Preparations of Tough and Conductive PAMPS/PAA Double Network Hydrogels Containing Cellulose Nanofibers and Polypyrroles

摘要

To afford an intact double network (sample abbr.: DN) hydrogel, two-step crosslinking reactions of poly(2-acrylamido-2-methylpropanesulfonic acid) (i.e., PAMPS first network) and then poly(acrylic acid) (i.e., PAA second network) were conducted both in the presence of crosslinker (N,N′-methylenebisacrylamide (MBAA)). Similar to the two-step processes, different contents of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) oxidized cellulose nanofibers (TOCN: 1, 2, and 3 wt.%) were initially dispersed in the first network solutions and then crosslinked. The TOCN-containing PAMPS first networks subsequently soaked in AA and crosslinker and conducted the second network crosslinking reactions (TOCN was then abbreviated as T for DN samples). As the third step, various (T–)DN hydrogels were then treated with different concentrations of FeCl3(aq) solutions (5, 50, 100, and 200 mM). Through incorporations of ferric ions into (T–)DN hydrogels, notably, three purposes are targeted: (i) strengthen the (T–)DN hydrogels through ionic bonding, (ii) significantly render ionic conductivity of hydrogels, and (iii) serve as a catalyst for the forth step to proceed with in situ chemical oxidative polymerizations of pyrroles to afford polypyrrole-containing (sample abbr.: Py) hydrogels [i.e., (T–)Py–DN samples]. The characteristic functional groups of PAMPS, PAA, and Py were confirmed by FT–IR. Uniform microstructures were observed by cryo scanning electron microscopy (cryo-SEM). These results indicated that homogeneous composites of T–Py–DN hydrogels were obtained through the four-step process. All dry samples showed similar thermal degradation behaviors from the thermogravimetric analysis (TGA). The T2–Py5–DN sample (i.e., containing 2 wt.% TOCN with 5 mM FeCl3(aq) treatment) showed the best tensile strength and strain at breaking properties (i.e., σTb = 450 kPa and εTb = 106%). With the same compositions, a high conductivity of 3.34 × 10−3 S/cm was acquired. The tough T2–Py5–DN hydrogel displayed good conductive reversibility during several “stretching-and-releasing” cycles of 50–100–0%, demonstrating a promising candidate for bioelectronic or biomaterial applications.