Mechanical and thermal properties of SiO2–PMMA monoliths

Organic–inorganic hybrid monoliths of cross-linked polymethylmethacrylate (PMMA) and silica (SiO₂) were prepared by sol–gel, using tetraethoxysilane (TEOS) and methylmethacrylate (MMA) as precursors and 3-(trimethoxysilyl) propylmethacrylate (TMSPM) to make compatible the organic and inorganic components. Two types of monoliths were prepared, H1-type using a molar ratio composition of 16:1:4 for water:TEOS:ethanol and 1:0.1:0.1 for TEOS:TMSPM:MMA and H2-type using 6.3:1:2.52 for water:TEOS:ethanol and 1:0.25:0.25 for TEOS:TMSPM:MMA. Semi-transparent monoliths were obtained in both cases after the gelation–solidification and drying processes, which took about seven days. Thermal properties of the samples were obtained by applying thermal lens spectroscopy and their mechanical properties were measured by depth sensing indentation and Vickers microhardness. FTIR spectroscopy measurements were performed to complement the characterization. We found that the hardness of the hybrid monoliths have values between those of commercial PMMA and a sol–gel SiO₂ monolith. This result is a consequence of the reinforcement produced by the SiO₂ component in the organic–inorganic hybrid matrix. The thermal diffusivity of the hybrid monoliths shows an appreciable increasing in the hybrid system with respect to the pure SiO₂ monolith. Mechanical behavior of monoliths is strong influenced by the SiO₂–PMMA ratio or changing the water:TEOS:ethanol contents.     

Studies of the pumping effect on the nanoporous microstructure of disordered mesoporous silica materials prepared by calcinations of PMMA-silica hybrids

We present the first comparative studies of pumping effect (i.e., exhaustive vacuum evacuation) on the as-prepared nanoporous microstructure silica to elucidate the effect of different preparative procedure on a series of obtained disordered mesoporous silica materials. The as-prepared hybrid materials (PMMA-silica) through the pumping treatment exhibited higher thermal decomposition temperature (T_d) and density (D) than these system without pumping treatment based on the studies of thermogravimetric analysis and density measurements and compared with the nanoporous materials by calcinations of PMMA-silica materials was found to exhibit a significant higher value of surface area (A_BET) based on N₂ adsorption–desorption isotherm. Furthermore, a marked decrease in A_BET and V_BJH of as-prepared mesoporous silica are observed as the feeding content of TEOS is increased. The morphological images of as-prepared hybrid sol–gel glasses and their corresponding disordered mesoporous silica materials were also studied by scanning electron microscopy and transmission electron microscopy.     

Novel polyether–inorganic hybrid mesoporous silica synthesized through in situ incorporation of organic functionality

A new polyether–inorganic hybrid mesoporous silica has been synthesized through in situ incorporation of hydroquinone (HQ) moiety bridging between two silica units using tetraethyl orthosilicate (TEOS) as silica source in the presence of the self assembly of cationic surfactant under acidic pH. Samples synthesized with TEOS:HQ mole ratio of 2.0 and 4.0 showed good organic loading, mesoporosity and stability. Decreasing this ratio to 1.0 resulted in a organic-rich mesoporous hybrid material, which collapsed during template removal, whereas, increasing this ratio to 8.0 resulted in very poor incorporation of hydroquinone in the mesoporous silica. XRD and N₂ sorption data suggested the mesopore structure. TEM images indicated the wormhole like structure of these mesoporous samples. Solid state NMR data suggested the existence of (–O–C₆H₄–O)₂Si¹(OSi)₂ and (–O–C₆H₄–O)Si¹(OSi)₃ sites in addition to (Si¹(OSi)₄) sites. UV–Visible and FT-IR data suggested the incorporation of hydroquinone species and Si–O–Ph bonding in the samples.     

Morphology control of MSU-1 silica particles

Mesoporous silica, MSU-1 with spherical morphology was prepared using TEOS (tetraethylorthosilicate) as a silica source in the presence of an alkyl polyethylene oxide surfactant via the novel two-step process proposed by Prouzet’s group: hydrolysis of TEOS conducted in highly acidic condition at room temperature followed by condensation promoted by fluoride salt addition at 35 °C. The particles produced were characterized by XRD, SEM, and N₂ adsorption/desorption isotherm. Static condensation period was found to be essential to have spherical morphology. Growth of spherical particles and evolution of porosity were studied as a function of time, temperature, NaF/TEOS, and TEOS/surfactant ratio. The MSU-1 particles prepared under different synthesis conditions were briefly tested for chromatographic separation of selected organic molecules, which demonstrates the governing influence of the pore size in MSU-1 on retention time.     

A comparative FTIR study of thermal and photo-polymerization processes in hybrid sol-gel films

Controlling the organic polymerization in organic-inorganic hybrids is a key point in the development of new materials with high homogeneity of the nanostructure. The main difficulty is related with the achievement of a simultaneous control of the organic and inorganic network formation. Thermal and photocuring represent the main routes to form the organic chains when polymerizable organic groups are present in the hybrid materials. In the present work hybrid organic-inorganic films were synthesized from 3-methacryloxypropyltrimethoxysilane (MPTMS) cohydrolyzed with tetraethylorthosilicate (TEOS) and N-[(3-trimethoxysilyl)propyl]ethylenediamine (TMESPE) or 3-(triethoxysilyl)-propylamine (TESPA). This an example of basic catalyzed hybrid material with a polymerizable methacrylate functionality whose micro-structure is modified by the amine groups. FTIR spectroscopy was used to compare the effects of thermal or photo-induced polymerization on the materials. TESPA and TMESPE showed a different catalytic effect on the condensation of the inorganic network, with TMESPE the more efficient one. The presence of a more extended silica backbone reduced the curing efficiency in TMESPE derived samples. UV curing was also very effective in catalyzing the inorganic condensation of un-reacted species still present in the film after the deposition. A photo-induced polymerization of the inorganic side was observed in the hybrid films. Thermal polymerization in TMESPE films induces the reaction between the secondary amine and CO bonds in MPTMS, this reaction is, instead, not observed in films cured by UV radiation.     

Fabrication of mesoporous polymer/silica hybrid using surfactant-mediated sol–gel method

A mesoporous polymer/silica hybrid was fabricated by a surfactant-mediated sol–gel method. Under our experimental conditions, acrylonitrile (AN) monomer was located at the exterior of micelles and the sol–gel reaction of tetraethoxyorthosilicate (TEOS) proceeded concurrently with the polymerization reaction of the AN monomer. In other words, the micelle/polyacrylonitrile/silica precursor was synthesized through the radical polymerization accompanied with a hydrolysis/condensation single reaction in a reaction system. This is a unique characteristic of our methodology, which embraces the concept of ‘micelle templating’. The pore diameter of the mesoporous polymer/silica hybrid could be tuned by varying the spacer length and concentration of surfactants. Furthermore, compared with conventional mesoporous carbons, the carbonized mesoporous polymer/silica hybrids displayed an enhanced electrical performance favorable for use as a supercapacitor.     

Preparation of hollow silica spheres with different mesostructures

Hollow silica spheres were quickly synthesized by an octylamine (OA) templating method using tetraethyl orthosilicate (TEOS) as the silica source. N₂-sorption results indicate that the hollow spheres have high surface areas and pore volumes. XRD and TEM measurements reveal that the structure of the hollow spheres depends on the amount of TEOS used in the synthesis. When low amount of TEOS is added, the template-containing precursor spheres depict an XRD pattern with two peaks, which can be indexed to a lamellar phase. After the removal of the template, the obtained hollow spheres show no diffraction peaks in the XRD pattern, suggesting that the nanopores in the silica shells are disordered. If increasing the amount of TEOS, either the uncalcined or the calcined sample gives an XRD pattern with a single diffraction peak. The mesostructure of these hollow silica spheres is typically as HMS materials. TGA analyses suggest that the interaction between the silica species and surfactant is stronger in the latter case.     

Luminescent porphyrinosilica obtained by the sol–gel method

Hybrid materials consisting of a substituted porphyrinic macrocycle covalently bonded to a porous silica matrix have been prepared. The organic macrocycle 5,10,15,20-tetra-(p-hydroxy)phenylporphyrin, H₂T(p-OH)PP, has been covalently bonded to silica gel porous networks, obtained by sol–gel reactions, by means of 3-isocyanatopropyl-triethoxysilane (IPTES), whose molecules act as bridges between the silica precursor tetraethoxysilane (TEOS) and the porphyrinic H₂T(p-OH)PP macrocycles. Electronic absorption spectra show Soret and Q bands characteristic of trapped porphyrins inside the silica networks. Infrared spectroscopy monitoring has been employed to demonstrate the formation of covalent bonds between some substituents of the porphyrin molecules and the isocyanato group of IPTES.     

Multigram scale synthesis and characterization of low-density silica xerogels

The synthesis of silica with preserved porosity and tailored morphology by sol–gel process can be achieved by hybrid organic–inorganic synthesis: a modified alkoxide, viz. 3-(2-aminoethylamino)propyltrimethoxysilane (EDAS), is introduced during the base catalysed synthesis with TEOS as main silica precursor. Additives with methoxy groups induce a nucleation mechanism because of their higher reactivity compared to main reagents with ethoxy groups. The nucleation model presented in previous papers was refined by taking into account the porosity of the particles and calculating the number of additive molecules by nucleus for each value of the ratio of additive/main reagent. The extrapolation of the synthesis process to semi-industrial scale goes through the replacement of laboratory grade reagents by industrial grade reagents and the scaling up to the production of higher quantities. At each of these two steps, the morphology and porosity of the samples has been compared to those of laboratory grade samples. It was shown that the texture and particle size has quasi totally been preserved.     

Understanding the mechanisms of reaction and release of acid–base indicators entrapped in hybrid gels

The reactivity and release of acid–base indicators entrapped in silica and hybrid silica gels were studied. Methyl orange (MO), methyl red (MR), and phenyl red (PR) were used as the indicators. Tetraethoxysilane (TEOS), n-propyltriethoxysilane (PTES), and bis(trimethoxysilyl)hexane (TSH) were used as gel precursors. HCl (0.01 M) and NaOH (0.01 M) solutions were used as the media for acid–base reaction and release in the experiments. The effects of organosilane addition were examined to understand the processes and mechanisms of reaction and release of the indicators entrapped in the gels. The experimental results suggest that adding the organosilanes lowers the pore size and pore volume of the gels, and therefore suppresses the indicator release, but does not present any obvious effects on the acid–base reactivity of the entrapped indicators. MR entrapped in the gels has no acid–base response, while MO and PR entrapped in the gels can present acid–base response without definite acid–base indicating pH ranges. Only the color change pH values can be determined, which present a ‘lag effect’ or ‘hysteresis’ compared with the cases of the free indicators in solutions. The reactivity of the entrapped indicators is suggested to be mainly determined by their chemical nature, the interactions between the indicators and the gel matrices, and the possible involvement of the indicators in the sol–gel process. In general more indicators were found to release in basic solutions than in acidic solutions. For all the entrapped indicators, in acidic solutions through the whole release process, and in basic solutions at the beginning of the release, the indicator release was found to follow the sequence of TEOS Gel > TEOS/PTES Gel > TEOS/TSH Gel. The overall release process is diffusion-controlled, and the release is mainly affected by the textural properties of the gels, the interactions between the gel matrices and the indicators, and the indicator solubility.     

Phase separation in the solution of water glass and poly(vinyl alcohol)

Silica gel samples with macropores were prepared from solutions of silicate and poly(vinyl alcohol) (PVA), where macropores were formed by fixing a transitional structure of phase separation. Among the silica sources tested, tetraethoxysilane (TEOS), colloidal silica and water glass, only the system with water glass shows phase separation and forms macroporous silica gel. In the system with TEOS, ethanol formed during hydrolysis of TEOS becomes good solution and stabilizes the system not to induce phase separation. In the system with colloidal silica, dense structure of silica is probably not suitable for controlling phase separation and gelation. In the system with water glass, driving force of phase separation is considered to be a repulsive interaction between solvent molecules and PVA interacting with silica surface and the solution separates into a phase rich in solvent and that rich in silica and PVA. One of the features in the water glass-PVA system is insensitivity of macropore size against compositional change in the solution, i.e. macroporous morphology in the resultant silica gel hardly changes by changing the composition ratio in the solution. This would be an advantage in the preparation of well-defined macroporous silica from water glass, whose composition varies among the product lot number, because reproducibility in macroporous morphology is ensured regardless of the lot number of the water glass.     

Observation of the aggregation behavior of silica sols using laser speckle contrast measurements

We report on a new optical method to observe the onset of aggregation in alcoholic tetraethoxysilane (TEOS) sols using laser speckle contrast measurements. The contrast in a speckle image produced by coherent light provides information about the internal contrast of the medium being studied. For silica sols, changing the amount of acid or base catalyst was the most important factor in determining the aggregation behavior of the sol. We investigated this effect by varying the TEOS/base ratio by a factor of 6. This shifted the onset of aggregation as determined by speckle contrast from 46% of the gel time for the lowest amount of base to 74% for the highest. Conversely, varying TEOS/acid ratio by a factor of 3, shifted the onset of aggregation from 74% of the gel time for the lowest amount of acid to 64% for the highest. Measurements of this type provide information that can be used to test models of sol aggregation and gel formation.     

Synthesis via sol–gel process and characterization of novel organic–inorganic coatings

Organic–inorganic coatings were synthesized from tetraethoxysilane (TEOS) and vinyltriacetoxysilane (VTAS) via dual process involving sol–gel reaction and radical polymerization. The deposition of the films was carried out using the spin-coating technique with the sample holder spinning at 1500 rpm. In order to determine the nature of products formed during the sol–gel reaction (i.e. polymerization) and to study the kinetics of this reaction, Fourier transform infrared (FTIR) spectroscopy experiments were performed. This technique allows also determining the optimal temperature of the final heat treatment. Thermogravimetric analysis (TGA) was used to study the influence of the ratio of organic and inorganic components on the thermal stability of the organic–inorganic hybrid, while differential scanning calorimetry (DSC) was used to determine its glass transition temperature. The chemical structure of this prepared hybrid material is also studied using FTIR with attenuated total reflection (ATR) device.Finally, the homogeneity of the chemical composition of the synthesized materials was checked by using the elemental distributions obtained by an energy dispersive spectrometer (EDS) attached to a scanning electron microscope (SEM). Moreover, nanoindentation measurements on thin films show enhanced hardness and elastic modulus with increasing silicate network.     

Organic–inorganic hybrid coatings for corrosion protection

The corrosion resistance of sol–gel derived, organic–inorganic, silica-based hybrid coatings with various amounts of organic content was studied. Hybrid sols were prepared by copolymerizing tetraethylorthosilicate (TEOS) and 3-methacryloxypropyltrimethoxysilane (MPS) with a two-step acid-catalyst process. Hybrid coatings were dip-coated on 304 stainless steel substrates and annealed at 300 °C for 30 min. Such prepared hybrid coatings were found to be relatively dense, uniform and defect free. The adhesion and flexibility of the coatings were characterized. The influences of the amount of organic component incorporated into the coatings and the aging of sols on corrosion protection were studied. Electrochemical analyses showed that the relatively dense hybrid coatings provided excellent corrosion protection by forming a physical barrier, which effectively separated the anode from the cathode. Some preliminary biocompatibility tests were also conducted on the hybrid coatings.     

Effect of the inclusion of a water soluble high molecular weight oligomer on the surface characteristics of silica gel

The surface characteristics of pure and polyglycol 4000 containing silica gels were investigated by nitrogen adsorption at ? 195°C and water adsorption at 35°C. The addition of polyglycol 4000 during the precipitation of silica gel led to a remarkable increase in the surface area as well as the pore volume and on the other hand a sharp drop in c-BET constant.Thermal treatment led to a variation in the surface characteristics of both pure and polyglycol containing silica gels, but in different ways. Inclusion of polyglycol 4000 led to a retardation of the dehydroxylation process that occurs at elevated temperature. The decrease in surface area at 400°C was much higher in polyglycol 4000 containing silica gel than in the pure simple, an effect which correlated with shrinkage of the polymer at high temperature. Slight increase in surface area at 500°C may be attributed to the phase change from β to α form. For the high content polyglycol sample the phase change effect was counteracted by the shrinkage of the polyglycol.Water vapor adsoprtion indicated that polyglycol 4000 containing silica gel was more lyophobic in character than the pure gel at all temperatures except at 200°C.     

Study of the influence of some DCCAs on the structure of sol–gel silica membranes

We obtained silica gel membranes by sol–gel processing. In order to study the effect of some drying control chemical additives, we used an alkoxide/additive molar ratio of 1/1. The performance of the drying additives in obtaining crack-free gels was evaluated through monolithicity measurements. The structural evolution occurring in the interconnected network of the membranes during thermal treatment was monitored by Fourier transform infrared spectroscopy, structural density measurements and nitrogen gas sorption. The degree of cross-linking of the silica network was inferred from the frequency of the Si–O(Si) vibration in the range. We noted that in the presence of formamide and N,N-dimethylformamide, the Si–O–Si bonds are stronger and belong to a more cross-linked structure. Changes in the chemical properties of the membranes, evaluated by quantities of molecular water and silanol groups on their surface, were monitored by absorption bands in the range of 3800–3000 cm⁻¹. Membranes obtained with additives have surfaces covered by a large content of isolated silanol groups even when annealed at 800 °C. The membrane obtained in the presence of amide has larger pore volume and its pore structure is in the range of mesoporosity. The membranes without additive and with propylene carbonate are microporous. Formamide and N,N-dimethylformamide allowed the preparation of crack-free membranes stabilized at high temperatures.     

In situ studies of order–disorder phenomena in the synthesis of mesoporous silica

The initial hydrolysis of a silicon alkoxide in the presence of a suitable structural directing agent (template) so as to form a mesoporous silica powder exhibiting long-range hexagonal ordering was monitored using in situ XRD (X-ray diffraction), SAXS (small angle X-ray scattering) and SANS (small angle neutron scattering). The non-ionic triblock copolymer P123 (EO₂₀PO₆₉EO₂₀) was employed as the organic templating agent and tetramethoxysilane (TMOS) was used as the silica source in the presence of a water/acid catalyst. The synthesis method described herein is based around a high volume concentration ratio of surfactant to TMOS. The formation of a long-range mesoscopically ordered organic–inorganic hybrid that could be subsequently calcined to form a hexagonally structured mesoporous oxide material was monitored over 6 days using the characteristic (1 0 0) reflection. It was seen that during this ‘maturation’ period the reaction is not progressive and SANS and SAXS data together with XRD experiments show that there is an initial kinetically rapid organic ordering process which provides a template for the formation of an ordered metastable organic–inorganic oxide phase which then becomes progressively more disordered before a final kinetically slow stable long-range ordered phase is formed. Discussions of the origin of the unexpected order–disorder phenomena are made.     

Percolation transition of siloxane domain in partially phenylated organic/inorganic hybrid glass

Organic-inorganic hybrid glass undergoes a percolation transition of the organic or inorganic moiety at a certain volume fraction of either phase. At the percolation threshold, various properties of the hybrid glass exhibit an abrupt change. We attempted to evaluate the threshold volume fraction of the percolation transition in partially phenylated glass from the measurable or observable behavior at the percolation transition. The volume fraction of the phenyl moiety in the hybrid glass was varied by variation of the mixed fraction of two starting silicon alkoxides, TEOS (tetraethylorthosilicate) and PTES (phenyltriethoxysilane). The threshold volume fraction was estimated as the point at which the dye-colored state with hydrophilic/hydrophobic dye, the Vickers hardness and siloxane bonding length exhibited a significant change. The percolation threshold of the phenyl moiety was estimated to be approximately 50 vol.%. At this threshold, the Vickers hardness showed a abrupt and almost discrete decrease and noticeable elasticity appeared. At the same time, the siloxane bondings were stretched by approximately 20% on the percolation of the phenyl part. In partially phenylated glass prepared from mixture of TEOS and PTES, the siloxane bondings seem to have a strong tendency to form a percolated siloxane network, and as a result of that, only the percolation of the phenyl moiety could be captured from the experimentally measurable quantities.     

Effects of organic content and H2O/TEOS molar ratio on the porosity and pore size distribution of hybrid naphthaleneaminepropylsilica xerogel

The hybrid naphthaleneaminepropylsilica material was obtained by a sol-gel route, varying the organic loading and the water/TEOS molar ratio. Infrared spectroscopy was used to identify the organic and inorganic phases. The morphology of the hybrid material was studied by using scanning electron microscopy and N₂ adsorption-desorption isotherms. It was observed that the increase in the organic content produces a decrease in the size and volume of the pores as well as in the surface area of the xerogel. The best porosity was obtained for water/TEOS molar ratio between 4 and 6.     

Assembling ultra-thick and crack-free colloidal crystals via an isothermal heating evaporation induced self-assembly method

Ultra-thick and crack-free colloidal crystals have many advantages in a number of existing and emerging applications. In this work, such systems are fabricated by a simple and reproducible method based on assembly of monodisperse silica particles by a crystalline layer assembly technique (CLAT). We find that high quality of colloidal crystals is obtained by using two simple processes: sintering of silica particles and thermal treatment of colloidal crystals. The crack-free colloidal crystal with a thickness of 100 μm is fabricated. The morphologies and microstructures of colloidal crystals are identified by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The reflection spectra are measured by UV-VIS spectrum measurement. The reflection spectra of the colloidal crystal with different thicknesses are calculated by using multiple scattering methods. When the thickness of the colloidal crystal is smaller than 60 μm, the reflection spectra of experimental measurements agree very well with that of theoretical calculations.