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1.
In this study binary and ternary blends of polylactide (PLA), polycaprolactone (PCL) and thermoplastic starch (TPS) are prepared using a one-step extrusion process and the morphology, rheology and physical properties are examined. The morphology and quantitative image analysis of the 50/50 PLA/TPS blend transverse phase size demonstrate a bimodal distribution and the addition of PCL to form a ternary blend results in a substantial number of fine dispersed particles present in the system. Focused ion beam irradiation, followed by atomic force microscopy (AFM) shows that dispersed PCL forms particles with a size of 370 nm in PLA. The TPS phase in the ternary blends shows some low level coalescence after a subsequent shaping operation. Dynamic mechanical analysis indicates that the temperature of the tan δ peak for the PLA is independent of TPS blend composition and that the addition of PCL in the ternary blend has little influence on the blend transitions. Both the α and β transitions for the thermoplastic starch are highly sensitive to glycerol content. When TPS of high glycerol content is blended with PLA, an increase in the ductility of the samples is achieved and this effect increases with increasing volume fraction of TPS. The ternary blend results in an even greater ductility with an elongation at break of 55% as compared to 5% for the pure PLA. A substantial increase in the notched Izod impact energy is also observed with some blends demonstrating three times the impact energy of pure PLA. The mechanical properties for the ternary blend clearly indicate a synergistic effect that exceeds the results obtained for any of the binary pairs. Overall, the ternary blend approach with PLA/TPS/PCL is an interesting technique to expand the property range of PLA materials.  相似文献   

2.
Poly(lactic acid)/poly(ε‐caprolactone)/organically modified montmorillonite (PLA/PCL/OMMT) nanocomposites were melt‐processed in a twin‐screw extruder under high shear conditions. As a result of the processing conditions employed, the OMMT layers located in the less compatible PCL phase in all the ternary nanocomposites. The morphology of the PLA/PCL blend evolved from “sea‐island” to co‐continuous upon the addition of OMMT. Both the X‐ray diffraction (XRD) and viscoelastic characterization suggested similar OMMT dispersion in the reference PLA binary and in the PLA/PCL ternary nanocomposites, regardless of its location in the PLA and PCL phase, respectively. The reinforcing effect of the organoclay was also similar. The addition of OMMT to the PLA/PCL blend fully compensated the loss in stiffness and oxygen barrier performance produced by PCL in PLA; the nanocomposite with 3% OMMT showed the same modulus and permeability values as those of pure PLA. Moreover, the ductile behavior (elongation at break > 80%) of the PLA/PCL blend remained constant even in the nanocomposite containing 5% OMMT. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43815.  相似文献   

3.
Poly(lactic acid)/poly(?‐caprolactone)/carbon nanotube (PLA/PCL/CNT) nanocomposites (NCs) were melt‐processed in a conventional industrial‐like twin‐screw extruder maintaining a constant PLA/PCL 80/20 wt. ratio. CNTs located in the thermodynamically favored PCL phase and, as a result, the “sea–island” morphology of the unfilled blend was replaced by a more continuous PCL dispersed phase in the ternary NCs. Rheological and electrical percolation took place at the same CNT contents (over 1.2 wt %) that TEM images suggest continuity of the PCL phase. The electrical and the low‐strain mechanical behaviors upon CNT addition were similar in the reference binary PLA/CNT and ternary PLA/PCL/CNT NCs. In the percolated NCs, the conductivity became 106–107 times higher than in the insulating compositions, while the Young modulus increased linearly upon the addition of CNT (12% increase at 4.9 wt % loading). Moreover, all the PLA/PCL/CNT NCs showed a ductile behavior (elongation at break >130%) similar to that of the unfilled PLA/PCL blend (140%), in contrast to the brittle behavior of binary PLA/CNT NCs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45265.  相似文献   

4.
在聚乳酸(PLA)中添加不同含量的聚己内酯(PCL)和滑石粉,同时添加增容剂柠檬酸三丁酯(TBC),通过熔融共混制备一系列PLA/PCL/滑石粉复合材料。主要研究了PCL、滑石粉以及TBC对PLA力学性能和结晶性能的影响。结果表明,PCL提高了PLA的韧性,但降低了强度,滑石粉主要起到了增强作用,但降低了PLA韧性,而将两者共同添加到PLA中可以起到一定的增强增韧作用,其异相成核作用也提高了PLA的结晶度。增容剂TBC的加入,改善了PLA和PCL的相容性,提高PCL的增韧效果以及复合材料的结晶度,但略微降低了PLA的拉伸强度。当PCL和滑石粉质量分数均为10%且加入0.5份的TBC后,PLA/PCL/滑石粉复合材料的断裂伸长率、拉伸强度、结晶度分别为13.3%,61.6 MPa,43.0%,相比纯PLA分别提高了533%,2%,73.4%。  相似文献   

5.
Poly(lactic acid) (PLA) blended with poly(ε‐caprolactone) (PCL) was prepared with various reactive processing agents. Four isocyanates‐lysine triisocyanate (LTI); lysine diisocyanate (LDI); 1,3,5‐tris(6‐isocyanatohexyl)‐1,3,5‐triazinane‐2,4,6‐trione (Duranate TPA‐100); 1,3,5‐tris(6‐isocyanatohexyl)biuret (Duranate 24A‐100)‐and an industrial epoxide‐trimethylolpropane triglycidyl ether (Epiclon 725)‐were used as reactive processing agents. PLA/PCL blended in the presence of LTI had the highest torque in a mixer test. The test specimens were prepared by injection molding. The mechanical properties, thermal properties, molecular weight, melt viscosity, phase behavior, and morphology were investigated using tensile strength, impact strength, differential scanning calorimetry, melt mass‐flow rate measurements, capillary rheometery, gel permeation chromatography, laser scanning confocal microscopy (LSCM), and visco‐elasticity atomic force microscopy (VE‐AFM). The impact strength increased considerably at 20 wt% PCL. The nominal tensile strain of PLA/PCL blended with LTI increased by 270%. The MFR values of PLA/PCL blends decreased with increasing LTI. Similar results were observed for shear viscosity. LSCM measurements showed that the diameters of PCL were dispersed about 0.4 μm in the presence of LTI. VE‐AFM showed that spherical particles with diameters of 50 nm were PCL‐rich domain. These results indicate that isocyanate groups of LTI react with both terminal hydroxyl or carboxyl groups of polymers, and the compatibility of PLA/PCL blends improves with LTI by reactive processing. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers  相似文献   

6.
The influence of talc loading on phase morphology of PLA/PCL/talc composites and improvement in resulting properties are reported. Talc‐based composites of PLA/PCL blends were prepared by melt blending. SEM analysis demonstrates that PLA appears as discrete domain phase, while PCL acts as a bulk phase in the blend. Talc addition decreases PLA domain sizes and voids in the matrix. This results in significant improvement of oxygen and water vapor barrier properties of composite by 33 and 25%, respectively, at 3 wt.‐% talc loading. DSC shows that talc acted as nucleating agent for PCL phase in the composite and improves its crystallinity. Various theoretical models based on dispersion and filler geometry are used to predict the tensile modulus and oxygen permeability.

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7.
The effects of stereo‐regularity and molecular weight of poly(lactic acid) (PLA) on ternary polymer blends was analyzed using optical clarity as the primary screening method. This enabled the ready identification of phase boundaries of optically clear and apparently miscible regions. Solvent‐mediated blends of amorphous poly(dl ‐lactide) (PDLLA) and semi‐crystalline poly(l ‐lactide) (PLLA) with various molecular weights from high to low, along with polycaprolactone (PCL) and cellulose acetate butyrate (CAB) were used in this study. The nature and extent of crystallinity of the blends was examined by X‐ray diffraction, which, in conjunction with differential scanning calorimetry, scanning electron microscopy, and Fourier transform infrared spectroscopy, provided information about the competition between polymer crystallization (self‐aggregating behavior) and intermixing of the macromolecules. Thus, allowing the primary physical cause of transparency loss to be identified. The results of the ternary blends optical clarity showed the position of the phase boundaries in PLLA/PCL/CAB and PDLLA/PCL/CAB blends are significantly affected by the stereo‐regularity and molecular weight of PLA. The PDLLA (amorphous) blend shows comparable regions of phase separation with high molecular weight and semi‐crystalline PLLA blends even though the molecular weight is much lower. The blends of the shorter chain PLLA1 tend to show more crystalline regions. The optical transparency, miscibility, and crystallinity of the blends are not only affected by the stereo‐regularity and molecular weight of PLA but also the crystallizable PCL, especially at high loading. These findings give useful information to the film‐packaging sector where good optical clarity is a critical performance requirement. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41780.  相似文献   

8.
An experimental study of binary and ternary phase equilibrium in the system polycaprolactone (PCL) poly(vi-nylchloride) (PVC)-77/23 styrene-acrylonitrile copolymer (SAN) is described. Miscibility is determined using differential scanning calorimetry (DSC) and turbidity. PCL/PVC and PCL/SAN are largely miscible systems but PVC/SAN is immiscible. The ternary system shows considerable miscibility. The blends are characterized by polarized light microscopy and wide-angle X-ray diffraction. The former measurement characterizes the structure of the spherulites. Additions of PVC, SAN, or PVC/SAN causes the spherulites observed in PCL to grow in size and become coarse. X-ray diffraction shows no movement of crystallographic peaks indicating the crystallographic unit cell is composed of PCL. Melting point depression measurements are used to calculate Flory χ interaction parameters for PCL/PVC and PCL/SAN. The melting point depression is also considered and used to investigate PVC/SAN interaction. An effort is made to compute the ternary phase diagram and tie lines.  相似文献   

9.
Ternary blends comprising bisphenol-A polycarbonate (PC), the polyhydroxyether of bisphenol-A (Phenoxy), and poly(ε-caprolactone) (PCL) were found to be generally miscible at PCL levels greater than 60% by weight and to show multiple amorphous phases at lower PCL levels. The melting point depression of PCL in the miscible region of the ternary and in the miscible binary blends with PC and Phenoxy was examined to obtain the enthalpic interaction parameters, Bij, for each of the three binary interactions. The parameters associated with the miscible binary blends were negative, as expected, and indicated that PCL interacts more exothermically with Phenoxy than with PC. The parameter associated with Phenoxy/PC interaction was strongly positive as expected from the complete immiscibility shown by these materials. The interaction parameters were used to calculate the locus of compositions for which the heat of mixing is zero. The locus was found to agree well with the observed boundary between miscible and multiphase behavior in the ternary. This suggests that the phase behavior of ternary blends is largely determined by the same enthalpic considerations known to govern the phase behavior of binary blends.  相似文献   

10.
Optically pure polylactides, poly(L ‐lactide) (PLLA) and poly(D ‐lactide) (PDLA), were blended across the range of compositions with poly(ε‐caprolactone) (PCL) to study their crystallization, morphology, and mechanical behavior. Differential scanning calorimetry and dynamic mechanical analysis (DMA) of the PLA/PCL blends showed two Tgs at positions close to the pure components revealing phase separation. However, a shift in the tan δ peak position by DMA from 64 to 57°C suggests a partial solubility of PCL in the PLA‐rich phase. Scanning electron microscopy reveals phase separation and a transition in the phase morphology from spherical to interconnected domains as the equimolar blend approaches from the outermost compositions. The spherulitic growth of both PLA and PCL in the blends was followed by polarized optical microscopy at 140 and 37°C. From tensile tests at speed of 50 mm/min Young's modulus values between 5.2 and 0.4 GPa, strength values between 56 and 12 MPa, and strain at break values between 1 and 400% were obtained varying the blend composition. The viscoelastic properties (E′ and tan δ) obtained at frequency of 1 Hz by DMA are discussed and are found consistent with composition, phase separation, and crystallization behavior of the blends. POLYM. ENG. SCI., 46:1299–1308, 2006. © 2006 Society of Plastics Engineers  相似文献   

11.
Nanocomposites with enhanced biodegradability and reduced oxygen permeability were fabricated via melt hybridization of organomodified clay and poly (lactic acid) (PLA) as well as a PLA/polycaprolactone (PCL) blend. The nanocomposite microstructure was engineered via interfacial compatibilization with maleated polypropylene (PP‐g‐MA). Effects of the compatibilizer structural parameters and feeding route on the dispersion state of the nanolayers and their partitioning between the PLA and PCL phases were evaluated with X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy. Although highly functionalized PP‐g‐MA with a low molecular weight was shown to be much more effective in the intercalation of PLA and the PLA/PCL blend into the clay gallery spaces, composite samples compatibilized by high‐molecular‐weight PP‐g‐MA with a lower degree of maleation exhibited lower oxygen permeability as well as a higher rate of biodegradation, which indicated the accelerating role of the dispersed nanolayers and their interfaces in the enzymatic degradation of PLA and PLA/PCL matrices. This evidenced a correlation between the nanocomposite structure and rate of biodegradation. The size of the PCL droplets in the PLA matrix was reduced by nanoclay incorporation, and this revealed that the nanolayers were preferentially wetted by PCL in the blend. However, PCL appeared as fine and elongated particles in the microstructure of the PLA/PCL/organoclay hybrids compatibilized by higher molecular weight and less functionalized PP‐g‐MA. All the PLA/organoclay and PLA/PCL/organoclay hybrids compatibilized with high‐molecular‐weight PP‐g‐MA displayed a higher dynamic melt viscosity with more pseudo solid‐like melt rheological responses, and this indicated the formation of a strong network structure by the dispersed clay layers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

12.
Injection molded β-crystalline phase polypropylene (PP) composites containing 5, 10, 20, 30 and 40% (by weight) of talc filler were studied by X-ray diffraction, scanning electron microscopy, static tensile and falling drop weight impact tests. The X-ray diffraction analysis showed that the talc filler suppresses the formation of β-form PP dramatically. As a result, the β-PP composites containing talc content ≥20 wt% consisted mainly of the α-form PP phase. The tensile test showed that the addition of talc filler up to 40 wt% leads to an increase in Young's modulus whereas little effect is observed on the yield strength of composites with the addition of talc up to 30%. This behavior can be attributed to the load bearing effect of talc particles with a platelike structure and to good interfacial bonding exists between the matrix and filler. The impact tests revealed that the critical stain energy release rate (Gc) of the β-PP polymers appears to increase initially with the addition of 5 wt% talc; thereafter it decreases significantly with increasing talc content.  相似文献   

13.
Miscibility, phase diagrams and morphology of poly(ε‐caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA)/poly(styrene‐co‐acrylonitrile) (SAN) ternary blends were investigated by differential scanning calorimetry (DSC), optical microscopy (OM), and scanning electron microscopy (SEM). The miscibility window of PCL/PBzMA/SAN ternary blends is influenced by the acrylonitrile (AN) content in the SAN copolymers. At ambient temperature, the ternary polymer blend is completely miscible within a closed‐loop miscibility window. DSC showed only one glass transition temperature (Tg) for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends; furthermore, OM and SEM results showed that PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 were homogeneous for any composition of the ternary phase diagram. Hence, it demonstrated that miscibility exists for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends, but that the ternary system becomes phase‐separated outside these AN contents. Copyright © 2003 Society of Chemical Industry  相似文献   

14.
采用两种不同分子量的聚(ε-己内酯)(PCL)(粘均分子量60 000和3 000)与聚乳酸(PLA)在175℃下共混10 min制备PLA/PCL共混物。通过动态流变、扫描电子显微镜(SEM)和力学性能等研究了PLA/PCL共混物的结构和性能。动态流变显示,在PCL低含量(质量分数小于15%)时,PCL与PLA是相容的,质量分数为15%时PCL与PLA表现出明显的相分离行为。SEM显示,随着PCL含量的增加,PCL相的尺寸变大;低分子量PCL(L-PCL)的相尺寸明显大于高分子量PCL(H-PCL),而且相形态不是规则的球状。随着PCL含量的增加,共混物的拉伸强度下降,而断裂伸长率增加。当H-PCL质量分数为8.3%时,PLA/H-PCL共混物的断裂伸长率为137.32%。当H-PCL质量分数为15%时,其断裂伸长率高达232.76%。在添加相同含量PCL时,PLA/H-PCL共混物的拉伸强度高于PLA/L-PCL;而PCL质量分数8%时,共混物的断裂伸长率相差不多,当PCL质量分数大于8%时,PLA/H-PCL共混物的断裂伸长率明显比PLA/L-PCL共混物的高。  相似文献   

15.
The morphology development of polypropylene (PP)/polyethylene terephthalate (PET)/styrene‐ethylene‐butylene‐styrene (SEBS) ternary blends and their fibers were studied by means of scanning electron microscopy (SEM) in conjunction with the melt linear viscoelastic measurements. The morphology of the blends was also predicted by using Harkin's spreading coefficient approach. The samples varying in composition with PP as the major phase and PET and SEBS as the minor phases were considered. Although SEM of the binary blends showed matrix‐dispersed type morphology, the ternary blend samples exhibited a morphological feature in which the dispersed phase formed aggregates consisting of both PET and SEBS particles distributed in the PP matrix. The SEM of the blend samples containing 30 and 40 wt % of total dispersed phase showed an agglomerated structure formed between the aggregates. The SEM of the PP/PET binary fiber blends showed long well‐oriented microfibrils of PET whereas in the ternary blends, the microfibrils were found to have lower aspect ratio with a fraction of the SEBS stuck on the microfibril fracture surfaces. These results were attributed to a core‐shell type morphology in which the PET and SEBS formed the core‐shells distributed in the matrix. The melt viscoelastic behavior of the ternary blends containing less than 30 wt % of the total dispersed phase was found to be similar to the matrix and binary blend samples whereas the samples containing 30 and 40 wt % of dispersed phases exhibited a pronounced viscosity upturn and nonterminal storage modulus in low frequency range. These results were found to be in good agreement with the morphological results. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

16.
In this work, stereocomplex‐poly(l ‐ and d ‐lactide) (sc‐PLA) was incorporated into poly(ε‐caprolactone) (PCL) to fabricate a novel biodegradable polymer composite. PCL/sc‐PLA composites were prepared by solution casting at sc‐PLA loadings of 5–30 wt %. Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) demonstrated the formation of the stereocomplex in the blends. DSC and WAXD curves also indicated that the addition of sc‐PLA did not alter the crystal structure of PCL. Rheology and mechanical properties of neat PCL and the PCL/sc‐PLA composites were investigated in detail. Rheological measurements indicated that the composites exhibited evident solid‐like response in the low frequency region as the sc‐PLA loadings reached up to 20 wt %. Moreover, the long‐range motion of PCL chains was highly restrained. Dynamic mechanical analysis showed that the storage modulus (E′) of PCL in the composites was improved and the glass transition temperature values were hardly changed after the addition of sc‐PLA. Tensile tests showed that the Young's modulus, and yield strength of the composites were enhanced by the addition of sc‐PLA while the tensile strength and elongation at break were reduced. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40208.  相似文献   

17.
This study demonstrates and discusses ternary miscibility in a three‐polymer blend system based on balanced binary interactions. A truly miscible ternary blend comprising poly(ε‐caprolactone) (PCL), poly(benzyl methacrylate) (PBzMA), and poly(vinyl methyl ether) (PVME), was discovered and reported. Miscibility with phase homogeneity (excluding the PCL crystalline domain) in a wide composition range has been demonstrated using criteria of thermal transition behavior, cloud point, and microscopy characterization. At ambient temperature, the three‐polymer ternary system is completely miscible within the entire composition range (i.e., no immiscibility loop). However, at slightly elevated temperatures above the ambient. phase separation readily occurred in this originally miscible ternary blend. A quite low “lower critical solution temperature” (LCST) near 75°C was found for the ternary blend, which is much lower than any of those for the binary pairs. Balanced interactions with no offsetting Δχ among the three binary pairs were a key factor leading to a ternary miscible system.  相似文献   

18.
Polylactic acid (PLA) has the beneficial properties of good mechanical strength, biodegradability and biocompatibility, and these properties make it suitable for use as an environmentally friendly packaging material. However, its use has been limited by its brittleness and poor stability. In this work, we successfully developed an efficient synthesis scheme to improve the mechanical properties, flexibility and gas barrier properties of PLA‐based polymers. Four different PLA‐based thermoplastic polyurethane (PLAPU) polymers were synthesized through the reaction of PLA diol with hexamethylene diisocyanate, followed by chain extension with polycaprolactone (PCL) diol. The relative compositions of the hard PLA and the soft PCL diols in the PLAPU polymers were controlled systematically to optimize the physical properties of the polymers. For example, increasing the content of PCL resulted in higher molecular weight PLAPU polymers that had increased tensile strengths and elongations at break, but their moduli were decreased. At the optimized PLA:PCL ratio of 1:3, the PLAPU polymer had an excellent elongation at break of 1053% with a relatively high Young's modulus of 51.8 MPa. In addition, the gas barrier properties of the PLAPUs were significantly enhanced depending on the molecular weight and PCL content of the polymers. To demonstrate the feasibility of using PLAPU polymers for biodegradable packaging materials, hydrolytic degradation tests were performed in phosphate buffer solution, and the PLAPU polymers were degraded gradually at rates that depended on the content of PCL in the polymers. This optimized PLAPU polymer exhibited excellent flexibility and gas barrier property, as well as high elongation, demonstrating its potential utility as packaging materials. © 2013 Society of Chemical Industry  相似文献   

19.
Important information concerning polymer's final fate in the environment can be achieved in biodegradation studies. In this context, the focus of this study was to evaluate the biodegradability of blends containing aliphatic polyesters using standard methods. Blends of high‐density polyethylene, biodegradable polymer, and polyethylene modified with maleic anhydride (used as compatibilizer) were prepared in a corotating twin‐screw extruder. Biodegradable polymers used were poly(lactic acid) (PLA), poly(ε‐caprolactone) (PCL), and Mater‐Bi (thermoplastic starch with PLA or PCL). Biodegradation tests were carried out using two standard methods: (i) ISO 14851 (1999), biochemical oxygen demand in a closed respirometer and (ii) ASTM G 22‐76, microbial growth of test microorganisms. Both biodegradability tests suggested that the blend containing PCL is more biodegradable than the one containing PLA. Addition of starch increased the biodegradability of the PLA blend. The biodegradability of the blends evaluated in this study by the biochemical oxygen demand method ranged from 22% (PLA 60) to 52% for corn starch/PCL 30/70 (% wt) (SPCL 70). Therefore, the blends may not be considered “readily biodegradable” according to the OECD standard. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

20.
The specific interactions between several low‐molecular‐weight diamino compounds and poly(ε‐caprolactone) (PCL) have been investigated by FT‐IR. It was found that PCL and 3,3′‐diaminodiphenylmethane (3,3′‐DADPM) interact through strong intermolecular hydrogen bonds in the blend. Thermal and mechanical properties of PCL/3,3′‐DADPM blends were investigated by DSC and tensile measurements, respectively. The glass transition temperature of the blend increases while both the melting point and the elongation‐at‐break of the blend decrease with the increase of 3,3′‐DADPM content. Besides 3,3′‐DADPM, several other low‐molecular‐weight compounds containing two amino groups, such as o‐phenylenediamine or 1,6‐diaminohexane, were also added into PCL and the corresponding blend systems were investigated by FT‐IR and DSC. The effect of the chemical structure of the additives on the properties of PCL is discussed. © 2001 Society of Chemical Industry  相似文献   

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