Crystallization behavior of biodegradable poly(L‐lactic acid) filled with a powerful nucleating agent: N,N′‐bis(benzoyl) suberic acid dihydrazide

Abstract

N,N 0 -Bis(benzoyl) suberic acid dihydrazide (NA) as nucleating agent for poly(L-lactic acid) (PLLA) was synthesized from benzoyl hydrazine and suberoyl chloride, which was deprived from suberic acid via acylation. PLLA/NA samples were prepared by melt blending and a hot-press forming process. The nonisothermal and isothermal crystallization, spherulite morphology, and melting behavior of PLLA/NA with different contents of NA were investigated with differential scanning calorimetry, depolarized-light intensity measurement, scanning electron microscopy, polarized optical microscopy, and wide-angle X-ray diffraction. With the incorporation of NA, the crystallization peak became sharper and shifted to a higher temperature as the degree of supercooling decreased at a cooling rate of 1 C/min from the melt. Nonisothermal crystallization indicated that the presence of NA accelerated the overall PLLA crystallization. In isothermal crystallization from the melt, the presence of NA affected the isothermal crystalline behaviors of PLLA remarkably. The addition of NA led to a shorter crystallization time and a faster overall crystallization rate; this meant that there was a heterogeneous nucleation effect of NA on the crystallization of PLLA. With the addition of 0.8% NA, the crystallization half-time of PLLA/NA decreased from 26.5 to 1.4 min at 115 C. The Avrami theory was used to describe the kinetics of isothermal crystallization of the PLLA/NA samples. Also, with the presence of NA, the spherulite number of PLLA increased, and the spherulite size decreased significantly.

Isothermal crystallization kinetics and melting behavior of poly(l-lactic acid)/WS2 inorganic nanotube nanocomposites

“…Effective nucleating agents reported for PLLA are zinc phenylphosphonate (PPZn) [9] and p-tert-butylcalix [8] arene [10], talc [11], uracil [12] and N,N 0 -bis(benzoyl) suberic acid dihydrazide [13], whilst cellulose nanocrystals (CNC) [14], titanium dioxide (TiO 2 ) nanowires [15], polyhedral oligomeric silsesquioxanes (POSS) [16,17], nanclay (MMT) [18], carbon nanotubes (CNTs) [19], nanocalcium carbonate (CaCO 3 ) [20], nano-zinc citrate (ZnCC) [21], graphene oxide (GO) [22] and fullerenes (C60) [23], are known as nanocomposite-forming additives. However, the fabrication of high quality nanocomposites normally requires chemical treatment to reduce the surface energy in order to ensure good particle dispersion and strong interaction and adhesion between the nanofiller and polymer matrix.…”

Study on Thermal Performance of Composites Prepared Using Poly(L-Lactic Acid) and Melamine

“…The detailed processing procedure of PLLA/TP composites with different TP content is similar to that of others composites in our earlier works [11,12].…”

Using depolarized light intensity to study the crystallization and degradation behavior of poly(l-lactic acid) and its blends with poly(ethylene oxide)

“…Therefore, the measured intensity of the total transmitted depolarized light can be used to monitor the changes in the relative crystallinity of spherulites during heating, melting, annealing, and crystallization [1][2][3][4][5][6][7][8]. When measured at regular intervals during a phase change, this property provides a unique perspective of melt crystallization of polymer spherulites as well as their thermal behavior during melting.…”