An understanding of how complex nanoscale morphologies emerge from synthesis would offer powerful strategies to construct soft materials with designed structures and functions. However, these kinds of morphologies have proven difficult to characterize, and therefore manipulate, because they are three-dimensional (3D), nanoscopic, and often highly irregular. Here, we studied polyamide (PA) membranes used in wastewater reclamation as a prime example of this challenge. Using electron tomography and quantitative morphometry, we reconstructed the nanoscale morphology of 3D crumples and voids in PA membranes for the first time. Various parameters governing film transport properties, such as surface-to-volume ratio and mass-per-area, were measured directly from the reconstructed membrane structure. In addition, we extracted information inaccessible by other means. For example, 3D reconstruction shows that membrane nanostructures are formed from PA layers 15-20 nm thick folding into 3D crumples which envelope up to 30% void by volume. Mapping local curvature and thickness in 3D quantitatively groups these crumples into three classes, "domes", "dimples", and "clusters", each being a distinct type of microenvironment. Elemental mapping of metal ion adsorption across the film demonstrates that these previously missed parameters are relevant to membrane performance. This imaging-morphometry platform can be applicable to other nanoscale soft materials and potentially suggests engineering strategies based directly on synthesis-morphology-function relationships.
Keywords: 3D reconstruction; nanoscale morphometry; polyamide membranes; polymer electron tomography; synthesis−morphology−function relationship.