Morphology,rheology, crystallization behavior,and mechanical properties of poly(lactic acid)/poly(butylene succinate)/dicumyl peroxide reactive blends

The reactive blends were prepared by the blending of poly(lactic acid) (PLA) with poly(butylene succinate) (PBS) in the presence of dicumyl peroxide (DCP) as a radical initiator in the melt state. The gel fractions, morphologies, crystallization behaviors, and rheological and mechanical properties of the reactive blends were investigated. Some crosslinked/branched structures were formed according to the rheological measurement and gel fraction results, and the crosslinked/branched structures played the role of nucleation site for the reactive blends. The PLA–PBS copolymers of the reactive blends acted as a compatibilizer for the PLA and PBS phases and, hence, improved the compatibility between the two components. Moreover, it was found that the reactive blends showed the most excellent mechanical properties as the DCP contents were 0.2 and 0.3 phr. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39580.     

Effect of dicumyl peroxide on biodegradable poly(lactic acid)/functionalized gum arabic based films

Blending of poly (lactic acid) (PLA)/functionalized gum arabic (FG) in presence of dicumyl peroxide (DCP) presents a simple process to produce film using melt extrusion (recycle time ~ 4 min, screw speed ~60 rpm) at 180°C with tailored characteristics. The FTIR investigation shows that the confirmation of grafting of PLA chains on FG through formation of new C─C linkage. Properties of fabricated films such as morphological, mechanical, UV barrier and contact angle are examined to develop film with improved interfacial interaction, increased toughness, UV–C blocking effect (~95%) and hydrophobicity (~14%). Polarized optical microscopy (POM) studies reveal that PLA/1FG with and without DCP has more crystal density as compared to PLA at 120°C. This melt extrusion permits straightforward, feasible bionanocomposite film and has great potential as a modification with DCP assists to overcome particular drawbacks of FG.     

Toughness enhancement of poly(lactic acid) by melt blending with natural rubber

Rubber toughened poly(lactic acid) (PLA) was prepared by blending with natural rubber (NR)‐based polymers. The blends contained 10 wt % of rubber and melt blended with a twin screw extruder. Enhancement of impact strength of PLA was primarily concernced. This study was focused on the effect of rubber polarity, rubber viscosity and molecular weight on mechanical properties of the blends. Three types of rubbers were used: NR, epoxidized natural rubber (ENR25 and ENR50), and natural rubber grafted with poly(methyl methacrylate) (NR‐g‐PMMA). Effect of viscosity and molecular weight of NR, rubber mastication with a two‐roll mill was investigated. It was found that all blends showed higher impact strength than PLA and NR became the best toughening agent. Viscosity and molecular weight of NR decreased with increasing number of mastication. Impact strength of PLA/NR blends increased after applying NR mastication due to appropriate particle size. DMTA and DSC characterization were determined as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical,barrier, and thermal properties of poly(lactic acid)/poly(trimethylene carbonate)/talc composite films

Poly(l ‐lactic acid) (PLA) is now a very attractive polymer for food packaging applications. In this study, PLA/poly(trimethylene carbonate) (PTMC)/talc composite films were prepared by solvent casting. The influence of the talc loading (0, 1, 2, and 3 wt %) on the phase morphology of the PLA/PTMC/talc composites and the improvement in the resulting properties are reported in this article. The scanning electron microscopy images of the composite films demonstrated good compatibility between the PLA and PTMC, whereas talc was not thoroughly distributed in the PLA matrix at talc contents exceeding 3 wt %. The tensile strength and elongation at break of the composite films significantly improved (p < 0.05). On the contrary, the water vapor permeability and oxygen properties of the composite films decreased by 24.7 and 39.2%, respectively, at the 2 wt % talc loading. Differential scanning calorimetry showed that the crystallinity of the PLA phase increased with the presence of talc filler in the PLA/PTMC/talc composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40016.     

High impact poly(lactic acid)/poly(ethylene octene) blends prepared by reactive blending

Poly(ethylene octene) grafted with glycidyl methacrylate (POE‐g‐GMA) was prepared and used to toughen poly (lactic acid) (PLA) via reactive blending. It was found that the notched Izod impact strength of PLA/POE‐g‐GMA blends improved dramatically when the content of elastomer was higher than 10 wt%. Reactive compatibilization between PLA and POE‐g‐GMA were studied by Fourier transform infrared spectroscopy (FTIR) and “Molau test,” the results showed the end carboxyl groups of PLA reacted with the epoxide groups of POE‐g‐GMA during blending. This considerably improved the compatibilization, leading to better wetting of the dispersed phase by the PLA matrix and finer dispersed POE‐g‐GMA particles with narrow distribution. Moreover, the critical interparticle distance (L_c) of the dispersed domains for PLA/POE‐g‐GMA blends system at room temperature was also identified. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effect of blending conditions on mechanical,thermal, and rheological properties of plasticized poly(lactic acid)/maleated thermoplastic starch blends

This research work has concerned a study on relationship between structure and properties of maleated thermoplastic starch (MTPS)/plasticized poly(lactic acid) (PLA) blend. The aim of this work is to investigate the effects of blending time, temperature, and blend ratio on mechanical, rheological, and thermal properties of the blend. The MTPS was prepared by mixing the cassava starch with glycerol and maleic anhydride (MA). Chemical structure of the modified starch was characterized by using a FTIR technique, whereas the degree of substitution was determined by using a titration technique. After that, the MTPS prepared by 2.5 pph of MA was further used for blending with triacetin‐plasticized PLA under various conditions. Mechanical, thermal, and rheological properties of the blends were evaluated by using a tensile test, dynamic mechanical thermal analysis, and melt flow index (MFI) test, respectively. It was found that tensile strength and modulus of the MTPS/PLA blend increased with the starch content, blending temperature, and time, at the expense of their toughness and elongation values. The MFI values also increased with the above factors, suggesting some chain scission of the polymers during blending. SEM images of the various blends, however, revealed that the blend became more homogeneous if the temperature was increased. The above effect was discussed in the light of trans‐esterification. Last, it was found that mechanical properties of the PLA/MTPS blend were more superior to those of the normal PLA/TPS blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and mechanical properties of poly(lactic acid)/starch/methylenediphenyl diisocyanate blending with triethyl citrate

Triethyl citrate (TC) was added as a plasticizer to a blend of poly(lactic acid) (PLA) and starch in the presence of methylenediphenyl diisocyanate (MDI). As expected, TC improved the elongation at break and toughness and, at the same time, decreased the tensile strength and modulus. However, TC did not significantly affect the coupling effects of MDI on starch and PLA. The tensile strength of the blend with MDI was much greater than the tensile strength without MDI at the same TC level. The tensile properties of the blend changed dramatically as the TC concentration increased from 5 to 12.5%. At a TC concentration of 7.5%, the blend produced desirable elongation and toughness with fairly good tensile strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2947–2955, 2003     

Thermal and mechanical properties of poly(lactic acid) modified by poly(ethylene glycol) acrylate through reactive blending

Poly(lactic acid) (PLA) was modified using a simple reactive blending method, where a low molecular weight poly(ethylene glycol) acrylate (PEGA) was blended with PLA in the presence of a radical initiator. To examine the initiation effect on the modification of PLA, various amounts of radical initiator (between 0 and 1.5 %) were added to the PLA/PEG acrylate mixture. The modified PLAs (PLMs) were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, and solvent extraction. The properties of the PLMs were investigated using tensile testing, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, and hydrolytic degradable analysis. The PEGA significantly influenced the molecular structure and properties of the modified PLA. The glass transition temperature of the PLMs was decreased by approximately 15 °C (for PLM15) from 59.3 °C of PLA, whereas their toughness increased considerably compared to PLA. In addition, PEG acrylate facilitates hydrolytic degradation, even after radical polymerization by reactive blending.     

Morphology,thermal, and dynamic mechanical properties of poly(lactic acid)/sisal whisker nanocomposites

Sisal whiskers were used as biobased nanofillers to prepare poly(lactic acid) (PLA)‐based nanocomposites. The whiskers were prepared from sisal fibers via sulfuric acid hydrolysis. Freeze drying of the aqueous whisker suspension was carried out to obtain loosely packed dry sisal whiskers. The nanocomposites were prepared by melt mixing, followed by hot melt pressing. The effect of the freeze drying of the nanofibers, the treatments of the samples with maleic anhydride (MA)/dicumyl peroxide (DCP) and with DCP, and the premixing of the powdered components on the dispersion of the whiskers in the PLA matrix and on the morphology, as well as the thermal and dynamic mechanical properties, of the resultant nanocomposites were investigated. Transmission electron microscopy micrographs show that the acid hydrolysis has led to separation of the whiskers, which had an approximate length and diameter of 195 and 15 nm, respectively. The TEM images of the nanocomposites show similar dispersion of the whiskers in the PLA matrix, whether untreated or MA/DCP or DCP treated. It was found that the crystallization behavior of the PLA matrix changed somewhat depending on whether the samples were treated or not. The thermogravimetric analysis results show a slight decrease in the thermal stabilities of the untreated and the MA/DCP‐treated nanocomposite samples compared to that of the neat PLA, whereas the DCP treatment slightly improved the thermal stability of the nanocomposites. The storage modulus of the nanocomposites increased over the investigated temperature region, and the incorporation of sisal whiskers reduced the intensity of the glass transition at 67°C. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of compounding procedure on mechanical properties and dispersed phase morphology of poly(lactic acid)/polycaprolactone blends containing peroxide

Side feeding technique was applied to poly (lactic acid) (PLA)/polycaprolactone (PCL) blends containing peroxide. Feeding procedures attempted were blanket and split feeding. In the former procedure, all the materials were fed into the main hopper at once. On the other hand, the feeding of materials was split by using main hopper and side feeder in the later procedure. The results indicated that static tensile properties were not dependent on feeding procedure, but the impact strength was superior in the case of the split feeding samples. It is noteworthy that the impact strength of the split feeding sample was considerably affected as it was four times better. Coarse dispersions such as continuous filament and layer dispersions were formed in the blend specimens without peroxide. On the other hand, fine dispersions were formed in the blend specimens containing peroxide which served as compatibilizer in this blend system. Peroxide addition through the side feeder brought about fine dispersions, promoted adhesion at the interface, and increased viscous nature of the PCL phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1066–1074, 2007     

Compatibilization of poly(lactic acid)/epoxidized natural rubber blend with maleic anhydride

The objective of this work was to determine the compatibilization effect of different concentrations of maleic anhydride (MA) in poly(lactic acid) blended with epoxidized natural rubber (PLA/ENR). ENR-grafted MA [ENR-g-MA] was synthesized using four concentrations of MA: 0.15, 0.30, 0.45, and 0.60 phr. Using an internal mixer, binary (PLA/ENR, PLA/ENR-g-MA) and ternary (PLA/ENR/ENR-g-MA) polymer blends were prepared with a constant rubber content of 10 wt %. ENR impaired the mechanical properties of PLA, perhaps due to the relatively large size of the rubber particles. The compatibilization effect of MA was evaluated from the results of impact strength testing. ENR-g-MA was a toughening agent for PLA when the concentration of MA was in the range of 0.30–0.60 phr. MA increased miscibility between PLA and ENR. This effect was indicated in the blends by reductions in rubber particle size, the glass transition temperature of PLA, and the α-transition temperatures of PLA and ENR. In the binary polymer blends, the MA concentration in ENR-g-MA that produced the optimal mechanical properties of PLA was 0.60 phr. In the ternary blends, mechanical properties of PLA did not improve at any concentration of MA in ENR-g-MA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48297.     

Effect of miscibility on mechanical and thermal properties of poly(lactic acid)/ polycaprolactone blends

Binary blends based on poly(lactic acid) (PLA) and polycaprolactone (PCL) were prepared by melt mixing in a twin‐screw co‐rotating extruder in order to increase the low intrinsic elongation at break of PLA for packaging applications. Although PLA and PCL show low miscibility, the presence of PCL leads to a marked improvement in the ductile properties of PLA. Various mechanical properties were evaluated in terms of PCL content up to 30 wt% PCL. In addition to tensile and flexural properties, Poisson's ratio was obtained using biaxial extensometry to evaluate transversal deformations when axial loads are applied. Very slight changes in the melt temperature and glass transition temperature of PLA are observed thus indicating the low miscibility of the PLA–PCL system. Field emission scanning electron microscopy reveals some interactions between the two components of the blend since the morphology is characterized by non‐spherical polycaprolactone drops dispersed into the PLA matrix. In addition to the improvement of mechanical ductile properties, PCL provides higher degradation rates of blends under conditions of composting for contents below 22.5% PCL. © 2016 Society of Chemical Industry     

Assessment of mechanical performance,thermal stability and water resistance of novel conductive poly(lactic acid)/modified natural rubber blends with low loading of polyaniline

Biodegradable conductive polymer blends made from poly(lactic acid) (PLA), liquid natural rubber (LNR) and polyaniline (PANI) were prepared via a melt‐blending technique assisted by ultrasonic treatment. The effects of PANI at low loading (0.03 to 0.11 wt%) on the electrical conductivity and mechanical, thermal and physical properties of PLA/LNR/PANI blends were investigated. It was found that the mechanical properties of samples improved when PANI was introduced into PLA/LNR. Tensile results showed that the optimum loading of PANI was achieved at 0.07 wt% with an improvement of 8% in tensile strength compared to neat PLA/LNR. Although it was at low loading, the incorporation of PANI promoted an outstanding electrical conductivity to PLA/LNR blends. Thermal analysis of the PLA/LNR/PANI blends was conducted using differential scanning calorimetry and thermogravimetry. The thermal stabilities of the blends were improved markedly with the presence of PANI. Comparing to PLA/LNR, the incorporation of PANI component improved the resistance towards water absorption. Variable‐pressure scanning electron microscopy micrographs of PLA/LNR/PANI confirmed the good mixing of PANI with PLA/LNR and strong interaction networks among the PANI, PLA and LNR components. © 2018 Society of Chemical Industry     

Melt processing of biodegradable poly(lactic acid)/functionalized chitosan nanocomposite films: mechanical modeling with improved oxygen barrier and thermal properties

The present work demonstrates about the formulation of functionalized chitosan (CH-g-OLLA) through the transformation of hydrophilic nature of chitosan into hydrophobic by grafting with oligo(L-lactic acid) (OLLA). The developed CH-g-OLLA is easily soluble in poly(lactic acid) (PLA) matrix, which provides an opportunity towards producing industrially viable nanocomposite films for stringent food packaging and beverages applications. The grafting of OLLA chains is confirmed at NH₂ group of chitosan through the presence of two new peaks at 4.2 and 5.1 ppm in ¹H–NMR spectra. Various parameters like yield (%), grafting efficiency (%) and percent grafting (%) are calculated as ~51.6, ~40 and ~150%, respectively. Functionalized chitosan has been utilized as nano-filler in PLA matrix to fabricate PLA/CH-g-OLLA nanocomposite films which have compounded successfully by co-rotating twin screw compounder cum cast film extrusion technique (distinctly advantageous over conventional solution casting) at bench scale as well as semi-pilot scale and further demonstrated for its application in the area of food packaging with tailored oxygen barrier properties. Uniform dispersion of spherical aggregates of functionalized chitosan is observed in PLA/CH-g-OLLA nanocomposite films using TEM analysis. A significant reduction up to ~11 °C in glass transition temperature of PLA is observed by adding 5 wt% of nano-filler as a result of plasticization effect, which is an essential property in designing of flexible packages. Mechanical modeling of extruded PLA/CH-g-OLLA films has been performed to compare the experimental values with theoretical results using various mathematical models in which modified foam model, Nielsen model and modified Mitsuishi model demonstrate the best match for Young’s modulus (±0.08), tensile strength (±0.06) and percentage elongation (±0.03), respectively. This may be a significant contribution towards commercialization of such formulation where elegant melt extrusion process of PLA with functionalized chitosan is capable of reducing oxygen permeability up to ~10 folds due to a drastic reduction (~96%) in oxygen solubility.     

聚乙二醇改性淀粉/聚乳酸薄膜的结构与性质研究

将热塑性淀粉(TPS)与聚乙二醇(PEG)、聚乳酸(PLA)共混后,采用溶剂蒸发法制备出完全生物降解的聚乙二醇改性淀粉/聚乳酸薄膜(SPLA)。研究了SPLA膜的力学性能、耐水性,并对薄膜的结构进行了研究,结果表明聚乳酸可以明显改善淀粉基薄膜的耐水性与力学强度;当w(PLA)≤20%时,共混物各组分间有较好的相容性。SPLA膜的玻璃化转变温度低于淀粉和聚乳酸,XRD显示共混膜中淀粉和聚乳酸的颗粒结晶结构均受到破坏。     

Mechanical,thermal, and dielectric properties of poly(lactic acid)/chitosan nanocomposites

Poly(lactic acid) (PLA) loaded with various levels of chitosan nanoparticles (CsNP) (0–5.0%) were prepared by twin‐screw extrusion. The nanocomposites were investigated based on their morphology, thermal, mechanical and dielectric properties. The SEM morphology showed that CsNP was dispersed uniformly in the PLA matrix. Thermal analysis through DSC revealed that the cold crystallization temperature of PLA in the case of nanocomposites slightly decreased with increasing content of CsNP; indicating a limit nucleating effect of CsNP. TGA analysis revealed that the incorporation CsNP slightly decreased the thermal stability of the PLA matrix. The mechanical analysis indicated that the incorporation of the CsNP in the PLA matrix improved the elongation and the impact strength, but decreased the tensile strength. The dielectric properties of these materials have been investigated for the α‐relaxation process as a function of the temperature and frequency. The α‐relaxation process was analyzed with Vogel–Fulcher–Tamman and Havriliak–Negami models and fitting parameters and their evolution were obtained. POLYM. ENG. SCI. 56:987–994, 2016. © 2016 Society of Plastics Engineers     

Improved thermal stability and mechanical properties of poly(propylene carbonate) by reactive blending with maleic anhydride

To extend the application of a carbon dioxide sourced environmental friendly polymer: poly (propylene carbonate) (PPC), a small amount of maleic anhydride (MA) was melt blended to end‐cap with PPC to improve its thermal stability and mechanical properties. Thermal and mechanical properties of end‐capped PPC were investigated by TGA, GPC, mechanical test, and DMA. TGA and titration results demonstrate that PPC can be easily end‐capped with MA through simple melt blending. TGA results show that the thermal degradation temperature of PPC could be improved by around 140°C by adding MA. GPC measurement indicates that the molecular weight of PPC can be maintained after blending with MA, where pure PPC experiences a dramatic degradation in molecular weight during melt process. More importantly, the tensile strength of PPC after blending with MA was found to be nearly eight times higher than that of pure PPC. It has approached the mechanical properties of polyolefin polymers, indicating the possibility of replacing polyolefin polymers with PPC for low temperature applications. The method described here could be used to extend the applications of PPC and fight against the well known global warming problem. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological and mechanical properties of poly(lactic acid)/polystyrene polymer blend

Properties modification by blending polymers has been an area of immense interest. In this work, rheological and mechanical properties of poly(lactic acid)/polystyrene (PLA/PS) blends were investigated. PLA/PS blends in different ratios were prepared using a laboratory scale single screw extruder to obtain (3 mm) granules. Rheological properties were studied using a capillary rheometer and the Bagley’s correction was performed. True shear rate (γ _r ), true shear stress (τ _r ), and true viscosity (η _r ) were determined, the relationship between true viscosity and (1/T) was studied for PLA70 blend and the flow activation energy at a constant shear stress (E _τ ) and a constant shear rate (E _γ ) was determined. The mechanical property measurements were performed at room temperature. Stress at break and strain at break were determined. The results showed that PLA/PS blend exhibited a typical shear-thinning behavior over the range of the studied shear rates, and the viscosity of the blend decreased with increasing PLA content. Also it was found that no equal-viscosity temperature exists between PLA and PS. The mechanical results showed immiscibility between PLA and PS in the blend.     

Crystallization behavior,morphology, and mechanical properties of poly(lactic acid)/tributyl citrate/treated calcium carbonate composites

In this article, poly(lactic acid) (PLA) composites containing titanate coupling agent treated calcium carbonate (T‐CaCO₃) and tributyl citrate (TBC) were prepared via melt blending. The crystallization, morphology, mechanical properties, and nonisothermal cold crystallization kinetics of PLA composites were studied by means of differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized light microscopy (PLM), scanning electron microscopy (SEM), and mechanical tests, respectively. The results show that TBC promotes crystallization of PLA. Both T‐CaCO₃ and TBC significantly decrease the spherulitic size, but the crystal structure of PLA is not changed. A synergistic toughening effect is obtained by the combination of T‐CaCO₃ and TBC. The nonisothermal cold crystallization kinetics of PLA composites is well described by Mo's method. The activation energies (ΔE) of nonisothermal cold crystallization were calculated by Kissinger and Takhor methods, respectively. It is found that the addition of T‐CaCO₃ and TBC increases ΔE, but it also increases the cold crystallization rate. POLYM. COMPOS., 35:1570–1582, 2014. © 2013 Society of Plastics Engineers     

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3‐butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T_g) and the melting temperature (T_m) of PLA. Moreover, crystallinity of PLA increased with increasing the content of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1583–1590, 2006