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.     

Synthesis and hydration study of Portland cement components prepared by the organic steric entrapment method

The four components of Portland cement; dicalcium silicate (Ca₂SiO₄), tricalcium silicate (Ca₃SiO₅), tricalcium aluminate (Ca₃Al₂O₆), and tetracalcium aluminate iron oxide (Ca₄Al₂Fe₃O₁₀), were made by the PVA complexation process. Powders prepared by this new method can make relatively high yields of pure, synthetic, cement components of nano or sub-micron crystallite dimensions, high specific surface area, and extremely high reactivity at relatively low calcining temperatures in comparison with conventional methods. The above advantages can enhance setting speed, increase strength, and lead to other desirable characteristics of Portland cement. Optimum synthesis conditions, such as PVA content, degree of polymerization of the PVA, and calcination temperature, were determined for each component. Hydration speed and strength of the synthesized, mixed cement paste were also studied at room temperature (25°C). The powders and hydration behavior were characterized by microstructural examination (XRD, SEM) and specific surface areas were measured by nitrogen gas adsorption BET. DSC and Instron were used to study setting speed and compression strength.     

Synthesis, characterization and formation mechanism of single-phase nanostructure bredigite powder

Single-phase nanocrystalline bredigite powder was successfully synthesized by mechanical activation of talc, calcium carbonate, and amorphous silica powder mixture followed by annealing. Simultaneous thermal analysis (STA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS),and Fourier transform infrared spectroscopy (FT-IR) techniques were employed to characterize various powders. Single-phase nanostructure bredigite powder with crystallite size of about 65 nm was synthesized by 20 h of mechanical activation with subsequent annealing at 1200 °C for 1 h. The bredigite formation mechanism was studied. During the formation process of nanostructure bredigite powder some intermediate compounds such as wollastonite (CaSiO₃), larnite (Ca₂SiO₄), merwinite (Ca₃MgSi₂O₈), and calcium magnesium silicate (Ca₅MgSi₃O₁₂) were formed. It was found that bredigite was not produced directly and that the formation of merwinite, enstatite and Ca₅MgSi₃O₁₂was unavoidable during the synthesis of bredigite.     

Microstructural evolution of oxide-dispersion-strengthened Fe–Cr model steels during mechanical milling and subsequent hot pressing

Oxide-dispersion-strengthened (ODS) ferritic steels of Fe–9Cr–0.3Y₂O₃ and Fe–9Cr–0.2Ti–0.3Y₂O₃ (in mass) incorporating nanoscale oxide particles, were produced by mechanical milling (MM) followed by hot pressing (HP). Microstructural evolution of these two types of ODS steels were structurally characterized at each step of the elaboration processes by means of scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), and optical microscope. The observations of structure of the mixed powders and the nanoscale oxide particles in both ODS steels after MM indicate that the initial powders, coupled with the original yttria powders, get fractured by severe plastic deformation and ultrafine bcc grains (~20 nm) of the matrix and Y₂O₃ nanocrystals with irregular edges are formed during MM. The addition of titanium (Ti) promotes the refinement of bcc grains, Y₂O₃ nanocrystals and the formation of amorphous phase of Y₂O₃ during MM. TEM observations of these two Oxide-dispersion-strengthened (ODS) steels exhibit a very fine structure of micrometer-scale grains in which large number of nanoscale oxide particles are distributed after HP process. The observation of some unreinforced domains without the nanoscale oxide particles indicates that there still exist inhomogeneous areas, although the size of those oxide particles reaches nanoscale. Threshold stress of the HPped Fe–9Cr–0.2Ti–0.3Y₂O₃ steel with the relatively homogeneous dispersion was carefully evaluated on the basis of higher magnified images of the nanoscale oxide particles. Different values of threshold stress were obtained due to the various dispersions of the nanoscale oxide particles within different areas. That may be the reason why the threshold stress cannot be clearly obtained by the results of creep tests.     

High purity synthesis of ZrB2 by a combined ball milling and carbothermal method: Structural and magnetic properties

The present work provides a new insight into the high purity synthesis of zirconium diboride (ZrB₂) powders and a method of controlling impurity during the synthesis process. The single phase ZrB₂ nano-powder was synthesized by a combined ball milling and carbothermal method using zirconium oxide (ZrO₂), boron oxide (B₂O₃) and carbon (C) as starting materials. The reaction pathway, phase purity, and morphology of the ZrB₂ produced are elucidated from X-ray diffraction (XRD) and scanning electron microscopy studies. The details of the impure phases generated during synthesis were obtained from multi-phase Rietveld refinements of XRD data. Experiments revealed that the method of synthesis carried out at 1750?°C involving ZrB₂:B₂O₃:C at a molar ratio of 1:4.5:7.5 could produce highly pure ZrB₂ nano-powders of 67?nm average crystallite size. The magnetometry studies on such pure form of ZrB₂ nano-powders indicated that both paramagnetic and diamagnetic characteristics coexisted in ZrB₂, which could be attributed to its polycrystallinity.     

Self-propagating high-temperature synthesis of Lu<Subscript>2</Subscript>O<Subscript>3</Subscript> powders for optical ceramics

A technique has been developed for the self-propagating high-temperature synthesis of lutetium oxide (Lu₂O₃) powders using citric acid, glycine, and lutetium acetate as fuels. We have carried out thermodynamic analysis of synthesis conditions and examined the effect of the nature of the fuel on the properties of the resultant powders. Using vacuum sintering at a temperature of 1780°C and powders prepared with glycine as a fuel and containing 25 mol % yttrium oxide and 5 mol % lanthanum oxide as sintering aids, we have obtained transparent lutetium oxide-based ceramics.     

Preparation of Fe2O3/Al composite powders by homogeneous precipitation method

The Fe₂O₃/Al composite powders were prepared by homogeneous precipitation method. The influence of the concentration of Fe²⁺ and the molar ratio of raw materials on the preparation of Fe₂O₃/Al composite powders were investigated. X-ray diffractometer, scanning electron microscope, Fourier transform infrared spectroscopy and differential thermal analysis were used to analyze the morphology and structure of the Fe₂O₃/Al composite powders. The results show that the content of iron oxide in the composite powders could be effectively controlled by adjusting the concentration of Fe²⁺ and the molar ratio of raw materials in the plating solution. The surface of Al particle was coated with a layer of thick and dense iron oxide. The core-shell Fe₂O₃/Al composite powders with Fe₂O₃ content of 14.1% were produced, the coating efficiency of Fe₂O₃ reaches more than 77%. The iron oxide, which coated on the surface of the aluminium particle is flower-like cluster structure, each flower-like cluster is constituted by nano-flaky iron oxide.     

Dispersant-assisted hydrothermal synthesis of MnZn ferrites from raw oxides

MnZn-ferrite powders were prepared using hydrothermal syntheses of a homogenous mixture of the raw oxides, i.e., Fe₂O₃, ZnO and Mn₃O₄, at 280°C in air. The hydrothermal synthesis was performed in the presence of various amounts of an anionic dispersant. The final results of the hydrothermal reaction between the raw oxides were fine powders with a heterogeneous phase composition mostly composed of iron oxide and spinel products. The composition of the spinel products depended to a great extent on the amount of dispersant in the hydrothermally treated suspension. Without the dispersant addition, Zn ferrite and Zn manganate spinel products were formed, while in the presence of the dispersant, the ferrimagnetic MnZn-ferrite spinel product was obtained. A larger amount of the dispersant in the reaction mixture increased the conversion rate of the raw oxides into the Mn,Zn ferrite spinel product. Additionally, polyvinyl alcohol (PVA) was used during the hydrothermal synthesis in order to bind the chlorine impurities, introduced into the hydrothermally prepared powder with the raw Fe₂O₃. With the PVA burnout, the level of chlorine impurities was decreased by approximately 50%.     

Novel wet-chemical synthesis and characterization of nanocrystalline CeO2 and Ce0.8Gd0.2O1.9 as solid electrolyte for intermediate temperature solid oxide fuel cell (IT-SOFC) applications

Novel wet-chemical methods of synthesis have been adopted to synthesize nano-crystalline CeO₂ and Gd-substituted compositions aiming to explore an efficient oxide ion conducting solid electrolyte for intermediate temperature solid oxide fuel cell (IT-SOFC) applications. Nano-crystalline CeO₂ powders were synthesized by combustion method using redox mixture of cerric ammonium nitrate or cerium nitrate and maleic acid or 1,3-dimethylurea and compared with high surface area CeO₂ powders prepared by hydrothermal technique with microwave precipitated precursor from aqueous solutions of (NH₄)₂Ce(NO₃)₆ and urea. The grain size achieved by the hydrothermal technique is ∼7 nm which is smaller than that of commercial nano CeO₂ powders. Conventional or microwave sintering was used to prepare dense Ce_0.8Gd_0.2O_1.9 pellets from the ceria powders made of redox mixture of cerium nitrate, 1,3-dimethylurea (DMU) and Gd₂O₃ as the starting ingredients. The samples were characterized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and ac impedance spectroscopy. The ionic conductivity measured for the pellet sintered at 1400 °C is 1 × 10⁻² and 2.4 × 10⁻² S/cm at 700 °C and 800 °C respectively.     

Physicochemical simulation of fusion processes of basalt and diabase with Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> and Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> + CaO

Fusion processes of basalt and diabase with sodium carbonate and its mixture with calcium oxide are investigated by methods of physicochemical simulation. Equilibrium compositions of the Si-Al-Fe-Ca-Mg-Na system are calculated at various ratios Na₂CO₃: basalt (diabase) and (Na₂CO₃ + CaO): basalt (diabase) in the temperature range of 1270–1470 K. It is shown that, on fusion with sodium carbonate, depending on conditions, the main components of fusion products are sodium metasilicate (Na₂SiO₃) and sodium metaaluminate (NaAlO₂), magnesium orthosilicate (CaMgSiO₄), sodium ferrite(III) (NaFeO₂), iron(III) oxide (Fe₂O₃), and sodium-aluminum orthosilicate (Na₂AlSiO₄). On fusion with the mixture of sodium carbonate and calcium oxide, respectively, the products are sodium metaaluminate, calcium pyrosilicate (Ca₃Si₂O₇), calcium-magnesium orthosilicate, and calcium ferrite (CaFe₂O₄).     

Microwave-assisted combustion synthesis of ZnAl2O4 and ZnO nanostructure particles for photocatalytic wastewater treatment

ZnAl₂O₄ and ZnO nanostructure particles and in situ crystallization of zinc aluminate and zinc oxide coating layers on sintered α-Al₂O₃ and γ-Al₂O₃ granules by the microwave-assisted combustion method were investigated. For powders, the effects of solution pH value and for coated samples the influence of support type on the structure, microstructure, and photocatalytic activity of powders were studied. Results showed that variation of synthesis pH value caused to considerable change in agglomeration, specific surface area, obtaining up to 88 and 92% yields for zinc aluminate and zinc oxide nanoparticles, respectively. γ-alumina granules were more appropriate supports than the α-alumina ones because of the better photocatalytic activities and lower extent of the attritions for both zinc aluminate and zinc oxide coating layers.     

Nanostructured Cu–Al2O3 composite produced by thermochemical process for electrode application

Nanostructured Cu–Al₂O₃ composite powders were synthesized by thermochemical process. The synthesis procedures are (1) preparation of precursor powder by spray-drying of solution made from water-soluble copper and aluminum nitrates, (2) air heat treatments to evaporate volatile components in the precursor powder and synthesis of nanostructured CuO+Al₂O₃, and (3) CuO reduction by hydrogen into pure Cu. The suggested procedures stimulated the formation of the γ-Al₂O₃, and different alumina formation behaviors appeared with various heat-treating temperatures. The mean particle size of the final Cu–Al₂O₃ composite powders produced was 20 nm, and the electrical conductivity and hardness in the hot-extruded bulk were competitive with Cu–Al₂O₃ composite by the conventional internal oxidation process.     

Preparation and characterization of NiO, Fe2O3, Ni0.04Zn0.96O and Fe0.03Zn0.97O nanoparticles

Nickel oxide (NiO), iron (III) oxide (Fe₂O₃), and mixed oxide (Ni_0.04Zn_0.96O and Fe_0.03Zn_0.97O) nanoparticles were synthesized by modified sol–gel method. The nanoparticle structural and morphological properties were investigated by infrared spectroscopy (FTIR), X-ray powder diffractometry (XRD), scanning electron microscopy (SEM), and Mössbauer spectroscopy. The mixed oxides were characterized by energy-dispersive X-ray spectroscopy (EDX). The oxide precursor powders were analyzed by thermogravimetry (TG) and differential scanning calorimetry (DSC). The average sizes of the obtained NiO and Ni_0.04Zn_0.96O nanocrystallites were evaluated by X-ray line broadening using Scherrer's equation and were found to be 36 and 23 nm, respectively. Fe₂O₃ and Fe_0.03Zn_0.97O nanoparticles presented similar sizes, around 19 nm. EDX spectroscopy indicated that the calculated compositions of the mixed oxides were nearly consistent with their estimated molar ratios.     

Molten salt synthesis and luminescence properties of Bi4Si3O12 powders

In this paper, Bismuth silicate (Bi₄Si₃O₁₂, BSO) powders were prepared by reaction in molten salts (NaCl and KCl) using Bi₂O₃ and SiO₂ powders as raw materials. The effects of salt contents and excessive contents of Bi₂O₃ and SiO₂ were characterized by X-ray diffraction and scanning electron microscopy. The properties of Bi₄Si₃O₁₂ powders were analyzed via fluorescence spectroscopy. Forming mechanism of platelets was discussed. The experimental results suggest that Bi₄Si₃O₁₂ powders are produced at 780 °C for 4 h with 40 wt% salts and 5 wt% excessive content of Bi₂O₃. The peaks of excitation spectrum and emission spectrum for BSO powders are separately located at 266 and 457.6 nm. Compared with crystal materials, the excitation spectrum and emission spectrum of Bi₄Si₃O₁₂ powders indicate blue shift. Interface reacting mechanism can be used to explain the coarsening process of bismuth silicate platelets produced in molten salt synthesis. In addition, dissolution–precipitation mechanism also plays an important role in the synthesis of bismuth silicate platelets.     

Processing and sintering of yttrium-doped tungsten oxide nanopowders to tungsten-based composites

Innovative chemical methods are capable of fabricating nanoscale tungsten oxide compounds doped with various rare-earth elements with high purity and homogeneity, which can be processed under hydrogen into nanostructured oxide-dispersed tungsten composite powders having several potential applications. However, hydrogen reduction of doped tungsten oxide compounds is rather complex, affecting the morphology and composition of the final powder. In this study, we have investigated the reduction of tungstic acid in the presence of Y and we provide the experimental evidence that Y₂O₃ can be separated from Y-doped tungstic acid via hydrogen reduction to produce Y₂O₃-W powders. The processed powders were further consolidated by spark plasma sintering at different temperatures and holding times at 75 MPa pressure and characterized. The optimized SPS conditions suggest sintering at 1400 °C for 3 min holding time to achieve higher density composites with an optimum finer grain size (3 µm) and a hardness value up to 420 H _V. Major grain growth takes place at temperatures above 1300 °C during sintering. From the density values obtained, it is recommend to apply higher pressure before 900 °C to obtain maximum density. Oxides inclusions present in the matrix were identified as Y₂O₃·3WO₃ and Y₂O₃·WO₃ during high resolution microscopic investigations.     

Synthesis and characterisation of rare earth oxysulphide phosphors. I. Studies on the preparation of Gd2O2S:Tb phosphor by the flux method

Terbium activated gadolinium oxysulphide phosphor (Gd₂O₂S:Tb) shows bright green luminescence and high efficiency under X-ray excitation. Phosphor utilisation depends on powder characteristics and luminescence properties that are regulated during the synthesis stage. The paper presents some of our new results on the synthesis of Gd₂O₂S:Tb phosphor by solid-state reaction route from oxide precursors. Efficient luminescent powders utilisable in the manufacture of X-ray intensifying screens for medical diagnosis were prepared from optimised synthesis mixtures containing oxide precursors, alkaline carbonate based flux, alkaline phosphate based mineralising additives and sulphur suppliers.     

Microstructures and properties of Cu-10Sn oil bearings reinforced by Al2O3 nanoparticles

Using Sn and Cu-Al powders as raw materials, three oxide dispersion-strengthened (ODS) Cu-10Sn alloy powders with different Al₂O₃ mass content (0.42%, 0.85% and 1.68%, respectively) were prepared by mechanochemical synthesis combined with diffusion alloying method. The oil bearings were then fabricated by pressing and sintering. The effects of Al₂O₃ on microstructures and properties of the powders and the oil bearings were investigated. The results show that Al₂O₃ nanoparticles with sizes of about 5 nm are uniformly distributed in the ODS Cu powders. The content of Al₂O₃ nanoparticles has no effect on the distribution uniformity of tin during the diffusion process. And three ODS Cu-10Sn alloy powders with homogeneous tin distribution are prepared. However, the temperatures of forming liquid phases in the ODS Cu-10Sn alloys decrease with increasing Al₂O₃ content. This affects the sintering behaviors and mechanical properties of oil bearings. Increasing Al₂O₃ content also has a significant promoting effect on the precipitation of Sn-rich particles. In order to synergize the solid solution strengthening of tin and the dispersion strengthening of Al₂O₃ nanoparticles, the content of Al₂O₃ in the ODS Cu-10Sn alloys will not exceed 0.85%. The ODS Cu-10Sn oil bearings with 0.42% Al₂O₃ sintered at 900 °C have the best comprehensive properties, with uniform radial and axial shrinkage, oil content of 19.1%, radial crushing strength of 284 MPa and micro-hardness of 142 HV.     

A Review on Iron Oxide Nanoparticles and Their Biomedical Applications

The iron oxide nanoparticles have a great attraction in biomedical applications due to their non-toxic role in the biological systems. The iron oxide nanoparticles have both magnetic behaviour and semiconductor property which lead to multifunctional biomedical applications. The iron oxide nanoparticles used in biomedical fields such as antibacterial, antifungal and anticancer were reviewed. The uses of hematite (α-Fe₂O₃), maghemite (γ-Fe₂O₃) and magnetite (Fe₃O₄) nanoparticles, for an inhibition time in biological activities, are listed in this work. Also, this review explains the use of iron oxide nanoparticles in the biomedical fields with particular attention to the application of hematite and superparamagnetic iron oxide nanoparticles. In this review, analysis reveals that the role of iron oxide in biological activity is good due to its biocompatibility, biodegradability, ease of synthesis and different magnetic behaviours. The change of properties of iron oxide nanoparticles such as particle size, morphology, surface, agglomeration and electronic properties has specific impact in biomedical application. The review mainly focused in and discussed about antibacterial, anticancer, bone marrow and cell labelling activities. From this review work, the iron oxide nanoparticle may be specialised in particular bacterial and cancer treatments. Also discussed are the iron oxide nanoparticle-specific biomedical applications like human placenta, insulin and retinal locus treatments.     

Preparation of Al2O3–TiB2 nanocomposite powder by mechanochemical reaction between Al,B2O3 and Ti

Mechanochemical processing is a novel technique for the synthesis of nano-sized materials. This research is based on the production of Al₂O₃–TiB₂ nanocomposite powder using mechanochemical processing. For this purpose, a mixture of aluminum, titanium and boron oxide powders was subjected to high energy ball milling. The structural evaluation of powder particles after different milling times was conducted by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results showed that during ball milling the Al/B₂O₃/Ti reacted with a combustion mode producing Al₂O₃–TiB₂ nanocomposite. In the final stage of milling, the crystallite sizes of Al₂O₃ and TiB₂ were estimated to be less than 50 nm.     

CO2 pretreatment and hydrothermal treatment of commercial γ-Al2O3 powders for purification and refinement

Ultrapure, nanosized alumina (Al₂O₃) powders are highly required for high performance Al₂O₃ ceramics. However, the synthesis of the powders via an efficient and low-cost way is still a challenge. In the present research, we treated commercial γ-Al₂O₃ powders via hydrothermal treatment combined with CO₂ pretreatment technique. The effect of hydrothermal pressure on the crystal phase, particle size and purity of the treated powders were investigated. In addition, the effect of CO₂ pretreatment on the purification of the powders was discussed. Commercial γ-Al₂O₃ powders are fully converted to boehmite (AlOOH, a derived form of Al₂O₃) at a hydrothermal pressure of 3.5 MPa. The boehmite powders reduce to the minimum particle size of 50–100 nm after being hydrothermal treated at 3.5 MPa. CO₂ pretreatment has been found to be very efficient in the purification of the powders. The Al₂O₃ content of the powders after being CO₂ pretreated at 1 MPa could reach up to 99.9410% which is much larger than that of commercial γ-Al₂O₃ powders (99.5096%). The as-received ultrapure, nanosized boehmite powders are promised raw materials for high performance Al₂O₃ ceramics.