Processability enhancement of poly(lactic acid-co-ethylene terephthalate) by blending with poly(ethylene-co-vinyl acetate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(butylene succinate)

Processability enhancement feasibility of an in-house synthesized poly(lactic acid-co-ethylene terephthalate), PLET, is investigated by blending with commercial poly(ethylene-co-vinyl acetate), EVA, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, and poly(butylene succinate), PBS. The three blend systems are prepared by varying PLET contents, and their properties are characterized. DSC, SEM, and FTIR results indicate that PLET/EVA blends are immiscible, while the corresponding PLET/PBS and PLET/PHBV blends are miscible and partially miscible, respectively. DMA results show that the three blend systems have storage modulus comparable to those of commercial EVA, PHBV, and PBS, when PLET content is kept lower than 50, 25, and 25 wt%, respectively. PLET/EVA blends show higher thermal stability, compared to those of the other two blend systems. Results on degradability tests indicate that PLET/PBS blends show highest hydrolytic degradability, compared to the other two blends, as both blend constituents are associated in the hydrolytic degradation.     

Single- and double-ring spherulites in poly(nonamethylene terephthalate)

A new mechanism of formation of ring-banded spherulites was discovered, where three different types of spherulites were present in poly(nonamethylene terephthalate) (PNT) cast in thin film forms. The growth and morphological features in three ring-banded spherulites were compared and analyzed using polarized/non-polarized light microscopy, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) and element analysis by energy dispersive spectroscopy (EDS) on surfaces of spherulites. Three types of spherulites (labeled: Type-0, 1, and 2) are possible in PNT when crystallized at wide range of crystallization temperature (T_c); however, only two of the three types can co-exist in PNT at a given T_c. At lower T_c (<55 °C), within Regime-III, the spherulites in PNT are either of Type-0 (appearing ringless in POM) or Type-2 (double-band in POM). When crystallized at temperature of T_c = 55 °C or higher (Regime-II), the morphology is featured with Type-1 (single-ring-banded in POM) spherulites as the majority species that co-exist with Type-2 (double-ring-banded in POM) spherulites as imbedded minority. Origins and morphological differences of the single-band vs. double-band spherulites were compared. The double-band spherulites have much larger inter-ring spacing than do the single-band spherulites. By comparison, the rod-like lamellae in the double-banded spherulites (Type-2) are longer and thicker, and more ordered than those in the single-banded spherulites (Type-1).     

Segregation morphology of poly(3-hydroxybutyrate)/poly(vinyl acetate) and poly(3-hydroxybutyrate-co-10% 3-hydroxyvalerate)/poly(vinyl acetate) blends as studied via small angle X-ray scattering

Segregation morphology of poly(3-hydroxybutyrate) (PHB)/poly(vinyl acetate) (PVAc) and poly(3-hydroxybutyrate-co-10% 3-hydroxyvalerate) (P(HB-co-10% HV)/PVAc blends crystallized at 70 °C have been investigated by means of small angle X-ray scattering (SAXS). Morphological parameters including the crystal thickness (l_c) and the amorphous layer thickness (l_a) were deduced from the one-dimensional correlation function (γ(z)). Blending with PVAc thickened the PHB crystals but not the P(HB-co-10% HV) crystals. On the basis of the composition variation of l_a, and the volume fraction of lamellar stacks (?_s) revealed that PHB/PVAc blends created the interlamellar segregation morphology when the weight fraction of PVAc (w_PVAc)≤0.2 and the interlamellar and interfibrillar segregation coexisted when w_PVAc>0.2, while P(HB-co-10% HV)/PVAc blends yielded the interfibrillar segregation morphology at all blend compositions. For both PHB/PVAc and P(HB-co-10% HV)/PVAc blends, the distance of PVAc segregation was promoted by increasing PVAc composition and the distance of PVAc segregation in P(HB-co-10% HV)/PVAc blends was greater than in PHB/PVAc at a given PVAc composition. The crystal growth rate played a key role in controlling the segregation of PVAc.     

Effect of poly(propylene carbonate) on the crystallization and melting behavior of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)

The crystallization and melting behavior of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) and a 30/70 (w/w) PHBV/poly(propylene carbonate) (PPC) blend was investigated with differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR). The transesterification reaction between PHBV and PPC was detected in the melt‐blending process. The interaction between the two macromolecules was confirmed by means of FTIR analysis. During the crystallization process from the melt, the crystallization temperature of the PHBV/PPC blend decreased about 8°C, the melting temperature was depressed by 4°C, and the degree of crystallinity of PHBV in the blend decreased about 9.4%; this was calculated through a comparison of the DSC heating traces for the blend and pure PHBV. These results indicated that imperfect crystals of PHBV formed, crystallization was inhibited, and the crystallization ability of PHBV was weakened in the blend. The equilibrium melting temperatures of PHBV and the 30/70 PHBV/PPC blend isothermally crystallized were 187.1 and 179°C, respectively. The isothermal crystallization kinetics were also studied. The fold surface free energy of the developing crystals of PHBV isothermally crystallized from the melt decreased; however, a depression in the relative degree of crystallization, a reduction of the linear growth rate of the spherulites, and decreases in the equilibrium melting temperature and crystallization capability of PHBV were detected with the addition of PPC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2514–2521, 2004     

Formation of ring-banded spherulites of α and β modifications in Poly(butylene adipate)

The morphology and crystalline structure of banded spherulites of poly(butylene adipate) (PBA) were investigated by polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), atomic force microscopy (AFM) and scanning electronic microscopy (SEM). It was found that after purification and fractionation, the obtained PBA fractions with different molecular weight formed ring-banded spherulites at different temperature ranges. Pure α and β form of PBA can form regular ring-banded spherulites. AFM and SEM observations of the thin film revealed that the alternative ridges and valleys along the radial direction consisted of edge-on and flat-on lamellae, respectively, indicating the ring-bands in PBA spherulites are the consequence of lamellar twisting. In addition, sequential growth of α and β form in one PBA spherulite at the same temperature is reported and interpreted by competition of primary nucleation and radial growth of the two crystalline modifications. At a certain temperature range, the α form PBA has larger primary nucleation rate but lower radial growth rate than the β form PBA, leading to formation of spherulites consisted of α form at center and β form at the outer region. But finally, a layer of α form ringless region appears at the outside of the β form ring-banded region before impingement of the neighboring spherulites. These results suggest that besides crystallization temperature, molecular weight has considerable effect on the formation of crystal modification of PBA and the corresponding banded spherulites.     

Thermal properties of blends comprising poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate) and epoxidized natural rubber

Blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with 12 mol% hydroxyvalerate (HV) content and epoxidized natural rubber (ENR) with 50 mol% epoxidation level were studied along with the thermal properties and morphologies. Glass transition temperatures reveal immiscibility of the polymers over the entire composition range. The equilibrium melting point (T _m⁰) of PHBV in blends was determined applying Hoffman–Weeks step-wise annealing procedure. There is no significant variation of T _m⁰ for PHBV with blend composition. Also the crystallinity of PHBV stays approximately constant in the blends, only a slight decrease might be recognized with increasing ENR content. The rate of crystallization of PHBV decreases with PHBV content according to a power law. Morphological studies by polarizing optical microscopy reveal a fine intraspherulitic dispersion of ENR in volume-filling PHBV spherulites, which develop during isothermal crystallization.     

Effects of molten poly(3-hydroxybutyrate) on crystalline morphology in stereocomplex of poly(L-lactic acid) with poly(D-lactic acid)

Effects of poly(3-hydroxybutyrate) (PHB) on crystalline morphology of stereocomplexing capacity of poly(L- and D-lactic acid) (PLLA and PDLA) were studied by differential scanning calorimetry (DSC), polarizing-light optical microscopy (POM), atomic-force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). When crystallized at high T_c (130 °C or above), morphology transition of stereocomplexed PLA (sc-PLA) occurs from original well-rounded Maltese-cross spherulites to dendritic form in blends of high PHB contents (50 wt.% or higher), where PHB acts as an amorphous species. Microscopy characterizations show that morphology of sc-PLA in PHB/sc-PLA blends crystallized at T_c = 170 °C no longer retain original complexed Maltese-cross well-rounded spherulites; instead, the spherulites are disintegrated and restructured into two types of dendrites: (1) edge-on feather-like dendrites (early growth) and (2) flat-on wedge-like crystal plates (later growth) by growing along different directions and exhibiting different optical brightness. The concentration and/or distribution of amorphous PHB at the crystal growth front, corresponding to variation of the slopes of spherulitic growth rates, is a factor resulting in alteration and restructuring of the sc-PLA spherulites in the blends. Despite of spherulite disintegration, WAXD result shows that these two PHB-induced dendrites still retain the original unit cells of complexes, and thus these two new dendrites are sc-PLA.     

Miscibility of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) with high molecular weight poly(lactic acid) blends determined by thermal analysis

An important strategy used in the polymer industry in recent years is blending two bio‐based polymers to attain desirable properties similar to traditional thermoplastics, thus increasing the application potential for bio‐based and bio‐degradable polymers. Miscibility of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) with poly(L ‐lactic acid) (PLA) were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Three different grades of commercially available PLAs and one type of PHBV were blended in different ratios of 50/50, 60/40, 70/30, and 80/20 (PHBV/PLA) using a micro‐compounder at 175°C. The DSC and TGA analysis showed the blends were immiscible due to different stereo configuration of PLA polymer and two distinct melting temperatures. However, some compatibility between PHBV and PLA polymers was observed due to decreases in PLA's glass transition temperatures. Additionally, the blends do not show clear separation by SEM analysis, as observed in the thermal analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structural and morphological development in poly(ethylene-co-hexene) and poly(ethylene-co-butylene) blends due to the competition between liquid-liquid phase separation and crystallization

Isothermal crystallization behavior of poly(ethylene-co-hexene) (PEH) and the 50/50 blend (H50) of PEH with amorphous poly(ethylene-co-butylene) (PEB) was studied by time-resolved synchrotron simultaneous small-angle X-ray scattering/wide-angle X-ray diffraction (SAXS/WAXD) techniques and optical microscopy (OM). The X-ray study revealed the changes of structural and morphological variables such as the scattering invariant, crystallinity and lamellar long period, et al. In H50, the lamellar morphology was found to be dependent on competition between liquid-liquid phase separation (LLPS) and crystallization. At high temperature, LLPS becomes dominating, resulted in crystallization of PEH with minimal influence of PEB. At low temperature, LLPS is suppressed, PEB component shows obvious influence on PEH crystallization, PEB is thought to be partially included into PEH lamellar stacks and PEH-PEB co-crystallization is unlikely, however, possible. Optical microscopy was used to monitor crystal nucleation and growth rates in PEH and H50, providing complementary information about the effect of temperature on LLPS and crystallization. Real-space lamellar morphologies in PEH and H50 were characterized by atomic force microscopy (AFM), PEH exhibited sheaf-like spherulites while H50 exhibited hedrites. Overall, the competition between LLPS and crystallization in H50 blend influences the structural and morphological development. Controlling the interplay between LLPS and crystallization of PEH/PEB blends, it is possible to control the structure and morphology as practically needed.     

Observation of banded spherulites in pure poly(l-lactide) and its miscible blends with amorphous polymers

Banded spherulites of pure poly(l-lactide) (PLLA) were observed via the ‘crystallization after annealing’ procedure, while only common spherulites were obtained via the ‘direct isothermal crystallization’ procedure. Wide angle X-ray diffraction revealed that the two types of spherulites had the same crystal lattice of α-modification. Atomic force microscopy demonstrated that the alternative negative and positive birefringent bands resulted from the alternative edge-on and flat-on lamellar orientations in the spherulites. Furthermore, the effect of thermal history on the spherulitic morphology was investigated in details. The PLLA samples melted for longer time or those with lower melting point were more likely to form banded spherulites. The possibility that the change of molecular weight was a determining factor of banding was excluded by the results on differently prepared samples with the same molecular weight. Therefore, we conclude that it was complete melting of the crystalline residues that favored formation of PLLA banded spherulites. Blending of PLLA with atactic poly(d,l-lactide) or poly[(R,S)-3-hydroxybutyrate], led to reduced band spacing. Effect of blending on the chain mobility, spherulite growth kinetics, supercooling and lamellar surface energy was quantitatively studied, which suggests that the blending-reduced band spacing cannot be attributed to the above factors. Therefore, there are other blending-relevant factors leading to the reduced band spacing.     

Morphology and properties of renewable poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) blends with thermoplastic polyurethane

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/thermoplastic polyurethane (PHBV/TPU) composites were prepared by solution blending combined with melt processing in an effort to improve the toughness of PHBV and overcome the coalescence phenomena of TPU at the same time. The compatibility, cross‐section morphology, crystal structure, thermal behaviour, and mechanical properties of composites were investigated. Field emission scanning electron microscopy results showed that no distinct interface was found in composites, uniformly dispersed PHBV/TPU composites were obtained. The incorporation of TPU did not change the basic crystalline structure of PHBV, but decreased its crystallinity. What's more, the integrity of PHBV spherulites structure was destroyed and the radial growth rate of spherulites was inhibited. Differential scanning calorimetry results analyzed by Jeziorny method indicated that the nucleation mode of composites did not change. Besides, when TPU content was up to 40 wt%, the initial degradation temperature of PHBV/TPU composite was increased by 5°C, and the elongation‐at‐break was increased by 225% compared with those of PHBV. POLYM. ENG. SCI., 54:1113–1119, 2014. © 2013 Society of Plastics Engineers     

Control and development of crystallinity and morphology in poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)/poly(propylene carbonate) blends

Two different methodologies (reactive blending and mechanical blending) for preparing blends of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) and poly(propylene carbonate) (PPC) were used. The miscibility, chemical structure, thermal behavior, crystallinity, morphology, and mechanical properties of the blends were investigated with Fourier transform infrared spectroscopy, differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and tensile tests. A certain extent of hydrogen‐bonding interactions between PHBV and PPC took place in the blends. The graft copolymerization was confirmed in the reactive system. The incorporation of PPC hampered the crystallization process of PHBV and evidently altered the morphology, and the effect was enhanced in the reactive blend. The mechanical properties of PHBV could be changed by 1–2 orders of magnitude by blending modification. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1427–1436, 2005     

Miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/poly(vinyl acetate) blends

The miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (P(HB‐co‐HV))/poly(vinyl acetate) (PVAc) blends have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that P(HB‐co‐HV)/PVAc blends were miscible in the melt over the whole compositions. Thus the blend exhibited a single glass transition temperature (T_g), which increased with increasing PVAc composition. The spherulitic morphologies of P(HB‐co‐HV)/PVAc blends indicated that the PVAc was predominantly segregated into P(HB‐co‐HV) interlamellar or interfibrillar regions during P(HB‐co‐HV) crystallization because of the volume‐filled spherulites. As to the crystallization kinetics study, it was found that the overall crystallization and crystal growth rates decreased with the addition of PVAc. The kinetics retardation was primarily attributed to the reduction of chain mobility and dilution of P(HB‐co‐HV) upon mixing with higher T_g PVAc. The overall crystallization rate was predominantly governed by the spherulitic growth rate and promoted by the samples treated with the quenched state because of the higher nucleation density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 980–988, 2006     

Effect of cholesteryl additive on poly(ethyl methacrylated)–poly(vinyl acetate) blend

Three different compositions (9 : 1, 7 : 3, and 1 : 1) of poly(ethyl methacrylate) (PEMA) and poly(vinyl acetate) (PVAc) are chosen to check the miscibility of a polymer pair. The 9 : 1 and 7 : 3 PEMA-PVAc blends are immiscible and have shown two distinct loss peaks in dynamic mechanical analysis (DMA) studies, while 1 : 1 PEMA-PVAc has shown a single loss peak. Immiscible composition 7 : 3 PEMA-PVAc is selected to study the effect of cholesteryl additives on the miscibility of the polymers. The additives chosen for the present studies are cholesteryl chloride, cholesteryl caprylate, and cholesteryl laurate. The DMA studies showed that all the additives caused a merging of the two loss peaks into one. X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) studies of the blend and blend with additive samples are utilized to get further information. The FTIR studies do not show any detectable change. The SEM micrographs of the blend and cholesteryl additive systems show a single-phase ordered structure, and XRD data studies indicate the presence of small crystallites.     

Spherulitic morphology and growth of poly(vinylidene fluoride)/poly(3-hydroxybutyrate-co-hydroxyvalerate) blends by optical microscopy

Poly(vinylidene fluoride) (PVDF) and poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV), both semicrystalline polymers, are miscible as shown by the single glass transition temperature over the entire composition range. Morphology of PVDF/PHBV blends was investigated by optical microscopy under two different crystallization conditions. PVDF showed the spherulitic morphology at 150 °C in the PVDF/PHBV blends, where PHBV acted as the noncrystallizing component. PHBV also showed the spherulitic morphology within the matrix of the pre-existing PVDF crystals when PVDF/PHBV blends were quenched from the melt to the crystallization temperature below the melting point of PHBV. The spherulitic growth of PHBV was investigated as the function of both blend composition and crystallization temperature.     

Amorphous phase and crystalline morphology in blend of two polymorphic polyesters: Poly(hexamethylene terephthalate) and poly(heptamethylene terephthalate)

Crystalline/crystalline blends of two polymorphic aryl-polyesters, poly(hexamethylene terephthalate) (PHT) and poly(heptamethylene terephthalate) (PHepT), were prepared and the crystallization kinetics, polymorphism behavior, spherulite morphology, and miscibility in this blend system were probed using polarized-light optical microscopy (POM), differential scanning calorimetry (DSC), temperature-resolved wide-angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS). The PHT/PHepT blends of all compositions were proven to be miscible in the melt state or quenched amorphous glassy phase. Miscibility in PHT/PHepT blend leads to the retardation in the crystallization rate of PHT; however, that of PHepT increases, being attributed to the nucleation effects of PHT crystals which are produced before the growth of PHepT crystals. In the miscible blend of polymorphic PHT with polymorphic PHepT, the polymorphism states of both PHT and PHepT in the blend are influenced by the other component. The fraction of the thermodynamically stable β-crystal of PHT in the blend increases with increasing PHepT content when melt-crystallized at 100 °C. In addition, when blended with PHT, the crystal stability of PHepT is altered and leads to that the originally polymorphic PHepT exhibits only the β-crystal when melt-crystallized at all T_c's. Apart from the noted polymorphism behavior, miscibility in the blend also shows great influence on the spherulite morphology of PHT crystallized at 100 °C, in which the dendritic morphology corresponding to the β-crystal of PHT changes to the ring-banded in the blend with higher than 50 wt% PHepT. In blends of PHT/PHepT one-step crystallized at 60 °C, PHepT is located in both PHT interlamellar and interfibrillar region analyzed using SAXS, which further manifests the miscibility between PHT and PHepT.     

Crystallization behavior of PEO in blends of poly(ethylene oxide)/poly(2‐vinyl pyridine)‐b‐(ethylene oxide) block copolymer

The crystallization behavior of two molecular weight poly(ethylene oxide)s (PEO) and their blends with the block copolymer poly(2‐vinyl pyridine)‐b‐poly(ethylene oxide) (P2VP‐b‐PEO) was investigated by polarized optical microscopy, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy (AFM). A sharp decreasing of the spherulite growth rate was observed with the increasing of the copolymer content in the blend. The addition of P2VP‐b‐PEO to PEO increases the degradation temperature becoming the thermal stability of the blend very similar to that of the block copolymer P2VP‐b‐PEO. Glass transition temperatures, T_g, for PEO/P2VP‐b‐PEO blends were intermediate between those of the pure components and the value increased as the content of PEO homopolymer decreased in the blend. AFM images showed spherulites with lamellar crystal morphology for the homopolymer PEO. Lamellar crystal morphology with sheaf‐like lamellar arrangement was observed for 80 wt% PEO(200M) and a lamellar crystal morphology with grain aggregation was observed for 50 and 20 wt% blends. The isothermal crystallization kinetics of PEO was progressively retarded as the copolymer content in the blend increased, since the copolymer hinders the molecular mobility in the miscible amorphous phase. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Miscibility and crystallization behavior of poly(3‐hydroxyvalerate‐co‐3‐hydroxyvalerate)/ poly(propylene carbonate) blends

Blends of synthetic poly(propylene carbonate) (PPC) with a natural bacterial copolymer of 3‐hydroxybutyrate with 3‐hydroxyvalerate (PHBV) containing 8 mol % 3‐hydroxyvalerate units were prepared with a simple casting procedure. PPC was thermally stabilized by end‐capping before use. The miscibility, morphology, and crystallization behavior of the blends were investigated by differential scanning calorimetry, polarized optical microscopy, wide‐angle X‐ray diffraction (WAXD), and small‐angle X‐ray scattering (SAXS). PHBV/PPC blends showed weak miscibility in the melt, but the miscibility was very low. The effect of PPC on the crystallization of PHBV was evident. The addition of PPC decreased the rate of spherulite growth of PHBV, and with increasing PPC content in the PHBV/PPC blends, the PHBV spherulites became more and more open. However, the crystalline structure of PHBV did not change with increasing PPC in the PHBV/PPC blends, as shown from WAXD analysis. The long period obtained from SAXS showed a small increase with the addition of PPC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4054–4060, 2003     

Melting point depression in poly(ɛ-caprolactone) / poly(styrene-co-acrylonitrile) blends

Summary The melting point depression of poly(-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends with changes in acrylonitrile content of SAN and in blend ratio was investigated by differential scanning calorimetry. For the melting points at a constant blend ratio occur a minimum in dependence on the copolymer composition for blends containing about 20 wt% acrylonitrile in SAN. From melting point depression data a negative, binary interaction parameter was obtained for PCL/SAN blends containing a SAN with 19.2 wt% AN. By optical microscopy it can be shown that the shape of the spherulites changes with copolymer composition of SAN and blend ratio.     

Crystallization behavior and mechanical properties of poly(ethylene oxide)/poly(L‐lactide)/poly(vinyl acetate) blends

Poly(vinyl acetate) (PVAc) was added to the crystalline blends of poly(ethylene oxide) (PEO) and poly(L ‐lactide) (PLLA) (40/60) of higher molecular weights, whereas diblock and triblock poly(ethylene glycol)–poly(L ‐lactide) copolymers were added to the same blend of moderate molecular weights. The crystallization rate of PLLA of the blend containing PVAc was reduced, as evidenced by X‐ray diffraction measurement. A ringed spherulite morphology of PLLA was observed in the PEO/PLLA/PVAc blend, attributed to the presence of twisted lamellae, and the morphology was affected by the amount of PVAc. A steady increase in the elongation at break in the solution blend with an increase in the PVAc content was observed. The melting behavior of PLLA and PEO in the PEO/PLLA/block copolymer blends was not greatly affected by the block copolymer, and the average size of the dispersed PEO domain was not significantly changed by the block copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3618–3626, 2001