This report describes the surface morphology and wetting behavior of one aryl and three fluorous polyphosphazenes: poly[bis(2,2,2-trifluoroethoxy)phosphazene], PTFEP, 1, poly[bis(para-fluorophenoxy) phosphazene] 2, poly[bis(meta-trifluoromethylphenoxy)phosphazene] 3, and poly(diphenoxyphosphazene) 4. Thermal analysis confirms high thermal stability for these polyphosphazenes. With phenyl side chains, 2-4 are particularly stable with T-5% >400 degrees C. Surface morphology via tapping mode atomic force microscopy (TM-AFM) and dynamic contact angles (DMA) are correlated with composition and crystallinity estimated by differential scanning calorimetry (DSC). The resulting structure property relationships define trends in processability, hydrophobicity and oleophobicity. Compared to 1, 3, and 4 poly[bis(para-fluorophenoxy) phosphazene] 2 is noteworthy by virtue of a high melting point (179 degrees C), high crystallinity (Delta H-f,, 302 J/g), and a moderate molecular weight. The remaining polyphosphazenes in this group have T-m <100 degrees C. Heats of fusion (J/g) are in the order 1 (29.4) approximate to 2 (302) > 3 (17) 4 (4.0). High molecular weights for 3 and 4 (>10(3) kDa) would make melt processability problematic. Thus 1 or 2 has a favorable combination of properties, with 2 favored for many applications due to a higher T-m. In summary, for performance and processing, high T-m, and resistance to water and hydrocarbons poly[bis(para-fluorophenoxy)phosphazene], 2 is attractive. This finding suggests other para-substituted phenyl phosphazenes are worth further study. (C) 2012 Elsevier Ltd. All rights reserved.