Structural evolution of nanostructured barium titanate thin film sol–gel derived

Ferroelectric nanostructured barium titanate (BT) thin films derived by a modified sol–gel process were formed by a deep coating method on Si (100) substrate. In this work was investigated the influence of different types and amounts of water (free water directly added in process and crystalline water from barium precursors) and of different barium precursors (hydroxide and acetate) on the gel-structure evolution and the barium titanate thin film crystallization. The IR-spectroscopy and X-ray diffraction analysis were used for sample characterization. Experimental results show that crystalline water from barium hydroxide octahydrate stabilizes the cubic phase of barium titanate. Barium titanate crystallizes in the tetragonal form in thin films when sols were prepared with free water and Ba-acetate or Ba-hydroxide monohydrate as precursors. The type of Ba-precursor used in preparation of sols effects the rate of crystallization of the BT in thin films, making it slower in the case when as precursor was used Ba-acetate than Ba-hydroxides. The prepared BT-thin films demonstrated good adhesion towards substrate and were smooth and uniform.     

Relevance of thermal analysis for sol–gel-derived nanomaterials

It is well known that the first step of the sol-gel method consists in obtaining of amorphous or incipient crystallized materials that could be kept in the same state or could be transformed into vitreous or crystallized materials by adequate thermal treatments. In the present study, examples regarding the relevance of the thermal analysis methods for the characterization of the sol–gel-derived oxide systems, inorganic–organic hybrids, and composite nanomaterials are discussed. For the oxide systems, case studies regarding undoped and doped monocomponent oxides and polycomponent systems are discussed. In the case of inorganic–organic hybrids, the correlation between the type of precursors and the thermal behavior is presented. For the composite nanomaterials, examples for thermal behavior of two types of nanocomposites, namely both compositionally and structurally different, as well as inorganic–organic hybrid sol-gel nanocomposites are shown. In all studied cases, the thermal analysis methods allow obtaining important information not only on thermal behavior but also on the chemical composition of the as-prepared gels and powders. Different structural investigations methods (XRD, FTIR, and Raman) sustain the results obtained by thermal investigations.

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Proton conduction in nanopores of sol–gel-derived porous glasses and thin films

Nanoporous glasses and nanoporous thin films were prepared using sol–gel method, and proton conductivities in nanopores of sol–gel-derived porous glasses and thin films are overviewed in this paper. Proton motions inside nanopores were monitored by impedance and nuclear magnetic resonance (NMR) spectroscopies. The impedance data is correlated with the proton motion in bulk scale, whereas NMR data is correlated with that in nanometer scale, respectively. From the comparison of the activation energies obtained from impedance and NMR spectroscopies, percolation of proton conducting path and its relation to the amount of absorbed water molecules are shown. In the case of nanoporous thin films, directions of pores can be controlled by using cationic and non-ionic surfactants. Relationship between direction of pores and proton conductivity is discussed based on impedance test results.     

Thermoplasticity of sol–gel-derived titanoxanes chemically modified with benzoylacetone

Titanium tetra-n-butoxide was hydrolyzed in the presence of benzoylacetone (BzAc), and the solution obtained was concentrated and served for spin-coating or dropping on substrates, followed by successive drying at 120, 200 and 250 °C. The dried products were transparent and amorphous, and the infrared absorption and Raman spectroscopic studies showed that BzAc forms chelate rings. Thermomechanical analysis showed that the 120 and 200 °C-dried products showed steep, thermoplastic shrinkage at around 30 and 70–85 °C, respectively, whereas the 250 °C-dried product did not show thermoplasticity. Thus as the drying temperature was increased, the thermoplasticity appeared at a higher temperature and finally disappeared. These changes in thermoplasticity with drying temperature were concluded to result from the progress of condensation between titanoxane polymers and/or clusters, which was evidenced in gel permeation chromatographic analysis.     

Synthesis and characterization of nanocrystalline tin oxide by sol–gel method

Nanocrystalline SnO₂ particles have been synthesized by a sol–gel method from the very simple starting material granulated tin. The synthesis leads a sol–gel process when citric acid is introduced in the solution obtained by dissolving granulated tin in HNO₃. Citric acid has a great effect on stabilizing the precursor solution, and slows down the hydrolysis and condensation processes. The obtained SnO₂ particles range from 2.8 to 5.1 nm in size and 289–143 m² g⁻¹ in specific surface area when the gel is heat treated at different temperatures. The particles show a lattice expansion with the reduction in particle size. With the absence of citric acid, the precursor hydrolyzes and condenses in an uncontrollable manner and the obtained SnO₂ nanocrystallites are comparatively larger in size and broader in size distribution. The nanocrystallites have been characterized by means of TG-DSC, FT-IR, XRD, BET and TEM.     

Prediction of hydroxyapatite crystallite size prepared by sol–gel route: gene expression programming approach

Excellent biocompatibility and its similar biological characteristics to bone apatite, extensively expand the hydroxyapatite (HA) usage in bioimplant applications. The crystallite size of HA is one of the most administrated parameter for determination of reaction rate at the interface of artificial/natural bones. This study tried to propose a new predictive model by employment of the gene expression programming (GEP), i.e., a powerful soft computing technique, to estimate the crystallite size of HA that were prepared by sol–gel route. Firstly, 37 different reliable experiments were carried out considering the type of phosphor precursor, pH, drying temperature, aging time, temperature and time of calcination as practical parameters as input variables, and HA crystallite size as output variable. Absolute fraction of variance (R²), mean absolute percentage error (MAPE), root relative squared error (RRSE), and mean squared error (MSE) were considered to validate the most appropriate GEP model/s. The experiment results were divided randomly into 29 training sets and 8 testing sets. Finally, the best model was selected in R²?=?0.9929, MAPE?=?2.8, RRSE?=?0.0956, and MSE?=?1.7. The results of simulation confirmed the unique features of GEP for the determination of HA crystallite size prepared by sol–gel route.

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Predicted vs. experimental HA crystallite size through GEP-3, GEP-8 and GEP-6 models in (a) training phase, and (b) testing phase.

     

Synthesis and characterization of sol–gel-derived molecular imprinted polymeric materials for cholesterol recognition

The sol–gel-derived host matrices are well known for biosensor applications where various types of organic and biological molecules can be immobilized and can act as recognition elements. The molecular imprinting technology is an attractive alternative method where expensive and labile biorecognition elements can be replaced by molecular imprinted polymers (MIPs), which are capable of recognizing a target molecule of an interest. In the present study, hybrid sol–gel MIPs were synthesized in the form of crushed powder (CP) by both non-hydrolytic and hydrolytic method for cholesterol recognition. These MIPs were characterized by scanning electron microscopy (SEM), fourier transform-infrared (FT-IR), liquid chromatography-mass spectrometry (LC–MS) and nitrogen adsorption–desorption isotherm measurements. The template molecule was extracted by means of soxhlet extraction and calcination method. The cholesterol adsorption experiments were performed by using non-imprinted (NI) and extracted crushed powder (ExCP) and the percentage of adsorption was determined by measuring the residual quantity in the analyte solution using Liebermann-Burchard (L-B) reagent. The adsorption studies with non-imprinted crushed powder (NICP) showed interference with L-B reagent as well as non-specific binding between analyte molecules and silica matrix. The percentage of adsorption or rebinding was found to be higher for phenyl triethoxysilane (PhTEOS)-derived ExCP (composition 3) which was synthesized by the aqueous sol–gel processing method at low pH as compared to PhTEOS-derived (composition 1) and 3-aminopropyltriethoxysilane (APTES)-derived ExCP (composition 2) prepared by non-hydrolytic method. The reusability of used ExCP after re-extraction was also investigated. The various factors affecting rebinding of template molecules were discussed along with interference study. The study provided information on molecular imprinting of cholesterol in sol–gel matrix and highlighted the importance of characterization of MIPs before applying it for sensing applications.     

Improved optical and electrical properties of sol–gel-derived boron-doped zinc oxide thin films

Sol–gel spin-coating was used to grow zinc oxide (ZnO) thin films doped with 0–2.5 at.% B on quartz substrates. The structural, optical, and electrical properties of the thin films were investigated using field-emission scanning electron microscopy, X-ray diffraction (XRD), photoluminescence (PL), ultraviolet–visible spectroscopy, and van der Pauw Hall-effect measurements. All the thin films had deposited well onto the quartz substrates and exhibited granular morphology. The average crystallite size, lattice constants, residual stress, and lengths of the bonds in the crystal lattice of the thin films were calculated from the XRD data. The PL spectra showed near-band-edge (NBE) and deep-level emissions, and B doping varied the PL properties and increased the efficiency of the NBE emission. The optical transmittance spectra for the undoped ZnO and boron-doped zinc oxide (BZO) thin films show that the optical transmittance of the BZO thin films was significantly higher than that of the undoped ZnO thin films in the visible region of the spectra and that the absorption edge of the BZO thin films was blue-shifted. In addition, doping the ZnO thin films with B significantly varied the absorption coefficient, optical band gap, Urbach energy, refractive index, extinction coefficient, single-oscillator energy, dispersion energy, average oscillator strength, average oscillator wavelength, dielectric constant, and optical conductivity of the BZO thin films. The Hall-effect data suggested that B doping also improved the electrical properties such as the carrier concentration, mobility, and resistivity of the thin films.     

Structural and optical properties of Na doped ZnO nanocrystalline thin films synthesized using sol–gel spin coating technique

Sodium (Na) doped Zinc oxide (ZnO) thin films have been deposited on a glass substrate by the sol–gel spin coating method. Effect of doping with various percentages of Na at a particular annealing temperature of 500 °C is studied. The samples were characterized by X-ray diffraction (XRD), micro-photoluminescence, Raman and Polarized Raman spectroscopy. The X-ray diffraction and micro-Raman spectroscopy confirmed the presence of Na substitution in zinc oxide and the wurtzite structure of the lattice is retained. An enhancement of resonant Raman scattering processes as well as longitudinal optical phonon overtones up to the fifth order were observed in the micro Raman spectra. The similar values of depolarization ratios obtained from Polarized Raman studies recommend no change in the symmetry. Photoluminescence showed a strong emission peak in the near UV at 3.2 eV and negligible visible emission.     

Synthesis and electrochemical characterization of sol–gel-derived RuO2/carbon nanotube composites

Ruthenium oxide was coated on multiwalled carbon nanotubes (MWCNTs) to obtain nanocomposite electrode which has a good response to the pH. To synthesize this electrode, gold and cobalt were coated on a stainless steel 304 substrates, respectively, and then, vertically aligned carbon nanotubes were grown on the prepared substrates by chemical vapor deposition. Gold reduced activity of the stainless steel, while cobalt served as a catalyst for growth of the carbon nanotube. Ruthenium oxide was then coated on MWCNTs via sol–gel method. At last, different techniques were used to characterize the properties of synthesized electrode including scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction, and cyclic voltammetry. SEM results showed that the length of the carbon nanotubes varied with reaction time, and in this research, it was maintained around 9 μm with a diameter about 100 nm. Electrochemical analysis revealed that optimum sol concentration and heat treatment temperature to meet the best pH sensing response were 0.1 M RuCl₃ sol and 200 °C, respectively. Moreover, the obtained electrode represented a linear and near-Nernstian response (about ?63 mV/pH) throughout the whole pH range (2–12) of Britton–Robinson buffer solutions.     

Preparation and characterization of nanocrystalline Ca-doped CeO2 by sol–gel process

The reactivity of CeO₂ is determined by grain size and oxygen vacancies, which can be achieved by doping elements with less oxidation state into CeO₂. In this study nanocrystalline Ca-doped CeO₂ sol was synthesized from the reaction of hydrate cerium (III) nitrate and calcium nitrate tetrahydrate in alcohol solution after being calcined at 600?°C. X-ray diffraction as well as selected area electron diffraction gave evidence that the synthesized Ca-doped CeO₂ samples were well crystalline and had a cubic fluorite structure. TEM observation revealed that Ca-doped CeO₂ was composed by nanoparticles with grain size around 8?nm. The Raman spectrum of pure CeO₂ consists of a single triple degenerate F_2g model characteristic of the fluorite-like structure. In the Ca-doped CeO₂ sample, two additional low-intensity Raman bands were detected, thus confirming the formation of the solid solution. The synthesized nanometric powder is expected to be used in solid oxide fuel cells as well as in the catalytic treatment of automobile exhaust fumes.     

Effect of particle size,dispersion, and particle–matrix adhesion on W reinforced polymer composites

W dispersed mixed polymers of ethylene propylene monomer and high density polyethylene were prepared by means of a twin-screw extruder by the conventional technique using a co-rotated two-roll mill. The W nanoparticles used as filler were prepared by pulse wire evaporation then coated with low-density polyethylene (LDPE) as polymeric surfactant. Surface treatment of the nanoparticles with LDPE was conducted to enhance the wettability and lubrication of the fillers in the polymer matrix. According to SEM images and mechanical properties, dispersion of W/LDPE nanoparticles in the polymer matrix was homogeneous, and adhesion of the nanoparticles to the matrix was strong. The polymer nanocomposites had better mechanical properties than those containing dispersed micro-W powder. The γ-ray attenuation factor of nanofiller-reinforced composites was substantially enhanced compared with that containing micro filler.     

The influence of cobalt incorporation and cobalt precursor selection on the structure and bioactivity of sol–gel-derived bioactive glass

Cobalt (Co) is a potential therapeutic ion used to enhance angiogenesis through a stabilizing effect on hypoxia-inducible factor 1 alpha (HIF-1α), and its incorporation into the structure of bioactive glass is a promising strategy to enable sustained local delivery of Co to a wound site or bone defect. Here Co-releasing bioactive glasses were obtained through the sol–gel method, comparing cobalt nitrate and cobalt chloride as precursors. The effect of using different Co precursors on the sol–gel synthesis and in the obtained bioactive glass structure, chemical composition, morphology, dissolution behaviour, hydroxycarbonate apatite (HCA) layer formation was investigated. When the chloride salt was used as Co precursor, evidence of crystalline cobalt (II, III) oxide (Co₃O₄) phase formation was found, along with the presence of Co³⁺ species as evaluated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), whereas an amorphous glass containing mainly Co²⁺ species was obtained when the nitrate salt was the Co source. The presence of a crystalline phase decreased the surface area and pore volume of the final glass, consequently reducing the Co-release rate. Evidence of HCA layer formation after immersion in simulated body fluid (SBF) was still found when different precursors were used, although the rate of formation was reduced by the presence of Co. Therefore, this study showed that Co incorporation and the proper selection of the precursor could affect the final material structure, and properties, and should be considered when designing new bioactive glass compositions for tissue engineering applications.

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Synthesis and characterization of hydroxyapatite obtained from different organic precursors by sol–gel method

The synthesis of four types of hydroxyapatite synthesized from calcium chloride and four different organic phosphites is presented. The method of synthesis chosen is the sol–gel route, which has a number of advantages compared to other methods, like the intimate contact between reactants and the milder synthesis conditions. The samples were thermally treated, the TG/DTG/DTA curves being obtained at four heating rates, namely: 7, 10, 12 and 15 °C min⁻¹. The samples were characterized before and after the thermal treatment using FT-IR analysis. The FT-IR spectra certified that the formed compounds represent hydroxyapatite. Based on the information from the TG curves and IR spectra interpretation, a reaction mechanism was proposed.