Structural, morphological and mechanical characteristics of polyethylene, poly(lactic acid) and poly(ethylene-co-glycidyl methacrylate) blends

In this work, uncompatibilized and compatibilized blends of low density polyethylene (LDPE) and poly(lactic acid) (PLA) were subjected to several investigations: Fourier transform infrared (FTIR) spectroscopy, morphological analysis and mechanical testing (tensile, impact, microhardness). The copolymer (ethylene-co-glycidyl methacrylate) (EGMA) was used as compatibilizer. The percentages of PLA in LDPE/PLA samples ranged from 0 to 100 wt% while the EGMA was added to the blend 60/40 (LDPE/PLA) at concentrations of 2, 5, 7, 10, 15 and 20 parts per hundred (phr). FTIR analysis showed the absence of any interaction between LDPE and PLA, but after addition of compatibilizer, reactions between epoxy groups of EGMA and carboxylic or hydroxyl groups of PLA were confirmed. Tensile and impact tests revealed a loss of ductility of LDPE with the incorporation of PLA, except for the composition 80/20 (LDPE/PLA). However, the addition of 15 phr of EGMA led to the maximum increase in the elongation-at-break (about three times the value of uncompatibilized blend) and in the impact strength, but a marginal improvement was observed for tensile strength. SEM micrographs confirmed that the enhancement of mechanical properties is due to the improvement of the interfacial adhesion between different phases owing to the presence of EGMA. The microhardness values of the different blends (uncompatibilized or compatibilized) were in good agreement with the macroscopic mechanical properties (tensile and impact strengths).     

Preparation and property testing of polymer blends of poly(lactic acid) and poly(butylene succinate) plasticised with long-chain fatty acids

This study investigates the influence of three fatty acids (lauric acid, palmitic acid, and stearic acid) on biodegradable polymer blends based on poly(lactic acid) (PLA) and poly(butylene succinate) (PBS), containing different weight ratios (100:0, 100:2, and 100:4) of fatty acids on the transparency, mechanical properties, morphology, contact angle, and water vapour permeability. All of the blends were pressed into thin films and tested. The experimental results showed that the properties of the samples varied with chain length and amounts of the fatty acids. Thus, it could be concluded that use of fatty acids opens up new ways for the plasticisation of PLA/PBS blends for use as new bioplastics.     

Study on the effect of dispersion phase morphology on porous structure of poly (lactic acid)/poly (ethylene terephthalate glycol-modified) blending foams

A methodology for blending foam of poly (lactic acid) (PLA)/poly (ethylene terephthalate glycol-modified) (PETG) was proposed. PLA/PETG blends were prepared through a melt blending method, using multiple functionality epoxide as reactive compatibilizer. The effects of blending ratio and compatibilizer content on the dispersion morphology, molecular structure, mechanical properties, and rheological behavior of PLA/PETG blends were studied. Then PLA/PETG blends were foamed using supercritical CO₂ as physical blowing agent, and their porous structure, pore size, as well as pore density were investigated. The results showed that the mechanical properties and rheological parameters such as melt strength and melt elasticity, as well as the porous structure of the foams dispersion morphology of PLA/PETG blends were affected strongly. The melt elasticity of PLA/PETG blends increased with increasing compatibilizer content. Dispersion phase morphology of PLA/PETG blends also had a significant effect on the pore density of all the samples. The results indicated that homogeneous and finer porous morphology of PLA/PETG foams with high expansion ratio could be achieved with a proper content of compatibilizer in the blends.     

Synergetic toughening of poly(phenylene sulfide) by poly(phenylsulfone) and poly(ethylene-ran-methacrylate-ran-glycidyl methacrylate)

Poly(phenylene sulfide) (PPS) is a high-performance super-engineering plastic, but is brittle. In this study, super-tough PPS-based blends were successfully generated by melt blending PPS with poly(ethylene-ran-methacrylate-ran-glycidyl methacrylate) (EGMA) and poly(phenylsulfone) (PPSU) at (56/14/30) PPS/EGMA/PPSU composition, and their toughening mechanisms were investigated in detail. It was demonstrated the interfacial reaction between PPS and EGMA and partial miscibility between PPS and PPSU, both play important synergistic roles on the toughening. The interfacial reaction between PPS and EGMA contributes to the reduction of the PPSU domain size by the increased viscosity of the PPS matrix containing EGMA, and the increased mobility of EGMA chains by negative pressure effect. The partial miscibility between PPS and PPSU contributes to the increased interfacial adhesion between PPS and PPSU, resulting in effective propagation of the impact to the domains, and the increased mobility of not only PPSU chains but also PPS chains, causing a reduction in crystallization.     

Enhanced mechanical properties and degradability of poly(butylene succinate) and poly(lactic acid) blends

To improve the tensile properties and degradability of poly(butylene succinate) (PBS) for biomedical usage, biodegradable polymer blends have been developed. A series of PBS and poly(lactic acid) (PLA) blends were prepared, and their degradation behaviors in simulated body fluid for 16 months were investigated based on morphology, tensile test, weight analysis, and molecular weight. The results showed that the incorporation of PLA into PBS increased the initial tensile strength to some extent, and the blends lost their tensile properties earlier than their parent polymers with the proceeding of hydrolysis. Both blends and parent polymers went through a plateau and subsequent rise stage in mass loss and water absorption, but the blends hydrolyzed faster than the parent polymers. The molecular weight variations also demonstrated faster hydrolysis of the blends. Moreover, both blends and their parent polymers underwent a slow-to-fast transition in their hydrolysis rates. When the M _n of PBS and PLA reached 4.0 × 10⁴ and 9.0 × 10⁴, the hydrolysis of parent polymers and blends began to accelerate, which is the start of auto-acceleration. The blends hydrolyzed faster in both stages. The interface between the components initiated accelerating hydrolysis in the first stage, and the reciprocal auto-acceleration effect resulted in faster hydrolysis of the blends in the second stage.     

Peculiar crystallization kinetics of biodegradable poly(lactic acid)/poly(propylene carbonate) blends

Binary blends of poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) were found to display a peculiar crystallization kinetics. The two biodegradable polymers were blended by melt mixing, to obtain binary blends at various compositions. Temperature‐modulated calorimetry and dynamic‐mechanical analysis indicated that the blend components are partially miscible, and display two separate glass transitions, at temperatures intermediate to those of the plain polymers. Electron microscopy analysis disclosed the morphology of PLA/PPC blends, made of PPC‐rich particles finely dispersed within the PLA‐rich matrix. The possible establishment of interactions between the functional groups of the two polymers upon melt mixing has been hypothesized as the reason for partial miscibility and compatibility of the two biodegradable polymers. The PLA/PPC blends display good mechanical properties, with enhanced performance at rupture compared with plain PLA. Most importantly, the addition of PPC affects also the crystallization kinetics of PLA, since the more mobile PPC chains favor diffusion of the stiffer PLA chain segments towards the growing crystals, which fastens the spherulite growth rate of PLA. Such positive influence of an amorphous polymer on crystal growth rate has been demonstrated here for the first time in blends that display phase‐separation in the melt. POLYM. ENG. SCI., 55:2698–2705, 2015. © 2015 Society of Plastics Engineers     

Morphology and properties of the biosourced poly(lactic acid)/poly(ethylene oxide‐b‐amide‐12) blends

Biosourced poly(lactic acid) (PLA) blends with different content of poly(ethylene oxide‐b‐amide‐12) (PEBA) were prepared by melt compounding. The miscibility, phase structure, crystallization behavior, mechanical properties, and toughening mechanism were investigated. The blend was an immiscible system with the PEBA domains evenly dispersed in the PLA matrix. The PEBA component suppressed the nonisothermal melt crystallization of PLA. With the addition of PEBA, marked improvement in toughness of PLA was achieved. The maximum for elongation at break and impact strength of the blend reached the level of 346% and 60.5 kJ/m², respectively. The phase morphology evolution in the PLA/PEBA blends after tensile and impact tests was investigated, and the corresponding toughening mechanism was discussed. It was found that the PLA matrix demonstrates obvious shear yielding in the blend during the tensile and impact tests, which induced energy dissipation and therefore lead to improvement in toughness of the PLA/PEBA blends. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

聚乳酸/聚丁二酸丁二醇酯共混物的研究

通过熔融共混制备了聚乳酸(PLA)/聚丁二酸丁二醇酯(PBS)共混物,采用扫描电子显微镜、差示扫描量热仪、旋转流变仪对其相容性、热性能和黏度等进行了研究,并研究了PBS的加入对PLA力学性能的影响。结果表明,PLA和PBS之间是部分相容的,PBS的少量添加并不影响PLA的拉伸强度,且其冲击强度随着PBS含量的增加呈先上升后下降的趋势,当PBS含量为10份时,共混物的冲击强度最好;与纯PLA相比,共混物的黏度有所增加,且随着PBS含量的增加,共混物的黏度逐渐增大;PBS的添加起到异相成核作用,促进了PLA的结晶。     

Effect of poly(butylenes succinate) on the microcellular foaming of polylactide using supercritical carbon dioxide

Microcellular Polylactide (PLA) and PLA/poly(butylenes succinate) (PBS) foams were prepared by batch foaming process with supercritical carbon dioxide. The introduced PBS phase was immiscible with the PLA matrix and separated as domains. The study of CO₂ solubility in PLA and PLA/PBS blends indicated the addition of PBS decreased the gas solubility due to the poor affinity of CO₂ for PBS. The crystallization behavior of PLA was enhanced by small amount of PBS with lower cold crystallization temperature and higher crystallinity. However, separated PBS droplets led to less perfect and small crystallites, which showed greatly effect for the PLA foaming process. The investigation on the foaming conditions dependence indicated the PLA/PBS blends required higher temperature and longer time for the cell growth, which were nucleated around the interface between PLA and PBS. With less CO₂ content in the PLA or PLA/PBS blends after different desorption time, the final cell morphology exhibited more uniform size distribution with bigger average cell size and smaller cell density. Different from the well closed-cell structure for neat PLA foam, the PLA/PBS foam presented open cell structure due to the cell nucleation around the PLA/PBS interface and the lower melt strength of PBS phase.     

The effect of poly(ethylene glycol) as plasticizer in blends of poly(lactic acid) and poly(butylene succinate)

The effect of polyethylene glycol (PEG) on the mechanical and thermal properties of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blends was examined. Overall, it was found that PEG acted as an effective plasticizer for the PLA phase in these microphase‐separated blends, increasing the elongation at break in all blends and decreasing the T_g of the PLA phase. Significant effects on other properties were also observed. The tensile strength and Young's modulus both decreased with increasing PEG content in the blends. In contrast, the elongation at break increased with the addition of PEG, suggesting that PEG acted as a plasticizer in the polymer blends. Scanning electron microscope images showed that the fracture mode of PLA changed from brittle to ductile with the addition of PEG in the polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43044.     

Biodegradable poly(lactic acid)/poly(butylene succinate)/wood flour composites: Physical and morphological properties

This work sought to improve the toughness and thermal stability of poly(lactic acid) (PLA) by incorporating poly(butylene succinate) (PBS) and wood flour (WF). The PLA/PBS blends showed a PBS‐dose‐dependent increase in the impact strength, elongation at break, degree of crystallinity, and thermal stability compared to the PLA, but the tensile strength, Young's modulus, and flexural strength were all decreased with increasing PBS content. Based on the optimum impact strength and elongation at break, the 70/30 (w/w) PLA/PBS blend was selected for preparing composites with five loadings of WF (5–30 phr). The impact strength, tensile strength, flexural strength, and thermal stability of the PLA/PBS/WF composites decreased with increasing WF content, and the degree of crystallinity was slightly increased compared to the 70/30 (w/w) PLA/PBS blend. Based on differential scanning calorimetry, the inclusion of PBS and WF into PLA did not significantly change the glass transition and melting temperatures of PLA in the PLA/PBS blends and PLA/PBS/WF composites. From the observed cold crystallization temperature of PLA in the samples, it was evident that the degree of crystallinity of PLA in all the blends and composites was higher than that of PLA. The PLA/PBS blend and PLA/PBS/WF composite degraded faster than PLA during three months in natural soil, which was due to the fast degradation rate of PBS. POLYM. COMPOS., 38:2841–2851, 2017. © 2016 Society of Plastics Engineers     

Property enhancement of poly(butylene succinate)/poly(ethyleneglycol-co-cyclohexane-1,4-dimethanolterephthalate) blends via high-speed extrusion and in situ fibrillation

In the current work, poly(butylene succinate)(PBS)/poly(ethylene glycol-co-cyclohexane-1,4-dimethanolterephthalate) (PETG) blends were first prepared by high-speed extrusion melt processing, and the dependence of the dispersed morphology(phase size) was investigated as function of screw speed. Then, the prepared blends were subjected to a “melt extrusion-uniaxial cold stretching” process to convert the dispersed phase into fibrillar structure, and the diameter change and property enhancement of PBS/PETG blends were further studied. It was found, at fixed ratio of PBS/PETG = 80/20 (wt/wt), the diameters of the PETG was changed from 2.25, 1.29, 1.11, 0.89 μm to 1.13, 0.64, 0.50, 0.38 μm, as increasing the screw speed from 150, 500, 700 rpm to 900 rpm, respectively. In addition, increasing the extrusion speed is favorable not only for smaller but more uniform dispersed phase particles, thus leading to finer microfibrils with narrower diameter distribution after cold stretching. As a result, the yield strength of PBS could be improved from 25.6 to 39.8 MPa for blend obtained via high-speed extrusion and stretching. Our work is important for the preparation of polymer blends with improved property. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47549.     

Preparation and characterization of polylactide/poly(polyethylene glycol-co-citric acid) blends

The blends of polylactide (PLA) and poly(polyethylene glycol-co-citric acid) (PEGCA) were prepared by melt mixing in an internal mixer. The effects of PEGCA content on the processibility, morphological, thermal, mechanical properties as well as hydrophilicity of PLA/PEGCA blends are investigated by rheometer, scanning electron microscopy, differential scanning calorimetry, mechanical testing, and water contact measurements. During thermal processing, the presence of PEGCA delayed the melting of PLA and lowered the viscosities of the blends. PLA/PEGCA blends exhibited a phase-separated morphology. The sizes of the dispersed phase increased with increased PEGCA content. The glass transition temperature of PLA decreased with the addition of PEGCA. The crystallization behaviors of PLA and PEGCA in their blends were influenced by each other. Ductility and toughness of PLA were significantly improved by the presence of PEGCA. PEGCA also greatly improved the hydrophilicity of PLA significantly.     

Effect of the shape of dispersed particles on the thermal and mechanical properties of biomass polymer blends composed of poly(L‐lactide) and poly(butylene succinate)

The structure and properties of binary blends composed of poly(lactic acid) (PLA) and fibrous poly(butylene succinate) (PBS), which were prepared by an uniaxial stretching operation in the molten state, were studied and compared with those of blends having spherical particles of PBS in a continuous PLA phase. We found from electron microscope observation that PBS nanofibers with a large aspect ratio were generated in the stretched samples. Enlargement of the surface area of the PBS particles, which showed nucleating ability for PLA, led to a high degree of crystallization and enhanced the cold crystallization in the heating process. Moreover, the PBS fibers in the stretched samples had a dominant effect on the mechanical properties in the point range between the glass‐transition temperature of PLA and the melting temperature of PBS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Phase behavior and morphology in blends of poly(L‐lactic acid) and poly(butylene succinate)

Blends of poly(L ‐lactic acid) (PLA) and poly(butylene succinate) (PBS) were prepared with various compositions by a melt‐mixing method and the phase behavior, miscibility, and morphology were investigated using differential scanning calorimetry, wide‐angle X‐ray diffraction, small‐angle X‐ray scattering techniques, and polarized optical microscopy. The blend system exhibited a single glass transition over the entire composition range and its temperature decreased with an increasing weight fraction of the PBS component, but this depression was not significantly large. The DSC thermograms showed two distinct melting peaks over the entire composition range, indicating that these materials was classified as semicrystalline/semicrystalline blends. A depression of the equilibrium melting point of the PLA component was observed and the interaction parameter between PLA and PBS showed a negative value of ?0.15, which was derived using the Flory–Huggins equation. Small‐angle X‐ray scattering revealed that, in the blend system, the PBS component was expelled out of the interlamellar regions of PLA, which led to a significant decrease of a long‐period, amorphous layer thickness of PLA. For more than a 40% PBS content, significant crystallization‐induced phase separation was observed by polarized optical microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 647–655, 2002     

Reactive compatibilization of poly(l‐lactide)/poly(butylene succinate) blends through polyester maleation: from materials to properties

The melt blending of poly(l ‐lactide) (PLLA) with biodegradable poly(butylene succinate) (PBS) is considered with a view to fine‐tuning its mechanical properties and its degradability. For this purpose, both maleic‐anhydride‐grafted PLLA (PLLA‐g‐MA) and maleic‐anhydride‐grafted PBS (PBS‐g‐MA) were prepared and used as reactive compatibilizers. The influence of PBS melt viscosity on the morphology and mechanical properties of PLLA/PBS blends was studied. Interestingly, the blending of low viscosity PBS with PLLA allows PLLA to be toughened while the use of high viscosity PBS led to PLLA/PBS blends exhibiting co‐continuous morphology. The nanostructure of the co‐continuous blends may be tuned through the joint action of organo‐modified clays and reactive compatibilizers. The effect of PBS on PLLA degradability was also investigated. The accelerated weathering testing of blends reveals that such combination of biodegradable polymers allows their degradability rate to be tailored. It is found that the addition of 20 wt% PBS to PLLA allows the molar mass loss fraction to be doubled after 425 h of testing. © 2014 Society of Chemical Industry     

Crystallization behavior of poly(lactide)/poly(β‐hydroxybutyrate)/talc composites

The morphology and miscibility of commercial poly(lactide) (PLA)/poly(β‐hydroxybutyrate) (PHB, from 5 to 20 wt %) blends prepared by melt extrusion method, were investigated using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) observations. The results show that for all the studied blend contents, PLA/PHB blends are immiscible. The effects of PHB and talc on the nonisothermal cold crystallization kinetics of PLA were examined using a differential scanning calorimetry (DSC) at different heating rates. PHB acted as a nucleating agent on PLA and the addition of talc to the blend yielded further improvement, since significant increase in the enthalpy peak was observed for samples containing 10 wt % PHB and talc (from 0.5 to 5 phr). The crystallization kinetics were then examined using the Avrami–Jeziorny and Liu–Mo approach. The simultaneous presence of PHB and talc induced a decrease of the crystallization half time. The evolution of activation energies determined with Kissinger's equation suggests that blending with PHB and incorporating talc promote nonisothermal cold crystallization of PLA. The synergistic nucleating effect of PHB and talc was also observed on isothermal crystallization of PLA from the melt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure evolution driven by phase separation and the corresponding foaming behavior of polystyrene/poly(methyl methacrylate) blends via a batch foaming process

Morphology evolution of immiscible polymer blends during processing is a common phenomenon, but how it affects the foaming behavior is still unknown. The present work aims to study the effect of morphology evolution of polystyrene/poly(methyl methacrylate) (PS/PMMA) blends driven by phase separation on foaming behavior via a batch foaming process. Morphology evolution of PS/PMMA blends were conducted via thermal annealing using a compression molding machine. Phase contrast optical microscope and scanning electron microscope were used to investigate the morphology evolution and cell structures. The diffusion coefficients were calculated to study the effect of morphology evolution on gas diffusion behavior. It was found that phase domain was increased in size with the annealing and that cell structure was significantly dependent on morphology evolution. The thermal annealing with a long time could dramatically impact cell structures, especially for the blends with a bi‐continuous phase structure or a sea‐island structure with very large phase domains. The diffusion coefficient for the interface was increased with the annealing, which resulted in the generally decreased expansion ratio. Therefore, annealing for a long time at melt states during processing should be avoided for obtaining well‐defined cell structures for immiscible polymer blends. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46704.     

Mechanical properties of poly(ε‐caprolactone) and poly(lactic acid) blends

The aim of this work was to better understand the performance of binary blends of biodegradable aliphatic polyesters to overcome some limitations of the pure polymers (e.g., brittleness, low stiffness, and low toughness). Binary blends of poly(ε‐caprolactone) (PCL) and poly(lactic acid) (PLA) were prepared by melt blending (in a twin‐screw extruder) followed by injection molding. The compositions ranged from pure biodegradable polymers to 25 wt % increments. Morphological characterization was performed with scanning electron microscopy and differential scanning calorimetry. The initial modulus, stress and strain at yield, strain at break, and impact toughness of the biodegradable polymer blends were investigated. The properties were described by models assuming different interfacial behaviors (e.g., good adhesion and no adhesion between the dissimilar materials). The results indicated that PCL behaved as a polymeric plasticizer to PLA and improved the flexibility and ductility of the blends, giving the blends higher impact toughness. The strain at break was effectively improved by the addition of PCL to PLA, and this was followed by a decrease in the stress at break. The two biodegradable polymers were proved to be immiscible but nevertheless showed some degree of adhesion between the two phases. This was also quantified by the mechanical property prediction models, which, in conjunction with material property characterization, allowed unambiguous detection of the interfacial behavior of the polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical properties and morphological changes of poly(lactic acid)/polycarbonate/poly(butylene adipate‐co‐terephthalate) blend through reactive processing

The mechanical properties and morphological changes of poly(lactic acid) (PLA), polycarbonate (PC), and poly(butylene adipate‐co‐terephthalate) (PBAT) polymer blends were investigated. Several types of blend samples were prepared by reactive processing (RP) with a twin‐screw extruder using dicumyl peroxide (DCP) as a radical initiator. Dynamic mechanical analyses (DMA) of binary polymer blends of PC/PBAT indicated that each component was miscible over a wide range of PC/PBAT mixing ratios. DMA of PLA/PBAT/PC ternary blends revealed that PBAT is miscible with PC even in the case of ternary blend system and the miscibility of PLA and PBAT can also be modified through RP. As a result, the tensile strain and impact strength of the ternary blends was increased considerably through RP, especially for PLA/PBAT/PC = 42/18/40 (wt/wt/wt) with DCP (0.3 phr). Scanning electron microscopy (SEM) analysis of the PLA/PBAT/PC blends revealed many small spherical island phases with a domain size of approximately 0.05–1 μm for RP, whereas it was approximately 10 μm without RP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011