Acid catalyst concentration effect on structure and ion relaxation studies of Li2O–P2O5–B2O3–SiO2 glasses synthesized by sol–gel process

Lithium phosphoborosilicate (LPBS) glasses were synthesized through the sol–gel process by varying nitric acid concentrations as a catalyst. The sol–gel process was monitored through XRD and DSC to optimize the LPBS glass forming treatment. Characterization of LPBS glasses was conducted using XRD, FTIR and DSC techniques. Impedance measurements were carried out at different temperatures on LPBS samples synthesized by sol–gel process with various nitric acid concentrations and impedance data were analyzed using Boukamp equivalent circuit software. The conductivity of LPBS samples was calculated from analyzed impedance data and it was found that sample synthesized with 2.5 N nitric acid concentration showed the high conductivity σ = 2.28(±0.02) × 10⁻⁷ S cm⁻¹ at 443 K. Activation energy (E_a) is obtained from Arrhenius plots of dc conductivity and it is found to be 0.39 (±0.02) eV for the high conductance sample. Ac conductivity data were analyzed using Jonscher’s power law (JPL) and the power law exponent (s) exhibits a low s value for high conducting LPBS sample and a non-linear behavior with temperature. The electric modulus data were fitted with Kohlraush–William–Watts (KWW) stretched exponential function and modulus formalism is used to study the ionic relaxation behavior at different temperatures in LPBS glasses synthesized with varying nitric acid concentrations.     

Preparation of TiO2–Na2O glass by sol–gel method and structural characterization

The applicability of sol–gel process in glass formation of binary system, (100 − x)TiO₂–xNa₂O (x = 10, 20, 30), was investigated and the glasses were prepared successfully by the sol–gel process for the first time. The process of glass formation was checked by using X-ray diffraction measurement and DTA–TG analysis. In the baking step, a DTA peak related to the crystallization of gel was found. The short-range structure of glassified samples was studied by neutron scattering measurement. It is found from the results of neutron scattering measurement that the coordination number of O atom around Ti atom is about 4, and the O atoms around Ti atom form a planer square rather than a regular tetrahedron.     

Formation of photonic structures in Sm2+-doped aluminosilicate glasses through phase separation

Sm²⁺-doped Al₂O₃–SiO₂ glasses with three-dimensionally interconnected macroporous morphology have been prepared via the alkoxide-derived sol–gel process containing poly(ethylene oxide) and SmCl₃ · 6H₂O. The macroporous morphology is obtained by concurrently inducing the phase separation and sol–gel transition. When the macroporous aluminosilicate glasses doped with Sm²⁺ are irradiated with a visible light laser at the wavelength of 488 nm, a hole or a dip appears in the plot of fluorescence intensity versus the incident angle of laser beam, indicating that the valence state of Sm²⁺ is spatially modulated through the interference of multiply scattered light. The hole profile can be controlled by adjusting the macroporous morphology.     

Thermally stimulated luminescence of Ce and Tb doped SiO2 sol–gel glasses

Thermally stimulated luminescence (TSL) properties of cerium and terbium doped SiO₂ sol–gel glasses were studied after X-ray irradiation in the temperature range 10–700 K. The role of Ce³⁺ and Tb³⁺ as recombination centers was shown. The existence of a distribution of trap levels was observed; the activation energies of such a distribution were calculated to extend from about 8 × 10⁻³ eV up to 1.8 eV for both cerium and terbium doped sol–gel glasses. The effect of a post-densification thermal treatment on TSL properties was also analyzed.     

Negative dielectric loss phenomenon in porous sol–gel glasses

The broadband dielectric spectroscopy method was employed to investigate glasses of a fine porosity produced via regular and fast sol–gel routes with different catalysts. The study was carried out in the frequency range 20 Hz to 1 MHz and temperature interval −100 to +300 °C. The process discussed in the paper demonstrates unusual dielectric behavior. Dielectric losses of this process are negative, in certain regions of frequency and temperature, and the corresponding real part of the dielectric permittivity increases with increasing frequencies, according to Kramers–Kronig relationships. This exceptional process is located in different temperature regions for each sample. The concentration and type of acids, used as catalysts, influence the amplitude and the temperature–frequency ranges of the negative losses process (NLP). In order to decipher the physical nature of the process, the experimental study has been accompanied by a theoretical one. It was shown that the NLP in the porous sol–gel samples can be attributed to the local non-compensated matrix-anchored charges, which accumulate both inside the glassy matrix bulk and on the interface of the pores therein.     

Influence of TiO2 on proton conductivity in fuel cell electrolytes based on sol–gel derived P2O5–SiO2 glasses

P₂O₅–TiO₂–SiO₂ based glasses have been prepared by a sol–gel process. The glasses were characterized by structural, thermal, nitrogen adsorption–desorption and conductivity measurements. The structural formation has been confirmed by the FTIR and NMR analysis. The proton conductivity of the glasses increased linearly with increase in temperature. Glasses with an average pore size less than 2 nm showed higher values of proton conductivity in humid atmosphere. The conductivity value increased from 6.47 × 10⁻⁴ S/cm to 3.04 × 10⁻² S/cm at 70% RH in the temperature range 30–90 °C. We observed in fuel cell measurements that the performance of the E1 electrode is superior to that of the other electrodes at the same operating condition. The power density shows a similar pattern to current density.     

A structural study of sol–gel and melt-quenched phosphate-based glasses

Phosphate-based glasses have recently attracted much interest as a new generation of biomaterials because of their ability to react and dissolve in the physiological environment and eventually to be replaced by regenerated hard or soft tissue. A series of phosphate-based glasses containing 45 mol% P₂O₅ and various amounts of CaO and Na₂O were synthesized by sol–gel and melt-quenching techniques. A comparison between the structure of the sol–gel glass and the structure of the analogous melt-quenched glasses has been undertaken. A broad-based characterization approach combining different techniques has been used to investigate the short-range structure of the glasses and the effect of adding modifier oxides to the network structure (conventional and high energy X-ray diffraction, infra-red spectroscopy, ³¹P solid state magic angle spinning NMR spectroscopy). Sol–gel and melt-quenched glasses appear to have a similar structure, showing similar Qⁿ distributions and atomic correlations.     

Synthesis and bioactive properties of macroporous nanoscale SiO2–CaO–P2O5 bioactive glass

A macroporous nanoscale bulk bioactive glass (SiO₂–CaO–P₂O₅ system) was prepared by sol–gel co-template method. Porosimeter analysis showed that the as-synthesized bioactive glasses (BGs) had a porosity of 85% and exhibited a multimodal pore size distribution, nanopores (10–40 nm) and macropores (100 nm–10 μm). Morphological and structural characterizations showed the pores were interconnected with pore walls of about 250 nm in width and 1 μm in length. In vitro bioactivity test indicated that the as-synthesized bulk BGs exhibited faster apatite layer formation capability than the conventional sol–gel BGs. Additionally, the deposited layer was identified as hydroxycarbonate apatite, which is similar to the inorganic part of human bone.     

Influence of phosphate precursors on the structures of sodium aluminophosphate sols,gels and glasses

Transparent and homogeneous aluminophosphate gels and glasses have been widely synthesized through an aqueous sol–gel route, extending significantly the glass-forming range compared to that accessible via the melt-cooling route. Different phosphorus precursors, sodium polyphosphate (NaPO₃) and orthophosphate species (NaH₂PO₄ and/or H₃PO₄) were compared with regard to the macroscopic properties and the microscopic structure of the resultant gels and glasses as characterized by extensive high-resolution liquid- and solid-state NMR. Sodium polyphosphate solution results in a substantially wider composition range of homogenous gel formation than orthophosphate solutions, and the two routes produce significant structural differences in the sol and xerogel states. Nevertheless, the structures of the glasses obtained upon gel annealing above 400 °C are independent of the P-precursors used.     

Mesoporous bioactive glasses. I. Synthesis and structural characterization

Highly ordered mesoporous bioactive glasses (MBGs) with different compositions have been synthesized by a combination of surfactant templating, sol–gel method and evaporation-induced self-assembly (EISA) processes. The texture properties and compositional homogeneity of MBGs have been characterized and compared with conventional bioactive glasses (BGs) synthesized in the absence of surfactants by evaporation method. The formation mechanism (pore – composition dependence) and compositional homogeneity in the case of MBG materials are different from those in conventional BGs. Unlike conventional sol–gel-derived BGs that shows a direct correlation between their composition and pore architecture, MBGs with different compositions may possess similar pore volume and uniformly distributed pore size when the same structure-directing agent is utilized. The framework of MBG is homogeneously distributed in composition at the nanoscale and the inorganic species generally exists in the form of amorphous phase. MBGs calcined at temperatures ⩽1073 K exhibit ordered mesopores; at higher temperature such as 1173 K, the inorganic wall becomes crystalline and the mesostructure is collapsed. The leaching test of MBG in water indicates that MBGs may have excellent degradability in body fluid, which is important for prospective bio-applications.     

Tetracycline and propolis incorporation and release by bioactive glassy compounds

This study compares the release of tetracycline and propolis incorporated into four silica-based bioactive glassy systems. The bioactive glasses, with composition (SiO₂)x(P₂O₅)y(CaO)z, were prepared using a sol–gel process at room temperature. Tetraethoxysilane (TEOS), triethylphosphate, and calcium chloride were used as Si, P, and Ca precursors, respectively. The quantities of tetracycline and propolis incorporated were 2% in weight. For delivery assays, the samples were individually immersed in deionized water and buffered with tris-hydroxymethyl amino methane, pH 7.4, and kept in water bath (37 °C) for thirty days. Aliquots were withdrawn and analyzed by ultraviolet spectrophotometry in the tetracycline (270 nm) and propolis (420 nm) wavelengths. For the glass–tetracycline compounds, it was observed that four days after release had started all samples had released about 90% of the total tetracycline concentration. In contrast, 90% of the propolis was released in about 30 days’ time. Sample characterization was made using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopic (FTIR), and thermogravimetry (TG).     

Preparation and characterization of ZnO particles embedded in organic–inorganic planar waveguide by sol–gel route

Hybrid organic–inorganic waveguides based on ZnO-(3-glycidoxypropil)trimethoxisilane (GPTS) have been fabricated by sol–gel route. A transparent sol of ZnO was added to the GPTS host and the resulting sol was deposited on silica substrates by spin coating technique. Waveguides with different molar composition (100?x)GPTS?xZnO (x = 10, 20, 30) were investigated by different diagnostic techniques. Morphological measurements were carried out by means of an AFM apparatus, and a roughness of few nanometers was estimated for all the waveguides. Optical properties such as refractive index, thickness, number of propagating modes and attenuation coefficient were measured at 632.8, 543.5, 1319 and 1542 nm by the prism coupling technique as a function of the ZnO content. Photoluminescence measurements, upon excitation at 325 nm, showed a large luminescence band in the region between 350 and 600 nm with a main peak centered at about 380 nm, due to the presence of ZnO nanoparticles.     

Synthesis and structural characterization of P2O5–CaO–Na2O sol–gel materials

Ternary phosphate-based glasses in the system P₂O₅–CaO–Na₂O were synthesized using the sol–gel approach. Glasses in this system have the potential for use as bioactive materials. A mixture of mono- and dialkyl phosphate PO(OH)_3−x(OC₂H₅)_x (x = 1, 2) and alkoxides of sodium and calcium in an ethylene glycol solution were used as precursors. One of the compositions has also been synthesized by sonocatalysis (application of ultrasonic vibration to the sol). The systems synthesized, which remain fully amorphous even after calcination at 400 °C given the appropriate composition, have been characterized using X-ray diffraction (XRD). Thermal properties have been examined by means of thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The structure of the phosphate network has been studied as a function of composition using Fourier transform infrared spectroscopy (FT-IR) and ³¹P MAS NMR.     

Processing optimization and optical properties of 3-D photonic crystals

The synthesis optimization of three-dimensional photonic crystals (direct and inverse opals) is discussed in terms of the influence of processing parameters on the final optical quality. A colloidal/sol–gel route, starting with the self-organization of polystyrene microspheres into opal structures by convective self-assembly, followed by infiltration with a dielectric matrix precursor sol and heat treatment, has been followed. Several substrate hydrophilization methods have been tested and different substrates. Sol–gel infiltration of the opal template interstices with silica was achieved by dip-coating or micro-syringe application and it was followed by removal of the polymeric template. The concentration of the colloidal sol, containing polystyrene spheres of 235 or 460 nm in diameter, was optimized. The structural and optical properties of the opals and inverse opals have been studied by field emission scanning electron microscopy and optical reflectivity spectroscopy, in order to assess the relationship between their structure and the photonic properties obtained. By using borosilicate glass substrates hydrophilized with hydrochloric acid, colloidal photonic crystals of good quality have been obtained, with well ordered regions up to ～100 μm². By monitoring the effective refractive index change with relative humidity of the surrounding atmosphere, using spectroscopic ellipsometry with an environmental chamber, it was concluded that the present photonic crystals are suitable for humidity sensing applications.     

Reactions between sol–gel coatings and some technical glass substrates during consolidation

SiO₂ and Na₂O–SiO₂ coatings have been applied on float glass and other technical glass substrates by a sol–gel dip-coating process. After drying and baking these films at temperatures up to 500 °C and for times up to 1020 min, the in-depth profiles of the different constituents were measured by secondary neutral mass spectrometry (SNMS). Sn, Al, and Si turned out to be immobile, whereas a diffusion coefficient of ≈10⁻¹⁷ cm²/s could be evaluated for Mg at 500 °C for the transport from float glass into the films. Ca diffused a little faster, however, especially for the Na₂O–SiO₂ films a saddle point and finally a peak occurred in the interface region. This interface peak was even stronger for Na, showing quite anomalous profiles. The mechanism of this peak formation is explained mainly as an up-hill diffusion process. According to this model at the interface non-bridging –O⁻ ions are formed, whose electroneutrality has to be maintained by mobile cations like Na⁺ and Ca²⁺, even diffusing against their own concentration gradient. The other glass substrates, two borofloat glasses and an alkali-poor display glass showed similar but less pronounced effects.     

Spectroscopic studies of tungsten ions in PbO–PbF2–SiO2 glasses

40PbO–(10 ? x)PbF₂–50 SiO₂:xWO₃ (where x = 1 to 7 mol%) glasses are prepared in the glass forming region. Spectroscopic studies (UV–Vis absorption, ESR, IR) are carried out for these glasses. Interesting changes are observed in the spectroscopic parameters of these glasses when the concentration of WO₃ is changing in the glass matrix. Two absorption bands are observed around at 830 and 620 nm. ESR signal are measured at room temperature for these glasses, the strength of the signal is increased and hyperfine splitting is resolved with increasing the concentration of WO₃ in the glass matrix. IR transmission gives valuable information about the nature of bonds in the glass matrix. The physical parameters along with spectroscopic parameters are measured.     

Fe3+ doped SiO2 nanostructured gel-glasses: Structural,optical and magnetic properties

Transparent crack-free and bubble-free Fe³⁺ doped SiO₂ nanostructured gel-glasses were obtained by the sol–gel process. The process involves the hydrolysis and condensation of an appropriate molar ratio of tetraethoxysilane (TEOS), absolute ethanol, nitric acid and ferric nitrate, followed by stepwise annealing at temperatures ranging from 110 °C to 1000 °C. The structural variation of the gel-glasses and their influence on physical properties during annealing has been studied. It has been observed that monolithicity and chemical environment around Fe³⁺ in the gel-glasses are strongly dependent on the annealing temperatures. The colour of gel-glass samples is different for different annealing temperatures, mainly due to the different co-ordination state of Fe³⁺ and the generation of Fe₂O₃ colloids of size 20–60 nm in the silica matrix. The annealing process facilitates the tuning of the UV–visible transmission cut-off edge in high optical quality Fe³⁺ doped silica gel-glasses. A marked difference in the magnetic properties of these glasses is also observed with annealing temperatures.     

In vitro changes in the structure of a bioactive calcia–silica sol–gel glass explored using isotopic substitution in neutron diffraction

Bioactive sol–gel derived glass scaffolds bond to bone and their dissolution products stimulate new bone growth in vitro and in vivo; they may therefore be used to regenerate diseased or damaged bone to its original state and function in bone tissue engineering applications. We seek herein to cast light upon these reaction mechanisms by attempting to quantify changes in the atomic-scale structure of the glass scaffold as a result of in vitro reaction with simulated body fluid (SBF). We report the results of a study using neutron diffraction with isotopic substitution (NDIS) to gain new insights into the nature of the atomic scale calcium environment in bioactive sol–gel glasses. This is augmented by high-energy X-ray total diffraction. We have thereby begun to explore the nature of the principal stages to the generation of hydroxyapatite (i.e. the mineral ‘building block’ of bone) on the bioactive glass surface. The data are examined in light of our complementary solid-state NMR and computer modelling studies. The results reveal that the Ca–O environment in an SBF exposed (CaO)_0.3(SiO₂)_0.7 sol–gel glass, which initially comprises three distinct but partially overlapping correlation shells centered at 2.3 Å, 2.5 Å and 2.75 Å, preferentially loses the shortest length correlation. A Ca⋯H correlation appears at 2.95 Å. The surface deposited Ca⋯P environment consists of three partially overlapping, but nonetheless distinct, correlation shells, at 3.15 Å, 3.40 Å and 3.70 Å.     

Erbium- and ytterbium-doped sol–gel SiO2–HfO2 crack-free thick films onto silica on silicon substrate

Aware of the difficulties in applying sol–gel technology on the preparation of thin films suitable for optical devices, the present paper reports on the preparation of crack-free erbium- and ytterbium-doped silica: hafnia thick films onto silica on silicon. The film was obtained using a dispersion of silica-hafnia nanoparticles into a binder solution, spin-coating, regular thermal process and rapid thermal process. The used methodology has allowed a significant increase of the film thickness. Based on the presented results good optical-quality films with the required thickness for a fiber matching single mode waveguide were obtained using the erbium- and ytterbium-activated sol–gel silica:hafnia system. The prepared film supports two transversal electric modes at 1550 nm and the difference between the transversal electric mode and the transversal magnetic mode is very small, indicating low birefringence. Photoluminescence of the ⁴I_13/2 → ⁴I_15/2 transition of erbium ions shows a broad band centered at 1.53 μm with full width at a half maximum of 28 nm. Up-conversion emission was carried out under different pump laser powers, and just one transition at red region was observed.     

Effects of rehydration on Tb3+ spectroscopy in sol–gel glasses

Spectroscopy of sol–gel silicate glasses containing Tb³⁺ is used to investigate the diffusion of water from the atmosphere into annealed glass samples. In materials that are annealed to 900 °C the blue–violet ⁵D₃ → ⁷F_J fluorescence is comparable in intensity to green emission from the ⁵D₄ level. However, the ⁵D₃ emission is reduced to ∼5% of its original strength in several hours if glasses are exposed to ambient conditions. Re-annealing restores the original intensity of the ⁵D₃ fluorescence. The degree of fluorescence quenching is shown to depend strongly on initial preparation of the sol–gel materials and on annealing conditions.