The effect of aminoalcohols (MEA, DEA and TEA) on morphological control of nanocrystalline ZnO powders and its optical properties

The potential of using encapsulation by MEA, DEA and TEA to control the morphology of ZnO powders was investigated. The crystallite and particle size decreased as a function of aminoalcohol concentration. We found that aminoalcohols can inhibit the crystal growth of ZnO along the c-axis. A steric effect by TEA more strongly influenced the formation of different ZnO shapes than did MEA and DEA. The value of the band gap was dependent on the crystallite size, particle size and particle shape.     

Facile synthesis of calcium silicate hydrate using sodium dodecyl sulfate as a surfactant assisted by ultrasonic irradiation

Calcium silicate hydrate (CSH) consisting of nanosheets has been successfully synthesized assisted by a tip ultrasonic irradiation (UI) method using calcium nitrate (Ca(NO₃)·4H₂O), sodium silicate (Na₂SiO₃·9H₂O) and sodium dodecyl sulfate (SDS) in water. Systematic studies found that reaction time of ultrasonic irradiation and concentrations of surfactant (SDS) in the system were important factors to control the crystallite size and morphologies. The products were characterized by X-ray power diffraction (XRD), field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectrometry (FTIR). The size–strain plot (SSP) method was used to study the individual contributions of crystallite sizes and lattice strain on the peak broadening of the CSH. These characterization techniques revealed the successful formation of a crystalline phase with an average crystallite size of about 13 nm and nanosheet morphology at a reaction time of 10 min UI with 0.2 g SDS in solvent which were found to be optimum time and concentrations of SDS for the synthesis of CSH powders.     

Effect of ball milling time on the substitution of carbon in glucose doped MgB2 superconductors: Dispersion behavior of glucose

The effect of the ball milling time (BMT) on the substitution of the carbon in the glucose doped MgB₂ samples is investigated here. Using in situ solid state reaction, four different doped samples of Mg(B_.98C_.02)₂ were prepared by mixing powders of Mg, boron and glucose for 2 h, 4 h, 8 h and 12 h using planetary ball milling. A reference sample of un-doped MgB₂ was also prepared under same conditions. The particle size distribution of the un-reacted samples show a decrease in the particle size as the BMT is increased. Both the average particle size as well as the standard deviation show a substantial decrease with the increase in the milling time up to 8 h. After 8 h, the size reduction is rather insignificant. From the XRD data, the crystallite size of the doped MgB₂ computed using the Scherrer formula was found to decrease with the increasing BMT, showing a saturation level after 8 h of the milling time. TEM images also confirm the crystallite size obtained from the XRD data. The substitution of the C in the MgB₂ lattice, measured from the change in the c/a ratio, increases with increasing BMT. The maximum carbon substitution is achieved at approximately 8 h of BMT. Moreover, a systematic enhancement of the residual resistivity and a decrease in T_C with an increasing BMT further confirms a progressive substitution of the carbon in the MgB₂. These results suggest that a minimum ball milling time is necessary to disperse the glucose uniformly for a maximum substitution of nano C in the B plane of MgB₂ lattice. The optimum BMT is found to be 8 h. Thus, the decrease in the particle size due to the ball milling enhances the dispersion of the constituent materials thereby favoring a greater substitution of the dopant in the MgB₂ during the solid-state reaction.     

Lattice dilatation of small silicon crystallites - implications for amorphous silicon

The lattice constant, d, of polycrystalline, hydrogenated silicon with a mean crystallite size less than 100 Å shows an expansion which increases with decreasing crystallite size, reaching a limiting value of Δd/d₀ ≈ 0.9 ? 1.2% for a crystallite size of about 30 Å. Implications of this result for some properties of amorphous silicon are briefly discussed.     

Raman Spectroscopy Investigation of Nano Hydroxyapatite Doped with Yttrium and Fluoride Ions

In this study, nano hydroxyapatite doped with yttrium (2.5, 5, and 7.5 mol%) and fluoride (2.5 mol%) ions were synthesized by precipitation method and sintered at 900°C, 1100°C, and 1300°C. Raman spectroscopy was applied to track the structural modifications in pure and doped hydroxyapatites. The results showed that the main characteristic band of pure hydroxyapatite at 963 cm^?1 was not affected significantly by ion doping but exhibited higher intensity with increasing sintering temperature. Due to fluoride substitution, the 1048 and 1034 cm^?1 bands of pure hydroxyapatites appeared with a wavenumber shift in the spectra of ion-doped hydroxyapatites. The 333 cm^?1 band of pure hydroxyapatite disappeared and an additional calcium–fluor bond at 322 cm^?1 was observable in ion-doped hydroxyapatites. Two fluorescence bands at 770 and 697 cm^?1, which were also observed in the spectra of pure hydroxyapatites, shifted to higher wavenumbers in the spectra of ion-doped hydroxyapatites. This was considered to result from the perturbation in the hexagonal structure of hydroxyapatite due to yttrium and fluoride codoping.     

Effect of the size factor on the magnetic properties of manganite La0.50Ba0.50MnO3

Nanocrystalline manganite La_0.50Ba_0.50MnO₃ was synthesized by an optimized sol-gel method. The initial sample was subjected to step-by-step heat treatment under air atmosphere. The ion stoichiometry, the morphology of crystallites of ceramics, and the magnetic properties were studied. It is established that the average crystallite size D increases from ～30 nm to ～7 μm with increasing annealing temperature. All of the samples studied are characterized by a perovskite-like cubic structure, with the unit cell parameter a increasing continuously from ～3.787 to ～3.904 Å with the average crystallite size. The most significant lattice compression (≈3%) occurs in the sample with an average crystallite size of ～30 nm. The increase in the average crystallite size causes a nonmonotonic increase in the Curic temperature T _C from ～264 to ～331 K and in the spontaneous magnetic moment σ _S from ～1.52 to ～3.31 μ_B/f.u. The anomalous behavior of the magnetic properties of the manganite La_0.50Ba_0.50MnO₃ obtained is explained by the competition between two size effects, namely, the frustration of the indirect exchange interactions Mn³⁺-O-Mn⁴⁺ on the nanocrystallite surface and the crystal lattice compression due to the crystallite surface tension.     

Magnetic properties of La-substituted NiFe2O4 via egg-white precursor route

Nano-sized NiFe_2−xLa_xO₄ ferrites (x=0.00, 0.01, 0.02, 0.03, 0.04, 0.5, 0.07 and 0.09) were synthesized for the first time by using metal nitrate and egg-white extract in aqueous medium. The ferrites were characterized by DTA-TG, XRD, TEM, FT-IR and VSM techniques. The thermal decomposition behavior revealed that the precursors were completely decomposed at about 420 °C. TEM image shows agglomerated nanoparticles with crystallite sizes agrees well with that estimated by XRD measurement. XRD patterns show a secondary phase of LaFeO₃ besides the cubic structure of the La-substituted ferrites. The lattice parameters, X-ray density and crystallite size were found to increase with the increasing La content. The VSM measurement exhibited a ferromagnetic property for all the samples at room temperature. With increasing La, M_s was found to decrease while H_c increased. The decrease in the saturation magnetization is attributed to the paramagnetic properties of lanthanum, which prefer to substitute iron present in the octahedral sites. The increase in the coercivity is due to either the stronger magnetocrystalline anisotropy induced by La substitution or the change in the crystallite size.     

Effect of sol–gel pH on XRD peak broadening,lattice strain,ferroelectric domain orientation,and optical bandgap of nanocrystalline Pb1.1(Zr0.52Ti0.48)O3

Nanocrystalline Pb_1.1(Zr_0.52Ti_0.48)O₃ (PZT) samples were prepared using a citrate–nitrate sol–gel process near the morphotropic phase boundary. The effect of pH on the lattice parameters (tetragonality and lattice constants), crystal structure [strain broadening, relative phase content, ferroelectric domain (FD) orientation and nanocrystallite size], microstructure (grain size and particle morphology) and optical bandgap was investigated. The samples were characterized using X-ray diffraction (XRD), the size strain plot (SSP) method, Fourier-transform infrared spectroscopy, and the classical Tauc relation. The particle morphology was investigated using field-emission scanning electron microscopy. The XRD results revealed a perovskite structure and coexisting tetragonal and rhombohedral phases for all PZT samples. Lattice strain and peak broadening were determined from SSP and XRD results. The behavior of these parameters was in agreement for all pH values. The optical bandgap for PZT was estimated from UV-vis absorption spectra. We found that for PZT the maximum relative tetragonal phase content, c/a ratio, and FD orientation along the a-axis occurred at pH 4.     

Local structure of hydroxy-peroxy apatite: A combined XRD, FT-IR, Raman, SEM, and solid-state NMR study

The synthesized hydroxyapatite (HAp) and hydroxy-peroxy apatite are studied using various techniques, such as X-ray powder diffraction, FT-IR and Raman spectroscopy, scanning electron microscopy, and solid-state NMR spectroscopy. The experimental data suggest that hydroxy-peroxy apatite contains a small amount of hydration of partially dehydroxylated hydroxyapatite phase and calcium hydroxide. The incorporation of peroxide ions into the lattice of HAp causes perturbations of the hydrogen environments and slight changes in its crystal morphology. The distance between H in some structural OH⁻ and adjacent O along the c-axis becomes longer instead of forming a hydrogen bond after the incorporation of peroxide ions.     

Macroscale and microscale evolutions of mechanically alloyed FeZn systems

The present work aims to correlate, in time, macroscale and microscale phenomenological evolutions of the microstructure of Fe and FeZn alloys processed by mechanical milling (MM) and alloying (MA), respectively. Powders were characterized for particle size distribution (PSD), particle morphology (optical microscopy, OM, scanning electron microscopy, SEM), microhardness, crystallite size, differential scanning calometry (DSC) and transmission electron microscopy (TEM). Two macroscopic regimes of PSD behavior were distinguished: the first one dominated by the cold welding process; and, the other where both fracture and agglomeration play a significant role. Solid solubilization of Zn on bcc Fe was found to reduce the final microhardness as well as increase the lattice parameter and is very well predicted by Miedema's thermodynamical approach. Microhardness and solid solution formation kinetics were correlated in time and both could be precisely described by a logistic function. After 5 h of planetary milling, microhardness and the lattice parameter become stable as well as the PSD and particle morphology, indicating that the system has already reached steady state. Indeed, this condition can be monitored by both macroscopic and microscopic parameters. Prior to an homogeneous powder, DSC results suggest an endothermic solid-state amorphization reaction for samples processed for up to 1 h as a result of the formation of clean Fe/Zn interfaces during MA.     

Mechanically Strain-Induced Modification of Selenium Powders in the Amorphization Process

For the fabrication of particles designed in the nanoscale structure, or the nanostructural modification of particles using mechanical grinding process, selenium powders ground by a planetary ball mill at various rotational speeds have been investigated. Structural analyses, such as particle size distributions, crystallite sizes, lattice strains and nearest neighbour distances were performed using X-ray diffraction, scanning electron microscopy and dynamical light scattering.By grinding powder particles became spherical composites consisting of nanocrystalline and amorphous phase, and had a distribution with the average size of 2.7 m. Integral intensities of diffraction peaks of annealed crystal selenium decreased with increasing grinding time, and these peaks broadened due to lattice strains and reducing crystallite size during the grinding. The ground powder at 200 rpm did not have the lattice strain and showed amorphization for the present grinding periods. It indicates that the amorphization of Se by grinding accompanies the lattice strain, and the lattice strain arises from a larger energy concerning intermolecular interaction. In this process, the impact energy is spent on thermal and structural changes according to energy accumulation in macroscopic (the particle size distribution) and microscopic (the crystallite size and the lattice strain) range.     

Magnetic and structural studies of the Mn-doped Mg–Zn ferrite nanoparticles synthesized by the glycine nitrate process

In this study, Nanocrystalline Mn–Mg–Zn ferrite with the chemical formula Mn_xMg_0.5−xZn_0.5Fe₂O₄ (x=0, 0.1, 0.2, 0.3, 0.4, 0.5) was successfully synthesized by the glycine-nitrate autocombustion process using glycine as a fuel and nitrates as oxidants. The as-synthesized powders were characterized by the X-ray diffraction analysis, field emission scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometer. The X-ray diffraction data was used to determine the lattice constant, cation distribution and the oxygen position parameter. The results reveal that the nanocrystalline Mn–Mg–Zn ferrite has an average crystallite size of 35–67 nm and particle size of 40 nm. The lattice parameter increases linearly with an increase in the Mn content. The FTIR analysis confirms the intrinsic vibrational frequencies of the tetrahedral and octahedral of the spinel structure. The magnetic measurements indicate that the coercivity decreases, and the magnetization increases by increasing the Mn content.     

Size dependence of lattice parameter for SixGe1−x nanoparticles

The phenomenon of the influence of the size of a material on its properties has been predicted theoretically and was confirmed for many materials experimentally by many researchers. It is a purpose of this paper to increase understanding of the influence of size on properties for silicon, germanium and alloy silicon-germanium nanoparticles. The relationships between lattice parameter and inverse particle radius had been investigated. The data obtained from the experiments show an unpredicted result that the lattice parameter of the Si_xGe_1−x nanoparticle expands by up to 1.5% when the size of the particle decreases to 7 nm. A calibration technique for a higher precision measurement of the lattice parameter is presented. The particles under investigation were deposited on an amorphous carbon substrate in order to prevent the influence of the misfit between deposit and crystalline substrate on the particle’s behavior.     

Observation of bulk like magnetic ordering below the blocking temperature in nanosized zinc ferrite

We investigated the magnetic behavior of nanosized zinc ferrite with the help of vibrating sample magnetometry and in-field Mössbauer spectroscopy. The nanoparticles of zinc ferrite with crystallite size ranging from 10 to 62 nm were synthesized by a nitrate method. The structure and phase were determined with the help of X-ray diffraction. Attributes of cation inversion were found with the calculated values of lattice parameter. The saturation magnetization decreases with the increase in crystallite size at room temperature, while these values are almost the same at 10 K for all the samples except the one with crystallite size of 10 nm. The thermal magnetization measurement shows a decrease in blocking temperature with increase in particle size for these samples. The synthesized samples exhibit the presence of antiferromagnetic ordering below the blocking temperature as investigated by in-field Mössbauer spectroscopy.     

Structural and magnetic properties of Co1−xZnxFe2O4 nanoparticles by co-precipitation method

Co_1−xZn_xFe₂O₄ nanoparticles were prepared by co-precipitation method with x varying from 0 to 1.0. The powder samples were characterized by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and Fourier transform infrared spectroscopy (FTIR). The average crystallite sizes of the particles were determined from XRD. X-ray analysis showed that the samples were cubic spinel. The average crystallite size (D_aveXR) of the particles precipitated was found to vary from 6.92 to 12.02 nm decreasing with the increase in zinc substitution. The lattice constant (a_o) increased with the increase in zinc substitution. The specific saturation magnetization (M_S) of the particles was measured at room temperature. The magnetic parameters such as M_S, H_c, and M_r were found to decrease with the increase in zinc substitution. FTIR spectra of the Co_1−xZn_xFe₂O₄ with x varying from 0 to 1.0 in the range 400–4000 cm⁻¹ were reported. The spinel structure and the crystalline water adsorption of Co_1−xZn_xFe₂O₄ nanoparticles were studied by using FTIR.     

Reverse microemulsion-directed synthesis of hydroxyapatite nanoparticles under hydrothermal conditions

Morphology controllable hydroxyapatite (HA) nanoparticles were synthesized using reverse microemulsion (aqueous solution/TX-100/n-butanol/cyclohexane) systems under hydrothermal conditions. The concentration of cetyltrimethylammonium bromide (CTAB) contained in the aqueous solution and pH value had significant effect on the morphology and crystal phases of the final products. All the as-synthesized HA nanoparticles had a larger a value but smaller c value compared with the standard values of the JCPDs card. The existence of CTAB could be attributed to the growth of HA along an axis, but inhibit the growth along the c-axis to some extent. A proposed model was established to explain the change of the lattice parameters.     

Low-temperature synthesis of nanocrystalline β-dicalcium silicate with high specific surface area

β-Dicalcium silicate (β-Ca₂SiO₄) was synthesized for the first time by a simple solution combustion method using citric acid as fuel. The influence of calcination temperature on the average crystallite size, specific surface area and morphology of the powders were investigated by X-ray diffraction technique (XRD), scanning electron microscopy (SEM) and N₂ adsorption measurements (BET). The results showed that the increase of calcination temperature from 650°C to 1100°C resulted in larger crystallite size and lower specific surface area of β-Ca₂SiO₄. The highest specific surface area could reach as high as 26.7 m²/g when the as-burnt powders were calcined at 650°C.     

Microstructural characterisation of nanoparticles using, XRD line profiles analysis, FE-SEM and FT-IR

In this investigation, the structural characteristics of α- Fe₂O₃ nanoparticles synthesised by a mechanical milling have been explored. The structure and morphology of samples were characterized by X-ray powder diffraction, field-emission scanning electron microscope (FE-SEM) and FT-IR measurements. The crystallite size and internal strain were evaluated by XRD patterns using Williamson-Hall and Scherrer methods. The results did not reveal any phase change during the milling. The average particle size decreases with a prolongation of milling times, while the lattice parameters and internal strain increase. It was found that using this method allowed the formation of hematite nanoparticles.     

Structural modification and band gap engineering of sol–gel dip-coated thin films of Zn<Subscript>0.75</Subscript>Mg<Subscript>0.25</Subscript>O alloy under vacuum annealing

In the present study, we investigated the effect of vacuum annealing on the structural and optical properties of sol–gel dip-coated thin films of Zn_0.75Mg_0.25O alloy. XRD studies revealed that all these films were polycrystalline with hexagonal wurtzite structure and there was no trace of additional phases other than ZnO. With increase in annealing temperature, the samples showed preferred orientation along the c-axis, (0 0 2) plane and also peak narrowing and peak shift towards higher angles. The calculated values of mean crystallite size increased with annealing temperature indicating the improvement in crystallinity. Heat treatment caused lattice contraction and a decrease in film thickness. The optical transmittance in the visible spectral range enhanced with increase in annealing temperature while the fundamental absorption edge in the near ultra-violet region got red-shifted with annealing. The calculated values of optical energy gap of the samples showed a decrease with heat treatment due to the improvement in crystallinity during annealing and hence the subsequent decrease in quantum size effect.     

Monodisperse Co,Zn-Ferrite nanocrystals: Controlled synthesis,characterization and magnetic properties

Co_xZn_yFe_3−x−yO₄ ferrite (x=1 to 0; y=0 to1) nanocrystals have been synthesized by reverse microemulsion method. The nanocrystals are then comprehensively characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Field emission transmission electron microscopy (FETEM), and magnetic properties were measured by using Vibrating sample magnetometer. X-ray analysis showed that all the crystals were cubic spinel. The lattice constant increased with the increase in Zn substitution. FETEM reveals that particle size varies in the range from 3 to 6 nm. As the concentration of Zn increases the magnetic behavior varies from ferromagnetic at y=0 and 0.2 to superparamagnetic to paramagnetic at y=1. The Curie temperature decreases with increasing concentration of Zn.