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Diffusivities of dichloromethane in poly(lactide‐ co ‐glycolide)
Author(s) -
Foss Willard R.,
Anderl Jeffrey N.,
Clausi Amber L.,
Burke Paul A.
Publication year - 2009
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.29554
Subject(s) - sorption , solvent , dichloromethane , differential scanning calorimetry , glass transition , polymer chemistry , materials science , polymer , thermal diffusivity , diffusion , lactide , chemical engineering , analytical chemistry (journal) , thermodynamics , chemistry , copolymer , organic chemistry , composite material , physics , adsorption , engineering
Abstract Diffusion of dichloromethane in poly(lactide‐ co ‐glycolide) (PLGA), the rate‐limiting step in the later stages of drying of microparticles formed in common encapsulation processes, was studied by the step‐change sorption technique in a dynamic vapor sorption apparatus. Methods were developed to create films of polymer with the appropriate thicknesses for accurate diffusion determination over a wide range of solvent composition. Mutual diffusivities were measured at 5, 25, and 35°C from 10 to 70 wt % solvent. Values range from 2 × 10 −10 m 2 /s at high solvent compositions to as low as 1 × 10 −13 m 2 /s at solvent compositions just above the glass transition of the mixture. Equilibrium sorption isotherms were measured in the same apparatus and agreed favorably with Flory‐Huggins theory using a value of χ = 0.31. The glass transition temperatures of the system were measured over the range of 0–11 wt % solvent content by modulated differential scanning calorimetry. The composition dependence was fit to the Fox equation, which estimated values of the pure polymer and the solvent T g to be 39.3 and −131°C, respectively. These values, along with the diffusivity data, were used to deduce the free‐volume parameters specific to PLGA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009