scholarly journals Poly (L-lactic acid) Modified by N, N -bis(Stearic acid)-1,4-Dicarboxybenzene Dihydrazide: Studies of Crystallization, Melting Behavior and Thermal Decomposition

2022 ◽  
Vol 58 (4) ◽  
pp. 73-83
Author(s):  
Hao Huang ◽  
Shuang-Qing Liu ◽  
Cheng-Pei Li ◽  
Shi-Tianle Luo ◽  
Li-Sha Zhao ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Lactic Acid ◽  
Stearic Acid ◽  
Isothermal Crystallization ◽  
Crystallization Process ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Melt Crystallization ◽  
Thermal Stability Of

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.

A 1H-Benzotriazole Derivative Nucleated Poly(L-lactic acid): Thermal Behavior and Physical Properties

2020 ◽  
Vol 42 (3) ◽  
pp. 383-383
Author(s):  
Li Sha Zhao and Yan Hua Cai Li Sha Zhao and Yan Hua Cai
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Melting Process ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Cold Crystallization ◽  
Melt Crystallization ◽  
Nucleation Effect ◽  
Lower Temperature ◽  
Thermal Stability Of

In this study, a 1H-benzotriazole derivative, N, Nand#39;-bis(1H-benzotriazole) succinic acid acethydrazide (SABHA), was synthesized to nucleate Poly(L-lactic acid) (PLLA). A series of comparative studies on the melt-crystallization, the cold-crystallization, the melting behavior, the thermal stability, as well as the fluidity between the pure PLLA and PLLA/SABHA were performed. The melt-crystallization behavior revealed that the SABHA as a heterogeneous nucleating agent could significantly facilitate the crystallization of PLLA, and a larger amount of SABHA concentration exhibited the better nucleation effect. However, for the cold-crystallization process, the crystallization peak shifted toward the lower temperature with increasing of SABHA concentration. The melting behavior after crystallization at different crystallization temperatures showed that the melting process of PLLA/SABHA samples depended on the crystallization temperature, and the appearance of the double melting peaks was attributed to the melt-recrystallization. The thermal decomposition profile of PLLA was not affected by SABHA, but the addition of SABHA reduced the thermal stability of PLLA. Fortunately, the presence of SABHA improved the fluidity of PLLA, and the effect of SABHA concentration on the fluidity was positive.

Thermal behavior of modified poly(L-lactic acid): effect of aromatic multiamide derivative based on 1H-benzotriazole

e-Polymers ◽  
2016 ◽  
Vol 16 (4) ◽  
pp. 303-311 ◽  
Author(s):  
Yan-Hua Cai ◽  
Li-Sha Zhao
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Crystallization Behavior ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Decomposition Temperature ◽  
Scanning Calorimetry ◽  
Onset Crystallization Temperature

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.

scholarly journals N, N’-sebacic bis(hydrocinnamic acid) dihydrazide: A crystallization accelerator for poly(L-lactic acid)

e-Polymers ◽  
2019 ◽  
Vol 19 (1) ◽  
pp. 141-153 ◽  
Author(s):  
Li-Sha Zhao ◽  
Yan-Hua Cai ◽  
Hui-Li Liu
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Cold Crystallization ◽  
Light Transmittance ◽  
Nucleation Density ◽  
Melt Crystallization ◽  
Hydrocinnamic Acid

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.

scholarly journals The Crystallization, Melting Behavior, and Thermal Stability of Poly(L-lactic acid) Induced byN,N,N′-Tris(benzoyl) Trimesic Acid Hydrazide as an Organic Nucleating Agent

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Yan-Hua Cai ◽  
Yan-Hua Zhang
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Cooling Rate ◽  
Acid Hydrazide ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Crystallization Peak ◽  
Trimesic Acid ◽  
Neat Plla ◽  
Thermal Stability Of

N,N,N′-Tris(benzoyl) trimesic acid hydrazide (TTAD), as a novel nucleating agent of poly(L-lactic acid) (PLLA), was synthesized and characterized by FT-IR and1H NMR. The crystallization, melting behavior, and thermal stability of PLLA induced by TTAD were investigated through DSC, TGA, depolarized-light intensity measurement, and so forth. The crystallization behavior indicated that the presence of TTAD accelerated the overall PLLA crystallization. Compared to neat PLLA, the crystallization onset temperature of PLLA/1%TTAD increased from 101.36°C to 125.26°C, the melt-crystallization peak temperature increased from 94.49°C to 117.56°C, crystallization enthalpy increased from 0.1023 J·g−1to 33.44 J·g−1at a cooling rate of 1°C/min from melt, and the crystallization half-time of PLLA/TTAD decreased from 2997.2 s to 108.9 s at 110°C. Moreover, the nonisothermal crystallization measurements also indicated that the crystallization peak became wider and shifted to a lower temperature with increasing cooling rate. With the presence of TTAD, the melting behavior of PLLA was affected significantly, and a double-melting peak occurred due to melting-recrystallization. Thermal stability research showed that there existed one degradation stage of PLLA and PLLA/TTAD samples, and the thermal degradation temperature of PLLA/TTAD decreased compared to neat PLLA.

scholarly journals Heterogeneous Nucleation Effect of N, N'-Adipic Bis(4-phenylbutyric Acid) Dihydrazide on Crystallization Process of Poly(L-lactic Acid)

2019 ◽  
Vol 25 (4) ◽  
pp. 446-454
Author(s):  
Yan-Hua CAI ◽  
Li-Sha ZHAO
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Heterogeneous Nucleation ◽  
Isothermal Crystallization ◽  
Crystallization Process ◽  
Melting Behavior ◽  
Light Transmittance ◽  
Crystallization Peak ◽  
Nucleation Effect ◽  
Phenylbutyric Acid

Enhancing crystallization ability is a fundamental challenges in Poly(L-lactic acid) (PLLA) industry, therefore, the goal of this work was to synthesis a new organic nucleating agent N, N'-adipic bis(4-phenylbutyric acid) dihydrazide (APAD), and investigate its effect on non-isothermal crystallization, isothermal crystallization, melting behavior, thermal stability, and optical property of PLLA. Non-isothermal melt crystallization results showed that APAD acted as more effective nucleating and accelerating agent for the crystallization of PLLA, as a result, upon cooling at 1 °C/min, PLLA/0.5 %APAD had the highest onset crystallization temperature 136.4 °C and the crystallization peak temperature 132.0 °C, as well as the largest non-isothermal crystallization enthalpy 48.1 J/g. However, with increasing of APAD concentration from 0.5 wt.% to 3 wt.%, the crystallization peak shifted to the lower temperature. In contrast, for the non-isothermal cold crystallization process, the effect of APAD concentration on the crystallization behavior of PLLA was negligible. Additionally, the non-isothermal crystallization process was also depended on the cooling rates and the final melting temperature. In isothermal crystallization section, to compare with the primary PLLA, the crystallization half-time of PLLA/APAD could decrease from 254.3 s to the minimum value 29.4 s, with 0.5 wt.% APAD contents at 125 °C. Melting behavior of PLLA/APAD samples under different conditions further confirmed the heterogeneous nucleation effect of APAD for PLLA, and the appearance of the double melting peaks was attributed to the melting-recrystallization. Finally, the addition of APAD decreased the thermal stability to some extent, although APAD could not change the thermal decomposition profile of PLLA. And a drop of PLLA/APAD samples in light transmittance resulted from the double influence of the enhancement of crystallization and the opaqueness of APAD.

scholarly journals The Synthesis of Biodegradable Poly(L-Lactic Acid)-Polyethylene Glycols Copolymer/Montmorillonite Nanocomposites and Analysis of the Crystallization Properties

Minerals ◽  
2021 ◽  
Vol 12 (1) ◽  
pp. 14
Author(s):  
Jiunn-Jer Hwang ◽  
Su-Mei Huang ◽  
Wen-Yang Lin ◽  
Hsin-Jiant Liu ◽  
Cheng-Chan Chuang ◽  
...  
Keyword(s):  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Crystallization Process ◽  
Crystallization Rate ◽  
Nucleating Agent ◽  
Silicate Layer ◽  
Polyethylene Glycols ◽  
Melt Crystallization ◽  
Scanning Calorimetry ◽  
Study Results

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.

PP/MWCNTs composites: Effects of length of MWCNTs on isothermal crystallization behaviors, crystalline structure, and thermal stability

2017 ◽  
Vol 52 (4) ◽  
pp. 503-517 ◽  
Author(s):  
Zheng-Ian Lin ◽  
Ching-Wen Lou ◽  
Yi-Jun Pan ◽  
Chien-Teng Hsieh ◽  
Chien-Lin Huang ◽  
...  
Keyword(s):  
Carbon Nanotubes ◽  
Thermal Stability ◽  
Crystalline Structure ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Nucleating Agent ◽  
Scanning Calorimetry ◽  
Crystallization Behaviors ◽  
Walled Carbon Nanotubes ◽  
Thermal Stability Of

This study adopts the melt compounding method to prepare /mutli-walled carbon nanotubes composites. The effects of different lengths of the mutli-walled carbon nanotubes on the isothermal crystallization behaviors, crystalline structure, and thermal stability of the polypropylene/mutli-walled carbon nanotubes composites are examined. The PLM results show that the combination of mutli-walled carbon nanotubes prevents the growth of polypropylene spherulites, and thus results in a small size of spherulites. The differential scanning calorimetry results show that the short (S-) or long (L-) mutli-walled carbon nanotubes can function as the nucleating agent of polypropylene, which accelerates the crystallization rate of polypropylene. Avrami theory analyses indicate that the addition of short-mutli-walled carbon nanotubes particularly provides polypropylene/mutli-walled carbon nanotubes composites with a high crystallization rate. The X-ray diffraction results show that the combination of mutli-walled carbon nanotubes does not pertain to the crystal structure. The TGA test results show that long-mutli-walled carbon nanotubes outperform short -mutli-walled carbon nanotubes in improving the thermal stability of polypropylene, and both can significantly improve it.

scholarly journals Exploring the Effects of MXene on Nonisothermal Crystallization and Melting Behavior of β-Nucleated Isotactic Polypropylene

Polymers ◽  
2021 ◽  
Vol 13 (21) ◽  
pp. 3815
Author(s):  
Wanxin Peng ◽  
Furui Sun ◽  
Yuke Liang ◽  
Jian Kang ◽  
Jinyao Chen ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Isotactic Polypropylene ◽  
Isothermal Crystallization ◽  
Polarized Light ◽  
Thermal Conditions ◽  
Melting Behavior ◽  
Polymorphic Behavior ◽  
Scanning Calorimetry ◽  
Cooling Rates ◽  
Thermal Stability Of

In this study, one of the commonly used MXene (Ti3C2Tx) and β nucleated isotactic polypropylene (β-iPP)/MXene composites of different compositions were fabricated. The effects of MXene on non-isothermal crystallization and polymorphic behavior of β-iPP/MXene composites were comparatively studied. The non-isothermal crystallization kinetics indicates that for all samples, the lower cooling rates promote composites to crystallize at higher temperatures. When MXene and β-Nucleating agent (β-NA) are added separately, the crystallization temperature of composites shifts towards higher temperatures at all cooling rates. When MXene and β-NA are added simultaneously, the composite shows different cooling rate dependence, and the effects of improving crystallization temperatures is more obvious under rapid cooling. The activation energy of four samples iPP, iPP/MXene, iPP/β-NA, and iPP/MXene/β-NA were −167.5, −185.5, −233.8, and −218.1 kJ/mol respectively, which agree with the variation tendency of crystallization temperatures. The polymorphic behavior analysis obtained from Differential Scanning calorimetry (DSC) is affected by two factors: the ability to form β-crystals and the thermal stability of β-crystals. Because β-crystals tend to recrystallize to α-crystals below a critical temperature, to eliminate the effect of β-α recrystallization, the melting curves at end temperatures Tend = 50 °C and Tend = 100 °C are comparatively studied. The results show that more thermally unstable β-crystals would participate in β-α recrystallization with higher cooling rates. Moreover, thermal stability of β-crystals is improved by adding MXene. To further verify these findings, samples of three different thermal conditions were synthesized and analyzed by DSC, X-Ray Diffraction (XRD), and Polarized Light Optical Microscopy (PLOM), and the results were consistent with the above findings. New understandings of synthesizing β-iPP/MXene composites with adjustable morphologies and polymorphic behavior were proposed.

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