Polyamide thin-film composite (TFC) membranes are the industry standard for membrane-based desalination. Negatively-charged carboxyl groups in the polyamide selective layer play an important role in membrane performance, affecting ion permeation, fouling, and scaling. As such, simple and accurate quantitation of the carboxyl group density is needed. While several methods already exist, each has important drawbacks that limit its application. In this study, we develop a simple bind-and-elute method utilizing silver ion probes, with silver quantitation performed using inductively coupled plasma mass spectrometry. First, the efficacy of the binding, wash, and elution steps is verified, most notably using ion exchange resin with known binding capacity. The method is then used to characterize the carboxyl group density and ionization behavior of six commercial polyamide TFC membranes, with total densities ranging from 7.2 to 37 sites/nm2 and ionization behaviors best described using two acid dissociation constants (pKa values). Comparison with data for polyamide layers isolated using dimethylformamide (DMF) shows a 35%–65% decrease in carboxyl density, suggesting that DMF may dissolve uncrosslinked polyamide oligomers. Lastly, the method is used to characterize the effect of two membrane surface modifications, with the results supporting an alternative physical interpretation of the ionization behavior in which a carboxyl group's pKa is dependent on whether it is located on the surface or buried within the polyamide network. The simplicity, accuracy, and accessibility of the developed method should allow for widespread usage in future studies involving membrane surface charge, as well as studies involving other charged interfaces.
Bibliographical noteFunding Information:
We acknowledge the support received from the National Science Foundation through the Engineering Research Center for Nanotechnology-Enabled Water Treatment (ERC-1449500) and via Grant CBET 1437630. We also acknowledge the National Science Foundation Graduate Research Fellowship awarded to J.R.W.
- Carboxyl group
- Inductively coupled plasma mass spectrometry
- Polyamide thin-film composite membranes
- Surface charge