Synthesis and characterisation of nanostructured silica-powellite-HAP composites

Well-defined calcium molybdate (CaMoO₄) and hydroxyapatite (HAP) nanocrystals were developed by thermal treatment on the surface of a SiO₂–CaO–P₂O₅–MoO₃ amorphous precursor synthesised at room-temperature by sol–gel route. The structural and morphological characterisaions were performed by several techniques: energy dispersive X-ray spectroscopy, thermal analyses (DTA/TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, electron paramagnetic resonance. Complementary, Fourier transform infrared and Raman spectroscopies provided a clear picture regarding the short range order structure, emphasising beside the CaMoO₄ phase development, the presence of HAP nanocrystals. The vibrational spectroscopic techniques proved to be valuable tools for evidencing very small HAP nanocrystallites that cannot be clearly observed by XRD and TEM analyses.     

Reactivity of biological and synthetic hydroxyapatite towards Zn(II) ion, solid-liquid investigations

The reaction of biological and synthetic hydroxyapatite Ca₅(PO₄)₃OH (HAP) with Zn²⁺ ions is investigated as a function of Zn²⁺/Ca²⁺ molar ratio, time, temperature and electrolyte type (NaCl, NaHCO₃, Na₂HPO₄) by means of pH, pZn, pCa measurements, in aqueous solution. Biological powdered HAP invariably affords an almost quantitative reaction, while Zn²⁺ precipitated only partially by reaction with cubelets of biological HAP. Using powdered biological HAP and synthetic HAP (dried at 100 °C), the reaction with Zn²⁺ ion is fast and takes place without addition of precipitating anion; synthetic HAP (dried at 1000 °C) reacts if free phosphate ions are present. The solid phases separated after different reaction times are investigated by means of X-ray diffraction (XRD), IR, SEM techniques and elemental analysis (C,H,N). The solid phases contain Zn₃(PO₄)₂ { 4H₂O (Hopeite) at the beginning of reaction and CaZn₂(PO_{4 2} { 2H₂O (Scholzite) at the equilibrium.     

Red light from ZrO2:Eu nanostructures

Zirconia nanocrystals doped with europium ions were developed envisaging optical applications. The nanostructures were produced using zirconyl nitrate (ZrO(NO₃)₂·H₂O) and europium nitrate (Eu(NO₃)₃·5H₂O) as cation precursors, and urea (C₂H₅NO₂) as the fuel, by the combustion synthesis process. The lanthanide-doped nanostructures were characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and photoluminescence. X-ray diffraction revealed the presence of tetragonal and monoclinic crystalline ZrO₂ phases. The latter was found to be a minority phase as identified by Raman and corroborated by the observed europium luminescence when compared to the intraionic emission in crystalline tetragonal fibres grown by the laser floating zone technique. Bright red europium luminescence is observed at room temperature when the combustion synthesized zirconia powders are excited with ultraviolet radiation. The spectroscopic properties of the europium ions in the powders are ascertained by comparing combined excitation–emission measurements with those from crystalline fibres.     

The influence of NaX zeolite particle size on crystallinity measured by the XRD method

The degree of crystallinity of NaX zeolite samples, previously determined by X-ray diffraction (DC_XRD), was measured by a series of methods (i.r. spectroscopy, specific area, and ion-exchange measurements). For NaX zeolite samples, crystallized with various amounts of added “seed” SASS, it was found that

• 1.(a) There were no significant changes in the position, number, and half-width of the diffraction lines.
• 2.(b) Only slight changes in the shape of the i.r. spectra, chemical composition, specific area, and ion-exchange capacity occurred.
• 3.(c) There was only a slight decrease in the intensity of the diffraction peaks caused by the increase of SASS up to 20%.
• 4.(d) With the addition of more than 20% SASS, there was a sharp decrease in the intensity of the diffraction lines, and on the basis of this a sudden decrease in DC_XRD a decrease of the mean particle size, as well as a decrease in the fraction of particles of dimensions less than 1 μm.

The decrease in degree of crystallinity DC_XRD is explained by the mosaic structure of zeolites and extinction effects that lead to a decrease in the intensity of the diffraction lines due to the decrease in the dimensions of mosaic blocks and increase in the angle of disorder.     

Co1−xZnxFe2O4 (0 ≤ x ≤ 1) nanocrystalline solid solution prepared by the polyol method: Characterization and magnetic properties

Highly crystalline stoichiometric Co_1?xZn_xFe₂O₄ (0 ≤ x ≤ 1) nanoparticles were successfully synthesized by the polyol process. X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), transmission electron microscopy (TEM), infrared spectroscopy (IR), zero-field ⁵⁷Fe Mössbauer spectrometry and magnetic measurements using a SQUID magnetometer were employed to investigate the effect of the substitution of Zn²⁺ ions for Co²⁺ ones on the structure, and the magnetic properties of the cobalt ferrite, CoFe₂O₄. The unit cell parameter almost increases linearly with increasing Zn concentration, x, following Vegard's law. The red and blue shifts observed for the metal-oxygen ν₁ and ν₂ IR vibration bands, respectively, were consistent with the preferential entrance of Zn²⁺ ions in tetrahedral sites. Besides, detailed magnetic investigation in correlation with the cation distribution has been reported. All the particles exhibit superparamagnetic behaviour at room temperature. In addition, the magnetic characteristics (blocking temperature, saturation magnetization, coercivity, Curie temperature) clearly depend on the chemical composition and cation distribution. Both the blocking temperature and Curie temperature decrease drastically with Zn composition, x, increase. Further, the saturation magnetization follows an almost bulk-like behaviour with values notably larger than that of the bulk, mainly attributed to cation distribution deviation.     

Sol-gel cobalt oxide-silica nanocomposite thin films for gas sensing applications

Various metal oxide-silica nanocomposite films have been recently proposed as gas-sensitive materials. This paper presents results on cobalt oxide-SiO₂ mesoporous nanocomposite thin films templated by a cationic surfactant. The films were deposited on glass substrate by dip-coating process, using [Co(CH₃COO)₂]·4H₂O and tetraethoxysilane (TEOS) as starting materials. The effect of withdrawal speed, number of layers and thermal treatment on the crystalline structure, morphology, Co-doping states, optical, electrical and gas sensing properties of the thin films has been investigated using X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, optical transmittance and room temperature photoreduction-oxidation data.     

Thermal stability of sputtered zirconium oxide films

In this work, the effect of post-growth annealing on the structural and optical properties of sputtered zirconium oxide films has been investigated. The temperature dependence of structure, density, and optical constants has been systematically studied by X-ray diffraction, X-ray reflectometry, atomic force microscopy (AFM) and optical spectroscopy. X-ray diffraction studies show no variation in the crystalline phase upon annealing except grain growth. X-ray reflectivity measurements determine a density increase of approximately 11% and a simultaneous thickness reduction of 10% upon annealing. The surface roughness of the films increases upon annealing as determined by XRR and confirmed by AFM measurements. Optical spectroscopy measurements confirm that the refractive index n of the films decreases with increasing annealing temperature. At the same time the optical band gap E_g of the films increases from 4.58 to 4.97 eV annealing at 900°C. The surprising decrease of refractive index upon annealing is attributed to both the intermixing of Si with ZrO₂ and the increasing surface roughness of the films.     

Plasma-chemical Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles for Doping of High-Temperature Superconductors

Ferrite nanoparticles (Fe₃O₄) have been produced by the direct low-pressure plasma-chemical synthesis. X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), vibration magnetometry (VSM), and Mössbauer spectroscopy (NGR) were used for measurements, showing that the produced nanoparticles have an average size of 9.4 nm, a crystalline phase of magnetite, possess a property of superparamagnetism at room temperature, and have a blocking temperature of 89 K. The peculiarities of nanoparticle behavior in the magnetic field, related to a large specific surface area, are discussed.     

Structure and properties of lead and lead sulfide nanoparticles in natural zeolite

We have synthesized lead and lead sulfide nanoparticles embedded in a natural zeolite (clinoptilolite) matrix by a simple hydrothermal process. The process steps involve the partial removing of the natural cations in clinoptilolite, the ion-exchange process to enclose Pb ions and nanoparticles and finally a sulfuration process at different temperatures to obtain lead sulfide phases in the zeolite matrix. The samples were studied by X-ray diffraction, diffuse reflectance spectroscopy, energy dispersive X-ray spectroscopy, X-ray photon spectroscopy and transmission electron microscopy. The experimental results show the inclusion of three Pb species with different valence states after the Pb ion-exchange step, namely Pb²⁺, Pb⁴⁺, and Pb⁰. At the end of the process, two simultaneous lead sulfide crystalline phases, PbS (Galena) and PbS₂ (tetragonal) were synthesized in the clinoptilolite matrix. The optical absorption spectra of the samples show the exciton absorption peaks typical of colloidal PbS nanoparticles. The average size of the PbS nanoparticles was about 10 nm and their crystalline structure was determined from diffraction electron patterns. The high-pressure phase PbS₂ was also identified and its formation was attributed to the influence of the special conditions of clinoptilolite matrix as crystallization media to induce some selective nucleation process of this crystalline phase.     

Triethanolamine Assisted Hydrothermal Synthesis of Superparamagnetic Co3O4 Nanoparticles and Their Characterizations

We present, for the first time, on a facile route for the fabrication of highly crystalline Co₃O₄ nanoparticles using trietanolamine (TEA) assisted hydrothermal synthesis route and single precursor. Synthesized material has been evaluated for its structural, morphological and magnetic properties using x-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and vibrating sample magnetometry (VSM) techniques. The material has been identified as highly crystalline Co₃O₄, with superparamagnetic character due to size confinement. Estimated particle size from SEM is about 10 nm, which is close to the magnetic domain size (estimated from VSM as 8.4 ± 1.7 nm) and the crystallite size (estimated from XRD as 11 pm 4 nm), which reveal nearly single crystalline character of Co₃O₄ nanoparticles. The suggested route is facile, which provides a good size control over the nanoparticles, and can be used for the fabrication of other ceramic materials.     

A novel, low temperature method for the preparation of ß-TCP/HAP biphasic nanostructured ceramic scaffold from natural cancellous bone

In this study, a novel method was used to synthesize ß-TCP/HAP biphasic ceramic scaffold from natural cancellous bone. Bovine bone was calcined to remove the organic content. The remaining material was then soaked in P₂O₅ solution for different periods. P ions were doped into cancellous bone and reacted with hydroxyapatite (HAP) to produce ß-tricalcium phosphate (ß-TCP) at room temperature without any subsequent high-temperature heat treatment. By increasing the soaking time, the crystalline phase composition of the calcined bone gradually changed from HAP into a HAP/ß-TCP biphasic structure with different HAP/TCP ratios. The crystallite size of HAP and ß-TCP was smaller than 100 nm.     

Substitution of manganese and iron into hydroxyapatite: Core/shell nanoparticles

The bioceramics, hydroxyapatite (HAP), is a material which is biocompatible to the human body and is well suited to be used in hyperthermia applications for the treatment of bone cancer. We investigate the substitution of iron and manganese into the hydroxyapatite to yield ceramics having the empirical formula Ca_9.4Fe_0.4Mn_0.2(PO₄)₆(OH)₂. The samples were prepared by the co-precipitation method. The formation of the nanocrystallites in the HAP structure as the heating temperatures were raised to obtain a glass–ceramic system are confirmed by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron diffraction (ED) and electron spin resonance (ESR). TEM images show the core/shell structure of the nanoparticles, with the core being formed by the ferrites and the shell by the hydroxyapatite. The ED patterns indicate the nanoparticles formed at 500 °C have an amorphous structure while the nanoparticles formed at 1000 °C are crystalline. ESR spectroscopy indicated that the Fe³⁺ ions have a g-factor of 4.23 and the Mn²⁺ ions have a g-factor of 2.01. The values of the parameters in the spin Hamiltonian which describes the interaction between the transition metal ions and the Ca²⁺ ions, indicate that the Mn²⁺ ion substitute into the Ca²⁺ sites which are ninefold coordinated, i.e., the Ca(1) sites.     

Annealing temperature dependence on the structural and optical properties of sputtering-grown high-k HfO2 gate dielectrics

High-k gate dielectric HfO₂ thin films have been deposited on Si and quartz substrates by radio frequency magnetron sputtering. The structural characteristics, surface morphology, and optical properties of the HfO₂/Si gate stacks at various post-annealing temperatures were examined by X-ray diffraction (XRD), atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), ultraviolet–visible spectroscopy (UV–Vis spectroscopy), and spectroscopic ellipsometry (SE). XRD measurement indicates that the 80 W-deposited HfO₂ films demonstrate a polycrystalline structure. AFM measurements illustrate that the root mean square of the HfO₂ thin films demonstrates an apparent increase with increasing the annealing temperature. Analysis from FTIR indicates that the Si–O–Si bonds vibration peak position shift toward lower wave numbers with increasing the annealing temperature. Combined with UV–Vis spectroscopy and SE measurements, it can be noted reduction in band gap with an increase in annealing temperature has been confirmed. Additionally, increase in refractive index (n) has been confirmed by SE.     

Preparation and characterization of Ln2Zr2O7 microspheres by an inorganic sol-gel route

Free-flowing Ln₂Zr₂O₇ microspheres (Ln=lanthanide) were prepared by an aqueous inorganic sol-gel route without any intermediate phase formation. The gel spheres obtained at room temperature were shown by X-ray diffraction to be amorphous but calcination to 750 °C produced fully crystalline fluorite phases. On calcination to 850 °C, pyrochlore phases were formed with suitable lanthanides. The microspheres were characterized by X-ray diffraction and scanning electron microscopy with energy dispersive analysis of X-rays to give accurate determination of structure, composition and crystallite size.     

Calcium phosphates formation on CaTiO<Subscript>3</Subscript> coated titanium

In this study, performance of calcium phosphate formation of CaTiO₃ coating film on Ti in Hanks’ balanced saline solution (HBSS) was investigated. CaTiO₃ thin films with a thickness of 50 nm were deposited on Ti using radiofrequency (RF) magnetron sputtering. The temperature of Ti substrate was adjusted to room temperature (RT) and 873 K. Thereafter, the specimens deposited at RT were annealed at 873 K in air for 7.2 ks. The films were characterized by grazing incident angle X-ray diffractometry (GI-XRD) and X-ray photoelectron spectroscopy (XPS). After immersion in HBSS for 60 d, on CaTiO₃ coated Ti, the formation of hydroxyapatite (HAP) was observed. Furthermore, HAP layer formed was thicker on the specimen on which CaTiO₃ film was deposited at RT and annealed than that prepared at 873 K. The major difference between both specimens was the chemical properties of the outermost surface. In summary, CaTiO₃ thin film deposited at RT and followed by annealing at 873 K for 7.2 ks in air enhances calcium phosphate formation ability on Ti.     

Preparation of sheet like polycrystalline NiFe2O4 nanostructure with PVA matrices and their properties

Sheet-like nickel ferrite (NiFe₂O₄) has been synthesised with PVA matrices using co-precipitation technique. The sheet is formed from the oriented aggregation of single crystalline NiFe₂O₄ nanoparticles with PVA as the structure directing template. The synthesised materials are characterised based on X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), high-resolution scanning electron microscopy (HRSEM), Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM). The XRD results show that the nanocrystal contains single phase spinel structure of Fd3m space group. The existence of PVA with nanoparticles has been confirmed by FTIR spectra. The room temperature ferromagnetic property is exhibited by the as synthesised sample with high saturation magnetisation.     

Microstructural,chemical and textural characterization of ZnO nanorods synthesized by aerosol assisted chemical vapor deposition

ZnO nanorods were synthesized by aerosol assisted chemical vapor deposition onto TiO₂ covered borosilicate glass substrates. Deposition parameters were optimized and kept constant. Solely the effect of different nozzle velocities on the growth of ZnO nanorods was evaluated in order to develop a dense and uniform structure. The crystalline structure was characterized by conventional X-ray diffraction in grazing incidence and Bragg–Brentano configurations. In addition, two-dimensional grazing incidence synchrotron radiation diffraction was employed to determine the preferred growth direction of the nanorods. Morphology and growth characteristics analyzed by electron microscopy were correlated with diffraction outcomes. Chemical composition was established by X-ray photoelectron spectroscopy. X-ray diffraction results and X-ray photoelectron spectroscopy showed the presence of wurtzite ZnO and anatase TiO₂ phases. Morphological changes noticed when the deposition velocity was lowered to the minimum, indicated the formation of relatively vertically oriented nanorods evenly distributed onto the TiO₂ buffer film. By coupling two-dimensional X-ray diffraction and computational modeling with ANAELU it was proved that a successful texture determination was achieved and confirmed by scanning electron microscopy analysis. Texture analysis led to the conclusion of a preferred growth direction in [001] having a distribution width Ω = 20° ± 2°.     

A Green Chemical Synthesis and Characterization of Mn3O4 nanoparticles

Mn₃O₄ nanoparticles were synthesized via an ionic liquid (IL) assisted process at room temperature, which is rather difficult to achieve by other techniques. The synthesized product was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetry (TG), and vibrating sample magnetometry (VSM). The prepared material showed a high purity, while crystallite size and particle size agree well with each other, 17±2 and 19±3?nm, respectively, revealing nearly single crystalline character of nanoparticles. The product contains 4?wt% of adsorbed water and ionic liquid. This method provides a facile, one-step, and low-cost route for the synthesis of nanostructures of metal oxides. In addition, [BMIM]BF₄ could be collected and reused for subsequent reactions.     

Preparation of amino-acid-regulated hydroxyapatite particles by hydrothermal method

The hydroxyapatite nanorods (about 80 nm in length and 15 nm in width) with uniform size were achieved by hydrothermal method at 100 °C and pH 10 in the presence of alanine and glutamic acid. A special instillment order was used and the prepared powders were characterized for phase composition by X-ray diffraction and Fourier Transform infrared spectroscopy. The size and morphology of HAP nanoparticles were studied by Transmission electron microscopy. The characterization showed that the amino acid could induce the synthesis of hydroxyapatite nanoparticle and control HAP crystal growth when HAP crystal was formed. An instable monetite phase (CaPO₃OH) was found in the progress of ACP transforming to HAP.     

Green and gentle synthesis of Cu2O nanoparticles using lignin as reducing and capping reagent with antibacterial properties

In this work, Cu₂O nanoparticles of a particular shape were prepared by an eco-friendly, gentle and low-cost synthetic method using lignin as a reducing and capping reagent. Structure and morphology of the Cu₂O nanoparticles were characterised by high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction (XRD) and Fourier-transform (FT-IR) spectroscopy. The results established that Cu₂O nanoparticles coated by lignin showed a particular shape. The morphology of Cu₂O nanoparticles presented as some loose accumulation of particles just like broccoli, and the particle size range was between 100 and 200 nm. And, the XRD revealed the structure of crystalline of the Cu₂O nanoparticles. In addition, the sterilisation of Cu₂O nanoparticles on Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) was also investigated. The Cu₂O nanoparticles showed effective bactericidal activity against E. coli and S. aureus. The antibacterial rate could get 100% after 30 min with 4.0 g/L Cu₂O nanoparticles. Furthermore, the Cu₂O nanoparticles were confirmed to have low cytotoxicity.