Low temperature synthesis of magnetite and maghemite nanoparticles

We report on the synthesis of iron oxide nanoparticles below 100 degrees C by a simple chemical protocol. The uniqueness of the method lies in the use of Ferrous ammonium sulphate (in conjugation with FeCl3) which helps maintain the stability of Fe2+ state in the reaction sequence thereby controlling the phase formation. Hexamine was added as the stabilizer. The nanoparticles synthesized at three different temperatures viz, 5 degrees, 27 degrees, and 95 degrees C are characterized by several techniques. Generally, when a mixture of Fe3+ and Fe2+ is added to sodium hydroxide, alpha-Fe2O3 (the anti-ferromagnetic phase) is formed after the dehydration process of the hydroxide. In our case however, the phases formed at all the three temperatures were found to be ferro (ferri) magnetic, implying modification of the formation chemistry due to the specifics of our method. The nanoparticles synthesized at the lowest temperature exhibit magnetite phase, while increase in growth temperature to 95 degrees C leads to the maghemite phase.     

Direct synthesis of strontium titanate phosphor particles with high luminescence by flame spray pyrolysis

SrTiO₃:Pr, Al phosphor particles with high luminescence intensities were directly prepared by flame spray pyrolysis without post-treatment. They had better crystallinity than those prepared by general spray pyrolysis with post-treatment and solid-state reaction methods. In addition, they had complete spherical shape and narrow size distribution. On the other hand, the particles prepared by general spray pyrolysis had irregular shape, and poorer brightness than those prepared by solid-state reaction method, while the particles prepared by flame spray pyrolysis had comparable photoluminescence and cathodoluminescence intensities with those of particles prepared by solid-state reaction method. The photoluminescence intensity of SrTiO₃:Pr, Al particles prepared by flame spray pyrolysis was as much as 4.7 times higher than that of particles prepared by general spray pyrolysis.     

Synthesis of ZnO nanoparticles by flame spray pyrolysis and characterisation protocol

There is uncertainty concerning the potential toxicity of zinc oxide (ZnO) nanoparticles, which may be attributed in part to a lack of understanding with regard to the physiochemical properties of the nanoparticles used in toxicological investigations. This paper reports the synthesis of a ZnO nanopowder by flame spray pyrolysis and demonstrates that the typically employed characterisation techniques such as specific surface area measurement and X-ray diffraction provide insufficient information on the sample, especially if it is intended for use in toxicity studies. Instead, a more elaborate characterisation protocol is proposed that includes particle morphology as well as detailed compositional analysis of the nanoparticle surface. Detailed transmission electron microscopy analysis illustrated the polydispersity within the sample: particles were elongated in the c-crystallographic direction, with average Ferret length ~23 nm and Ferret width ~14 nm. Dynamic light scattering (0.1 w/v% in deionised water, pH 7.4) revealed the particles were agglomerated with a modal secondary particle size of ~1.5 μm. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy indicated the presence of carbonate and hydroxide impurities on the surface of the ZnO nanoparticles and an increase of such impurities was observed as the sample was aged, which might influence the nanoparticle dissolution and/or cellular uptake behaviour. These data will be utilised, in order to facilitate the interpretation and understanding of results from toxicological investigations using in vitro cell lines.     

Direct synthesis of highly crystalline transparent conducting oxide nanoparticles by low pressure spray pyrolysis

In this article, we firstly reported a general preparation method for the production of highly crystallized and single crystalline transparent conducting oxide (TCO) nanoparticles: tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO), and gallium-doped zinc oxide (GZO). Low-pressure spray pyrolysis was applied by means of a modified-atomizer and preheated carrier gas. The effects of pyrolysis pressure, temperature and carrier gas temperature on the size and morphology of the synthesized TCO nanoparticles were systematically investigated. The synthesized TCO nanoparticles were 17 nm large with crystallite size of 8–11 nm. The resistivities of the formed pellets were measured and compared. These results showed that this method successfully produces various TCO nanoparticles using neither dispersing agents nor post-heating treatments, which allows rapid, continuous, single-step preparation.     

Ultrasonic spray pyrolysis for nanoparticles synthesis

This article presents new findings regarding the effects of precursor drop size and precursor concentration on product particle size and morphology in ultrasonic spray pyrolysis. Large precursor drops (diameter > 30 m) generated by ultrasonic atomization at 120 kHz yielded particles with holes due to high solvent evaporation rate, as predicted by the conventional one particle per drop mechanism. Precursor drops 6–9 m in diameter, generated by an ultrasonic nebulizer at 1.65 MHz and 23.5 W electric drive power, yielded uniform spherical particles 90 nm in diameter with proper control of precursor concentration and residence time. Moreover, air-assisted ultrasonic spray pyrolysis at 120 kHz and 2.3 W yielded spherical particles about 70% of which were smaller than those produced by the ultrasonic spray pyrolysis of the 6–9 m precursor drops, despite much larger precursor drop size (28 m peak diameter versus 7 m mean diameter). These particles are much smaller than predicted by the conventional one particle per drop mechanism, suggesting that a gas-to-particle conversion mechanism may also be involved in spray pyrolysis.     

Co-Al spinel-based nanoparticles synthesized by flame spray pyrolysis for glycerol conversion

The catalytic properties of Co-Al spinel nanoparticles prepared by liquid-feed flame spray pyrolysis (L-F FSP) were investigated in the glycerol conversion in gas phase in an atmosphere of hydrogen. Reduction at 1123?K of the as-synthesized spinel nanoparticles induced the formation a new phase containing metallic cobalt species. Although, the reducibility of cobalt oxides is greatly decreased due to interaction with aluminium species, this strong interaction may prevent the aggregation of Co particles under the harsh reduction conditions. X-ray photoelectron spectroscopy (XPS) of the reduced spinel nanoparticles at 1123?K revealed that the Co/Al atomic ratio has decreased to Co/Al?=?0.11, which may indicate a redistribution of the aluminum and cobalt species at the surface of the sample submitted to the reduction in a flow of hydrogen at 1123?K. X-ray diffraction (XRD) and high resolution electron microscopy (HRTEM) also reinforced the formation of metallic cobalt species after reduction of cobalt from the spinel nanoparticles at 1123?K. The main products obtained from the conversion of glycerol in the gas phase were hydroxyacetone, pyruvaldehyde, lactic acid and lactide. FSP ensured uniform dispersion of the active metal on a support material.     

Synthesis of zinc oxide/silica composite nanoparticles by flame spray pyrolysis

Zinc oxide (ZnO)/silica (SiO₂) composite nanoparticles were made by flame spray pyrolysis. The effects of the Zn/Si ratio on particle properties were examined and compared with those of the pure ZnO and SiO₂ particles made at the same conditions. Polyhedral aggregates of nano-sized primary particles were obtained in all experiments. The mixed-oxide primary particle size was smaller than that of pure oxides. The primary particles consisted of ZnO nano-crystals and amorphous SiO₂, as seen by high-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) analysis using the fundamental parameter approach. The XRD size of ZnO was controlled from 1.2 to 11.3 nm by the initial precursor composition and it was consistent with HR-TEM. The composite particles exhibited an excellent thermal stability and little crystalline growth of ZnO (e.g., from 1.9 to 2.2 nm) was observed even after calcination at 600°C.     

Evaluation for protein binding affinity of maghemite and magnetite nanoparticles

We investigated the protein binding affinity of magnetite (Fe3O4) and maghemite (gamma-Fe2O3) nanoparticles with against non-characterized protein from human lung cancer A549 cell line on sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The binding ability of maghemite was 400 ng/mg. According to the SDS-PAGE results, the protein binding affinity of maghemite nanoparticles is stronger than magnetite nanoparticles. These data suggest that a protein can be detected with maghemite nanoparticles.     

Direct synthesis of highly crystalline single-phase hexagonal tungsten oxide nanorods by spray pyrolysis

The metastable state hexagonal-tungsten oxide (h-WO₃) has been attracting attention over the past decade because of its high reactivity that arises from the hexagonal channels in its crystal structure. Simplification of the process used to synthesize h-WO₃ is an important step to facilitate the industrial applications of this material. In this study, we addressed this challenge by developing a spray pyrolysis process to synthesize highly crystalline h-WO₃. The ratio of the monoclinic to the hexagonal phase was controlled by adjusting the segregation time. Single-phase h-WO₃ nanorods were synthesized using a carrier gas flow rate of 1?L/min, which was equivalent to a segregation time of 18.4?s. The ability of the h-WO₃ nanorods to adsorb nitrogen and carbon dioxide was evaluated to confirm the presence of hexagonal channels in the crystal structure.     

Rapid synthesis and characterization of maghemite nanoparticles

Fe2O3-SiO2 nanocomposites were prepared by a sol-gel method using various evaporation surface to volume (S/V) ratios ranging from 0.03 to 0.2. The Fe2O3-SiO2 sols were gelated at various temperatures ranging from 50 degrees C to 70 degrees C, and subsequently they were calcined in air at 400 degrees C for 4 hours. The structure and the magnetic properties of the prepared Fe203-SiO2 nanocomposites were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), differential thermal analysis (DTA), and vibrating sample magnetometer (VSM) measurements. The gelation temperature of the Fe2O3-SiO2 sols influenced strongly the particle size and crystallinity of the maghemite nanoparticles. It was observed that the particle size of maghemite nanoparticles increased with the increasing of the gelation temperature of the sols, which may be due to the agglomeration of the maghemite particles at elevated temperatures inside the microporosity of the silica matrix during the gelation process, and the subsequent calcination of these gels at 400 degrees C resulted in the formation of large size iron oxide particles. Magnetization studies at temperatures of 10, 195, and 300 K showed superparamagnetic behavior for all the nanocomposites prepared using the evaporation surface to volume ratio (S/V) of 0.1, 0.2, 0.09, and 0.08. The saturation magnetization, Ms, values measured at 10 K were 5.5, 8.5, and 9.5 emu/g, for the samples gelated at 50, 60, and 70 degrees C, respectively. At the gelation temperature of 70 degrees C, gamma-Fe2O3 crystalline superparamagnetic nanoparticles with the particle size of 9 +/- 2 nm were formed in 12 hours for the samples prepared at the S/V ratio of 0.2.     

Nano-alpha-Al2O3 by liquid-feed flame spray pyrolysis

Nanometre-sized particles of transition (t)-aluminas are important for the fabrication of high-quality alumina ceramics. Multiple tons are produced each year using a variety of gas-phase processes. The nanoparticles produced by these methods consist mainly of the undesired delta phase with some gamma- and theta-Al(2)O(3). Nano-t-aluminas should provide access to dense nano/submicrometre-grained alpha-Al(2)O(3) shapes offering significant advantages over micrometre-grained shapes. Unfortunately, polymorphism coupled with the high activation energy for nucleating alpha-Al(2)O(3) greatly impedes efforts to process dense alpha-Al(2)O(3) with controlled grain sizes, especially for submicrometre materials. Typically alpha-Al(2)O(3) nucleation within t-aluminas is sporadic rather than uniform, leading to exaggerated grain growth and vermicular microstructures without full densification (5). Thus, production of quantities of nano-alpha-Al(2)O(3) from multiple nano-t-aluminas for seeding or direct processing of alpha-Al(2)O(3) monoliths could greatly change how alpha-Al(2)O(3) components are processed. We report here that liquid-feed flame spray pyrolysis of nano-t-aluminas converts them to dispersible 30-80 nm alpha-Al(2)O(3) powders (50-85% phase transformed). Surprisingly, the powder surfaces are fully dehydrated. These powders pressureless sinter to more than 99.5% dense alpha-Al(2)O(3) with final grain sizes < or =500 nm without sintering aids.     

Extracellular synthesis of magnetite and metal-substituted magnetite nanoparticles

We have developed a novel microbial process that exploits the ability of Fe(III)-reducing microorganisms to produce copious amounts of extracellular magentites and metal-substituted magnetite nanoparticles. The Fe(III)-reducing bacteria (Theroanaerobacter ethanolicus and Shewanella sp.) have the ability to reduce Fe(III) and various metals in aqueous media and form various sized magnetite and metal-substituted magnetite nano-crystals. The Fe(III)-reducing bacteria formed metalsubstituted magnetites using iron oxide plus metals (e.g., Co, Cr, Mn, Ni) under conditions of relatively low temperature (<70 degrees C), ambient pressure, and pH values near neutral to slightly basic (pH = 6.5 to 9). Precise biological control over activation and regulation of the biosolid-state processes can produce magnetite particles of well-defined size (typically tens of nanometers) and crystallographic morphology, containing selected dopant metals into the magnetite (Fe(3-y)XyO4) structure (where X = Co, Cr, Mn, Ni). Magnetite yields of up to 20 g/L per day have been observed in 20-L vessels. Water-based ferrofluids were formed with the nanometer sized, magnetite, and metal-substituted biomagnetite particles.     

Direct synthesis of ultralong carbon nanotube bundles by spray pyrolysis and investigation of growth mechanism

A mass of ultralong aligned carbon nanotube (CNT) bundles up to about 8?mm in length was synthesized by utilizing the spray pyrolysis of ferrocene/xylene solutions in the absence of promoters, such as thiophene or pure sulfur, and etching agents, such as plasma, oxygen, ethanol or water. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) results indicated the continuous and multi-walled nanotube structure for the CNTs in the macroscopical bundles. A graph demonstrating the correlation between growth time and length of CNT arrays revealed that the maximum growth rate reaches approximately 4612?nm?s(-1). Based on the experimental phenomena and results, a continuous rapid growth mechanism in both directions was proposed, which suggests that longer CNT arrays can be synthesized at this rapid growth rate if the growth time is extended.     

Preparation of BaTiO3 nanoparticles by combustion spray pyrolysis

BaTiO₃ nanoparticles were synthesized by combustion spray pyrolysis using a 1:1 molar ratio of oxidizer and fuel. To prepare solution precursor, Ba(NO₃)₂, TiO(NO₃)₂, CH₆N₄O, and NH₄NO₃ with the molar ratio of 1:1:4:2.75 were mixed in distilled water with 10% ethyl alcohol. A 0.01 M solution was ultrasonically sprayed into a quartz tube heated at 800 °C. The number concentration of droplets was decreased and large particles were removed by passing the droplets through a metal screen filter. The synthesized particles were well crystallized tetragonal BaTiO₃. The median diameter of BaTiO₃ was 60 nm.     

Tuning of magnetite nanoparticles to hyperthermic thermoseed by controlled spray method

Magnetite nanoparticles with super-paramagnetic properties have great potential to achieve advances in fields such as hyperthermia, magnetic resonance imaging and magnetic drug targeting. In particular, magnetic particles less than 50 nm are easily incorporated into cells and generate heat under an alternating magnetic field by hysteresis loss. Various methods of preparing magnetic particles have attracted attention, such as spray pyrolysis, microwave irradiation of ferrous hydroxide, microemulsion technique and hydrothermial preparation technique. In this study, magnetite nanoparticles were synthesized with various molar ratio of Fe²⁺ and Fe³⁺ by coprecipitation using spray-guns and dropping syringe. Experiments at different molar concentrations of Fe ions were conducted, which shows the ideal molar concentration of Fe²⁺ to be 0.5 M for pure magnetite. Both in the spray and drop method, pure magnetite nanoparticles could be synthesized when the molar concentration of Fe²⁺ was 0.5 M. With increasing the molar ratio of Fe²⁺, the particle size of the magnetite nanoparticles was increased. The smallest size could be reduced to approximately 7 nm by the spray method. The shape of the synthesized nanoparticles was nearly spherical. The calculated highest loss power by hysteresis losses was 597 W/g, generated with a molar concentration ratio of 0.5:1 (Fe²⁺:Fe³⁺).     

Towards carbon-free flame spray synthesis of homogeneous oxide nanoparticles from aqueous solutions

Flame-assisted spray pyrolysis (FASP) is a versatile process for synthesis of nanoparticles from a broad choice of precursors and solvents. Water is an attractive solvent particularly for inexpensive inorganic precursors (e.g. metal nitrates) as it can effectively reduce the process cost. Furthermore when water usage is combined with a carbon-free fuel (e.g. H₂), nanoparticles can be made without forming CO₂. Here such a FASP process is explored for synthesis of Bi₂O₃ and other oxide nanoparticles from aqueous precursor solutions. The flame temperature was measured by FTIR emission–transmission spectroscopy while powders were characterized by X-ray diffraction and N₂ adsorption. At low FASP fuel gas (H₂ or C₂H₂) flow rates or process temperatures, product powders had a bimodal crystal size distribution. Its large and small modes were made by droplet- and gas-to-particle conversion, respectively. Homogeneous Bi₂O₃ and CeO₂ powders were obtained for sufficiently high flow rates of either C₂H₂ or H₂. Prolonged high temperature residence times promoted precursor evaporation from the spray droplets and yielded homogeneous nanostructured powders by gas-to-particle conversion. In contrast, FASP of aqueous solutions of aluminum nitrate yielded rather large particles by droplet-to-particle conversion at all fuel flows investigated.     

Direct synthesis of submicron FeNi particles via spray pyrolysis using various reduction agents

Preparing spherical and submicron FeNi particles in a simple, rapid, and harmless process is highly desirable for various applications yet severely challenging. Herein, we successfully synthesized the FeNi particles from their metal salts in a relatively low reduction atmosphere using three types of reduction agent, i.e., ethanol, ethylene glycol, and formic acid, via spray pyrolysis. The reduction agents were tested over a concentration range of 0–30 vol%. The type and concentration of reduction agents show a crucial role in the formation of FeNi particles. At higher concentrations (25 vol%), ethanol and ethylene glycol produced smooth and spherical FeNi particles of submicron size, 284 ± 1.6 and 399 ± 1.5 nm respectively, whereas formic acid produced particles with an irregular and Janus shape comprising FeNi and FeO, with a size of 396 ± 1.5 nm. A plausible metal salt reduction mechanism was proposed for the different reduction agents. The reduction agent type not only influences the reduction degree but also particle morphology during synthesis. This finding opens new opportunities to adjust the FeNi particles with respect to varied purposes by manipulating reduction agents.     

Characteristics of annealed ZnO:Cu nanoparticles prepared by spray pyrolysis

The effect of the annealing temperature (T _a) on the thermoluminescence, surface morphology, electrical and structural properties of the ZnO:Cu nanoparticles obtained by the spray pyrolysis method at 500°C substrate temperature was studied. All the ZnO:Cu nanoparticles annealed in the range from 200 to 450 °C are polycrystalline with (002) preferential orientation. The resistivity decreases as T _a increases until it reaches a value of 0.07 Ohm cm for T _a = 350 °C. For higher temperatures the resistivity experiences a slight increase. The grain size also increases when T _a increases as observed in data calculated from X-ray measurements.     

Generation of metal and metal oxide nanoparticles by liquid flame spray process

A liquid flame spray (LFS) process has been investigated for the generation of single component nanoparticles. In the LFS process, a solution consisting of metal nitrate dissolved in water is sprayed into a turbulent, high temperature H₂-O₂-flame. The primary spray droplets evaporate and subsequent reactions in the flame produce metal or metal oxide vapours which nucleate to final particulate form. In the study, the process characteristics were examined to produce 10–60 nm particles from silver, palladium and iron containing precursors. A systematic study using variable process parameters proved that the size of the generated nanoparticles is set by the mass flow rate of the metal precursor, only. The geometric standard deviation of the size distributions was seen to vary in a limited range of 1.35–1.4. The particle size was verified by aerosol instrumentation, the composition and morphology by X-ray diffraction (XRD) and transmission electron microscopy (TEM), correspondingly. The Ag and Pd particles were seen to consist of pure metals. For iron, the presence of all three of the following compounds were detected: Fe, Fe₂O₃ and Fe₃O₄.     

Plasmachemical synthesis of maghemite nanoparticles in atmospheric pressure microwave torch

The powder of γ − Fe₂O₃ nanoparticles was synthesized in microwave torch at atmospheric pressure from 0.05 sccm of Fe(CO)₅ vapors in 670 sccm of argon. The optimization of the torch reactor design and deposition conditions allowed continual synthesis of γ − Fe₂O₃ nanoparticles at low power consumption. The synthesized powder was collected at the reactor walls and analyzed by TEM, X-ray diffraction and Raman spectroscopy without any further purification or treatment. The mean diameter of NPs, as observed by TEM, was 12 nm with a 90% confidence interval 5.5-22 nm.