Poly(N-isopropylacrylamide) assisted microwave synthesis of magnesium aluminate spinel oxide for production of highly transparent films by hot compression

Magnesium aluminate spinel oxides have been prepared via poly(N-isopropylacrylamide) assisted microwave technique. The prepared MgAl₂O₄ powders showed a crystalline cubic structure with spinel phase after calcination at 600 °C only. The poly(N-isopropylacrylamide) amount showed a high effect on the crystallite size and the densification behavior of MgAl₂O₄. The increase of the amount of poly(N-isopropylacrylamide) reduced the sintering temperature of MgAl₂O₄ from 1400 °C to 1050 °C. The hot-pressed of MgAl₂O₄ powders in the presence of 3 wt% of poly(N-isopropylacrylamide) exhibited a full density at sintering temperature 1100 °C in 15 min only. The sintered films showed high transparency (81 ± 2%) in the wavelength range 500–1000 nm.     

White luminescence of bismuth and samarium codoped Y2O3 phosphors

In this work Sm³⁺ (0–2.0 at%) and Bi³⁺ (0–2.0 at%) doped Y₂O₃ luminescent powders were prepared by a sol–gel method from yttrium acetylacetonate, samarium and bismuth nitrates as metal sources. The as prepared powders (chemical composition is close to stoichiometric Y₂O₃) present the cubic structure from 700 °C, and at 900 °C are characterized by the presence of rounded particles with heterogeneous size of 42.9 nm. Luminescent effect of ions of Sm³⁺ and Bi³⁺ into Y₂O₃ host as was studied on heat treated powders from 800 to 1100 °C. The combination of the red luminescence from the Sm³⁺ ions and the bluish from Bi³⁺, makes the synthesized phosphors candidates to be used in fabrication of phosphor-converted light-emitting diodes (LEDs).     

Intense photoluminescence emission at room temperature in calcium copper titanate powders

A study was undertaken about the structural and photoluminescent properties at room temperature of CaCu₃Ti₄O₁₂ (CCTO) powders synthesized by a soft chemical method and heat treated between 300 and 800 °C. The decomposition of precursor powder was followed by thermogravimetric analysis (TG-DTA), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman) and photoluminescence (PL) measurements. XRD analyses revealed that the powders annealed at 800 °C are becoming ordered and crystallize in the cubic structure. The most intense PL emission was obtained for the sample calcined at 700 °C, which is not highly disordered (300–500 °C) and neither completely ordered (800 °C). From the spectrum it is clearly visible that the lowest wavelength peak is placed around 480 nm and the highest wavelength peak at about 590 nm. The UV/vis absorption spectroscopy measurements showed the presence of intermediate energy levels in the band gap of structurally disordered powders.     

Synthesis of (Ni,Mn,Co)O4 nanopowder with single cubic spinel phase via combustion method

(Ni,Mn,Co)O₄ nanopowders with single cubic phase were successfully synthesized using combustion methods. Particle size of the as-burnt nanopowders after combustion was about 20 nm. Crystallization behavior of the NMC was investigated using various techniques such as X-ray diffraction (XRD), thermogravimetric (TG), Fourier transform infrared (FT-IR) spectroscopy, and transmission electron microscopy (TEM). Calcination at different temperature from 400 °C to 700 °C provides the powders with increased crystallinity and grain size. However, further increasing temperature above 800 °C for calcination, cubic spinel phase of NMC partly transformed to tetragonal spinel phase, which implies that cubic spinel phase of NMC nanopowder synthesized by combustion method becomes unstable above 800 °C.     

Chromium substituted copper ferrites via gluconate precursor route

CuFe_2−xCr_xO₄ spinel (0≤x≤2) powders were synthesized by a soft chemistry method—the gluconate multimetallic complex precursor route. The complex precursors were characterized by elemental chemical analysis, infrared (IR) and ultraviolet–visible (UV–vis) spectroscopy, thermal analysis and Mössbauer spectroscopy. The oxide powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), IR, Raman and Mössbauer spectroscopy. It was shown that the structure, morphology and magnetic properties of the obtained spinel powders depend on the concentration of Cr³⁺ ion. The XRD of the chromium substituted copper ferrite powders calcined at 700 °C/1 h indicated the formation of a cubic spinel type structure for x=0.5, 1.0 and a tetragonal structure for x=0, 0.2, 2. The crystallite size ranged from 19 nm to 39 nm. The Mössbauer spectroscopy revealed the site occupancy of iron ions, relative abundance and internal hyperfine magnetic fields in both tetrahedral and cubic CuFe_2−xCr_xO₄ spinels.     

A comparative study of the magnetic and microwave properties of Al3+ and In3+ substituted Mg–Mn ferrites

The effect of substitution of diamagnetic Al³⁺ and In³⁺ ions for partial Fe³⁺ ions in a spinel lattice on the magnetic and microwave properties of magnesium–manganese (Mg–Mn) ferrites has been studied. Three kinds of Mg–Mn based ferrites with compositions of Mg_0.9Mn_0.1Fe₂O₄, Mg_0.9Mn_0.1Al_0.1Fe_1.9O₄, and Mg_0.9Mn_0.1In_0.1Fe_1.9O₄ were prepared by the solid-state reaction route. Each mixture of high-purity starting materials (oxide powders) in stoichiometric amounts was calcined at 1100 °C for 4 h, and the debinded green compacts were sintered at 1350 °C for 4 h. XRD examination confirmed that the sintered ferrite samples had a single-phase cubic spinel structure. The incorporation of Al³⁺ or In³⁺ ions in place of Fe³⁺ ions in Mg–Mn ferrites increased the average particle size, decreased the Curie temperature, and resulted in a broader resonance linewidth as compared to un-substituted Mg–Mn ferrites in the X-band. In this study, the In³⁺ substituted Mg–Mn ferrites exhibited the highest saturation magnetization of 35.7 emu/g, the lowest coercivity of 4.1 Oe, and the highest Q×f value of 1050 GHz at a frequency of 6.5 GHz.     

Effect of calcination temperature on morphology of mesoporous YSZ

A nano-structured mesoporous yttria-stabilized zirconia (YSZ) powders were prepared for the first time using cetyltrimethylammonium bromide (CTAB) as the surfactant and urea as the hydrolyzing agent and using ZrO(NO₃)·6H₂O and Y(NO₃)₃·6H₂O as inorganic precursors. The Brunauer–Emmett–Teller (BET) surface area, Barrett–Joyner–Halender (BJH) pore size distribution and crystallite/particle size of mesoporous YSZ varied with calcine temperatures were studied. Characterizations revealed that the mesoporous YSZ powder calcined at 600 °C was weakly agglomerated and had a high surface area of 137 m²/g with an average grain size of ∼5.8 nm. It was demonstrated that the mesoporous structure remained up to 900 °C. The low-densified YSZ sample with porosity as high as 33% was prepared from mesoporous YSZ powder sintered at 1500 °C for 6 h.     

Sol–gel synthesis of La0.6Sr0.4CoO3−x and Sm0.5Sr0.5CoO3−x cathode nanopowders for solid oxide fuel cells

Nano-powders of La_0.6Sr_0.4CoO_3?x (LSC) and Sm_0.5Sr_0.5CoO_3?x (SSC) compositions, which are being investigated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) with La(Sr)Ga(Mg)O_3?x (LSGM) as the electrolyte, were synthesized by low-temperature sol–gel method using metal nitrates and citric acid. Thermal decomposition of the citrate gels was followed by simultaneous DSC/TGA methods. Development of phases in the gels, on heat treatments at various temperatures, was monitored by X-ray diffraction. Sol–gel powders calcined at 550–1000 °C consisted of a number of phases. Single perovskite phase La_0.6Sr_0.4CoO_3?x or Sm_0.5Sr_0.5CoO_3?x powders were obtained at 1200 °C and 1300 °C, respectively. Morphological analysis of the powders calcined at various temperatures was done by scanning electron microscopy. The average crystallite size of the powders was ～15 nm after 700 °C calcinations and slowly increased to 70–100 nm after heat treatments at 1300–1400 °C.     

Synthesis and sintering of pre-mullite powders obtained via carbonate precipitation

Ultrafine pre-mullite powders, which yield mullite at high temperatures, have been prepared from colloidal silica and aluminium nitrate via carbonate coprecipitation and followed by calcination. The chemical and structural evolutions of the as-prepared precipitation powder during thermal treatment were studied and the sinterability of pre-mullite powders were investigated. The as-prepared powders are comprised of ammonium aluminum carbonate hydroxide and amorphous silica, which convert to mullite via the Al–Si spinel phase at 1250 °C. Calcination of the as-prepared powders at 1000 °C gives a very active powder which can be reactively sintered to 98.2% theoretical density at 1550 °C. The sintered body possesses a relatively uniform chemical composition with Al₂O₃/SiO₂ mole ratio of 1.48 and exhibits a very fine interlocking equiaxed and polygonal grain morphology with grain size of 100–200 nm.     

Chemical oxidation of residual carbon from ZnAl2O4 powders prepared by combustion synthesis

The removal of carbon residue from ZnAl₂O₄ nanopowders by annealing at 500–800 °C leads to a decrease of specific surface area from 228.1 m²/g to 47.6 m²/g. At the same time, the average crystallite size increased from 5.1 nm to 14.9 nm. In order to overcome these drawbacks, a new solution for removing the carbon residue has been suggested: chemical oxidation using hydrogen peroxide. In terms of carbon removal, a H₂O₂ treatment for 8 h at 107 °C proved to be equivalent to a heat treatment of 1 h at 600 °C. The benefits of chemical oxidation over thermal oxidation were obvious. The specific surface area was much larger (188.1 m²/g) in the case of the powder treated with H₂O₂. The average crystallite size (5.8 nm) of ZnAl₂O₄ powder treated with H₂O₂ was smaller than the crystallite size (8.2 nm) of the ZnAl₂O₄ powder annealed at 600 °C.     

Dense bulk silicon oxycarbide glasses obtained by spark plasma sintering

Dense silicon oxycarbide glasses (SiOC) have been produced by spark plasma sintering (SPS) of SiOC powders. Raw powders were obtained by pyrolysis under nitrogen at 1100 °C of tetraethylorthosilcate/polydimethylsiloxane (TEOS/PDMS) hybrids. SPS experiments were carried out at 1300 and 1500 °C at 10 and 80 MPa and then were studied by chemical analysis, ²⁹Si and ¹³C MAS NMR, ATR, Raman, XRD, FE-SEM, density, porosity, microhardness (H_v) and thermal conductivity (K). The SiOC materials are formed by Si_xOC_4?x units within a silica matrix where silicon carbide and graphite nanodomains are also present. After the SPS treatment the silicon carbide crystallite size is close to 2.5 nm. At 1300 °C and 1500 °C the carbon nanodomain size is close to 3 nm and 2 nm, respectively. H_v values vary from 3.4 to 9.15 GPa, for 30% and 1% of porosity, respectively. Finally, K is always close to 1.38 W m^?1 K^?1.     

Dielectric properties of nano-sized Ba0.7Sr0.3TiO3 powders prepared by spray pyrolysis

Nano-sized Ba_0.7Sr_0.3TiO₃ powders are prepared by post-treatment of the precursor powders with hollow and thin wall structure at temperatures between 900 and 1100 °C. Ethylenediaminetetraacetic acid and citric acid improve the hollowness of the precursor powders prepared by spray pyrolysis. The mean sizes of the powders post-treated at temperatures of 900, 1000 and 1100 °C are 42, 51 and 66 nm, respectively. The densities of the Ba_0.7Sr_0.3TiO₃ pellets obtained from the powders post-treated at 900, 1000 and 1100 °C are each 5.36, 5.55 and 5.38 g cm^?3 at a sintering temperature of 1300 °C. The pellet obtained from the powders post-treated at 1000 °C has higher maximum dielectric constant than those obtained from the powders post-treated at 900 and 1100 °C.     

Nanocrystalline/nanosized manganese substituted nickel ferrites – Ni1−xMnxFe2O4 obtained by ceramic-mechanical milling route

Manganese substituted nickel ferrites, Ni_1−xMn_xFe₂O₄ (x=0, 0.3, 0.5 and 0.7) have been obtained by a combined method, heat treatment and subsequent mechanical milling. The samples were characterised by X-ray diffraction, differential scanning calorimetry and magnetic measurements. The increase of the Mn²⁺ cations amount into the spinel structure leads to a significant expansion of the cubic spinel structure lattice parameter. The crystallite size decreases with increasing milling time up to 120 min, more rapidly for the nickel–manganese ferrites with a large amount of Mn²⁺ cations (x=0.7). After only 15 min of milling the mean crystallites size is less than 25 nm for all synthesised ferrites. The Néel temperature decreases by increasing Mn²⁺ cation amount from 585 °C for x=0 up to 380 °C for x=0.7. The magnetisation of the ferrite increases by introducing more manganese cations into the spinel structure. The magnetisation of the milled samples decreases by increasing milling time for each ratio among Ni and Mn cations and tends to be difficult to saturate, a behaviour assigned to the spin canted effect.     

Optimization of processing parameters for designing an efficient AC driven powder electroluminescent device

This paper reports various critical processing parameters for the development of efficient ZnS doped with Cu, Al phosphors optimized to exhibit AC electroluminescence. Different firing atmospheres and temperatures were used for the synthesis of electroluminescent phosphor materials. As synthesized ZnS: Cu, Al phosphor powders were characterized by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Photoluminescence (PL) and Electroluminescence (EL) spectroscopy studies. Average crystallite size calculated from XRD lies in a range of 44–49 µm and average grain size as revealed by SEM lies in the range 3–5 µm. The results showed that the phosphor powders have hexagonal phase and exhibit near band edge luminescence in the blue region. This is one of very few reports that depict the observation of EL from hexagonal ZnS:Cu,Al phosphor system. Polycrystalline powders emit PL in a broad band with a maximum at 2.53–2.74 eV above the valence band. The PL spectrum of the ZnS:Cu,Al phosphor showed emission peaks at 453 nm, 467 nm, 485 nm and 490 nm that could be attributed to the generation of deep level energy traps. The prototype of an alternating current driven thick (40±2 µm) film EL device has been fabricated and the threshold voltage was observed to be around 95–120 V at a frequency of 1 kHz. The critical processing parameters for designing an efficient EL device have been highlighted and discussed thoroughly in the current paper.     

Densification of nanocrystalline Y2O3 ceramic powder by spark plasma sintering

Nanocrystalline Y₂O₃ powders with 18 nm crystallite size were sintered using spark plasma sintering (SPS) at different conditions between 1100 and 1600 °C. Dense specimens were fabricated at 100 MPa and 1400 °C for 5 min duration. A maximum in density was observed at 1400 °C. The grain size continuously increased with the SPS temperature into the micrometer size range. The maximum in density arises from competition between densification and grain growth. Retarded densification above 1400 °C is associated with enhanced grain growth that resulted in residual pores within the grains. Analysis of the grain growth kinetics resulted in activation energy of 150 kJ mol^?1 and associated diffusion coefficients higher by 10³ than expected for Y³⁺ grain boundary diffusion. The enhanced diffusion may be explained by combined surface diffusion and particle coarsening during the heating up with grain boundary diffusion at the SPS temperature.     

Red-brown ceramic pigments based on chromium doped ferrian armalcolite,effect of mineralizers

A new red-brown ceramic pigment based on chromium-doped ferrian armalcolite have been synthesized and characterized. (MgFe)(Cr_xTi_3−xFe)O₁₀ powders (x=0–0.3) fired at 1200 °C crystallize ferrian armalcolite as the only crystalline phase detected. Samples fired at 1000 °C show red-brown shades in glazes that darken and bluish (b* turns to negative values) at 1200 °C. The x=0.2 sample fired at 1000 °C shows the best red colour (L*a*b*=49.5/15.2/10.3). Assignment of bands in the UV–Vis–NIR spectra is difficult due to the overlapping of Cr³⁺, Cr⁴⁺ and Fe³⁺ absorptions in octahedral coordination. Analysis of UV–Vis–NIR spectra of powders shows that these spectra are dominated by the strong absorption associated to Fe³⁺ ions in octahedral sites. In contrast, an intense band at 520 nm dominates the UV–Vis–NIR spectra of glazed samples, which should be associated to Cr⁴⁺ in octahedral coordination. This absorption increases when the amount of chromium increases, indicating that chromium is the real chromophore of the system. Finally, the weak shoulder at 600 nm and the double weak band at 700 nm, detected more evidently when chromium amount in sample increases, indicate the progressive presence of Cr³⁺ in octahedral sites. The entrance of Cr⁴⁺ in x=0.1 sample shrinks the crystalline cell, but when chromium amount in the samples increases, both Cr⁴⁺ and Cr³⁺enter simultaneously and the unit cell remains practically stable. The microstructure of the powders analysed by SEM microscopy indicates aggregates of 6–10 fine particles of 200–400 nm of diameter. The addition of mineralizers (boric acid, sodium perborate, NaF and a mixture BaF₂.4MgF₂) does not modify significantly the reactivity of the system; at 1000 °C hematite and rutile remain as residual crystalline phases, except in NaF additions where the crystallization of NaFeTi₃O₈ is detected. SEM-EDX mapping analyses of pigment powders confirm in all cases a homogeneous distribution of ions in the particles.     

Synthesis,calcination and characterization of Nanosized ceria powders by self-propagating room temperature method

Nanometric ceria powders with fluorite-type structure were obtained by applying self-propagating room temperature method. The obtained powders were subsequently thermally treated (calcined) at different temperatures for different times. Powder properties such as specific surface area, crystallite size, particle size and lattice parameter have been studied. Roentgen diffraction analysis (XRD), BET and Raman scattering measurements were used to characterize the as-obtained (uncalcined) powder as well as powders calcined at different temperatures.It was found that the average diameter of the as-obtained crystallites is in the range of 3–5 nm whereas the specific surface area is about 70 m²/g. The subsequent, 15 min long, calcination of as-obtained powder at different temperatures gradually increased crystallite size up to ～60 nm and reduced specific surface down to 6 m²/g. Raman spectra of synthesized CeO_2?y depicts a strong red shift of active triply degenerate F_2 g mode as well as additional peak at 600 cm^?1. The frequency of F_2 g mode increased while its line width decreased with an increase in calcination temperature. Such a behavior is considered to be the result of particle size increase and agglomeration during the calcination. After the heat treatment at 800 °C crystallite size reached value larger than 50 nm. Second order Raman mode, which originates from intrinsic oxygen vacancies, disappeared after calcination.     

Properties of NiFe2O4 ceramics from powders obtained by auto-combustion synthesis with different fuels

Nickel ferrite (NiFe₂O₄) powders derived by auto-combustion synthesis using three different fuels (citric acid, glycine and dl-alanine) have been characterized. The sintering behavior of ceramics using these powders has been compared. Oxygen balance (OB) setting for the chemical reaction is found to regulate the combustion reaction rate. A rapid reaction rate and a high flame temperature are achieved with dl alanine fuel yielding single phase NiFe₂O₄ powder in the as-burnt stage, whereas powders derived with citric acid and glycine fuels show poor crystallinity and necessitate post-annealing. The powder particles are largely agglomerated with a non-uniform distribution in shape and size, and the average particle size is estimated in the range ~ 54–71 nm. Powders derived from dl-alanine fuel show better phase purity, smaller crystallite size, larger surface area and superior sintering behavior. Additional Raman modes discerned for dl-alanine derived powder support a 1:1 ordering of Ni²⁺ and Fe³⁺ at the octahedral sites relating to microscopic tetragonal P4₁22 symmetry expected theoretically for the formation of NiFe₂O₄ with inverse spinel structure. Microstructure of sintered ceramics depends on the precursor powders that are used and sintering at 1200 °C is found to be optimum. Citric acid and glycine derived powders yield high saturation magnetization (M_s~47–49 emu/g), but poor dielectric properties, whereas dl-alanine derived powders yield ceramics with high resistivity (~3.4×10⁸ Ω cm), low dielectric loss (tan δ~0.003 at 1 MHz) and high magnetization (46 emu/g). Dielectric dispersion and impedance analysis show good correlation with the changes in the ceramic microstructure.     

Photocatalytic activity of titanium dioxide coatings: Influence of the firing temperature of the chemical gel

Heterogeneous photocatalysis can be exploited for the decomposition of micro-organisms which have developed on the surfaces of building materials. In this work, the efficiency of titanium dioxide coatings on fired clay products is examined. The sol–gel method is used to synthesize a fine TiO₂ powder with a specific surface area of 180 m² g^?1. Thermal treatment of the chemical gel at 340 °C leads to crystallisation in the anatase phase and with further temperature increase, crystallite growth. For thermal treatments in the range 580–800 °C, there is a progressive transition from anatase to rutile. However, despite a decrease in specific surface area of the powder attributed to aggregation/agglomeration, the coherent domain size deduced from X-ray diffraction measurements remains almost constant at 23 nm. Once the transition is completed, increase of thermal treatment temperature above 800 °C leads to further crystallite growth in the rutile phase. The thermally treated titania powders were then sprayed onto fired clay substrates and the photocatalytic activity was assessed by the aptitude of the coating to degrade methylene blue when exposed to ultraviolet light. These tests revealed that the crystallite size is the important controlling factor for photocatalytic activity rather than the powder specific surface area or the anatase/rutile polymorph ratio.     

Preparation of ultra-fine Sm0.2Ce0.8O1.9 powder by a novel solid state reaction and fabrication of dense Sm0.2Ce0.8O1.9 electrolyte film

A novel solid state reaction was adopted to prepare Sm_0.2Ce_0.8O_1.9 (SDC) powder. A mixed oxalate Sm_0.2Ce_0.8(C₂O₄)_1.5·2H₂O was synthesized by milling a mixture of cerium acetate hydrate, samarium acetate hydrate, and oxalic acid for 5 h at room temperature. An ultra-fine SDC powder with the primary particle size of 5.5 nm was obtained at 300 °C. The ultra-low temperature for the formation of SDC phase was due to the atomic level mixture of the Sm³⁺ and Ce⁴⁺ ions. The crystal sizes of SDC powders at 300 °C, 550 °C, 800 °C, and 1050 °C were 5.5 nm, 11.4 nm, 24.1 nm and 37.5 nm, respectively. The sintering curves showed that the powder calcined at lower temperature was easier to be sintered owning to its smaller particle size. A solid oxide electrolytic cell (SOEC), comprising porous La_0.8Sr_0.2Cu_0.1Fe_0.9O_3−δ (LSCF) for substrate, LSCF–SDC for active electrode, SDC for electrolyte, and LSCF–SDC for symmetric electrode, was fabricated by dip-coating and co-sintering techniques. An extremely dense SDC film with the thickness of 20 μm was obtained at only 1200 °C, which was about 100–300 °C lower than the literatures׳ reports. The designed SOEC was proved to work effectively for decomposing NO (3500 ppm, balanced in N₂), 80% NO can be decomposed at 600 °C.