Effect of fuel characteristics on synthesis of calcium hydroxyapatite by solution combustion route

The effect of fuel characteristics on the processing of nano sized calcium hydroxyapatite (HA) fine powders by the solution combustion technique is reported. Urea, glycine and glucose were used as fuels in this study. By using different combinations of urea and glycine fuels and occasional addition of small amounts of highly water-soluble glucose, the flame temperature (T _f) of the process as well as product characteristics could be controlled easily. The powders obtained by this modified solution combustion technique were characterized by XRD, FTIR spectroscopy, SEM, FESEM-EDX, particle size analyser (PSD) and specific surface area (SSA) measurements. The particle size of phase pure HA powder was found to be <20 nm in this investigation. The effects of glucose addition with stoichiometric (μ = 1) and fuel excess (μ > 1) urea and glycine precursor batches were investigated separately.     

Synthesis of alumina powders by the glycine-nitrate combustion process

The combustion synthesis technique using glycine as fuel and aluminum nitrate as an oxidizer is able to produce alumina powders. Thermodynamic modeling of the combustion reaction shows that as the fuel-to-oxidant ratio increases, the amount of gases produced and adiabatic flame temperatures also increases. X-ray diffractions showed the amorphous structure for as-synthesized powder and presence of well-crystallized α-Al₂O₃ after calcination at 1100 °C during soaking time of 1 h. Alumina's largest measured specific surface area was 15 m²/g with BET method and 0.51 glycine-to-nitrate ratio.     

Combustion synthesis of Sr0.5Ba0.5Nb2O6 and effect of fuel on its microstructure and dielectric properties

Nano-sized Sr_0.5Ba_0.5Nb₂O₆ (SBN50) powder has been synthesized, at very short reaction time, for the first time by a novel combustion method. Ba(NO₃)₂ and Sr(NO₃)₂ were used as source of Sr and Ba, respectively, while Nb-oxalate was used as the source of niobium. Urea, hexamethyltetramine (HMT) and glycine were used as fuel. The crystallite sizes in the powder ranged between 14-125 nm. X-ray diffraction analysis showed complete SBN50 phase formation at 700 °C, when urea/HMT was used as fuel, and at 800 °C when glycine was used as fuel. Ferroelectric-paraelectric phase transition temperature (T_c) close to 40 °C was observed when urea and HMT were used and the T_c was −49 °C when glycine was used. When urea was used as fuel highest dielectric constant was observed for the pellets sintered at 1250 °C for 4 h. Low dielectric loss was observed when HMT was used as fuel. Larger grain sizes in the sintered pellets were observed when glycine was used as fuel.     

Nanostructured cobalt oxides (Co3O4 and CoO) and metallic Co powders synthesized by the solution combustion method

The combustion synthesis technique using glycine and urea as fuels and cobalt nitrate as an oxidizer is capable of producing well-crystallized Co₃O₄, CoO, as well as metallic Co powders. An interpretation based on the thermodynamic viewpoint and the measurement of the combustion temperatures during the reactions occurring for various fuel-to-oxidant ratios was proposed for a study of the nature of combustion and its correlation with the characteristics of as-synthesized powders. The largest measured specific surface area of the powders was 36 m²/g at a 0.14 glycine-to-nitrate ratio. The crystallites were nano-sized ranging from approximately 23 to 90 nm.     

Structural, morphological and optical investigations on BaMgAl10O17:Eu elaborated by a microwave induced solution combustion synthesis

Blue-emitting Eu²⁺-doped barium magnesium aluminate (BaMgAl₁₀O₁₇:Eu²⁺) for advanced displays and lighting devices was prepared by a microwave induced solution combustion synthesis using urea as combustion fuel and nitrates as oxidizer. Purity control of as-synthesized blue phosphor particles was undertaken by modifying the fuel to oxidizer molar ratio. X-ray diffraction, scanning electron microscopy and photoluminescence were used to investigate powders crystallinity, particles size, morphology and luminescent properties, respectively. Fuel-rich urea reactions preferentially lead to pure phases compared to the powders synthesized with a stoichiometric fuel to oxidizer ratio. In both cases, we produce a nearly pure well-crystallized and nanostructured BaMgAl₁₀O₁₇:Eu²⁺. Photoluminescence measurements exhibit the characteristic blue emission of Eu²⁺ under UV light excitation however a weak red emission associated to Eu³⁺ is also detected.     

Chemical synthesis of Al18B4O33 whiskers via a combustion method

The Al₁₈B₄O₃₃ whiskers were successfully synthesized by a combustion method with urea as fuel. The synthesis parameter φ ([urea]:[precursors] = φ) was studied to optimize the synthesis conditions for preparing high-quality Al₁₈B₄O₃₃ whiskers. In our present work, it was found that a urea-precursors ratio close to 2, calcination temperature of 1050 °C and reaction time around 3 h lead to high-quality Al₁₈B₄O₃₃ whiskers.     

Fabrication of transparent La2Hf2O7 ceramics from combustion synthesized powders

Transparent La₂Hf₂O₇ (LHO) ceramics were, for the first time, successfully fabricated from combustion-synthesized powders. Nanosized La₂Hf₂O₇ powders were obtained through combustion reaction, using glycine or EDTA as a fuel. The as-made powders were isostatically pressed at 180 MPa and then sintered at 1850 °C for 6 h in hydrogen atmosphere. The resulting ceramics have high optical transmittance.     

Combustion synthesis of La0.7Sr0.3Co0.5Fe0.5O3 (LSCF) porous materials for application as cathode in IT-SOFC

La_0.7Sr_0.3Co_0.5Fe_0.5O₃ (LSCF) porous materials have attracted a substantial interest for application as cathode in solid oxide fuel cells of intermediate temperature (IT-SOFC). This work investigates the effect of different propellants (urea, glycine, citric acid and sucrose) in the preparation of LSCF powders by the combustion method and also the influence of the sintering temperature on the porosity and electrical conductivity. TGA profiles of the as-prepared samples showed a lower weight loss for the sample prepared with glycine, associated with the higher combustion temperature. XRD patterns presented characteristic reflections of LSFC perovskite and a small formation of secondary phases, with nanometric crystallite sizes (9-20 nm). SEM analysis revealed the loose and porous structure of the powder materials. Densification studies were carried within 950-1100 °C, showing that porosity decreased with increasing sintering temperature. Electrical conductivity was measured in the temperature range 300-800 °C and correlated with the sintering temperature.     

Effect of fuel type on microstructure and electrical property of combustion synthesized nanocrystalline scandia stabilized zirconia

Nanocrystalline 10 mol% scandia stabilized zirconia (10ScSZ) powders were prepared by combustion synthesis using three different types of fuels (urea, glycine and citric acid). The influence of nature of fuel on phase formation, particle size and morphological characteristics was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effect of fuel type on electrical conductivity was also evaluated. The 10ScSZ prepared by urea and glycine was fully crystalline whereas citric acid resulted in amorphous form. The powder turned crystalline on calcination at 800 °C. Urea resulted in highly agglomerated powder whereas porous and loose agglomerates were formed with glycine and citric acid as fuels. The powder processed with urea showed higher crystallite size compared to powders processed with glycine and citric acid. The ScSZ electrolyte pellet processed with glycine and citric acid exhibited better conductivity and lower activation energy compared to the electrolyte processed with urea.     

One-step synthesis of diopside (CaMgSi2O6) ceramic powder by solution combustion method

We report the synthesis of diopside (CaMgSi₂O₆) ceramic powder, a multifunctional material, through an energy efficient, quick and one-step solution combustion (SC) method. Synthesis of diopside by SC method requires oxidizers, especially metal-nitrates, and a suitable fuel. However, unavailability of the silicon-nitrate makes the process of diopside formation by SC method challenging, which forces researchers to synthesize diopside by alternate high temperature solid state reaction route. Here, we demonstrate a simple way to overcome this difficulty by using an extra amount of ammonium nitrate (AN, as the suitable oxidizer), but still using the fumed-silica (an economical ceramic powder) and the solution of Ca-nitrate, Mg-nitrate and the fuel. A systematic investigation was carried out using different extra amounts (0, 5 or 10 mol) of AN, in combination with stoichiometric amounts of one of the three chosen fuels, viz., urea, glycine and alanine. For a specific combination of the fuel and extra oxidizer, namely ‘alanine and 10 mol of AN’, we observed the formation of nano-crystalline diopside phase, which generates enough heat for the incorporation of Si atoms from the SiO₂ precursor into diopside phase directly during the combustion process in one-step. This one-step process does not require any extra high temperature calcination step, thereby saving time, cost and complex equipments, whereas all other powders synthesized using other fuels require an extra calcination step, although the calcination temperature is low (≤ 900 °C), for crystalline diopside phase formation. Hence, our work demonstrates the one-step synthesis of diopside nanopowders by SC method through the direct use of the earth abundant SiO₂ ceramics.     

NiAl2O4 catalysts prepared by combustion reaction using glycine as fuel

The aim of this work is to evaluate the influence of glycine fuel used in a stoichiometric proportion and with a 10% and 20% excess of this fuel in the preparation of NiAl₂O₄ catalyst by combustion reaction. The powders were characterized by XRD, textural analysis by the BET nitrogen adsorption method, particle size distribution, and FTIR. The results show the presence of NiAl₂O₄ as a major phase and traces of NiO and Ni in all the catalysts studied here. The crystallite sizes were 22 nm in the stoichiometric composition and 18 and 9 nm, respectively, in the composition containing 10% and 20% excess glycine. The powder obtained from all the compositions presented morphological characteristics with irregular plate-shaped agglomerates. The increase in excess glycine caused the particle size in the three compositions to decrease to 59, 54 and 38 nm and the agglomerate size to increase to 7, 8 and 12 μm, respectively.     

Synthesis by the solution combustion process and magnetic properties of iron oxide (Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> and α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>) particles

This article describes the solution combustion synthesis technique as applicable to iron oxide powder production using urea as fuel and ferric nitrate as an oxidizer. It focuses on the thermodynamic modeling of the combustion reaction under different fuel-to-oxidant ratios. X-ray diffraction showed magnetite (Fe₃O₄) and hematite (α-Fe₂O₃) phase formations for the as-synthesized powders. The smallest crystallite size was obtained by stoichiometric chemical reaction. The magnetic properties of the samples are also carefully discussed as superparamagnetic behavior.     

Preparation of hydroxyapatite by the hydrolysis of brushite

The conversion of brushite (CaHPO₂ · 2H₂O; DCPD) into hydroxyapatite (HAp) by hydrolysis has been studied by separating the conversion process into two stages, i.e. the structural change of DCPD into HAp (1) and the subsequent compositional increase in Ca/P ratio of the HAp (II). In Reaction I at 40°C, HAp formed most rapidly at around pH 7.5 to 8.0. The complete conversion was observed within 2.5 h at 40°C, 1 h at 60°C and only 5 min at 80°C. The compositions of HAp thus formed were nonstoichiometric and had a Ca/P ratio below 1.60. It was difficult to increase the Ca/P ratio up to the stoichiometric value 1.67, because the adjustment of pH to higher values and/or the addition of Ca²⁺ ions to accelerate the increase in Ca/P ratio, retarded the proceeding of Reaction I. On the other hand, in Reaction II, such pH adjustment and Ca²⁺ addition were remarkably effective in increasing the Ca/P ratio. Consequently, two-stage processing was reasonable and convenient for the preparation of stoichiometric HAp, because it was possible to manage the controlling factors in both Reactions I and II independently. The resulting HAp powders showed a comparatively low crystallinity similar to precipitated HAp and large weight losses (above 6%) on heating, and were composed of dense aggregates of irregular thin microcrystals.     

Microstructure and electrical conductivity of LaNi0.6Fe0.4O3 prepared by combustion synthesis routes

The continuing development of new materials suitable for solid oxide fuel cells operating at about 650-800 °C is of great interest in recent days. The present investigation deals with the development of a perovskite composition-LaNi_0.6Fe_0.4O₃ (LNF)-prepared following two combustion synthesis routes: citrate-gel (LNC) and urea (LNU). The powders were sintered over a wide temperature range (900-1400 °C) and sintering behavior for LNC and LNU was compared. The thermal expansion coefficient (TEC), electrical and microstructural characteristics of LNF was thoroughly investigated. Electrical conductivities were found to be one and a half times higher than that of most commonly used cathode material, La(Sr)MnO₃. Moreover, the TEC value of LNF was found to be ≈11.4×10⁻⁶ K⁻¹ at 800 °C. The study opens up a possibility of using LNF as a promising cell component for SOFC.     

Magnetic properties of nano-clusters lanthanum chromite powders doped with samarium and strontium ions synthesized via a novel combustion method

A novel approach to synthesize a single-phase orthorhombic perovskite lanthanum chromite LaCrO₃ clusters doped with Sm³⁺ and Sr²⁺ ions via gel combustion route was reported. The producing materials were synthesized using metal nitrates as oxidizers and triethanol amine (TEA), N-butyl amine (NBA) or ethylene diamine (EDA) as a fuel. The effect of the annealing temperature, type of organic fuel and the variation of the samarium and/or strontium substitution and its impact on crystal structure, crystallite size, microstructure and magnetic properties of the LaCrO₃ powders formed was systematically studied. The results revealed that a well crystalline single phase of pure LaCrO₃ can be achieved at annealing temperature from 800 to 1000 °C for 2 h. Moreover, each organic carrier materials exhibited a different degree of effectiveness in the synthesis of the mixed oxide powders. The crystal structure was influenced by doped Sm³⁺ and/or Sr²⁺ ions. The crystallite size of the produced powders was increased with the increase the annealing temperature, increasing the Sm³⁺ ion and the decrease of Sr²⁺ ion substitution. The microstructures of the produced powders were found to be nanoclusters octahedra-like shaped. The saturation magnetization of the LaCrO₃ powders increased continuously with an increase in the Sm³⁺ ion concentration and it decreased with an increase in the Sr²⁺ ion up to 0.3 at annealing temperature of 1000 °C for 2 h. The maximum saturation magnetization (0.279 emu/g) was achieved at the Sm³⁺ ion molar ratio 0.3 and annealing temperature 1000 °C. Moreover, wide coercivities can be obtained at different synthesis conditions (49.25 to 522  Oe).     

Nanocrystalline pirochromite spinel through solution combustion synthesis

The production of magnesium–chromium oxides by solution combustion synthesis was investigated using glycine and urea for the first time. Ammonium dichromate, urea/glycine and ammonium nitrate aqueous solutions were used as the precursors of the oxides. The effect of different reaction parameters, such as fuel richness, stoichiometry and fuel leanness was evaluated; such parameters were modified by changing the reagents and the fuel/oxidant ratio. The results suggest that glycine is an interesting complexing/combustible agent for ammonium dichromate to produce chromite spinel. Addition of extra ammonium nitrate to stoichiometric compositions improved the specific surface area and reduced the crystallite size. The highest specific surface area (153.40 m²/g) was obtained for the stoichiometric fuel/oxidant mixtures containing glycine as combustible in combination with ammonium nitrate; however, the smallest crystallite size (approximately 9 nm) of Pirochromite (MgCr₂O₄) was synthesized using urea as combustible.     

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.     

Solution combustion synthesis of CeO2-CeAlO3 nano-composites by mixture-of-fuels approach

Nano-composites of CeO₂-CeAlO₃ are synthesised by solution combustion method employing (a) urea and (b) a mixture of urea and glycine as fuels with corresponding metal nitrates. The as-prepared powders are all nano-sized (5-30 nm) and the same is confirmed by broadening of the X-ray diffraction peaks and transmission electron microscopy. A starting composition of Ce:Al in the atomic ratio 4:6 gives rise to different phases depending on the fuel being used for combustion. When urea alone is used as fuel, nano-crystalline CeO₂ phase is formed with Al₂O₃ being in the amorphous state. When the mixture of fuels is used, a mixture of nano-sized CeO₂ and CeAlO₃ phases is obtained. However, upon sintering at 1400 ° C in air, the stable phases CeO₂ and -Al₂O₃ are formed in both the cases. Combustion synthesis using mixture-of-fuels is proposed to be a route to stabilise low oxidation compounds such as CeAlO₃.     

Combustion Synthesis: Effect of Urea on the Reaction and Characteristics of Ni-Zn Ferrite Powders

The purpose of this study was to evaluate the effect of the urea content (fuel) on the reaction and the characteristics of Ni-Zn ferrite powders obtained by combustion synthesis. Several batches were prepared with different fuel contents, ranging from the stoichiometric composition between 20 and 100% (excess), while the desired molar proportion of the metal precursors was kept constant. The solutions were heated on a hot plate and then transferred to a muffle furnace preheated to 700°C, in which ignition took place. The resulting powders were characterized by XRD, BET, SEM, and sedimentation, aided by rotation measured through an optic light. The crystalline hematite (-Fe₂O₃) and Ni-Zn ferrite phases were present in all the compositions studied, and the appearance of the agglomerates varied from soft to hard with increasing urea content. The increased urea content, which promoted a longer flame time, influenced the growth and/or formation of hard agglomerates. After sintering at 1200°C/2 h using the stoichiometric composition, only the spinel structure Ni-Zn ferrite, with homogeneous microstructure, was present.     

Synthesis and crystallographic study of Pb-Sr hydroxyapatite solid solutions by high temperature mixing method under hydrothermal conditions

The solid solutions in the system of Pb and Sr hydroxyapatite, Sr_10−xPb_xHAp (x = 0-10), were successfully synthesized by high-temperature mixing method (HTMM) at 160 °C for 12 h under hydrothermal conditions. The samples were characterized by X-ray diffraction, chemical analysis and electron microscopic observation, and the site of the metal ions in the solid solutions was analyzed with the Rietveld method. The lattice constants, both a and c, of the solid solutions varied linearly with Pb content. It was found that Pb ions in the solid solutions preferentially occupied the M(2) site in the apatite structure. HTMM gives Sr-Pb HAp solid solutions much better crystallization. However, due to the formation of intermediate compound of Pb₃O₂(OH)₂ in the Pb(NO₃)₂·4H₂O solution before mixing with (NH₄)₂HPO₄ solution at 160 °C, HTMM causes the decrease of crystallization of the samples with high Pb content.