The effect of the concentration of citric acid and pH values on the preparation of MgAl2O4 ultrafine powder by citrate sol-gel process

Ultrafine MgAl₂O₄ was synthesized by citrate sol-gel process. A model was presented to evaluate the concentration of species in a citric solution for preparing MgAl₂O₄ ultrafine powder. The evaluated concentration of species can provide valuable information and help in selecting the optimal condition for preparation of MgAl₂O₄ powder by citrate sol-gel process. The influence of molar ratio of cations, citric acid and pH on the formation of MgAl₂O₄ was studied. The spinel precursor gel and the ultrafine MgAl₂O₄ spinel were characterized by X-ray diffraction (XRD), differential thermal analysis, thermogravimetric (TG-DTA) and scanning electron microscope (SEM). The results show that the MgAl₂O₄ spinel phase begins to form at 600 °C, and most of MgAl₂O₄ crystals are spherical with a crystal size about 30-50 nm.     

Synthesis and characterization of nanocrystalline MgAl2O4 spinel via sucrose process

Nanocrystalline MgAl₂O₄ spinel powder was synthesized using metal nitrates and a polymer matrix precursor composed of sucrose and polyvinyl alcohol (PVA). The precursor and the calcined powders were characterized by simultaneous thermal analysis (STA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). According to XRD results, the inceptive formation temperature of spinel via this technique was between 600 and 700 °C. The calcined powder at 800 °C for 2 h has faced shaped morphology and its crystallite size is in the range of 8-12 nm. Further studies also showed that the amount of polymeric matrix to metal ions has significant influence on the crystallite size of synthesized magnesium aluminate spinel powder.     

Synthesis of nanocrystalline yttria doped ceria powder by urea-formaldehyde polymer gel auto-combustion process

Nanocrystalline yttria doped ceria powder has been prepared by auto-combustion of a transparent gel formed by heating an aqueous acidic solution containing methylol urea, urea, cerium(III) nitrate and yttrium(III) nitrate. The TGA and DSC studies showed the combustion reaction of the gel initiated at 225 °C and completed within a short period of time. XRD spectrum of the combustion product reveals the formation of phase pure cubic yttria doped ceria during the combustion process. Loose agglomerate of yttria doped ceria particle obtained by the combustion reaction could be easily deagglomerated by planetary ball milling and the powder obtained contains particles in the size range of 0.05-3.3 μm with D₅₀ value of 0.13 μm. The powder particles are aggregate of nanocrystallites with a wide size range of 14-105 nm. Pellets prepared by pressing the yttria doped ceria powder sintered to 95.2% TD at 1400 °C.     

Synthesis of nanocrystalline MgAl2O4 spinel powders by a novel chemical method

A novel chemical method for the preparation of nanocrystalline MgAl₂O₄ spinel powders has been developed in this paper. The mixed magnesium-aluminum hydroxide precipitates were initially formed in a three-dimensional space network microarea. After being calcined at above 700 °C, the nanocrystalline MgAl₂O₄ spinel powders were obtained. The precursor and as-calcined powders were characterized using TGA-DTA, XRD and TEM. The MgAl₂O₄ spinel powders calcined at 850 °C for 2 h are of narrow distribution, little agglomeration and small particle size of ∼ 24 nm. The reason for the synthesis of high-quality powders was explained.     

The novel low temperature synthesis of nanocrystalline MgAl2O4 spinel using “gel” precursors

Nanocrystalline MgA1₂O₄ was synthesized by pyrolysis of the homogeneous spinel precursor, Mg(C₄H₅O₂)₂·(H₂O):Al₂(OH)₃(C₃H₃O₂)₃·(H₂O)₂:NH₄(C₃H₃O₂)·(H₂O). The spinel precursor gel is composed of a mixture of magnesium and aluminum acrylate salts dissolved in an ammonium acrylate gel. The reaction of acrylic acid with magnesium hydroxide in water produced magnesium methacrylate, and a similar reaction of basic aluminum acetate produced the aluminum salt of acrylic acid. The reaction of acrylic acid with ammonium hydroxide produced the ammonium acrylate gel. Ammonium acrylate gel was found to absorb many times its own weight of water. Although similar properties have been identified in PMMA and in the polymer of sodium acrylate, only the ammonium acrylate gel exists as an unpolymerized monomer. The spinel precursor gel is a pre-ceramic material that yields an amorphous oxide phase at 425°C that begins to crystallize to the MgAl₂O₄ spinel at 600°C and is fully crysta1line at 1030°C with a uniform particle size of 7-100 nm. The spinel precursor gel and the nanocrystalline MgA1₂O₄ spinel were characterized by XRD and TEM.     

The effect of Tb doping on the structure and spectroscopic properties of MgAl2O4 nanopowders

In this paper, a modified sol-gel method was employed to prepare nanostructured MgAl₂O₄ spinel powders doped with Tb³⁺ ions and thermally treated at 700 and 1000 °C for 3 h. The structural properties of the prepared at 700 and 1000 °C powders where characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). According to obtained XRD patterns the formation of single-phase spinels after calcination was confirmed. The XRD analyses demonstrated that the powders were single-phase spinel nanopowders with high crystallite dispersion. The Rietveld method was applied to calculate lattice parameters. The averaged spinel particle size was determined to be ∼10 nm for calcination at 700 °C and ∼20 nm at 1000 °C. The emission and excitation spectra measured at room and low temperature (77 K) for the samples calcined at 700 and 1000 °C demonstrated characteristic spectra of Tb³⁺ ions. The effect of MgAl₂O₄:Tb³⁺ grain sizes on luminescence properties was noticed.     

The effect of Cu content on the structure of Ni1−xCuxFe2O4 spinels

A series of Ni_1−xCu_xFe₂O₄ (0 ≤ x ≤ 0.5) spinels were synthesized employing sol-gel combustion method at 400 °C. The decomposition process was monitored by thermal analysis, and the synthesized nanocrystallites were characterized by X-ray diffraction, transmission electron microscopy, infra-red and X-ray photoelectron spectroscopy. The decomposition process and ferritization occur simultaneously over the temperature range from 280 °C to 350 °C. TEM indicates the increase of lattice parameter and particle size with the increase of copper content in accordance with the XRD analysis. Cu²⁺ can enter the cubic spinel phase and occupy preferentially the B-sites within x = 0.3, and redundant copper forms CuO phase separately. A broadening of the O 1s region increases with the increment of copper content compared to pure NiFe₂O₄, showing different surface oxygen species from the spinel and CuO. Cu²⁺ substitution favors the occupancy of A-sites by Fe³⁺.     

Mixture of fuels approach for the solution combustion synthesis of Al2O3-ZrO2 nanocomposite

A modified solution combustion approach was used for the first time in the preparation of nanosize zirconia toughened alumina (ZTA) composite. ZTA-1 with an average particle size of ∼37 nm was prepared using corresponding metal nitrates and urea. ZTA-2 with an average particle size of <10 nm was prepared by using mixture of fuels such as ammonium acetate, urea and glycine. The products formed were characterised by powder X-ray diffractometry, Transmission electron microscopy and BET surface area analysis. By using mixture of fuels, the energetics of the combustion reaction and eventually the properties of the combustion product have been changed. A series of combustion reactions were carried out to optimise the fuel ratio combinations required to obtain <10 nm ZTA particles. The microstructure of ZTA consisted of crystallites of Al₂O₃ and ZrO₂ both of which were nanocrystalline as evident from TEM.     

Synthesis and characterization of nanocrystalline La2Mo2O9 fast oxide-ion conductor by an in-situ polymerization method

A nanocrystalline La₂Mo₂O₉ powder was synthesized via the pyrolysis of polyacrylate salt precursor prepared by an in situ polymerization of the metal salts and acrylic acid. The pyrolysis behavior of the polymeric precursor was studied by thermal (TG/DTA) analysis. The obtained product was characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM) analysis. The results revealed that the average particle size is ∼25 nm for La₂Mo₂O₉ with good crystallinity. The synthesized nanocrystalline La₂Mo₂O₉ powder showed good sinterability and reached ∼99% of theoretical density when sintered at 800 °C for 4 h. The La₂Mo₂O₉ sample sintered at 800 °C, yield good microstructure with improved conductivity value of about 0.12 S/cm at 800 °C.     

Polymer-assisted synthesis and luminescence properties of MgAl2O4:Tb nanopowder

In the present work, terbium doped magnesium alluminate (MgAl₂O₄:Tb) nanopowder was synthesized by a polyacrylamide gel method. Structure, morphology and luminescence spectra were investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), and photoluminescence spectroscopy (PL) measurements. The results showed that the single-phase MgAl₂O₄ could be formed at a relatively low temperature about 800 °C without unreacted Al₂O₃ and MgO phases. Powders with nanosized microstructures were formed. The polyacrylamide gel method resulted in a powder with smaller particle size and fewer agglomerates than the conventional sol-gel method. Luminescence analysis indicated that, the prepared MgAl₂O₄:Tb powders had strong green emission with ⁵D₄-⁷F₅ as the most prominent group. The emission intensity increased with increasing the calcination temperature.     

Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

The CaFe₂O₄ spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 °C which was lower than that of ferrite prepared by other methods. CaFe₂O₄ catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H₂O₂ (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H₂O₂ molar ratio and solvents on the conversion and product distribution were studied.     

Alanine-assisted low-temperature combustion synthesis of nanocrystalline LiMn2O4 for lithium-ion batteries

Nanocrystalline LiMn₂O₄ powders have been synthesized by combustion process in a single step using a novel fuel, l-alanine. Thermogravimetric analysis and differential thermal analysis of the gel indicate a sharp combustion at a temperature as low as 149 °C. Quantitative phase analysis of X-ray diffraction data shows about 97% of phase purity in the as-synthesized powder, which on further calcination at 700 °C becomes single phase LiMn₂O₄. High Brunauer, Emmett, and Teller surface area values obtained for ash (53 m²/g) and calcined powder (23 m²/g) indicate the ultrafine nature of the powder. Average crystallite size is found to be ∼60-70 nm from X-ray diffraction analysis and transmission electron microscopy. Fourier transformed infra-red spectrum shows two strong bands at 615 and 511 cm⁻¹ originating from asymmetrical stretching of MnO₆ octahedra. A nominal composition of Li_0.88 Mn₂O₄ is calculated from the inductive coupled plasma analysis. From UV-vis spectroscopy, an optical band gap of 1.43 eV is estimated which is assigned to a transition between t_2g and e_g bands of Mn 3d. Electrochemical charge-discharge profiles show typical LiMn₂O₄ behavior with a specific capacity of 76 mAh/g.     

Solid state and solution synthesis of Ba(Mg1/3Ta2/3)O3: A comparative study

Ba(Mg_1/3Ta_2/3)O₃ [BMT] dielectric ceramics are prepared by solid state (one step, two step and molten salt synthesis) and wet chemical methods (precipitation, citrate gel and sol-gel). The formation mechanism of BMT in each synthesis technique is discussed. The formation temperature and particle size of the formed BMT were found to be much lesser (in nanometer range) for solution synthesized powders. It is found that synthesis by sol-gel method resulted in the formation of ultra pure nanopowders of BMT at about 600 °C with average crystallite size of about 18 nm where as in solid state synthesis the formation of BMT was formed at about 1100 °C with average crystallite size of 220 nm. On sintering these powders, densification and grain growth of the chemically derived powders were found to be lower than that of solid state synthesized BMT powder. This has resulted in a slight decrease in density and microwave dielectric properties of the solution synthesized BMT samples. It is found that the microwave dielectric properties improved with increase in the average grain diameter of the sintered BMT ceramics.     

(ZnO)3In2O3 fine powder prepared by combustion reaction of nitrates-glycine mixture

Conducting fine powder was obtained in the ZnInO system by combustion of the gel prepared from an aqueous solution of mixed zinc and indium nitrates in the presence of glycine. Glycine worked as a fuel as well as a gelling agent in the combustion under the strong oxidizing power of the nitrates. In spite of the low furnace temperature of 350 °C, the product was (ZnO)₃In₂O₃ which has been obtained above 1260 °C in a solid state reaction of a mixture of ZnO and In₂O₃. The combustion synthesis led to an aggregated fine powder of hexagonal platelets of about 40 nm in diameter. Its compacted mass showed an electrical resistivity of about 700 Ω cm. The agglomeration was improved by dispersing the fine powder in an acetic acid aqueous solution.     

Hydrothermal synthesis and magnetic properties of Co0.2Cu0.03Fe2.77O4 nanoparticles

Co_0.2Cu_0.03Fe_2.77O₄ nanoparticles with different morphologies have been synthesized directly via a simple hydrothermal method. The effects of pH value, precursor concentration, reaction temperature and surfactant on the particle size were discussed. X-ray diffraction analyses showed that the as-synthesized Co_0.2Cu_0.03Fe_2.77O₄ nanoparticles possessed typical spinel structure. Scanning electron microscope images showed different morphologies of the particles, including truncated octahedron and octahedron. It was indicated that well-dispersed Co_0.2Cu_0.03Fe_2.77O₄ nanoparticles can be synthesized at pH values ranging from 11 to 13, and reaction temperature of 160 °C. The particle size decreased from 18 to 10 nm after the addition of sodium dodecyl sulphate at the pH value of 9. The magnetic measurement showed that the as-prepared Co-Cu spinel ferrite nanoparticles possessed hard magnetic property.     

The effect of solution chemistry on the preparation of MgAl2O4 by hydrothermal-assisted sol-gel processing

Preparation of magnesium aluminate spinel powder by hydrothermal-assisted sol-gel processing from MgAl₂(OCH₂CH₂OR)₈, RCH₃ (1), CH₂CH₂OCH₃ (2), MgAl₂[OCH(CH₃)₂]₈ (3) and MgAl₂(O-^sBu)₈ (4) in toluene and parent alcohol has been investigated. Coordination status of aluminum atom in precursors was determined by ²⁷Al NMR and correlation between coordination number of aluminum and development of spinel phase in hydrothermal-assisted sol-gel processing has been studied. The gels obtained from hydrothermal-assisted hydrolysis of magnesium-aluminum alkoxides that contain six-coordinated aluminum atoms in solution (1 and 2) after calcination at 700 °C resulted in the formation of pure spinel phase, whereas in similar hydrolysis and calcination processes of precursors that contain four-coordinated aluminum (3 and 4) spinel phase forms along with some Al₂O₃ and MgO. Selected powders obtained from hydrothermal-assisted sol-gel processing were characterized by thermal analysis (TGA/DSC), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Results indicate that the coordination status of aluminum in the precursor is very crucial for the formation of pure phase spinel. The morphology of prepared spinels was studied by SEM and the results showed that the solvent in hydrothermal-assisted sol-gel processing has a marked effect on the morphology of the resulting MgAl₂O₄. In hydrothermal-assisted sol-gel processing of aluminum-magnesium alkoxides in hydrophobic solvent, spherical particles are formed, while in the parent alcohol, non-spherical powders are formed.     

Synthesis of nanocrystalline Mn3O4 at 100 °C

A simple gel to crystal conversion route has been followed for the preparation of nanocrystalline tetragonal Mn₃O₄ powders at 80-100 °C under refluxing conditions. Freshly prepared manganese hydroxide gel is allowed to crystallize under refluxing and stirring conditions for 4-6 h. Formation of nano crystallites of Mn₃O₄ is confirmed by X-ray diffraction (XRD) study. Transmission electron microscope (TEM) investigations revealed that the average particle size is 50 nm for these powders.     

Synthesis of submicron-sized spherical Y2O3 powder for transparent YAG ceramics

Spherical monodispersed, submicron-sized Y₂O₃ powder was prepared via a homogeneous precipitation method using nitrate and urea as raw materials. The structure, phase evolution and morphology of Y₂O₃ precursor and the calcined powder were studied by FTIR, TG/DTA, XRD and SEM methods. The sphere size of the precursor was about 250 nm and that of Y₂O₃ powder calcined at 800 °C for 2 h was about 200-210 nm. With the spherical Y₂O₃ powder and a commercial Al₂O₃ ultrafine powder, high transparent YAG ceramics was fabricated by vacuum sintering at 1780 °C for 6 h through a solid-state reaction method. The in-line transmittances of the as-fabricated YAG ceramics at the wavelength of 1064 nm and 400 nm were 82.8% and 79.5%, respectively, which were much higher than that of the YAG ceramics with a commercial Y₂O₃ powder and a commercial Al₂O₃ ultrafine powder directly. The superior properties are attributed to the good morphology, dispersibility and uniform grain size of the as-prepared spherical Y₂O₃ powder, which matches that of the commercial Al₂O₃ powder.     

Grain growth and microstructural evolution of yttrium aluminum garnet nanocrystallites during calcination process

An yttrium aluminum garnet (YAG) precursor precipitate was synthesized by urea method using yttria (Y₂O₃) and aluminum nitrate (Al(NO₃)₃·9H₂O) as raw materials. The fresh wet precipitate was dried by supercritical carbon dioxide (CO₂) fluid and the resulting powder was calcined at temperatures from 600 to 1600 °C. Crystallization of YAG was detected at 800 °C, and completed at 900 °C. HRTEM images of the YAG product obtained above 900 °C revealed crystallographically specific oriented attachment along the [1 1 2] direction. Based on the observation of the particle morphology a possible growth mechanism of YAG nanoparticles was presented. The fast increase on the average crystallite size of YAG at temperatures from 900 to 1300 °C is attributed to the crystallographically specific oriented attachment growth process. As the growth process proceeds at higher temperatures, oriented attachment based growth becomes less important because of the increase on particle size, and the self-integration assisted by the Ostwald ripening becomes dominant.     

Low temperature combustion synthesis of CoxMg1−xAl2O4 nano pigments using oxalyldihydrazide as a fuel

Oxalyldihydrazide as a fuel was used to prepare new nano size blue refractory ceramic pigments MgAl₂O₄: xCo²⁺ (0.00 ≤ x ≤ 0.10) using low temperature combustion synthesis (LCS) method. The synthesized and calcined powders were characterized by Fourier transform infra red (FTIR) spectrometry, electronic spectra, thermogravimetry, differential thermogravimetry, differential thermal analysis, X-ray diffraction (XRD) analysis, and transmission electron microscopy (TEM). Also, the color measurements of nano pigments are studied by diffuse reflectance spectroscopy (DRS) using CIE-L*a*b* parameter method. The FTIR spectra show frequency bands in range the 422–700 cm⁻¹ correspond to metal oxygen bonds through vibrations for the spinel structure compound. The average particle size of prepared samples as determined from XRD and TEM was 30 nm at 1100 °C. Also, the results revealed the varying bulk density, particle size, shape and color with different calcination times and temperatures.