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Surface chemical heterogeneity modulates silica surface hydration.

ABSTRACT: An in-depth knowledge of the interaction of water with amorphous silica is critical to fundamental studies of interfacial hydration water, as well as to industrial processes such as catalysis, nanofabrication, and chromatography. Silica has a tunable surface comprising hydrophilic silanol groups and moderately hydrophobic siloxane groups that can be interchanged through thermal and chemical treatments. Despite extensive studies of silica surfaces, the influence of surface hydrophilicity and chemical topology on the molecular properties of interfacial water is not well understood. In this work, we controllably altered the surface silanol density, and measured surface water diffusivity using Overhauser dynamic nuclear polarization (ODNP) and complementary silica-silica interaction forces across water using a surface forces apparatus (SFA). The results show that increased silanol density generally leads to slower water diffusivity and stronger silica-silica repulsion at short aqueous separations (less than ?4 nm). Both techniques show sharp changes in hydration properties at intermediate silanol densities (2.0-2.9 nm-2). Molecular dynamics simulations of model silica-water interfaces corroborate the increase in water diffusivity with silanol density, and furthermore show that even on a smooth and crystalline surface at a fixed silanol density, adjusting the spatial distribution of silanols results in a range of surface water diffusivities spanning ?10%. We speculate that a critical silanol cluster size or connectivity parameter could explain the sharp transition in our results, and can modulate wettability, colloidal interactions, and surface reactions, and thus is a phenomenon worth further investigation on silica and chemically heterogeneous surfaces.

SUBMITTER: Schrader AM

PROVIDER: S-EPMC5866604 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature

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Surface chemical heterogeneity modulates silica surface hydration.

Schrader Alex M AM Monroe Jacob I JI Sheil Ryan R Dobbs Howard A HA Keller Timothy J TJ Li Yuanxin Y Jain Sheetal S Shell M Scott MS Israelachvili Jacob N JN Han Songi S

Proceedings of the National Academy of Sciences of the United States of America 20180305 12

An in-depth knowledge of the interaction of water with amorphous silica is critical to fundamental studies of interfacial hydration water, as well as to industrial processes such as catalysis, nanofabrication, and chromatography. Silica has a tunable surface comprising hydrophilic silanol groups and moderately hydrophobic siloxane groups that can be interchanged through thermal and chemical treatments. Despite extensive studies of silica surfaces, the influence of surface hydrophilicity and chem ...[more]

PMID: 29507240

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Project description:Antifouling properties of materials play crucial roles in many important applications such as biomedical implants, marine antifouling coatings, biosensing, and membranes for separation. Poly(ethylene glycol) (or PEG) containing polymers and zwitterionic polymers have been shown to be excellent antifouling materials. It is believed that their outstanding antifouling activity comes from their strong surface hydration. On the other hand, it is difficult to develop underwater glues, although adhesives with strong adhesion in a dry environment are widely available. This is related to dehydration, which is important for adhesion for many cases while water is the enemy of adhesion. In this research, we applied sum frequency generation (SFG) vibrational spectroscopy to investigate buried interfaces between mussel adhesive plaques and a variety of materials including antifouling polymers and control samples, supplemented by studies on marine animal (mussel) behavior and adhesion measurements. It was found that PEG containing polymers and zwitterionic polymers have very strong surface hydration in an aqueous environment, which is the key for their excellent antifouling performance. Because of the strong surface hydration, mussels do not settle on these surfaces even after binding to the surfaces with rubber bands. For control samples, SFG results indicate that their surface hydration is much weaker, and therefore mussels can generate adhesives to displace water to cause dehydration at the interface. Because of the dehydration, mussels can foul on the surfaces of these control materials. Our experiments also showed that if mussels were forced to deposit adhesives onto the PEG containing polymers and zwitterionic polymers, interfacial dehydration did not occur. However, even with the strong interfacial hydration, strong adhesion between mussel adhesives and antifouling polymer surfaces was detected, showing that under certain circumstances, interfacial water could enhance the interfacial bio-adhesion.

Project description:The main objective of this study is to evaluate the effect of the textural properties and surface chemical nature of silica nanoparticles obtained from different synthesis routes and silicon precursors, on their interactions with asphaltenes and further viscosity reduction of heavy crude oil (HO). Four different SiO2 nanoparticles were used, namely, commercial fumed silica nanoparticles (CSNs) and three in-house-synthesized nanoparticles (named based on the silicon source) modifying the silicon precursor: sodium silicate (SNSS), tetraethylorthosilicate (TEOS) (SNT), and rice husk (SNRH). The nanomaterials were characterized through dynamic light scattering (DLS), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, N2 physisorption (S BET), atomic force microscopy (AFM), and X-ray photoelectron (XP) spectroscopy (XPS). The adsorption of asphaltenes over the different nanoparticles was evaluated at a concentration of 1000 mg·L-1 in toluene. The asphaltene-nanoparticle interactions are closely related to several textural properties, such as roughness, surface area, and hydrodynamic diameter, as well as the surface chemical nature of the materials. The results in the textural characterization exhibited that the sizes of the nanoparticles from TEM ranged between 6.9 and 11.5 nm. Nevertheless, the standard deviation of the measurements showed that the sizes are statistically similar. Inversely, the hydrodynamic diameter changed, affecting the surface silanol group's availability due to a hindering effect on functional groups as the hydrodynamic size of the material increased. The rheological measurements were performed at a fixed nanoparticle dosage of 1000 mg·L-1 and showed that the trend of the degree of viscosity reduction (DVR) was CSN > SNT > SNSS > SNRH with the highest value yielding at 30%. The results of DVR are in accordance with the nanoparticles' adsorptive capacity as higher values were obtained with the material that leads to a higher amount of adsorbed asphaltenes. Also, the oxygen amount related to silanol groups, estimated by the XPS analysis, showed a direct relation regarding adsorption capacity and further HO viscosity reduction.

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Surface chemical heterogeneity modulates silica surface hydration.

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Surface chemical heterogeneity modulates silica surface hydration.

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