scholarly journals Cationic Cyclopentadienyliron Complex as a Novel and Successful Nucleating Agent on the Crystallization Behavior of the Biodegradable PHB Polymer

Molecules ◽  
2018 ◽  
Vol 23 (10) ◽  
pp. 2703 ◽  
Author(s):  
Safaa El-Taweel ◽  
Arwa Al-Ahmadi ◽  
Omaima Alhaddad ◽  
Rawda Okasha

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.

Polymers ◽  
2022 ◽  
Vol 14 (2) ◽  
pp. 224
Author(s):  
Siyu Pan ◽  
Zhiguo Jiang ◽  
Zhaobin Qiu

Poly(ethylene succinate-co-1,2-propylene succinate) (PEPS) is a novel aliphatic biodegradable polyester with good mechanical properties. Due to the presence of methyl as a side group, the crystallization rate of PEPS is remarkably slower than that of the poly(ethylene succinate) homopolymer. To promote the potential application of PEPS, the effect of cellulose nanocrystals (CNC) on the crystallization behavior, crystalline morphology, and crystal structure of PEPS was investigated in this research with the aim of increasing the crystallization rate. CNC enhanced both the melt crystallization behavior of PEPS during the cooling process and the overall crystallization rate during the isothermal crystallization process. The crystallization rate of PEPS became faster with an increase in CNC content. The crystalline morphology study directly confirmed the heterogeneous nucleating agent role of CNC. The crystal structure of PEPS remained unchanged in the composites. On the basis of the interfacial energy, the nucleation mechanism of PEPS in the composites was further discussed by taking into consideration the induction of CNC.


2012 ◽  
Vol 268-270 ◽  
pp. 37-40 ◽  
Author(s):  
Yan Hua Cai

The Poly(L-lactic acid)(PLLA)/surface-grafting silica(g-SiO2) nanocomposites were prepared by melt blending. The isothermal crystallization behavior of PLLA/g-SiO2 nanocomposites with different content of g-SiO2 was investigated by optical depolarizer. In isothermal crystallization from melt, the induction periods and half times for overall PLLA crystallization (95°C Tc 120°C) were affected by the crystallization temperature and the content of g-SiO2 in nanocomposites. The results showed that g-SiO2 as a kind of heterogeneous nucleating agent can reduce induction periods and half times for overall PLLA crystallization. The thermal properties of PLLA/g-SiO2 samples were also investigated by differential scanning calorimetry (DSC), The results showed that the crystalline degree of PLLA was improved as the presence of g-SiO2.


2020 ◽  
pp. 096739112096510
Author(s):  
Pan Wang ◽  
Qing Lin ◽  
Yaming Wang ◽  
Chuntai Liu ◽  
Changyu Shen

This work aims to perform a systematic investigation on the crystallization behavior and morphologies of carbon and glass fiber reinforced PEEK. The nonisothermal and isothermal crystallization behavior was investigated by differential scanning calorimetry (DSC). The resultant morphologies were assessed by wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS), and polarized optical microscopy (POM) to provide details on spherulitic level, crystalline structure at unit cell, and lamellar levels. It was found that the crystallization ability of carbon fiber filled PEEK was better than that of neat PEEK, while the behavior of glass fiber filled PEEK was in an opposite trend. The incorporation of carbon fiber (or glass fiber) led to a looser packing of the unit cell or a less crystal perfection of PEEK but did not change its crystal form as well as its long period of lamellae. The isothermal crystallization kinetics was analyzed by the Avrami model, suggesting that the crystallization mechanism of carbon fiber filled PEEK was different from that of neat PEEK and its glass fiber filled composites. Nevertheless, the POM results showed that fiber-induced transcrystallization in PEEK matrix was not evidenced for either carbon or glass fiber filled PEEK. Finally, the effect of carbon and glass fiber on the crystallization of PEEK matrix was discussed to some extent.


2012 ◽  
Vol 627 ◽  
pp. 827-830
Author(s):  
Bing Xin Sun ◽  
Xu Qiao Feng ◽  
Cheng Zhi Chuai ◽  
Ying Guo ◽  
Si Luo

The crystallization properties of P(3HB-co-4HB) modified with nucleating agent BN was studied. DSC is used to analyze the melting crystallization behavior and POM is used to characterize crystal structure and morphology. The results show the incorporation of BN decreased the spherulite size, increased the crystallization rate and improved the crystallization properties of P(3HB-co-4HB).


2010 ◽  
Vol 59 (10) ◽  
pp. 1441-1450 ◽  
Author(s):  
Linli Xu ◽  
Xiuju Zhang ◽  
Kai Xu ◽  
Shaoquan Lin ◽  
Mingcai Chen

e-Polymers ◽  
2016 ◽  
Vol 16 (4) ◽  
pp. 303-311 ◽  
Author(s):  
Yan-Hua Cai ◽  
Li-Sha Zhao

AbstractThe goal of this work was to synthesis a novel aromatic multiamide derivative based on 1H-benzotriazole (PB) as an organic nucleating agent for poly(L-lactic acid) (PLLA), and investigate the effect of PB on the non-isothermal crystallization, melting behavior and thermal decomposition of PLLA. Here, PB was firstly synthesized through 1H-benzotriazole aceto-hydrazide and terephthaloyl chloride, then PB-nucleated PLLA was fabricated via melt-blending technology at various PB concentration from 0.5 wt% to 3 wt%. Finally, the thermal performances were evaluated through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The high thermal decomposition temperature of PB indicated that PB possessed possibility as a nucleating agent for PLLA, and the non-isothermal crystallization behavior confirmed the crystallization accelerating effectiveness of PB for PLLA. Upon optimum concentration of 2 wt%, the onset crystallization temperature, the crystallization peak temperature and the non-isothermal crystallization enthalpy increased from 101.4°C, 94.5°C and 0.1 J·g-1 to 121.3°C, 115.8°C and 35.1 J·g-1, respectively. In addition, the non-isothermal crystallization behavior was also affected by the cooling rate and the final melting temperature. The melting behavior further evidenced the advanced nucleating ability of PB, and the competitive relationship between PB and the heating rate, the nuclear rate and crystal growth rate. Thermal stability measurement showed that PB with a concentration of 1 wt%–2 wt% could slightly improve the thermal stability of PLLA.


2011 ◽  
Vol 335-336 ◽  
pp. 1299-1302 ◽  
Author(s):  
Xin Qian ◽  
Mi Zhou ◽  
Dong Xu ◽  
Shu Jun Xu ◽  
Yang Fu Jin

The effects of Amide type nucleating agents SX , talc and nucleating agents SX combination with talc on crystallization behavior of poly (L-lactic acid)(PLLA) were analyzed by means of Differential scanning calorimetry (DSC).The results of non-isothermal crystallization showed that SX is an efficient nucleating agent. The crystallization peak temperature and degree of crystallization of PLLA sample with 0.6 wt% SX are both higher than that of PLLA sample with 4 wt% Talc,which proved that the nucleating ability of SX is stronger.Nucleating agent SX and talc combination has obvious coordination effects, the sample of PLLA/0.2 wt % SX + 4 wt % talc has the minimal crystallization undercooling temperature, the highest crystallization peak temperature and crystallinity. Isothermal crystallization kinetics of PLA showed that when the four nucleating agents added in are all with the Avrami exponent n between 2.1-2.5, crystallization tended to be heterogeneous nucleation. When the nucleating agents added in are 0.6 wt%, the crystallization time is greatly decreased to 0.75min. Meanwhile, the PLLA crystallinity could be significantly increased by adding SX nucleating agents; besides, with the decrease of the isothermal crystallization temperature, the half crystallization time of the PLLA/0.6 wt% SX sample was decreased.


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