Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3‐butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T_g) and the melting temperature (T_m) of PLA. Moreover, crystallinity of PLA increased with increasing the content of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1583–1590, 2006     

Mechanical and thermal properties of poly(lactic acid)/starch blends with dioctyl maleate

Poly(lactic acid) (PLA)/starch blends were prepared blending with dioctyl maleate (DOM). DOM acted as a compatibilizer at low concentrations (below 5%), and markedly improved tensile strength of the blend. However, DOM functioned as a plasticizer at concentrations over 5%, significantly enhancing elongation. Compatibilization and plasticization took place simultaneously according to the analysis of, for example, mechanical properties and thermal behavior. With DOM as a polymeric plasticizer, thermal loss in the blends was not significant. Water absorption of PLA/starch blends increased with DOM concentration. DOM leaching in an aqueous environment was inhibited. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1697–1704, 2004     

The effects of plasticizers on the dynamic mechanical and thermal properties of poly(lactic acid)

Poly(lactic acid) (PLA) was blended with five plasticizers in a batchwise mixer and pressed into films. The films were analyzed by means of dynamic mechanical analysis and differential scanning calorimetry to investigate the properties of the blends. Triacetine and tributyl citrate proved to be effective as plasticizers when blended with PLA. The glass transition temperature of PLA decreased linearly as the plasticizer content was increased. Both plasticizers were miscible with PLA to an extent of ～ 25 wt %. At this point, the PLA seemed to be saturated with plasticizer and the blends tended to phase separate when more plasticizer was added. There were also signs of phase separation occurring in samples heated at 35, 50, and 80°C, most likely because of the material undergoing crystallization. The presence of the plasticizers induced an increased crystallinity by enhancing the molecular mobility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1227–1234, 2002     

Effect of cooling conditions on the mechanical properties of crystalline poly(lactic acid)

Appropriate cooling conditions in melt processing were found to provide crystalline poly(lactic acid) (PLA) with greater mechanical toughness in tensile tests. PLA films cooled near its glass transition temperature T_g showed ductile behavior, whereas those obtained by a quenching process exhibited brittle fracture. The content of gauche‐gauche (gg) conformer, which leads to low critical onset stress for shear yielding, increased in the films cooled near T_g. The crystallinity of the films hardly affected their mechanical toughness and proportion of gg conformer except for that with a high degree of crystallinity (>50%). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44960.     

Plasticized properties of poly (lactic acid) and triacetine blends

Systematically investigations of the plasticizing effects of triacetine (TAc) on crystallization, chain mobility, microstructure, and tensile properties of the Poly (lactic acid)/triacetine (PLA/TAc) blends are reported. A new transition hump was observed on the tan δ curve of PLA_xTAc_y specimens at temperatures ranging from ?80 to ?20°C. Thermal, wide angle X‐ray diffraction (WAXD) and dynamic mechanical analysis properties of PLA and PLA_xTAc_y series specimens suggest that PLA and PLA_xTAc_y series specimens can hardly crystallize by cooling the melt in room temperature. However, significant recrystallization of α form PLA crystals was found during the annealing processes of PLA_xTAc_y series specimens. Some “less perfect” β form PLA crystals were found as the TAc contents of PLA_xTAc_y specimens reach 30 wt %. Further morphological analysis show that the inherent brittle deformation behavior of the PLA specimen was successfully transformed into relatively ductile fracture behavior after blending sufficient but optimum amounts of TAc in PLA resins. Possible reasons accounting for this interesting recrystallization, thermal, microstructure and tensile properties of PLA_xTAc_y specimens are proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚（乳酸⁃乙醇酸）薄膜制备及其性能研究

以左旋乳酸（L?LA）和乙醇酸（GA）为原料,利用一步法熔融共聚合成聚（乳酸?乙醇酸）（PLLGA）共聚物,通过差示扫描量热仪（DSC）对共聚物薄膜的结晶性能进行了表征,并利用Avrami方程对其进行了等温结晶动力学研究,通过万能拉伸试验机和压差法气体透过仪对共聚物薄膜的力学性能和气体阻隔性能进行测试。结果表明,PLLGA共聚物薄膜中GA的引入对材料结晶性能有较大影响,在GA含量为4 %（摩尔分数,下同）的PLLGA中,GA表现为成核剂作用,共聚物结晶比纯聚左旋乳酸（PLLA）薄膜快,半结晶时间减少;而在GA含量为8 %的PLLGA中,GA则表现出限制分子链运动的作用,破坏共聚物分子间的规整度,导致材料结晶性能大幅度降低,处于非晶态;随着GA含量的增加,PLLGA薄膜的拉伸强度和弹性模量逐步下降,而断裂伸长率大幅度增加,GA含量为8 %的PLLGA的断裂伸长率达到了130.1 %,是纯PLLA薄膜的21.3倍;同时,PLLGA薄膜的气体阻隔性显著增加,5 ℃时,相比于纯PLLA薄膜,GA含量为8 %的PLLGA薄膜的O₂、CO₂、N₂透过量分别降低了47 %、41 %和39 %。     

Effect of acrylonitrile content of acrylonitrile butadiene rubber on mechanical and thermal properties of dynamically vulcanized poly(lactic acid) blends

We report here the morphology, thermal and tensile properties of poly(lactic acid) (PLA) blends composed of acrylonitrile butadiene rubber (NBR) with different acrylonitrile contents with/without dynamic vulcanization by dicumyl peroxide (DCP). The interfacial tension of PLA and NBR measured by contact angle measurement decreased as the acrylonitrile content of NBR decreased. Likewise, SEM images showed that the rubber particle size reduced with decreasing acrylonitrile content owing to the stronger interfacial adhesion between the PLA matrix and NBR domains. Incorporation of DCP at 1.0 phr for dynamic vulcanization led to higher crosslink density and, in turn, optimal tensile strength and tensile toughness as a result of the action of PLA‐NBR copolymer as a reactive compatibilizer. The dynamic vulcanization of the blends containing low acrylonitrile NBR gave the most improved tensile properties because the free radicals from DCP decomposition preferentially attacked the allylic hydrogen atoms or double bonds of the butadiene backbone. Accordingly, more NBR macroradicals were generated and probably more PLA‐NBR copolymers were produced. Moreover, further addition of DCP at 2.0 phr provided a large amount of crosslinked NBR gel, which significantly degraded the tensile properties. From the DSC results, dynamic vulcanization lowered the cold crystallization temperature, implying an improvement of cold crystallization. Finally, TGA results showed a higher degradation temperature as a function of DCP content, which suggested that thermal stability increased due to stronger interfacial adhesion as well as higher gel content. © 2019 Society of Chemical Industry     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997     

Effect of miscibility on mechanical and thermal properties of poly(lactic acid)/ polycaprolactone blends

Binary blends based on poly(lactic acid) (PLA) and polycaprolactone (PCL) were prepared by melt mixing in a twin‐screw co‐rotating extruder in order to increase the low intrinsic elongation at break of PLA for packaging applications. Although PLA and PCL show low miscibility, the presence of PCL leads to a marked improvement in the ductile properties of PLA. Various mechanical properties were evaluated in terms of PCL content up to 30 wt% PCL. In addition to tensile and flexural properties, Poisson's ratio was obtained using biaxial extensometry to evaluate transversal deformations when axial loads are applied. Very slight changes in the melt temperature and glass transition temperature of PLA are observed thus indicating the low miscibility of the PLA–PCL system. Field emission scanning electron microscopy reveals some interactions between the two components of the blend since the morphology is characterized by non‐spherical polycaprolactone drops dispersed into the PLA matrix. In addition to the improvement of mechanical ductile properties, PCL provides higher degradation rates of blends under conditions of composting for contents below 22.5% PCL. © 2016 Society of Chemical Industry     

The morphology,rheological, and mechanical properties of wood flour/starch/poly(lactic acid) blends

An entirely biosourced blend composed of poly(lactic acid) (PLA), starch, and wood flour (WF) was prepared by a co‐extruder with glycerol as a plasticizer. The morphology, rheological properties, and mechanical properties of the WF/starch/PLA blends were comprehensively analyzed. The results showed that with the decrease of the starch/WF ratio, the morphology experienced a large transformation, and the compatibility of the blends was found to be superior to other blends, with a starch/wood flour ratio of 7/3. The dynamic mechanical thermal analysis (DMA) results demonstrated the incompatibility of the components in WF/starch/PLA blends. Following the decrease of the starch/WF ratio, the storage modulus (G″) and the complex viscosity (η*) of the blends increased. The mechanical strength first increased, and then decreased with the increase of the WF concentration. The water absorption results showed that the water resistance of the blends was reduced with the lower starch/WF ratio. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44743.     

聚乳酸/环氧大豆油共混物的性能

聚乳酸（PLA）与环氧大豆油（ESO）经熔融共混制得具有高韧性的PLA/ESO共混物,并研究了ESO含量对PLA微观形态、力学和流变性能的影响规律。结果表明：ESO可显著降低PLA的熔体黏度,提高PLA的韧性;PLA/ESO共混物在低ESO含量（10%）时为部分相容,而在高ESO含量（20%和30%）时发生了相分离,从而使共混物的断裂伸长率和冲击强度随ESO含量增加先增大后减小,且分别在ESO含量为20%和15%时达到最大值,约为PLA的17倍和2.9倍,而拉伸强度则随之减小。     

Strengthening blends of poly(lactic acid) and starch with methylenediphenyl diisocyanate

Poly(lactic acid) (PLA) is a biodegradable polymer, but its applications are limited by its high cost. Blending granular starch with PLA reduces the cost, but the blend has poor strength properties. In this study, a 55/45 (w/w) mixture of PLA (weight‐average molecular weight = 120,000 Da) and dried wheat starch was blended thermally in an intensive mixer with or without a low level of methylenediphenyl diisocyanate (MDI). Blends with MDI had enhanced mechanical properties that could be explained by the in situ formation of a block copolymer acting as a compatibilizer. Scanning electron micrographs showed reduced interfacial tension between the two phases. The presence of MDI also enhanced the mechanical properties of the blend at temperatures above the glass‐transition temperature. Water uptakes by the PLA/starch blends with and without MDI did not differ. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1761–1767, 2001     

Improved processability and performance of biomedical devices with poly(lactic acid)/poly(ethylene glycol) blends

To improve the processability of micropolymer‐based devices used for biomedical applications, poly(lactic acid) (PLA) was melt‐blended with poly(ethylene glycol)s (PEGs) of different molecular weights (MWs; weight‐average MWs = 200, 800, 2000, and 4000; these PEGS are referred to as PEG200, PEG800, PEG2000, and PEG4000, respectively, in this article). The thermal properties, mechanical properties, and rheological properties of the PLA and the PLA–PEG blends were investigated. The tensile samples’ morphologies showed that the low‐MW PEGs filled molds well. The rheological properties confirmed that the low‐MW PEGs decreased the complex viscosity, and improved the processability. With decreasing PEG MW, the PLA glass‐transition temperature decreased. The nanoindenter data show that the addition of PEG decreased the modulus and hardness of PLA. The morphologies of the tensile samples showed that with increasing PEG MW, the thicknesses of the core layers increased gradually. The elongation at break was improved by approximately 247% with the addition of PEG200. Such methods can produce easily processed biological materials for producing biomedical products. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45194.     

Effect of organoclay chemistry and morphology on properties of poly(lactic acid) nanocomposites

Poly(lactic acid) (PLA) nanocomposites with different layered organoclays (variation in the surface treatment of silicate) and one special nanofiller (mixed mineral thixotrope) were melt-compounded using a semi-industrial co-rotating twin-screw extruder. Effects of the silicate surface treatment and shape on the structure as well on processing and utility properties in PLA matrix were investigated. The structural changes in polymer matrix were evaluated from dynamic experiments in the shear flow using low-amplitude oscillatory measurements. Moreover, new approach for morphological investigation of nanocomposites using small-angle X-ray scattering was presented. Concerning utility properties, tests of mechanical and barrier properties were performed to compare enhancement of PLA matrix due to incorporation of different nanoparticles. Surprisingly, filling the PLA matrix with mixed mineral thixotrope resulted into very high material performance (in particular, significant improvement in barrier properties) compared to filling with commercial layered silicates. In this way, new type of nanofiller for PLA applications has been successfully tested.     

Mechanical properties and crystallization behavior of poly(lactic acid) blended with dendritic hyperbranched polymer

Mechanical properties of poly(lactic acid) (PLA) blended with a small amount of dendritic hyperbranched polymer (DHP) were investigated. Effects of DHP and starch on mechanical properties of PLA were compared. DHP significantly improved tensile strength and elongation at break of PLA. A small amount of starch in PLA slightly improved PLA's elongation, but had no effect on tensile strength. Isothermal crystallization kinetics of PLA blended with DHP and starch were also studied. Both DHP and starch acted as nucleation agents and significantly increased crystallization rate and crystallinity of PLA. Copyright © 2004 Society of Chemical Industry     

Chitosan/poly(lactic acid) blends as drug delivery systems

Abstract

The immobilization and controlled release of salicylic acid (SA) in chitosan/poly(lactic acid) (Ch/LA) blends were studied in the present work. The Ch/PLA bland’s morphology was studied by SEM. FT-IR and DSC were used to investigate the interactions between the polymer matrix and the SA. The SA release kinetics was interpreted by the Weibull and Higuchi models. The SA release was the fastest in Ch/PLA systems with inhomogeneous and porous structure. It was slower in neat PLA matrix due to its dense structure and hydrophobic behavior, and in neat chitosan matrix, because of specific electrostatic chitosan/SA interactions and complex formation.     

Thermal properties and non‐isothermal crystallization behavior of poly(trimethylene terephthalate)/poly(lactic acid) blends

Thermal properties and non‐isothermal melt‐crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(lactic acid) (PLA) blends were investigated using differential scanning calorimetry and thermogravimetric analysis. The blends exhibit single and composition‐dependent glass transition temperature, cold crystallization temperature (T_cc) and melt crystallization peak temperature (T_mc) over the entire composition range, implying miscibility between the PLA and PTT components. The T_cc values of PTT/PLA blends increase, while the T_mc values decrease with increasing PLA content, suggesting that the cold crystallization and melt crystallization of PTT are retarded by the addition of PLA. The modified Avrami model is satisfactory in describing the non‐isothermal melt crystallization of the blends, whereas the Ozawa method is not applicable to the blends. The estimated Avrami exponent of the PTT/PLA blends ranges from 3.25 to 4.11, implying that the non‐isothermal crystallization follows a spherulitic‐like crystal growth combined with a complicated growth form. The PTT/PLA blends generally exhibit inferior crystallization rate and superior activation energy compared to pure PTT at the same cooling rate. The greater the PLA content in the PTT/PLA blends, the lower the crystallization rate and the higher the activation energy. Moreover, the introduction of PTT into PLA leads to an increase in the thermal stability behavior of the resulting PTT/PLA blends. Copyright © 2011 Society of Chemical Industry     

Synthesis and physical properties of poly(l‐lactic acid)‐poly(dimethyl siloxane) multiblock copolymers prepared by direct polycondensation

Multiblock copolymers consisting of poly(l ‐lactic acid) and poly(dimethyl siloxane) were prepared by the polycondensation of oligo(l ‐lactic acid) (OLLA) with dihydroxyl‐terminated oligo(dimethyl siloxane) and dicarboxyl‐terminated oligo(dimethyl siloxane). Copolymers with number‐average molecular weights of 18,000?33,000 Da and various content ratios of oligo(dimethyl siloxane) (ODMS) unit were obtained by changing the feed ratio of these oligomers. A film prepared from the copolymer with an ODMS content ratio of 0.37 exhibited two independent peaks at ?107°C and 37°C in the mechanical loss tangent for temperature dependence, suggesting the formation of microphase separation between the OLLA and ODMS segments. The film had a tensile strength of 3.2 MPa and a high elongation of 132%. The film also exhibited a high strain recovery even after repeated straining. The incorporation of dimethyl siloxane units as multiblock segments was confirmed to improve the flexibility of poly(l ‐lactic acid). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40211.     

Mechanical,thermal and combustion properties of intumescent flame retardant biodegradable poly (lactic acid) composites

ABSTRACT

Despite extraordinary mechanical properties and excellent biodegradability, poly (lactic acid) (PLA) still suffers from a highly inherent flammability, restricting its applications in the electric and automobile fields. Although a wide range of flame retardants have been developed to reduce the flammability, they normally compromise the mechanical strength of PLA. In this study, a series of composites based on PLA, have been prepared by melt-blending with intumescent flame retardants (IFRs). The morphology, thermal stability and burning behaviour of the composites were investigated using a scanning electron microscope–energy dispersive spectrometer (SEM–EDS), thermogravimetric analysis (TGA), the limiting oxygen index (LOI), vertical burning (UL-94) and the cone calorimeter test (CCT). The LOI value reached 38.5% and UL-94 could pass V-0 for the PLA/IFR composite containing only 12 wt-% IFR. The dispersion of IFR in PLA was observed using SEM–EDS. A significant improvement in fire retardant performance was observed for the PLA/IFR composite from the CCT (reducing the heat release rate and the total heat release). More importantly, compared to pure PLA, the addition of IFR did not seriously deteriorate the mechanical properties of the material.     

High‐performance bio‐based poly(lactic acid)/natural rubber/epoxidized natural rubber blends: effect of epoxidized natural rubber on microstructure,toughness and static and dynamic mechanical properties

Attempts have been made to prepare high‐performance bio‐based blends through blending of poly(lactic acid) (PLA) with natural rubber (NR) in the presence of epoxidized natural rubber (ENR) as a compatibilizer. The prepared samples were characterized using differential scanning calorimetry, measuring the tensile properties and impact resistance, scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy and dynamic mechanical analysis (DMTA). Morphological studies revealed a matrix‐dispersed morphology for all blends, in which the average droplet size significantly decreased with the use of ENR. The elongation at break and impact strength of the blend containing 3 wt% ENR were 45 and 16 times those of neat PLA, respectively. These values are significantly higher than those previously reported for various simple and dynamically vulcanized rubber‐toughened PLAs. The influence of ENR on compatibility was confirmed by rheological tests, FTIR spectra and DMTA. DMTA also showed a marked increase in elastic modulus for the blend in the presence of 3 wt% ENR. The tensile properties and impact resistance were directly dependent on the ENR content and rubber droplet size. © 2018 Society of Chemical Industry