Crystallization Of PLA Research Articles

Titanium-catalyzed synthesis of polymyrcene and polyanethol and application as sustainable additives for poly(lactic acid)

The replacement of fossil-derived plastics with those obtained from bio-based resources, which present suitable performance to be employed as commodity plastics is currently an important field of research, given the urgent need to transition from a fossil-based to a more sustainable economy. In this context, this work is focused on the application of a catalytic system based on silsesquioxane-cyclopentadienyl titanium complexes for the preparation of bio-based polymers, which can be used as additives to improve the poor material properties of a biodegradable polymer such as poly(lactic acid) (PLA). These titanium complexes, when activated with methylaluminoxane or with triflate salts, are shown to be capable of the polymerization of two bio-based monomers: myrcene and anethole. It is notable that polymerizations with these two distinct monomers take place through different mechanisms. The resulting polymyrcene (PMy) and polyanethol (PAN) have been applied as modifiers for PLA. Binary blends of PMy and PLA exhibited a considerable decrease in Tg and the promotion of PLA crystallization for a PMy content below 15 wt%. The mechanical properties of the PLA/PMy blends also displayed plasticization, with a decrease in the elastic modulus and enhanced plasticity, which resulted in less fragile systems compared to pure PLA. Morphological analysis has indicated a partially miscible, phase-separated system with micron-sized domains. In contrast, PAN completely inhibited PLA crystallization and the PLA/PAN blends were immiscible, but well-dispersed, a phase-separated system was obtained in solvent-casting film preparation with very small PAN domains. The blends showed higher tensile modulus than pure PLA and an absence of plastic behaviour, resulting in more fragile systems upon the addition of PAN to PLA.

Influence of Epoxidized Natural Rubber of the thermoformability of Poly(Lactic Acid) biopolymer films using elevated temperature ball burst tests

In this paper, we investigated the thermoformability of Epoxidized Natural Rubber (ENR)-filled Poly(Lactic Acid) (PLA) films using elevated temperature tensile and ball burst tests. Three different d-Lactide contents of PLA were used to be able to analyze the effect of crystallization and crystallinity. We observed that the ENR acted as a nucleating agent in PLA when the blend was cooled from melt or cold crystallized, but it retarded the drawing-induced crystallization of PLA at elevated temperature tensile testing since ENR droplets acted as obstacles. The effect of NR on PLA crystallization was also found to be dependent on d-Lactide content. In the ball burst test, different behaviors were observed for PLA with the lowest d-Lactide content, which was caused by the complex stress state that even more induced crystallization of PLA and then a single-axis tensile test.

Weathered coal-based carbon dots modified by organic amine for enhanced crystallinity and toughness of poly(lactic acid) film

Poly(lactic acid) (PLA) has its own limitations in terms of slow crystallization rate and low crystallinity during processing, resulting in poor toughness and thermal stability, which seriously restricts the practical application of PLA. Blending nanoparticles into the PLA matrix is an effective way to improve PLA crystallization. In this study, carbon dots (CDs) were prepared by green oxidation using weathered coal as carbon source and then surface-modified with dodecylamine (DDA) and octadecylamine (ODA). Modified CDs (MCDs)/PLA composite films were prepared using MCDs as filler to improve the crystallinity and toughness of PLA films. The results showed that the improvement effect of ODA-modified CDs (ODACDs) was better than that of DDA-modified CDs (DDACDs). The crystallinity of PLA composite film (0.05 wt% ODACDs) was increased from 7.20% (pure PLA film) to 35.44%, and its elongation at break was increased by 5.01 times compared with that of the pure PLA film. Moreover, thermogravimetric analysis suggested that the thermal stability of MCDs/PLA films was also improved. The results of simultaneous rheology and in-situ FTIR analysis as well as molecular dynamics simulations confirmed that MCDs had a strong interaction with PLA molecules, which promoted the crystallization of PLA film, thereby improving its toughness and thermal stability.

Turning waste into treasure: Effects of waste polyphenylene sulfide (PPS) microfibers as potential synergists on flame retardancy and mechanical property of polylactic acid

In this work, we prepare flame-retardant and toughened PLA using waste PPS microfibers prepared from waste PPS filter bags. Waste PPS microfibers not only act as synergists to improve the impact properties and flame retardancy of PLA composites, but also act as heterogeneous nucleating agents to promote PLA crystallization. Specifically, when only 5 wt% waste PPS microfibers are added, the crystallinity of the AP/PLA system increases from 3.6% of 15AP PLA to 44.06% of 15AP5PPS PLA. When 10 wt% waste PPS microfibers are added, the UL-94 rating of 15AP10PPS PLA increases to V-0 rating, which is significantly improved compared to the V-1 rating of 15AP PLA. Under the premise of passing the UL-94 V-0 rating, the impact properties of 15AP10PPS PLA and 10AP15PPS PLA are significantly better than 20AP PLA, with an increase of 34.8% and 50.6%, respectively. This study provides a new strategy for polymer flame retardant and toughening modification and waste recycling.

Fabrication of poly(lactic acid) foam with high expansion ratio and oriented cellular structure by restricting cold crystallization

The foaming behavior of semi-crystalline polymers is significantly affected by their crystallization. To achieve high expansion ratio of poly(lactic acid) (PLA) foams, we thought its cold crystallization should be restricted. Therefore, we used a short soaking time of CO2 to fabricate high-expansion PLA foams. Dynamic mechanical analysis of unfoamed PLA showed that only one rubbery plateau was observed owing to complete cold crystallization under a soaking time of 40 min at 10 MPa. The crystal morphology demonstrated that a short soaking time of 3 min could restrict the cold crystallization of PLA. Owing to plasticization of CO2, PLA crystallization of was accelerated at low temperatures (40–80 °C) but hindered at high temperatures (80–130 °C) at 10 MPa. Foaming results showed that under a soaking time of 3 min, a high expansion ratio exceeding 10 was achievable over a wide foaming temperature range of 90 to 115 °C because more amorphous regions were preserved at 10 MPa. In addition, the prepared foams presented an oriented cellular structure. Compared with the isotropic foam, the anisotropic foam exhibited higher compressive strength and heat resistance. The prepared PLA foams have good application prospects in the fields such as cushioning, packaging, and construction.

Simultaneous enhancement of the strength and the roughness of poly(lactic acid) using palmitoylated cellulose nanocrystal

AbstractThe nanocomposite films from poly(lactic acid) (PLA) and palmitoylated cellulose nanocrystals (e‐CNCs) were characterized using different techniques. Raman spectra showed the formation of hydrogen bonding interactions between the PLA and the e‐CNCs. The proper amount (1.0 wt%) of the e‐CNCs led to the formation of greater amounts of smaller PLA spherulites and increased the PLA crystallinity in comparison with the neat PLA sample. The scanning and transmission electron microscopy images showed that 1.0 wt% of the e‐CNCs could uniformly be dispersed in the PLA matrix and that the nanocomposite exhibited some elasticity. The dynamic rheological properties showed the formation of interconnected networks in the PLA/e‐CNCs composite at 1.0 wt% of the e‐CNCs. The analysis of the mechanical performance of the ensuing nanocomposite showed a 74% increase in tensile strength, a 62.1% increase in Young's modulus, and a 68.4% increase in the elongation at the break after the incorporation of 1.0 wt% of the e‐CNCs into the PLA. Therefore, the palmitoylated CNCs were highly promising for the simultaneous enhancement in the strength and the toughness of PLA.Highlights Reinforcement of poly(lactic acid) (PLA) by the palmitoylated CNCs. Simultaneous improvement in the strength and roughness of PLA sample. Entanglement and H‐bond between the palmitoylated CNCs and PLA molecular chain. More and smaller PLA crystals induced by the palmitoylated CNCs.

Preparation of Supertough Polylactide/Polybutylene Succinate/Epoxidized Soybean Oil Bio-Blends by Chain Extension

Poly(lactic acid) (PLA) was toughened using ductile biodegradable poly(butylene succinate) (PBS) and biobased epoxidized soybean oil (ESO). A reactive reagent (Joncryl ADR 4370 S) was introduced for preparing reactive compatibilized bio-blends by melt-processing in situ. The compatibility, rheology, crystallization, mechanical properties, and microstructures of the PLA, PBS, and ESO bio-blends were measured using theoretical compatibility predication, Fourier transform infrared (FTIR) spectroscopy, dynamic mechanical analysis (DMA), dynamic rheological analysis, wide-angle X-ray diffraction (WAXD), mechanical tests, field-emission scanning electron microscopy (FESEM), and optical stereomicroscopy (OM). The introduction of 4370 S induced “graft copolymerization in situ” among PLA, PBS, and ESO and considerably improved the bio-blend compatibility. The PBS and PLA crystal structures were not altered, while the PBS crystallinity reduced in the bio-blends because of chain extensions among the components. The refined PBS particles and evenly distributed ESO drops in the PLA matrix were ascribed to enhanced adhesion and improved compatibility due to the “formation of graft copolymers in situ”. Owing to the combination of ESO and 4370 S, the supertough PLA and PBS bio-blends exhibited a tensile strain at break and notched impact strength above 300% and 30 kJ/m2, respectively.

Effect of matrix composition on the performance of calcium carbonate filled poly(lactic acid)/poly(butylene adipate-co-terephthalate) composites

Abstract The ratio of poly(lactic acid) (PLA), poly(butylene adipate-co-terephthalate) (PBAT), and calcium carbonate (CaCO3) fillers in PLA/PBAT/CaCO3 composites was set at 90/10/5, 70/30/5, and 30/70/5. The effect of nano- and micro-CaCO3 on the melting and crystallization performance of the composites was investigated by differential scanning calorimetry. PLA crystallization was related to the PLA and PBAT ratio, cooling rate, and CaCO3 particle size in PLA/PBAT/CaCO3 composites. Nano-CaCO3 prevented the crystallization of PLA in PLA/PBAT/CaCO3 90/10/5 and 70/30/5 but did not prevent the crystallization of PLA in PLA/PBAT/CaCO3 30/70/5. Unlike nano-CaCO3, micro-CaCO3 did not prevent PLA crystallization regardless of the PLA and PBAT ratio. Nano- and micro-CaCO3 enhance PLA90 and PLA70 to some extent, due to the aggregation and dissociation of the CaCO3 filler in polylactic acid. But nano- and micro-CaCO3 improved the mechanical properties of PLA30 several times, due to the good compatibility of the CaCO3 filler and PBAT. The effect of nano-CaCO3 and micro-CaCO3 on the mechanical properties of PLA/PBAT/CaCO3 composites had no significant difference.

The properties investigations of PLA/TiO2 and PLA/doped-TiO2 composites films

ABSTRACT This research aims to study the mechanical, thermal, and dielectric properties of composite films made from poly(lactic acid) (PLA) and titanium dioxide (TiO2). The samples were fabricated by solution casting method with different content of TiO2. Furthermore, the doped-TiO2 addition was also comparatively investigated. The SEM results revealed the non-uniform distribution of the fillers. DSC and XRD results evidenced the PLA crystallization due to the fillers acting as the nucleating agent. Moreover, the fillers addition improved the Young’s modulus but decreased tensile strength and elongation at break. The composites dielectric constant was enhanced by fillers addition in all samples.

Effects of self‐assembled nucleating agent on the crystallization behavior, thermal properties, and mechanical properties of polylactic acid

AbstractPolylactic acid (PLA) is a biodegradable polyester, but its low crystallization rate and excessive embrittlement limit its application. Decanedioic acid 1,10‐bis (2‐benzoylhydrazide) (TMC‐300) as an effective nucleating agent of PLA will induce PLA epitaxial crystallization and improve the crystallization rate of PLA. This article studied the promoting behavior of TMC‐300 with different contents in composite systems on PLA crystallization. The results showed that with the increase of TMC‐300 content, the crystallinity can be significantly increased, up to 22 times, and t1/2 significantly decreases. Meanwhile, with the addition of TMC‐300, the typical spherical crystal morphology of PLA gradually became attached to TMC‐300 fibrous crystal morphology. In terms of mechanical properties, the tensile strength reached its maximum at 0.5 wt% of TMC‐300 content, increasing from 60.60 MPa (PLA) to 74.59 MPa (0.5‐TMC‐300), an increase of 23.09%. At this time, due to the reduction in spherical crystal size, the elongation at break also increased significantly. However, the thermal stability of PLA composites deteriorated with the increase of nucleating agent content due to the low thermal decomposition temperature of TMC‐300 itself, and the Tmax decreased from 372°C (PLA) to 353°C (5‐TMC‐300), a decrease of 19°C.

In situ preparation of carbon fiber fabric reinforced poly(lactic acid) composites by vacuum‐assisted resin transfer molding

AbstractCarbon fiber fabric reinforced poly(lactic acid) (CFF/PLA) composites were manufactured using both vacuum‐assisted resin transfer molding (VARTM) and compression molding (CM) methods. Of the two methods, the CFF/PLA‐VARTM composite shows superior carbon fiber infiltration and interfacial adhesion compared to the CFF/PLA‐CM composite. The improved infiltration enables the carbon fibers to induce a dense group of PLA crystal nuclei along their surface, resulting in the formation of a trans‐crystalline layer (TCL) structure where the PLA lamellae grow perpendicular to the fiber axis. As a result, the interfacial adhesion is improved, and the crystallinity of the PLA in the CFF/PLA‐VARTM composite is 4.1 times higher than that of pure PLA. However, the weak infiltration of fibers and matrix in CFF/PLA‐CM composite results in poor load‐bearing ability. Conversely, CFF/PLA‐VARTM composite presents better interlayer bonding and tight fiber‐matrix wrapping, promoting effective tensile load transfer to carbon fibers, which results in higher strength and modulus. The presence of TCL structures also plays a key role in improving mechanical properties. Overall, these findings demonstrate a promising method for producing high‐performance PLA composites.

A Relatively Simple Look at the Rather Complex Crystallization Kinetics of PLLA.

This work demonstrates that, despite the existence of a significant number of works on PLA crystallization, there is still a relatively simple way, different from those already described, in which its complex kinetics can be observed. The X-ray diffraction (XRD) results presented here confirm that the PLLA under study crystallizes mostly in the α and α' forms. An interesting observation is that at any temperature in the studied range of the patterns, the X-ray reflections stabilize with a given shape and at a given angle, different for each temperature. That means that both α and α' forms coexist and are stable at the same temperatures so that the shape of each pattern results from both structures. However, the patterns obtained at each temperature are different because the predominance of one crystal form over the other depends on temperature. Thus, a two-component kinetic model is proposed to account for both crystal forms. The method involves the deconvolution of the exothermic DSC peaks using two logistic derivative functions. The existence of the rigid amorphous fraction (RAF) in addition to the two crystal forms increases the complexity of the whole crystallization process. However, the results presented here show that a two-component kinetic model can reproduce the overall crystallization process fairly well over a broad range of temperatures. The method used here for PLLA may be useful for describing the isothermal crystallization processes of other polymers.

Improved compatibility of PLA/Starch blends with Binary functional monomers through UV-induced reactive extrusion

In this work, we chose starch as a biomass nucleating agent for PLA to enhance the crystalline properties without affecting the biodegradability of the composite. Under the synergistic effect of glycidyl methacrylate (GMA) and trimethylpropane triacrylate (TMPTA), biodegradable PLA/Starrch composites were prepared by a unique UV-induced reactive extrusion technique. GMA was grafted onto PLA with the help of TMPTA and the modified PLA enhanced compatibility with starch via epoxidation reaction during extrusion. The rheological properties, mechanical properties, and crystallization behavior of PLA/Starch composites were researched. The rheological and FITR results demonstrated that the introduction of GMA/TMPTA in PLA/Starch blends not only promoted the reactive compatibilization of PLA with starch but also produced a certain degree of chain branching effect. Meanwhile, starch provides heterogeneous nucleation sites for PLA crystallization, which improved the crystallization performance of PLA. In addition, the mechanical properties of the composite were improved. Compared with pure PLA, the tensile stress of the composite was increased by 116% and the elongation at break was increased by 118%. In summary, this work provides a new strategy for the preparation of PLA/starch composites, which is expected to expand the application of PLA in the packaging field.

Ductile poly(lactic acid)-based blends derived from poly(butylene succinate-co-butylene 2,5-thiophenedicarboxylate): Structures and properties

Because of superior tensile strength, biodegradability, and biocompatibility, poly(lactic acid) (PLA) has emerged as one among the growth-oriented biodegradable materials. But it has been limited to some extent in practical applications due to poor ductility. Consequently, in order to improve the drawback of poor ductility of PLA, ductile blends were obtained by melt-blending of poly(butylene succinate-co-butylene 2,5-thiophenedicarboxylate) (PBSTF25) with PLA. PBSTF25 has a good improvement on the ductility of PLA due to its excellent toughness. Differential scanning calorimetry (DSC) showed that PBSTF25 promoted the cold crystallization of PLA. Wide-angle X-ray diffraction (XRD) results revealed that PBSTF25 experienced stretch-induced crystallization throughout the stretching procedure. Scanning electron microscopy (SEM) showed neat PLA had a smooth fracture surface, but the blends had rough fracture surface. PBSTF25 can improve the ductility and processing properties of PLA. When the addition of PBSTF25 reached 20 wt%, tensile strength was 42.5 MPa and elongation at break increased to 156.6 %, approximately 19 times as much as PLA. The toughening effect of PBSTF25 was better than that of poly(butylene succinate).

Structure and properties of polylactic acid/butenediol vinyl alcohol copolymer blend fibers

Polylactic acid/butenediol vinyl alcohol copolymer (PLA/BVOH) blends with different weight ratios were prepared by melt mixing. PLA and BVOH in PLA/BVOH blends were immiscible while the weak interaction between PLA and BVOH existed. The introduction of BVOH facilitated the crystallization of PLA. Moreover, the crystallization of PLA hindered the crystallization of BVOH. Due to introduction of BVOH, PLA/BVOH blends exhibited shear thinning characteristic except that PLA/BVOH blends with 5–10 % BVOH showed similar rheological property to neat PLA. With the increase of BVOH content, the contact angle of PLA/BVOH blends decreased from 79.75° to 67.33° at 120 s. The hydrophilicity of PLA/BVOH blends was improved. In addition, PLA/BVOH fibers with 5–40 % BVOH and PLA/BVOH/rutin fibers with 3 % rutin were manufactured by melt spinning. The effect of BVOH on the mechanical property of PLA/BVOH fibers was small. However, BVOH improved significantly the rutin release rate and antioxidant properties of PLA/BVOH/rutin fibers.

Effect of PGMA-saponite brushes on the rheology, crystallization and supercritical CO2 foaming behavior of poly(lactic acid)

In this work, poly(glycidyl methacrylate) (PGMA) were grafted onto the surface of saponite to form polymer brushes (m@g-Sap) via surface-initiated atom transfer radical polymerization (SI-ATRP). Moreover, PLA/m@g-Sap nanocomposites foams were prepared by supercritical carbon dioxide foaming with m@g-Sap as fillers. And its comprehensive performance, structure-properties relationship were investigated. It was shown that m@g-Sap as an efficient nucleating agent enhanced the rheological properties, crystallization behavior and foamability of PLA. The pore density of PLA4 (PLA/m@g-Sap (0.7 wt%) nanocomposites foams) is increased by 3 orders of magnitude and its average pore size is reduced by 84.94%. Furthermore, the unique intercalation structure and branched interpenetration network structure of m@g-Sap effectively improved the compression resistance of PLA based nanocomposites foams. Compared with pure PLA foam, the compressive strength of PLA4 platform region increased by 282%. Finally, what's more, the results of simultaneous rheological and in situ IR, molecular dynamics simulations indicate that there was a significant interaction between m@g-Sap and PLA and CO2, which in turn enhanced the melt strength of PLA based nanocomposites and induced the rapid crystallization of PLA. The above results demonstrated that m@g-Sap had great potential to improve the foaming behavior of PLA.

Study on the crystallization behavior and conformation adjustment scale of poly(lactic acid) in the terahertz frequency range.

The observed properties of crystalline polymers are determined by their internal structure, which in turn is the result of their different crystallization behaviors. Here, we investigate the crystallization behavior of poly(lactic acid) (PLA) by terahertz time-domain spectroscopy (THz-TDS) at varied temperatures. We find that the changes in the chain packing and conformation of PLA are characterized by THz spectroscopy. Combining X-ray diffraction (XRD) and infrared spectroscopy (IR), we attributed the blue-shift of the THz peak to the tightness of the chain packing, while its absorption enhancement is caused by the conformation transition. The effects of chain packing and chain conformation on the characteristic peak are phased. Furthermore, absorption discontinuities of the characteristic peaks of PLA crystallized at different temperatures are observed, which originated from differences in the degree of conformational transition caused by different thermal energies. We find that the crystallization temperature at which the absorption mutation of PLA occurs corresponds to the temperature at which the motion of the segment and molecular chain is excited, respectively. At these two temperatures, PLA exhibits different scales of conformational transitions leading to stronger absorption and larger absorption changes at higher crystallization temperatures. The results demonstrate that the driving force of PLA crystallization is indeed from changes in chain packing and chain conformation, and the molecular motion scale can also be characterized by THz spectroscopy.

Poly(lactic acid)/Poly(vinyl alcohol) Biodegradable Blends Using Monobutyl Maleate as a Plasticizer and Compatibilizer

The Covid-19 pandemic situation has contributed to sparking discussions about an increase in packaging combined with the nonrecommendation of reuse. For this reason, many countries have encouraged the use of biodegradable polymers. In this study, blends of poly(lactic acid) (PLA) and poly(vinyl alcohol) (PVAL) were prepared at 80/20 (w/w) in the presence of specific amounts of monobutyl maleate (MBM) as a compatibilizer. All of these components are proven biodegradable. PLA/PVAL/MBM blend films were obtained by thermopressing, and the thermal, mechanical, and morphological properties were evaluated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile tests, stress relaxation, and scanning electron microscopy (SEM). DSC results suggest that MBM can act as a plasticizer, at least for the PLA matrix, reducing the Tg from 60.2 °C (without MBM) to 23.5 °C in the case of the highest quantity of plasticizer (20%). Due to increase in macromolecular mobility, MBM also affects PLA crystallization. As a consequence of brittleness of the other samples, only those containing 15 and 20% of MBM (in PLA basis) did not fail the tensile and relaxation tests, showing more than 25% of elongation at break. Both the elastic and viscous parameters and the equilibrium modulus (Eeq) of the Maxwell–Wiechert mechanical system show lower values for the sample with higher MBM content. The SEM images show that the presence of the compatibilizer improves the adhesion between the PLA-rich phase and PVAL-rich phase.

Effect of Micro- and Nano-Lignin on the Thermal, Mechanical, and Antioxidant Properties of Biobased PLA-Lignin Composite Films.

Bio-based poly(lactic acid) (PLA) composite films were produced using unmodified soda micro- or nano-lignin as a green filler at four different contents, between 0.5 wt% and 5 wt%. The PLA-lignin composite polymers were synthesized by solvent casting to prepare a masterbatch, followed by melt mixing. The composites were then converted into films, to evaluate the effect of lignin content and size on their physicochemical and mechanical properties. Differential scanning calorimetry (DSC), supported by polarized light microscopy (PLM), infrared spectroscopy (FTIR-ATR), X-ray diffraction (XRD), and transmission electron microscopy (TEM) were employed to investigate the PLA crystallization and the interactions with Lignin (L) and Nanolignin (NL). The presence of both fillers (L and NL) had a negligible effect on the glass transition temperature (chain diffusion). However, it resulted in suppression of the corresponding change in heat capacity. This was indicative of a partial immobilization of the PLA chains on the lignin entities, due to interfacial interactions, which was slightly stronger in the case of NL. Lignin was also found to facilitate crystallization, in terms of nucleation; whereas, this was not clear in the crystalline fraction. The addition of L and NL led to systematically larger crystallites compared with neat PLA, which, combined with the higher melting temperature, provided indications of a denser crystal structure in the composites. The mechanical, optical, antioxidant, and surface properties of the composite films were also investigated. The tensile strength and Young's modulus were improved by the addition of L and especially NL. The UV-blocking and antioxidant properties of the composite films were also enhanced, especially at higher filler contents. Importantly, the PLA-NL composite films constantly outperformed their PLA-L counterparts, due to the finer dispersion of NL in the PLA matrix, as verified by the TEM micrographs. These results suggest that bio-based and biodegradable PLA films filled with L, and particularly NL, can be employed as competitive and green alternatives in the food packaging industry.

Evident improvement in burning anti-dripping performance, ductility and electrical conductivity of PLA/PVDF/PMMA ternary blend-based nanocomposites with additions of carbon nanotubes and organoclay

In this study, carbon nanotubes (CNTs) and organoclay (30B) were introduced into poly(lactic acid) (PLA)/poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) (70/30/30) ternary blend, with PMMA acting as a compatibilizer for the PLA and PVDF phases. Morphological results indicated that PMMA tended to entangle more with PVDF than with PLA, and thus formed a pseudo co-continuous PLA(rich)-PVDF(rich) phase morphology in the blend. The added CNTs and 30B clay were mainly distributed in the PVDF(rich) phase and PLA(rich) phase, respectively, to achieve nanocomposites. The co-continuous bi-phasic morphology was more evident in the composites than in the parent blend. Thermal property results revealed the nucleation effect of CNTs and 30B on the crystallization of PLA and PVDF; the presence of PMMA obviously retarded the crystal growth of PVDF due to their miscibility. Adding CNTs or hybrid CNT/30B evidently improved the anti-dripping performance of the ternary blend in burning tests. The ductility (elongation at break) of PLA/PVDF blend drastically improved with PMMA inclusion, and the composites also showed excellent ductility. The ductility of PLA and PLA/PVDF blend increased by up to 18.9 and 14.4 times, respectively, after forming the 3-phr hybrid CNT/30B-loaded composite. Rigidity of the ternary blend increased after forming the composites; flexural modulus increased by 16% with 3 phr CNT inclusion. Rheological properties revealed the (pseudo)network structure development in the composites. The electrical resistivity of the ternary blend reduced by 11 orders at 2 phr CNT loading (double percolation achieved), and the percolation threshold was at 0.5 phr CNT loading.