Since the late 1960s, ceric hydrogen phosphates have attracted the attention of scientists due to remarkable ion exchange, sorption, proton-conduction and catalytic properties. In this work, through the application of various solvents, we, for the first time, have obtained monolithic aerogels based on ceric hydrogen phosphates with high porosity (~99%) and extremely low density (~10?μg/cm3). The composition and structure of aerogels were thoroughly studied with XRD, TEM, SEM, XPS, low temperature nitrogen adsorption methods, TGA/DSC, Fourier-transform infrared spectroscopy (FTIR) and small-angle neutron scattering (SANS). The aerogels were found to belong to the fibrous macroporous aerogels family.
Dual-network aerogels (HPSA) with improved mechanical property and thermal insulation were prepared by vacuum impregnation of HNTs/PVA aerogels (the first network aerogel, HPA) in tetraethoxysilane (TEOS). Scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, and N2 adsorption–desorption analysis were used to study micromorphology and microstructure of HPSA, while compression tests and thermal conductivity tests were used to investigate related properties. The results showed that the dual-network frame was successfully constructed, this enabled HPSA to display enhanced compressive properties with increased HNTs content. The addition of silica sol improved the mesoporous characteristics including specific surface area and pore volume and also reduced the thermal conductivities. The first network made it possible for HPSA to possess good mechanical property, while SiO2 aerogel allowed HPSA greater thermal insulation. The obtained aerogel samples exhibited a high compressive strength (i.e., 1.36?MPa) and a low thermal conductivity (i.e., 0.022?W/(m?K)). HNTs/SiO2 dual-network aerogels with improved strength and thermal insulation could show great potential in a wide variety of applications.
Pain is already known to cause delays in wound healing. Therefore, providing suitable therapeutic solutions for less painful wound healing should attract significantly more attention in the development of future novel wound care solutions. In this study, the nonsteroidal anti-inflammatory drug (NSAID) diclofenac sodium (DCS) and the local anesthetic lidocaine (LID) were combined in wound-dressing materials prepared using two different techniques. We compared the release of the mentioned drugs from a 3D bioprinted carboxymethyl cellulose (CMC)-based scaffold with their release from an electrospun CMC-based nano-mesh. As a well-defined and controlled drug release is of great importance for any material to be used in the clinics, we have put a lot of effort into a systematic evaluation of both prepared materials, using the two different techniques. For this purpose, we used different methods to characterize their physico–chemical, structural and morphological properties. Further, the influence of the respective preparation procedures were tested on the release profile and biocompatibility with human skin cells. Both prepared materials were proven biocompatible. We have also shown that the drug release of both incorporated drugs was affected significantly by the preparation method. The resulting release performances of the respective materials were shown to benefit the treatment of specific wounds. Finally, several advantageous properties could be achieved by combining both preparation techniques for the preparation of a single dressing.
A facile procedure was developed for the production of Al2O3 aerogels modified with tris(8-hydroxyquinolinato)aluminum complex (AlQ3). The addition of 8-hydroxyquinoline during the stage of alumina lyogel formation was found to increase gelation duration. The translucent monolithic aerogels were obtained by supercritical drying of lyogels in CO2. The composition and properties of aerogels were analyzed using low-temperature nitrogen adsorption, helium pycnometry, IR spectroscopy, UV–visible spectroscopy, luminescence spectroscopy, powder X-ray diffraction, scanning and transmission electron microscopy, and thermogravimetry combined with mass spectrometry. The obtained aerogels had low density (0.15–0.18?g?cm?3), high specific surface area (480–550?m2/g), high porosity (90–95%), and showed bright luminescence upon excitation in the UV range.
Trimethylethoxysilane (TMES) has been recognized as a good co-precursor to increase the degree of hydrophobicity during the synthesis of a silica aerogel because of its methyl groups. Therefore, some physical properties of silica aerogels, including the contact angle and porosity, were investigated using TMES as a co-precursor at different molar ratios with the main precursor such as tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS). In contrast to TMES, most silylating agents such as hexamethyldisilazane (HMDZ) and trimethylchlorosilane (TMCS) have been used for surface modification because of their ability to enhance the hydrophobicity of the aerogel surface. This work examines the silylation effect, which includes increasing hydrophobicity by TMES to determine the possibility of using it as an alternative silylating agent during ambient pressure drying in the synthesis of sodium silicate-based silica aerogel. In addition, the physical properties of sodium silicate-based silica aerogels with silylation under different TMES/TMCS volume ratio are investigated. The physical properties of sodium silicate-based aerogels can be changed by the TMES/TMCS volume ratio during the surface modification step. Aerogels with a high specific surface area (458?m2/g), pore volume (3.215?cm3/g), porosity (92.7%), and contact angle (131.8°) can be obtained TMES/TMCS volume ratio of 40/60.
Natural dyes, namely, indigo carmine, cochineal carmine, curcumin and annatto, were encapsulated in silica by a sol-gel method and applied in the dyeing of different textile fibers by exhaustion. For comparative reasons, dyeing using the free (non-encapsulated) bare dyes was also carried out. The hybrid materials were analyzed by a set of techniques to investigate their elemental, structural, textural and morphological properties, and the results showed that it was possible to obtain stable natural dyes for applications in textile dyeing. The silica-structured dyes showed better affinities with the fibers (WO, PA, PAC and PET) in dyeing with cochineal carmine, while cotton (CO) showed better affinities with the encapsulated curcumin and annatto dyes. The performances of the encapsulated dyes were evaluated by color and washing fastness measurements and resulted in improved dye absorption and wash fastness properties. The color change and color transfer measurements of the encapsulated dyes were better (rated at 4–5 on a scale of 1–5) compared to the bare dyes.
In this paper the results obtained in the last ten years by the authors in the field of sol-gel nanocomposites for optical applications are reviewed. Two type of applications are, in particular, discussed: (a) nanocomposite materials containing semiconductor quantum dots for photonic and optoelectronic applications; (b) nanocomposite materials for optical gas sensing. Nanocomposite multifunctional materials, based on the incorporation of QDs in inorganic or hybrid organic-inorganic matrices, characterized by stable optical properties, good chemical stability, and easy processability, can be obtained using the sol-gel method in combination with colloidal methods. Optical gas sensors based on surface plasmon resonance (SPR) demonstrate great potential both for better understating the chemical interactions at the nanoscale and the development of real devices. A careful control of the film structure allows to achieve very selective gas sensors with tailored microstructure. In both type of applications, the general aspects related to the synthesis and characterization of the materials, and the results obtained in the specific cases, are described with the aim to give an overview of the development of these materials.
Mixed-metal compounds, especially for the sulfides, have been investigated as a very attractive type of electroactive materials for supercapacitors. In this work, we demonstrate nickel?manganese (Ni?Mn) sulfides are very attractive for supercapacitors with promising electrochemical performance. The Ni?Mn sulfides with different Ni to Mn ratios have been synthesized via a facile one-pot hydrothermal method, which show a similar structure of interconnected particles and are very porous in microstructure. And then, the Ni?Mn sulfides are investigated by three-electrode measurements and demonstrate strong synergy between Ni and Mn. The Ni?Mn sulfide with a Ni to Mn ratio of 2:1 demonstrates superior performance of 1068?F?g?1 at 1?A?g?1. Lastly, The Ni?Mn sulfide with a Ni to Mn ratio of 2:1 are used as positive electrode for two-electrode test, and the asymmetric supercapacitor shows both high energy and power densities combined with excellent cycling stability. Our work demonstrates that the Ni?Mn sulfides are also very electrochemical active for supercapacitors and their performance can be tuned by changing the Ni to Mn ratio.
Powders of Sm0.6Sr0.4CoO3-δ and La0.6Sr0.4CoO3-δ were synthesized using wet chemical technique. Structural and surface properties of synthesized materials were studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), IR spectroscopy, and scanning electron microscopy (SEM). The influence of pH on the phase state, chemical composition, morphology, and fractal dimension of the synthesized powders were investigated. It was found that the change of pH has the influence on phase composition of synthesized powders. The increase of solution pH allows one to obtain homogeneous samples at lower temperatures down to 900–950?°C.
The influence of the water content in the initial composition on the size of silica particles produced using the Stöber process is well known. We have shown that there are three morphological regimes defined by compositional boundaries. At low water levels (below stoichiometric ratio of water:tetraethoxysilane), very high surface area and aggregated structures are formed; at high water content (>40?wt%) similar structures are also seen. Between these two boundary conditions, discrete particles are formed whose size are dictated by the water content. Within the compositional regime that enables the classical Stöber silica, the structural evolution shows a more rapid attainment of final particle size than the rate of formation of silica supporting the monomer addition hypothesis. The clearer understanding of the role of the initial composition on the output of this synthesis method will be of considerable use for the establishment of reliable reproducible silica production for future industrial adoption.
In this study, stearic acid/silica phase change composites were prepared by the sol-gel method using stearic acid as phase change materials (PCMs). The effects of mass fraction of stearic acid were comprehensively investigated. The structures and thermal properties of the obtained composites were characterized by various methods, including scanning electron microscopy (SEM), differential scanning calorimetry (DSC), leakage tests, and thermogravimetry analysis (TG). The results indicated that composite containing 76% stearic acid had the best thermal properties and low mass leakage, making 76% stearic acid as the maximum content that silica matrix could protect in the composites. The latter was further confirmed by morphological analyses of the silica matrix. Silica matrix exhibited spherical particle clusters, following big–small–big–small size pattern as stearic acid rose. The composite with 76% stearic acid was at the key point of change in particle size. These findings look promising for future to prepare silica-based phase change composites with good thermal properties easily.
A novel ZrCO composite aerogel is synthesized using zirconium oxychloride and resorcinol–formaldehyde (RF) as precursors through the sol–gel route and carbothermal reduction process. The effects of different Zr/R molar ratios and calcination temperatures on the physical chemistry properties of ZrCO aerogels are investigated. The ZrCO composite aerogel consists of the C/ZrO2/ZrC ternary aerogel. The results show that with the increase of R/Zr molar ratios, the specific surface area and bulk density increase with calcination temperature up to 1300?°C, but decrease at even temperature (1500?°C). The specific surface area is as high as 637.4?m2/g for ZrCO composite aerogel (R:Zr?=?2:1), which was higher than ever reported. As the heat-treatment temperature increases to 1500?°C, the ZrC crystalline phase occurs and the t-ZrO2 phase still appears within the composite. The thermal conductivity of the carbon fiber mat-reinforced composite aerogel is as low as 0.057?W/m/K at room temperature (25?°C).
The mesoporous silica samples with different concentrations of phosphonic acid groups on the surface were obtained by direct template synthesis. The block-copolymer Pluronic P123 was used as a template, and sodium meta-silicate with diethylphosphatoethyltriethoxysilane as precursors. According to the SAXS diffractograms, mesoporous silica samples have a p6mm hexagonal symmetry. In addition, we used sol–gel method to synthesize xerogel with the same groups for comparison. All samples possess high values of specific surface area 615–730?m2/g and sorption pore volume. FTIR and potentiometric titration methods were used to investigate the surface layer of these samples. Sorption properties of the samples with phosphonic acid groups were studied in respect to a row of metal cations, among which we focused on lead(II), cadmium(II), and dysprosium(III) cations.
In this work, sol–gel-based non-stick ceramic coating formulations were prepared and coated onto aluminum panels in order to investigate their surface properties. The effect of the addition of optimal amount of fluorine-containing silane compound (FAS) on the surface and adhesion properties were also investigated. The morphology, structure, and elemental chemical composition of the coatings were characterized by scanning electron microscopy, atomic force microscopy (AFM), energy dispersion spectrum (SEM/EDAX), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), respectively. Moreover, several properties of the coatings such as cross-cut adhesion, hardness, gloss, and contact angle (CA) were determined. When fluorine was introduced, the pencil hardness was increased to 6H. Fluorinated non-stick ceramic coatings were found to have good adhesion on the aluminum substrates.
The behaviour of alginate gel film in response to the tensile load is analysed in this paper. The bubbles of 0.5?mm diameter were embedded in the film by the fluidic method prior to gelation, thus providing uniform voidage over the entire film. Further, the intrinsic porosity of the gel matrix around the voids was varied by removing water through either evaporation under vacuum, or employing lyophilisation. The Poisson’s ratio and the modulus of elasticity were estimated from direct measurements. The viscoelasticity of the gel matrix was characterized from stress-relaxation measurement. The transient response to tensile loading and the evolution of stress contours were studied through numerical simulation in ANSYS. The ultimate strength was studied for the gel films with embedded voids of different sizes. The numerical simulations were validated by experimental measurements.
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.
The aim of this work was an investigation of structural and electrical properties of ZnO/Zn2-xFexTiO4 (x?=?0.7, 1, 1.4) powders. The compounds obtained by sol-gel method are characterized by several techniques: X-ray diffraction (XRD), N2 adsorption–desorption isotherms, scanning and transmission electron microscopy (SEM and TEM), X-ray photoelectron spectroscopy (XPS), electrical and dielectrical measurements. The XRD, SEM and XPS analysis confirmed the formation of ZnFeTiO4 inverse spinel structure. The electrical and dielectrical properties of ZnO/Zn2-xFexTiO4 (x?=?0.7, 1, 1.4) were measured by impedance spectroscopy, revealing a decrease in the electrical conductivity and the dielectric constant with Fe content.
Nuclear magnetic resonance (NMR) spectroscopy offers an element-selective, inherently quantitative and experimentally very flexible approach for the structural elucidation of non-crystalline materials. The present review introduces the basic concepts of this technique, highlighting the use of advanced NMR methodology for characterizing short- and intermediate range order in bioactive glass systems. The current state of the literature in this field is summarized in a comprehensive manner. NMR can give clear-cut and quantitative answers about the extent of network polymerization, the spatial distribution of the network former and network modifier species, and the structural roles of Group III elements introduced into these networks. These results facilitate our understanding of the influence of bioglass compositions upon the dissolution kinetics and bioactivities of these glasses. A particular mission of this review is to highlight the utility of non-routine, more advanced experimentation, in the hope of their increased usage and circulation in future applications.
The main six nuclear isotopes used in obtaining high-resolution magic-angle spinning NMR spectra for the structural characterization of bioactive glasses
YAG:Ce and YAG:Eu sols were synthesized by a polymeric sol-gel route. The crystallization temperature of YAG was determined by X-ray diffraction as a function of the calcination temperature, revealing that YAG starts to crystallize directly from the amorphous phase at 800?°C. The effects of the thermal treatment and the dopant amount on the photoluminescent properties were studied, observing the highest emission after calcination at 1000?°C for 1?h in both cases and with a concentration of 1 and 3?mol% of Ce and Eu, respectively. Core-shell materials were prepared by dipping YAG:Ce or YAG:Eu sintered pellets into the synthesized sols and then, these materials were calcined at 1000?°C for 1?h. An effective energy transfer from Ce to Eu was observed in the sample YAG:Eu (core)–YAG:Ce (shell) when blue light (λ?=?465?nm) is used as excitation source. This wavelength excites the Ce but not the Eu; however, in the photoluminescence emission spectrum, the bands associated to both ions can be clearly detected, confirming that the core-shell strategy is a good method for the preparation of warmer white LEDs.
Fiber needle felt–silica aerogel composite was successfully prepared by via sol–gel process based on water glass. The thermal conductivity show V-type variation tendency with the increase of water to Si. Thermogravimetric analysis-differential scanning calorimetry analysis revealed that the thermal stability was up to approximately 390.58?°C. It has been found that the fire hazard of the composites decreased with the increased ratio of water to Si according to the cone calorimeter test, which can be characterized by peak heat release rate, fire performance index, and fire growth rate index. The fiber needle felt/aerogels present greatly improved compressive and flexural strength (elastic modulus: 0.1–0.97?MPa; flexural modulus: 0.33–0.66?MPa) while keeping inherent properties of pure silica aerogel: low bulk density (0.166?g/cm3), low thermal conductivity of 0.0236?W/m·K, and high specific surface area (1091.62?m2/g). As a result, the as-prepared composite shows a great potential to be applied in the thermal insulation field.
