Preparation and characterization of alumina-doped powders for the design of multi-phasic nano-microcomposites

The composite powders 90 vol.% Al₂O₃–5 vol.% YAG–5 vol.% ZrO₂ were produced by doping commercial alumina powders with zirconium and yttrium chloride aqueous solutions. Both a nanocrystalline transition alumina and a pure α-phase powder were used as starting materials. The obtained materials were characterized by DTA-TG, XRD and dilatometric analyses and compared to the respective biphasic systems developed by the same procedure. Pressureless sintering at 1500 °C for 3 h was able to consolidate the doped powders in fully dense bodies, characterized by a very fine and homogeneous dispersion of the second phases into the micronic alumina matrix.     

Investigation of catalytic activity of ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles in the thermal decomposition of ammonium perchlorate

A new powder metallurgy technique was developed in order to increase the reinforcement proportion of aluminum with two different fractions of Al₂O₃. Aluminum powders were mixed with 20 % vol of alumina particles as primarily reinforcement, and additional alumina was produced in situ as a result of reaction between Al and additional 7.5 % vol of Fe₂O₃ powder. The three grades of powders were milled and hot-pressed into small preforms, and differential scanning analysis (DSC) was performed to determine the kinetics of microstructural transformations produced on heating. DSC curves were mathematically processed to separate the superposing effects of thermal reactions. Transformation points on resulting theoretical curves evidenced two distinct exothermal reaction peaks close to the melting point of aluminum that were correlated with formation of Fe–Al compounds and oxidation of aluminum. Microstructural investigations by means of SEM-EDX and XRD suggested that these exothermal reactions produced complete decomposition of iron (III) oxide and formation of Fe–Al compounds during sintering at 700 °C, and therefore, heating at higher temperatures would not be necessary. These results, along with calculation of activation energies, based on Kissinger’s method, could be used to optimize the fabrication of Al-Al₂O₃ composites by means of reactive sintering at moderate temperatures.     

Changes to the physicochemical characteristics of wheat straw by mechanical ultrafine grinding

To investigate changes on the physicochemical characteristics of wheat straw by mechanical ultrafine grinding, wheat straw powders of four different particle sizes and distributions were produced using a sieve-based Retsch ZM100 grind mill and CJM-SY-B ultrafine vibration grind mill. Changes on the microstructure and physicochemical characteristics of the different powders were assessed by scanning electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and relevant standard laboratory analysis methods. Ultrafine grinding reduced the crystallite size and crystallinity of the wheat straw. New surfaces were exposed on the ultrafine powder with high levels of cellulose/hemicelluloses components but there was no apparent change in chemical structure. Wheat straw powders were smaller in size but had a higher bulk density (from 0.19 to 0.54 g/mL) and angle of repose (from 46.02° to 55.61°) and slide (from 37.26° to 41.00°). The hydration properties (water-holding capacity and swelling capacity) decreased with reduction in particle size of the wheat straw. Both the sieve-based and ultrafine powder exhibited a good ability to remove Pb²⁺ and Cd²⁺ and there was marginal improvement when using the ultrafine powder. The thermal stability of the ultrafine powder measured by thermogravimetric analysis decreased significantly because of the low cellulose crystallinity.     

Preparation of aluminum nitride fibers from alumina gel fibers by nitridation in ammonia

Aluminum nitride (AlN) fibers were prepared from alumina gel fibers and by heat-treatment in ammonia. The influence of silica on the formation of AlN was investigated. It was shown that phase transformation of alumina (γ-Al₂O₃ to α-Al₂O₃) and nitridation reaction took place above 1,100 °C for pure alumina fiber. The addition of a small amount of silica (3 wt%) suppressed the formation of α-Al₂O₃ and preserved the highly reactive metastable alumina, and nitridation rate was enhanced. Fine grain (~20 nm) AlN fibers were obtained for pyrolysis at 1,150–1,250 °C for 3 h in ammonia, and AlN was identified as the sole crystalline phase.     

Crystallization of mould powders used in the continuous casting of steel

Mould powders used in the continuous casting of steel play an important role in the heat transfer and lubrication between the liquid metal strand and mould. A range of industrial fluxes was investigated, each sample being decarburized and milled prior to DTA. On heating, the powders undergo silicate crystallization producing exotherms in the range 600°–1000°C, before melting. The activation energy of crystallization (E _a) was determined from the peak shifts of each flux heated at different rates, and ranged from 100–450 kJ/mol.E _a values increased with flux viscosity and decreased with basicity, suggesting that DTA can be applied to mould powder evaluation for use in continous steel casting.     

Characterization of metal oxide-doped lutetium orthoferrite powders from the pigmentary point of view

This thesis deals with the preparation and characterization of inorganic pigments based on perovskite structure of metal oxide-doped LuFeO₃. Powder samples were prepared by the conventional ceramic method, i.e., solid-state reaction. Heating temperature was chosen according to results of TG/DTA. Prepared pigments were incorporated into an organic binder system, and their color properties were evaluated by measuring the reflectance in the visible region of light. The most interesting color properties were obtained by preparation of sample Lu_0.98Ca_0.02FeO_3?δ with mineralizer LiF at the temperature 900 °C. Mean size of its particles is 4 μm. X-ray diffraction analysis confirmed a single-phase orthorhombic structure with lattice parameters a = 0.521310 nm, b = 0.55535 nm, and c = 0.75626 nm. Thermal stability of the sample is limited by the temperature of 1,150 °C. Further, the effectiveness of other metal oxide (CoO-, ZnO-, Bi₂O₃-, and Sb₂O₃)-doped Lu_0.98Ca_0.02FeO_3?δ system was evaluated with respect to their phase composition, thermal stability, particle size distribution, and color properties. The conclusions of the research showed that a sample containing antimony oxide is the mixture with the best pigmentary-application properties. The powder has a clear orange color, high thermal stability up to 1,340 °C, and mean particle size 4 μm.     

Influence of Cu powders on the properties and characteristics of nano-MgO based aluminate cementitious materials

From the perspective of practical application, the development of desirable thermal and mechanical performance of solid sensible materials for thermal energy storage (TES) is highly needed. Here, we report the improved properties of nano-MgO optimized aluminate cementitious materials incorporated with Cu powders for TES. The composite TES materials were heated at 105, 350, and 900 °C, respectively. The results show that as the Cu powders content increases the thermal conductivity and volume heat capacity significantly increase, but there is a gradual decrease in compressive strength. Through the characterizations such as calorimetric test, XRD, FESEM, TG-DSC, and MIP, a significant feature of mass compensation also has been obtained, which might result from the oxidation reaction of the Cu powder at elevated temperatures.     

Olivine-type nanoparticle for hybrid supercapacitors

LiCoPO₄ nanoparticles were precipitated from polyethylene glycol solution of lithium acetate, cobalt acetate, and ammonium dihydrogen phosphate by refluxing at 250 °C for 35 h. The resultant powder samples were heated at 800 °C for different time periods of 2 and 4 h to study the effect of annealing time on the growth of samples. The X-ray diffraction pattern of the obtained samples exhibited olivine phase. The scanning electron microscopic images of dried powder sample and samples heated at 800 °C for 2 and 4 h showed a homogenous orthorhombic morphology with a particle size of few nanometers range. For the first time, orthorhombic olivine was introduced as positive electrode for a hybrid electrochemical supercapacitor cell with carbon nanofoam as negative electrode in 1 M LiClO₄ in ethylene carbonate and propylene carbonate (1:1 in volume) solution. A sloping voltage profile of 2 to 0 V is observed for all the three hybrid cells. From the impedance results, we inferred that LiCoPO₄ nanoparticles synthesized by polyol process offers less resistance than lithium titanium oxide. According to the results of electrochemical testing for the first time, maximum power density of 192 W/kg at 11 Wh/kg energy density was obtained for LiCoPO₄ nanoparticles annealed at 800 °C for 2 h. The dried sample and the sample heated at 800 °C for 2 and 4 h exhibited high capacitances of 5, 19, and 4 F/g, respectively, with an excellent rate capability over 1,000 cycles.     

Zirconium titanate synthesis by diethanol amine based sol-gel route

ZrTiO₄ powder are synthesized by a modified sol-gel route via bimetallic diethanol amine complex of zirconium and titanium alkoxides. Samples are cured at 140°C and calcined between 500–800°C. Powders are characterized with XRD, TGA, DTA, SEM and TEM methods. The ZrTiO₄ powders are obtained at 650°C from the amorphous form. No identified peaks can be attibuted to other phases, namely, zirconia and titania are not observed.     

Preparation and characterization of a nitrogen-doped mesoporous carbon aerogel and its polymer precursor

Nitrogen-containing carbon aerogel was prepared from resorcinol–melamine–formaldehyde (R–M–F) polymer gel precursor. The polymer gel was supercritically dried with CO₂, and the carbonization of the resulting polymer aerogel under nitrogen atmosphere at 900 °C yielded the carbon aerogel. The polymer and carbon aerogels were characterized with TG/DTA–MS, low-temperature nitrogen adsorption/desorption (??196 °C), FTIR, Raman, powder XRD and SEM–EDX techniques. The thermal decomposition of the polymer aerogel had two major steps. The first step was at 150 °C, where the unreacted monomers and the residual solvent were released, and the second one at 300 °C, where the species belonging to the polymer network decomposition could be detected. The pyrolytic conversion of the polymer aerogel was successful, as 0.89 at.% nitrogen was retained in the carbon matrix. The nitrogen-doped carbon aerogel was amorphous and possessed a hierarchical porous structure. It had a significant specific surface area (890 m² g^?1) and pore volume (4.7 cm³ g^?1). TG/DTA–MS measurement revealed that during storage in ambient conditions surface functional groups formed, which were released upon annealing.     

Thermal and spectral behavior of (Y,Eu)VO4 powder

Thermal analysis of Y_xEu_1?xVO₄ powder (used as “phosphor” coating for a high pressure mercury lamp) was done under a non-isothermal linear regime, both in a dynamic air regime and in a nitrogen atmosphere. The heating in air atmosphere gave on TG curve small rate of mass increase due to oxygenation and two endothermic effects are observed on DTA and DSC curves. By contrary, in nitrogen atmosphere a continuous stepped mass loss of powder (around 0.65 %), is recorded in the range of temperatures from room temperatures to 1,200 °C, and only one endothermic effect, to eliminate the gases accumulated on the crystallite surface. The powder was heated for 3 h in a Nabertherm furnace at 350, 800, and 1,100 °C using quite similar rate for heating program followed by a furnace cooling to room temperature. XRD and FTIR analyses showed the sample purification by thermal treatment and a very small increase of nanocrystallite sizes. The time evolution of the optical emission spectra in the range from 186.2 to 877.47 nm were recorded for different lamp powers in two different situations: with the outer bulb coated with Y_xEu_1?xVO₄ type “phosphor”, and without it. We observed that UV-Hg lines are absorbed by Y_xEu_1?xVO₄ type “phosphor” with different percents (100 % for 253.73 nm, 95 % for 312.65 nm, and 33 % for 365.12 nm) but the heating of the powder do not influence the UV-absorption properties of the powder.     

Influence of some lime-containing additives on the thermal behavior of urea

Urea is one of the main nitrogen fertilizers used in agriculture. But being well soluble in water, hardly 50% of its nitrogen is assimilated by plants. One possibility to eliminate this disadvantage is to use coating agents for modification of urea to obtain a controlled-realized fertilizer. The aim of this research was to study the influence of different lime-containing additives on the thermal behavior and decomposition kinetics of urea in oxidizing atmosphere. Commercial fertilizer-grade urea (46.4% N) and analytical-grade CaO, MgO, CaCO₃, MgCO₃ were used in the experiments. In addition, one Estonian limestone and one dolomite sample were used as additive or coating material. The experiments with a Setaram Setsys 1750 thermoanalyzer coupled to a Nicolet 380 FTIR Spectrometer by a heated transfer line were carried out under non-isothermal conditions up to 900 °C at the heating rate of 5 °C min^?1 and to calculate kinetic parameters, additionally, at 1, 2, and 10 °C min^?1 in the atmosphere containing 80% of Ar and 20% of O₂. The differential isoconversional method of Friedman was used to calculate the kinetic parameters. The results obtained indicate that thermooxidative decomposition of urea as well as the blends of urea with lime-containing materials and urea prills coated with limestone or dolomite powder follows a complex reaction mechanism.     

Influence of powder preparation process on piezoelectric properties of PZT sol-gel composite thick films

In this work, piezoelectric PbZr_0.52Ti_0.48O₃ (PZT) thick films were deposited onto silicon and alumina substrates using sol-gel composite slurry. Thick films prepared with rough and attrited powders are compared. A time stable polymeric PZT sol was first synthesised as the binder. It was then used as a precursor for PZT powder fabrication. Powder attrition ball milling was optimised to reduce the particles size to 200 nm. Composite slurries were obtained by mixing PZT sol with attrited or rough powders and thick films were deposited by dip-coating. The film thickness, roughness and microstructure were studied as a function of powder content, particle size, sol concentration and slurry ageing. Electromechanical measurements were performed. By strictly controlling each step of the thick film fabrication, high coupling factor (thickness mode, k_t) can be obtained using both types of powder. Nevertheless, with attrited powder, better and more reproducible effective coupling coefficients in thickness mode (k_t up to 46%) were reported on silicon and alumina substrates.     

Synthesis and Characterization of Yttria-Stabilized Zirconia (YSZ) Nano-Clusters for Thermal Barrier Coatings (TBCs) Applications

Yttria-stabilized zirconia (YSZ) nano-clusters were synthesized by a sol–gel process. The aim was to produce YSZ powders in order to prepare thick coatings for thermal barrier to be applied on gas turbine engine components. Yttrium nitrate hexahydrate and zirconium oxy-chloride octahydrate were used as a source of zirconium, citric acid was taken as a chelating agent, and ethylene glycol was used as a polysterification agent. The synthesized powders were characterized by X-ray diffraction, transmission electron microscopy, thermo-gravimetric analysis and differential scanning calorimetry, and Raman spectroscopy. Furthermore, parameters were critically analyzed in order to synthesize non-transformable (t′) tetragonal crystal structure, which is the best zirconia phase for high temperature thermal barrier coatings applications. In this regard, tetragonal YSZ nano-clusters were heated in an alumina crucible at a temperature of 1200 °C for 100 h.     

Influence of annealing temperature on the electrochemical and surface properties of the 5-V spinel cathode material LiCr0.2Ni0.4Mn1.4O4 synthesized by a sol–gel technique

LiCr_0.2Ni_0.4Mn_1.4O₄ was synthesized by a sol–gel technique in which tartaric acid was used as oxide precursor. The synthesized powder was annealed at five different temperatures from 600 to 1,000 °C and tested as a 5-V cathode material in Li-ion batteries. The study shows that annealing at higher temperatures resulted in improved electrochemical performance, increased particle size, and a differentiated surface composition. Spinel powders synthesized at 900 °C had initial discharge capacities close to 130 mAh g^?1 at C and C/2 discharge rates. Powders synthesized at 1,000 °C showed capacity retention values higher than 85 % at C/2, C, and 2C rates at 25 °C after 50 cycles. Annealing at 600–800 °C resulted in formation of spinel particles smaller than 200 nm, while almost micron-sized particles were obtained at 900–1,000 °C. Chromium deficiency was detected at the surface of the active materials annealed at low temperatures. The XPS results indicate presence of Cr⁶⁺ impurity when the annealing temperature was not high enough. The study revealed that increased annealing temperature is beneficial for both improved electrochemical performance of LiCr_0.2Ni_0.4Mn_1.4O₄ and for avoiding formation of Cr⁶⁺ impurity on its surface.     

Synthesis and Characterization of Nanocrystalline MoSi2 by Mechanical Alloying and Heat Treating

In order to synthesize nanocrystalline MoSi₂, pure molybdenum and silicone powders were milled using an attritor mill with the molar ratio of Mo:Si being equal to 1:2. Mechanically alloyed (MAed) powders were heated in an atmosphere controlled furnace at various temperatures and holding times. The nanopowder characteristics were evaluated by field emission scanning electron microscopy, X-ray diffraction technique, and differential thermal analysis. The obtained results were compared for all prepared samples. The results did not confirm the presence of any related intermetallics after MA. However, Mo₅Si₃ was formed during heating at 900 °C. An increase in temperature caused the enhancement of the volume fraction of Mo₅Si₃ and formation of MoSi₂. Further heating at 1,100 °C caused the enhancement of the volume fraction of MoSi₂, while that of Mo₅Si₃ was decreased, as during heating at 1,100 °C for 7 h the volume fraction of Mo₅Si₃ was negligible.     

Growth of Nd-doped YAG powder by sol spray process

Yttrium aluminum garnet (YAG) and neodymium-doped yttrium aluminum garnet (Nd-YAG) nano-crystalline powders were successfully grown using cost effective sol spray process without the addition of any chelating agent or organic templates. Thermal decomposition behavior was studied by thermogravimetry (TG) and differential thermal analysis (DTA). Results revealed that crystallization of YAG started around 920 °C. The shrinkage/expansion behavior of synthesized powder was examined by dilatometer and revealing that sintering kinetics of these materials can be related to the evaporation of binder and formation of crystalline phases. Nano-crystallinity and garnet structure of YAG and Nd-YAG specimens were analyzed by Raman, fourier transform infra red (FTIR), and X-ray diffraction (XRD) techniques. XRD patterns were indexed using Rietveld refinement method. Smaller lattice parameter and a small change in atomic position of oxygen were found in Nd-YAG when compared with YAG structure. Scanning electron microscope (SEM) results indicated that particle size of Nd-YAG was <150 nm. The morphology of Nd-YAG nanosized powder was rounded in shape.     

Synthesis of nanometric β-barium metaborate powder from different borate solutions by ultrasound-assisted precipitation

In this study, the synthesis of barium metaborate powder (BaB₂O₄) was carried out by ultrasound-assisted precipitation using different borate solutions. Different solutions such as borax (Na₂B₄O₇, BD), boric acid (H₃BO₃, BA), and sodium metaborate (NaBO₂, SMB) were used in the synthesis and an ultrasonic immersion horn probe was used as the major source of ultrasound. The effect of reaction temperature and time, pH, and crystallization time on the BaB₂O₄ yield (%) was investigated. The ultrasound-assisted synthesis up to 90 % yield could be achieved using a 0.2 M BD solution at 80 °C, reacting for 5 min at pH 13 followed by 2 h of crystallization. Following crystallization, the obtained powder was heated up to 140, 250, 650, and 750 °C for 2.5 h, and it was shown that β-BaB₂O₄ nanometric powders were obtained after the 750 °C heat treatment.     

Chemical synthesis of tungsten-copper nanocomposite powder

In this study homogeneous powders of CuWO₄ and WO₃ was produced from ammonium para-tungstate (APT) and copper nitrate. Then, the product was used to prepare nano-sized W-Cu powder. Hence, a mixture of ammonium paratungstate and copper nitrate with predetermined weight proportion was made in distilled water, while the content of the beaker was being stirred at a certain speed to reach the desired composition of W-20 wt % Cu. Mixture was heated to 80–100°C for 6 h. Also, pH range was adjusted at about 3–4. The mixture was then evaporated and dried in the air. To reach W-Cu composite powder, the precursor powders burned out at 520°C for 2 h in the air to form W-Cu oxide powder and then were ball milled and reduced in H₂ atmosphere to convert it into W-Cu composite powder. The resulting powders were evaluated using scanning electron microscopy, X-ray diffraction, thermogravimetric analysis and differential thermal analysis techniques. The results showed that homogeneous powders of W-Cu with particle size of around 100 nm and a nearly spherical shape could be obtained by this process. Each particle include smaller parts with size of around 20–30 nm.     

Thermal characterization of iron oxide powders by emanation thermal analysis

Emanation thermal analysis (ETA) using a surface-impregnation method of Ra-226 nuclide was applied for the thermal characterization of near-surface of iron oxide powders with various preparation histories in the heating and grinding treatments. Peaks I and II appeared at the temperature regions lower and higher than 0.4 – 0.5 T_m, respectively, where T_m is a melting temperature (K) of powders. Further, peak I′ appeared at the temperature region of 0.4 – 0.5 T_m. The appearance of peak I was explained by the mechanochemical effects due to the grinding treatment, and it disappeared in the repeated run. The shift of peak II 900°C to 1000°C in the repeated run was explained by the orderingeffect of crystal lattice due to the heating treatment. The behavior of peak I′ was complicated.