Step-by-Step Analysis of a Copper-Mediated Surface-Initiated Atom-Transfer Radical Polymerization Process for Polyacrylamide Brush Synthesis Through Infrared Spectroscopy and Contact Angle Measurements

Polymer brushes (PBs) are transformative surface-modifying nanostructures, yet their synthesis via controlled methods like copper-mediated surface-initiated atom-transfer radical polymerization (Cu⁰-SI-ATRP) faces reproducibility challenges due to a lack of understanding of parameter interdependencies. This study systematically evaluates the Cu⁰-SI-ATRP process for polyacrylamide brushes (PAM-PBs), aiming to clarify key parameters that influence the synthesis process. This evaluation followed a step-by-step characterization that tracked molecular changes through infrared spectroscopy (IR) and surface development by contact angle (CA) through two different mixing methods: ultrasonic mixing and process simplification (Method A) and following literature-based parameters (Method B). Both methods, consisting of surface activation, 3-aminopropyltriethoxysilane (APTES) deposition, bromoisobutyryl bromide (BiBB) anchoring, and polymerization, were analyzed by varying parameters like concentration, temperature, and time. Results showed ultrasonication during surface activation enhanced siloxane (1139→1115 cm^-1) and amine (1531 cm^-1) group availability while reducing APTES concentration to 1 Vol% without drying sufficed for BiBB anchoring. BiBB exhibited insensitivity to concentration but benefited from premixing, evidenced by sharp C-Br (~1170 cm^-1) and methyl (3000-2800 cm^-1) bands. Additionally, it was observed that PAM-PBs improved with Method A, which had reduced variance in polymer fingerprint regions compared to Method B. Adding to the above, CA measurements gave complementary step-by-step information along the modifications of the surface, revealing distinct wettability behaviors between bulk PAM and synthesized PAM-PBs (from 51° to 37°). As such, this work identifies key parameter influence (e.g., mixing, BiBB concentration), simplifies steps (drying omission, lower APTES concentration), and demonstrates a step-by-step, systematic parameter decoupling that reduces variability. In essence, this detailed parameter analysis addresses the PAM-PBs synthesis process with better reproducibility than the previously reported synthesis method and achieves the identification of characteristic behaviors across the step-by-step process without the imperative need for higher-cost characterizations.