4.6 Article

Biobased superhydrophobic coating enabled by nanoparticle assembly

Journal

NANOSCALE ADVANCES
Volume 3, Issue 14, Pages 4037-4047

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1na00296a

Keywords

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Funding

  1. Iowa Space Grant Consortium under NASA [80NSSC20M0107]
  2. Iowa EPSCoR Research Building Seed Grant
  3. EPSCoR Grant under NASA [ID-NNH20ZHA001C]
  4. American Chemical Society Petroleum Research Fund [60264-DNI7]
  5. State of Iowa Biosciences Initiative
  6. NASA fellowship from the Iowa Space Grant Consortium (ISGC)

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This study investigates the correlation between the assembly structures of biobased nanocomposites and their performance, revealing new opportunities for developing high-performance sustainable materials using biobased polymers. The unique fractal assembly structures observed in silica nanoparticle assemblies with hydroxyethyl cellulose greatly improve adhesion and hydrophobicity of coatings, showcasing the potential for waterborne superhydrophobic formulations. These findings highlight the importance of molecular conformation in biobased polymers in influencing nanoscale assembly structures and macroscopic coating performance.
Understanding biobased nanocomposites is critical in fabricating high performing sustainable materials. In this study, fundamental nanoparticle assembly structures at the nanoscale are examined and correlated with the macroscale properties of coatings formulated with these structures. Nanoparticle assembly mechanisms within biobased polymer matrices were probed using in situ liquid-phase atomic force microscopy (AFM) and computational simulation. Furthermore, coatings formulated using these nanoparticle assemblies with biobased polymers were evaluated with regard to the hydrophobicity and adhesion after water immersion. Two biobased glycopolymers, hydroxyethyl cellulose (HEC) and hydroxyethyl starch (HES), were investigated. Their repeating units share the same chemical composition and only differ in monomer conformations (alpha- and beta-anomeric glycosides). Unique fractal structures of silica nanoparticle assemblies were observed with HEC, while compact clusters were observed with HES. Simulation and AFM measurement suggest that strong attraction between silica surfaces in the HEC matrix induces diffusion-limited-aggregation, leading to large-scale, fractal assembly structures. By contrast, weak attraction in HES only produces reaction-limited-aggregation and small compact cluster structures. With high particle loading, the fractal structures in HEC formed a network, which enabled a waterborne formulation of superhydrophobic coating after silane treatment. The silica nanoparticle assembly in HEC was demonstrated to significantly improve adhesion, which showed minimum adhesion loss even after extended water immersion. The superior performance was only observed with HEC, not HES. The results bridge the assembly structures at the nanoscale, influenced by molecular conformation of biobased polymers, to the coating performance at the macroscopic level. Through this study we unveil new opportunities in economical and sustainable development of high-performance biobased materials.

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