Mesoporous Li<Subscript>2</Subscript>FeSiO<Subscript>4</Subscript>/C nanocomposites with enhanced performance synthesized from fumed nano silica

Mesoporous Li₂FeSiO₄/C nanocomposites (LFS-FNS and LFS-NS) were prepared from fumed nano silica (FNS) and nano silica (NS) through facile solid-state reactions, respectively. XRD analysis indicates that the crystalline structures of LFS-FNS and LFS-NS are indexed to monoclinic Li₂FeSiO₄ of P2₁. SEM results prove that the particle size of LFS-FNS and FNS (25~40 nm) is smaller than that of LFS-NS and NS, revealing the particle size of Li₂FeSiO₄/C nanocomposites can be tuned by choosing different silica. TEM further indicates Li₂FeSiO₄ nanoparticles are uniformly dispersed in the amorphous carbon networking of LFS-FNS. Pore structure analysis indicates the external surface areas of LFS-FNS as well as LFS-NS are 51.4 and 36.1 m² g^?1, indicating the pore properties of mesoporous Li₂FeSiO₄/C nanocomposites can be controlled by using different silica as silicon resource. The reduced particle size and high external surface area shorten the lithium-ion diffusion path and make LFS-FNS possess better electrochemical performance over LFS-NS. The discharge capacity of LFS-FNS is as high as 172 mA h g^?1 at 0.1 C.     

In vitro effects of cisplatin-functionalized silica nanoparticles on chondrocytes

In this study, we evaluated the combined effect of a known toxic molecule, cisplatin, in combination with relatively nontoxic nanoparticles, amorphous fumed silica, on chondrocyte cells. Cisplatin was attached to silica nanoparticles using aminopropyltriethoxy silane as a linker molecule, and characterized in terms of size, shape, specific surface area, as well as the dissolution of cisplatin from the silica surface. The primary particle diameter of the as-received silica nanoparticles ranged from 7.1 to 61 nm, estimated from measurements of specific surface area, and the primary particles were aggregated. The effects of cisplatin-functionalized silica particles with different specific surface areas (41, 85, 202, 237, and 297 m²/g) were compared in vitro on chondrocytes, the parenchymal cell of hyaline cartilage. The results show that adverse effects on cell function, as evidenced by reduced metabolic activity measured by the MTT assay and increased membrane permeability observed using the Live/Dead stain, can be correlated with specific surface area of the silica. Cisplatin-functionalized silica nanoparticles with the highest specific surface area incited the greatest response, which was almost equivalent to that induced by free cisplatin. This result suggests the importance of particle specific surface area in interactions between cells and surface-functionalized nanomaterials.     

Morphological, structural and adsorption features of oxide composites with silica and titania matrices

Morphological, structural, electronic, and adsorption characteristics of complex oxides such as fumed silica/alumina and silica/titania, fumed silica with deposited oxides of Mg, Ti, Mn, Ni, Cu, Zn and Zr, silica gel with grafted ZrO₂, sol-gel titania doped by 3d-metals (Cr, Fe, Mn, V) were compared using adsorption, TEM, AFM, XRD, XPS, Mössbauer and Raman spectroscopy data. It was shown that surface, volume, and phase compositions of oxides, particle size distributions (5 nm-3 μm), specific surface area (S_BET ∼ 50-500 m²/g), and porosity (V_P ∼ 0.1-2 cm³/g) affected by synthesis technique and subsequent treatment determine electronic structure (bandgap, valence band and core levels structure) of the materials, adsorption of molecules and metal ions as well as other characteristics.     

Influence of surface treatment on mechanical behaviour of fumed silica/epoxy resin nanocomposites

The present paper shows the potential of fumed silica as nano-reinforcements in polymers, by considering the limitations and challenges one has to face dealing with nanoparticles in general. The dominating effect of the manufacturing route and surface properties of fumed silica influencing the resulting degree of dispersion and the interfacial adhesion were investigated by electron microscopy (TEM, SEM). The resulting (fracture-) mechanical properties of the fumed silica/epoxy composites were investigated for volume contents of 0.5 vol% and below. Independent of the surface modification, static and dynamic modulus decreased slightly by adding the fumed silica. Hence, the fracture toughness K _Ic turned out to be significantly increased (54%) adding only 0.5 vol% of surface modified fumed silica.     

A Survey of Complementary Methods for the Characterization of Dense Colloidal Silica

The aim of this study is to enhance existing knowledge of different techniques developed for the characterization of stability and particle sizing of nanoparticles in dense dispersions subjected to interparticulate and hydrodynamic forces. Silica suspension, commercially known as Klebosol^® 30R50 and consisting of a particle size of 80 nm on average, was investigated in the study over a wide range of concentrations. The investigations were carried out using different optical and acoustic techniques such as laser diffraction, multiple light scattering, photon correlation spectroscopy and acoustic spectroscopy. The study details the capabilities and limitations of these modern techniques based on the different physical principles behind the characterization of the size distribution of particles in suspensions. The results are presented in terms of particle size ranges, solid concentration and technological aspects such as online and offline analysis. An important finding is that many of these modern techniques need to be improved for applications at higher concentrations since the standard models become practically invalid because of the complex interaction of acoustic and optical waves with particles in suspensions of silica.     

Superhydrophobic sol-gel nanocomposite coatings with enhanced hardness

Sol-gel superhydrophobic coatings with improved hardness were prepared by embedding fumed silica nanoparticles in a partially condensed hybrid sol of methyltriethoxysilane (MTEOS) and colloidal silica. Fumed silica particles of size 25-30 nm were incorporated in the sol and the mixture was spray-coated on glass substrate. Water contact angle (WCA) of the composite coating increased with increase in silica content of the sol mixture. The concentration of silica in the sol mixture was optimized to obtain robust superhydrophobic coatings with a WCA of 162.5° and a pencil hardness of 5H. The wetting state of water droplet on the sol-gel composite coatings was analysed with both Wenzel and Cassie-Baxter models.     

Y2SiO5:Tb phosphor particles prepared from colloidal and aqueous solutions by spray pyrolysis

Green-emitting Y₂SiO₅:Tb phosphor particles with fine size, spherical shape, filled morphology, high crystallinity, and good brightness were synthesized by a spray pyrolysis process. The effect of silicon precursor type on the morphology, crystal structure, crystallinity, and photoluminescence efficiency of Y₂SiO₅:Tb phosphor particles was investigated. The particles prepared from an artificial colloidal solution obtained by dispersing fumed silica particles had a pure monoclinic X2 crystalline phase, which is more appropriate for application to displays, after post-treatment at 1300 °C. On the other hand, the particles prepared from 100% tetraethyl orthosilicate (TEOS) reagent had an X2 phase and small amounts of X1 and impurity phases such as Y₂Si₂O₇ and Y_4.67Si₃O₁₃ due to the phase-segregation characteristics of the TEOS precursor. The photoluminescence characteristics of Y₂SiO₅:Tb phosphor particles were strongly affected by the silicon source used. The photoluminescence intensities increased with the fumed silica/TEOS ratio. The particles prepared from 100% fumed silica showed the maximum photoluminescence intensity, which is 22% higher than that of particles prepared from 100% TEOS. PACS 81.20.Rg; 78.55.Hx; 78.40.Ha; 81.05.Hd; 81.40.Tv     

Influence of synthesis conditions on structural properties of MCM-48

The influence of synthesis variables such as time, cetyltrimethyl ammonium hydroxide (CTAOH) concentration, water content, pH, temperature and silica source on the structural properties of Si-MCM-48 is investigated. Time-dependent studies on the progressive development of MCM-48 have indicated that synthesis time is a crucial parameter, which influences the unit cell parameter. The formation of different mesophases was observed when the concentration of CTAOH and pH of the initial gel were varied. The ²⁹Si MASNMR results showed that the (Q²+Q³)/Q⁴ ratio decreases with the increase in synthesis temperature. On account of increase in Q⁴ units at high-temperature synthesis run, Si-MCM-48 with highly polymerized silica walls with lower surface area was obtained when compared with Si-MCM-48 prepared at lower temperature. Such effect was not significant when Si-MCM-48 was synthesized at the same temperature but using silica sol as a source in place of fumed silica.     

Composite polymeric electrolytes based on PMMA-LiCF3SO3-SiO2

Preliminary results on the mechanical, optical and electrical properties of composite gel electrolytes (CGEs) with fumed silica (SiO₂) as a filler added to gel polymeric electrolyte (GPE) based on PMMA, LiCF₃SO₃ and PC are presented in this paper. Added fumed silica is seen to enhance the mechanical properties of the GPE without changing the conductivity significantly. The high ionic conductivity (×10⁻³ S/cm), high transmission in the visible region and nominal variance of conductivity and viscosity over a wide temperature window show that these CGEs are potential electrolytes for electrochromic windows (ECWs).     

1 and 2-Photon Fluorescence Anisotropy Decay to Probe the Kinetic and Structural Evolution of Sol-Gel Glasses: A Summary

We review recent 1- and 2-photon fluorescence studies of the formation dynamics and structure of sol-gel glasses, from nanometre-sized particles to clusters, prepared from both aqueous silicates and tetramethylorthosilicate (TMOS), over a broad pH range. Through the careful choice of a fluorescent probe, anisotropy decay has been shown to provide both silica particle size and viscosity information and offers advantages over traditional techniques for silica particle sizing based on small-angle neutron, Xray, or light scattering. Subsequently, we are now able to observe the self-assembly mechanisms (or recently termed kinetic life history) of silica, produced under both acidic and alkaline conditions from sodium silicate solution (water glass) in the case of hydrogels and from alkoxides in the case of alcogels. The controlled preparation of hydrogels, often deemed a blackart, is also discussed in some detail, as are the potential applications and benefits of fluorescence anisotropy decay to industrial sol-gel systems. The insight into the sol-gel process provided by these new interpretations of fluorescence decay data, promises to have implications for both our fundamental understanding and the production of sol-gel systems in general.     

Comparative studies of Zr-based MCM-41 and MCM-48 mesoporous molecular sieves: Synthesis and physicochemical properties

Two surfactant-templated synthetic routes are developed for the preparation of new types of mesoporous molecular sieves, Zr-MCM-41 and Zr-MCM-48, using different Si sources but keeping the same zirconium precursor (zirconium-n-propoxide). When fumed silica was used as Si precursor, a Zr-MCM-48 material of cubic structure was formed with a surface area of 654.8 m²/g and an unimodal pore diameter distribution. It shows low stability: after calcination at 600 °C, the ordered structure was transformed into a relatively disordered worm-like mesostructure with many defects and silanol groups. The use of tetraethyl orthosilicate as Si source led to the formation of a Zr-MCM-41 mesoporous solid, which had good thermal stability and a highly ordered hexagonal arrangement, with a surface area 677.9 m²/g and an uniform pore diameter distribution. Fourier transform infrared (FT-IR) characterization and ²⁹Si NMR analysis confirm that zirconium ions indeed incorporated into the framework of the solid. The in situ FT-IR spectroscopy of pyridine adsorption reveals that both, Lewis and Brönsted acid sites, were formed on the surface of these mesoporous materials. The strength and number of the Brönsted acid sites of the Zr-MCM-48 solid were greater than those of the Zr-MCM-41, due to a lower degree of condensation reaction during the synthesis that led to more structural defects in the framework and more silanol groups stretching from the solid surface.     

Composite polymeric electrolytes based on PMMA-LiCF3SO3-SiO2

Preliminary results on composite gel electrolytes (CGEs) with fumed silica (SiO₂) as filler added to gel polymeric electrolyte (GPE) based on PMMA, LiCF₃SO₃ and PC are presented in this paper. Added fumed silica is seen to enhance the mechanical properties of the GPE without changing the σ significantly. The high ionic conductivity (×10⁻³ S/cm), high transmission in the visible region and nominal variance of σ and ν over a wide temperature window makes these CGEs potential electrolytes for electrochromic windows (ECWs). Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Effect of drying technique on the physicochemical properties of sodium silicate-based mesoporous precipitated silica

The conventional drying (oven drying) method used for the preparation of precipitated mesoporous silica with low surface area (>300 m²/g) and small pore volume is often associated with a high production cost and a time consuming process. Therefore, the main goal of this study was to develop a cost-effective and fast drying process for the production of precipitated mesoporous silica using inexpensive industrial grade sodium silicate and spray drying of the precipitated wet-gel silica slurry. The precipitated wet-gel silica slurry was prepared from an aqueous sodium silicate solution through the drop-wise addition of sulfuric acid. Mesoporous precipitated silica powder was prepared by drying the wet-gel slurry with different drying techniques. The effects of the oven drying (OD), microwave drying (MD), and spray drying (SD) techniques on the physical (oil, water absorption, and tapping density), and textural properties (specific BET surface area, pore volume, pore size, and % porosity) of the precipitated mesoporous silica powder were studied. The dried precipitated mesoporous silica powders were characterized with field-emission scanning electron microscopy; Brunauer, Emmett and Teller and BJH nitrogen gas adsorption/desorption methods; Fourier-transform infrared spectroscopy; thermogravimetric and differential analysis; N₂ physisorption isotherm; pore size distribution and particle size analysis. There was a significant effect of drying technique on the textural properties, such as specific surface area, pore size distribution and cumulative pore volume of the mesoporous silica powder. Additionally, the effect of the microwave-drying period on the physicochemical properties of the precipitated mesoporous silica powder was investigated and discussed.     

Electrical characterization of nano-composite polymer gel electrolytes containing NH4BF4 and SiO2: role of donor number of solvent and fumed silica

Nano-composite polymer gel electrolytes were synthesized by using polyethylene oxide (PEO), ammonium tetrafluoroborate (NH₄BF₄), fumed silica (SiO₂), dimethylacetamide (DMA), ethylene carbonate (EC), and propylene carbonate (PC) and characterized by conductivity studies. The effect of donor number of solvent on ionic conductivity of polymer gel electrolytes has been studied. The mechanical strength of the gel electrolytes has been increased with the addition of nano-sized fumed silica along with an enhancement in conductivity. Maximum room temperature ionic conductivity of 2.63 × 10⁻³ and 2.92 × 10⁻³ S/cm has been observed for nano-composite gel electrolytes containing 0.1 and 0.5 wt% SiO₂ in DMA+1 M NH₄BF₄+10 wt% PEO, respectively. Nano-composite polymer gel electrolytes having DMA have been found to be thermally and electrically stable over 0 to 90 °C temperature range. Also, the change in conductivity with the passage of time is very small, which may be desirable to make applicable for various smart devices.

     

Hybrid Polyurethane-Poly(2-hydroxyethyl methacrylate) Semi-IPN–Silica Nanocomposites: Interfacial Interactions and Glass Transition Dynamics

Polyurethane-poly(2-hydroxyethyl methacrylate) semi-IPN-silica nanocomposites with low content (0.25 and 3 wt%) of differently functionalized 3-D fumed silica nanoparticles were studied using a combined AFM/DSC/CRS approach over the ?100 to 160°C range. The pronounced heterogeneity of the PHEMA and PU glass transitions’ dynamics and the effects of considerable suppression of dynamics and increasing elastic properties by silica additives were shown. It was caused by formation of peculiarly cross-linked structures due to “double hybridization,” in particular via selective covalent bonding of the silica surface, functionalized by ?OH, ?NH₂ or ?CH?CH₂ groups, with the matrix constituents. The silica dispersion remained unchanged in these nanocomposites; therefore the relationships between interfacial interactions and dynamics/modulus behavior could be followed.     

Relationship between surface structure and morphology of Fe3O4/silica composite nanospheres and nucleic acid extraction

Fe₃O₄/silica composite nanospheres with different surface structure and morphology were synthesized by changing reaction conditions. As-synthesized nanospheres were characterized by high performance particle sizer (HPPS), transmission electron microscopy (TEM), nitrogen adsorption and thermogravimetry (TGA). Besides thoroughly characterization, the particles were used for DNA extraction. We found that the particle surface structure and morphology affected the nucleic acid extraction efficiency. When comparing different samples with the same silanol density (10¹⁸), the one with a surface area of 60.37 m²/g extracted DNA most effectively. Also, with increasing silanol density per surface area, DNA extraction efficiency increased.     

Rapid sonochemical synthesis of MCM-41 type benzene-bridged periodic mesoporous organosilicas

Benzene-bridged periodic mesoporous organosilicas (PMOs) with the MCM-41 were synthesized by a rapid sonochemical process via co-condensation of tetraethoxysilane (TEOS) and 1,4-bis(triethoxysilyl) benzene (BTEB) under basic conditions within a few minutes using cetyltrimethylammoniumbromide (CTMABr) as a structure-directing agent. The molar ratio of the silicon precursors and the synthesis time were varied in order to investigate their influence on the structural ordering of the materials. The characteristics of the materials were evaluated by X-ray diffraction (XRD), N₂-sorption, transmission electron microscopy (TEM) and solid-state NMR spectroscopy. The resultant materials exhibited well-ordered hexagonal mesostructures with surface areas in the range of 602–1237 m²/g, pore volumes of 0.37–0.68 cm³/g, and pore diameters in the range of 2.5–3.5 nm. Two dimensional ²⁹Si{¹H} heteronuclear correlation (HETCOR) NMR spectra confirmed the formation of a single mesophase with various Q (from TEOS) and T (from BTEB) silicon species located randomly within the pore walls due to the co-condensation of BTEB and TEOS, which excluded the possibility of formation of island or two separate phases within such a short synthesis time. The prime advantage of the present synthesis route is that it can effectively reduce the total synthesis time from days to a few minutes, much shorter than the conventional benzene-bridged PMOs synthesis methods.     

Preparation of ZnO–Al2O3 Particles in a Premixed Flame

Zinc oxide (ZnO) and alumina (Al₂O₃) particles are synthesized by the combustion of their volatilized acetylacetonate precursors in a premixed air–methane flame reactor. The particles are characterized by XRD, transmission electron microscopy, scanning mobility particle sizing and by measurement of the BET specific surface area. Pure (-)alumina particles appear as dendritic aggregates with average mobile diameter 43–93 nm consisting of partly sintered, crystalline primary particles with diameter 7.1–8.8 nm and specific surface area 184–229 m²/g. Pure zinc oxide yields compact, crystalline particles with diameter 25–40 nm and specific surface area 27–43 m²/g. The crystallite size for both oxides, estimated from the XRD line broadening, is comparable to or slightly smaller than the primary particle diameter. The specific surface area increases and the primary particle size decreases with a decreasing flame temperature and a decreasing precursor vapour pressure. The combustion of precursor mixtures leads to composite particles consisting of zinc aluminate ZnAl₂O₄ intermixed with either ZnO or Al₂O₃ phases. The zinc aluminate particles are dendritic aggregates, resembling the alumina particles, and are evidently synthesized to the full extent allowed by the overall precursor composition. The addition of even small amounts of alumina to ZnO increases the specific surface area of the composites significantly, for example, zinc aluminate particles increases to approximately 150 m²/g. The gas-to-particle conversion is initiated by the fast nucleation of Al₂O₃ or ZnAl₂O₃, succeeded by a more gradual condensation of the excess ZnO with a rate probably controlled by the cooling rate for the flame.     

Surface activity studies on carbon-silica dual phase fillers using flow microcalorimetry and multiple probe temperature programmed inverse gas chromatography

Carbon–silica hybrid particles (or carbon silica dual phase fillers (CSDPF)) are used as high performance fillers for elastomers and were originally developed to combine the best aspects of carbon black and silica in one package. In this work a range of such fillers with differing silicon content have been analysed, together with a range of carbon black and silica samples, using flow micro-calorimetry (FMC) and multiple probe temperature programmed inverse gas chromatography (MPTPIGC). The probe set for FMC comprised: ethyl acetate, pyridine, tributylamine; and propan1-ol. The linear increase in both heat and level of adsorption (from dry heptane) of all the probes within the CSDPF silicon content range investigated indicated that the interactions in the FMC were with the silica phase of the CSDPFs. FMC data for a variety of silica reference samples clearly indicates that the linear increase in adsorption activity does not continue beyond ca. 15% w/w silicon. MPTPIGC data obtained using a range of saturated and unsaturated linear and cyclic hydrocarbons together with benzene and pinacolone showed no clear relationship to silicon content. In fact the retention characteristics of CSDPF resembled those of carbon black more than silica. Differences in the carbon phase of the CSDFS and carbon blacks could be resolved using MPTPIGC. This study therefore highlights the complimentary nature of FMC and MPTPIGC in surface analytical studies of fillers.     

Polydimethylsiloxane at the interfaces of fumed silica and zirconia/fumed silica

Polydimethylsiloxane (PDMS)/fumed silica A-300 and PDMS/ZrO₂/A-300 were studied using adsorption, thermogravimetry, temperature-programmed desorption (TPD) mass-spectrometry, infrared spectroscopy, XRD, and broadband dielectric relaxation spectroscopy. ZrO₂ was synthesized on fumed silica with zirconium acetylacetonate in CCl₄ at 350 K for 1 h and calcinated at 773 K for 1 h (1-4 reaction cycles). PDMS (5-40 wt.%) was adsorbed onto silica and zirconia/silica from hexane solution and then dried. Grafted zirconia changes the chemistry of the surface (because of its catalytic capability) and the topology of secondary particles (because of occupation of voids in aggregates of primary silica particles by zirconia nanoparticles) responsible for the textural porosity of the powders. Therefore, many properties (such as structural characteristics of the composites, reactions on heating in air and vacuum, interfacial relaxation phenomena, hydrophobicity as a function of treatment temperature, etc.) of PDMS/zirconia/silica strongly differ from those of PDMS/A-300. Broadening of the α-relaxation of PDMS at the interfaces of disperse oxides suggests both weakening of the PDMS-PDMS interaction and strengthening of the PDMS-oxide interaction.