Microwave-assisted synthesis and photoluminescence of MMoO4 (M=Ca,Ba) particles via a metathetic reaction

MMoO₄ (M=Ca, Ba) particles were synthesized by a metathetic reaction in ethylene glycol assisted by cyclic microwave irradiation followed by further heat-treatment. The MMoO₄ (M=Ca, Ba) particles were well crystallized after heat-treatment at 400–600 °C for 3 h. The microstructures exhibited fine morphologies with sizes of 0.5–1 μm and 1.5–2 μm for the CaMoO₄ and BaMoO₄ particles, respectively. The synthesized MMoO₄ (M=Ca, Ba) particles were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. The optical properties were examined by photoluminescence emission and Raman spectroscopy.     

Sonochemically synthesized MnO2 nanoparticles as electrode material for supercapacitors

In this study, manganese oxide (MnO₂) nanoparticles were synthesized by sonochemical reduction of KMnO₄ using polyethylene glycol (PEG) as a reducing agent as well as structure directing agent under room temperature in short duration of time and characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscope (SEM), Transmission electron microscopy (TEM) and Brunauer–Emmett–Teller (BET) analysis. A supercapacitor device constructed using the ultrasonically-synthesized MnO₂ nanoparticles showed maximum specific capacitance (SC) of 282 Fg⁻¹ in the presence of 1 M Ca(NO₃)₂ as an electrolyte at a current density of 0.5 mA cm⁻² in the potential range from 0.0 to 1.0 V and about 78% of specific capacitance was retained even after 1000 cycles indicating its high electrochemical stability.     

Maximum magnetic entropy change modulated toward room temperature in perovskite manganites La0.7−xNdx(Ca,Sr)0.3MnO3

With Nd³⁺ doping and Ca²⁺, Sr²⁺ modulating in the sol–gel technique, a series of polycrystalline perovskite samples La_0.7?xNd_x(Ca,Sr)_0.3MnO₃ (x = 0, 0.05, 0.1, 0.15, 0.20, 0.25) was prepared, their maximum magnetic entropy changes were tuned to room temperature (ΔS_H = ?1.47 J/kg K at 298 k for La_0.45Nd_0.25(Ca,Sr)_0.3MnO₃), an enhancement of the maximum magnetic entropy change (ΔS_H = ?1.89 J/kg K at 315 k) and its refrigerant capacity (about 45.3 J/kg) had also been obtained under 9 kOe magnetic field variation for La_0.55Nd_0.15(Ca,Sr)_0.3MnO₃ contrast to La_0.7(Ca,Sr)_0.3MnO₃.     

Synthesis and electrical properties of nanocrystalline Ca1 − xEuxMnO3 ± δ (0.1 ≤ x ≤ 0.4) powders prepared at low temperature using citrate gel method

Nanopowders of Ca_1 − xEu_xMnO₃ (0.1 ≤ x ≤ 0.4) manganites were synthesized as a single phase using the auto gel-combustion method. The citrate method shows to be simple and appropriate to obtain single phases avoiding segregation or contamination. The Ca_1 − xEu_xMnO₃ system has been synthesized at 800 °C during 18 h, against the conventional method of mixing oxides used to obtain these materials at higher temperatures of synthesis. The formation reaction was monitored by X-ray diffraction (XRD) analysis and an infrared absorption technique (FTIR). The polycrystalline powders are characterised by nanometric particle size, ∼ 48 nm as determined from X-ray line broadening analysis using the Scherrer equation. Morphological analysis of the powders, using the scanning electron microscope (SEM), revealed that all phases are homogeneous and the europium-substituted samples exhibit a significant decrease in the grain size when compared with the undoped samples. The structure refinement by using the Rietveld method indicates that the partial calcium substitution by europium (for x ≥ 0.3) modifies the orthorhombic structure of the CaMnO₃ perovskite towards a monoclinic phase. All manganites show two active IR vibrational modes around 400 and 600 cm^− 1. The high temperature dependence of electrical resistivity (between 25 and 600 °C) allows us to conclude that all the samples exhibit a semiconductor behaviour and the europium causes a decrease in the electrical resistivity by more than one order of magnitude. The results can be well attributed to the Mn⁴⁺/Mn³⁺ ratio.     

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.     

Investigation on the microscopic features of layered oxide Li[Ni1 / 3Co1 / 3Mn1 / 3]O2 and their influences on the cathode properties

Three kinds of samples of Li[Ni_1 / 3Co_1 / 3Mn_1 / 3]O₂ were prepared respectively from direct solid-state reaction method, combustion method and co-precipitation route and their microscopic structural features have been investigated using Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), magnetic susceptibility measurement and X-ray photoelectron spectroscopy (XPS). The microscopic features such as uniform distribution of transition metal ions at 3b-site and the site-exchange ratio between lithium and nickel were found to be significantly dependent on the synthetic routes. The electrochemical properties of three samples were monitored using 2016 coin-cell by galvanostatic charge–discharge cycling test and cyclic voltammetry, which showed that the microscopic structural features are deeply related with the electrochemical performance. The obtained results also suggested that the combustion method may become a much simple alternative synthetic route to the complicate co-precipitation method.     

Spray pyrolyzed NiO–C nanocomposite as an anode material for the lithium-ion battery with enhanced capacity retention

NiO–C nanocomposite was prepared by a spray pyrolysis method using a mixture of Ni(NO₃)₂ and citric acid solution at 600 °C. The microstructure and morphology of the NiO–C composite were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) mapping, and thermogravimetric analysis (TGA). The results showed that the NiO nanoparticles were surrounded by amorphous carbon. Electrochemical tests demonstrated that the NiO–C nanocomposites exhibited better capacity retention (382 mAh g^− 1 for 50 cycles) than that of pure NiO (141 mAh g^− 1 for 50 cycles), which was also prepared by spray pyrolysis using only Ni(NO₃)₂ as precursor. The enhanced capacity retention can be mainly attributed to the NiO–C composite structure, composed of NiO nanoparticles surrounded by carbon, which can accommodate the volume changes during charge–discharge and improve the electrical conductivity between the NiO nanoparticles.     

Preparation of cube micrometer potassium niobate (KNbO3) by hydrothermal method and sonocatalytic degradation of organic dye

Cube micrometer potassium niobate (KNbO₃) powder, as a high effective sonocatalyst, was prepared using hydrothermal method, and then, was characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). In order to evaluate the sonocatalytic activity of prepared KNbO₃ powder, the sonocatalytic degradation of some organic dyes was studied. In addition, some influencing factors such as heat-treatment temperature and heat-treatment time on the sonocatalytic activity of prepared KNbO₃ powder and catalyst added amount and ultrasonic irradiation time on the sonocatalytic degradation efficiency were examined by using UV–visible spectrophotometer and Total Organic Carbon (TOC) determination. The experimental results showed that the best sonocatalytic degradation ratio (69.23%) of organic dyes could be obtained when the conditions of 5.00 mg/L initial concentration, 1.00 g/L prepared KNbO₃ powder (heat-treated at 400 °C for 60 min) added amount, 5.00 h ultrasonic irradiation (40 kHz frequency and 300 W output power), 100 mL total volume and 25–28 °C temperature were adopted. Therefore, the micrometer KNbO₃ powder could be considered as an effective sonocatalyst for treating non- or low-transparent organic wastewaters.     

Preparation and characterization of Fe3O4(1 1 1) nanoparticles and thin films on Au(1 1 1)

Fe₃O₄ nanoparticles and thin films were prepared on the Au(1 1 1) surface and characterized using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Fe₃O₄ was formed by annealing α-Fe₂O₃(0 0 0 1) structures on Au(1 1 1) at 750 K in ultrahigh vacuum (UHV) for 60 min. Transformation of the α-Fe₂O₃(0 0 0 1) structures into Fe₃O₄ nanoparticles and thin films was supported by XPS. STM images show that during the growth procedure used, Fe₃O₄ initially appears as nanoparticles at low coverages, and forms thin films at ～2 monolayer equivalents (MLE) of iron. Two types of ordered superstructures were observed on the Fe₃O₄ particles with periodicities of ～50 and ～42 Å, respectively. As the Fe₃O₄ particles form more continuous films, the ～50 Å feature was the predominant superstructure observed. The Fe₃O₄ structures at all coverages show a hexagonal unit cell with a ～3 Å periodicity in the atomically resolved STM images.     

Obtaining Ca(H2PO4)2·H2O,monocalcium phosphate monohydrate,via monetite from brushite by using sonication

Brushite was synthesized by precipitation of calcium chloride (CaCl₂) and sodium phosphate monobasic (Na₂HPO₄) dried in vacuum and monetite was obtained from this brushite by sonication with a frequency of 90 kHz at 500 W for 90 min. Monetite itself was also transformed in Ca(H₂PO₄)₂·H₂O, monocalcium phosphate monohydrate (MCPM), by sonication with a frequency of 90 kHz at 500 W for 60 min followed by lyophilization. The MCPM was sonicated and lyophilized by three times more until reach over 240 min, but any other phase transformation was observed. All these phase transformations were analyzed by X-ray diffraction (XRD) and infrared spectroscopy (FTIR). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicated a grain size of about 200 nm in all the samples. The morphology observed was a corn-flake-like grain for brushite, a pseudo-needle-like grains for monetite, and lamellar-like grains for MCPM.     

Effect of processing conditions on sonochemical synthesis of nanosized copper aluminate powders

Nanosized copper aluminate (CuAl₂O₄) spinel particles have been prepared by a precursor approach with the aid of ultrasound radiation. Mono-phasic copper aluminate with a crystallite diameter of 17 nm along the (3 1 1) plane was formed when the products were synthesized using Cu(NO₃)₂·6H₂O and Al(NO₃)₃·9H₂O as starting materials, with urea as a precipitation agent at a concentration of 9 M. The reaction was carried out under ultrasound irradiation at 80 °C for 4 h and a calcination temperature of 900 °C for 6 h. The synthesized copper aluminate particles and the effect of different processing conditions such as the copper source, precipitation agents, sonochemical reaction time, calcination temperature and time were analyzed and characterized by the techniques of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and Fourier transformation infrared spectroscopy (FT–IR).     

Ultrasonic-assisted magnetic solid phase extraction of morphine in urine samples by new imprinted polymer-supported on MWCNT-Fe3O4-NPs: Central composite design optimization

Multiwalled carbon nanotubes (MWCNTs) were magnetized with Fe₃O₄ nanoparticles (MWCNTs-Fe₃O₄-NPs) and subsequently coated by vinyl end groups (Vinyltrimethoxysilane). MWCNT-Fe₃O₄-NPs were used as support for a new morphine (MO) molecularly imprinted polymer (MWCNT-Fe₃O₄-NPs@MO-MIP) by surface imprinting polymerization method. The MWCNT-Fe₃O₄-NPs@MO-MIP was characterized by FTIR, VSM and SEM techniques and successfully used for determination of MO. Ultrasonic-assisted magnetic solid phase extraction followed by UV–vis spectrophotometer (UAMSPE-UV–vis) was investigated for MWCNT-Fe₃O₄-NPs@MO-MIP and compared with non-imprinted polymer (NIP) using batch method. Central composite design under response surface methodology was used for the evaluation of the effect of variables, individually, as well as their possible interaction effects on the adsorption process. The variables such as sonication time, MWCNT-Fe₃O₄-NPs@MO-MIP mass, initial concentration of MO and pH were investigated in this study. At optimum experimental conditions, UAMSPE-UV–vis method was exhibited a linear range of 0.8–8.7 mg L⁻¹ of the MO concentration with a detection limit of 0.18 mg L⁻¹. The relative standard deviation for the analyte was found to be lower than 2.32%. The MWCNT-Fe₃O₄-NPs@MO-MIP adsorption capacity was found to be 37.01 mg g⁻¹. The enrichment and preconcentration factors were found to be 107.01 and 98.21, respectively. The developed method was finally applied successfully to the determination of MO in urine and wastewater samples with the recoveries ranged from 96.40 to 105.6%.     

Thermoluminescence response in gamma and UV irradiated Dy2O3 nanophosphor

Low temperature solution combustion method was employed to synthesize Dy₂O₃ nanophosphors using two different fuels (sugar and oxalyl dihydrazine (ODH)). Powder X-ray diffraction confirm pure cubic phase and the estimated particle size from Scherrer's method in sugar and ODH fuel was found to be 26 and 78 nm, respectively, and are in close agreement with those obtained using TEM and W–H plot analysis. SEM micrographs reveal porous, irregular shaped particles with large agglomeration in both the fuels. An optical band gap of 5.24 eV and 5.46 eV was observed for Dy₂O₃ for sugar and ODH fuels, respectively. The blueshift observed in sugar fuel is attributed to the particles size effect. Thermoluminescence (TL) response of cubic Dy₂O₃ nanophosphors prepared by both fuels was examined using gamma and UV radiations. The thermoluminescence of sugar used samples shows a single glow peak at 377 °C for 1–4 kGy gamma irradiations. When dose is increased to 5 kGy, two more shouldered peaks were observed at 245 and 310 °C. However, in TL of ODH used samples, a single glow peak at 376 °C was observed. It is observed that TL intensity is found to be more in sugar used samples. In UV irradiated samples a single glow peak at 365 °C was recorded in both the fuels with a little variation in TL intensity. The trapping parameters were estimated by different methods and the results are discussed.     

Photochemistry of methyl bromide on the α-Cr2O3(0001) surface

The photochemical properties of the Cr-terminated α-Cr₂O₃(0001) surface were explored using methyl bromide (CH₃Br) as a probe molecule. CH₃Br adsorbed and desorbed molecularly from the Cr-terminated α-Cr₂O₃(0001) surface without detectable thermal decomposition. Temperature programmed desorption (TPD) revealed a CH₃Br desorption state at 240 K for coverages up to 0.5 ML, followed by more weakly bound molecules desorbing at 175 K for coverages up to 1 ML. Multilayer exposures led to desorption at ~ 130 K. The CH₃Br sticking coefficient was unity at 105 K for coverages up to monolayer saturation, but decreased as the multilayer formed. In contrast, pre-oxidation of the surface (using an oxygen plasma source) led to capping of surface Cr³⁺ sites and near complete removal of CH₃Br TPD states above 150 K. The photochemistry of chemisorbed CH₃Br was explored on the Cr-terminated surface using post-irradiation TPD and photon stimulated desorption (PSD). Irradiation of adsorbed CH₃Br with broad band light from a Hg arc lamp resulted in both photodesorption and photodecomposition of the parent molecule at a combined cross section of ~ 10^? 22 cm². Photodissociation of the CH₃–Br bond was evidenced by both CH₃ detected in PSD and Br atoms left on the surface. Use of a 385 nm cut-off filter effectively shut down the photodissociation pathway but not the parent molecule photodesorption process. From these observations it is inferred that d-to-d transitions in α-Cr₂O₃, occurring at photon energies < 3 eV, do not significantly promote photodecomposition of adsorbed CH₃Br. It is unclear to what extent band-to-band versus direct CH₃Br photolysis play in CH₃–Br bond dissociation initiated by more energetic photons.     

Characterization of NaTaO3 synthesized by ultrasonic method

NaTaO₃ perovskite-like materials were synthesized using sodium acetate and tantalum ethoxide as precursors in an ultrasonic bath at room temperature. The pristine sample was thermally treated at 600 °C and characterized using XRD, N₂ physisorption, DRS, SEM and TEM techniques. The structural characterization by X-ray powder diffraction revealed that the crystallization of the NaTaO₃ phase prepared at 600 °C showed agglomerates sizes in the micrometric scale, as confirmed by scanning electron microscopy (SEM). On the other hand, well-defined NaTaO₃ particles in the nanometric scale were determined using TEM. It was found that, for the treated sample, the band gap and BET area was 3.8 eV and 9.5 m² g^?1, respectively. The annealed perovskite, deposited onto ITO glass, presented an important variation in the open circuit potential transient during UV light irradiation in neutral solution, compared with its counterpart prepared by solid-state method. These intrinsic properties, given by the preparation route, might be appropriate for increase its photocatalytic activity.     

Verifying the presence of low levels of neptunium in a uranium matrix with electron energy-loss spectroscopy

This paper examines the problems associated with analysis of low levels of neptunium in a uranium matrix with electron energy-loss spectroscopy (EELS) on the transmission electron microscope (TEM). The detection of neptunium in a matrix of uranium can be impeded by the occurrence of a plural scattering event from uranium (U-M₅ + U-O_4,5) that results in severe overlap on the Np-M₅ edge at 3665 eV. Low levels of Np (1600–6300 ppm) can be detected in a uranium solid, uranophane [Ca(UO₂)₂(SiO₃OH)₂(H₂O)₅], by confirming that the energy gap between the Np-M₅ and Np-M₄ edges is at 184 eV and showing that the M₄/M₅ ratio for the neptunium is smaller than that for uranium. The Richardson–Lucy deconvolution method was applied to energy-loss spectral images and was shown to increase the signal to noise ratio.     

Luminescence and defect studies of YAlO3:Dy3+, Sm3+ single crystals exposed to 100 MeV Si7+ ion beam

Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm³⁺ and Dy³⁺) activated YAlO₃ single crystals have been induced with 100 MeV Si⁷⁺ ions with fluence of 7.81×10¹² ions cm^?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm³⁺ and 482–574 nm in Dy³⁺ were recorded. Variation of IL intensity in Dy³⁺ doped YAlO₃ single crystals was studied in the fluence range 7.81×10¹²–11.71×10¹² ions cm^?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×10¹² ions cm^?2 on pure and doped crystals at a warming rate of 5 °C s^?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg₁) and 328 °C (Tg₂). However, in Sm³⁺ doped crystals three glow peaks at 278 (Tg₁), 332 (Tg₂) and 384 °C (Tg₃) and two glow peaks at 278 (Tg₁) and 331 °C (Tg₂) in Dy³⁺ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.     

Structural and electrical properties of a high-k SmAlO3 charge trapping flash memory

In this study, we proposed the Al/Al₂O₃/SmAlO₃/SiO₂/Si flash memory devices using high-k SmAlO₃ film as a charge trapping layer and high-k Al₂O₃ film as a blocking layer. The structural and morphological features of these films were explored by X-ray diffraction, X-ray photoelectron spectroscopic and atomic force microscopy. The SmAlO₃ flash memory devices annealed at 800 °C showed excellent electrical properties, such as a large memory window of ～2.61 V (measured at a sweep voltage range of ±5 V) and a small charge loss of ～7.1% (measured time up to 10⁴ s). In addition, the charge trap centroid and charge trap density were extracted by constant current stress method.     

New investigation for Tc depression by Ca in Y1−xCax:123 superconducting systems

Two similar sets of the series Y_1?xCa_xBa₂Cu₃O_Y (0.00 ? x ? 0.50) are prepared by two different heat treatments at the final process of calcinations. The first set is quenched in air down to room temperature (ssq); while the second is left in the furnace and slowly cooled to room temperature (sss). After that, the samples are separately sintered in two different oxygen purity (99.99% Hp and 93% Lp, respectively) to obtain four different sets called ssqHp, sssHp, ssqLp and sssLp. Then, the considered samples are tested by XRD, SEM, resistivity and microhardness (VHN) techniques. It is found that c-parameter for ssqHP and sssLP samples increases slightly with Ca doping; while orthorhombic distortion remains nearly invariant. Interestingly, unlike for ssqHp and sssLp samples, the OD decreases continuously with Ca doping in sssHp and ssqLp samples; while c-parameter increases. SEM micrographs indicate that Ca generally improve the link between superconducting grains for all set of samples. The oxygen content is gradually decreased by Ca for all set of samples and generally follow the relation, y = 6.93 ? 0.5x. The effective Cu valence slightly decreases, as compared to pure samples, but stays nearly independent of Ca content for all the series. The relative decrease in critical temperature T_c by Ca is more in ssqHp and sssLp samples, when compared with those of sssHp and ssqLp samples. Although, an approximately linear increase in VHN with various Ca is obtained, the relative increase is more in ssqHp and sssLp samples with respect to sssHp and ssqLp samples. These results indicate that substitution of Ca at Y site leads towards oxygen vacancies predominantly created in CuO₂ planes (CuO chains) of ssqHp and sssLp (sssHp and ssqLp) based samples, and far from overdoping.     

Influence of fabrication processing on phase transition and electrical properties of 0.8Pb(Zr1/2Ti1/2)O3–0.2Pb(Ni1/3Nb2/3)O3 ceramics

The binary system of 0.8Pb(Zr_1/2Ti_1/2)O₃–0.2Pb(Ni_1/3Nb_2/3)O₃ ceramics were synthesized by conventional mixed oxide and columbite method. X-ray diffraction analysis demonstrated the coexistence of both the rhombohedral and tetragonal phases for the columbite prepared sample. Rhombohedral to tetragonal phase transition for columbite method was different compared with those of the mixed oxide method. The permittivity shows a shoulder at the rhombohedral to tetragonal phase transition temperature T_Rho–Tetra = 195 °C, and then a maximum permittivity (36,000 at 10 kHz) at the transition temperature T_m = 277 °C on ceramics prepared with the columbite method. However, piezoelectric coefficient (d₃₃) was measured to be 282 pC/N for the conventional method and higher than the columbite method. The results were related to the phase compositions and porosity of the ceramics.