Abstract
Cationic cyclopentadienyliron (CpFe+) is one of the most fruitful organometallic moieties that has been utilized to mediate the facile synthesis of a massive number of macromolecules. However, the ability of this compound to function as a nucleating agent to improve other macromolecule properties has not been explored. This report scrutinizes the influence of the cationic complex as a novel nucleating agent on the spherulitic morphology, crystal structure, and isothermal and non-isothermal crystallization behavior of the Poly(3-hydroxybutyrate) (PHB) bacterial origin. The incorporation of the CpFe+ into the PHB materials caused a significant increase in its spherulitic numbers with a remarkable reduction in the spherulitic sizes. Unlike other nucleating agents, the SEM imageries exhibited a good dispersion without forming agglomerates of the CpFe+ moieties in the PHB matrix. Moreover, according to the FTIR analysis, the cationic organoiron complex has a strong interaction with the PHB polymeric chains via the coordination with its ester carbonyl. Yet, the XRD results revealed that this incorporation had no significant effect on the PHB crystalline structure. Though the CpFe+ had no effect on the polymer’s crystal structure, it accelerated outstandingly the melt crystallization of the PHB. Meanwhile, the crystallization half-times (t0.5) of the PHB decreased dramatically with the addition of the CpFe+. The isothermal and non-isothermal crystallization processes were successfully described using the Avrami model and a modified Avrami model, as well as a combination of the Avrami and Ozawa methods. Finally, the effective activation energy of the PHB/CpFe+ nanocomposites was much lower than those of their pure counterparts, which supported the heterogeneous nucleation mechanism with the organometallic moieties, indicating that the CpFe+ is a superior nucleating agent for this class of polymer.
Highlights
The development of biopolymers has attracted great interest over the years as a replacement for petroleum polymers
Successful examples in this field include the synthesis of thermoplastic starch, poly(hydroxyalkanoic acid)s (PHAs), poly(lactic) acid, and their blends or copolymers with other biopolymers [5,6]
The characteristic Bragg reflection peaks of the CpFe++ complex can be observed at nanocomposites
Summary
The development of biopolymers has attracted great interest over the years as a replacement for petroleum polymers. Among the poly(hydroxyalkanoic acid)s, polyester of 3-hydroxybutyrate (PHB) is an attractive example of a biodegradable and biocompatible polymer [7,8], which could be accessible via bacteria as intracellular carbon and energy storage compounds and accumulated as granules in the cytoplasm of cells [9,10]. This thermoplastic polymer has been recognized as one of the most promising biopolymers in packaging and biomedical applications [11,12]
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