Gl. Siparsky et al., WATER TRANSPORT IN POLYLACTIC ACID (PLA), PLA POLYCAPROLACTONE COPOLYMERS, AND PLA POLYETHYLENE-GLYCOL BLENDS/, Journal of environmental polymer degradation, 5(3), 1997, pp. 125-136
Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyest
er, and water vapor permeability ability may have a significant influe
nce on the rate of degradation. A method is devised to use bags prepar
ed from PLA films and filled with molecular sieves to determine the wa
ter vapor permeability in the polymer, its copolymers with caprolacton
e, and blends with polyethylene glycol. The ''solution-diffusion'' mod
el is used to determine the permeability parameters. These include the
solubility coefficient, S, a measure of the equilibrium water concent
ration available for hydrolysis and the diffusion coefficient, D, whic
h characterizes the rate of water vapor diffusion into the film under
specific conditions. Values of S and D at 50 degrees C and 90% relativ
e humidity ranged from 400 x 10(-6) to 1000 x 10(-6) cm(3) (STP)/(cm(3
) Pa) and 0.20 x 10(-6) to 1.0 x 10(-6) cm(2)/s, respectively. The S a
nd D coefficients were also measured at 20 and 40 degrees C and compar
ed to those of other polymers. The degree of crystallinity was found t
o have little influence on the measured permeability parameters. The h
eat of sorption, Delta H-s, and the activation energy of diffusion, ED
, were used to show that the permeability process is best described by
the ''water cluster'' model for hydrophobic polymers. Finally, the di
ffusion coefficient is used to compare the rate of water diffusion to
the rate of water consumption by ester hydrolysis. Results indicate th
at hydrolytic degradation of PLA is reaction-controlled.