Matrimid (R) hollow fiber membranes with silicone rubber (PDMS) calked fused nodular selective layers display much higher CO2/N-2 selectivity as well as higher CO2 permeance than those with isotropic dense selective layers at 253.15 K. Two kinds of asymmetric hollow fiber membranes were successfully spun: fibers with fused nodular skins and fibers with truly dense skins. The skin morphologies were confirmed with SEM images. CO2/N-2 mixed gas permeation characterization was carried out within the temperature range of 253.15 K to 308.15 K. Permeation results showed that, at 253.15 K, the nodular skinned fibers displayed CO2/N-2 selectivity of 90.5, and CO2 permeance of 63.3 GPU after standard PDMS calking; while the dense skinned fibers displayed CO2/N-2 selectivity of 52.5, and CO2 permeance of 16.6 GPU. The PDMS calking had negligible effect on the dense skinned fibers, but it was necessary for the fused nodular skinned fibers. A hypothesis regarding the introduction of Langmuir sorption sites and a local orientation of polymer chain segments is proposed to explain the better performance of the calked nodular skinned fibers. This work provides a promising method for improved hollow fiber membranes for the removal of CO2 from flue gas. (C) 2013 Elsevier B.V. All rights reserved