ABSTRACT
Nanometer thin films of Nafion ionomer interfaced with platinum form the functional electrodes in many electrochemical devices including fuel cells and electrolyzers. To impart facile proton conduction in a Nafion ionomer, sufficient hydration of the Nafion ionomer is necessary to create a percolating network of water-filled nanometer-sized hydrophilic domains that manifest as macroscopic swelling. This hydration behavior of the ionomer thin films is poorly understood especially for films confined on electrochemically relevant Pt substrates. In this work, we present the evolution of hydration-dependent microscopic hydrophilic domains and macroscopic expansion of a 55 nm thin Nafion film on a Pt substrate. The cross-correlation among the film macro-expansion from ellipsometry, the micro-expansion from GISAXS, and the water distribution from neutron reflectometry (NR) explains the observed non-affine behavior of the film which can be attributed to the randomly and spatially non-uniform distribution of water domains. A correlation between the macroscopic factor (ε/τ) for protonic conductivity, and the domain size and swelling is presented for the first time. In addition, interfacial water between Pt and the ionomer interface is estimated at 75% and 84% RH, and an increase in domain size with RH is discussed to explain the increased activity and oxygen diffusivity with RH.
ABSTRACT
Water uptake and swelling in a thin (â¼15 nm) Nafion film on SiO2 native oxide on a Si wafer is studied as a function of relative humidity (8-97%) at room temperature and as a function of temperature (25-60 °C) at 97% relative humidity by neutron reflectometry. This is the first report on the behavior of thin Nafion films at elevated temperatures and high humidity. Large hysteresis is observed during the temperature cycle. The observed swelling strain in the film at 60 °C is 48% as compared to the as-deposited state, which is far above any previously observed trend at room temperature. A small decrease in the average SLD suggests that part of the additional swelling is due to thermal expansion, but the estimated D2O/SO3 ratio also increases by 70%. Half of the "excess" absorption and 73% of the additional swelling are retained during cooling back to room temperature. The results provide new insights into the dynamics of Nafion on nanometer scales under fuel cell operating conditions.
ABSTRACT
Neutron reflectometry data and modeling support the existence of a relatively thick, continuous phase of water stemming from within an antifouling monoethylene glycol silane adlayer prepared on oxidized silicon wafers. In contrast, this physically distinct (from bulk) interphase is much thinner and only interfacial in nature for the less effective adlayer lacking internal ether oxygen atoms. These results provide further insight into the link between antifouling and surface hydration.
Subject(s)
Ethylene Glycol/chemistry , Fluoroacetates/chemistry , Organosilicon Compounds/chemistry , Silanes/chemistry , Water/chemistry , Biocompatible Materials/chemistry , Molecular Structure , Neutron Diffraction , Surface PropertiesABSTRACT
The effect of chromium and vanadium alloying on the hydrogenation of a magnesium thin film is studied by neutron reflectometry. Immediate formation of a blocking MgD(2) layer is observed in pure Mg, however in the alloyed film deuteration is rapid and almost completely homogeneous.
ABSTRACT
Neutron reflectometry was used to determine the distribution of salt ions and water in thin poly(acrylic acid) and poly(allylamine hydrochloride) polyelectrolyte multilayers assembled with and without salt. Increasing salt concentration reverses the exclusion of water from the substrate region, eventually leading to an asymmetric segregation of water near the substrate at high salt concentration. The counterions were found to localize near the substrate in films that were either assembled with salt or were exposed to salt solutions. In addition, the capping layer of the film was found to greatly influence the counterion distribution in the multilayer.
Subject(s)
Electrolytes , Neutrons , Acrylic Resins/chemistry , Chemistry, Physical/methods , Drug Delivery Systems , Hydrogen-Ion Concentration , Ions , Kinetics , Polyamines/chemistry , Salts/chemistry , Solvents , Temperature , Water/chemistryABSTRACT
The water localization in thin polyelectrolyte multilayers assembled from poly(acrylic acid) and poly(allylamine hydrochloride) was investigated with neutron reflectivity in an atmosphere of controlled humidity and with bulk water. Water was found to be distributed asymmetrically within the multilayer and to localize preferentially at the polymer surface. The diffusion of water into the multilayer did not completely penetrate to the substrate, but instead there appeared to be an exclusion zone near the Si substrate. These results help to explain previous observations of anomalous water transport kinetics in weak polyelectrolyte systems.
