scholarly journals The Effect of WS2 Nanosheets on the Non-Isothermal Cold- and Melt-Crystallization Kinetics of Poly(l-lactic acid) Nanocomposites

Polymers ◽  
2021 ◽  
Vol 13 (13) ◽  
pp. 2214
Author(s):  
Mohammed Naffakh ◽  
Pablo Rica ◽  
Carmen Moya-Lopez ◽  
José Antonio Castro-Osma ◽  
Carlos Alonso-Moreno ◽  
...  
Keyword(s):  
Lactic Acid ◽  
Transition Metal Dichalcogenides ◽  
Crystallization Rate ◽  
Melting Behavior ◽  
Hybrid Nanocomposites ◽  
Melt Crystallization ◽  
Heating Rates ◽  
Solution Blending ◽  
New Perspective ◽  
Ws2 Nanosheets

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.

scholarly journals Nanocomposite Materials with Poly(l-lactic Acid) and Transition-Metal Dichalcogenide Nanosheets 2D-TMDCs WS2

Polymers ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 2699
Author(s):  
Mohammed Naffakh ◽  
Miriam Fernández ◽  
Peter S. Shuttleworth ◽  
Ana M. García ◽  
Diego A. Moreno
Keyword(s):  
Lactic Acid ◽  
Transition Metal ◽  
Transition Metal Dichalcogenides ◽  
Crystallization Rate ◽  
Nanocomposite Materials ◽  
Melt Processing ◽  
Transition Metal Dichalcogenide ◽  
Melt Crystallization ◽  
Metal Dichalcogenides ◽  
Ws2 Nanosheets

Layered transition-metal dichalcogenides (TMDCs) based on tungsten disulfide nanosheets (2D-WS2) were introduced via melt processing into poly(l-lactic acid) (PLLA) to generate PLLA/2D-WS2 nanocomposite materials. The effects of the 2D-WS2 on the morphology, crystallization, and biodegradation behavior of PLLA were investigated. In particular, the non-isothermal melt-crystallization of neat PLLA and PLLA/2D-WS2 nanocomposites were analyzed in detail by varying both the cooling rate and 2D-WS2 loading. The kinetic parameters of PLLA chain crystallization are successfully described using the Liu model. It was found that the PLLA crystallization rate was reduced with 2D-WS2 incorporation, while the crystallization mechanism and crystal structure of PLLA remained unchanged in spite of nanoparticle loading. This was due to the PLLA chains not being able to easily adsorb on the WS2 nanosheets, hindering crystal growth. In addition, from surface morphology analysis, it was observed that the addition of 2D-WS2 facilitated the enzymatic degradation of poorly biodegradable PLLA using a promising strain of actinobacteria, Lentzea waywayandensis. The identification of more suitable enzymes to break down PLLA nanocomposites will open up new avenues of investigation and development, and it will also lead to more environmentally friendly, safer, and economic routes for bioplastic waste management.

scholarly journals Biopolymer Nanocomposite Materials Based on Poly(L-lactic Acid) and Inorganic Fullerene-like WS2 Nanoparticles

Polymers ◽  
2021 ◽  
Vol 13 (17) ◽  
pp. 2947
Author(s):  
Mohammed Naffakh
Keyword(s):  
Lactic Acid ◽  
High Performance ◽  
Transition Metal Dichalcogenides ◽  
Crystallization Rate ◽  
Industrial Applications ◽  
Melt Processing ◽  
Hybrid Nanocomposites ◽  
Processing Route ◽  
Melt Crystallization ◽  
Inorganic Fullerene

In the current study, inorganic fullerene (IF)-like tungsten disulphide (WS2) nanoparticles from layered transition metal dichalcogenides (TMDCs) were introduced into a poly (L-lactic acid) (PLLA) polymer matrix to generate novel bionanocomposite materials through an advantageous melt-processing route. The effectiveness of employing IF-WS2 on the morphology and property enhancement of the resulting hybrid nanocomposites was evaluated. The non-isothermal melt–crystallization and melting measurements revealed that the crystallization and melting temperature as well as the crystallinity of PLLA were controlled by the cooling rate and composition. The crystallization behaviour and kinetics were examined by using the Lui model. Moreover, the nucleating effect of IF-WS2 was investigated in terms of Gutzow and Dobreva approaches. It was discovered that the incorporation of increasing IF-WS2 contents led to a progressive acceleration of the crystallization rate of PLLA. The morphology and kinetic data demonstrate the high performance of these novel nanocomposites for industrial applications.

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
Keyword(s):  
Lactic Acid ◽  
Heating Rate ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Melting Behavior ◽  
Melting Peak ◽  
Melt Crystallization ◽  
Biodegradable Poly ◽  
Crystallization And Melting Behavior ◽  
Double Melting Peak

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.

scholarly journals Crystallization Kinetics of Poly(lactic acid)–Graphene Nanoscroll Nanocomposites: Role of Tubular, Planar, and Scrolled Carbon Nanoparticles

2021 ◽  
Vol 7 (4) ◽  
pp. 75
Author(s):  
Oluwakemi Ajala ◽  
Caroline Werther ◽  
Rauf Mahmudzade ◽  
Peyman Nikaeen ◽  
Dilip Depan
Keyword(s):  
Mechanical Properties ◽  
Lactic Acid ◽  
Crystallization Kinetics ◽  
Crystallization Rate ◽  
Melting Behavior ◽  
Degree Of Crystallinity ◽  
Poly Lactic Acid ◽  
Avrami Model ◽  
Superior Mechanical Properties ◽  
Kinetics Of

Graphene nanoscrolls (GNS) are 1D carbon-based nanoparticles. In this study, they were investigated as a heterogeneous nucleating agent in the poly(lactic acid) (PLA) matrix. The isothermal and non-isothermal melting behavior and crystallization kinetics of PLA-GNS nanocomposites were investigated using a differential scanning calorimeter (DSC). Low GNS content not only accelerated the crystallization rate, but also the degree of crystallinity of PLA. The Avrami model was used to fit raw experimental data, and to evaluate the crystallization kinetics for both isothermal and non-isothermal runs through the nucleation and growth rate. Additionally, the effect of the dimensionality and structure of the nanoparticle on the crystallization behavior and kinetics of PLA is discussed. GNS, having a similar fundamental unit as CNT and GNP, were observed to possess superior mechanical properties when analyzed by the nanoindentation technique. The scrolled architecture of GNS facilitated a better interface and increased energy absorption with PLA compared to CNTs and GNPs, resulting in superior mechanical properties.

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.

Non-isothermal crystallization kinetics of poly (lactic acid)/graphene nanocomposites

2013 ◽  
Vol 33 (2) ◽  
pp. 163-171 ◽  
Author(s):  
Yanhua Chen ◽  
Xiayin Yao ◽  
Qun Gu ◽  
Zhijuan Pan
Keyword(s):  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Nucleating Agent ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
Graphene Nanocomposites ◽  
Solution Blending ◽  
Transmission Electron ◽  
Graphene Nanocomposite

Abstract Poly(lactic acid) (PLA)/graphene nanocomposites were prepared by solution blending and the dispersibility of graphene in the PLA matrix was examined by transmission electron microscopy (TEM). The non-isothermal crystallization behaviors of pure PLA and PLA/graphene nanocomposites from the melt were investigated by differential scanning calorimetry (DSC). The results showed that the graphene could play a role as a heterogeneous nucleating agent during the non-isothermal crystallizing process of PLA, and accelerate the crystallization rate. The non-isothermal crystallizing data were analyzed with the Avrami, Ozawa and Mo et al. models and the crystallization parameters of the samples were obtained. It is demonstrated that the combination of the Avrami and Ozawa models developed by Mo et al. was successful in describing the non-isothermal crystallization process for pure PLA and its nanocomposite. According to the Kissinger equation, the activation energies were found to be -154.3 and -179.5 kJ/mol for pure PLA and PLA/0.1 wt% graphene nanocomposite, respectively. Furthermore, the spherulite growth behavior was investigated by polarized optical microscopy (POM) and the results also supported the DSC data.

scholarly journals Effect of Organic Modifier and Clay Content on Non-Isothermal Cold Crystallization and Melting Behavior of Polylactide/Organovermiculite Nanocomposites

Polymers ◽  
2020 ◽  
Vol 12 (2) ◽  
pp. 364
Author(s):  
M. Jesús Fernández ◽  
M. Dolores Fernández
Keyword(s):  
Rate Coefficient ◽  
Crystallization Rate ◽  
Clay Content ◽  
Melting Behavior ◽  
Cold Crystallization ◽  
Heating Rates ◽  
Scanning Calorimetry ◽  
Crystallization And Melting Behavior ◽  
Kinetics Of ◽  
Nucleating Effect

In clay/polymer nanocomposites, the crystallization behavior and kinetics of the polymer can be affected by the presence of clay, its content and the degree of miscibility between the clay and the polymer matrix. The effect of two different organomodified vermiculites on the non-isothermal cold crystallization and melting behavior of polylactide (PLA) was studied by differential scanning calorimetry (DSC). In the presence of vermiculites, the cold crystallization of PLA occurred earlier, particularly for the highest content of the most miscible organovermiculite with PLA. The cold crystallinity of PLA decreased at low heating rates, notably at high organoclay loadings, and increased at high heating rates, especially at low vermiculite contents. According to the crystallization half-time, crystallization rate coefficient (CRC), and crystallization rate parameter (CRP) approaches, the cold crystallization rate of PLA increased by incorporating vermiculites, with the effect being most noteworthy for the vermiculite showing better compatibility. The Mo model was successful in describing the non-isothermal cold crystallization kinetics of the PLA/vermiculite composites. The melting behavior was affected by the heating rate and the type and content of clay. The nucleating effect of the most compatible clay resulted in the less perfect crystallites. The activation energy was evaluated using the Kissinger and Takhor methods.

scholarly journals Study on the Performances of PLLA/CaSiO3 Composites

2021 ◽  
Vol 236 ◽  
pp. 02037
Author(s):  
Qiuhe Zhang ◽  
Lisha Zhao ◽  
Ting Deng ◽  
Yanhua Cai
Keyword(s):  
Thermal Decomposition ◽  
Crystallization Temperature ◽  
Melting Process ◽  
Melting Behavior ◽  
Decomposition Temperature ◽  
Melt Crystallization ◽  
Heating Rates ◽  
Promoting Effect ◽  
Decomposition Behavior ◽  
Relationship Of

In the current work, calcium silicate (CaSiO3) was blended with the poly (L-lactic acid) (PLLA) to prepare the PLLA/CaSiO3 composites, and the crystallization process, melting process and thermal decomposition behavior of PLLA/CaSiO3 composites were studied. The promoting effect of CaSiO3 on the crystallization of PLLA was proved by the melt-crystallization, and the CaSiO3 content was a crucial factor to the crystallization behavior of PLLA. The crystallization temperature significantly affected the melting behavior of PLLA, and the double melting peaks degenerated into the single melting peak with the increasing of crystallization temperature from 90 °C to 130 °C. Additionally, for a given PLLA/CaSiO3 sample, the different melting processes in heating after the melt-crystallization results from the different heating rates, and the appearance of the cold-crystallization peak indicated the medium nucleation capacity of CaSiO3. The presence of CaSiO3 decreased the onset thermal decomposition temperature of PLLA, and this effect depended on the competitive relationship of the poor compatibility of PLLA with CaSiO3 and the content of CaSiO3 with high thermal stability.

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.

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.

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