Polyvinylpyrrolidone macromolecules function as a diffusion barrier during dealloying

The inhibition effect of polyvinylprrolidone (PVP) during dealloying on the formation of nanoporous Cu from a Ti60Cu40 amorphous alloy in hydrofluoric acids (HF) was investigated. A bicontinuous nanoporous Cu structure formed on Ti60Cu40 after dealloying. The pore size of nanoporous Cu formed in HF solution was 71 nm, but this decreased to 12 nm and 11 nm after dealloying for the same period of dealloying time of 43.2 ks when 0.01 M and 0.03 M PVP, respectively, was added into the 0.03 M HF base solution. The surface diffusivity was estimated to decrease from 2.5 x 10(-18) m(2) s(-1) in 0.03 M HF solution to 1.84 x 10(-21) m(2) s(-1) when 0.01 M PVP was added, and to 1.42 x 10(-21) m(2) s(-1) when 0.03 M PVP was added. More PVP macromolecules were adsorbed onto the nanoporous Cu surface in the 0.03 M HF solution with the addition of 0.03 M PVP than when 0.01 M PVP was added to the solution, which resulted in the formation of smaller nanopores. The suppressed diffusion of Cu adatoms due to the PVP macromolecule resulted in the formation of finer Cu ligaments than that formed in 0.03 M HF solution. This long chain organic molecule was shown to act as a diffusion barrier for the diffusion of metal adatoms during dealloying and to elaborate the nanoporous structure. (C) 2014 Elsevier B.V. All rights reserved.