RESUMO
Stable silicone fluid-carbon nanotube dispersions were prepared in minutes by simple mixing processes, without the addition of solvents or surfactants and without the chemical modification of the nanotubes. With linear silicones of sufficient viscosity, a dual asymmetric centrifuge (SpeedMixer) was sufficient for dispersion; lower viscosity silicones required a brief ultrasound treatment. Optical microscopy indicates a homogeneous dispersion of multiwalled carbon nanotube (MWCNT) bundles in linear poly(dimethylsiloxane) (PDMS) oils. The facile dispersion of carbon nanotubes in PDMS has been reported in several previous publications and this appears to be general for silicones. MWCNTs also disperse readily, and to a greater extent, as assessed by optical microscopy, in poly(methylphenylsiloxane) and, in particular, poly(diethylsiloxane). Linear PDMS/MWCNT dispersions are stable against agglomeration for months. Platinum-catalyzed hydrosilylation of MWCNT-containing vinyl-/hydride-functionalized PDMS liquids yielded filled elastomers that unexpectedly exhibit significantly increased thermal stability. This enhancement occurs with only fractions of a weight percent of MWCNTs. Thermal gravimetric analysis shows a 54 °C increase in peak weight loss temperature (446-500 °C), an increased decomposition activation energy (158-233 kJ/mol), a second higher temperature decomposition process, and doubled char formation (20-40%) with only 0.5 wt %-added MWCNT. Pyrolysis combustion flow calorimetry confirmed the enhancement in thermal stability. Improvements in electrical conductivity were observed at loadings as low as 0.025 wt %. Spontaneous adsorption of dialkylsiloxane chains to MWCNT surfaces (wetting) and the resulting changes in the composite structure are implicated as the basis for dispersion and thermal behavior changes.
RESUMO
The rapid, room-temperature covalent attachment of alkylhydridosilanes (R3Si-H) to silicon oxide surfaces to form monolayers using tris(pentafluorophenyl)borane (B(C6F5)3, BCF) catalysis has recently been described. This method, unlike alternative routes to monolayers, produces only unreactive H2 gas as a byproduct and reaches completion within minutes. We report the use of this selective reaction between surface silanols and hydridosilanes to prepare surface-grafted poly(dimethylsiloxane)s (PDMSs) with various graft architectures that are controlled by the placement of hydridosilane functionality at one end, both ends, or along the chain of PDMS samples of controlled molecular weight. We also report studies of model methylsiloxane monolayers prepared from pentamethyldisiloxane, heptamethyltrisiloxane (two isomers), heptamethylcyclotetrasiloxane, and tris(trimethylsiloxy)silane. These modified silica surfaces with structurally defined methylsiloxane groups are not accessible by conventional silane surface chemistry and proved to be useful in exploring the steric limitations of the reaction. Linear monohydride- and dihydride-terminated PDMS-grafted surfaces exhibit increasing thickness and decreasing contact angle hysteresis with increasing molecular weight up to a particular molecular weight value. Above this value, the hysteresis increases with increasing molecular weight of end-grafted polymers. Poly(hydridomethyl-co-dimethylsiloxane)s with varied hydride content (3-100 mol %) exhibit decreasing thickness, decreasing contact angle, and increasing contact angle hysteresis with increasing hydride content. These observations illustrate the importance of molecular mobility in three-phase contact line dynamics on low-hysteresis surfaces. To calibrate our preparative procedure against both monolayers prepared by conventional approaches as well as the recent reports, a series of trialkylsilane (mostly, n-alkyldimethylsilane) monolayers was prepared to determine the reaction time required to achieve the maximum bonding density using dynamic contact angle analysis. Monolayers prepared from hydridosilanes with BCF catalysis have lower bonding densities than those derived from chlorosilanes, and the reactions are more sensitive to alkyl group sterics. This lower bonding density renders greater flexibility to the n-alkyl groups in monolayers and can decrease the contact angle hysteresis.
