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.     

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.     

High-Performance Silicone Rubber Composites via Non-Covalent Functionalization of Carbon Nanotubes

A high-performance silicone rubber (SR) composite (denoted as SCT) filled with 5 phr functionalized carbon nanotubes (CNTs) and 40 phr fumed silica (SiO₂) was prepared by mechanical blending. The CNTs were functionalized by tetrakis (phenylmethyl)-thioperoxydi (carbothioamide) (TBzTD); it contains four benzene rings that can interact with the CNTs via π–π interactions. Raman spectroscopy and X-ray photoelectron spectroscopy analysis demonstrated the existence of the π-π interactions between the CNTs and the TBzTD. Transmission electron microscopy and scanning electron microscopy confirmed the uniform dispersion of the CNTs in SR matrix and strong interfacial interactions between the SR and the CNTs. The effects of these non-covalently functionalized CNTs on the mechanical properties of the silica filled SR composites were fully investigated. The results showed that the tear strength of the SCT composite with TBzTD functionalized CNTs was significantly improved, by 249%, compared with that of the composite containing only SiO₂. An obvious crack deflection occurred in the SCT during the tearing process, resulting in the enhanced tear strength.     

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).     

Conductivity variations in composites of α-zirconium phosphate and fumed silica

Composite proton-conducting solid electrolytes have been formed from α-zirconium phosphate (α-Zr(HPO₄)₂·H₂O, α-ZrP) and high surface area non-porous fumed silica in varying mole ratios. Conductivity variations as a function of temperature and relative humidity have been characterised and compared to that for a similarly prepared delaminated ZrP (no silica). Conductivities increase with relative humidity and E_a decreases at high silica mole fractions. Conduction is via exposed lamellar surfaces and other microstructural imperfections in the composites.     

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.     

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     

Controlled Formation of Patchy Anisometric Fumed Silica Supraparticles in Droplets on Bent Superhydrophobic Surfaces

This article presents a study on the formation of anisometric, ellipsoidal supraparticles by evaporation‐induced self‐assembly from multicomponent colloidal dispersion droplets deposited on a superhydrophobic surface. Performing the formation process on bent surface substrates grants precise control on the shape and spatial orientation of the final dried supraparticles. Due to the V‐shaped surfaces providing interfacial blockage, anisotropic evaporation rates occur with respect to the direction of the bending channel. This proportionally leads to inhomogeneous accumulation of fumed silica (FS), used as structure guiding component. Thus, upon the increase of FS‐particle interaction via ionic strength (NaCl), this so‐formed shell provides enough anisotropic stiffness resulting in predictable droplet deformation with the elongation orientation being perpendicular to the bending axis. The anisotropic evaporation rates were monitored and quantified using an established, empiric kinetic model and taking into account surface geometry. Employing this reliable control of elongation direction and using additional Fe₃O₄@SiO₂ core–shell nanoparticles, anisometric magnetic Janus supraparticles with defined patch position were prepared, which are not accessible on flat surfaces. The results can find application in the controlled, easy to scale up, nanofabrication process of patchy anisometric supraparticles.     

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.     

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.

     

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.     

Preparation of well-structured organosilane layers on silica

An efficient grafting process of monofunctional alkylchlorosilanes (general formula: CH₃-(CH₂) _n-1-Si(CH₃)₂Cl with n varying from 4 to 30) onto silica nanoparticules was developed by varying the surface preparation and the solvent used for the deposition process. A vapor phase deposition method was considered as reference and silicon wafers with a native SiO₂ layer were used as a model surface of the silica particles. The grafting method was evaluated by studying the wettability and the grafting densities of the resulting monolayers. The chain conformation of the monolayers was determined by comparing the thickness measured by SE ellipsometry and AFM. By comparing the solvent and vapor phase deposition methods, it was demonstrated that the deposition process had a large influence on the structure of the grafted monolayers. The same structure as from a vapor phase method can be obtained from a solvent deposition process by a suitable choice of the solvent and by a strict cleaning of the surface before deposition. The grafting of much longer chains of such silane-terminated polyethylenes with different molar mass on the silica surface was also investigated in order to study the effects of the chain length on the grafting density and the layer structure. For both the short alkylchlorosilanes and polymeric grafted chains, the proposed organization of the grafted chains at the silica surface is found to be strongly dependent on the length of the alkyl chains.     

Nanocomposites with fumed silica/poly(vinyl pyrrolidone) prepared at a low content of solvents

Highly disperse nanocomposites with fumed silica/poly(vinyl pyrrolidone) (PVP) prepared using different methods were studied by infrared spectroscopy, adsorption, and quantum chemistry methods. Low amounts of water or ethanol (30 wt.% with respect to the silica content) promote appropriate distribution of PVP on silica particles. The use of ethanol leads to a smaller loss of the specific surface area (S_BET) than in the case of water used as a solvent. On PVP distribution on a silica surface, treatment of the system in a pseudo-liquid state reactor (PLSR) provides slightly better results (a lower loss in S_BET) in comparison with mechanochemical activation (MCA) in a ball mill at the PVP monolayer coverage. An increase in the activation time to 6-9 h leads to an increase in the |ΔS_BET/S_BET| value to 0.29-0.35 for both treatment methods.     

Interparticle forces in silica nanoparticle agglomerates

To improve the understanding of the poor dispersability of fumed silica nanoparticle agglomerates, the stability of highly defined agglomerated model particles was investigated. The high temperature synthesis conditions for fumed silica were simulated by tempering. Along with electron-microscopical analysis of the sintering necks, the interparticle forces were investigated by energy resolved fragmentation analysis based on low pressure impaction. At temperatures above 1,000 °C the fragmentability of the agglomerates rapidly decreased while the energy necessary for fragmentation increased. The development of sintering necks was observed for temperatures exceeding 1,300 °C. Comparison of the experimental data with the fragmentation behaviour of a commercially produced fumed silica indicated solid state contacts (sintering necks) as being most numerous in the agglomerates resulting in limited fragmentability.     

Particle Sizes of Fumed Silica

Fumed silica is a synthetic amorphous silicon dioxide produced by burning silicon tetrachloride in an oxygen-hydrogen flame. Surface areas range from 50 up to 400 m²/g. Using particle sizing techniques, fumed silica shows micro-sized particles leading to surface areas markedly lower than expected. Fumed silica appears as a fluffy solid with bulk densities down to 0.03 g/cm³, being invariant over the wide range of surface areas. Attempts to relate the variation of the surface area directly to the performance of fumed silica in technical applications, such as its thickening efficiency in fluids, mainly fail and remain ambiguous. The aim of this work was to investigate the particle sizes and structures of fumed silica aggregates and agglomerates, using different particle dispersion and sizing techniques.     

Effects of alumina nano-particulates addition on mechanical and electrical properties of barium titanate ceramics

Ferroelectric BaTiO₃/xAl₂O₃ nanocomposite ceramics (when x = 0, 0.5, 1, 3 and 5 vol%) were fabricated from an in-house prepared BaTiO₃ powder and nano-sized Al₂O₃ powder by a solid state mixed-oxide method. Densities and grain sizes of the ceramics were found to gradually decrease with increasing content of Al₂O₃ addition. Mechanical properties such as Knoop hardness and Young’s modulus of BaTiO₃ were found to be improved with only 0.5 vol% of Al₂O₃ addition. Dielectric and piezoelectric properties of the nanocomposites with <1 vol% Al₂O₃ addition could be maintained and were comparable to the values of the monolithic BaTiO₃. Within the range of the BaTiO₃/Al₂O₃ nanocomposites investigated, this study suggested materials with acceptable electrical properties and better structural stability.     

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.     

NMR T1–T2 correlation analysis of molecular absorption inside a hardened cement paste containing silanised silica fume

ABSTRACT

The influence of silanised silica fume addition on the pore size distribution and wettability of white cement paste was investigated using T₁–T₂ correlation nuclear magnetic resonance (NMR) relaxometry. Surface silanisation of silica fume particles was achieved by the hydrolysis reaction of APTES (3-Aminopropyltriethoxysilane) and condensation of the silanol functional groups on the surface. The methods used for characterisation of the silanised silica fume particles were scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). By adding silanised silica fume to the cement paste, the accessibility of water molecules to the porous system becomes restricted, leading to a lower permeability in comparison with the unmodified cement paste. Differential scanning calorimetry (DSC) measurements on the cement pastes saturated with Octamethylcyclotetrasiloxane confirm also that the size of inter-C–S–H and capillary pores is not influenced by the addition of silica fume in a detectable manner.     

Effect of Polyethylene Functionalization on Mechanical Properties and Morphology of PE/SiO2 Composites

In this study composites of high density polyethylene (HDPE) with various SiO₂ content were prepared by melt compounding using maleic anhydride grafted polyethylene (PE-g-MAH) as a compatibilizer. The composites containing 2, 4 and 6% by weight of SiO₂ particles were melt-blended in a co-rotating twin screw extruder. In all composites, polyethylene-graft-maleic anhydride copolymer (PE-g-MAH, with 0.85% maleic anhydride content) was added as a compatibilizer in the amount of 2% by weight. Morphology of inorganic silica filler precipitated from emulsion media was investigated. Mechanical properties and composite microstructure were determined by tensile tests and scanning electron microscopy technique (SEM). Tensile strength, yield stress, Young's modulus and elongation at break of PE/SiO₂ composites were mainly discussed against the properties of PE/PE-g-MAH/SiO₂ composites. The most pronounced increase in mechanical parameters was observed in Young's modulus for composites with polyethylene grafted with maleic anhydride. The increase in the E-modulus of PE/PE-g-MAH/SiO₂composites was associated with the compatibility and improvement of interfacial adhesion between the polyethylene matrix and the nanoparticles, leading to an increased degree of particle dispersion. This finding was verified on the basis of SEM micrographs for composites of PE/PE-g-MAH/4% by weight of SiO₂. The micrographs clearly documented that addition of only 2 wt% of the compatibilizer changed the composite morphology by reducing filler aggregates size as well as their number. Increased adhesion between the PE matrix and SiO₂ particles was interpreted to be a result of interactions taking place between the polar groups of maleic anhydride and silanol groups on the silica surface. These interactions are responsible for reduction of the size of silica aggregates, leading to improved mechanical properties.     

Composition dependence of AgSbO3/NaNbO3 composite on surface photovoltaic and visible-light photocatalytic properties

The visible-light-active xAgSbO₃/NaNbO₃ (x=0.5, 1, 2, 4, 6) composite photocatalysts were prepared by a conventional solid-state reaction method. Composition dependences on the structure, optical, surface photoelectronic and photocatalytic properties were investigated. The absorption edge of the composites could be red-shifted increasing the amount of AgSbO₃ in comparison with that of NaNbO₃. The surface photovoltage response shows the selectivity for the amount of AgSbO₃ in the samples. The photocatalytic activities for Rhodamine B degradation exhibit a parabola-like behavior with the amount of AgSbO₃. The highest photocatalytic activity is observed on the AgSbO₃/NaNbO₃ composite due to the better dispersiveness, electron transfer and surface photoelectric properties.