The method relates to the fabrication of a polymer microspheres comprised of an asymmetric layer surrounding a hollow interior. The fabricated hollow microsphere is generated from a nascent hollow microsphere comprised of an inner core of core fluid surrounded by a dope layer of polymer dope, where the thickness of the dope layer is at least 10% and less than 50% of the diameter of the inner core. The nascent hollow microsphere is exposed to a gaseous environment, generating a vitrified hollow microsphere, which is subsequently immersed in a coagulation bath. Solvent exchange produces a fabricated hollow microsphere comprised of a densified outer skin surrounding a macroporous inner layer, which surrounds a hollow interior. In an embodiment, the polymer is a polyimide or a polyamide-imide, and the non-solvent in the core fluid and the coagulation bath is water. The fabricated hollow microspheres are particularly suited as solvent supports for gas separation processes.
The United States Government has rights in this invention pursuant to the employer-employee relationship of the Government to the inventors as U.S. Department of Energy employees and site-support contractors at the National Energy Technology Laboratory.