title: Tailoring of interfacial mechanical shear strength by surface chemical modification of silicon microwires embedded in Nafion membranes.
abstract: The interfacial shear strength between Si microwires and a Nafion membrane has been tailored through surface functionalization of the Si. Acidic (-COOH-terminated) or basic (-NH2-terminated) surface-bound functionality was introduced by hydrosilylation reactions to probe the interactions between the functionalized Si microwires and hydrophilic ionically charged sites in the Nafion polymeric side chains. Surfaces functionalized with SiOx, Si-H, or Si-CH3 were also synthesized and investigated. The interfacial shear strength between the functionalized Si microwire surfaces and the Nafion matrix was quantified by uniaxial wire pull-out experiments in an in situ nanomechanical instrument that allowed simultaneous collection of mechanical data and visualization of the deformation process. In this process, an axial load was applied to the custom-shaped top portions of individual wires until debonding occurred from the Nafion matrix. The shear strength obtained from the nanomechanical measurements correlated with the chemical bond strength and the functionalization density of the molecular layer, with values ranging from 7 MPa for Si-CH3 surfaces to ∼16-20 MPa for oxygen-containing surface functionalities. Hence surface chemical control can be used to influence the mechanical adhesion forces at a Si-Nafion interface.
authors: †Division of Chemistry and Chemical Engineering, ‡Division of Engineering and Applied Sciences, §The Kavli Nanoscience Institute at Caltech, and ∥The Beckman Institute at Caltech, California Institute of Technology, Pasadena, California 91125, United States.
authors: Betar M
authors: BM
authors: Gallant
authors: †Division of Chemistry and Chemical Engineering, ‡Division of Engineering and Applied Sciences, §The Kavli Nanoscience Institute at Caltech, and ∥The Beckman Institute at Caltech, California Institute of Technology, Pasadena, California 91125, United States.
authors: X Wendy
authors: XW
authors: Gu
authors: †Division of Chemistry and Chemical Engineering, ‡Division of Engineering and Applied Sciences, §The Kavli Nanoscience Institute at Caltech, and ∥The Beckman Institute at Caltech, California Institute of Technology, Pasadena, California 91125, United States.
authors: David Z
authors: DZ
authors: Chen
authors: †Division of Chemistry and Chemical Engineering, ‡Division of Engineering and Applied Sciences, §The Kavli Nanoscience Institute at Caltech, and ∥The Beckman Institute at Caltech, California Institute of Technology, Pasadena, California 91125, United States.
authors: Julia R
authors: JR
authors: Greer
authors: †Division of Chemistry and Chemical Engineering, ‡Division of Engineering and Applied Sciences, §The Kavli Nanoscience Institute at Caltech, and ∥The Beckman Institute at Caltech, California Institute of Technology, Pasadena, California 91125, United States.
authors: Nathan S
authors: NS
authors: Lewis
keywords: Nafion; Si microwires; in situ tension; nanomechanical; surface functionalization