Mechanical properties,crystallization characteristics,and foaming behavior of polytetrafluoroethylene‐reinforced poly(lactic acid) composites

In this study, poly(lactic acid) (PLA)/polytetrafluoroethylene (PTFE) composites containing different amounts of PTFE were prepared by melt blending. The mechanical, crystallization, and foaming properties of the prepared composites were investigated. Tensile test results indicated that the mechanical properties of the composite with PTFE showed significant reinforcement and toughening effects. The average elongation‐at‐break of the composite increased by 72% compared with pure PLA. Scanning electron microscopy (SEM) showed that the PTFE elongated into fibrils during blending and formed a physical network of entanglements in the melt. Differential scanning calorimetry (DSC) also showed that PTFE had a significant nucleation effect on polymer crystals and greatly increased the crystallinity of the PLA matrix. Moreover, PTFE dramatically enhanced the melt viscosity of PLA, which was investigated by rheological tests. The injection molding foaming experiments revealed that adding 1 wt% PTFE had the most notable heterogeneous nucleation effect on foamed cells, with the cell size decreasing from 81.5 μm for neat PLA to 25.2 μm, and the cell density increasing from 1.34 × 10⁸ cells/cm³ to 2.53 × 10⁹ cells/cm³. POLYM. ENG. SCI., 57:570–580, 2017. © 2016 Society of Plastics Engineers     

Crystallization behavior of α‐cellulose short‐fiber reinforced poly(lactic acid) composites

The isothermal crystallization behavior of α‐cellulose short‐fiber reinforced poly(lactic acid) composites (PLA/α‐cellulose) was examined using a differential scanning calorimeter and a petrographic microscope. Incorporating a natural micro‐sized cellulose filler increased the spherulite growth rate of the PLA from 3.35 μm/min for neat PLA at 105°C to a maximum of 5.52 μm/min for the 4 wt % PLA/α‐cellulose composite at 105°C. In addition, the inclusion of α‐cellulose significantly increased the crystallinities of the PLA/α‐cellulose composites. The crystallinities for the PLA/α‐cellulose composites that crystallized at 125°C were 48–58%, higher than that of the neat PLA for ～13.5–37.2%. The Avrami exponent n values for the neat and PLA/α‐cellulose composites ranged from 2.50 to 2.81 and from 2.45 to 3.44, respectively, and the crystallization rates K of the PLA/α‐cellulose composites were higher than those of the neat PLA. The activation energies of crystallization for the PLA/α‐cellulose composites were higher than that of the neat PLA. The inclusion of α‐cellulose imparted more nucleating sites to the PLA polymer. Therefore, it was necessary to release additional energy and initiate molecular deposition. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Core‐shell structure of carbon nanotube nanocapsules reinforced poly(lactic acid) composites

In this study “core‐shell” structure of carbon nanotube (CNT) nanocapsules, which aimed at toughening poly(lactic acid) (PLA) were designed by a synthetic strategy consisting of two reaction steps. The first step was to produce reactive chemical bond to bridge CNTs and PLA. So coupling agent KH570 was used to modify CNTs (CNTs‐KH570). The second step involved ring open polymerization of lactide (LA). Lactide polymerized into PLA under catalysis and meanwhile grafted onto CNTs via KH570 (CNTs‐KH570‐PLA). Thus, the CNTs nanocapsules were constructed. Fourier transform infrared spectroscopy (FTIR) showed coupling agent KH570 succeeded in linking CNTs and PLA during LA polymerization. In addition, scanning electron microscopy (SEM) and transmission electron microscope (TEM) indicated CNTs dispersed homogeneous in PLA matrix and the compatibility between them was excellent. The mechanical test also suggested the designed nanocapsules had good effect on toughening PLA composites. This research found one economical and simple way to improve PLA mechanical properties and further broaden its application in many fields. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44919.     

Preparation and thermomechanical properties of nanocrystalline cellulose reinforced poly(lactic acid) nanocomposites

A two‐step process was developed to prepare nanocrystalline cellulose (NCC) reinforced poly(lactic acid) (PLA) nanocomposites using polyethylene glycol (PEG) as a compatibilizer. It was composed of solvent mixing and melt blending. The NCC was well dispersed in the PLA matrix. A network was formed at high NCC‐to‐PEG ratio at which the amount of the PEG was not enough to cover all the surfaces of the NCC. The formation of the network was confirmed by the occurrence of a plateau for the storage modulus at low frequency. The incorporation of the PEG and NCC could improve the crystallinity of the PLA. The elongation at break increased from 11.0% for the neat PLA to 106.0% for the composites including 6 wt % NCC, impact strength was improved from 0.864 to 2.64 kJ m^?2 and tensile strength did not change significantly for the same 6 wt % NCC composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44683.     

Chemomechanical,morphological, and rheological studies of chitosan‐graft‐lactic acid oligomer reinforced poly(lactic acid) bionanocomposite films

Various compositions of nontoxic biodegradable poly(lactic acid) (PLA)/chitosan‐graft‐lactic acid oligomer (CH‐g‐OLLA) bionanocomposite films were fabricated with a solution casting technique by the dispersal of CH‐g‐OLLA copolymer at different amounts (1, 3, and 5 wt %) into the PLA matrix. The filler (CH‐g‐OLLA) was synthesized by an in situ condensation polymerization reaction in a microwave, and the grafting of lactic acid oligomer chains at the C2 position of the chitosan backbone was confirmed by the presence of new peaks at 179.08 and 174.41 ppm in ¹³C‐NMR analysis. The transparency results show the synergic effect of CH‐g‐OLLA in the form of reduced transparency and excellent blocking capability of UV light. Dynamic mechanical analysis confirmed a reduction in the glass‐transition temperature (up to ～13 °C) with increasing filler concentration; this signified the improvement in the elongation of bionanocomposite films. The rheological studies showed the viscous behavior of the PLA and PLA–CH‐g‐OLLA bionanocomposite films as the storage modulus values were found to be lower than the loss modulus values over the entire range of angular frequency at 180 °C. Furthermore, a Cole–Cole plot and Han plot described the uniform dispersion of the filler in the PLA matrix, its agglomeration at higher loading, and the structural change between the PLA and PLA–CH‐g‐OLLA bionanocomposite films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45546.     

Relationship between the crystallization behavior of poly(ethylene glycol) and stereocomplex crystallization of poly(L‐lactic acid)/poly(D‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a good biomedical polymer material with wide applications. The addition of poly(ethylene glycol) (PEG) as a plasticizer and the formation of stereocomplex crystals (SCs) have been proved to be effective methods for improving the crystallization of PLLA, which will promote its heat resistance. In this work, the crystallization behavior of PEG and PLLA/poly(d ‐lactic acid) (PDLA) in PLLA/PDLA/PEG and PEG‐b‐PLLA/PEG‐b‐PDLA blends has been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both SCs and homocrystals (HCs) were observed in blends with asymmetric mass ratio of PLLA/PDLA, while exclusively SCs were observed in blends with approximately equal mass ratio of PLLA/PDLA. The crystallization of PEG was only observed for the symmetric blends of PLLA_39k/PDLA_35k/PEG_2k, PLLA_39k/PDLA_35k/PEG_5k, PLLA_69k/PDLA_96k/PEG_5k and PEG‐b‐PLLA_31k/PEG‐b‐PDLA_27k, where the mass ratio of PLLA/PDLA was approximately 1/1. The results demonstrated that the formation of exclusively SCs would facilitate the crystallization of PEG, while the existence of both HCs and SCs could restrict the crystallization of PEG. The crystallization of PEG is related to the crystallinity of PLLA and PDLA, which will be promoted by the formation of SCs. © 2017 Society of Chemical Industry     

Thermomechanical properties of poly(lactic acid) films reinforced with hydroxyapatite and regenerated cellulose microfibers

Novel composite films constituted of poly(lactic acid) (PLA), hydroxyapatite (HAp), and two types of regenerated cellulose fillers—particulate and fibrous type—were produced by melt extrusion in a twin‐screw micro‐compounder. The effect of the film composition on the tensile and dynamic mechanical behavior and the HAp dispersion in the PLA matrix were investigated thoroughly. Appearance of crazed regions and prevention of HAp aggregation in the PLA matrix were elucidated in the composites with up to 15 wt % particulate cellulose content, which was the main reason for only slight reduction in the tensile properties, and consequently trivial degradation of their pre‐failure energy absorption as compared to neat PLA films. Superior dynamical energy storage capacities were obtained for the particulate cellulose modified composites, while their fibrous counterparts had not as good properties. Additionally, the anisotropic mechanical behavior obtained for the extruded composites should be favorable for use as biomaterials aimed at bone tissue engineering applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40911.     

Biodegradable composites of poly(butylene succinate‐co‐butylene adipate) reinforced by poly(lactic acid) fibers

Biodegradable composites of poly(butylene succinate‐co‐butylene adipate) (PBSA) reinforced by poly(lactic acid) (PLA) fibers were developed by hot compression and characterized by Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic mechanical analyzer, and tensile testing. The results show that PBSA and PLA are immiscible, but their interface can be improved by processing conditions. In particular, their interface and the resulting mechanical properties strongly depend on processing temperature. When the temperature is below 120 °C, the bound between PBSA and PLA fiber is weak, which results in lower tensile modulus and strength. When the processing temperature is higher (greater than 160 °C), the relaxation of polymer chain destroyed the molecular orientation microstructure of the PLA fiber, which results in weakening mechanical properties of the fiber then weakening reinforcement function. Both tensile modulus and strength of the composites increased significantly, in particular for the materials reinforced by long fiber. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43530.     

Miscibility,melting, and crystallization behavior of poly(hydroxybutyrate) and poly(D,L‐lactic acid) blends

Melting behavior and crystal morphology of poly(3‐hydroxybutyrate)‐poly(D ,L ‐lactic acid) (PHB‐RPLA) blends with various compositions have been investigated by modulated temperature differential scanning calorimetry (mt‐DSC), polarized optical thermomicroscopy (POTM), modulated force thermomechanometry (mf‐TM), and small angle X‐ray scattering (SAXS). Thermal properties were investigated after fast cooling crystallization treatment. Multiple melting peak behavior was observed for all polymers. mt‐DSC data revealed that PHB‐RPLA blends undergo melting‐recrystallization‐remelting during heating, as evidenced by exothermic peaks in the nonreversing heat capacity. A decrease in degree of crystallinity due to significant melt‐recrystallization was observed for blends. PHB‐RPLA showed different crystal morphologies for various compositions. POTM results showed that the crystallization rates and sizes of spherulites were significantly reduced as RPLA content increased. mf‐TM results confirmed miscibility of these two polymers. SAXS data provided evidence of lamella thickness of blends, which increased with increasing RPLA content. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Characterization of lignocellulosic–poly(lactic acid) reinforced composites

The effects of adding poly(lactic acid) (PLA) to the physical strength of paper test sheets prepared from three unbleached loblolly pine kraft pulps with different amounts of lignin and an aspen bleached chemothermomechanical pulp were studied. The physical strength studies demonstrated that relatively low levels of PLA addition (0.5–4.0%) could dramatically improve the tensile and burst strength properties as a function of the amount of PLA added. Hot pressing the test sheets was shown to be an important treatment for enhancing the strength properties. An analysis of untreated and PLA‐treated hot‐pressed test sheets by atomic force microscopy indicated that the addition of PLA markedly altered the surface properties of the sheets. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1346–1349, 2006     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol) copolymer and poly(L‐lactic acid) by electron beam irradiation

This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties of biodegradable composites from poly lactic acid (PLA) and microcrystalline cellulose (MCC)

Biodegradable composites were prepared using microcrystalline cellulose (MCC) as the reinforcement and polylactic acid (PLA) as a matrix. PLA is polyester of lactic acid and MCC is cellulose derived from high quality wood pulp by acid hydrolysis to remove the amorphous regions. The composites were prepared with different MCC contents, up to 25 wt %, and wood flour (WF) and wood pulp (WP) were used as reference materials. Generally, the MCC/PLA composites showed lower mechanical properties compared to the reference materials. The dynamic mechanical thermal analysis (DMTA) showed that the storage modulus was increased with the addition of MCC. The X‐ray diffraction (XRD) studies on the materials showed that the composites were less crystalline than the pure components. However, the scanning electron microscopy (SEM) study of materials showed that the MCC was remaining as aggregates of crystalline cellulose fibrils, which explains the poor mechanical properties. Furthermore, the fracture surfaces of MCC composites were indicative of poor adhesion between MCC and the PLA matrix. Biodegradation studies in compost soil at 58°C showed that WF composites have better biodegradability compared to WP and MCC composites. The composite performances are expected to improve by separation of the cellulose aggregates to microfibrils and with improved adhesion. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2014–2025, 2005     

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     

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     

Combustion properties and transference behavior of ultrafine microencapsulated ammonium polyphosphate in ramie fabric‐reinforced poly(L‐lactic acid) biocomposites

Flame‐retardant biocomposites have attracted much attention in past decades. They can provide many advantages, such as total biodegradability and their abundant renewable sources. In the work reported, biocomposites based on poly(L ‐lactic acid) (PLLA), ramie fabric (FAB) and microencapsulated ammonium polyphosphate (MCAPP) were synthesized via hot press molding using the powder‐stacking procedure. The effects of transference behavior of the flame retardant on sustaining flame retardancy of the biocomposites were investigated. Thermogravimetric analysis shows that the improved flame retardancy is due to an increased char residue at high temperature. Field emission scanning electron microscopy images and wide‐angle X‐ray diffraction data were used to investigate the hydrolysis reaction and transference behavior of ammonium polyphosphate in the biocomposites. UL‐94 testing and limiting oxygen index measurements show that the PLLA/FAB/MCAPP biocomposites retain their flame retardancy even after 21 days in UV‐irradiation hydrothermal aging tests. The good sustained flame retardancy of the PLLA/FAB/MCAPP biocomposites is attributed to the docking interactions and good distribution of MCAPP in the biocomposites. Copyright © 2010 Society of Chemical Industry     

Crystallization behavior and mechanical properties of crosslinked plasticized poly(L‐lactic acid)

Enhancing the stability of plasticized poly(L ‐lactic acid) (PLLA) with poly (ethylene glycol) (PEG) is necessary for its practical application. In this study, plasticized PLLA (PLLA/PEG 80/20 wt/wt) was crosslinked under γ‐ray (Co⁶⁰) in the presence of triallyl isocyanurate (TAIC) as crosslinking agent. FTIR analysis revealed that PLLA, PEG, and TAIC formed a cocrosslinking structure. Crystallization behavior and mechanical properties of the crosslinked plasticized PLLA were investigated by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), and tensile tests. Experimental results indicated that the crystallization behaviors of both PEG and PLLA in the blends were restrained after irradiation. The melting peak of PEG in the crystallized samples disappeared at a low irradiation doses about 10 kGy. Although PLLA still owned the behavior of crystallize, its cold crystallization temperature and glass transition temperature shifted to higher temperature. Mechanical properties of the plasticized PLLA were strengthened through crosslinking. Both yield strength and elastic modulus of the samples increased after crosslinking. Elongation at break of the crosslinked plasticized PLLA decreased with the increase of crosslinking density but remained a high value over 200%. SEM images of fracture surfaces confirmed that the ductile fracture behavior of plasticized PLLA was kept after suitable crosslinking. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization behavior of fully biodegradable poly(lactic acid)/poly(butylene adipate‐co‐terephthalate) blends

Both poly(lactic acid) (PLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) are fully biodegradable polyesters. The disadvantages of poor mechanical properties of PLA limit its wide application. Fully biodegradable polymer blends were prepared by blending PLA with PBAT. Crystallization behavior of neat and blended PLA was investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and wide angle X‐ray diffraction (WAXD). Experiment results indicated that in comparison with neat PLA, the degree of crystallinity of PLA in various blends all markedly was increased, and the crystallization mechanism almost did not change. The equilibrium melting point of PLA initially decreased with the increase of PBAT content and then increased when PBAT content in the blends was 60 wt % compared to neat PLA. In the case of the isothermal crystallization of neat PLA and its blends at the temperature range of 123–142°C, neat PLA and its blends exhibited bell shape curves for the growth rates, and the maximum crystallization rate of neat PLA and its blends all depended on crystallization temperature and their component. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L‐lactic acid) copolymer by electron beam radiation

This article investigates the effects of electron beam (EB) radiation on poly(D ,L ‐lactic acid)‐b‐poly (ethylene glycol) copolymer (PLA‐b‐PEG‐b‐PLA). The copolymer films were EB irradiated at doses from 0 to 100 kGy. The degradation of these films was studied by measuring the changes in their molecular weight, mechanical and thermal properties. The dominant effect of EB radiation on PLA‐b‐PEG‐b‐PLA is chain‐scission. With increasing irradiation dose, recombination reactions or partial crosslinking may occur in addition to chain scission. The degree of chain scission G_s and crosslinking G_x of sample are calculated to be 0.213 and 0.043, respectively. A linear relationship is also established between the decreases in molecular weight with increasing irradiation dose. Elongation at break of the irradiated sample decreases significantly, whereas its tensile strength decreases slightly. The glass transition temperature (T_g) is basically invariant as a function of irradiation dose. Thermogravimetric analysis shows that its thermal stability decreases with increasing dose. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Biodegradable poly(L‐lactic acid)/poly(butylene succinate‐co‐adipate) blends: Miscibility,morphology, and thermal behavior

Blends of two biodegradable and semicrystalline polymers, poly(L ‐lactic acid) (PLLA) and poly(butylene succinate‐co‐adipate) (PBSA), were prepared by solvent casting in different compositions. The miscibility, morphology, and thermal behavior of the blends were investigated using differential scanning calorimetry and optical microscopy. PLLA was found to be immiscible with PBSA as evidenced by two independent glass transitions and biphasic melt. Nonisothermal crystallization measurements showed that fractionated crystallization behavior occurred when PBSA was dispersed as droplets, evidenced by multiple crystallization peaks at different supercooling levels. Crystallization and morphology of the blends were also investigated through two‐step isothermal crystallization. For blends where PLLA was the major component, different content of PBSA did not make a significant difference in the crystallization mechanism and rate of PLLA. For blends where PBSA was the major component, the crystallization rate of PBSA decreased with increasing PLLA content, while the crystallization mechanism did not change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The difference of equilibrium melting point between poly(l‐lactic acid) and poly(l‐lactic acid)/poly(d‐lactic acid) blends: cases with three molecular weights

In order to explore the origin of the higher melting point of poly(lactic acid) (PLA) stereocomplex crystal (SC) than that of homo‐crystal (HC), the equilibrium melting point () differential between SC and HC was determined using the Hoffman–Weeks method. The results showed that, for PLA samples with M_n around 16, 20 and 65 kg mol^?1, the differential between SC and HC is around 36, 42 and 55 °C, respectively. Thus, the higher melting point of SC compared to HC does not stem from differential only. For PLA samples with lower M_n, the supercooling differential between poly(l ‐lactic acid) (PLLA)/poly(d ‐lactic acid) (PDLA) blends and PLLA is smaller than that with higher M_n, which means chain diffusion behavior is crucial for SC formation in PLLA/PDLA blends. The fact that the SC adopts the intermolecular parallel arrangement rather than the adjacent chain folding is verified by the greater slope of the melting point of SC versus crystallization temperature fitting curve when M_n is relative higher. © 2018 Society of Chemical Industry