Synthesis and characterization of nanocrystalline cerium oxide powders by two-stage non-isothermal precipitation

Nanocrystalline CeO₂ particles were firstly prepared by two-stage non-isothermal precipitation, i.e. precipitating at 70 °C and aging at another temperature. Experimental results showed that the intermediates at the end of precipitation stage were needle-like mixtures of Ce³⁺-Ce⁴⁺ compounds. The subsequent aging temperature played an important role on the shape and size of final products. As the aging temperature suddenly reduced to 0 °C, the resultant particles retained their original needle-like structure via the topotactic mechanism, which cannot be obtained by isothermal precipitation. As raising the aging temperature above 50 °C, the products were hexagonal and grown up with increasing temperature via the dissolution-recrystallization mechanism. Moreover, all products were cubic-fluorite structured CeO₂ with negligible Ce³⁺ content. As compared to the nanohexagons (aged at 90 °C), the nanoneedles (aged at 0 °C) exhibited an unordinary red shift in the UV absorption and possessed a smaller bandgap energy.     

Characterization of nanocrystalline FeSiCr powders prepared by ball milling

FeSi₁₀Cr₁₀ powder was mechanically alloyed by high energy planetary ball milling, starting from elemental powders. The microstructural and magnetic properties of the milled powders were characterized by scanning electron microscopy, X-ray diffraction, ⁵⁷Fe Mössbauer spectrometry and a vibratory sample magnetometer.After 3 h of milling, the formation of two bcc solid solutions α-Fe₁ (Si, Cr) and α-Fe₂ (Si, Cr) is observed. Their grain sizes decrease with increase in milling time attaining, at 15 h of milling, 23 and 11 nm, respectively. Mössbauer spectra of the milled powder show the presence of two components. One is a ferromagnetic type with a broad sextuplet. Its distribution of hyperfine field is characterized by high and low hyperfine field’s peaks and a mean value of 26.5 T. The other is a single paramagnetic peak. Its low concentration increases to ∼4% at 15 h of milling. These results can be explained by different atomic environments affected by Si or/and Cr elements, as well as the increased disordered grain boundaries.Magnetic measurements of the milled FeSi₁₀Cr₁₀ alloy powder exhibit a soft ferromagnetic character with a decrease of both magnetization at saturation (Ms) and coercive force (Hc) with milling time attaining values of Ms=151 emu/g and Hc=2500 A/m at 30 h of milling time.     

Study of nanocrystalline and amorphous powders prepared by mechanical alloying

The process of mechanical alloying consists of intimate mixing and mechanical working of elemental powders in a high-energy ball mill. It has been well established that this process is able to produce nanocrystalline and amorphous material. In this study, the structural effects of mechanical alloying of pure Fe, Fe₅₀W₅₀ and Fe₅₀Mo₅₀ powders were investigated by X-ray diffraction and Mössbauer spectroscopy. For all cases, nanocrystalline and/or amorphous fractions were found after milling. The resulting particle size was determined by X-ray diffraction. Pure Fe does not amorphize even after prolonged milling times. For the nanocrystalline powder, significant changes in the linewidth and the hyperfine field are found. Powder mixtures of Fe₅₀Mo₅₀ and Fe₅₀W₅₀ are completely amorphous after milling times of 10 h, as seen by Mössbauer spectroscopy, but nanocrystalline fractions of the non-iron part are still found in X-ray diffraction. Also in the amorphous state, further changes in the hyperfine parameters are found with increasing milling time.     

Synthesis and optical properties of nanocrystalline ZnO powders prepared by a direct thermal decomposition route

This paper reports the synthesis and optical properties of nanocrystalline ZnO powders with crystallite sizes of 32.5 (±1.4)–43.4 (±0.4) nm prepared by a direct thermal decomposition of zinc acetate at the temperatures of 400, 500, 600, and 700°C for 4 h. The structure of the prepared samples was studied by XRD and FTIR spectroscopy, confirming the formation of wurtzite structure. The morphology of the samples revealed by SEM was affected by the thermal decomposition temperature, causing the formations of both nanoparticles and nanorods with different size and shape in the samples. The synthesized powders exhibited the UV absorption below 400 nm (3.10 eV) with a well defined absorption peak at around 285 nm (4.35 eV). The estimated direct bandgaps were obtained to be 3.19, 3.16, 3.14, and 3.13 eV for the ZnO samples thermally decomposed at 400, 500, 600, and 700°C, respectively. All the samples exhibited room-temperature photoluminescence (PL) showing a strong UV emission band at ∼395 nm (3.14 eV), a weak blue band at ∼420 nm (2.95 eV), a blue–green band at ∼485 nm (2.56 eV), and a very weak green band at ∼529 nm (2.35 eV). The mechanisms responsible for photoluminescence of the samples are discussed.     

CoFe2O4 nanocrystalline powders prepared by citrate-gel methods: Synthesis, structure and magnetic properties

Nanocrystalline CoFe₂O₄ powders were prepared by decomposition of metal ion citrate precursors. Four samples were synthesized from precursor solutions having different pH values in the range <1–7.0. The powders were characterized by X-ray Diffraction, Thermogravimetry, Differential Thermal Analysis, N₂ physisorption and Transmission Electron Microscopy. Magnetic properties were explored by a SQUID magnetometer. Three out of the four samples, coming from solutions of pH 2, 4 and 7, were produced by an autocombustion reaction and are very similar as regards average size of the nanoparticles (about 20 nm), their morphology and the magnetic properties, while the fourth sample was produced by a slower thermal decomposition and is composed of smaller nanoparticles (about 10 nm).     

Low-temperature green synthesis of boron carbide using aloe vera

The unique structural and physical properties of boron carbide, which make it suitable for a wide range of applications,demands the development of low-cost and green synthesis method. In the present work, the commonly available leaves of aloe vera are hydrothermally treated to form the carbon precursor for the synthesis of boron carbide. The morphological characterization reveals the porous nature of the precursor turning into a tubular structure upon boron carbide formation.The structural characterization by x-ray diffraction and other spectroscopic techniques such as Fourier transform infrared,Raman, photoluminescence and uv-visible near-infrared spectroscopy confirm the formation of boron carbide. The thermogravimetric analysis of the sample is found to exhibit good thermal stability above 500 °C. When the sample is annealed to 600 °C, boron carbide with phase purity is obtained, which is confirmed through XRD and FTIR analyses. The optical emission properties of the sample are studied through CIE plot and power spectrum. Compared with other natural precursors for boron carbide, the aloe vera is found to give a good yield above 50%.     

Preparation and structural characterization of nanocrystalline SnO2 powders

Nanocrystalline SnO₂ powders have been prepared by solid–liquid reaction and solid-state thermal oxidizing techniques. The microstructures and phase compositions of the product were characterized by thermogravimetry analysis, X-ray diffraction, and the Raman spectrum. It is shown that at least two phases, SnO₂ and SnO_x, coexist at 450 °C. However, only the tetragonal rutile structure SnO₂ phase is detected after the Sn powders were annealed at 550 °C. The Raman peaks of the nanocrystalline SnO₂ powders reveal remarkable red shift and broadening, which could be attributed to the phonon confinement effect, oxygen vacancies, and the stress effect. PACS 81.07.Wx; 81.10.Jt; 78.30.-j     

Synthesis and characterization of nanocrystalline TaN

Tantalum nitride (TaN) nanocrystals have been successfully synthesized at 650 °C through a solid-state reaction in an autoclave. The X-ray powder diffraction pattern indicates that the product is a mixture of hexagonal and metastable cubic TaN. Transmission electron microscopy images and selected area electron diffraction patterns show that the hexagonal TaN crystallites consist of nanorod with a typical size of about 50×1000 nm and the cubic TaN crystallites are composed of uniform particles with an average size of about 30 nm.     

Structural characterization of supported nanocrystalline ZnO thin films prepared by dip-coating

Nanocrystalline ZnO thin films prepared by the sol-gel dip-coating technique were characterized by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). The structures of several thin films subjected to (i) isochronous annealing at 350, 450 and 550 °C, and (ii) isothermal annealing at 450 °C during different time periods, were characterized. The studied thin films are composed of ZnO nanocrystals as revealed by analysing several GIXD patterns, from which their average sizes were determined. Thin film thickness and roughness were determined from quantitative analyses of AFM images and XR patterns. The analysis of XR patterns also yielded the average density of the studied films. Our GISAXS study indicates that the studied ZnO thin films contain nanopores with an ellipsoidal shape, and flattened along the direction normal to the substrate surface. The thin film annealed at the highest temperature, T = 550 °C, exhibits higher density and lower thickness and nanoporosity volume fraction, than those annealed at 350 and 450 °C. These results indicate that thermal annealing at the highest temperature (550 °C) induces a noticeable compaction effect on the structure of the studied thin films.     

Synthesis and characterization of ZnS:Cu,Al phosphor prepared by a chemical solution method

A novel and simple synthesis route for the production of ZnS:Cu,Al sub-micron phosphor powder is reported. Both the host and activator cations were co-precipitated from an ethanol medium by mixing with a diluted ammonium sulfide solution. The co-precipitated ZnS:Cu,Al was in cubic zinc blende structure after an intermediate-temperature furnace annealing. Strong photoluminescent and cathodoluminescent (CL) emission were observed, which was attributed to the 3d¹⁰-3d⁹4s¹ radiative transition at those copper sites. At an accelerating voltage of 1 kV, the CL intensity of the co-precipitated ZnS:Cu,Al sample was recorded 94% of the commercial reference phosphor with the same composition made by high temperature solid-state-reaction method. The particle size of the co-precipitated phosphor powders was found to be controllable simply through adjusting the reactant concentrations. The particle size of the annealed samples was measured by dynamic light scattering, which showed a mean particle diameter between 200 and 700 nm depending on the co-precipitation conditions.     

High temperature stability of nanocrystalline anatase powders prepared by chemical vapour synthesis under varying process parameters

Systematic variation in the high temperature stability of nanocrystalline anatase powders prepared by chemical vapour synthesis (CVS) using titanium (IV) isopropoxide under varying flow rates of oxygen and helium was obtained by progressively shifting the decomposition product from C₃H₆ to CO₂. The as-synthesised powders were characterised by high temperature X-ray diffraction (HTXRD), simultaneous thermo-gravimetric analyses (STA), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). It was observed that the anatase to rutile transformation temperature progressively increased for samples synthesised at higher O₂/He flow rate ratios. The improved anatase stability was attributed to the presence of incorporated carbon within the titania structure and confirmed by a high temperature carbon desorption peak.     

Synthesis of nanocrystalline CdS thin film by SILAR and their characterization

Cadmium sulphide (CdS) thin film was prepared by successive ion layer adsorption and reaction (SILAR) technique using ammonium sulphide as anionic precursor. Characterization techniques of XRD, SEM, TEM, FTIR and EDX were utilized to study the microstructure of the films. Structural characterization by x-ray diffraction reveals the polycrystalline nature of the films. Cubic structure is revealed from X-ray diffraction and selected area diffraction (SAD) patterns. The particle size estimated using X-ray line broadening method is approximately 7 nm. Instrumental broadening was taken into account while particle size estimation. TEM shows CdS nanoparticles in the range 5–15 nm. Elemental mapping using EFTEM reveals good stoichiometric composition of CdS. Characteristic stretching vibration mode of CdS was observed in the absorption band of FTIR spectrum. Optical absorption study exhibits a distinct blue shift in band gap energy value of about 2.56 eV which confirms the size quantization.     

多元纳米稀土六硼化物Nd1-xEuxB6粉末的制备及光吸收研究

在真空环境中采用固相烧结法成功制备出了多元稀土六硼化物Nd1-xEuxB6纳米粉末.系统研究了Eu掺杂对纳米NdB6物相、形貌及光吸收性能的影响规律.结果表明,所有合成的纳米粉末物相均为单相的CsCl型晶体结构,具有立方形貌,平均晶粒尺度为30 nm.光吸收实验结果表明,随着Eu掺杂量的增加,纳米NdB6透射光波长从629 nm红移至1000 nm以上,表现出了透射光波长的可调特性.此外,NdB6和EuB6同步辐射吸收图谱表明,Nd和Eu原子分别以Nd^3+和Eu^2+形式存在于纳米NdB6和EuB6中,充分说明了Eu掺杂使NdB6传导电子数量减少,从而导致其等离子共振频率能量的降低.采用第一性原理计算了NdB6和EuB6的能带结构、态密度、介电函数以及等离子共振频率能量,从而定性解释了Eu掺杂使NdB6透射光波长红移的特性.     

Synthesis and optical characterization of nanocrystalline CdTe thin films

From several years the study of binary compounds has been intensified in order to find new materials for solar photocells. The development of thin film solar cells is an active area of research at this time. Much attention has been paid to the development of low cost, high efficiency thin film solar cells. CdTe is one of the suitable candidates for the production of thin film solar cells due to its ideal band gap, high absorption coefficient. The present work deals with thickness dependent study of CdTe thin films. Nanocrystalline CdTe bulk powder was synthesized by wet chemical route at pH≈11.2 using cadmium chloride and potassium telluride as starting materials. The product sample was characterized by transmission electron microscope, X-ray diffraction and scanning electron microscope. The structural characteristics studied by X-ray diffraction showed that the films are polycrystalline in nature. CdTe thin films with thickness 40, 60, 80 and 100 nm were prepared on glass substrates by using thermal evaporation onto glass substrate under a vacuum of 10⁻⁶ Torr. The optical constants (absorption coefficient, optical band gap, refractive index, extinction coefficient, real and imaginary part of dielectric constant) of CdTe thin films was studied as a function of photon energy in the wavelength region 400–2000 nm. Analysis of the optical absorption data shows that the rule of direct transitions predominates. It has been found that the absorption coefficient, refractive index (n) and extinction coefficient (k) decreases while the values of optical band gap increase with an increase in thickness from 40 to 100 nm, which can be explained qualitatively by a thickness dependence of the grain size through decrease in grain boundary barrier height with grain size.     

Structure and magnetic properties of nanocrystalline Fe75Si25 powders prepared by mechanical alloying

Nanocrystalline Fe₇₅Si₂₅ powders were prepared by mechanical alloying in a planetary ball mill. The evolution of the microstructure and magnetic properties during the milling process were studied by X-ray diffraction, scanning electron microscope and vibrating sample magnetometer measurements. The evolution of non-equilibrium solid solution Fe (Si) during milling was accompanied by refinement of crystallite size down to 10 nm and the introduction of high density of dislocations of the order of 10¹⁷ m⁻². During the milling process, Fe sites get substituted by Si. This structural change and the resulting disorder are reflected in the lattice parameters and average magnetic moment of the powders milled for various time periods. A progressive increase of coercivity was also observed with increasing milling time. The increase of coercivity could be attributed to the introduction of dislocations and reduction of powder particle size as a function of milling time.     

Synthesis and characterization of nanocrystalline MgAl2O4 spinel by polymerized complex method

Ultrafine MgAl₂O₄ powder has been synthesized by a polymerized complex method. Heating of a precursor solution containing citric acid (CA), ethylene glycol (EG) and Mg and Al salts with a molar ratio of Mg/Al/CA/EG=1/2/8/32 at 180°C produced a transparent polymeric gel, which have been characterized by FT-IR spectroscopy and TG/DTA. The organic fraction was removed by controlled thermal treatments (350–1200°C) whereby the bimetallic oxide was formed. XRD analysis showed the presence of MgAl₂O₄ at 600°C. TEM observation showed that the spherical nanosized powders with good uniformity was obtained. Furthermore, these powders showed excellent sinterability, relative density up to 99.8% was achieved when sintered at 1550°C for 3 h in air without any sintering additive.     

Synthesis and magnetic characterization of nickel ferrite nanoparticles prepared by co-precipitation route

Magnetic nanoparticles of nickel ferrite (NiFe₂O₄) have been synthesized by co-precipitation route using stable ferric and nickel salts with sodium hydroxide as the precipitating agent and oleic acid as the surfactant. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses confirmed the formation of single-phase nickel ferrite nanoparticles in the range 8-28 nm depending upon the annealing temperature of the samples during the synthesis. The size of the particles (d) was observed to be increasing linearly with annealing temperature of the sample while the coercivity with particle size goes through a maximum, peaking at ∼11 nm and then decreases for larger particles. Typical blocking effects were observed below ∼225 K for all the prepared samples. The superparamagnetic blocking temperature (T_B) was found to be increasing with increasing particle size that has been attributed to the increased effective anisotropy energy of the nanoparticles. The saturation moment of all the samples was found much below the bulk value of nickel ferrite that has been attributed to the disordered surface spins or dead/inert layer in these nanoparticles.     

Synthesis and characterization of organic soluble polyaniline prepared by one-step emulsion polymerization

Emeraldine salt of polyaniline-dodecylbenzenesulfonic acid (PANI-DBSA) in organic solvents such as toluene and xylene was obtained by a direct one-step emulsion polymerization technique. When the molar ratio of DBSA to aniline monomer was 1.5:1, solubility and electrical property showed a maximum value. The solid contents of PANI-DBSA was 8 wt.% in toluene. The casting film of PANI-DBSA was obtained on glass or plastic substrate under ambient conditions. PANI solution can also be easily blended with polyurethane and polystyrene polymers in toluene. Better electrical performance (up to 5 S/cm), good light transmittance (up to 70% at 500 nm thickness), were obtained and more homogeneous morphology was observed for the casting film of PANI-DBSA prepared by the present method as compared with that prepared by the aqueous emulsion polymerization. The partially dispersed PANI-DBSA particles of 50–400 nm sizes in organic solvents such as toluene and xylene were observed and the crystalline nature of these powder samples was confirmed from the XRD patterns.     

Synthesis and characterization of LiFePO4 prepared by sol–gel technique

LiFePO₄ powder was synthesized by means of a new route, using a two step process. In the first step, an intermediate compound was synthesized by the sol–gel method. This precursor compound to LiFePO₄ was characterized by thermal analysis (TG/DTG and DSC), Mössbauer spectroscopy, Transmission Electronic Microscopy (TEM) and Small Angle Scattering (SAXS). In the second step, the precursor was sintered and analyzed by X-ray diffraction (XRD), showing the formation of the proposed single phase material.     

Synthesis and characterization of micrometric ceramic powders for electro-rheological fluids

Micrometric lamellar ceramic powders of the displacive ferroelectric oxide Bi₄Ti₃O₁₂ were synthesized by co-precipitation of bismuth nitrate and ammonia titanyl solutions followed by a heat treatment. It was found that a complete thermal decomposition is reached at 1000 °C. Structural and thermal evolution of these ceramic powders were studied by X-ray diffraction, thermogravimetry and differential thermal analysis. The homogeneity in size and morphology of these ferroelectric particles are appropriate to prepare electro-rheological fluids. One of these fluids was prepared by dispersing the powders in silicone oil; the complex cluster structure formed by the particles, under an applied AC electric field, was observed.