Solid State NMR and TG/MS Study on the Transformation of Methyl Groups During Pyrolysis of Preceramic Precursors to SiOC Glasses

The sol-gel method was used to prepare two different starting gels containing SiCH₃-groups for the preparation of SiOC ceramics. To understand the role of Si—H bonds in the incorporation of carbon into the SiOC network, gels prepared from a 1:2 mixture of triethoxysilane and methyldiethoxysilane (T^HD^H2) and solely methyltriethoxysilane (T^Me) were investigated. Thermogravimetric analysis coupled with mass spectroscopy (TG-MS) in inert atmosphere was performed to attain an insight into the decomposition reactions involved during gel-glass transformation. Samples calcined at different temperatures up to 1000°C were characterized by ²⁹Si and ¹³C magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. The presence of SiH groups in the starting gel allows an efficient conversion of Si—CH₃ groups into CSi₄ sites at lower temperatures. As a result, despite a much lower amount of carbon in the starting T^HD^H2 gel (C/Si = 0.33) compared to the T^Me gel (C/Si = 1), the amount of carbon inserted into the SiOC network of both glasses is equivalent, but the T^Me sample contains the 10 fold amount of free carbon.     

Gels dried under supercritical and ambient conditions: a comparative study and their subsequent conversion to silica–carbon composite aerogels

In present work, we have prepared gels with various compositions of methyltrimethoxysilane—3-(2,3-epoxypropoxy) propyltrimethoxysilane (MTMS-GPTMS) using a two-step acid base sol–gel process. To make a comparative study between the two common drying routes, we prepared gels under supercritical and also under ambient conditions. The density of the supercritically dried hybrid aerogels lies between 0.18 and 0.31 gcm^?3, while the density of the ambient dried ones ranges between 0.35 and 0.42 gcm^?3. The surface area of MTMS-0.25 GPTMS aerogel dried under supercritical conditions, has been found to be 464 m² g^?1 with a pore volume and average pore diameter of 1.24 cm³ g^?1 and 11 nm respectively. The same composition dried under ambient conditions is found to have similar properties i.e. a BET surface area of 439 m² g^?1, pore volume of 1.22 cm³ g^?1 and average pore diameter of 11 nm. The aerogels were later pyrolyzed yielding silica/carbon composite aerogels. The pyrolized aerogels possessed a surface area as high as 207 m² g^?1 with a total pore volume of 0.98 cm³ g^?1. The pyrolysed aerogels were also calcined to yield carbon free materials.     

A comparative study of microstructural development in the sol–gel derived alumina–mullite nanocomposites using colloidal silica and tetraethyl orthosilicate

This paper compares the microstructure development of two alumina–15 vol% mullite composites during the sintering. The nanopowders of alumina–mullite composite were synthesized by the sol–gel method using aluminum chloride hexahydrate and two different silicon sources (colloidal silica in route 1 and tetraethyl orthosilicate in route 2). The alumina–mullite composites were prepared by pressing and sintering of the nanopowders. Although the intergranular mullites were observed in both routes, there were mullite particles in route 2 formed inside the alumina grains (intragranular mullite). Formation of the intragranular mullite is attributed to the drop in silica solubility, which occurs during the transition from metastable alumina to stable alumina. Compared to route 1, the relative density and the average grain size were increased and accelerated by route 2. The two-stage sintering is not useful for the mullite decomposition.     

Ambient pressure drying: a successful approach for the preparation of silica and silica based mixed oxide aerogels

Silica aerogels have received much attention in recent years as it has got a wide range of properties like high surface area, low density, high porosity, low dielectric constant, low thermal conductivity. Recently to make aerogels for commercial application ambient pressure drying has been preferred and also a cheap precursor like sodium silicate has been employed as the starting material instead of the alkoxides. In this review, attention will be given to the synthesis adopted for the preparation of silica and silica based mixed oxide/composite aerogels through ambient pressure drying. The properties of the prepared aerogels are also discussed in detail.     

Influence of the polymer architecture on the high temperature behavior of SiCO glasses: A comparison between linear- and cyclic-derived precursors

Two series of cross-linked polysiloxanes, precursors for silicon oxycarbide glasses, have been synthesized from a linear and a cyclic Si-H-containing siloxane having the same chemical formula (SiCOH₄). The crosslinking has been achieved by hydrosilylation reaction with various amounts of divinylbenzene (DVB). A detailed structural characterization has been performed by ²⁹Si and ¹³C MAS NMR, FT-IR and chemical analysis. As a result, two different structural models have been proposed for the two series of resins. The two resins have been pyrolyzed at 1400 °C and the resulting SiCO ceramics characterized by X-ray diffraction. It has been shown that the stability of the amorphous silica phase present in the SiCO ceramics is strongly influenced by the molecular organization of the starting precursors. The presence of siloxane rings in the cyclic-derived polysiloxane decreases the stability of the amorphous SiO₂ and promotes the crystallization of cristobalite.     

Hybrid RSiO1.5/B2O3 Gels from Modified Silicon Alkoxides and Boric Acid

A new sol-gel route, without any external water addition, for the preparation of hybrid RSiO_1.5/B₂O₃ gels (R = Me, Et, Vi) is reported. The gels are easily synthesized by reacting B(OH)₃ with the liquid silicon alkoxide. The gels have been characterized mainly by FT-IR and ¹¹B MAS NMR spectroscopy. The results show that this new sol-gel process allows the formation of a homogeneous borosilicate gel in which trigonal BO₃ units are incorporated into the siloxane network via B—O—Si bonds.