Swelling and Orientation Behavior of End-Grafted Polymer Chains by In Situ Attenuated Total Reflection Fourier Transform Infrared Spectroscopy Complementing <i>In Situ</i> Ellipsometry

The literature lacks established concrete parameters for assigning grafted chain regimes. In this context, dichroic in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and in situ ellipsometry were used complementarily, offering new opportunities for conformational analysis of end-grafted polymer chains. Especially polymer chain orientation was studied as a new parameter, among others, for proper chain regime assignment in this report. Alkyne-functionalized poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) with a molecular weight of 49.8 kg/mol and a contour length of around 80 nm was grafted to self-assembled monolayers bearing triazole end groups as reported. Different chain regimes were generated by using three different grafting densities. ATR-FTIR spectroscopy based on the ν(CO) stretching vibration at around 1728 cm–1 provided a new direct approach to determine the GD of polymer chains. Significant shifts in the position of the ν(CO) band comparing dry and wet states were observed, caused by increased hydrogen bonding interactions between PDMAEMA and water. Finally, the averaged orientation of PDMAEMA chains along the z-axis was determined using dichroic ATR-FTIR spectroscopy based on the dichroic ratios of the ν(CO) band and molecular order parameters SZ,MOL calculated thereof. High SZ,MOL values were found for the wet state compared to the dry state, confirming that all GD PDMAEMA samples are in the brush regime in the swollen state