Thermal,mechanical and electroactive shape memory properties of polyurethane (PU)/poly (lactic acid) (PLA)/CNT nanocomposites

Polymer blend nanocomposites based on thermoplastic polyurethane (PU) elastomer, polylactide (PLA) and surface modified carbon nanotubes were prepared via simple melt mixing process and investigated for its mechanical, dynamic mechanical and electroactive shape memory properties. Chemical and structural characterization of the polymer blend nanocomposites were investigated by Fourier Transform infrared (FT-IR) and wide angle X-ray diffraction (WAXD). Loading of the surface modified carbon nanotube in the PU/PLA polymer blends resulted in the significant improvement on the mechanical properties such as tensile strength, when compared to the pure and pristine CNT loaded polymer blends. Dynamic mechanical analysis showed that the glass transition temperature (T_g) of the PU/PLA blend slightly increases on loading of pristine CNT and this effect is more pronounced on loading surface modified CNTs. Thermal and electrical properties of the polymer blend composites increases significantly on loading pristine or surface modified CNTs. Finally, shape memory studies of the PU/PLA/modified CNT composites exhibit a remarkable recoverability of its shape at lower applied dc voltages, when compared to pure or pristine CNT loaded system.     

Reactive blending toughened PLA by in situ formation of polyurethane crosslinked elastomer

Polylactide (PLA)/polyurethane (PU) composites were prepared by reactive blending method with in-situ formation of PU particles via the reaction between polyester polyol (PPG) and toluene-2,4-diisocyanate (TDI). The interfacial compatibility and adhesion between the PLA and PU phases were greatly improved by the reaction of the terminal hydroxyl groups of PLA and N=C=O groups of TDI forming graft copolymer, as confirmed by FTIR spectroscopy. The elongation at break and notch impact strength of PLA/PU composites increased considerably with increasing PU content, and the tensile strength of PLA/PU composites decreased slightly compared with that of pure PLA. The excellent interfacial adhesion, dispersed PU elastomeric particles acting as stress concentration areas and the triggering of large matrix shearing yielding and many fibrils by internal cavitation were the main mechanical toughening mechanisms.     

Toughening polylactide by dynamic vulcanization with castor oil and different types of diisocyanates

Dynamic vulcanization of polylactide (PLA) with castor oil (CO) and three different diisocyanates, namely 4,4′-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI), was performed to study the effect of diisocyanate type on the vulcanization process and on the morphology as well as mechanical properties of the PLA/CO-based polyurethane blends. The reactivity of the three diisocyanate followed the order of MDI > HDI > IPDI when reacting with castor oil. Interfacial compatibilization between PLA and the CO-based polyurethane occurred when the less reactive HDI and IPDI was used. Among all the blends, PLA/CO-IPDI showed the finest morphology and the best toughening efficiency. Incorporation of 20 wt% CO-IPDI increased the elongation at break and notched impact strength of PLA by 47.3 and 6.6 times, respectively. Cavitation induced matrix plastic deformation was observed as the toughening mechanism for the PLA blends with CO-based polyurethane. The effect of CO-IPDI content on the morphology and mechanical properties of PLA was studied in detail. The particle size of dispersed CO-IPDI and the elongation at break increased gradually, the tensile strength and Young's modulus decreased gradually, while the impact strength first increased and then decreased with increasing CO-IPDI content from 5 to 30 wt%. The maximum impact strength appeared for the blends with 20 wt% CO-IPDI.     

Improvement in Toughness of Polylactide by Melt Blending with Bio-based Poly（ester）urethane

Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The miscibility, mechanical properties, phase morphology and toughening mechanism of the blend were investigated. Both DSC and DMTA results manifested that the addition of TPU elastomer not only accelerated the crystallization rate, but also increased the final degree of crystallinity, which proved that TPU has limited miscibility with PLA and has functioned as a plasticizer. All the blend samples showed distinct phase separation phenomenon with sea-island structure under SEM observation and the rubber particle size in the PLA matrix increased with the increased contents of TPU. The mechanical property variation of PLA/TPU blends could be quantitatively explained by Wu＇s model. With the variation of TPU, a brittle-ductile transition has been observed for the TPU/PLA blends. When these blends were under tensile stress conditions, the TPU particles could be debonded from the PLA matrix and the blends showed a high ability to induce large area plastic deformation before break, which was important for the dissipation of the breaking energy. Such mechanism was demonstrated by tensile tests and scanning electron microcopy （SEM） observations.     

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.     

可生物降解的聚乳酸弹性体的性能研究

对制备的聚乳酸（聚醚）酯型聚氨酯弹性体进行了动态力学、力学性能和降解性能的测试．结果表明，弹性体的强度和弹性都较好，它们受交联度、ＰＥＧ含量和ＰＥＧ分子量的影响．该弹性体的降解速度较快．降解过程中存在自催化效应，而且是从表面开始由表及里逐渐降解的．但材料降解过程中也会出现内部降解较快的现象．动物实验表明，该弹性体是一种能满足尿道支撑管要求的有实际应用价值的材料．     

Simultaneously toughening and reinforcing poly(lactic acid)/thermoplastic polyurethane blend via enhancing interfacial adhesion by hydrophobic silica nanoparticles

This work focuses on satisfactorily toughening and reinforcing poly(lactic acid)/thermoplastic polyurethane (PLA/TPU) blend with low TPU content (10 wt%) using appropriate amounts of hydrophobic silica nanoparticles (SiO₂) via simple melt mixing. Both thermodynamic prediction and transmission electron microscopy micrographs demonstrate that most SiO₂ nanoparticles distribute at interfaces between the PLA and TPU phases. This improves interfacial adhesion between the phases, which is attributed to good bonding strength between the PLA and SiO₂ via hydrophobic interaction and formation of hydrogen bonds between the TPU and SiO₂. The PLA/TPU (90/10) ternary blend nanocomposite with 2 wt% SiO₂ exhibits obviously high impact strength (about 5.0 and 12.6 times that of the corresponding blend and PLA, respectively) and higher tensile strength than the blend and even the PLA. Crazing is the main reason for improved impact toughnesses of the blend nanocomposites. This work provides a simple and effective strategy to endow PLA/elastomer blends with optimum strength–toughness balance by adding appropriate amounts of nanoparticles.     

Toughening Poly(lactic acid) with Imidazolium-based Elastomeric Ionomers

Imidazolium-based elastomeric ionomers (i-BIIR) were facilely synthesized by ionically modified brominated poly(isobutylene-co-isoprene) (BIIR) with different alkyl chain imidazole and thoroughly explored as novel toughening agents for poly(lactic acid) (PLA). The miscibility, thermal behavior, phase morphology and mechanical property of ionomers and blends were investigated through dynamic mechanical analyses (DMA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), tensile and impact testing. DMA and SEM results showed that better compatibility between the PLA and i-BIIR was achieved compared to the PLA/unmodified BIIR elastomer. A remarkable improvement in ductility with an optimum elongation at break up to 235% was achieved for the PLA/i-BIIR blends with 1-dodecylimidazole alkyl chain (i-BIIR-12), more than 10 times higher than that of pure PLA. The impact strengths of PLA were enhanced from 1.9 kJ/m² to 4.1 kJ/m² for the PLA/10 wt% i-BIIR-12 blend. Toughening mechanism had been established by systematical analysis of the compatibility, intermolecular interaction and phase structures of the blends. Interfacial cavitations initiated massive shear yielding of the PLA matrix owing to a suitable interfacial adhesion which played a key role in the enormous toughening effect in these blends. We believed that introducing imidazolium group into the BIIR elastomer was vital for the formation of a suitable interfacial adhesion.     

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.     

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.     

Effects of Wood Flour (WF) Pretreatment and the Addition of a Toughening Agent on the Properties of FDM 3D-Printed WF/Poly(lactic acid) Biocomposites

In order to improve the properties of wood flour (WF)/poly(lactic acid) (PLA) 3D-printed composites, WF was treated with a silane coupling agent (KH550) and acetic anhydride (Ac₂O), respectively. The effects of WF modification and the addition of acrylicester resin (ACR) as a toughening agent on the flowability of WF/PLA composite filament and the mechanical, thermal, dynamic mechanical thermal and water absorption properties of fused deposition modeling (FDM) 3D-printed WF/PLA specimens were investigated. The results indicated that the melt index (MI) of the specimens decreased after WF pretreatment or the addition of ACR, while the die swell ratio increased; KH550-modified WF/PLA had greater tensile strength, tensile modulus and impact strength, while Ac₂O-modified WF/PLA had greater tensile modulus, flexural strength, flexural modulus and impact strength than unmodified WF/PLA; after the addition of ACR, all the strengths and moduli of WF/PLA could be improved; after WF pretreatment or the addition of ACR, the thermal decomposition temperature, storage modulus and glass transition temperature of WF/PLA were all increased, and water absorption was reduced.     

Biobased PLA/NR-PMMA TPV with balanced stiffness-toughness: In-situ interfacial compatibilization,performance and toughening model

Using rubber to toughen polylactide (PLA) is always accompanied by the sharp reduction in stiffness. Herein, PLA/poly (methyl methacrylate) grafted natural rubber (NR-PMMA) thermoplastic vulcanizates (TPVs) with balanced stiffness-toughness were fabricated. With the addition of 40 wt % NR-PMMA, the impact strength and tensile toughness of PLA/NR-PMMA TPV significantly improved to about 102.7 kJ/m² and 66.1 MJ/m³, respectively, compared with those of 2.7 kJ/m² and 2.4 MJ/m³ for the pure PLA. Meanwhile, the yielding stress was maintained at 34.5 MPa. Fourier transform infrared spectroscopy (FTIR) confirmed the formation of in-situ interfacial compatibilization between PLA and rubber phases. Both tensile and impact toughening mechanism were studied and deduced as considerable energy dissipation provided by the continuous rubber phase. Instrumented notched impact tests demonstrated that the energy dissipating in crack propagation process contributed to the main part of impact toughness. In addition, a novel toughening model based on bicontinuous structure was incorporated, which showed good applicability in predicting the impact strength of PLA/NR-PMMA TPVs.     

Tough crystalline blends of polylactide with block copolymers of ethylene glycol and propylene glycol

The effect of crystallinity of polylactide (PLA) on the structure and properties of tough PLA blends with PEG-b-PPG-b-PEG block copolymers was studied. PLA was melt blended with a set of the copolymers with varying ratio of the hydrophilic (PEG) and hydrophobic (PPG) blocks. Although the blend phase structure depended on the copolymer molar mass and PEG content, as well as on the copolymer concentration in the blend, crystallinity also played an important role, increasing the copolymer content in the amorphous phase and enhancing phase separation. The influence of crystallinity on the thermal and mechanical properties of the blends depended on the copolymer used and its content. The blends, with PLA crystallinity of 25 ÷ 34 wt%, exhibited relatively high glass transition temperature ranging from 45 to 52 °C, and melting beginning above 120 °C. Although with a few exceptions crystallinity worsened the drawability and toughness, these properties were improved with respect to neat crystalline PLA in the case of partially miscible blends, in which fine liquid inclusions of the modifier were dispersed in PLA rich matrix. About 20-fold increase of the elongation at break and about 4-fold increase of the tensile impact strength were reached at a small content (10 wt%) of the modifier. Moreover, crystallinity decreased oxygen and water vapor transmission rates through neat PLA and the blend, and the barrier property for oxygen of the latter was better than that of neat polymer.     

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.     

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.     

Highly efficient toughening effect of ultrafine full-vulcanized powdered rubber on poly(lactic acid)(PLA)

A unique ultrafine full-vulcanized powdered ethyl acrylate rubber (EA-UFPR) was used as the toughening modifier for poly (lactic acid) (PLA). Largely improved tensile toughness was successfully achieved with the incorporation of only 1 wt% EA-UFPR, while the tensile strength and modulus of the blends were almost the same as pure PLA. The highly efficient toughening of PLA by UFPR is mainly ascribed to the strong interfacial interaction between PLA and UFPR and good dispersion of UFPR particles in PLA matrix. Our work provides an effective toughening method to largely improve the mechanical properties of PLA without sacrificing its stiffness, which is very important for the wide application of PLA materials.     

Graft interpenetrating polymer networks of polyurethane and epoxy. II. Toughening mechanism

Graft interpenetrating polymer networks (graft-IPNs) of polyurethane (PU) and the diglycidyl ether of bisphenol A (epoxy) were prepared by first grafting excess PU prepolymer to the epoxy and then simultaneously polymerizing the PU prepolymer and epoxy. The fracture properties, at high shear rate (e.g., impact) and low shear rate (e.g., pseudostatic tensile fracture energy measurement) of these graft-IPNs exhibit opposite behavior. Although dispersed rubber particles can enhance the Izod impact strength, toughening of the matrix of graft-IPNs was found to be the main contribution. In contrast, it was found that a heterogeneous morphology with suitably dispersed rubber domains of appropriate size as well as the toughness of the matrix are requirements for effectively increasing the fracture energy at low shear rate. A reinitiating crack in the plastic matrix is proposed as the main toughening mechanism and can be invoked to interpret the fracture behavior at high and low shear rates of the graft-IPNs.     

聚丁二酸丁二醇酯与氯醚弹性体协同增韧改性聚乳酸多元共混体系

以来源于可再生资源聚丁二酸丁二醇酯(PBS)和氯醚橡胶(ECO)作为聚乳酸(PLA)的增韧改性剂,通过熔融共混的方法制备了PLA/PBS/ECO三元共混体系。动态力学分析和扫描电子显微镜结果表明,ECO促进了PBS和PLA之间的相容性。力学性能测试表明,ECO与PBS可实现对聚乳酸基体的协同增韧: PLA/PBS/ECO(70/20/10)显示出最优的拉伸性能,断裂伸长率高达270%;PLA/PBS/ECO(70/10/20)的冲击强度提高至23.7 kJ/m²,是纯聚乳酸的12倍。结合形态结构和冲击断面形貌分析表明ECO的存在可起到增容/增韧双重作用, 与柔性PBS产生良好的协同效应,有效改善聚乳酸材料的韧性。我们的研究表明,构造PLA-柔性生物聚酯和生物基弹性体多元共混体系是一种获得高性能生物基材料简单高效的手段。     

Improving Impact Toughness of Polylactide/Ethylene-co-vinyl-acetate Blends via Adding Fumed Silica Nanoparticles: Effects of Specific Surface Area-dependent Interfacial Selective Distribution of Silica

Adding fumed silica(SiO_2) has been considered as an effective method for tailoring the phase morphology and performance of elastomer-toughened plastic binary blends. It has been demonstrated that the selective distribution of SiO_2 plays a decisive role in the mechanical properties of plastic/elastomer/SiO_2 nanocomposites, especially for the impact toughness. In this work, we aim to illuminate the role of specific surface area in controlling their selective distribution of fumed SiO_2 and consequent mechanical properties of plastic/elastomer binary blends. Three types of SiO_2 with different specific surface areas were incorporated into polylactide/ethylene-co-vinyl-acetate(PLA/EVA) model blends by melt blending directly. It was found that the selective distribution of SiO_2 is largely determined by their specific surface areas, i.e. SiO_2 nanoparticles with low specific surface area has a stronger tendency to be located at the interface between PLA matrix and EVA dispersed phase as compared to those with high specific surface area. The specific surface area-dependent interfacial selective distribution of SiO_2 is mainly attributed to the extent of increased viscosity of EVA dispersed phase in which SiO_2 nanoparticles are initially dispersed and resultant migration rate of SiO_2 nanoparticles. The interfacial localized SiO_2 nanoparticles induce an obvious enhancement in the impact toughness with strength and modulus well maintained. More importantly, in the case of the same interfacial distribution, toughening efficiency is increased with the specific surface area of SiO_2. Therefore, this is an optimum specific surface area of SiO_2 for the toughening. This work not only provides a novel way to manipulate the selective distribution of SiO_2 in elastomer-toughened plastic blends toward high-performance, but also gives a deep insight into the role of interfacial localized nanoparticles in the toughening mechanism.     

Impact fracture toughness of polyamide‐6/montmorillonite nanocomposites toughened with a maleated styrene/ethylene butylene/styrene elastomer

Polyamide‐6 (PA6)/montmorillonite (MMT) nanocomposites toughened with maleated styrene/ethylene butylene/styrene (SEBS‐g‐MA) were prepared via melt compounding. Before melt intercalation, MMT was treated with an organic surfactant agent. Tensile and impact tests revealed that the PA6/4% MMT nanocomposite fractured in a brittle mode. The effects of SEBS‐g‐MA addition on the static tensile and impact properties of PA6/4% MMT were investigated. The results showed that the SEBS‐g‐MA addition improved the tensile ductility and impact strength of the PA6/4% MMT nanocomposite at the expenses of its tensile strength and stiffness. Accordingly, elastomer toughening represents an attractive route to novel characteristics for brittle clay‐reinforced polymer nanocomposites. The essential work of fracture (EWF) approach under impact drop‐weight conditions was used to evaluate the impact fracture toughness of nanocomposites toughened with an elastomer. Impact EWF measurements indicated that the SEBS‐g‐MA addition increased the fracture toughness of the PA6/4% MMT nanocomposite. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 585–595, 2005