Modeling and optimization of densification of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powder prepared by a sol–gel method using response surface methodology

Response surface methodology (RSM) based on central composite design (CCD) was successfully applied to the optimization and modeling of densification of nanocrystalline Al₂O₃ powder prepared by sol–gel method. The effects of three operating variables, sintering temperature, calcination temperature and milling time on the densification of nanocrystalline Al₂O₃ were systematically evaluated. A quadratic model for densification was proposed. Analysis of variance (ANOVA) indicated that the proposed quadratic model could be used to navigate the design space. The simulated values obtained from the statistical model were in conformity with the experimental results within an average error of ±1.5%. The optimum operating conditions for densification were found to be 1,579 °C of sintering temperature, 909 °C of calcination temperature and 117 min of milling time. The obtained density under the optimum conditions determined by RSM was 98.5%. The results confirmed that RSM based on central composite design was an accurate and reliable method to optimize the densification conditions of nanocrystalline Al₂O₃ powder.     

Optimization of process conditions for biodiesel production over CaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript> catalyst using response surface methodology

CaO–Al₂O₃/ZrO₂ mixed oxide catalyst was prepared using free-solvent method. The catalyst was characterized using X-ray diffraction, BET surface area, acidity index (obtained by titration method), and scanning electron microscopy (SEM). With calcium aluminate and calcium zirconate been successfully formed, the mix exhibited small crystal size, high acidity, and large surface area, pore size, and pore volume, making it a catalyst of choice for biodiesel production. The activity of catalyst was evaluated in the course of esterification of oleic acid as well as transesterification of waste cooking oil (WCO) into biodiesel. Based on a four-variable central composite design (CCD), response surface methodology (RSM) was used to optimize effective variables on oleic acid conversion. The optimum yield of 94.68% was obtained at the following set of optimum conditions: reaction temperature of 120 °C, methanol/oleic acid molar ratio of 15.64, catalyst concentration of 2.94 wt%, and reaction time of 4 h; the result was in excellent agreement with the predicted values. Furthermore, under the optimum conditions, the catalyst succeeded to convert 93.48% of WCO into biodiesel.     

Novel sol–gel method for preparation of high concentration ε-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> nanocomposite

ε-Fe₂O₃/SiO₂ nanocomposite was prepared by novel solgel method using single precursor for both nanoparticles and matrix. This method allows to prepare the samples free of α-Fe₂O₃ with 40% of Fe₂O₃ in SiO₂. Nanoparticles of 12 nm diameter were obtained by annealing at 1,000 °C. The samples were characterized by powder X-ray diffraction and transmission electron microscopy. Mössbauer spectroscopy identified ε-Fe₂O₃ as the only magnetically ordered phase at room temperature. Magnetic measurements revealed progressive necking of hysteresis loops measured at 300 and 2 K. In both cases the intrinsic coercivity reaches only 0.25 T. Measurements up to 14 T shows monotonous decreasing trend of saturated magnetization with increasing temperature.     

Low temperature and size controlled synthesis of monodispersed γ-Fe<Subscript>2</Subscript>O<Subscript>3 </Subscript>nanoparticles by an epoxide assisted sol–gel route

Monodispersed γ-Fe₂O₃ nanoparticles were prepared by a procedure-simple and precursor-cheap route, epoxide assisted sol–gel method. The γ-Fe₂O₃ nanoparticles were obtained by the reaction of FeCl₂ in ethanol solution with propylene oxide to form the sol, following by the boiling of the solution. As compared with other metal ions of +2 formal charge, the unexpected acidity of FeCl₂ in ethanol solution assure the formation of sol. As an advantage, the unique chemistry of this route results in the low temperature of synthesis, leading to the extremely small particle size of 2.3 nm and non-aggregation state of the particles.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-based pigments synthesized by a new proteic sol–gel method

Alumina-based pigments were synthesized by the proteic sol–gel method. In this method, coconut water is employed as polymeric agent instead of the conventional alkoxide precursors. To this study, three common chromophore metallic ions (Mn³⁺, Co³⁺, and Cr³⁺) were chosen in order to verify the method efficiency. Differential thermal analysis (DTA), thermogravimetry (TG), and XRD techniques were used to characterize the synthesis process. The colorimetric characterization of the produced pigments was done according to the CIE-L*a*b* 1976 norm which is recommended by the CIE (International Commission on Illumination). The synthesized pigments presented intense and uniform colors in accordance to the literature results for each chromophore ion. The produced pigments also presented agglomerated with an average grain size of 180 nm when calcined at 800 °C.     

Structure and magnetic properties of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> ferrites synthesized by sol–gel and microwave calcination

CoFe₂O₄ ferrites were synthesized sol–gel with cobalt chloride, ferric chloride and citric acid as the main raw material. X-ray diffraction, vibrating sample magnetometer and simultaneous thermal analysis were applied to character the structure and magnetic properties of traditional and microwave calcined samples. The samples with pH 5 and molar ratio of citric acid to metal nitrate 1–1.2 showed the optimal structure and magnetic properties. Microwave calcination reduces the synthesis time from 2 h for conventional calcination to 15–30 min. The saturation magnetization (σ _s ) for sample microwave-calcined at 550 °C for 30 min reaches to 75.89 emu/g, much higher than that of conventional-calcined samples.     

High-temperature low-friction behaviors of γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>@SiO<Subscript>2</Subscript> nanocomposite coatings obtained through sol–gel method

In the present paper, the γ-Fe₂O₃@SiO₂ nanocomposite is prepared by sol–gel method and the γ-Fe₂O₃@SiO₂ nanocomposite coatings are deposited on the steel substrate. The microstructure, surface topography, and tribological properties of the γ-Fe₂O₃@SiO₂ nanocomposite were measured and investigated by X-ray diffraction (XRD), fourier transform infrared spectrometry (FTIR), transmission electron microcopy (TEM), and high-temperature tribometer, respectively. The tribotest were performed by high-temperature tribometer in the temperature ranges from 400 to 600?°C to investigate the tribological properties of the nanocomposites under high temperature. The experimental results show that there is the core-shell structure in the γ-Fe₂O₃@SiO₂ nanocomposite. It is also found that the γ-Fe₂O₃@SiO₂ nanocomposite coatings exhibit low friction (0.05) from 500 to 600?°C. XRD measurements show that low-friction behavior of the friction pair under high temperature is involved in the transformation between α-Fe₂O₃ and γ-Fe₂O₃ and the oxidations of the steel substrate during sliding. The core-shell structure of the nanocomposites inhibits γ-Fe₂O₃ of the soft phase changing into α-Fe₂O₃ phase and the thermal energy of the friction heat activates the oxidation of the steel substrate in ambient air, which are beneficial to form low shear interface and achieve high temperature low friction.

Open image in new window

The γ-Fe₂O₃@SiO₂ nanocomposite coatings by sol–gel method with amorphous and multi-core SiO₂ wrapping nano crystalline γ-Fe₂O₃ exhibit low coefficient of friction (CoF) from 500 to 600?°C.

     

A general ultra large scale strategy for low temperature sol–gel synthesis of nearly monodispersed metal ions doped γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

A general sol–gel strategy was established for the synthesis of metal ions doped γ-Fe₂O₃ nanoparticles with narrow particle size distribution. The unique chemistry of the route guarantees the simple preparation procedure for the preparation of doped γ-Fe₂O₃ nanoparticles, which includes the boiling of the ethanolic solution of precursor salts after the addition of gelation agent, and the following drying of the obtained sol solution. On the other hand, it guarantees the production of the nanoparticles with nearly monodispersed state and median size of about 5 nm on an ultra large scale of about 60 g in a single reaction. The doping of metal ions in γ-Fe₂O₃ allows the great promotion of phase transformation temperature from γ-Fe₂O₃ to α-Fe₂O₃. Due to the advantages of this strategy over other routes, it is very promising to be applied in the industrial production of undoped and doped γ-Fe₂O₃ nanoparticles as a general route.     

Bright blue pigment CoAl<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocrystals prepared by modified sol–gel method

Nanocrystalline films of magnetite have been prepared by a novel sol–gel route in which, a solution of iron (III) nitrate dissolved in ethylene glycol was applied on glass substrates by spin coating. Coating solution showed Newtonian behaviour and viscosity was found as 0.0215 Pa.s. Annealing temperature was selected between 291 and 350 °C by DTA analysis in order to obtain magnetite films. In-plane grazing angle XRD and TEM studies showed that magnetite phase was present upon annealing the films at 300 °C. The films had crack free surfaces and their thicknesses varied between ~10 and 200 nm. UV–Vis spectrum results showed that transmittance of the films increases with decreasing annealing temperature and increasing spinning rate. Up to 96% transmittance was observed between the wavelengths of 900–1,100 nm. Vibrating sample magnetometer measurements indicated that magnetite thin films showed ferromagnetic behavior and the saturation magnetization value was found as ~35 emu/cm³.     

Synthesis and characterization of nanostructured Ba<Subscript>5</Subscript>Ta<Subscript>4</Subscript>O<Subscript>15</Subscript> by sol–gel process

Hexagonal Ba₅Ta₄O₁₅ were synthesized by a sol–gel process at temperatures of 700–900 °C. The microstructure properties and morphology are studied by X-ray diffraction and scanning electron microscope. Traces of the Ba₅Ta₄O₁₅ component were detected by energy dispersive X-ray analysis. A higher temperature enhanced higher atom mobility and caused the growth direction to change and created hexagonal square makes obvious good quality of samples. The visible light absorption edges of the Ba₅Ta₄O₁₅ nanorods and were corresponded to band-gap energies of 4.0 eV.     

In vitro degradability and bioactivity of mesoporous CaO-MgO-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-SiO<Subscript>2</Subscript> glasses synthesized by sol–gel method

Two glasses of the CaO-MgO-P₂O₅-SiO₂ system with different MgO contents (0 and 10 mol%, respectively) have been synthesized by sol–gel method. The degradation of glass samples was evaluated through the weight loss in the tris-(hydroxymethyl)-aminomethane and hydrochloric acid (Tris–HCl) buffer solution, and the in vitro bioactivity was assessed by determining the changes in surface morphology and composition after soaking in a simulated body fluid. Formation of the apatite-like layer on glasses surface was studied by means of X-ray diffraction, Fourier-transform infrared, scanning electron microscopy. Results indicate that, with the partial substitution of MgO for CaO in glass composition, the glass degradation decrease and the formation of apatite-like layer is delayed. Furthermore, it is observed that the glass bioactivity is relative to its dissolution, and the effects of MgO on glass degradability and bioactivity may be attributed to the influence of ionic field strength and distinct bonding configuration of glass.     

Evaluation of phosphate removal capacity of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>–ZVINPs from aqueous solution: optimization using response surface analysis

The present research aims to optimize the removal of phosphate (PO₄ ^3?) from aqueous solution by Fe₃O₄ stabilized zero-valent iron nanoparticles (Fe₃O₄–ZVINPs). A three-factor, three-level, Box–Behnken design combined with response surface methodology was applied to design the experiments, to develop a mathematical model, and for evaluating the individual and also the interactive effects of the operating variables like pH, temperature, and PO₄ ^3? concentration on removal efficiency. The analysis of variance has been used to evaluate the adequacy of the developed mathematical model in order to predict the optimal conditions of independent process variables, and to get maximum removal efficiency. Three-dimensional response surface plots were constructed to visualize the simultaneous interactive effects between two process variables. All three factors had a significant impact on removal of PO₄ ^3?. The predicted value of the model (166.0 mg g^?1PO₄ ^3?) was in good agreement with the experimental value (164.92 mg g^?1 PO₄ ^3?) under the optimum conditions of temperature 49.2 °C; pH 3.5; and PO₄ ^3? concentration 79.8 mg L^?1. The removal of PO₄ ^3? in the presence of environmental matrix (other ions) was also investigated at optimum conditions as predicted by the model. The results suggest that the presence of these ions had no significant effect on PO₄ ^3? removal. In addition, the adsorbed PO₄ ^3? can be effectively desorbed at higher pH of the solution. The findings suggest that removal of PO₄ ^3? from aqueous solution using Fe₃O₄–ZVINPs can be an effective method.     

Synthesis of MgNb<Subscript>2</Subscript>O<Subscript>6</Subscript> nanocrystalline powders by an improved citrate sol–gel technique

MgNb₂O₆ nanocrystalline powders have been synthesized at a low temperature by improved citrate sol–gel method in this paper. The high quality solution of Nb⁵⁺ was prepared using Nb₂O₅ as the starting material. The crystal structure and microstructure of MgNb₂O₆ powders were characterized by XRD and SEM techniques, and the effects of preparation craft including pH value and the proportion of citric acid to the niobium ions on the crystal structure and microstructure of powders were also investigated. XRD and TG/DTA results show that the single phase of MgNb₂O₆ for synthesized powders can be obtained by calcining the precursor at 700 °C. SEM results indicate that the average particle size of MgNb₂O₆ exhibits a significantly dependence on the pH values and the proportion of citric acid to the niobium ions, where it was found that particle size of a 20 nm can be obtained for the MgNb₂O₆ powders by sol–gel process.     

Synthesis and characterization of spinel-type CuAl<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocrystalline by modified sol–gel method

Nanocrystalline Copper aluminate (CuAl₂O₄) was prepared by sol–gel technique using aluminum nitrate, copper nitrate, diethylene glycol monoethyl ether and citric acid were used as precursor materials. This method starts from of the precursor complex, and involves formation of homogeneous solid intermediates, reducing atomic diffusion processes during thermal treatment. The formation of pure crystallized CuAl₂O₄ nanocrystals occurred when the precursor was heat-treated at 600 °C in air for 2 h. The stages of the formation of CuAl₂O₄, as well as the characterization of the resulting compounds were done using thermo–gravimetric analysis, X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The products were analyzed by transmission electron microscopy and ultraviolet–visible (UV–Vis) spectroscopy to be round, about 17–26 nm in size and E _g = 2.10 eV.     

Synthesis and characterization of Fe doped mesoporous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> by sol–gel method and its use in trichloroethylene combustion

Two mesoporous alumina samples were synthesized using the sol–gel method, and these samples were tested as catalysts in trichloroethylene combustion reaction. One alumina sample was doped with Fe to study the influence of a small amount of this agent on the characteristics and properties of alumina as a catalyst. Both catalysts (pure alumina and alumina doped with Fe) were thoroughly characterized by different techniques, such as DTA/TGA, FT-IR, XRD, SEM and TEM, and the porous characterization was conducted using a N₂ physisorption technique. The doping agent presented a particular influence on the morphology and textural porosity in the alumina catalyst and therefore, it exhibited different catalytic behavior than the pure alumina catalyst. For both catalysts, the crystalline phase of γ-alumina was reported using XRD technique, and the crystallite size ranged from 7.8 to 12.8 nm. Using TEM images, the alumina catalyst doped with Fe revealed to contain a mixture of three types of iron oxide (maghemite, magnetite and hematite), mainly as roughly spherical nanoparticles. For both alumina catalysts, trichloroethylene catalytic combustion was conducted on a packed bed reactor in air at a temperature range of 50 to 600 °C. The alumina catalyst doped with Fe showed a higher catalytic activity than pure alumina, mainly due to the presence of micropores and grain morphology of flat faces.     

The sol–gel chromium-modified V<Subscript>6</Subscript>O<Subscript>13</Subscript> as a cathodic material for lithium batteries

A new V₆O₁₃-based material has been synthesized via the sol–gel route. This sol–gel mixed oxide has been obtained from an appropriate heat treatment of the chromium-exchanged V₂O₅ xerogel performed under reducing atmosphere. This new compound, with the chemical formula Cr_0.36V₆O_13.50, exhibits a monoclinic structure (C2/m) with the following unit cell parameters, a=11.89 Å, b=3.68 Å, c=10.14 Å, β=101.18°. The electrochemical characterization of this compound has been performed using galvanostatic discharge–charge experiments in the potential range 4–1.5 V and completed by ac impedance spectroscopy measurements. It exhibits a specific capacity of about 370 mAh g^?1, which makes the compound Cr_0.36V₆O_13.50 the best one in the V₆O₁₃-based system: 85% of the initial capacity (315 mAh g^?1) after the 35th cycle is still available at C/25 without any polarization. From impedance spectroscopy, a high kinetics of Li transport (D _Li=1.8×10^?9 cm² s^?1) is found at mid-discharge.     

B<Subscript>2</Subscript>O<Subscript>3</Subscript> additives on sintering and microwave dielectric behaviors of Mg<Subscript>4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics synthesized through the aqueous sol–gel Process

The relationships between the sintering temperatures and the microwave dielectric properties of (1−x)Mg₄Nb₂O₉-xB₂O₃ (x = 0.5–10 wt. %) compounds were investigated by the sol–gel method in order to reduce the sintering temperature in this study. A suitable amount of B₂O₃ doping was effective in allowing low sintering temperatures without a little detrimental effect on these dielectric properties of the Mg₄Nb₂O₉ compounds. The variations in the dielectric constant (ε _r ) and the quality factor (Q·f) of the Mg₄Nb₂O₉ compounds depended on the amount of B₂O₃ doping and the sintering temperature. As a result, a ε _r value of ~12.8 and a Q·f value of ~142,570 GHz were obtained when the Mg₄Nb₂O₉ compound with x = 3% was sintered at 1,200 °C for 4 h. The temperature coefficient of resonant frequency (τ _f ) of the 3%-B₂O₃ doping Mg₄Nb₂O₉ compound slightly changed from −33 to −48 ppm/°C with an increased sintering temperature.     

Atmospheric control of gel-oxide transformation in sol–gel derived Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> fibers

Via sol–gel processing metal–organic fibers were produced and dried up to 140 °C. For these gel fibers the influence of a treatment in different atmospheres was investigated for the temperature range of 200–850 °C. The atmospheres were nitrogen, water vapor, evaporated nitric and hydrochloric acid and evaporated hydrogen peroxide. In the presence of moisture and especially with acidic moisture fibers were transformed almost completely to their oxide composition (82 mol% Al₂O₃·18 mol% Y₂O₃). In these inorganic amorphous structures considerable differences were observed on several structural levels. On the atomic scale, the coordination of Al ions was investigated by ²⁷Al MAS NMR and skeletal density by He-pycnometry. Porosity in the nm scale was characterized by N₂-sorption. As a macroscopic effect of different treatment atmospheres, the longitudinal shrinkage was observed. For fibers treated at 500 °C the relative shrinkage varied by 100% (comparing water vapor and nitrogen atmosphere). No simple correlation between the release of organic constituents, the formation of porosity and the shrinkage could be found. These aspects were controlled by the rigidity of the inorganic network against atomic reconstitution. The kind of atmosphere was found to be an effective parameter to control various aspects of the xerogel structure.     

Highly transparent UV absorption TiO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> films without oxidation catalytic activity prepared by a room temperature sol–gel route

TiO₂-SiO₂-Fe₂O₃ films as new UV absorption material were prepared through an epoxide derived sol–gel route. The films were formed at room temperature by doping of a little amount of γ-Fe₂O₃ nanoparticles in TiO₂-SiO₂. The obtained films show advantages such as high stability, efficient absorption in the UV region, high transparency in the visible range, and low oxidation catalytic activity to organic materials. It was found that 2.3 nm γ-Fe₂O₃ nanoparticles doped films exhibit stronger UV absorption than the films doped with 5.1 nm particles because of the increased grain strain of the nanoparticles with smaller size. These advantages of the films guarantee the broad application of this inorganic UV absorption film in the protection of heat sensitive organic materials such as artworks.