. For inhomogeneities comparable and larger than the wavelength extended EMTs work better but for smaller inclusions non-extended EMTs show more accurate results. Large volume fractions of the inclusions in the mixture (>10%) essentially reduce the accuracy of the results obtained with EMTs. Based on our study we do not recommend to use EMTs in the back-scattering domain and at the scattering angles 30°<θ<70°.     

The surface structure of catalysts activated with hydrogen donors as elucidated by multinuclear solid-state NMR

¹H, ²⁷Al and ³¹P MAS, and ¹³C and ²⁹Si CP/MAS NMR spectroscopies, were used to characterize catalysts of Pd supported on various solids including SiO₂, AlPO₄ and Mg₃(PO₄)₂ that were activated with the chiral hydrogen-donor limonene. The above-mentioned techniques were used to check for the formation of an organopalladium complex between Pd²⁺ atoms and the olefin bonds in the limonene molecule on the catalyst surface. The results are compared with those obtained for catalysts activated in a hydrogen stream.     

TiO2/SiO2 multilayer as an antireflective and protective coating deposited by microwave assisted magnetron sputtering

In this paper designing, preparation and characterization of multifunctional coatings based on TiO₂/SiO₂ has been described. TiO₂ was used as a high index material, whereas SiO₂ was used as a low index material. Multilayers were deposited on microscope slide substrates by microwave assisted reactive magnetron sputtering process. Multilayer design was optimized for residual reflection of about 3% in visible spectrum (450–800 nm). As a top layer, TiO₂ with a fixed thickness of 10 nm as a protective film was deposited. Based on transmittance and reflectance spectra, refractive indexes of TiO₂ and SiO₂ single layers were calculated. Ultra high vacuum atomic force microscope was used to characterize the surface properties of TiO₂/SiO₂ multilayer. Surface morphology revealed densely packed structure with grains of about 30 nm in size. Prepared samples were also investigated by nanoindentation to evaluate their protective performance against external hazards. Therefore, the hardness of the thin films was measured and it was equal to 9.34 GPa. Additionally, contact angle of prepared coatings has been measured to assess the wetting properties of the multilayer surface.     

Stability and characterization of mesoporous molecular sieve using natural clay as a raw material obtained by microwave irradiation

Mesoporous molecular sieve was synthesized via microwave irradiation method, and using natural clay, sodium silicate and aluminum chloride as raw materials and cetyl trimethyl ammonium bromide (CTAB) as a template agent under alkaline condition. The samples were characterized by various analytic and spectroscopic tools such as XRD, FT-IR, TEM, TG-DSC and N₂ physical adsorption, respectively. The results show that the synthesized sample has typical mesoporous structure and exhibits good mesoporous ordering. On the other hand, the as synthesized sample after calcination at 550 °C for 10 h has a surface area of 576.0 m²/g and an average pore size of 4.83 nm. Furthermore, the synthesized mesoporous molecular sieve still exhibits good mesoporous ordering after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 10 days.     

Investigation on the transition crystal of ordinary rutile TiO2 powder by microwave irradiation in hydrogen peroxide solution and its sonocatalytic activity

The transition crystal TiO(2) catalyst with high sonocatalytic activity was obtained utilizing the microwave irradiation in hydrogen peroxide solution. At the same time a series of affecting factors (microwave irradiation time, heat-treated time and heat-treated temperature) to prepare the TiO(2) catalyst on the sonocatalytic degradation of parathion were considered in this paper. The ultrasound of low power was used as an irradiation source to induce treated TiO(2) particles to perform catalytic activity. The results show that the sonocatalytic activity of the transition crystal TiO(2) powder is obviously higher than those of pure ordinary rutile and anatase TiO(2) powders. At last, the parathion in aqueous solution was degraded completely and became some simple inorganic ions such as NO(3)(-), PO(4)(3-), SO(4)(2-), etc. The degradation ratio of parathion in the presence of the transition crystal TiO(2) catalyst attains nearly 80% within 60 min ultrasonic irradiation, while corresponding ones are only 65.23% and 53.88%, respectively, for pure ordinary rutile and anatase TiO(2) powders.     

Facile synthesis of calcium silicate hydrate using sodium dodecyl sulfate as a surfactant assisted by ultrasonic irradiation

Calcium silicate hydrate (CSH) consisting of nanosheets has been successfully synthesized assisted by a tip ultrasonic irradiation (UI) method using calcium nitrate (Ca(NO₃)·4H₂O), sodium silicate (Na₂SiO₃·9H₂O) and sodium dodecyl sulfate (SDS) in water. Systematic studies found that reaction time of ultrasonic irradiation and concentrations of surfactant (SDS) in the system were important factors to control the crystallite size and morphologies. The products were characterized by X-ray power diffraction (XRD), field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectrometry (FTIR). The size–strain plot (SSP) method was used to study the individual contributions of crystallite sizes and lattice strain on the peak broadening of the CSH. These characterization techniques revealed the successful formation of a crystalline phase with an average crystallite size of about 13 nm and nanosheet morphology at a reaction time of 10 min UI with 0.2 g SDS in solvent which were found to be optimum time and concentrations of SDS for the synthesis of CSH powders.     

Ultrasound assisted chitosan coated iron oxide nanoparticles: Influence of ultrasonic irradiation on the crystallinity,stability, toxicity and magnetization of the functionalized nanoparticles

Due to unique reaction conditions of the acoustic cavitation process, ultrasound-assisted synthesis of nanoparticles has attracted increased research attention. In this study, we demonstrate the effect of ultrasonic irradiation on the crystallinity, stability, biocompatibility, and magnetic properties of chitosan-coated superparamagnetic iron oxide nanoparticles (CS-SPIONs). CS solution and colloidal suspension of SPIONs were mixed and sonicated using an ultrasonic probe of 1.3 cm tip size horn, frequency (20 kHz), and power (750 W). Different samples were sonicated for 1.5, 5, and 10 min with corresponding acoustic powers of 67, 40 and 36 W, and the samples were denoted S_1.5, S_5, and S₁₀, respectively. The samples were characterized using X-ray diffractometer (XRD), Energy dispersive X-ray (EDX), Transmission electronic microscope (TEM), Fourier transform infrared spectroscopy (FTIR), Zeta sizer, and vibrating sample magnetometer (VSM). Cell cytotoxicity and cell uptake were investigated with human embryonic kidney 293 (HEK-293) cells through MTT assay and Prussian blue staining, respectively. The sharp peaks of the XRD pattern were disappearing with an increase in the sonication period but a decrease in acoustic power. EDX analysis also demonstrates that atomic and weight percentages of the various elements in the samples were decreasing with an increase in the sonication period. However, the Zeta potential (ζ) values increase with an increase in the sonication period.The saturation magnetization (M_s) of the S_1.5 before and after the coating is 62.95 and 86.93 emu/g, respectively. Cell cytotoxicity and uptake of the S_1.5 show that above 70% of cells were viable at the highest concentration and the longest incubation duration. Importantly, the CS-SPIONs synthesized by the sonochemical method are non-toxic and biocompatible.