Comparative characterization of polymethylsiloxane hydrogel and silylated fumed silica and silica gel

Polymethylsiloxane (PMS) hydrogel (CPMS=10 wt%CPMS=10 wt%, soft paste-like hydrogel), diluted aqueous suspensions, and dried/wetted xerogel (powder) were studied in comparison with suspensions and dry powders of unmodified and silylated nanosilicas and silica gels using 1H NMR, thermally stimulated depolarization current (TSDC), quasielastic light scattering (QELS), rheometry, and adsorption methods. Nanosized primary PMS particles, which are softer and less dense than silica ones because of the presence of CH3 groups attached to each Si atom and residual silanols, form soft secondary particles (soft paste-like hydrogel) that can be completely decomposed to nanoparticles with sizes smaller than 10 nm on sonication of the aqueous suspensions. Despite the soft character of the secondary particles, the aqueous suspensions of PMS are characterized by a higher viscosity (at concentration CPMS=3–5 wt%CPMS=3–5 wt%) than the suspension of fumed silica at a higher concentration. Three types of structured water are observed in dry PMS xerogel (adsorbed water of 3 wt%). These structures, characterized by the chemical shift of the proton resonance at δH≈1.7,3.7δH≈1.7,3.7, and 5 ppm, correspond to weakly associated but strongly bound water and to strongly associated but weakly or strongly bound waters, respectively. NMR cryoporometry and QELS results suggest that PMS is a mesoporous–macroporous material with the textural porosity caused by voids between primary particles forming aggregates and agglomerates of aggregates. PMS is characterized by a much smaller adsorption capacity with respect to proteins (gelatin, ovalbumin) than unmodified fumed silica A-300.

Graphical abstractBranched polymethylsiloxane molecules form primary nanoparticles (<10 nm<10 nm) structured in soft mesoporous/macroporous secondary particles (0.1–5 μm) with textural porosity responsible for adsorption of proteins and other macromolecules.Figure optionsDownload full-size imageDownload as PowerPoint slide