Tailoring the chain packing in ultrathin polyelectrolyte films formed by sequential adsorption: nanoscale probing by positron annihilation spectroscopy

John F. Quinn, Steven J. Pas, Anthony Quinn, Heng Pho Yap, Ryoichi Suzuki, Filip Tuomisto, Bijan S. Shekibi, James I. Mardel, Anita J. Hill, Frank Caruso

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19 Citations (Scopus)


Depth profiling experiments by positron annihilation spectroscopy have been used to investigate the free volume element size and concentration in films assembled using the layer-by-layer (LbL) adsorption method. Films prepared from strong polyelectrolytes, weak polyelectrolytes, hydrogen-bonding polymers, and blended polyelectrolyte multilayers have different chain packing that is reflected in the free volume characteristics. The influence of various parameters on free volume, such as number of bilayers, salt concentration, solution pH, and molecular weight, has been systematically studied. The free volume cavity diameters vary from 4 to 6 Å, and the free volume concentrations vary from (1.1-4.3) × 1020 cm-3, depending on the choice of assembly polymers and conditions. Films assembled from strong polyelectrolytes have fewer free volume cavities with a larger average size than films prepared from weak polyelectrolytes. Blending the weak polyanion poly(acrylic acid), PAA, with the strong polyanion poly(styrene sulfonate), PSS, to layer alternately with the polycation poly(allyamine hydrochloride), PAH, is shown to be a viable method to achieve intermediate free volume characteristics in these LbL films. An increase in salt concentration of the adsorption solutions for films prepared from strong polyelectrolytes makes these films tend toward weaker polyelectrolyte free volume characteristics. Hydrogen-bonded layered films show larger free volume element size and concentration than do their electrostatically bonded counterparts, while reducing the molecular weight of these hydrogen-bonded polymers results in slightly reduced free volume size and concentration. A study of the effect of solution pH on films prepared from weak polyelectrolytes shows that when both polyelectrolytes are substantially charged in solution (assembly pH = 7.5), the chains pack similarly to strong polyelectrolytes (i.e., lower free volume concentration), but with smaller average cavity sizes. These results give, for the first time, a clear indication of how the free volume profile develops in LbL thin films, offering numerous methods to tailor the Ångström- scale free volume properties by judicious selection of the assembly polymers and conditions. These findings can be potentially exploited to tailor the properties of thin polymer films for applications spanning membranes, sensing, and drug delivery.

Original languageEnglish
Pages (from-to)19808-19819
Number of pages12
JournalJournal of the American Chemical Society
Issue number48
Publication statusPublished - 5 Dec 2012

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