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     

Preparation and characterization of poly(ethylene carbonate)/poly(lactic acid) blends

Poly(ethylene carbonate)/poly(lactic acid) blends were successfully prepared by means of a solution film-casting method, and their physicochemical properties were investigated. PEC/PLA blends exhibit partial miscibility and are characterized by the interaction of the ester and carbonic ester groups. One such interaction is between partial charges in –C–O– in –O–C=O of PLA and the carbonyl –C=O of PEC. Another is between –C–O– in –O–C=O of PLA and –C–O– in –CH₂–O– of PEC. The value of T_g varies by more than 10 °C across the blends. PEC does not significantly influence the melting temperature of neat PLA, but non-spherical spherulites are formed in PEC-rich blends, whereas the spherulites are spherical with an average size of 30 μm in PLA-rich blends. Crystallization of PLA is influenced by the addition of flexible PEC and by the proportion of PLA in the blends. Interestingly, addition of at least 10 wt% PLA increased T_g, with a crystallinity, X_c of 47% and better thermal degradation properties, with the temperature at 5 wt% weight loss (T_d5) more than 30 °C higher than for neat PEC.     

In situ fibrous structure oriented polymer blends composed of poly(lactic acid) and polycaprolactone containing peroxide

A fibrous dispersed phase stuffed with polycaprolactone (PCL) was constructed in a poly(lactic acid) (PLA) matrix during an injection‐molding process. The injection‐molding process showed efficiency in forming dispersions with fibrous shapes, and they could impart the ductile property of PCL to the brittle PLA matrix, with appropriate interfacial adhesion arising from the cocrosslinking structure at the PLA/PCL interface by dicumyl peroxide (DCP). However, the addition of excess DCP caused a split of the dispersions resulting from the compatibility increment and the excess crosslinking reaction at the interface and inside each phase. The addition of a small amount of DCP could adhere the interface without splitting of the dispersions. The observed internal structure in the injection moldings showed a morphology transition that changed gradually from a fine fibrous morphology to a coarse morphology at a deeper position in the injection moldings. The tensile properties of sliced local layers, which were fabricated with a sliding microtome, proved that the fibrous morphology was effective in the improvement of ductility of the blends. An X‐ray analysis showed that the shear flow increased the crystalline orientation and formed a different crystalline structure only in the PCL dispersed phase, but its crystalline structure was not the main factor for ductility improvement. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization behavior of poly(lactic acid)/elastomer blends

Differential Scanning Calorimetry (DSC) was used to evaluate the crystallization behavior of poly(lactic acid) and its blends with elastomer. It has been observed that the cold crystallization temperature of the blends decreased as the weight fraction of elastomer increased as well as the onset temperature of cold crystallization also shifted to lower temperature. In non-isothermal crystallization experiments, the crystallinity of poly(lactic acid) increased with a decrease in the heating and cooling rate. The melt crystallization of poly(lactic acid) appeared in the low cooling rate (1, 5 and 7.5 °C/min). The presence of low elastomer tends also to increase the crystallinity of poly (lactic acid). The DSC thermogram at ramp of 10 °C/min showed the maximum crystallinity of poly(lactic acid) is 36.95% with 20 wt% elastomer contents in blends. In isothermal crystallization, the cold crystallization rate increased with increasing crystallization temperature in the blends. The Avrami analysis showed that the cold crystallization was in two stages process and it was clearly seen at low temperature. The Avrami exponent (n) at first stage was varying from 1.59 to 2 which described a one-dimensional crystallization growth with homogeneous nucleation, whereas at second stage was varying from 2.09 to 2.71 which described the transitional mechanism to three dimensional crystallization growth with heterogeneous nucleation mechanism. The equilibrium melting point of poly(lactic acid) was also evaluated at 176 °C.     

聚乳酸/聚乙二醇共混物的结晶与降解行为

针对聚乳酸（PLLA）亲水性差、降解周期长的问题,利用与亲水性高分子聚乙二醇（PEG）共混的方法对其进行改性。采用转矩流变仪制备了不同组成的PLLA/PEG共混物颗粒,系统研究了PLLA/PEG共混物的结晶和熔融、亲水性和在酸碱介质中的降解行为。结果表明,PEG的加入增强了共混物中PLLA的结晶能力,提高了PLLA在降温过程中的熔融结晶温度。PLLA/PEG共混物在等温结晶中表现出比纯PLLA更快的结晶速度。通过改变PLLA/PEG共混物的组成,可调控材料的表面亲水性和降解速率。随着PEG含量的增多,PLLA/PEG共混物的表面接触角降低。PLLA与PLLA/PEG共混物均可在水溶液中降解,共混物的降解速率高于纯PLLA,随着PEG含量的升高和降解液中酸碱浓度的提高,PLLA/PEG共混物的降解速率加快。     

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     

Properties of linear poly(lactic acid)/polyethylene glycol blends

Poly(lactic acid) (PLA) has great potentials to be processed into films for packaging applications. However, film production is difficult to carry out due to the brittleness and low melt strength of PLA. In this investigation, linear PLA (L‐PLA) was plasticized with poly(ethylene glycol) (PEG) having MW of 1000 g mol^?1 in various PEG concentrations (0, 5, 10, 15, and 20 wt%). In relation to plasticizer content, the impact resistance and crystallinity of L‐PLA was increased, whereas a decrease in glass transition temperature and lower stiffness was observed. Nevertheless, the phase separation has been found in samples which contained PEG greater than 10 wt%. The dynamic and shear rheological studies showed that the plasticized PLA possessed lower viscosity and more pronounced elastic properties than that of pure PLA. Both storage and loss moduli decreased with PEG loading at all frequencies while storage modulus exhibited weak frequency dependence with increasing PEG content. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

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。     

聚乳酸/聚乙烯醇纳米纤维的制备及结构

以二甲基亚砜为溶剂,制备不同配比的聚乳酸(PLLA)和聚乙烯醇(PVA)的混合溶液,静电纺丝制得PLLA/PVA纳米纤维。采用红外光谱仪、原子力显微镜等对PLLA/PVA纳米纤维结构与性能进行了表征。结果表明:PLLA/PVA纳米纤维中PVA上的羟基与PLLA上的羰基形成了氢键,PLLA与PVA之间存在一定的相互作用,但PLLA/PVA纳米纤维存在相分离现象;混合溶液的PLLA质量分数为11%,PVA质量分数为8%时可以得到较好的PLLA/PVA纳米纤维,但PVA质量分数为6%时出现液滴及珠丝,PVA质量分数为4%时,不能制得纳米纤维。     

Hydrolytic degradation of poly(l‐lactic acid)/poly(methyl methacrylate) blends

The hydrolytic degradation of poly(l ‐lactic acid)/poly(methyl methacrylate) (PLLA/PMMA) blends was carried out by the immersion of thin films in buffer solutions (pH = 7.24) in a shaking water bath at 60 °C for 38 days. The PLA/PMMA blends (0/100; 30/70; 50/50; 70/30; 100/0) were obtained by melt blending using a Brabender internal mixer and shaped into thin films of about 150 µm in thickness. Considering that PMMA does not undergo hydrolytic degradation, that of PLLA was followed via evolution of PLA molecular weight (recorded by size exclusion chromatography), thermal parameters (differential scanning calorimetry (DSC)) and morphology of the films (scanning transmission electron microscopy). The results reveal a completely different degradation pathway of the blends depending on the polymethacrylate/polyester weight ratio. DSC data suggest that, during hydrolysis at higher PMMA content, the polyester amorphous chains, more sensitive to water, are degraded before being able to crystallize, while at higher PLLA content, the crystallization is favoured leading to a sample more resistant to hydrolysis. In other words, and quite unexpectedly, increasing the content of water‐sensitive PLLA in the PLLA/PMMA blends does not mean de facto faster hydrolytic degradation of the resulting materials. © 2018 Society of Chemical Industry     

Effect of compounding procedure on mechanical properties and dispersed phase morphology of poly(lactic acid)/polycaprolactone blends containing peroxide

Side feeding technique was applied to poly (lactic acid) (PLA)/polycaprolactone (PCL) blends containing peroxide. Feeding procedures attempted were blanket and split feeding. In the former procedure, all the materials were fed into the main hopper at once. On the other hand, the feeding of materials was split by using main hopper and side feeder in the later procedure. The results indicated that static tensile properties were not dependent on feeding procedure, but the impact strength was superior in the case of the split feeding samples. It is noteworthy that the impact strength of the split feeding sample was considerably affected as it was four times better. Coarse dispersions such as continuous filament and layer dispersions were formed in the blend specimens without peroxide. On the other hand, fine dispersions were formed in the blend specimens containing peroxide which served as compatibilizer in this blend system. Peroxide addition through the side feeder brought about fine dispersions, promoted adhesion at the interface, and increased viscous nature of the PCL phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1066–1074, 2007     

High impact poly(lactic acid)/poly(ethylene octene) blends prepared by reactive blending

Poly(ethylene octene) grafted with glycidyl methacrylate (POE‐g‐GMA) was prepared and used to toughen poly (lactic acid) (PLA) via reactive blending. It was found that the notched Izod impact strength of PLA/POE‐g‐GMA blends improved dramatically when the content of elastomer was higher than 10 wt%. Reactive compatibilization between PLA and POE‐g‐GMA were studied by Fourier transform infrared spectroscopy (FTIR) and “Molau test,” the results showed the end carboxyl groups of PLA reacted with the epoxide groups of POE‐g‐GMA during blending. This considerably improved the compatibilization, leading to better wetting of the dispersed phase by the PLA matrix and finer dispersed POE‐g‐GMA particles with narrow distribution. Moreover, the critical interparticle distance (L_c) of the dispersed domains for PLA/POE‐g‐GMA blends system at room temperature was also identified. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effect of the melt‐mixing condition on the physical property of poly(l‐lactic acid)/poly(d‐lactic acid) blends

The effect of the mixing condition in a mill‐type mixer on the thermal property and the crystal formation of the poly(l ‐lactide)/poly(d ‐lactide) blends is investigated. The blends melt‐mixed at 200 and 210 °C under application of a high shear flow tend to show a single melting peak of the stereocomplex crystal (SC) in the differential scanning calorimetry first and second heating processes without indicating the trace of the melting of homo‐chiral crystal. The mixing at an elevated temperature causes a serious thermal degradation. Further kneading of the blends at an elevated temperature higher than T_m of SC causes the transesterification between the same enatiomeric chains forming block copolymers of l ‐ and d ‐chains. This block copolymer acts as a nucleating agent of SC and the compatibilizing agent between poly(l ‐lactide) and poly(d ‐lactide) and promotes the formation of SC. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45489.     

Effect of organoclay on non-linear rheological properties of poly(lactic acid)/poly(caprolactone) blends

The nonlinear viscoelastic properties of PLA/PCL blends with and without clay (montmorillonite, MMT) under large amplitude oscillatory shear (LAOS) flow were investigated. The G′ and G″ as a function of strain amplitude, Lissajous plots and FT-rheology methods were used to interpret nonlinear behavior of PLA/PCL blends with and without MMT. Additionally, scanning electron microscopy (SEM) images of PLA/PCL with MMT blends were taken to investigate the effects of clay on the internal structure of the PLA/PCL blends. A relationship between morphological changes and linear and nonlinear rheological properties was observed. SEM image analysis revealed that clay acted as a compatibilizer and then reduced the size of droplets in the PCL domain of the PLA matrix. As a result, nonlinear properties sensitively reflect morphological changes with increasing MMT amount. The nonlinear rheological properties of PLA/PCL/MMT/metallocene-LLDPE (mLLDPE) were also investigated when mLLDPE was used as an impact modifier to improve mechanical properties, and the nonlinear rheological properties of PLA/PCL/MMT and PLA/PCL/MMT/mLLDPE were also compared.     

Rheological and mechanical characterization of poly(lactic acid)/polypropylene polymer blends

Poly(lactic acid) (PLA) was melt blended with polypropylene (PP) with the aim of replacing commodity polymers in future applications. Since cost of PLA is quite high, it is not economically feasible to use it alone for day to day use as a packaging material without blending. This paper reports the preparation of poly(lactic acid)/polypropylene polymer blends (PLA/PP) using a laboratory scale single screw extruder. Rheological and mechanical properties of the prepared blends were determined. The rheological experiments were carried out on a capillary rheometer, the effect of shear rate, temperature and PLA content on the flow activation energy and true viscosity of the blends were described. Mechanical properties of the blends were investigated on dog bone-shaped samples obtained by injection molding; tensile tests were performed using Testometric M350-10KN. The effect of PLA content on Young’s modulus, strain at break and stress at break of the blends were described. The rheological results showed that the true viscosity of the blends is between that of the pure polymers, whereas the flow activation energy of the blends is less than that of the pure polymers. The mechanical results showed incompatibility between PLA and PP in the blend.     

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.     

连续挤出发泡聚乳酸泡孔结构的影响因素

介绍了采用超临界CO2作为发泡剂,连续挤出聚乳酸泡沫塑料的方法。在不同的实验条件下,对聚乳酸进行挤出发泡,得到聚乳酸发泡样品。通过对样品的ESM照片的分析研究,得出了不同的发泡条件对挤出聚乳酸泡沫泡孔结构的影响。结果表明螺杆转速的增加使得泡孔数量增加,泡孔形态更加规整均匀。模头温度影响了泡孔形态,较高的温度会使得样品的泡孔形态受到不利的影响。水分的存在不利于聚乳酸发泡成为均匀发泡倍率高的泡沫制品。成核剂促进异相成核,使发泡样品的泡孔结构更加均匀,大大提高了聚乳酸泡沫塑料的泡孔密度。     

Crystallization, hydrolytic degradation, and mechanical properties of poly (trimethylene terephthalate)/poly(lactic acid) blends

Crystallization, melting, hydrolytic degradation, and mechanical properties of poly(trimentylene terephthalate)/poly(lactic acid) (PTT/PLA) blends have been investigated. The blends show a single and composition-dependent glass-transition temperature (T _g) over the entire composition range, implying that these blends are fully miscible in the amorphous state. The observed T _g is found to increase with increasing PLA content and fitted well with the Gordon–Taylor equation, with the fitting parameter k being 0.91. The cold-crystallization peak temperature increases, while the melt-crystallization peak decreases with increasing the PLA content. Both the pure PTT and PTT/PLA blends cannot accomplish the crystallization during the cooling procedure and the recrystallization occurs again on the second heating. Therefore, on the thermogram recorded, there is exothermal peak followed by endothermal peak with a shoulder. However, to pure PLA, no crystallization takes place during cooling from the melt, therefore, no melting endothermic peak is found on the second heating curve. WAXD analysis indicates PLA and PTT components do not co-crystallize and the crystalline phase of the blends is that of their enriched pure component. With increasing PLA content, the hydrolytic degradation of the blend films increases, while both the tensile strength and the elongation at break of the blend films decrease. That is to say, the hydrolytic degradation of the PTT/PLA blends increases with the introduction of PLA at the cost of the decrease of the flexibility of PTT.     

High‐performance biosourced poly(lactic acid)/polyamide 11 blends with controlled salami structure

High‐performance biosourced poly(l ‐lactide) (PLLA)/polyamide 11 (PA11) (55/45) blends with small amounts of rubber, ethylene glycidyl methacrylate‐graft‐styrene‐co‐acrylonitrile (EGMA‐g‐AS), were fabricated by simple melt compounding. Epoxide groups in EGMA‐g‐AS are ready to react with both PA11 and PLLA, and thus EGMA‐g‐AS could be manipulated to locate mainly in either PA11 phase or PLLA phase by variation of the blending sequence. It was found that the blend with salami structure in which EGMA‐g‐AS is predominantly dispersed in the PLLA phase provides not only significantly improved tensile ductility, but also excellent film impact strength, while keeping relatively high modulus. The elongation at break and the film impact strength of such materials with 6 phr EGMA‐g‐AS are 322% and 361 kJ m^?2, which are 78 and 5.2 times those of unmodified PLLA, respectively. In contrast, the blends with EGMA‐g‐AS mainly in the PA11 phase fracture in a brittle mode with low toughness. The toughening mechanism of the PLLA/PA11 blends with the sub‐inclusion salami structure was investigated using a double‐notch technique. The brittle‐to‐tough transition was observed on increasing the rubber sub‐inclusion concentration in the PLLA phase. © 2013 Society of Chemical Industry     

Structural evolution of poly(lactic acid)/poly(ethylene oxide)/unmodified clay upon ambient ageing

Poly(lactic acid) (PLA) and poly(ethylene oxide) (PEO)/unmodified clay masterbatches are compounded together in order to investigate the ambient ageing of the resulting PLA/PEO/clay ternary blends. Binary blends are miscible up to 20 wt PEO% and in ternary counterparts, clay is intercalated at a nanometric scale, similarly to the clay dispersion state in masterbatches. PEO/clay interactions are strong, as confirmed by the lower plasticization of ternary blends. Furthermore, structural modifications occurring over time are evidenced for all blends through the observation of changes in thermal responses. Over the 220‐day observation period, lower plasticized samples undergo physical ageing only whereas blends close to the miscibility limit know a rapid PLA/PEO phase separation without physical ageing. For blends with intermediate PEO concentrations, both phenomena are observed with slower PLA chain mobility transition. Remarkably clay appears to affect both phenomena, ternary blends having limited physical ageing and slower PLA/PEO segregation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40426.