Confined crystallization morphology of poly(ϵ‐caprolactone) block within poly(ϵ‐caprolactone)–poly(l‐lactide) copolymers

The confined crystallization of poly(?‐caprolactone) (PCL) block in poly(?‐caprolactone)–poly(l ‐lactide) (PCL‐PLLA) copolymers was investigated using differential scanning calorimetry, polarized optical microscopy, scanning electronic microscopy and atomic force microscopy. To study the effect of crystallization and molecular chain motion state of PLLA blocks in PCL‐PLLA copolymers on PCL crystallization morphology, high‐temperature annealing (180 °C) and low‐temperature annealing (80 °C) were applied to treat the samples. It was found that the crystallization morphology of PCL block in PCL‐PLLA copolymers is not only related to the ratio of block components, but also related to the thermal history. After annealing PCL‐PLLA copolymers at 180 °C, the molten PCL blocks are rejected from the front of PLLA crystal growth into the amorphous regions, which will lead to PCL and PLLA blocks exhibiting obvious fractionated crystallization and forming various morphologies depending on the length of PLLA segment. On the contrary, PCL blocks more easily form banded spherulites after PCL‐PLLA copolymers are annealed at 80 °C because the preexisting PLLA crystal template and the dangling amorphous PLLA chains on PCL segments more easily cause unequal stresses at opposite fold surfaces of PCL lamellae during the growth process. Also, it was found that the growth rate of banded spherulites is less than that of classical spherulites and the growth rate of banded spherulites decreases with decreasing band spacing. © 2019 Society of Chemical Industry     

Part 7. Effects of poly(L‐lactide‐co‐ϵ‐caprolactone) on morphology,structure, crystallization,and physical properties of blends of poly(L‐lactide) and poly(ϵ‐caprolactone)

Blended films of poly(L ‐lactide) [ie poly(L ‐lactic acid)] (PLLA) and poly(?‐caprolactone) (PCL) without or mixed with 10 wt% poly(L ‐lactide‐co‐?‐caprolactone) (PLLA‐CL) were prepared by solution‐casting. The effects of PLLA‐CL on the morphology, phase structure, crystallization, and mechanical properties of films have been investigated using polarization optical microscopy, scanning electron microscopy, differential scanning calorimetry and tensile testing. Addition of PLLA‐CL decreased number densities of spherulites in PLLA and PCL films, and improved the observability of spherulites and the smoothness of cross‐section of the PLLA/PCL blend film. The melting temperatures (T_m) of PLLA and PCL in the films remained unchanged upon addition of PLLA‐CL, while the crystallinities of PLLA and PCL increased at PLLA contents [X_PLLA = weight of PLLA/(weight of PLLA and PCL)] of 0.4–0.7 and at most of the X_PLLA values, respectively. The addition of PLLA‐CL improved the tensile strength and the Young modulus of the films at X_PLLA of 0.5–0.8 and of 0–0.1 and 0.5–0.8, respectively, and the elongation at break of the films at all the X_PLLA values. These findings strongly suggest that PLLA‐CL was miscible with PLLA and PCL, and that the dissolved PLLA‐CL in PLLA‐rich and PCL‐rich phases increased the compatibility between these two phases. © 2003 Society of Chemical Industry     

Super‐toughened poly(l‐lactic acid) fabricated via reactive blending and interfacial compatibilization

Super‐toughened poly(l ‐lactic acid) (PLLA) was prepared by reactive blending of PLLA with poly(?‐caprolactone) (PCL), glycerol and 4,4′‐methylenediphenyl diisocyanate. The reactive interfacial compatibility between PLLA and the formed crosslinked polyurethane (CPU) in the PLLA matrix was studied in detail. The morphology and the toughness of the blends can be tuned by changing the CPU content. The results indicate that the impact strength of PLLA shows a tendency to higher values with the increasing PCL content up to 20 wt%. The notched impact strength of the blend with 20 wt% PCL increases to 55.01 kJ m^?2, which is 24.9 times higher than that of neat PLLA. The elongation at break is also increased from 5% to 139.4%, indicating the brittle ? ductile transition. The increased interfacial binding strength through the reactive interfacial compatibility and the formation of a CPU network in the PLLA matrix account for the improved toughness of PLLA/CPU blends. Dynamic mechanical analysis results indicate that the compatibility between PLLA and CPU is improved with increasing CPU content resulting in the formation of more interfacial phase. In addition, rheological property measurements indicate that the improvement in storage modulus and complex viscosity is ascribed to the formation of a CPU network in the PLLA matrix. © 2016 Society of Chemical Industry     

Porous biodegradable polyester blends of poly(L‐lactic acid) and poly(ε‐caprolactone): physical properties,morphology, and biodegradation

Poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their films without or blended with 50 wt% poly(ethylene glycol) (PEG) were prepared by solution casting. Porous films were obtained by water‐extraction of PEG from solution‐cast phase‐separated PLLA‐blend‐PCL‐blend‐PEG films. The effects of PLLA/PCL ratio on the morphology of the porous films and the effects of PLLA/PCL ratio and pores on the physical properties and biodegradability of the films were investigated. The pore size of the blend films decreased with increasing PLLA/PCL ratio. Polymer blending and pore formation gave biodegradable PLLA‐blend‐PCL materials with a wide variety of tensile properties with Young's modulus in the range of 0.07–1.4 GPa and elongation at break in the range 3–380%. Pore formation markedly increased the PLLA crystallinity of porous films, except for low PLLA/PCL ratio. Polymer blending as well as pore formation enhanced the enzymatic degradation of biodegradable polyester blends. Copyright © 2006 Society of Chemical Industry     

Compatibilizing effect of starch‐grafted‐poly(L‐lactide) on the poly(ε‐caprolactone)/starch composites

The poly(ε‐caprolactone) (PCL)/starch blends were prepared with a coextruder by using the starch grafted PLLA copolymer (St‐g‐PLLA) as compatibilizers. The thermal, mechanical, thermo‐mechanical, and morphological characterizations were performed to show the better performance of these blends compared with the virgin PCL/starch blend without the compatibilizer. Interfacial adhesion between PCL matrix and starch dispersion phases dominated by the compatibilizing effects of the St‐g‐PLLA copolymers was significantly improved. Mechanical and other physical properties were correlated with the compatibilizing effect of the St‐g‐PLLA copolymer. With the addition of starch acted as rigid filler, the Young's modulus of the PCL/starch blends with or without compatibilizer all increased, and the strength and elongation were decreased compared with pure PCL. Whereas when St‐g‐PLLA added into the blend, starch and PCL, the properties of the blends were improved markedly. The 50/50 composite of PCL/starch compatibilized by 10% St‐g‐PLLA gave a tensile strength of 16.6 MPa and Young's modulus of 996 MPa, respectively, vs. 8.0 MPa and 597 MPa, respectively, for the simple 50/50 blend of PCL/starch. At the same time, the storage modulus of compatibilized blends improved to 2940 MPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the composition and degree of crosslinking on the properties of poly(l‐lactic acid)/crosslinked polyurethane blends

Poly(l ‐lactic acid)/crosslinked polyurethane (PLLA/CPU) blends which were prepared via reactive blending of PLLA with poly(?‐caprolactone) (PCL), glycerol and 4,4′‐methylenediphenyl diisocyanate showed excellent toughness. The effects of the composition of the mixture and degree of crosslinking of CPU on the toughness of the PLLA/CPU blends (80/20 w/w) were studied in detail. Dynamic mechanical analysis and rheological measurements were used to characterize the structure of the in situ formed CPU in the PLLA matrix. A novel netlike phase structure was observed when the average molecular weight of PCL and degree of crosslinking were 1 kDa and 10%, respectively. The impact strength of the blend was enhanced from 2.2 kJ m^?2 for pure PLLA to 62.4 kJ m^?2; meanwhile, the elongation at break was increased to 489.8%. Therefore, the mechanical properties of PLLA/CPU blends can be easily tailored by tuning the composition of the mixture and the degree of crosslinking of CPU. © 2018 Society of Chemical Industry     

Miscibility of block copolymers of poly(ε‐caprolactone) and poly(ethylene glycol) with poly(3‐hydroxybutyrate) as well as the compatibilizing effect of these copolymers in blends of poly(ε‐caprolactone) and poly(3‐hydroxybutyrate)

Atactic poly(3‐hydroxybutyrate) (a‐PHB) and block copolymers of poly(ethylene glycol) (PEG) with poly(ε‐caprolactone) (PCL‐b‐PEG) were synthesized through anionic polymerization and coordination polymerization, respectively. As demonstrated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) measurements, both chemosynthesized a‐PHB and biosynthesized isotactic PHB (i‐PHB) are miscible with the PEG segment phase of PCL‐b‐PEGs. However, there is no evidence showing miscibility between both PHBs and the PCL segment phase of the copolymer even though PCL has been block‐copolymerized with PEG. Based on these results, PCL‐b‐PEG was added, as a compatibilizer, to both the PCL/a‐PHB blends and the PCL i‐PHB blends. The blend films were obtained through the evaporation of chloroform solutions of mixed components. Excitingly, the improvement in mechanical properties of PCL/PHB blends was achieved as anticipated initially upon the addition of PCL‐b‐PEG. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2600–2608, 2001     

Characterization of the mechanical and thermal properties and morphological behavior of biodegradable poly(L‐lactide)/poly(ε‐caprolactone) and poly(L‐lactide)/poly(butylene succinate‐co‐L‐lactate) polymeric blends

Two series of biodegradable polymer blends were prepared from combinations of poly(L ‐lactide) (PLLA) with poly(?‐caprolactone) (PCL) and poly(butylene succinate‐co‐L ‐lactate) (PBSL) in proportions of 100/0, 90/10, 80/20, and 70/30 (based on the weight percentage). Their mechanical properties were investigated and related to their morphologies. The thermal properties, Fourier transform infrared spectroscopy, and melt flow index analysis of the binary blends and virgin polymers were then evaluated. The addition of PCL and PBSL to PLLA reduced the tensile strength and Young's modulus, whereas the elongation at break and melt flow index increased. The stress–strain curve showed that the blending of PLLA with ductile PCL and PBSL improved the toughness and increased the thermal stability of the blended polymers. A morphological analysis of the PLLA and the PLLA blends revealed that all the PLLA/PCL and PLLA/PBSL blends were immiscible with the PCL and PBSL phases finely dispersed in the PLLA‐rich phase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) on miscibility and properties of atactic poly(methyl methacrylate)

Miscibility and properties of two atactic poly(methyl methacrylate)‐based blends [containing 10 and 20% of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)] have been investigated as a function of thermal treatments. Differential scanning calorimetry and dynamic mechanical thermal analysis of blends quenched in liquid nitrogen or ice/water, after annealing at T > 190 °C, showed a single glass transition temperature, indicating miscibility of the components for the time‐temperature history. Two glass transition temperatures, equal to those of the pure components, are instead found for blends after annealing at T < 190 °C. Scanning electron microscopy confirmed the homogeneity for the former quenched blends and phase separation for the latter. These results indicate the presence of an upper critical solution temperature (UCST). Tensile experiments, performed on two series of samples annealed at temperatures above and below the UCST, showed that the copolyester induces a decrease of Young's modulus and stresses at yielding and break points, and a marked increase of elongation at break. Differences in tensile properties between the two series of annealed blends are accounted for by the physical state of the components at room temperature after annealing above or below the UCST. Copyright © 2004 Society of Chemical Industry     

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

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

Enhanced crystallization rate and mechanical properties of poly(l‐lactic acid) by stereocomplexation with four‐armed poly(ϵ‐caprolactone)‐block‐poly(d‐lactic acid) diblock copolymer

Poly(l ‐lactic acid) (PLLA) was blended with a series of four‐armed poly(? ‐caprolactone)‐block ‐poly(d ‐lactic acid) (4a‐PCL‐b ‐PDLA) copolymers in order to improve its crystallization rate and mechanical properties. It is found that a higher content of 4a‐PCL‐b ‐PDLA copolymer or longer PDLA block in the copolymer lead to faster crystallization of the blend, which is attributed to the formation of stereocomplex crystallites between PLLA matrix and PDLA blocks of the 4a‐PCL‐b ‐PDLA copolymers. Meanwhile, the PDLA block can improve the miscibility between flexible PCL phase and PLLA phase, which is beneficial for improving mechanical properties. The tensile results indicate that the 10% 4a‐PCL_5k‐b ‐PDLA_5k/PLLA blend has the largest elongation at break of about 72% because of the synergistic effects of stereocomplexation between enantiomeric PLAs, multi‐arm structure and plasticization of PCL blocks. It is concluded that well‐controlled composition and content of 4a‐PCL‐b ‐PDLA copolymer in PLLA blends can significantly improve the crystallization rate and mechanical properties of the PLLA matrix. © 2017 Society of Chemical Industry     

Super‐Tough and Highly‐Ductile Poly(l‐lactic acid)/Thermoplastic Polyurethane/Epoxide‐Containing Ethylene Copolymer Blends Prepared by Reactive Blending

Ethylene‐methyl acrylate‐glycidyl methacrylate copolymer (E‐MA‐GMA) is employed to improve the impact toughness of poly(l ‐lactic acid) (PLLA)/thermoplastic polyurethane (TPU) blends by reactive melt‐blending. The reaction and miscibility between the components are confirmed by Fourier transform infrared spectroscopy, dynamic mechanical analysis, and differential scanning calorimetry. A super‐tough PLLA/TPU/E‐MA‐GMA multiphase blend (75/10/15) exhibits a significantly improved impact strength of 77.77 kJ m^?2, which is more than 17 times higher than that of PLLA/TPU (90/10) blend. A co‐continuous‐like TPU phase structure involving E‐MA‐GMA phase at the etched cryo‐fractured surface and the high‐orientated matrix deformation at the impact‐fractured surface are observed by scanning electron microscopy. The high‐orientated matrix deformation induced by the co‐continuous TPU phase structure is responsible for the super toughness of PLLA/TPU/E‐MA‐GMA blends.     

Crystallization kinetics of thermosetting polymer blends of poly(ε‐caprolactone) and unsaturated polyester resin

A study has been made of the isothermal crystallization kinetics of poly(ε‐caprolactone) (PCL) in partially miscible crosslinked polyester resin (PER)/PCL blends by using differential scanning calorimetry (DSC). For comparison, miscible blends of PCL with uncured polyester resin, i.e., oligoester resin (OER), were also investigated. The overall crystallization rate of PCL remarkably decreased with the addition of amorphous component, OER or PER. The kinetic rate constant K_n decreased sharply for both the OER/PCL blends and the crosslinked PER/PCL blends with decreasing PCL concentration. The mechanism of nucleation and geometry of the growing PCL crystals was not remarkably affected by the incorporation of OER, but changed considerably with the addition of PER. However, the overall crystallization rate of PCL in the crosslinked PER/PCL blends was much higher compared with the corresponding uncured OER/PCL blends, which is attributable to the phase‐separated structure and the reduced miscibility in the crosslinked blends. According to the nucleation and growth theories, the nucleation process was considered to be the rate controlling step in the crystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 322–327, 1999     

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) as a compatibilizer for cellulose acetate/poly(ε‐caprolactone) blends

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) (PVPVAc‐g‐PCL) was synthesized by radical copolymerization of N‐vinyl‐2‐pyrrolidone (VP)/vinyl acetate (VAc) comonomer and PCL macromonomer containing a reactive 2‐hydroxyethyl methacrylate terminal. The graft copolymer was designed in order to improve the interfacial adhesiveness of an immiscible blend system composed of cellulose acetate/poly(ε‐caprolactone) (CA/PCL). Adequate selections of preparation conditions led to successful acquisition of a series of graft copolymer samples with different values of molecular weight ( ), number of grafts (n), and segmental molecular weight of PVPVAc between adjacent grafts (M_n (between grafts)). Differential scanning calorimetry measurements gave a still immiscible indication for all of the ternary blends of CA/PCL/PVPVAc‐g‐PCL (72 : 18 : 10 in weight) that were prepared by using any of the copolymer samples as a compatibilizer. However, the incorporation enabled the CA/PCL (4 : 1) blend to be easily melt‐molded to give a visually homogeneous film sheet. This compatibilizing effect was found to be drastically enhanced when PVPVAc‐g‐PCLs of higher and M_n (between grafts) and lower n were employed. Scanning electron microscopy revealed that a uniform dispersion of the respective ingredients in the ternary blends was attainable with an assurance of the mixing scale of several hundreds of nanometers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrospun poly(L‐lactide)/poly(ε‐caprolactone) blend fibers and their cellular response to adipose‐derived stem cells

Polymer blending is one of the most effective methods for providing new, desirable biocomposites for tissue‐engineering applications. In this study, electrospun poly(L ‐lactide)/poly(ε‐caprolactone) (PLLA/PCL) blend fibrous membranes with defect‐free morphology and uniform diameter were optimally prepared by a 1 : 1 ratio of PLLA/PCL blend under a solution concentration of 10 wt %, an applied voltage of 20 kV, and a tip‐to‐collector distance of 15 cm. The fibrous membranes also showed a porous structure and high ductility. Because of the rapid solidification of polymer solution during electrospinning, the crystallinity of electrospun PLLA/PCL blend fibers was much lower than that of the PLLA/PCL blend cast film. To obtain an initial understanding of biocompatibility, adipose‐derived stem cells (ADSCs) were used as seed cells to assess the cellular response, including morphology, proliferation, viability, attachment, and multilineage differentiation on the PLLA/PCL blend fibrous scaffold. Because of the good biocompatibility and nontoxic effect on ADSCs, the PLLA/PCL blend electrospun fibrous membrane provided a high‐performance scaffold for feasible application in tissue engineering using ADSCs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization,melting behavior,and wettability of poly(ε‐caprolactone) and poly(ε‐caprolactone)/ poly(N‐vinylpyrrolidone) blends

Both wettability and crystallizability control poly(ε‐caprolactone)'s (PCL) further applications as biomaterial. The wettability is an important property that is governed by both chemical composition and surface structure. In this study, we prepared the PCL/poly(N‐vinylpyrrolidone) (PVP) blends via successive in situ polymerization steps aiming for improving the wettability and decreasing crystallizability of PCL. The isothermal crystallization of PCL/PVP at different PVP concentrations was carried out. The equilibrium melting point (T), crystallization rate, and the melting behavior after isothermal crystallization were investigated using differential scanning calorimetry (DSC). The Avrami equation was used to fit the isothermal crystallization. The DSC results showed that PVP had restraining effect on the crystallizability of PCL, and the crystallization rate of PCL decreased clearly with the increase of PVP content in the blends. The X‐ray diffraction analysis (WAXD) results agreed with that. Water absorptivity and contact angle tests showed that the hydrophilic properties were improved with the increasing content of PVP in blends. The coefficient for the water diffusion into PCL/PVP blends showed to be non‐Fickian in character. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and some properties of stereocomplex‐type poly(lactic acid)/layered silicate nanocomposites

Stereocomplex‐type poly(lactic acid)‐ [PLA]‐ based blends were prepared by solution casting of equimolar PLLA/PDLA with different amounts of organo‐modified montmorillonite. The homocrystallization and stereocomplexation of PLAs were enhanced by annealing of the blends. The stereocomplexation of PLAs, intercalation of the polymer chains between the silicates layers, and morphological structure of the filled PLAs were analyzed by wide‐angle X‐ray diffraction and transmission electron microscope. Thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), and tensile test were performed to study the thermal and mechanical properties of the blends. The homo‐ and stereocomplex crystallization of neat PLLA/PDLA were enhanced by annealing. The effect of annealing on the crystallization was emphasized by the addition of clay. With this structural change, thermal stabilities properties were also improved by the addition of clay. The silicate layers of the clay were slightly stacked but intercalated and distributed in the PLA‐matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallization behavior and crystallite morphology control of poly(L‐lactic acid) through N,N′‐bis(benzoyl)sebacic acid dihydrazide

Adding a nucleating agent is one of the best ways to accelerate the crystallization rate of poly(L ‐lactic acid) (PLLA) so as to obtain a high degree of crystallinity during the process, which will improve the heat distortion temperature of final products. In the work reported, N, N′‐bis(benzoyl)sebacic acid dihydrazide (BSAD) was synthesized and used as a nucleating agent for PLLA. Isothermal and non‐isothermal crystallization behaviors were investigated using differential scanning calorimetry (DSC). The addition of BSAD successfully enhances the crystallization rate of PLLA. A unique phase separation behavior of PLLA/BSAD blends is found from DSC as well as from polarized optical microscopy, which explains the difference of optimal BSAD concentration between isothermal and non‐isothermal crystallization. This is the first recording of a phase separation peak in PLLA/nucleating agent blends using DSC. In thermogravimetric analysis, the enhanced thermal stability indicates that there are strong hydrogen bonds between BSAD and PLLA matrix. BSAD can dissolve in PLLA melt below its melting point through intermolecular hydrogen bonding with PLLA and self‐assemble upon cooling, leading to the surface being capable of nucleating PLLA. Different phase separation temperatures can be used to control the morphology of BSAD, which finally determines the crystallite morphology of PLLA. © 2012 Society of Chemical Industry     

Structure and mechanical properties of blends of poly(ε‐caprolactone) with a poly(amino ether)

Poly(ε‐caprolactone) (PCL)/poly(amino ether) (PAE) blends were obtained by injection molding without any previous extrusion step in an attempt to (i) contribute to the knowledge of the relation between structure and mechanical properties in these type of blends composed of a rubbery and a glassy polymer and (ii) to find out to which extent are the PCL/PAE blends compatible, and therefore whether the biodegradability of PCL can be added as a characteristic of PAE‐based applications. PCL/PAE blends are composed of a crystalline PCL phase, a pure amorphous PCL phase, and a PAE‐rich phase where some PCL is present. The presence of some dissolved and probably unreacted PCL in the PAE‐rich phase led to a low interfacial tension as observed by the small size of the dispersed particles and the large interfacial area. The dependence on composition of both the modulus of elasticity and the yield stress of the blends was parallel to that of the orientation level. The elongation at break showed values similar to those of PAE in PAE‐rich blends, and was slightly synergistic in very rich PCL compositions; this behavior reflects a change in the nature of the matrix, from glassy to rubbery. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Disclosing the crystallization behavior and morphology of poly(ϵ‐caprolactone) within poly(ϵ‐caprolactone)/poly(l‐lactide) blends

In this work, the effect of poly(l ‐lactide) (PLLA) components on the crystallization behavior and morphology of poly(?‐caprolactone) (PCL) within PCL/PLLA blends was investigated by polarized optical microscopy, DSC, SEM and AFM. Morphological results reveal that PCL forms banded spherulites in PCL/PLLA blends because the interaction between the two polymer components facilitates twisting of the PCL lamellae. Additionally, the average band spacing of PCL spherulites monotonically decreases with increasing PLLA content. With regard to the crystallization behaviors of PCL, the crystallization ability of PCL is depressed with increase of the PLLA content. However, it is interesting to observe that the growth rate of PCL spherulites is almost independent of the PLLA content while the overall isothermal crystallization rate of PCL within PCL/PLLA blends decreases first and then increases at a given crystallization temperature, indicating that the addition of PLLA components shows a weak effect on the growth rate of the PCL but mainly on the generation of nuclei. © 2018 Society of Chemical Industry