Morphology,biodegradability, mechanical,and thermal properties of nanocomposite films based on PLA and plasticized PLA

In this study, melt intercalation method is applied to prepare poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG)‐plasticized PLA nanocomposite films including 0, 3, and 5% organoclay (Cloisite 30B) using a laboratory scale compounder, which is connected to a microcast film device. To evaluate the nanomorphology and the dispersion state of the clays, X‐ray diffraction (XRD) and transmission electron microscopy (TEM) are conducted. Tensile tests are performed to characterize the mechanical behavior of the films. Biodegradation rate is determined by degradation tests in composting medium. Differential scanning calorimeter (DSC) is applied to observe the thermal behavior of the films. XRD and TEM show that the exfoliation predominantly occurrs in plasticized PLA nanocomposites, whereas unexfoliated agglomerates together with exfoliated clays are observed in the nonplasticized PLA. Tensile tests indicate that the addition of 3% clay to the neat‐PLA does not affect the strength; however, it enhances the modulus of the nanocomposites in comparison to neat‐PLA. Incorporation of 3% clay to the plasticized PLA improves the modulus with respect to PLA/PEG; on the other hand, the strain at break value is lowered ～ 40%. The increase in the rate of biodegradation in composting medium is found as in the order of PLA > PLA/PEG > 3% Clay/PLA/PEG > 5% Clay/PLA/PEG > 3% Clay/PLA. DSC analysis shows that the addition of 3% clay to the neat PLA results in an increase in T_g. The addition of 20% PEG as a plasticizer to the neat‐PLA decreases T_g about 30°C, however incorporation of clays increases T_g by 4°C for the plasticized PLA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties and weldability of plasticized polylactic acid films

The objectives of the presented work were to investigate films based on polylactic acid (PLA) and polyethylene glycol (PEG) in order to improve ductility and weldability of PLA films. The effect of plasticizer amount on the thermal, rheological, and mechanical properties of PLA plasticized films was investigated. The PEG content does affect the glass transition and the cold crystallization temperature of PLA in blends, while the melting temperature was not affected by the addition of PEG. The complex viscosity of the neat PLA granules and of plasticized films showed strong temperature and angular velocity dependence. The Young's modulus and tensile strength of plasticized films were improved with increasing plasticizer concentration, while the elongation at break stays rather constant. Plasticized PLA films were furthermore heat welded. These investigations showed that plasticized PLA films can be welded by heat welding. The obtained weld strength is strongly depending on the PEG amount as well as on selected welding parameters. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40394.     

Mechanical,thermal, and morphology properties of poly(lactic acid) plasticized with poly(ethylene glycol) and epoxidized palm oil hybrid plasticizer

Poly(lactic acid) (PLA) has received great attention recently due to its good physical and mechanical properties such as high tensile strength and modulus, good processability and biodegradability. In this study, low molecular weight poly(ethylene glycol) (PEG) and epoxidized palm oil (EPO) were used as hybrid plasticizers to improve toughness and ductility of PLA. Using the solubility parameter, a tentative evaluation of the hybrid plasticizer that could act as the most effective plasticizer for PLA has been performed and the obtained results have been corroborated with the materials physical properties. Excellent plasticizing effect was obtained by hybrid plasticizer PEG:EPO with ratio 2:1. Addition of PEG:EPO (2:1) hybrid plasticizer to PLA shows a significant improvement of 12,402%, compared to neat PLA. The improvement in flexibility and decrease in rigidity for the plasticized PLA is well evidenced by lower glass transition temperature (T_g) and tensile modulus values. In relation to the thermal stability, a decrease in thermal properties of the hybrid plasticized PLA was observed due to the volatility of the plasticizers. Scanning electron microscopy (SEM) shows that the hybrid plasticizer was turned PLA's smooth surface to fibrous structure and rough fracture surface. POLYM. ENG. SCI., 56:1169–1174, 2016. © 2016 Society of Plastics Engineers     

PLA/chain‐extended PEG blends with improved ductility

Melt blending of polylactic acid (PLA) and a chain‐extended polyethylene glycol (CE‐PEG) have been performed in an effort to toughen the PLA without significant loss of modulus and ultimate tensile strength. The chain‐extended PEG was prepared with melt condensation of a low molecular weight PEG and 4,4′‐methylenebis(phenylisocyanate) (MDI) for enhancement of the molecular weight of PEG. The thermal and mechanical properties, miscibility and phase morphologies of blends were investigated. By using thermal and fracture surface analysis, the blends were found to be a partially miscible system with shifted glass transition temperatures. The addition of CE‐PEG leads to slight decrease in tensile strength and modulus, while the elongation at break is characterized by an important increase (540%), compared with neat PLA and PLA/PEG (low molecular weight PEG, M_n = 35,000). The relative ductility of PLA/CE‐PEG is 40 times higher than that of neat PLA. The brittle fracture of neat PLA was transformed into a ductile fracture by the addition of CE‐PEG. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of surface-modified Al2O3 on the thermomechanical properties of polybutylene succinate/Al2O3 composites

This study investigates the effect of the incorporation of alumina particles on the thermomechanical properties of polybutylene succinate (PBS)/Al₂O₃ composites. The alumina surface was modified with the carboxylic groups of maleic acid through simple acid-base and in situ polymerization reactions. Scanning electron microscope (SEM) results revealed the introduction of maleic acid treated alumina significantly affect the morphology of the PBS/Al₂O₃ composites as compared to the neat PBS. The thermal conductivity of the composite (0.411?W?m^?1 K^?1) was more than twice that of neat PBS. The composite containing polymerization-modified alumina showed a 50% increase in storage modulus compared with that of neat PBS. In addition, universal testing machine (UTM) and differential scanning calorimetry (DSC) measurements indicated an increase in the tensile strength and degree of crystallinity after the incorporation of modified alumina in the PBS/Al₂O₃ composite.     

The effect of poly(ethylene glycol) as plasticizer in blends of poly(lactic acid) and poly(butylene succinate)

The effect of polyethylene glycol (PEG) on the mechanical and thermal properties of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blends was examined. Overall, it was found that PEG acted as an effective plasticizer for the PLA phase in these microphase‐separated blends, increasing the elongation at break in all blends and decreasing the T_g of the PLA phase. Significant effects on other properties were also observed. The tensile strength and Young's modulus both decreased with increasing PEG content in the blends. In contrast, the elongation at break increased with the addition of PEG, suggesting that PEG acted as a plasticizer in the polymer blends. Scanning electron microscope images showed that the fracture mode of PLA changed from brittle to ductile with the addition of PEG in the polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43044.     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

Poly(lactic acid) blends with desired end-use properties by addition of thermoplastic polyester elastomer and MDI

The disadvantages of the poor mechanical properties of polylactic acid (PLA) limit its ability to be used in a wide number of applications. Melt blending of PLA and thermoplastic polyester elastomer (TPEE) has been performed in an effort to toughen the PLA without significant losses in modulus and ultimate tensile strength. In order to enhance the compatibility of PLA and TPEE, a diisocyanate compound was used as a reactive modifier. The thermal and mechanical properties, miscibility and phase morphologies of the blends were investigated. A blend of PLA and TPEE with a modifier does not lead to an important drop in tensile strength and modulus whereas the elongation at break is characterized by a significant increase (above 300%), compared with that of neat PLA and PLA/TPEE. The blends of PLA/TPEE/Modifier were found by thermal and fractured surface analysis to be an immiscible system with the addition of a modifier. However, the relative ductility of PLA/TPEE/Modifier is 34 times higher than that of neat PLA. The brittle fracture of neat PLA was transformed into a ductile fracture by the addition of a modifier.     

Synergistic effects of polyethylene glycol and organic montmorillonite on the plasticization and enhancement of poly(lactic acid)

Poly(lactic acid) (PLA)/polyethylene glycol (PEG)/organic montmorillonite (OMMT) composites were prepared by melt blending, and their mechanical, rheological behavior, crystalline behavior, and thermal stability were investigated. Results showed that the elongation-at-break and notch-impact strength of PLA/15PEG/1.5OMMT were 466.45% and 4.34 kJ m⁻², respectively, which were nearly 42 and 2 times higher than those of PLA, respectively. The elongation-at-break of PLA/15PEG/1.5OMMT was also 33 times higher than that of PLA/15PEG and 30 times that of PLA/1.5OMMT. With addition of PEG, PLA chains could insert to OMMT effectively and increase the layer space of OMMT. The characteristics of dynamic behavior and fracture morphology showed that the plasticizer PEG could soften the PLA matrix, leading to easy plastic deformation. OMMT was well distributed in the PLA matrix and able to transfer the stress of external forces, thereby contributing to the matrix yielding initiation and expansion of polymer composites. The synergistic effect of OMMT and PEG was determined by studying the mechanical properties of PLA/PEG/OMMT composite. Differential scanning calorimetry and thermogravimetry studies revealed that OMMT as a nucleating agent improved crystallization and thermal stability. Thus, the synergistic effect of OMMT and PEG balanced the stiffness and toughness of PLA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47576.     

Poly(lactic acid) formulations with improved toughness by physical blending with thermoplastic starch

This work focuses on poly(lactic acid) (PLA) formulations with improved toughness by physical blending with thermoplastic maize starch (TPS) plasticized with aliphatic–aromatic copolyester up to 30 wt %. A noticeable increase in toughness is observed, due to the finely dispersed spherical TPS domains in the PLA matrix. It is worth to note the remarkable increase in the elongation at break that changes from 7% (neat PLA) up to 21.5% for PLA with 30 wt % TPS. The impact‐absorbed energy is markedly improved from the relatively low values of neat PLA (1.6 J m^?2) up to more than three times. Although TPS is less thermally stable than PLA due to its plasticizer content, in general, PLA/TPS blends offer good balanced thermal stability. The morphology reveals high immiscibility in PLA/TPS blends, with TPS‐rich domains with an average size of 1 μm, finely dispersed which, in turn, is responsible for the improved toughness. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45751.     

Preparation and thermomechanical properties of nanocrystalline cellulose reinforced poly(lactic acid) nanocomposites

A two‐step process was developed to prepare nanocrystalline cellulose (NCC) reinforced poly(lactic acid) (PLA) nanocomposites using polyethylene glycol (PEG) as a compatibilizer. It was composed of solvent mixing and melt blending. The NCC was well dispersed in the PLA matrix. A network was formed at high NCC‐to‐PEG ratio at which the amount of the PEG was not enough to cover all the surfaces of the NCC. The formation of the network was confirmed by the occurrence of a plateau for the storage modulus at low frequency. The incorporation of the PEG and NCC could improve the crystallinity of the PLA. The elongation at break increased from 11.0% for the neat PLA to 106.0% for the composites including 6 wt % NCC, impact strength was improved from 0.864 to 2.64 kJ m^?2 and tensile strength did not change significantly for the same 6 wt % NCC composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44683.     

Highly Tough and Thermally Stable Polylactide Blends Compatibilized with Glycidyl Methacrylate-Grafted Polypropylene

To attain eco-friendly and sustainable polylactide (PLA) materials possessing highly enhanced toughness, thermal stability, and processability without significant loss in elastic modulus, for the first time, PLA-dominant blends with 1–30 wt% glycidyl methacrylate-grafted polypropylene (PPGMA) loadings are fabricated via an efficient masterbatch melt-compounding process. For the purpose, PPGMA is fabricated via in situ grafting reaction of PP with GMA and styrene. The scanning electron microscope images reveal that PLA/PPGMA blends do not show recognizable phase-separated domains, unlike immiscible PLA/PP blends. The Fourier-transform infrared spectroscopic and melt-rheological analyses support the presence of specific interactions between PLA and PPGMA as well as the compatibilizing effect of PPGMA-g-PLA formed during the melt-compounding. The thermal analyses demonstrate that PPGMA component accelerates the crystallization of PLA in the blends and that the thermal decomposition temperatures of PLA/PPGMA blends are higher than those of neat PLA and PPGMA components. The dynamic mechanical analysis shows that a maximum storage modulus is attained for PLA-dominant blend with 30 wt% PPGMA. Noticeably, the impact strength (≈305.6 J m⁻¹) of PLA-dominant blend with only 5 wt% PPGMA loading is almost three times higher than that (≈111.6 J m⁻¹) of neat PLA and it is very comparable to the value (≈316.9 J m⁻¹) of neat PP.     

Properties of linear poly(lactic acid)/polyethylene glycol blends

Poly(lactic acid) (PLA) has great potentials to be processed into films for packaging applications. However, film production is difficult to carry out due to the brittleness and low melt strength of PLA. In this investigation, linear PLA (L‐PLA) was plasticized with poly(ethylene glycol) (PEG) having MW of 1000 g mol^?1 in various PEG concentrations (0, 5, 10, 15, and 20 wt%). In relation to plasticizer content, the impact resistance and crystallinity of L‐PLA was increased, whereas a decrease in glass transition temperature and lower stiffness was observed. Nevertheless, the phase separation has been found in samples which contained PEG greater than 10 wt%. The dynamic and shear rheological studies showed that the plasticized PLA possessed lower viscosity and more pronounced elastic properties than that of pure PLA. Both storage and loss moduli decreased with PEG loading at all frequencies while storage modulus exhibited weak frequency dependence with increasing PEG content. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

A Comparative Study on the Mechanical, Thermal and Morphological Characterization of Poly(lactic acid)/Epoxidized Palm Oil Blend

In this work, poly(lactic acid) (PLA) a fully biodegradable thermoplastic polymer matrix was melt blended with three different epoxidized palm oil (EPO). The aim of this research was to enhance the flexibility, mechanical and thermal properties of PLA. The blends were prepared at various EPO contents of 1, 2, 3, 4 and 5 wt% and characterized. The SEM analysis evidenced successful modification on the neat PLA brittle morphology. Tensile tests indicate that the addition of 1 wt% EPO is sufficient to improve the strength and flexibility compared to neat PLA. Additionally, the flexural and impact properties were also enhanced. Further, DSC analysis showed that the addition of EPO results in a decrease in T(g), which implies an increase in the PLA chain mobility. In the presence of 1 wt% EPO, TGA results revealed significant increase in the thermal stability by 27%. Among the three EPOs used, EPO(3) showed the best mechanical and thermal properties compared to the other EPO's, with an optimum loading of 1 wt%. Conclusively, EPO showed a promising outcome to overcome the brittleness and improve the overall properties of neat PLA, thus can be considered as a potential plasticizer.     

Properties and structures of polylactide filled with poly(ε-caprolactone)-coated calcium carbonate

The poly(ε-caprolactone) (PCL)-coated microsized calcium carbonate (CaCO₃) was prepared by high-speed hybrid mechanical coating. Polylactide (PLA) was melt-blended with neat and modified CaCO₃ particles. Phase morphology, microstructure, and thermal dynamic rheological and mechanical properties of the composites were investigated. Differential scanning calorimetry reveals that the addition of coated CaCO₃ remarkably makes the cold crystallization temperature decrease but has little influence on the final degree of crystallinity of PLA. Dynamic rheological tests indicate that complex viscosity and loss modulus of modified CaCO₃ system are lower than those of neat CaCO₃ system. Scanning electron microscopic results show that the coated CaCO₃ microparticles disperse more uniformly in the PLA matrix compared with neat particles. The smooth and round coated particles promote the dispersion of CaCO₃ particles in the PLA matrix, and PCL enhances the interfacial adhesion between CaCO₃ particles and the PLA matrix. From mechanical tests, it is found that toughness of the composites is greatly improved by the incorporation of PCL-coated CaCO₃ microparticles. It is glad to see that the elongation at break of the composite with 15 phr coated CaCO₃ is as high as 310%. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of maleinized linseed oil as biobased plasticizer in poly(lactic acid)‐based formulations

The use of maleinized linseed oil (MLO) as a potential biobased plasticizer for poly(lactic acid) (PLA) industrial formulations with improved toughness was evaluated. MLO content varied in the range 0–20 phr (parts by weight of MLO per hundred parts by weight of PLA). Mechanical, thermal and morphological characterizations were used to assess the potential of MLO as an environmentally friendly plasticizer for PLA formulations. Dynamic mechanical thermal analysis and differential scanning calorimetry revealed a noticeable decrease in the glass transition temperature of about 6.5 °C compared to neat PLA. In addition, the cold crystallization process was favoured with MLO content due to the increased chain mobility that the plasticizer provides. PLA toughness was markedly improved in formulations with 5 phr MLO, while maximum elongation at break was obtained for PLA formulations plasticized with MLO content in the range 15–20 phr. Scanning electron microscopy revealed evidence of plastic deformation. Nevertheless, phase separation was detected in plasticized PLA formulations with high MLO content (above 15–20 phr MLO), which had a negative effect on overall toughness. © 2017 Society of Chemical Industry     

Influence of montmorillonite layered silicate on plasticized poly(l-lactide) blown films

Plasticized poly(l-lactide) (PLA) montmorillonite layered silicate (MLS) nanocomposites were compounded and blown-film processed using a co-rotating twin screw extruder. PLA was mixed with 10 wt% acetyltriethyl citrate ester plasticizer and 5 wt% of an organically modified montmorillonite at various screw speeds. Wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) determined that the compounded pellets and the blown film PLA/MLS nanocomposites were intercalated. The effect of processing screw speeds on the barrier, thermal, mechanical, and biodegradation properties of the nanocomposites were analyzed and compared to the neat polymer. Nanocomposite films show a 48% improvement in oxygen barrier and a 50% improvement in water vapor barrier in comparison to the neat PLA. The thermogravimetric analysis (TGA) showed an overall 9 °C increase in the decomposition temperature for all of the nanocomposites. Differential scanning calorimetry (DSC) has determined that the glass transition, cold crystallization and melting point temperatures were not significantly influenced by the presence of MLS. Mechanical properties of the nanocomposites showed that the Young's modulus increased by 20% and the ultimate elongation of the nanocomposites were not sacrificed in comparison to the neat samples. Biodegradation rates in soil were slightly greater for the PLA/MLS nanocomposite than the pure PLA. However, none of the PLA pure and nanocomposites achieved significant biodegradation levels after 180 days.     

Effect of lignin on mechanical,biodegradability, morphology,and thermal properties of polypropylene/polylactic acid/lignin biocomposite

ABSTRACT

The effects of lignin on mechanical, biodegradability, morphology, and thermal properties of PP/PLA/lignin were investigated. PP/PLA/lignin film were manufactured by adding PP, PLA, lignin and compatibilizer into rheomix at 200°C, at 70?rev?min^?1 for 30?minthen pressed using Hydraulic Hot Press at 200°C–210°C, at 6 bar for 20?min. The functional groups of PP/PLA/lignin were analyzed using FTIR. The surface morphology, mechanical properties and thermal stability was measured by SEM, tensile strenght and TGA respectively. TThe FTIR intensity of vibration peak of –CH₃?cm^-1 from PP/lignin and PP/PLA/lignin at 997–993, 1458–1451 and 2966–2904?cm^-1 was lower than neat PP. The addition of lignin into PP/lignin, PLA/lignin and PP/PLA/lignin can reduce tensile strength and elongation at break. The thermal stability PP/PLA/lignin was lower than the PP/lignin but higher compared to PP/PLA biocomposites. The biodegradability of PP/PLA/lignin biocomposites was two times higher than that of PP/lignin.     

Polylactide composites with waste cotton fibers: Thermal and mechanical properties

Recently, agricultural by‐products, for instance, corn husks, oat husks, or cocoa shells, have gained attention as a source of cellulose fibers and fillers because they can save the land and other natural resources required to grow fiber crops. It has to be noted, however, that textile processing, for example, shearing, is also a source of waste fibers. Our study focuses on utilization of waste cotton fibers, amassed during shearing of textiles, as a filler for polylactide (PLA). PLA composites with 10–30 wt% of waste cotton fibers were prepared and their thermal and mechanical properties were studied. The composite with 30 wt% of fibers exhibited markedly higher storage and loss moduli as compared with neat PLA; at 25°C the storage moduli increased by 53% whereas the loss modulus increased by 76%. In addition, the yield strength was slightly improved, by 11% at 25°C. Although the composites were thermally less stable than neat PLA, their 5% weight loss temperature remained high, about 300°C. POLYM. COMPOS., 35:747–751, 2014. © 2013 Society of Plastics Engineers     

Preparation of poly(lactic acid)/poly(ethylene glycol)/organoclay nanocomposites by melt compounding

Poly(lactic acid) (PLA)/organoclay nanocomposites were prepared by melt compounding in a co‐rotating twin screw extruder. Two types of commercialized organoclay (dimethyl benzyl stearyl ammonium ion and dimethyl distearyl ammonium ion intercalated between clay platelets named as Clay A and Clay B, respectively) and two grades of poly(ethylene glycol) (PEG) with different molecular weight (M_w = 2,000 and 300,000–500,000 named as PEG2k and PEG500k, respectively) were used in this study. The Young's modulus improved by the addition of organoclay to PLA matrix. The Young's modulus decreased with the addition of PEG to PLA/organoclay nanocomposites. The tensile strength and elongation of PLA/Clay B nanocomposites increased with the addition of PEG2k. The effect of the addition of PEG on d‐spacing of PLA/organoclay nanocomposites is dependent upon the kind of organoclay. The sizes of clay agglomerations in PLA/PEG/organoclay nanocomposites are larger than those of PLA/organoclay ones in the same organoclay. Addition of PEG to PLA/organoclay nanocomposites during melt compounding will not be useful for the preparation of PLA/organoclay having fully exfoliated clay platelets. The shear thinning properties of the nanocomposites are independent of the addition of PEG. On the whole, PEG2k is good plasticizer for PLA/organoclay nanocomposites. POLYM. COMPOS. 27:256–263, 2006. © 2006 Society of Plastics Engineers