scholarly journals Poly(ε-Caprolactone)/Poly(Lactic Acid) Blends Compatibilized by Peroxide Initiators: Comparison of Two Strategies

Polymers ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 228 ◽  
Author(s):  
Marta Przybysz-Romatowska ◽  
Józef Haponiuk ◽  
Krzysztof Formela

Poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) blends were compatibilized by reactive blending and by copolymers formed during reaction in the solution. The reactive blending of PCL/PLA was performed using di-(2-tert-butyl-peroxyisopropyl)benzene (BIB) or dicumyl peroxide (DCP) as radical initiator. PCL-g-PLA copolymers were prepared using 1.0 wt. % of DCP or BIB via reaction in solution, which was investigated through a Fourier transform infrared spectrometry (FTIR) and nuclear magnetic resonance (NMR) in order to better understand the occurring mechanisms. The effect of different additions such as PCL-g-PLA copolymers, DCP, or BIB on the properties of PCL/PLA blends was studied. The unmodified PCL/PLA blends showed a sea-island morphology typical of incompatible blends, where PLA droplets were dispersed in the PCL matrix. Application of organic peroxides improved miscibility between PCL and PLA phases. A similar effect was observed for PCL/PLA blend compatibilized by PCL-g-PLA copolymer, where BIB was used as initiator. However, in case of application of the peroxides, the PCL/PLA blends were cross-linked, and it has been confirmed by the gel fraction and melt flow index measurements. The thermal and mechanical properties of the blends were also investigated by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and tensile strength.

Materials ◽  
2020 ◽  
Vol 13 (5) ◽  
pp. 1242
Author(s):  
Olga Mysiukiewicz ◽  
Paulina Kosmela ◽  
Mateusz Barczewski ◽  
Aleksander Hejna

Investigations related to polymer/metal composites are often limited to the analysis of the electrical and thermal conductivity of the materials. The presented study aims to analyze the impact of aluminum (Al) filler content (from 1 to 20 wt%) on the rarely investigated properties of composites based on the high-density polyethylene (HDPE) matrix. The crystalline structure, rheological (melt flow index and oscillatory rheometry), thermal (differential scanning calorimetry), as well as static (tensile tests, hardness, rebound resilience) and dynamic (dynamical mechanical analysis) mechanical properties of composites were investigated. The incorporation of 1 and 2 wt% of aluminum filler resulted in small enhancements of mechanical properties, while loadings of 5 and 10 wt% provided materials with a similar performance to neat HDPE. Such results were supported by the lack of disturbances in the rheological behavior of composites. The presented results indicate that a significant content of aluminum filler may be introduced into the HDPE matrix without additional pre-treatment and does not cause the deterioration of composites’ performance, which should be considered beneficial when engineering PE/metal composites.


2019 ◽  
Vol 33 (10) ◽  
pp. 1383-1395
Author(s):  
Hongjuan Zheng ◽  
Zhengqian Sun ◽  
Hongjuan Zhang

Poly(lactic acid) (PLA) has good environmental compatibility, however, its high brittleness, slow rate of crystallization, and low heat distortion temperature restrict its widespread use. To overcome these limitations, in this study, PLA was mixed with walnut shell (WS) powders. The effects of WS powders on the morphology and the thermal and mechanical properties of PLA were investigated. The products were characterized by differential scanning calorimetry (DSC), infrared (IR) spectroscopy, polarizing optical microscopy (POM), and various mechanical property testing techniques. The results showed that WS powders had a significant effect on the morphology and the thermal and mechanical properties of PLA. The tensile strength, impact strength, and elongation at break of the PLA/WS composites first increased and then decreased with the increasing addition of WS powders. When the addition of WS powders was about 0.5 wt%, they reached maximum values of 51.2 MPa, 23.3 MPa, and 19.0%, respectively. Compared with neat PLA, the spherulite grain size of the composites could be reduced and many irregular polygons were formed during crystallization. The melting, cold crystallization, and glass-transition temperatures of the composites were lower than those of neat PLA.


2021 ◽  
Author(s):  
Daniele Rigotti ◽  
Luca Fambri ◽  
Alessandro Pegoretti

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.


Polymers ◽  
2018 ◽  
Vol 10 (9) ◽  
pp. 1013 ◽  
Author(s):  
Xuan Wang ◽  
Yuan Jia ◽  
Zhen Liu ◽  
Jiaojiao Miao

Poly(lactic acid) (PLA)/lignin-containing cellulose nanofibrils (L-CNFs) composite films with different lignin contents were produced bythe solution casting method. The effect of the lignin content on the mechanical, thermal, and crystallinity properties, and PLA/LCNFs interfacial adhesion wereinvestigated by tensile tests, thermogravimetric analysis, differential scanning calorimetry (DSC), dynamic mechanical analysis, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The tensile strength and modulus of the PLA/9-LCNFs (9 wt % lignin LCNFs) composites are 37% and 61% higher than those of pure PLA, respectively. The glass transition temperature (Tg) decreases from 61.2 for pure PLA to 52.6 °C for the PLA/14-LCNFs (14 wt % lignin LCNFs) composite, and the composites have higher thermal stability below 380 °C than pure PLA. The DSC results indicate that the LCNFs, containing different lignin contents, act as a nucleating agent to increase the degree of crystallinity of PLA. The effect of the LCNFs lignin content on the PLA/LCNFs compatibility/adhesion was confirmed by the FTIR, SEM, and Tg results. Increasing the LCNFs lignin content increases the storage modulus of the PLA/LCNFs composites to a maximum for the PLA/9-LCNFs composite. This study shows that the lignin content has a considerable effect on the strength and flexibility of PLA/LCNFs composites.


2017 ◽  
Vol 37 (9) ◽  
pp. 897-909
Author(s):  
Li Zhang ◽  
Weijun Zhen ◽  
Yufang Zhou

Abstract Poly(lactic acid) (PLA) was synthesized using a green catalyst, nano-zinc oxide (ZnO). The optimum synthesis conditions of PLA were as follows: a stoichiometric amount of 0.5 wt% of nano-ZnO, polymerization time of 14 h, and polymerization temperature of 170°C. Gel permeation chromatography results showed that the weight-average molecular weight (Mw) of PLA was 13,072 g/mol with a polydispersity index (PDI) of 1.7. Furthermore, PLA-α-cyclodextrin inclusion compounds (PLA-CD-ICs) were prepared by ultrasonic co-precipitation techniques. X-ray diffraction analysis and Fourier transform infrared spectroscopy demonstrated the change in lattice of α-CD from a cage configuration to a tunnel structure and the existence of some physical interactions between α-CD and PLA in the PLA-CD-ICs. To enhance the crystallization properties of PLA, PLA/PLA-CD-IC composites were blended with different contents of PLA-CD-ICs as nucleating agents. The crystallization behavior and comprehensive performance were investigated by differential scanning calorimetry, polarized optical microscopy, tensile testing, dynamic mechanical analysis, and scanning electron microscopy. Compared to PLA, the crystallinities of PLA/PLA-CD-IC composites were increased by 24.0%, 26.3%, 27.3%, and 31.8%. The results of all the analyses proved that PLA-CD-ICs were useful as green organic nucleators and improved the comprehensive performance of PLA materials.


2014 ◽  
Vol 71 (12) ◽  
pp. 3305-3321 ◽  
Author(s):  
Kyung-Man Choi ◽  
Sung-Wook Lim ◽  
Myeon-Cheon Choi ◽  
Young-Min Kim ◽  
Dong-Hun Han ◽  
...  

2018 ◽  
Vol 32 (3) ◽  
pp. 312-327 ◽  
Author(s):  
Omid Yousefzade ◽  
Javad Jeddi ◽  
Elham Vazirinasab ◽  
Hamid Garmabi

The effect of stearic acid-coated nano calcium carbonate (NCC) on transitions and chain mobility of poly(lactic acid) (PLA) was investigated. Dispersion state of NCC in polymeric matrix was explored using scanning electron microscopy and surface tension component measurements. Trends of PLA transitional phenomena were investigated using the results of dynamical mechanical analysis (DMA) and differential scanning calorimetry (DSC) in the nanocomposite systems based on PLA and NCC. In addition, two types of crystal structures and decreasing the glass transition temperature were distinguished using temperature-modulated DSC (TMDSC). Higher melting points of polymer crystals were found in TMDSC experiments due to low and dynamic heating rate compared to the conventional DSC. Dynamics of polymer chains, affected by NCC, were quantified using cooperativity length, ξ α, and the number of relaxing structural units, Nα, in the glass transition region. NCC particles hindered the cooperative motion of polymer chains at glass transitions and crystallization in TMDSC measurements, whereas the DMA results indicated that NCC particles may act as lubricant and simplified chain mobility.


2017 ◽  
Vol 751 ◽  
pp. 283-289 ◽  
Author(s):  
Ployrawee Kaewlamyai ◽  
Amornrat Lertworasirikul

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.


Polymers ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 1381
Author(s):  
Maria-Eirini Grigora ◽  
Zoi Terzopoulou ◽  
Konstantinos Tsongas ◽  
Panagiotis Klonos ◽  
Nikolaos Kalafatakis ◽  
...  

Fused deposition modeling (FDM) is currently the most popular 3D printing method, where thermoplastic polymers are predominantly used. Among them, the biobased poly(lactic acid) (PLA) governs the FDM filament market, with demand higher than supply, since not all grades of PLA are suitable for FDM filament production. In this work, the effect of a food grade chain extender (Joncryl ADR® 4400) on the physicochemical properties and printability of PLA marketed for injection molding was examined. All samples were characterized in terms of their mechanical and thermal properties. The microstructure of the filaments and 3D-printed fractured surfaces following tensile testing were examined with optical and scanning electron microscopy, respectively. Molecular weight and complex viscosity increased, while the melt flow index decreased after the incorporation of Joncryl, which resulted in filaments of improved quality and 3D-printed constructs with enhanced mechanical properties. Dielectric spectroscopy revealed that the bulk properties of PLA with respect to molecular mobility, both local and segmental, were, interestingly, not affected by the modifier. Indirectly, this may suggest that the major effects of the extender are on chain length, without inducing chain branching, at least not to a significant extent.


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