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.

Preparation and Isothermal Crystallization Behavior of Poly(lactic acid)/Graphene Nanocomposites

2011 ◽  
Vol 284-286 ◽  
pp. 246-252 ◽  
Author(s):  
Yan Hua Chen ◽  
Xia Yin Yao ◽  
Zhi Juan Pan ◽  
Qun Gu
Keyword(s):  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Graphene Nanosheets ◽  
Nucleating Agent ◽  
Optical Microscope ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
Avrami Model ◽  
Graphene Nanocomposites ◽  
Solution Blending

Poly(lactic acid) (PLA)/graphene nanocomposites were prepared by solution blending using chloroform as a mutual solvent. Transmission electron microscopy (TEM) was used to examine the quality of the dispersion of graphene in the PLA matrix. The isothermal crystallization behaviors of PLA and PLA/graphene nanocomposites were investigated by differential scanning calorimetry (DSC). The isothermal crystallization kinetics were analyzed by Avrami model based on the DSC data. The results showed that the well dispersed graphene nanosheets could act as a heterogeneous nucleating agent and lead to an acceleration of crystallization during the PLA isothermal crystallization process. According to the Arrhenius equation, the activation energies were found to be -106.9 and -46.6 kJ/mol for pure PLA and PLA/0.1 wt % graphene nanocomposite, respectively. The crystal morphology were characterized with polarizing optical microscope (POM).

Isothermal Crystallization Behavior and Kinetics of Poly (lactic acid) Filled with a Novel Nucleating Agent

2014 ◽  
Vol 887-888 ◽  
pp. 716-722
Author(s):  
Nai Xu ◽  
Xing Hui Wang ◽  
Li Sha Pan ◽  
Su Juan Pang ◽  
Xuan Chen ◽  
...  
Keyword(s):  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Crystallization Behavior ◽  
Nucleating Agent ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
Nucleation Effect ◽  
Amide Derivatives ◽  
Aromatic Amide ◽  
Kinetics Of

The crystallization behavior and crystalline structure of poly (lactic acid) (PLA) filled with a novel nucleating agent (TMC328), which is a kind of aromatic amide derivatives, were investigated using differential scanning calorimetry (DSC) and wide angle X-ray (XRD). In isothermal crystallization from the melt, the present of TMC328 remarkably affected the isothermal crystalline behaviors of PLA. PLA/0.5% TMC328 sample exhibited very short crystallization half-times at 90-130 °C. Furthermore, the Avrami theory was used to describe the isothermal crystallization kinetics of PLA/TMC328 samples. It is confirmed that TMC328 showed a significant heterogeneous nucleation effect on the crystallization of PLA matrix. Moreover, XRD measurement indicates that TMC328 is a kind of α-form nucleating agent for PLA.

Effect of Poly(D-Lactic Acid)-co-Polyethylene Glycol on the Crystallization of Poly(L-Lactic Acid)

2017 ◽  
Vol 751 ◽  
pp. 283-289 ◽  
Author(s):  
Ployrawee Kaewlamyai ◽  
Amornrat Lertworasirikul
Keyword(s):  
Lactic Acid ◽  
Polyethylene Glycol ◽  
Weight Ratio ◽  
Crystallization Rate ◽  
Heat Stability ◽  
Nucleating Agent ◽  
Degree Of Crystallinity ◽  
Poly Lactic Acid ◽  
Infrared Spectrometry ◽  
Scanning Calorimetry

Poly (lactic acid) (PLA) is a biopolymer derived from renewable resources and can be disposed of without creating harm to the environment. PLA can be formed by thermoplastic processes and has good mechanical properties. However, its disadvantages are a high crystallization temperature, slow crystallization rate, poor heat stability and low ductility. In the past, it was found that poly (D-lactic acid) (PDLA) can form complexes with poly (L-lactic acid) (PLLA) and the complexes could accelerate the crystallization and increase the degree of crystallinity of the PLA, but decrease the ductility. It is known that polyethylene glycol (PEG) can improve the ductility of PLLA. In this research, PDLA was copolymerized with PEG in an attempt to improve both crystallization behavior and ductility of PLLA. Poly (D-lactic acid)-co-polyethylene glycol (PDEG) was synthesized by ring opening polymerization using D-lactide and PEG at a D-lactide:PEG weight ratio of 10:3. The PDEG was blended with PLLA with a PDEG content of 0wt% to 50wt% by melt blending process. Fourier transform infrared spectrometry (FT-IR) and X-Ray diffractometry (XRD) confirmed the stereocomplex formation between PDEG and PLLA. Characterization by differential scanning calorimetry (DSC) revealed that crystallization temperatures of the blends were decreased in the presence of PDEG. Storage moduli and tan of the blends obtained from dynamic mechanical analysis (DMA) decreased as PDEG content increased. Polarized optical microscopy (POM) micrographs of blends with PDEG content of 1wt% to 5wt% obviously showed that crystallization rate was increased. PDEG has the potential to be an effective nucleating agent and efficient plasticizer for PLLA.

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.

Isothermal Crystallization Behavior of Poly (L-lactic Acid)/ Surface-Grafted Silica Nanocomposites

2012 ◽  
Vol 268-270 ◽  
pp. 37-40 ◽  
Author(s):  
Yan Hua Cai
Keyword(s):  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Crystallization Behavior ◽  
Nucleating Agent ◽  
Melt Blending ◽  
Scanning Calorimetry ◽  
Silica Nanocomposites ◽  
Induction Periods ◽  
Sio2 Nanocomposites ◽  
Different Content

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.

scholarly journals Multifunctional PLA Blends Containing Chitosan Mediated Silver Nanoparticles: Thermal, Mechanical, Antibacterial, and Degradation Properties

Nanomaterials ◽  
2019 ◽  
Vol 10 (1) ◽  
pp. 22 ◽  
Author(s):  
Agueda Sonseca ◽  
Salim Madani ◽  
Gema Rodríguez ◽  
Víctor Hevilla ◽  
Coro Echeverría ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Silver Nanoparticles ◽  
Lactic Acid ◽  
Food Packaging ◽  
Synthesis Method ◽  
Crystallization Rate ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
The Matrix ◽  
Degradation Properties

Poly(lactic acid) (PLA) is one of the most commonly employed synthetic biopolymers for facing plastic waste problems. Despite its numerous strengths, its inherent brittleness, low toughness, and thermal stability, as well as a relatively slow crystallization rate represent some limiting properties when packaging is its final intended application. In the present work, silver nanoparticles obtained from a facile and green synthesis method, mediated with chitosan as a reducing and stabilizing agent, have been introduced in the oligomeric lactic acid (OLA) plasticized PLA in order to obtain nanocomposites with enhanced properties to find potential application as antibacterial food packaging materials. In this way, the green character of the matrix and plasticizer was preserved by using an eco-friendly synthesis protocol of the nanofiller. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) results proved the modification of the crystalline structure as well as the crystallinity of the pristine matrix when chitosan mediated silver nanoparticles (AgCH-NPs) were present. The final effect over the thermal stability, mechanical properties, degradation under composting conditions, and antimicrobial behavior when AgCH-NPs were added to the neat plasticized PLA matrix was also investigated. The obtained results revealed interesting properties of the final nanocomposites to be applied as materials for the targeted application.

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.

Crystallization Properties of Nucleated Poly(lactic acid)

2012 ◽  
Vol 549 ◽  
pp. 322-326 ◽  
Author(s):  
Yong Chen ◽  
Qiang Dou
Keyword(s):  
Lactic Acid ◽  
Crystallization Behavior ◽  
Polarized Light ◽  
Nucleating Agent ◽  
Poly Lactic Acid ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Crystallization Properties ◽  
Melting And Crystallization

The effect of a nucleating agent (NT-C) on the crystallization behavior of poly(lactic acid) (PLA) was studied. The melting and crystallization behavior and spherulitic morphology of the nucleated PLA were investigated by means of differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarized light microscopy (PLM). It is found that the crystallization temperature and crystallinity increase, the spherulitic size decrease for the nucleated PLA. But the crystal structure of the nucleated PLA is not changed.

Poly(lactic acid)/Graphene Nanocomposites Prepared via Solution Blending Using Chloroform as a Mutual Solvent

2011 ◽  
Vol 11 (9) ◽  
pp. 7813-7819 ◽  
Author(s):  
Yanhua Chen ◽  
Xiayin Yao ◽  
Xufeng Zhou ◽  
Zhijuan Pan ◽  
Qun Gu
Keyword(s):  
Lactic Acid ◽  
Poly Lactic Acid ◽  
Graphene Nanocomposites ◽  
Solution Blending

scholarly journals Bio-composites for Fused Filament Fabrication. Effects of Maleic Anhydride Grafting on Poly(Lactic Acid) and Microcellulose

2021 ◽  
Author(s):  
Daniele Rigotti ◽  
Luca Fambri ◽  
Alessandro Pegoretti
Keyword(s):  
Lactic Acid ◽  
Maleic Anhydride ◽  
Nucleating Agent ◽  
Mechanical Analysis ◽  
Poly Lactic Acid ◽  
Crystalline Cellulose ◽  
Fused Filament Fabrication ◽  
Scanning Calorimetry ◽  
Electron Microscopy Analysis ◽  
Reactive Mixing

Abstract Composite filaments consisting of poly(lactic acid) (PLA) and micro crystalline cellulose (MCC) were successfully used for additive manufacturing (AM) by fused filament fabrication (FFF). PLA and MCC bio-composites were obtained by direct mixing in a melt compounder; maleic anhydride (MAH) was also grafted onto PLA in reactive mixing stage to evaluate its effect on the final properties of the printed material. Filaments with various concentrations of MCC (up to a maximum content of 10 wt%) were produced with a single screw extruder and used to feed a commercial desktop FFF printer. Upon grafting of PLA with MAH, a more coherent interfacial morphology between PLA and MCC was detected by electron microscopy analysis. The thermal degradation of the PLA was unaffected by the presence of MCC and MAH. According to differential scanning calorimetry and dynamic mechanical analysis results, micro-cellulose acted as nucleating agent for PLA. In fact, the crystallization peak shifted towards lowers temperature and a synergistic effect when MCC was added to PLA grafted with MAH was observed possibly due to the increase of the chain mobility. Micro cellulose led to an increase in the stiffness of the material in both filaments and 3D printed specimen, however, a different fracture behavior was observed due to the peculiar structure of printed samples.

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