The spherulite growth of stereocomplex crystallites in the blend from low-molecular-weight poly(L-lactide) [i.e., poly(L-lactic acid) (PLLA)] and poly(D-lactide) [i.e., poly(D-lactic acid) (PDLA)] from the melt, together with that of the homocrystallites in pure PLLA and PDLA films, was investigated using polarization optical miscroscopy. The spherulite growth of stereocomplex crystallites occurred at a wider temperature range (=190 degrees C) compared with that of homocrystallites (=140 degrees C). At 140 degrees C, the spherulite radius growth rate (G) for the stereocomplex crystallites (136.4 microm min(-1)) was an order of magnitude higher than those for the homocrystallites of PLLA (11.8 microm min(-1)) and PDLA (15.7 microm min(-1)), whereas the induction period was shorter for the spherulties of stereocomplex crystallites (0.0 min) than for the spherulties of homocrystallites of PLLA (2.6 min) and PDLA (0.7 min). In addition to these two factors, the higher spherulite density of stereocomplex crystallites compared with those of the homocrystallites of PLLA and PDLA resulted in rapid completion of overall crystallization of stereocomplex. The front factor (G(0)) and nucleation constant (K(g)) for the stereocomplex crystallites in the temperature range of 140-190 degrees C were estimated to be 3.56 x 10(12) microm min(-1) and 8.42 x 10(5) K(2), respectively. The G(0) value for stereocomplex crystallites was 1 and 2 orders of magnitude higher than those for the homocrystallites of PLLA (9.69 x 10(11) microm min(-1)) and PDLA (8.79 x 10(10) microm min(-1)), whereas the K(g) value for stereocomplex crystallites was twice those for the homocrystallites of PLLA (4.95 x 10(5) K(2)) and PDLA (4.20 x 10(5) K(2)).
The physical properties, crystallization, and spherulite growth behavior and mechanism of linear and 3-arm poly(L-lactide) [i.e., poly(L-lactic acid) (PLLA)] have been investigated using absolute molecular weight as a molecular index. The branching reduces the chain mobility of PLLA and must be excluded from the crystalline regions. The former factor gives the higher glass transition temperature (T(g)) and starting temperature for thermal degradation (T(d,S)) of 3-arm PLLA compared with those of linear PLLA. On the other hand, both the former and the latter factors lead to the higher cold crystallization temperature (T(cc)), the longer induction period for spherulite growth (t(i)), the lower melting temperature (T(m)), crystallinitiy (X(c)), and radius growth rate of the spherulties (G) for the 3-arm PLLA compared with those for the linear PLLA. The G of 3-arm PLLA showed the vague dependence on number-average molecular weight (M(n)), probably because the branching effect was balanced with the molecular weight effect. At the M(n) exceeding critical values, the linear and 3-arm PLLA crystallize in regime II or regime III kinetics, depending on crystallization temperature (T(c)). In contrast, at the M(n) below critical values, the linear and 3-arm PLLA crystallize according solely to regime III and regime II kinetics, respectively, for all the T(c).
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