Constrained amorphous interphase in poly(l-lactic acid): Estimation of the Tensile elastic modulus

The mechanical properties of semicrystalline PLLA containing exclusively α′- or α-crystals have been investigated. The connection between experimental elastic moduli and phase composition has been analyzed as a function of the polymorphic crystalline form. For a complete interpretation of the mechanical properties, the contribution of the crystalline regions and the constrained amorphous interphase or rigid amorphous fraction (RAF) has been quantified by a three-phase mechanical model. The mathematical approach allowed the simultaneous quantification of the elastic moduli of (i) the α′- and α-phases (11.2 and 14.8 GPa, respectively, in excellent agreement with experimental and theoretical data reported in the literature) and (ii) the rigid amorphous fractions linked to the α′- and α-forms (5.4 and 6.1 GPa, respectively). In parallel, the densities of the RAF connected with α′- and α-crystals have been measured (1.17 and 1.11 g/cm3, respectively). The slightly higher value of the elastic modulus of the RAF connected to the α-crystals and its lower density have been associated to a stronger chain coupling at the amorphous/crystal interface. Thus, the elastic moduli at Troom of the crystalline (EC), mobile amorphous (EMAF), and rigid amorphous (ERAF) fractions of PLLA turned out to be quantitatively in the order of EMAF < ERAF < EC, with the experimental EMAF value equal to 3.6 GPa. These findings can allow a better tailoring of the properties of PLLA materials in relation to specific applications.