FTIR and XPS studies on corrosion resistant SiO2 coatings as a function of the humidity during deposition

The degradation of SiO2 coatings deposited on alloys by metal organic chemical vapour deposition (MOCVD) in sulphidizing high-temperature environments is determined by delamination and crack formation. With increasing water concentration during deposition, the crack density in silica decreases and the critical thickness for delamination of SiO2 coatings increases. This improvement is supposed to be caused by compositional changes in the SiO2 coating. In this study presence of water and silanol groups as measured by Fourier transform infrared spectroscopy(FTIR) and the Si:O ratio as measured by XPS are discussed in relation to the protective properties. The FTIRmeasurements show that the coatings deposited in more humid environments contain more silanol groups and have lower stress levels. The coatings obtained under all deposition conditions consisted of stoichiometric SiO2.0 as determined by XPS. The presence of silanol groups reduces the viscosity of the coating, and stress relaxation by viscous flow becomes enhanced, thereby improving the coating performance

Facile synthesis of cooperative acid-base catalysts by clicking cysteine and cysteamine on an ethylene-bridged periodic mesoporous organosilica

A periodic mesoporous organosilica (PMO) that contains ethylene bridges was functionalized to obtain a series of cooperative acid-base catalysts. A straightforward, single-step procedure was devised to immobilize cysteine and cysteamine on the support material by means of a photoinitiated thiol-ene click reaction. Likewise, PMO materials capped with hexamethyldisilazane (HMDS) were used to support both compounds. This resulted in different materials in which the amine site was promoted by carboxylic acid groups, surface silanol groups, or both. The catalysts were tested in the aldol reaction of 4-nitrobenzaldehyde and acetone. It was found that silanol groups have a stronger promoting effect on the amine than the carboxylic acid group. The highest turnover frequency (TOF) was obtained for an amine-functionalized material that contained only silanol promoting sites. The loading of the active sites also had a significant effect on the activity of the catalysts, which was rationalized on the basis of a computational study

The Nature of Silanol Groups on the Surfaces of Silica, Modified Silica and Some Silica Based Materials

-Silica gel, a material that is produced from the condensation polymerisation of silicic acid, contains surface silanol groups formed during the condensation. The silanol groups on the surface are mostly of free and vicinal silanol groups. These silanol groups can be modified in several different ways. Thermal treatment and hydrothermal treatment can be carried out to alter the concentration proportions between free and hydrogen bonded silanol groups on the surface. They can also be chemically treated with suitable chlorosilanes to modify the silanol groups into polar or non polar materials that can be used in separation science.This article explores the chemical nature of silanol groups on the surfaces of different materials. Near infrared reflectance spectroscopy was used as the instrumental technique in this study. The silanol groups classifications were made by analyzing the near infrared spectra obtained during the adsorption of water molecules. Absorption of the combination frequencies of water molecules in the region 5500- 5000 cm -1 were used in characterizing the silanol groups on the surfaces. Second derivative technique was employed in the resolution and detailed analysis of these absorptions.The study reveals that the materials contain free, vicinal and gem silanol groups. Silica gel contains free and vicinal silanol groups, thermally treated silica gel contains fewer vicinal silanol groups compared to the base silica gel, and hydrothermally treated silica gel contains higher concentrations of vicinal silanol groups compared to the base silica gel. Furthermore, the chemically modified silica gel contains vicinal or geminal silanol groups depending on the type of functionality introduced

Water adsorption on amorphous silica surfaces: A Car-Parrinello simulation study

A combination of classical molecular dynamics (MD) and ab initio Car-Parrinello molecular dynamics (CPMD) simulations is used to investigate the adsorption of water on a free amorphous silica surface. From the classical MD SiO_2 configurations with a free surface are generated which are then used as starting configurations for the CPMD.We study the reaction of a water molecule with a two-membered ring at the temperature T=300K. We show that the result of this reaction is the formation of two silanol groups on the surface. The activation energy of the reaction is estimated and it is shown that the reaction is exothermic.Comment: 12 pages, 6 figures, to be published in J. Phys.: Condens. Matte

Selective Enzymatic Oxidation of Silanes to Silanols

Compared to the biological world's rich chemistry for functionalizing carbon, enzymatic transformations of the heavier homologue silicon are rare. We report that a wild‐type cytochrome P450 monooxygenase (P450_(BM3) from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to give silanols. Directed evolution was applied to enhance this non‐native activity and create a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as the terminal oxidant. The evolved enzyme leaves C−H bonds present in the silane substrates untouched, and this biotransformation does not lead to disiloxane formation, a common problem in silanol syntheses. Computational studies reveal that catalysis proceeds through hydrogen atom abstraction followed by radical rebound, as observed in the native C−H hydroxylation mechanism of the P450 enzyme. This enzymatic silane oxidation extends nature's impressive catalytic repertoire

Multi-scale modelling of silicon nanocrystal synthesis by Low Pressure Chemical Vapor Deposition.

A multi-scale model has been developed in order to represent the nucleation and growth phenomena taking place during silicon nanocrystal (NC) synthesis on SiO2 substrates by Low Pressure Chemical Vapor Deposition from pure silane SiH4. Intrinsic sticking coefficients and H2 desorption kinetic parameters were established by ab initio modelling for the first three stages of silicon chemisorption on SiO2 sites, i.e. silanol Si―OH bonds and siloxane Si―O―Si bridges. This ab initio study has revealed that silane cannot directly chemisorb on SiO2 sites, the first silicon chemisorption proceeds from homogeneously born unsaturated species like silylene SiH2. These kinetic data were implemented into the Computational Fluid Dynamics Fluent code at the industrial reactor scale, by activating its system of surface site control in transient conditions. NC area densities and radii deduced from Fluent calculations were validated by comparison with experimental data. Information about the deposition mechanisms was then obtained. In particular, hydrogen desorption has been identified as the main limiting step of NC nucleation and growth, and the NC growth rate highly increases with run duration due to the autocatalytic nature of deposition

Aging mechanism in tunable Pickering emulsion

We study the stability of a model Pickering emulsion system. A special counter-flow microfluidics set-up was used to prepare monodisperse Pickering emulsions, with oil droplets in water. The wettability of the monodisperse silica nanoparticles (NPs) could be tuned by surface grafting and the surface coverage of the droplets was controlled using the microfluidics setup. A surface coverage as low as 23$\%$ is enough to stabilize the emulsions and we evidence a new regime of Pickering emulsion stability where the surface coverage of emulsion droplets of constant size increases in time, in coexistence with a large amount of dispersed phase. Our results demonstrate that the previously observed limited coalescence regime where surface coverage tends to control the average size of the final droplets must be put in a broader perspective