Synthesis and characterization of sol–gel alumina nanofibers

Abstract Alumina nanofibers of high aspect ratio with surface area of >300 m² g⁻¹ has been prepared successfully in bulk quantities by the sol–gel method. The synthesis parameters including the binary water–alcohol solvent system to aluminium isopropoxide ratio, pH, type of solvent and aging temperature affect the uniformity and formation of nanofibers. It is proposed that alumina nanofibers were formed by the curling of the nanosheets upon condensation after the hydrolysis. The phase evolution of alumina nanofibers from pseudoboehmite to α phase has been shown by XRD and FTIR. ²⁷Al NMR investigations show that the Al atoms are six and four coordinated. The morphology of the alumina nanofibers does not change much as the calcination temperature was increased. In addition, the average pore size increases and the BET surface area decreases as a function of calcination temperature. The thermal behavior of alumina nanofibers was investigated by TGA. Graphical Abstract      

Influence of process parameters on the sol–gel synthesis of nano hydroxyapatite using various phosphorus precursors

Hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ has attracted widespread interest from both orthopedic and dental fields due to its excellent biocompatibility and tissue bioactivity properties. Since nanophase materials can mimic the dimensions of constituent components of natural tissues, the implants developed from nanophase material could serve as a successful alternative. However, the defects of hydroxyapatite ceramics, mainly brittleness and low fracture toughness, have been overcome by the use of nanophase hydroxyapatite coatings on the implant surfaces that integrate the good mechanical properties of metals and the bioactivity of hydroxyapatite. In the present investigation, Sol?Cgel hydroxyapatite was prepared from two different phosphorus precursors such as triethyl phosphate and phosphorus pentoxide respectively with calcium nitrate tetrahydrate as a calcium precursor. The effects of pH and liquid P³¹ Nuclear Magnetic Resonance spectroscopy for the solution aged at different periods were investigated and the synthesized hydroxyapatite powder was characterized by Transmission electron microscopy, X-ray Powder Diffraction, Fourier transform infrared spectroscopy and thermal analysis respectively. In order to fully understand the bioactivity of the synthesized materials, they were coated on 316L Stainless Steel implant surface by spin coating method at the spin speed of 2,000 Revolutions per minute. The effect of nanoparticles on the surface of 316L Stainless Steel implant was studied by adhesive strength measurements. The corrosion resistance property of the hydroxyapatite coatings was evaluated by electrochemical impedance analysis. From the results, it was observed that the hydroxyapatite coatings obtained from different precursors have very high resistance to corrosion with higher adhesive strength.     

Aqueous sol–gel synthesis and thermoanalytical study of the alkaline earth molybdate precursors

The preparation and characterization of the M′–Mo–O nitrate–tartrate (M′ = Mg, Ca, Sr, and Ba) gels, which were produced by the simple aqueous sol–gel method and calcined at 500, 600, 700, 800, 900, and 1,000 °C temperatures are reported. The crystalline alkaline earth metal molybdates (MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄) and as-prepared M′–Mo–O nitrate–tartrate gels investigated by thermal analysis (TG/DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). TG/DSC analysis showed the possible decomposition mechanism of synthesized gels. XRD studies allowed the identification of main types of crystalline structures in the MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄ systems. Moreover, SEM analysis revealed the changes of surface morphology of the final compounds depending on annealing temperatures.     

Surface sol–gel synthesis of silica films on polyimide substrate

Silica films were grown on polyimide substrate using surface sol–gel reaction, and the film growth process was characterized by ellipsometry, atomic force microscopy, and X-ray photoelectron spectroscopy. On the activated polyimide surface, silica film was grown by sequential immersion in SiCl₄ solution and H₂O. The thickness of silica films is linear with the depositing cycle, about 5.0 nm per cycle. The silica films present an island-like growth type and are not a strict equilibrium SiO₂ structure. Moreover, the result of the tensile test suggests that the silica films have a good adhesion to the polyimide substrate.     

Non-hydrolytic sol–gel synthesis of tantalum sulfides

Non-hydrolytic sol–gel synthesis provides a low temperature solution based approach to solid-state materials. In this work, reactions of TaX₅ (X = F, Cl, Br, I) with the thio-ethers di-tert-butylsulfide and hexamethyldisilathiane were carried out in chloroform or acetonitrile. The influence of synthetic parameters such as temperature, reaction time, starting sulfur to tantalum ratio, and solvent volume were explored, and optimized conditions for the preparation of phase pure crystalline TaS₂ were established. Amorphous powders were recovered for most of the samples, but crystalline 1T- and 3R-TaS₂ modifications could be selectively prepared by heat treatments of the as-recovered precursors at 700 and 800 °C, respectively. The crystallite sizes could be adjusted by tuning the starting sulfur to tantalum ratios, and by choice of solvent. For specific conditions, nanocrystalline 1T-TaS₂ was directly recovered from solution. To our knowledge, this is the first time that crystalline TaS₂ was directly obtained from low temperature solution based routes.     

Surface characterization and dissolution study of biodegradable calcium metaphosphate coated by sol–gel method

Coatings of biomedical implant surfaces by a bioactive calcium phosphate film render bioactivity to the implant surface and shorten the healing time. In this present study, calcium metaphosphate (CMP) sol was synthesized by sol–gel method and coated onto the titanium alloys (Ti-6Al-4V). CMP sol was first synthesized by reacting Ca(NO₃)₂4H₂O (Sigma–Aldrich 99%, USA) with (OC₂H₅)₃P (Fluka 97%, Japan) in methyl alcohol. A stoichiometric Ca/P ratio of 0.5 was obtained by varying the amounts of the reactants. Sol was then coated on Ti-6Al-4V substrates by spin coating. The coated-specimens were then dried at 70 °C for 24 h, followed by a heat treatment at 650 °C for 1 h. Structural and chemical properties of the coatings were evaluated using XRD, SEM, and EPMA. The dissolution property of the coated-CMP layer was investigated by immersing the samples in the simulated body fluid (SBF) for 1, 3, 7 and 21 days. The concentration of Ca²⁺ released was measured using ICP. After heat treatment, SEM indicated a smooth and uniform CMP layer, with CMP grains of approximately 100 nm. The CMP phase was identified with δ-CMP (JCPDS #9-363). After immersion in SBF, coatings were observed to be roughened and porous. The concentration of Ca²⁺ in SBF was observed to increase over time, indicating continuous dissolution. The presence of titanium oxide phosphate compounds were also observed on CMP surfaces after immersion. It was thus concluded that the ability to control coating properties as well as the need for low heat treatment temperature offers advance for the use of CMP coating by sol–gel process on Ti-6Al-4V implant surfaces.     

Different morphologies of ZnO nanostructures via polymeric complex sol–gel method: synthesis and characterization

Various morphologies of ZnO nanostructures, such as nanoparticles, nanorods and nanoflowers have been achieved controllably by polymeric sol–gel method. In this approach, zinc nitrate Zn(NO₃)₂·6H₂O, citric acid and ethylene glycol were used as the source of Zn²⁺, the chelating agent and the solvent agent, respectively. The microstructure of the ZnO nanostructures was characterized by X-ray diffractometry, scanning electron microscopy with the energy dispersive X-ray spectroscopy, transmission electron microscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy. The effect of ethylene glycol to citric acid mole ratio on the morphology and structure of the products was discussed. The ZnO nanoparticles with diameter between 24 ± 2 nm was obtained with EG:CA mole ratio equal to 2:1. The optical properties of as-obtained power were investigated by ultraviolet–visible spectroscopy.     

Aqueous sol–gel synthesis of lanthanum phosphate nano rods starting from lanthanum chloride precursor

Aqueous sol–gel technique is reported for synthesizing nanosize, rod shaped lanthanum phosphate particles starting from lanthanum chloride, which is suitable for variety of applications such as machinable ceramics, thermal barrier coatings and luminescent materials. The phosphate particles are having rod like morphology having an overall size in the range 25–100 nm and with an average aspect ratio 4. The morphology is retained even after calcination at 800 °C. The average crystallite size for the as prepared particles was calculated to be 8 nm using Scherrer equation applied on X-ray diffraction (XRD) data. The particles obtained were characterized using photon correlation spectroscopy (PCS), FT-IR spectroscopy, XRD and Electron Microscopy techniques (TEM and SEM). The phase stability was found using thermo gravimetric analysis. The surface wettability monitored using tensiometer through dynamic contact angle method indicated that lanthanum phosphate surface possesses considerable hydrophobic character.     

ITO films on glass substrate by sol–gel technique: synthesis,characterization and optical properties

The present paper extensively demonstrates synthesis, characterization and optical properties of semiconductor indium tin oxide (ITO) thin films on glass substrate using sol–gel technique for gas sensor applications. Turbidity, pH values, wettability and rheological properties of the prepared solutions were measured to determine solution characteristics by turbidimeter, pH meter, contact angle goniometer and rheometer machines prior to coating process. Thermal, structural, microstructural, mechanical and optical properties of the coatings were characterized by differential thermal analysis–thermogravimetry (DTA/TG), fourier transform infrarared, X-ray diffraction (XRD), scanning electron microscopy, scratch tester, refractometer and spectrophotometer. Four different solutions were prepared by changing solvent concentration. Turbidity, pH, contact angle and viscosity values of the solutions were convenient for coating process. Glass substrates were coated using the solutions of InCl₃, SnCl₂, methanol and glacial acetic acid. The obtained gel films were dried at 300 °C for 10 min and subsequently heat-treated at 500 °C for 10 min in air. The oxide thin films were annealed at 600 °C for 60 min in air. DTA/TG results revealed that endothermic and exothermic reactions are observed at temperature between 70 and 560 °C due to solvent removal, combustion of carbon based materials and oxidation of Sn and In. The spectrum of ITO precursor film annealed at 500–600 °C shows an absence of absorption bands corresponding to organics and hydroxyls. In₂Sn₂O_7−x phase was dominantly found as well as SnO₂ with low intensity from XRD patterns. It was found that surface morphologies of the film change from coating island with homogeneous structures to regular surface and thinner film structures with increasing solvent concentration. The films prepared from the solutions with 8 mL methanol have better adhesion strength to the glass substrate among other coatings. Refractive index, thickness and band gap of ITO thin films were determined to be 1.3171, 0.625 μm and 3.67, respectively.     

FTIR study of the sol–gel synthesis of cementitious gels: C–S–H and N–A–S–H

The study explored the compatibility between the main product of Portland cement hydration and the main product of the alkali activation of fly ash: C–S–H and N–A–S–H gels, respectively. Both gels were synthesized with laboratory reagents at different pH values. Blends of the two were synthesized as well, using the sol–gel procedure. All the gels were characterized with Fourier transform IR spectroscopy (FTIR). The gels synthesized with this procedure were shown to precipitate together with a silica-rich gel. In addition, the pH level was found to play a determinant role in both C–S–H and N–A–S–H gel synthesis. The C–S–H gel is the major phase formed at pH > 11 and N–A–S–H gel for pH > 12. The results relating to the joint synthesis of the two (C–S–H and N–A–S–H) gels were not conclusive. Technique used for the characterization failed to differentiate between them in the blended material.

Preparation and characterization of Ce-doped and Zr-doped sol–gel inks of titanium alkoxide

Inks of titanium diisopropoxide bisacetylacetonate ([(CH₃)₂CHO]₂Ti(C₅H₇O₂)₂) are suitable for the fabrication of photonic bandgap materials by direct ink writing (DIW). Using this method we are able to obtain micro-periodic titania (TiO₂) structures with high refractive index by calcining the structures built with those inks. Calcining at high temperatures causes titania grain growth and surface roughness of the structure, which has an influence over its optical properties. In order to inhibit the grain growth of titania nanocrystals when the structures are calcined, we have synthesized using the sol–gel technique titanium diisopropoxide bisacetylacetonate inks doped with Cerium (III) nitrate hexahydrate (Ce(NO₃)₃·6H₂O) and Zirconyl nitrate hydrate (ZrO(NO₃)₂·xH₂O). The grain growth process of titania powders derived from the calcined doped sol–gel inks during various heat-treatment programs has been investigated by the X-ray line-broadening analysis. It was demonstrated how the dopants reduce the grain growth of the rutile phase after heat treatment. The influence of the dopants on the rheological behaviour of doped inks were studied and compared with the undoped. The flow and oscillation curves as a function of time demonstrate that doped inks have the same rheological behaviour than undoped inks. Thermogravimetric analysis also proves that doped inks keep the same mass loss after calcination than undoped inks. These results show how doped inks can be applied for DIW in the same conditions than undoped inks with a significant reduction of titania grain growth.     

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.     

Synthesis and characterization of nanostructured aluminum borate by sol–gel method

Nanostructured aluminum borate was synthesized using sol?Cgel technique. X-ray diffraction study revealed that the synthesized aluminum borate was single crystal. These nanorods have very uniform diameter. High-resolution transmission electron microscope images indicate that aluminum borate is well crystallized. The alternating current (AC) conductivity of the aluminum borate was studied as a function of temperature and frequency. The AC conductivity mechanism of the aluminum borate was found to be proportional to ??^s. The exponent s is almost independent with temperature. This suggests that AC conductivity mechanism of the aluminum borate can be interpreted by localized hopping model.     

Synthesis and characterization of lead oxide nano-powders by sol–gel method

Our goal in this research was to obtain lead oxide nano-powders by sol–gel method. In this method, lead oxide nano-powders were synthesized through the reaction of citric acid (C₆H₇O₈·H₂O) solution and lead acetate [Pb(C₂H₃O₂)₂] solution as stabilizer and precursor, respectively. The effect of different parameters including calcination temperature, (molar ratio of citric acid to lead acetate) and drying conditions were investigated. The prepared lead oxide nano-powders were characterized by FT-IR spectroscopy, X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. The prepared PbO samples consist of the particles in the range of 50–120 nm or the thick plate like structures with thickness of 53 nm depending on the drying conditions.     

Effect of nickel and cobalt ions on low temperature synthesis of mullite by sol–gel technique

Synthesis of mullite has been achieved at a low temperature of 600 °C by sol–gel technique in presence of nickel and cobalt ions. Samples were characterized by DTA, XRD, FESEM and FTIR spectroscopy. Mullite formation was found to depend on the concentration of the ions to a certain extent. Highly crystalline spherical mullite particles of dimension 35 nm were obtained at 0.02 M nickel or cobalt concentration.