scholarly journals Crystallization and Melting Behavior of Biodegradable Poly(L-lactic acid)/Talc Composites

2012 ◽  
Vol 9 (3) ◽  
pp. 1569-1574 ◽  
Author(s):  
Yan-Hua Cai

Crystallization and melting behavior of Poly(L-lactic acid)(PLLA)/Talc composites with different talc content were investigated in detail. The addition of talc can increase the overall crystallization rate of PLLA, 5%talc makes the melt-crystallization peak temperature of PLLA increase from 96.28 °C to 105.22 °C, and the crystallization enthalpy increases from 1.379 J•g-1to 28.99 J•g-1. The melting behavior of PLLA/5%talc composites at a different heating rate during non-isothermal crystallization at different cooling rate shows that heating rate can affect the melting behavior of PLLA, with increasing of heating rate, the double melting peak degenerates to single melting peak. Melting behavior after isothermal crystallization and after cold isothermal crystallization and hot isothermal crystallization indicates that the double-melting peak of PLLA/5%talc composites results from melting-recrystallization.

Polymers ◽  
2021 ◽  
Vol 13 (13) ◽  
pp. 2214
Author(s):  
Mohammed Naffakh ◽  
Pablo Rica ◽  
Carmen Moya-Lopez ◽  
José Antonio Castro-Osma ◽  
Carlos Alonso-Moreno ◽  
...  

In the present work, hybrid nanocomposite materials were obtained by a solution blending of poly(l-lactic acid) (PLLA) and layered transition-metal dichalcogenides (TMDCs) based on tungsten disulfide nanosheets (2D-WS2) as a filler, varying its content between 0 and 1 wt%. The non-isothermal cold- and melt-crystallization and melting behavior of PLLA/2D-WS2 were investigated. The overall crystallization rate, final crystallinity, and subsequent melting behavior of PLLA were controlled by both the incorporation of 2D-WS2 and variation of the cooling/heating rates. In particular, the analysis of the cold-crystallization behavior of the PLLA matrix showed that the crystallization rate of PLLA was reduced after nanosheet incorporation. Unexpectedly for polymer nanocomposites, a drastic change from retardation to promotion of crystallization was observed with increasing the nanosheet content, while the melt-crystallization mechanism of PLLA remained unchanged. On the other hand, the double-melting peaks, mainly derived from melting–recrystallization–melting processes upon heating, and their dynamic behavior were coherent with the effect of 2D-WS2 involved in the crystallization of PLLA. Therefore, the results of the present study offer a new perspective for the potential of PLLA/hybrid nanocomposites in targeted applications.


2022 ◽  
Vol 58 (4) ◽  
pp. 73-83
Author(s):  
Hao Huang ◽  
Shuang-Qing Liu ◽  
Cheng-Pei Li ◽  
Shi-Tianle Luo ◽  
Li-Sha Zhao ◽  
...  

In this study, a new organic nucleating agent N, N -bis(stearic acid)-1,4-dicarboxybenzene dihydrazide (PASH) to improve crystallization behavior of poly(L-lactic acid) (PLLA) along with the effect of PASH on melting behavior, thermal stability of PASH-nucleated PLLA was holistically reported. The melt-crystallization process illustrated that PASH as an effective heterogeneous nucleating agent could boost PLLA�s crystallization rate, but increasing PASH concentration and cooling rate conversely inhibited melt-crystallization process of PLLA in this study. With respect to melt-crystallization process, a larger amount of PASH leaded to a shift of cold-crystallization peak to lower temperature level. Isothermal crystallization revealed, in comparison to pure PLLA, that the half time of overall crystallization of PLLA/PASH was significantly decreased with PLLA containing 3 wt% PASH having the minimum t1/2= 67.3 s at 105şC. The different melting behaviors of PLLA/PASH under different conditions were attributed to the nucleating effect of PASH within PLLA. In particular, the melting behavior at a heating rate of 10�C/min after isothermal crystallization depended primarily on the crystallization temperature. Whereas, the impact of crystallization time on melting behavior was negligible. Nonetheless, the melting behavior was influenced by the heating rate after non-isothermal crystallization. The thermal stability of PLLA was detrimental with the addition of PASH owing to a typical drop in onset thermal decomposition temperature.


e-Polymers ◽  
2019 ◽  
Vol 19 (1) ◽  
pp. 141-153 ◽  
Author(s):  
Li-Sha Zhao ◽  
Yan-Hua Cai ◽  
Hui-Li Liu

AbstractDeveloping more organic nucleating agent with different molecular structure is very instructive to improve the crystallization of poly(L-lactic acid) (PLLA) and explore the crystallization mechanism. In this study, N, N’-sebacic bis(hydrocinnamic acid) dihydrazide (HAD) was synthesized to serve as a nucleating agent for PLLA. The effects of HAD on the non-isothermal crystallization, melting behavior, thermal stability and optical performance of PLLA were investigated by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), and light transmittance meter. The melt crystallization behavior showed that HAD was able to promote the crystallization of PLLA via heterogenous nucleation in cooling, and it was found that, upon the cooling of 1°C/min, the incorporation of 1 wt% HAD made the crystallization temperature and non-isothermal crystallization enthalpy increase from 94.5°C and 0.1 J/g to 131.6°C and 48.5 J/g comparing with the pure PLLA. Additionally, the melt crystallization significantly depended on the cooling rate and the final melting temperature. For the cold crystallization, when the nucleation density from HAD and PLLA itself was saturated, the influence of the HAD concentration on the cold crystallization process of the PLLA/HAD samples is negligible. The melting behavior after isothermal or non-isothermal crystallization further confirmed the crystallization accelerating effect of HAD for PLLA, and the appearance of the double melting peaks was attributed to the melting-recrystallization. Unfortunately, the addition of HAD decreased the thermal stability and light transmittance of PLLA.


Minerals ◽  
2021 ◽  
Vol 12 (1) ◽  
pp. 14
Author(s):  
Jiunn-Jer Hwang ◽  
Su-Mei Huang ◽  
Wen-Yang Lin ◽  
Hsin-Jiant Liu ◽  
Cheng-Chan Chuang ◽  
...  

This study makes use of polycondensation to produce poly (L-lactic acid)-(polyethylene glycols), a biodegradable copolymer, then puts it with organically modified montmorillonite (o-MMT) going through an intercalation process to produce a series of nanocomposites of PLLA-PEG/o-MMT. The exfoliation and intercalation of the montmorillonite-layered structure could be found through X-ray diffraction and transmission electron microscopy. The lower the molecular weight of poly (ethylene glycol), the more obvious the exfoliation and dispersion. The nanocomposites were investigated under non-isothermal crystallization and isothermal crystallization separately via differential scanning calorimetry (DSC). After the adding of o-MMT to PLLA-PEG copolymers, it was found that the PLLA-PEG nanocomposites crystallized slowly and the crystallization peak tended to become broader during the non-isothermal crystallization process. Furthermore, the thermal curve of the non-isothermal melt crystallization process of PLLA-PEG copolymers with different proportions of o-MMT showed that the melting point decreased gradually with the increase of o-MMT content. In the measurement of isothermal crystallization, increasing the o-MMT of the PLLA-PEG copolymers would increase the t1/2 (crystallization half time) for crystallization and decrease the value of ΔHc. However, the present study results suggest that adding o-MMT could affect the crystallization rate of PLLA-PEG copolymers. The o-MMT silicate layer was uniformly dispersed in the PLLA-PEG copolymers, forming a nucleating agent. The crystallization rate and the regularity of the crystals changed with the increase of the o-MMT content, which further affected the crystallization enthalpies.


2021 ◽  
Author(s):  
Lisha ZHAO ◽  
Yanhua CAI

N, N'-oxalyl bis(piperonylic acid) dihydrazide (PAOD) was obtained through the amination of piperonylic acid chloride and its structure was characterized by Fourier transform infrared spectrometer and nuclear magnetic resonance. Melting blend technology was used to prepare the modified poly(L-lactic acid) (PLLA) containing the various loading PAOD as a new organic nucleating agent. The thermal performances including crystallization, melting behavior and thermal decomposition process, as well as the fluidity of PAOD-nucleated PLLA were investigated via a series of tests. The DSC results showed that, in comparison to DSC curve of the virgin PLLA, the DSC curves of all PLLA/PAOD appeared the sharp melt-crystallization peak, and a higher PAOD concentration caused the melt-crystallization to occur in the higher temperature region and reduced the negative effect of the high cooling rate on the melt-crystallization process. However, with increasing of PAOD concentration, the cold-crystallization enthalpy decreased from 24.4 J/g to 16.7 J/g. The melting peak after melt-crystallization depended on the heating rate and the PAOD concentration; and the double melting peaks appeared after isothermal crystallization in low temperature region was thought to be due to the melting-recrystallization. The addition of PAOD decreased the onset decomposition temperature of PLLA, but the onset decomposition temperature was determined by the PAOD concentration and the intermolecular interaction of PLLA and PAOD. Additionally, the PAOD could considerably improve the fluidity of PLLA.


2017 ◽  
Vol 89 (1) ◽  
pp. 125-140 ◽  
Author(s):  
Ioanna-Georgia I. Athanasoulia ◽  
Maximos N. Christoforidis ◽  
Dimitrios M. Korres ◽  
Petroula A. Tarantili

AbstractIn this study, hydroxyapatite (HA) was incorporated in a poly(L-lactic acid) (PLLA) matrix and the thermal properties and crystallization behavior of the derived composites were investigated. The nanocomposites, containing 0–20 wt% HA, were prepared by melt extrusion employing a twin-screw extruder. XRD experiments verified an increase in the intensity of the characteristic diffraction peak of the α-form crystalline phase of PLLA with increasing HA content. By DSC experiments it was observed that the presence of HA increased the crystallinity during cold crystallization, leading to a shift of cold-crystallization temperature to lower values and to an increase in the melting temperature of the PLLA phase. Isothermal crystallization experiments at 100, 110, 115 and 120°C, revealed a maximum in crystallization kinetic around 100°C after the addition of HA compared to 115°C for pure PLLA. The crystallization rate of PLLA matrix in the nanocomposites decreased with increasing crystallization temperature. By using the Avrami and Lauritzen-Hoffman equations the exponent n was calculated in the range 2–3 and a theoretical approach verified that the HA/PLLA systems belong to Regime II of crystallization behavior. The investigated melting behavior of PLLA was attributed to better organized crystalline structure with increasing isothermal crystallization temperatures and might be related with the longer time necessary for the completion of crystallization.


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