Nonlinear Layer-by-Layer Films: Effects of Chain Diffusivity on Film Structure and Swelling

Selin, Victor; Ankner, John F.; Sukhishvili, Svetlana A.

doi:10.1021/acs.macromol.7b01218

Nonlinear Layer-by-Layer Films: Effects of Chain Diffusivity on Film Structure and Swelling

Journal Article · Wed Aug 09 00:00:00 EDT 2017 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.7b01218· OSTI ID:1426565

Selin, Victor ^[1]; Ankner, John F. ^[2]; ^[1]

Texas A & M Univ., College Station, TX (United States). Dept. of Materials Science & Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Here in this paper, we report on the role of molecular diffusivity in the formation of nonlinearly growing polyelectrolyte multilayers (nlPEMs). Electrostatically bound polyelectrolyte multilayers were assembled from poly(methacrylic acid) (PMAA) as a polyanion and quaternized poly(2-(dimethylamino)ethyl methacrylate) (QPC) as a polycation. Film growth as measured by ellipsometry was strongly dependent on the time allowed for each polymer deposition step, suggesting that the diffusivities of the components are crucial in controlling the rate of film growth. Uptake of polyelectrolytes within nlPEMs was relatively slow and occurred on time scales ranging from minutes to hours, depending on the film thickness. Spectroscopic ellipsometry measurements with nlPEM films exposed to aqueous solutions exhibited high (severalfold) degrees of film swelling and different swelling values for films exposed to QPC or PMAA solutions. FTIR spectroscopy showed that the average ionization of film-assembled PMAA increased upon binding of QPC and decreased upon binding of PMAA, in agreement with the charge regulation mechanism for weak polyelectrolytes. The use of neutron reflectometry (NR) enabled quantification of chain intermixing within the film, which was drastically enhanced when longer times were allowed for polyelectrolyte deposition. Diffusion coefficients of the polycation derived from the uptake rates of deuterated chains within hydrogenated films were of the order of 10^–14 cm²/s, i.e., 5–6 orders of magnitude smaller than those found for diffusion of free polymer chains in solution. Exchange of the polymer solutions to buffer inhibited film intermixing. Taken together, these results contribute to understanding the mechanism of the growth of nonlinear polyelectrolyte multilayers and demonstrate the possibility of controlling film intermixing, which is highly desirable for potential future applications.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1426565

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 16 Vol. 50; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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