Largely improved toughness of poly(lactic acid) by unique electrospun fiber network structure of thermoplastic polyurethane

Oriented thermoplastic polyurethane (TPU) fiber and fiber network were first prepared by electrospinning. The as-prepared TPU fiber or fiber network was then pre-fixed in poly(lactic acid) (PLA)/TPU composite to improve the toughness of PLA. For comparison purpose, TPU/PLA composites with sea-island morphology were also prepared by traditional solution blending and mechanical blending. The results show that the toughness of PLA is greatly increased by the special pre-fixed oriented TPU fibers even at a low content, and the toughness is further increased by the TPU fiber network. Our results indicate for the first time that the toughening effect of special TPU fibers or fiber network is much better than that of traditional TPU with sea-island morphology. This study provides guidance to largely improve the toughness of PLA by designing the special phase morphology of TPU.     

Structure and blood compatibility of highly oriented poly(lactic acid)/thermoplastic polyurethane blends produced by solid hot stretching

Highly oriented poly(lactic acid) (PLA)/thermoplastic polyurethane (TPU) blends were fabricated through solid hot stretching technology in an effort to improve the mechanical properties and blood biocompatibility of PLA as blood‐contacting medical devices. It was found that the tensile strength and modulus of the blends can be improved dramatically by stretching. With the increase of draw ratio, the cold crystallization peak became smaller, and the glass transition and the melting peak moved to high temperature, while the crystallinity increased, and the grain size of PLA decreased, indicating of the stress‐induced crystallization during drawing. The oriented blends exhibited structures with longitudinal striations which indicate the presence of micro‐fibers. TPU phase was finely and homogeneously dispersed in the PLA, and after drawing, TPU domains were elongated to ellipsoid. The introduction of TPU and orientation could enhance the blood compatibility of PLA by prolonging kinetic clotting time, and decreasing hemolysis ratio and platelet activation. Copyright © 2013 John Wiley & Sons, Ltd.     

Enhancing toughness of poly (lactic acid)/Thermoplastic polyurethane blends via increasing interface compatibility by polyurethane elastomer prepolymer and its toughening mechanism

Due to the environmental pollution caused by the petroleum-based polymer, poly (lactic acid) (PLA), a biodegradable and biocompatible polymer that obtained from natural and renewable sources, has attracted widespread attention. However, the brittleness of PLA greatly limits its application. In this study, the super toughened PLA-based blends were obtained by compatibilizing the PLA/thermoplastic polyurethane (TPU) blends with the polyurethane elastomer prepolymer (PUEP) as an active compatibilizer. The mechanical properties, thermal properties and corresponding toughening mechanism of PLA/TPU/PUEP system were studied by tensile test, instrumented impact test, dynamic mechanical analysis (DMA), scanning electronic microscope (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). All the results demonstrate that the isocyanate (−NCO) group in PUEP is successfully reacted with the –OH groups at both sides of the PLA and the obtained polyurethane (PU)~PLA copolymer (PU ~ cõ PLA) significantly improves the interfacial compatibility of PLA/TPU blends. The gradually refined dispersed phase size and fuzzy phase interface as displayed in SEM images suggest a good interfacial compatibilization in the PLA/TPU/PUEP blends, probably due to the isocyanate reaction between PLA and PUEP. And the interfacial reaction and compatibilization among the components led to the formation of super toughened PLA/TPU/PUEP blends. And the instrumented impact results indicate that most of the impact toughness is provided by the crack propagation rather than the crack initiation during the entire fracture process.     

Effects of compatibility of poly(l‐lactic‐acid) and thermoplastic polyurethane on mechanical property of blend fiber

Blending poly(l ‐lactic‐acid) (PLLA) and thermoplastic polyurethane (TPU) has been performed in an effort to toughen PLLA without compromising its biodegradability and biocompatibility. The mixing enthalpy calculation of PLLA and TPU predicted that the blend was a thermodynamic miscible system. The viscoelastic properties and phase morphologies of PLLA/TPU blends were investigated further by dynamic mechanical analysis and scanning electron microscopy. It was found that the blend was a partially miscible system. The dynamic mechanical analysis showed that T_g of PLLA and TPU shifted toward with TPU content increasing. Scanning electron microscopy photos showed that the morphologies of the blends changed from a sea island structure to a bicontinuous structure as an increment in TPU content, which suggested that the miscibility of PLLA and TPU was enhanced when the TPU increased. PLLA/TPU blend fibers were fabricated. With the TPU content increasing from 0 wt% to 30 wt%, the tensile strength and initial modulus of blend fibers decreased first then increased, while elongation at break and fracture work gradually increased. The change of tensile properties indicated the toughening effects of TPU on PLLA fibers, also suggested that the formation of blend fibers was influenced by the blend rheological behavior other than the compatibility. Copyright © 2014 John Wiley & Sons, Ltd.     

Enhanced properties of poly(lactic acid) with silica nanoparticles

The objective of this article is to fabricate poly(lactic acid) (PLA) and nano silica (SiO₂) composites and investigate effect of SiO₂ on the properties of PLA composites. Surface‐grafting modification was used in this study by grafting 3‐Glycidoxypropyltrimethoxysilane (KH‐560) onto the surface of silica nanoparticles. The surface‐grafting reaction was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis. Then the hydrophilic silica nanoparticles became hydrophobic and dispersed homogeneously in PLA matrix. Scanning electron microscope and Dynamic thermomechanical analysis (DMA) results revealed that the compatibility between PLA and SiO₂ was improved. Differential scanning calorimetry and polarized optical microscope tests showed that nano‐silica had a good effect on crystallization of PLA. The transparency analysis showed an increase in transparency of PLA, which had great benefit for the application of PLA. The thermal stability, fire resistance, and mechanical properties were also enhanced because of the addition of nano silica particles. Copyright © 2016 John Wiley & Sons, Ltd.     

Poly(lactic acid)/coplasticized thermoplastic starch blend: Effect of plasticizer migration on rheological and mechanical properties

Polylactic acid (PLA) and thermoplastic starch (TPS) are known as bio‐based and biodegradable thermoplastic polymers that can be used in different applications owing to their inherent physical and mechanical properties. In order to reduce the higher costs of PLA and tuning its physical and mechanical properties suitable for short life packaging applications, blending of PLA with the TPS, more economical biodegradable polymer, has been considered in academic and industrial researches. However, melt blending of PLA with TPS without compatibilization process caused some drawbacks such as coarsening morphology and declining mechanical properties and ductility because of thermodynamic immiscibility, which may restrict its usage in packaging applications. Subsequently, our approach in this research is compatibilization of PLA/TPS blends by utilization of primary well tuning of TPS formulation with a combination of sorbitol and glycerol plasticizers. In this work, the wide composition range of melt mixed PLA/TPS blends was prepared using a laboratory twin screw extruder. The effects of microstructure on the rheological and mechanical properties of PLA/TPS blends were studied using different methods such as scanning electron microscopy (SEM) images, contact angle, oscillatory shear rheological measurements, and tensile and impact strength mechanical tests. The rheological and mechanical properties were interpreted according to the morphological features and considering the possibility of plasticizer migration from TPS to PLA phase during melt blending. Reduction in complex viscosity and storage modulus of PLA matrix samples indicates the improved melt processability of blends. Finally, in comparison with mechanical results reported in literature, our simple approach yielded the blends with elastic modulus and ductility comparable with those of chemically compatibilized PLA/TPS blends.     

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.     

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.     

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.     

Preparation and Properties of Poly（vinyl alcohol）/Chitosan Blend Bio-nanocomposites Reinforced by Cellulose Nanocrystals

The aim of this paper is to report the effect of the addition of cellulose nanocrystals（CNCs） on the mechanical, thermal and barrier properties of poly（vinyl alcohol）/chitosan（PVA/Cs） bio-nanocomposites films prepared through the solvent casting process. The characterizations of PVA/Cs/CNCs films were carried out in terms of X-ray diffraction（XRD）, transmission electron microscopy（TEM）, scanning electron microscopy（SEM）, thermogravimetric analysis（TGA and DTG）, oxygen transmission rate（OTR）, and tensile tests. TEM and SEM results showed that at low loading levels, CNCs were dispersed homogenously in the PVA/Cs matrix. The tensile strength and modulus in films increased from 55.1 MPa to 98.4 MPa and from 395 MPa to 690 MPa respectively, when CNCs content went from 0 wt% to 1.0 wt%. The thermal stability and oxygen barrier properties of PVA/Cs matrix were best enhanced at 1.0 wt% of CNCs loading. The enhanced properties attained by incorporating CNCs can be beneficial in various applications.     

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.     

Influence of size reduction of crosslinked rubber particles on phase interface in dynamically vulcanized poly (vinylidene fluoride)/silicone rubber blends

In this paper, the influence of rubber particle size on the phase interface in dynamically vulcanized poly(vinylidene fluoride)/silicone rubber (PVDF/SR) blends without any modifier is discussed through the studies of specific surface of crosslinked SR particles, crystallization behavior and crystal morphology of the PVDF phase, interfacial crystallization, melt rheological behavior and mechanical properties of blends. A series of decreased average particle size was successfully obtained by control of rotor rate. It was found that properly high rotor rate helped to achieve a reduced particle size and a narrowing size distribution. The reduced SR particle size enlarged the PVDF/SR interface which has a positive effect on the interfacial crystallization and the melt rheological behavior. At high SR content, the negative effect of the poor interface interactions played the dominate role on determining the mechanical properties. However, the blend exhibited a unique stiffness-toughness balance at the PVDF/SR = 90/10. We hope that the present study could help to lay a scientific foundation for further design of a useful PVDF/SR blend with promoted properties to partly replace the high-cost synthetic fluorosilicone materials.     

Biodegradable poly(lactic acid)/chitosan-modified montmorillonite nanocomposites: Preparation and characterization

In this study, the biodegradable poly(lactic acid) (PLA)/montmorillonite (MMT) nanocomposites were successfully prepared by the solution mixing process of PLA polymer with organically-modified montmorillonite (m-MMT), which was first treated by n-hexadecyl trimethyl-ammonium bromide (CTAB) cations and then modified by biocompatible/biodegradable chitosan to improve the chemical similarity between the PLA and m-MMT. Both X-ray diffraction data and transmission electron microscopy images of PLA/m-MMT nanocomposites indicate that most of the swellable silicate layers were disorderedly intercalated into the PLA matrix. Mechanical properties and thermal stability of the PLA/m-MMT nanocomposites performed by dynamic mechanical analysis and thermogravimetric analysis have significant improvements in the storage modulus and 50% loss in temperature when compared to that of neat PLA matrix. The degradation rates of PLA/m-MMT nanocomposites are also discussed in this study.     

Enhanced stereocomplex formation of poly(L-lactic acid) and poly(D-lactic acid) in the presence of stereoblock poly(lactic acid)

Stereoblock poly(lactic acid) (sb-PLA) is incorporated into a 1:1 polymer blend system of poly(L-lactic acid) (PLLA) and poly(D-lactic acid) (PDLA) that has a high molecular weight to study its addition effect on the stereocomplex (sc) formation of PLLA and PDLA. The ternary polymer blend films are first prepared by casting polymer solutions of sb-PLA, PLLA, and PDLA with different compositions. Upon increasing the content of sb-PLA in the blend films the sc crystallization is driven to a higher degree, while the formation of homo-chiral (hc) crystals is decreased. Lowering the molecular weight of the incorporated sb-PLA effectively increases the sc formation. Consequently, it is revealed that sb-PLA can work as a compatibilizer to improve the poor sc formation in the polymer blend of PLLA and PDLA.     

Structure,properties and interfacial interactions in poly(lactic acid)/polyurethane blends prepared by reactive processing

Polyurethane elastomers are promising candidates for the impact modification of PLA producing blends for example for biomedicine. Poly(lactic acid) (PLA)/polyurethane elastomer (PU) blends were prepared by reactive processing and physical blending as comparison. The blends were characterized by a number of techniques including microscopy (scanning electron microscopy, SEM, and atomic force microscopy, AFM), rotational viscometry, thermal (dynamic mechanical analysis, DMA), and mechanical (tensile) measurements. The analysis and comparison of the structure and properties of physical and reactor blends proved the successful coupling of the phases. Coupling resulted in more advantageous structure and superior mechanical properties compared to those of physical blends as confirmed by morphology, macroscopic properties and the quantitative estimation of interfacial interactions. Structural studies and the composition dependence of properties indicated the formation of a submicron, phase-in-phase structure which positively influenced properties at large PU contents. The results strongly support that reactive processing is a convenient, cost-effective and environmentally friendly technique to obtain blends with superior properties.     

Preparation and properties of poly(vinyl alcohol)/silica nanocomposites derived from copolymerization of vinyl silica nanoparticles and vinyl acetate

Nanocomposites of poly(vinyl alcohol)/silica nanoparticles (PVA-SNs) were prepared by in-situ radical copolymerization of vinyl silica nanoparticles functionalized by vinyltriethoxysilane (VTEOS) and vinyl acetate with benzoyl peroxide (BPO, i.e., initiator), subsequently saponified via direct hydrolysis with NaOH solution. The resulting vinyl silica nanoparticles, PVA-SNs were characterized by means of fourier transformation spectroscopy (FTIR), transmission electron microscopy (TEM) and the elemental analysis method. Effects of silica nanoparticles on viscosity and alcoholysis of PVA-SNs were studied by a ubbelohode capillary viscometer and the back titration method. The morphological structure of PVA-SN films was investigated by scanning electron microscopy (SEM). Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile test were used to determine the thermal and mechanical properties of PVA-SN films. The results indicated that the content of vinyl groups on the surface of the vinyl silica nanoparticles was up to 3.02 mmol/g and vinyl silica nanoparticles had been successfully copolymerized with vinyl acetate. Furthermore, compared to pure PVA, silica nanoparticles bonded with polymer matrix in a low concentration affected the viscosity and alcoholysis of the PVA-SNs materials. At the same time, it resulted in the improvement of the thermal and mechanical properties of the PVA-SN materials due to a strong interaction between silica nanoparticles and the polymer matrix via a covalent bond. It could be found that the optical clarity of the membrane was changed through UV-Vis absorption spectrum due to the introduction of silica nanoparticles.     

Tensile and Thermal Properties of Poly(lactic acid)/Eggshell Powder Composite Films

Biodegradable composite films of poly(lactic acid) (PLA)/eggshell powder (ESP) were prepared by the composite film casting method using chloroform as the solvent. ESP was loaded in PLA in 1 to 5 wt.%. The films were subjected to tensile, FT-IR spectral, thermogravimetric, X-ray, and microscopic analyses. The tensile strength and modulus of the composite films were found to be higher than those of PLA and increased with ESP content up to 4 wt.% and then decreased. A reverse trend was observed in the case of percentage elongation at break. The X-ray diffractograms of the composite films indicated an increase in crystallinity with ESP content. The optical micrographs indicated uniform distribution of ESP particles in the composite films. However, the fractographs indicated agglomeration of ESP particles at 5 wt.% loading. The FT-IR spectra revealed no specific interactions between PLA and ESP. The thermal stability of the composite films increased with ESP content.     

Physical and degradation properties of binary or ternary blends composed of poly (lactic acid), thermoplastic starch and GMA grafted POE

Binary and ternary blends composed of poly (lactic acid) (PLA), thermoplastic starch (TPS) and glycidyl methacrylate grafted poly (ethylene octane) (GPOE) were prepared using Haake Mixer. The mechanical morphology, thermal properties, water absorption, and degradation properties of the blends were also investigated. The elongation at break and impact strength of the ternary blends were greatly increased by the filling of GPOE. Compared to non-GPOE binary blends, the morphology of ternary blends with GPOE indicated that starch granules melted and there was good compatibility between PLA matrix and TPS. The mechanism and schematic diagram of the reactions in PLA, TPS, and GPOE were proposed and proved by testing and observing the morphology. Moreover, the biodegradation and thermal decomposition were studied through compost testing and thermal gravimetric analysis, respectively. Biodegradation results indicated that the blends have the excellent biodegrade ability.     

Synthesis and characterization of poly(lactic acid) and glucosamine-formaldehyde/dodecylbenzenesulfonate composite films

The composite films of poly(lactic acid) (PLA) doped with glucosamine(Gluc)-formaldehyde(FA) polymer/sodium dodecylbenzenesulfonate (SDBS) complexes at 1–5 wt% were synthesized to demonstrate striking improvement of their structural and mechanical properties. The polymer complexes were obtained by the hydrothermal polymerization of Gluc and FA at a molar ratio of 1:2 in the presence of SDBS. The atomic ratios of S in to N in (=S/N) in the polymer complexes limitedly range from 0.52 to 0.69, indicating that the complexation develops through the nonstoichiometric reaction between groups of (Gluc-FA) polymer and ones of SDBS and 31–48% of the groups remain unbound. The PLA composite film doped with 1 wt% (Gluc-FA)/SDBS showed the elongation-at-break of as large as 194% compared with 37% for PLA film, together with an appreciable increase of the crystallites size (D ₂₀₀) of PLA from 21.8 to 33.3 nm.     

Physical characterization of coupled poly(lactic acid)/starch/maleic anhydride blends plasticized by acetyl triethyl citrate

Acetyl triethyl citrate (ATC) was used as a plasticizer for poly(lactic acid) (PLA)/starch blends coupled with maleic anhydride and an initiator of 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (L101). Elongation of the blend at break was markedly increased when the ATC content was above the 8% loading level, which is referred to as the percolation threshold. The extended elongation was achieved at the expense of tensile strength and elastic modulus. Thermal transitions of the blend, including the glass transition temperature (T(g)), cold crystallization temperature (T(c)) and melting temperature (T(m)), decreased with ATC content. Thermally induced ATC migration affected the thermal behavior of the plasticized blends and reduced elongation and tensile strength, whereas the elasticity modulus increased. ATC migration increased with ambient temperature, which was controlled by the activation energy of the blend system. Leaching of ATC was slow at room temperature in distilled water, but significant in boiling water. Additionally, the leaching rate was also directly proportional to the ATC content of the blend. Glass transition temperatures of PLA/starch/MA/L101 blends with various acetryl triethyl citrate contents.