Poly(lactic acid)/poly(butylene succinate)/calcium sulfate whiskers biodegradable blends prepared by vane extruder: Analysis of mechanical properties,morphology, and crystallization behavior

Ternary blends of PLA/PBS/CSW with different weight fractions were prepared using a vane extruder. The mechanical properties, morphology, crystallization behavior and thermal stability of the blends were investigated. For the PLA/CSW blend, the tensile strength decreased, the flexural strength and modulus increased compared with pure PLA. For PBS, the addition of CSW had little influence on the mechanical properties. For the ternary blends PLA/PBS/CSW, the tensile strength, flexural strength and modulus decreased compared with pure PLA, while the elongation at break and the impact strength increased significantly. The brittle-ductile transition of the blends took place when the PBS weight fraction reaching 30 wt%. As a soft component in the blends, PBS was beneficial to improve the tensile ductility and the toughness of PLA. SEM measurements reveal that PLA/PBS/CSW blends were immiscible. When the weight fraction of PBS was 50 wt%, significant phase separation was observed, and CSW had preferential location in the PBS phase of the blend. DSC measurement and POM observation reveal that CSW had a heterogeneous nucleation effect on PLA and PBS matrix. The addition of PBS improved the crystallization of PLA and the thermal resistance of the PLA/PBS/CSW blends significantly.     

Effect of poly(vinyl acetate) (PVAc) on thermal behavior and mechanical properties of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blends

To assess the compatibility of blends of synthetic poly(propylene carbonate) (PPC), with a natural bacterial poly(3-hydroxybutyrate) (PHB), a simple casting procedure of blend was used. poly(3-hydroxybutyrate)/poly(propylene carbonate) blends are found to be incompatible according to DSC and DMA analysis. In order to improve the compatibility and mechanical properties of PHB/PPC blends, poly(vinyl acetate) (PVAc) was added as a compatibilizer. The effects of PVAc on the thermal behavior, morphology, and mechanical properties of 70PHB/30PPC blend were investigated. The results show that the melting point and the crystallization temperature of PHB in blends decrease with the increase of PVAc content in blends, the loss factor changes from two separate peaks of 70PHB/30PPC blend to one peak of 70PHB/30PPC/12PVAc blend. It is also found that adding PVAc into 70PHB/30PPC blend can decrease the size of dispersed phase from morphology analysis. The result of tensile properties shows that PVAc can increase the tensile strength and Young’s modulus of 70PHB/30PPC blend, and both the elongation at break and the tensile toughness increase significantly with PVAc added into 70PHB/30PPC.     

Highly toughened poly(lactic acid) (PLA) prepared through melt blending with ethylene-co-vinyl acetate (EVA) copolymer and simultaneous addition of hydrophilic silica nanoparticles and block copolymer compatibilizer

In this study, a highly toughened PLA was prepared through physical melt-blending with EVA at the presence of hydrophilic nanosilica and SEBS-g-MA block copolymer compatibilizer. The effect of nanosilica and compatibilizer on the morphology, mechanical properties, and linear rheology of the PLA/EVA blends was also investigated. According to TEM images, nanosilica was selectively located in the PLA matrix while some were placed on the interface between the two polymers as was also predicted by thermodynamic and kinetic analysis. Upon the addition of nanoparticles, the interfacial adhesion between the phases was enhanced and the average droplet size decreased. Interestingly, incorporation of SEBS-g-MA induced morphological changes as the spherical EVA droplets turned into a cylindrical shape. DSC results indicated that blending with EVA copolymer resulted in the reduction of crystallization of PLA matrix; however, the crystallinity increased at the presence of nanoparticles up to 5 wt%. The addition of compatibilizer considerably hindered the crystallization of the PLA phase. PLA/EVA blend containing optimum levels of nanosilica exhibited considerably enhanced tensile toughness, elongation at break, and impact strength. On the other hand, the simultaneous addition of nanoparticles and SEBS-g-MA led to synergistic toughening effects and the compatibilized blend containing nanosilica exhibited excellent impact toughness. For instance, the elongation at break of the compatibilized PLA/EVA blend containing the optimal content of nanosilica was increased from 7% to 121% (compared to neat sample). The notched Izod impact strength was also increased from 5.1 to 65 kJ/m². Finally, the microstructure of the blends was assessed by rheological measurements.     

New approach on the development of plasticized polylactide (PLA): Grafting of poly(ethylene glycol) (PEG) via reactive extrusion

In this work, new ways of plasticizing polylactide (PLA) with low molecular poly(ethylene glycol) (PEG) were developed to improve the ductility of PLA while maintaining the plasticizer content at maximum 20 wt.% PLA. To this end, a reactive blending of anhydride-grafted PLA (MAG-PLA) copolymer with PEG, with chains terminated with hydroxyl groups, was performed. During the melt-processing, a fraction of PEG was grafted into the anhydride-functionalized PLA chains. The role of the grafted fraction was to improve the compatibility between PLA and PEG. Reactive extrusion and melt-blending of neat and modified PLA with PEG did not induce any dramatic drop of PLA molecular weight. The in situ reactive grafting of PEG into the modified PLA in PLA/PEG blends showed a clear effect on the thermal properties of PLA. It was demonstrated by DSC that the mobility gained by PLA chains in the plasticized blends yielded crystallization. The grafting of a fraction of PEG into PLA did not affect this process. However, DSC results obtained after the second heating showed an interesting effect on the T_g when 20 wt.% PEG were melt blended with neat PLA or 10 wt.% MAG-PLA. In the latter case, the T_g displayed by the reactive blend was shifted to even lower temperatures at around 14 °C, while the T_g of neat PLA and PLA blended with 20 wt.% PEG was around 60 and 23 °C, respectively. Regarding viscoelastic and viscoplastic properties, the presence of MAG-PLA does not significantly influence the behavior of plasticized PLA. Indeed, with or without MAG-PLA, elastic modulus and yield stress decrease, while ultimate strain increases with the addition of PEG into PLA.     

Thermal behaviors and characteristics of polylactide/poly(butylene succinate) blend films via reactive compatibilization and plasticization

Polylactide (PLA)/poly(butylene succinate) (PBS) blend films modified with a compatibilizer and a plasticizer were hot‐melted through a twin screw extruder and prepared by hydraulic press. Toluene diisocyanate (TDI) and polylactide‐grafted‐maleic anhydride (PLA‐g‐MA) were used as compatibilizers, while triethyl citrate and tricresyl phosphate acted as plasticizers. The effects of the type and content of compatibilizer and plasticizer on the mechanical characteristics, thermal properties, crystallization behavior, and phase morphology of the PLA/PBS blend films were investigated. Reactive compatibilization at increasing levels of TDI improved the compatibility of the PLA and PBS, affecting the toughness of the films. As evidenced by scanning electron microscope, the addition of TDI enhanced the interfacial adhesion of the blends, leading to the appearance of many elongated fibrils at the fracture surface. Furthermore, PLA/PBS blending with both TDI and PLA‐g‐MA led to an acceleration of the cold crystallization rate and an increment of the degree of crystallinity ( ). Toluene diisocyanate could be a more effective compatibilizer than PLA‐g‐MA for PLA/PBS blend films. The synergistic combination of compatibilizer and plasticizer brought a significant improvement in elongation at break and tensile‐impact toughness of the PLA/PBS blends, compared with neat PLA. Their failure mode changed from brittle to ductile due to the improved compatibility and molecular segment mobility of the PLA and PBS phases. Differential scanning calorimeter results revealed that the plasticizers triethyl citrate and tricresyl phosphate changed the thermal behavior of T_cc and T_m, affecting α′ and α crystal formations. However, these plasticizers only slightly improved the thermal stability of the films.     

Thermal Properties and Morphology of Poly(Ester-Urethanes) Prepared from Polycaprolactone-Diol

The soft segment crystallinity and morphology of poly(ester-urethanes) (PEUs) based on poly(ε-caprolactone) (PCL) as a soft segment and an aliphatic diisocyanate in the hard segment were studied. It was found that the restriction of the crystallization of the PCL soft segment depends on the hard segment concentration, the length of the soft segment, and the total molecular mass of the PEUs. The PEU based on a low molecular mass PCL (M=2000) is an amorphous elastic material during a long time after casting from solution or after melt crystallization. A soft-hard segment endothermal mixing transition (T_mix) of about 70-80°C is observed in the DSC curves of this PEU sample. This revised version was published online in August 2006 with corrections to the Cover Date.     

Characterization of the effect of REC on the compatibility of PHBH and PLA

This study reports the compatibility of the biobased polymers poly(3-hydroxybutyrate-co-3- -hydroxyhexanoate) (PHBH) and poly(lactic acid) (PLA), as well as the effect of the addition of a reactive epoxy compatibilizer (REC) to the PHBH/PLA blend. The chemical structure, thermal performance, surface morphology and mechanical properties of the blends were measured using fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic thermo-mechanical analysis, thermogravimetric analysis, scanning electron microscopy, and impact and tensile testing.PHBH and PLA were partially compatible, and a PHBH/PLA mass ratio of 80:20 was selected for evaluation with an REC. The REC decreased the difference between the glass-transition temperatures of PHBH and PLA, decreased the particle size of the dispersed phase of the PHBH/PLA blend and produced uniform particle distribution. Moreover, the REC improved the elongation at break and impact strength of the PHBH/PLA blend. These results show that the addition of an REC improves the compatibility of PHBH and PLA.     

Mechanical,thermal and rheological properties and morphology of poly (lactic acid)/poly (propylene carbonate) blends prepared by vane extruder

In this study, the poly (lactic acid) (PLA) and poly (propylene carbonate) (PPC) blends with different compositions were prepared by a novel vane extruder based on elongation rheology. The mechanical properties, morphologies, crystallization behavior, thermal stability, and rheological properties of the blends were investigated. Mechanical test showed that PLA could be toughened by PPC to some extent, and the impact strength of the PLA was maximized when PPC content was about 30%. Differential scanning calorimetry analysis revealed that PPC had little effect on the melting process, the crystallization behavior of PLA component in the blend was improved, and the cold crystallizability of PLA decreased with the increase of PPC content when the PPC content was less than 50%. Thermogravimetry analysis showed that the thermal stability of the blends was improved by compounding with PLA. Scanning electron microscope showed that the dispersion of PLA droplets in PPC matrix was better than that of PPC droplets in PLA matrix. Rheological test showed that the melt viscosity of the pure PLA and the blend with 10% PPC was insensitive to shear rate, and the blends melt appeared shear thinning phenomenon with the increase of PPC content. It also showed that the blends microstructure changed with the addition of PPC and the blends with PPC content in a certain range had similar stress relaxation mechanism. Copyright © 2016 John Wiley & Sons, Ltd.     

Mechanical,aging, optical and rheological properties of toughening polylactide by melt blending with poly(ethylene glycol) based copolymers

Two novel biodegradable copolymers, including poly(ethylene glycol)-succinate copolymer (PES) and poly(ethylene glycol)-succinate-l-lactide copolymer (PESL), have been successfully synthesized via melt polycondensation using SnCl₂ as a catalyst. The copolymers were used to toughen PLA by melt blending. The DSC and SEM results indicated that the two copolymers were compatible well with PLA, and the compatibility of PESL was superior to that of PES. The results of tensile testing showed that the extensibility of PLA was largely improved by blending with PES or PESL. At same blending ratios, the elongation at break of PLA/PESL blends was far higher than that of PLA/PES ones. The elongation maintained stable through aging for 3 months. The moisture absorption of the blends enhanced due to the strong moisture absorption of PEG segments in PES or PESL molecules, which did not directly lead to enhance the hydrolytic degradation rate of the PLA. The PLA blends containing 20–30 wt% PES or PESL were high transparent materials with high light scattering. The toughening PLA materials could potentially be used as a soft biodegradable packaging material or a special optical material.     

Thermal,mechanical and rheological properties of biodegradable poly(propylene carbonate) and poly(butylene carbonate) blends

Poly(propylene carbonate)(PPC) was melt blended in a batch mixer with poly(butylene carbonate)(PBC) in an effort to improve the toughness of the PPC without compromising its biodegradability and biocompatibility. DMA results showed that the PPC/PBC blends were an immiscible two-phase system. With the increase in PBC content, the PPC/PBC blends showed decreased tensile strength, however, the elongation at break was increased to 230% for the 50/50 PPC/PBC blend. From the tensile strength experiments, the Pukanszky model gave credit to the modest interfacial adhesion between PPC and PBC, although PPC/PBC was immscible. The impact strength increased significantly which indicated the toughening effects of the PBC on PPC. SEM examination showed that cavitation and shear yielding were the major toughening mechanisms in the blends subjected the impact tests. TGA measurements showed that the thermal stability of PPC decreased with the incorporation of PBC. Rheological investigation demonstrated that the addition of PBC reduced the value of storage modulus, loss modulus and complex viscosity of the PPC/PBC blends to some extent. Moreover, the addition of PBC was found to increase the processability of PPC in extrusion. The introduction of PBC provided an efficient and novel toughened method to extend the application area of PPC.     

Transparent and ductile poly(lactic acid)/poly(butyl acrylate) (PBA) blends: Structure and properties

Poly(butyl acrylate) was prepared by the free radical polymerization of butyl acrylate as an initiator in the presence of 2,2′-Azoisobu-tyronitrile (AIBN) and the average molecular weight, polydispersity and thermal stability were evaluated. PLA and PBA were melt blended using a Haake Rheometer, and the light transmission, thermal properties, dynamic rheological properties, mechanical properties, phase morphology of blends and toughening mechanism were investigated. Dynamic rheology, SEM and DSC results show that the PLA is partial miscible with PBA. The PBA component improved the crystallization ability of PLA and the crystallinity of PLA increased with content of PBA (<15 wt.%). With the increase of PBA, the tensile strength and modulus of the blend decreased slightly while the elongation at break and toughness were dramatically increased. With the addition of PBA, the failure mode changes from brittle fracture of neat PLA to ductile fracture of the blend. Rheological results revealed the complex viscosity and melt elasticity of the blends decreased with increasing content of PBA and phase segregation occurred at loading above 11 wt.% PBA. UV–vis light transmittance showed that PLA/PBA blends with a high transparency, and the transmittance decreased with the amount of PBA.     

Synthesis and properties of cationic ionomers from poly(ester‐urethane)s based on polylactide

l ‐Lactide (l ‐LA) was polymerized in the presence of N‐methyldiethanolamine as an initiator and Sn(Oct)₂ as a catalyst to give hydroxy‐telechelic poly(l ‐lactide) (PLLA‐diol) bearing a tertiary amine group at the center of the polymer chain. Successive chain extension of the PLLA‐diol with hexamethylene diisocyanate afforded PLLA‐based poly(ester‐urethane)s (PEU) with equally spaced tertiary amine groups. Treatment of the PEU with iodomethane converted tertiary amine groups to quaternary ammonium groups to give cationic ionomers (PEU‐MeI). The thermal, mechanical, hydrophilic, and biodegradation properties of the obtained polymers were investigated. The thermal properties of the PEUs and the PEU‐MeIs were similar each other. The PEU‐MeIs exhibited higher tensile modulus than those of the starting PEUs. The contact angles of water on the PEU‐MeIs were lower than those of the PEUs with similar NMDA content indicating their higher hydrophilicity. In compost degradation tests, the PEU‐MeIs showed slower degradation than those of the PEUs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4423–4428     

Compatibility and phase structure of binary blends of poly(lactic acid) and glycidyl methacrylate grafted poly(ethylene octane)

This work study is the compatibility, phase structure, and component interaction of poly(lactic acid) (PLA) and glycidyl methacrylate grafted poly(ethylene octane) (GMA-g-POE denoted as mPOE) blend by Fourier transform infrared (FTIR) spectra, dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and wide-angle X-ray diffraction (WAXD), respectively. All the binary blend compositions exhibit two distinct glass transition temperatures corresponding to the mPOE-rich and PLA-rich phases, respectively. Moreover, these two peaks approach each other with increasing mPOE content, indicating partial compatibility between the PLA and mPOE. Chemical reactions between the end carboxyl groups of the PLA and epoxy groups of the mPOE are considered as the driving force of the enhanced compatibility. They lead to an increase in viscosity of the blends and a decrease in the structural symmetry of PLA. This result brings about a decrease in the spherulite growth rate and the degree of crystallinity. Glass transition temperature (T_g) depression of mPOE is attributed to the negative pressure imposed on the dispersed rubber phase, resulting from differential contraction due to the thermal shrinkage mismatch upon cooling from the melt state. The negative pressure in the dispersed particles, in turn, would cause a dilational effect for the matrix ligament between the particles, and therefore increases the ductility and toughness of PLA.     

Inherent flame retardation of bio-based poly(lactic acid) by incorporating phosphorus linked pendent group into the backbone

The molecular design for inherently flame-retardant poly(lactic acid) (IFR-PLA) was outlined and achieved by chemically incorporating an effective organophophorus-type flame retardant (FR) into the PLA backbone via the chain extension of the dihydroxyl-terminated prepolymer with 1, 6-hexamethylene diisocyanate (HDI). The structure of IFR-PLA was characterized by ¹H- and ³¹P-nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. IFR-PLA was further blended with the commercial PLA to prepare flame retardant PLA blends (PLA-FR blend). The relevant properties of IFR-PLA and PLA-FR blends were evaluated by differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), limiting oxygen index (LOI) measurements and UL-94 tests. The thermal analysis revealed that the char yield of IFR-PLA and PLA-FR blend above 400 °C was greatly enhanced compared to that of pure PLA. The LOI value was significantly improved from 19 for pure PLA to 29 when 1 wt% of phosphorus content was introduced and all IFR-PLA samples achieved V-0 rating in the UL-94 tests. PLA-FR blends had an LOI value of 25-26 and UL-94 V-2 rating at 20 wt% of IFR-PLA content. The tensile strength of all the FR PLA systems was ca. 60 MPa. The method used in this study provided a novel route to permanently flame retard PLA.     

Miscibility and properties of poly(l-lactic acid)/poly(butylene terephthalate) blends

Binary blends of poly(l-lactide) (PLLA) and poly(butylene terephthalate) (PBT) containing PLLA as major component were prepared by melt mixing. The two polymers are immiscible, but display compatibility, probably due to the establishment of interactions between the functional groups of the two polyesters upon melt mixing. Electron microscopy analysis revealed that in the blends containing up to 20% of poly(butylene terephthalate), PBT particles are finely dispersed within the PLLA matrix, with a good adhesion between the phases. The PLLA/PBT 60/40 blend presents a co-continuous multi-level morphology, where PLLA domains, containing dispersed PBT units, are embedded in a PBT matrix. The varied morphology affects the mechanical properties of the material, as the 60/40 blend displays a largely enhanced resistance to elongation, compared to the blends with lower PBT content.     

Organically modified rectorite toughened poly(lactic acid): Nanostructures, crystallization and mechanical properties

To improve the toughness of PLA, poly(lactic acid) (PLA)/organically modified rectorite (OREC) nanocomposites were prepared via the melt-extrusion method. A partially exfoliated and partially intercalated structure was confirmed by WAXD and TEM. The crystallization behaviors of neat PLA and nanocomposite were studied by POM and DSC, and it was found that OREC had a great effect on the overall crystallization rate and spherulitic texture of PLA. The presence of OREC could toughen PLA greatly. For example, when 1 wt.% OREC was added, the elongation at break of the nanocomposite was increased to 210%. The toughening mechanism was analyzed through the observation of the inner structure of the tensile test bar using SEM.     

Improvement of compatibility,mechanical, thermal and dielectric properties of poly(lactic acid) and poly(butylene adipate-co-terephthalate) blends and their composites with porous clay heterostructures from mixed surfactant systems

In this study, nanocomposite poly(lactic acid) and poly(butylene adipate-co-terephthalate) (PLA/PBAT) blends were prepared through polymer blending in the presence of multi-functional epoxy as a compatibilizer that could react with epoxy group and terminated end group of two phases to increase interfacial adhesion between PLA and PBAT and improve the toughness of PLA. The effects of porous clay heterostructure from mixed CTAB:CTAC surfactant in the mole ratio of 1:2 (B1C2-PCH) were also investigated. The elongation at break of the blends reached 38%, which was eight times that of neat PLA. The cryo-fractured surface demonstrated the interfacial adhesion caused by the interaction of the epoxy group of the reactive compatibilizer with the terminal carboxyl and hydroxyl groups of PLA and PBAT. Moreover, PBAT reduced the crystallization rate and percent crystallinity of the PLA matrix and further decreased when compatibilizer was used. Alternatively, B1C2-PCH accelerated the heterogeneous nucleation and crystallization of the nanocomposite films. After adding small amount of B1C2-PCH, the nanocomposite films demonstrated excellent dielectric properties. Therefore, the improvement of PLA/PBAT nanocomposite blends are capable to be further developed as polymeric capacitor films.     

Toughening of poly(propylene carbonate) by carbon dioxide copolymer poly(urethane-amine) via hydrogen bonding interaction

A carbon dioxide copolymer poly(urethane-amine)(PUA) was blended with poly(propylene carbonate)(PPC) in order to improve the toughness and flexibility of PPC without sacrificing other mechanical properties. Compared with pure PPC, the PPC/PUA blend with 5 wt% PUA loading showed a 400% increase in elongation at break, whilst the corresponding yielding strength remained as high as 33.5 MPa and Young's modulus showed slightly decrease. The intermolecular hydrogen bonding interaction in PPC/PUA blends was comfirmed by FTIR, 2D IR and XPS spectra analysis, and finely dispersed particulate structure of PUA in PPC was observed in the SEM images, which provided good evidence for the toughening mechanism of PPC.     

The effect of free radical reactions on structure and properties of poly(lactic acid) (PLA) based blends

The blending of PLA with poly(butylene-adipate-co-terephthalate) (PBAT) is a promising strategy to achieve a toughened multiphase material. The blends ductility could be further improved through reactive compatibilization, i.e. inducing the formation of comb PLA-PBAT copolymers during the melt blending. In the present work a non-selective strategy was adopted which consisted in the use of a peroxide, 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane. The phase morphology development and the final properties (torque, fluidity in the melt, tensile behaviour, thermal and dynamical-mechanical features) of the blends were studied as a function of the peroxide concentration. The elongation at break was improved up to a maximum value thanks to this approach and a corresponding minimum was observed in the value of the dispersed phase diameter. A structural characterization of the macromolecules formed during the reactive process was attempted by using size exclusion chromatography of the blends and comparison with the pure polymers obtained by processing in the presence of the peroxide.     

Chemical modification of poly(lactic acid) and its use as matrix in poly(lactic acid) poly(butylene adipate-co-terephthalate) blends

Poly(lactic acid), PLA, was chemically modified with maleic anhydride (MA) by reactive extrusion. The effect of this modification on molar mass (MM) and acidity was assessed by means of size-exclusion chromatography (SEC) and titration, respectively. PLA MM decreased in the presence of MA solely and of MA and peroxide. Reduction in MM was monitored by the increase in acidity. PLA blends containing poly(butylene adipate-co-terephthalate) (PBAT) were prepared through different mixing protocols, PLA/PBAT, PLA-g-MA/PBAT and PLA/PBAT/MA/peroxide (PLA/PBAT in situ). SEC results and rheological properties revealed reduction in MM and viscosity of the modified blends. PLA/PBAT presented increase in MM and bimodal MM distribution. The calculated interfacial tension was significantly lower for the modified blends, despite the lower average particle area of PLA/PBAT. Surprisingly, the modified blends presented higher yield strength than that predicted by the rule of mixtures, which might indicate interfacial reactions.