Skinless nylon 12 microporous membranes were prepared via a cold‐solvent‐induced phase‐separation process from a binary nylon 12–formic acid system. Through the incorporation of an aging step, polymer nucleation in the dope was enhanced, and the formed membranes exhibited a special particulate structure composed of interlocked sticklike or sheaflike crystallites, which coexisted with continuous microporosity. The crystallite size was affected by the polymer concentration in the dope and the aging time; for example, aging alone allowed for the reduction of the particle diameter from about 20 μm to about 1 μm. Because the membranes were skinless and hydrophobic (contact angles ≈ 105°), they were potentially appropriate for desalination via membrane distillation (MDi). For the case of desalting 3.5% NaCl(aq) by means of direct‐contact MDi, very high rejection ratios (∼99.6%) were achieved for all membranes under the operation conditions (temperature of the hot stream = 50°C, temperature of the cold stream = 20°C, and circulation rate = 0.7 L/min), whereas the highest permeation flux obtainable was 5.15 L/m2 h. The membranes were strong, with tensile strengths ranging from 4.7 to 6.3 N/mm2. Finally, we discovered a shift from α to γ structure as the dope polymer increased, whereas the crystallinity was about 27% in all cases.
Journal of Applied Polymer Science 136(5), p.47036