Crystallization in poly(L-lactide)-b-poly(epsilon-caprolactone) double crystalline diblock copolymers: a study using X-ray scattering, differential scanning calorimetry, and polarized optical microscopy

The crystallization of well-defined poly(L-lactide)-b-poly(epsilon-caprolactone) diblock copolymers, PLLA-b-PCL, was investigated by time-resolved X-ray techniques, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). Two compositions were studied that contained 44 and 60 wt % poly(L-lactide), PLLA (they are referred to as (L44C5614)-C-11 and (L60C409)-C-12, respectively, with the molecular weight of each block in kg/mol as superscript). The copolymers were found to be initially miscible in the melt according to small-angle X-ray scattering measurements (SAXS). Their thermal behavior was also indicative of samples whose crystallization proceeds from a mixed melt. Sequential isothermal crystallization from the melt at 100 degreesC (for 30 min) and then at 30 degreesC (for 15 min) was measured. At 100 degreesC only the PLLA block is capable of crystallization, and its crystallization kinetics was followed by both WAXS and DSC; comparable results were obtained that indicated an instantaneous nucleation with three-dimensional superstructures (Avrami index of approximately 3). The spherulitic nature of the superstructure was confirmed by POM. When the temperature was decreased to 30 degreesC, the PCL block was able to crystallize within the PLLA negative spherulites (with an Avrami index of 2, as opposed to 3 in homo-PCL), and its crystallization rate was much slower than an equivalent homo-PCL. Time-resolved SAXS experiments in (L60C409)-C-12 revealed an initial melt mixed morphology at 165 degreesC that upon cooling transformed into a transient microphase-separated lamellar structure prior to crystallization at 100 degreesC.

Bionanocomposites based on Plla, Pcl and montmorillonite: synthesis, characterization and crystallization

Poly(lactide) is one of the best candidate to replace conventional petroleum-based polymers, since it is biobased, biocompatible and biodegradable. However, commercial PLA materials typically have low crystallization rate resulting in long processing time and low production efficiency. In this work the effects of two nanofillers MMT30B and MMT30B-g-P(LA-co-CL) on the crystallization rate of neat PLA and PLA/PCL blend were investigated. MMT30B-g-P(LA-co-CL) was synthetized by in situ grafting reaction. The synthesis was carried in xylene at 140°C, upon the results of a screening. The grafted copolymers were evaluated by 1H-NMR ,ATR–IR and TGA. Solvent casted films were obtained by mixing MMT30B-g-P(LA-co-CL) at 5% (w/w) with neat PLA and PLA/PCL blend, comparing the properties with the corresponding blends with and without a 5% of (w/w) unmodified clay. SEM images on PLA based blends shows that MMT30B is aggregated into larger particles compared to MMT30B-g-P(LLA-co-CL). This behavior is correlated to the better exfoliation of MMT30B-g-P(LA-co-CL) clay layers. SEM images on PLA/PCL based blends exhibit the typical sea-island morphology, characteristic of immiscible blends. PLA is the matrix while PCL is finely dispersed in droplets. MMT30B does not reduce PCL droplets size, while MMT30B-g-P(LA-co-CL) reduces the size of PCL droplets. This means that MMT30B-g-P(LA-co-CL) can migrate to the PLA-PCL interface, acting as a compatibilizer. Non-isothermal DSC cooling scans show a fractionated crystallization of the PCL phase in PLA/PCL/MMT30B-g-P(LA-co-CL), confirming the compatibilizer effect of MMT30B-g-P(LA-co-CL). At the same timeMMT30B-g-P(LA-co-CL) can better nucleate the PLA phase, both in neat PLA and PLA/PCL blend, promoting the crystallization during the heating scans. In isothermal condition, both the nanofillers increase the crystallization rate of PLA phase in neat PLA, while in PLA/PCL blends the effect is covered by the nucleating effect of PCL.

Crystallization and morphology of the PLLA phase within random poly (L-lactide-ran-É›-caprolactone)

This work has mainly focused on the poly (L-lactide) (PLLA) which is a material for multiple applications with performances comparable to those of petrochemical polymers (PP, PS, PET, etc. ...), readily recyclable and also compostable. However, PLLA has certain shortcomings that limit its applications. It is a brittle, hard polymer with a very low elongation at break, hydrophobic, exhibits low crystallization kinetics and takes a long time to degrade. The properties of PLLA may be modified by copolymerization (random, block, and graft) of L-lactide monomers with other co-monomers. In this thesis it has been studied the crystallization and morphology of random copolymers poly (L-lactide-ran-ε-caprolactone) with different compositions of the two monomers since the physical, mechanical, optical and chemical properties of a material depend on this behavior. Thermal analyses were performed by differential scanning calorimetry (DSC) and thermogravimetry (TGA) to observe behaviors due to the different compositions of the copolymers. The crystallization kinetics and morphology of poly (L-lactide-ran-ε-caprolactone) was investigated by polarized light optical microscopy (PLOM) and differential scanning calorimetry (DSC). Their thermal behavior was observed with crystallization from melt. It was observed that with increasing amounts of PCL in the copolymer, there is a decrease of the thermal degradation. Studies on the crystallization kinetics have shown that small quantities of PCL in the copolymer increase the overall crystallization kinetics and the crystal growth rate which decreases with higher quantities of PCL.

Melt structure and its transformation by sequential crystallization of the two blocks within poly(L-lactide)-block-poly(epsilon-caprolactone) double crystalline diblock copolymers

Sequential crystallization of poly(L-lactide) (PLLA) followed by poly(epsilon-caprolactone) (PCL) in double crystalline PLLA-b-PCL diblock copolymers is studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). Three samples with different compositions are studied. The sample with the shortest PLLA block (32 wt.-% PLLA) crystallizes from a homogeneous melt, the other two (with 44 and 60% PLLA) from microphase separated structures. The microphase structure of the melt is changed as PLLA crystallizes at 122 degrees C (a temperature at which the PCL block is molten) forming spherulites regardless of composition, even with 32% PLLA. SAXS indicates that a lamellar structure with a different periodicity than that obtained in the melt forms (for melt segregated samples). Where PCL is the majority block, PCL crystallization at 42 degrees C following PLLA crystallization leads to rearrangement of the lamellar structure, as observed by SAXS, possibly due to local melting at the interphases between domains. POM results showed that PCL crystallizes within previously formed PLLA spherulites. WAXS data indicate that the PLLA unit cell is modified by crystallization of PCL, at least for the two majority PCL samples. The PCL minority sample did not crystallize at 42 degrees C (well below the PCL homopolymer crystallization temperature), pointing to the influence of pre-crystallization of PLLA on PCL crystallization, although it did crystallize at lower temperature. Crystallization kinetics were examined by DSC and WAXS, with good agreement in general. The crystallization rate of PLLA decreased with increase in PCL content in the copolymers. The crystallization rate of PCL decreased with increasing PLLA content. The Avrami exponents were in general depressed for both components in the block copolymers compared to the parent homopolymers. Polarized optical micrographs during isothermal crystalli zation of (a) homo-PLLA, (b) homo-PCL, (c) and (d) block copolymer after 30 min at 122 degrees C and after 15 min at 42 degrees C.

Isothermal crystallization behavior of the poly(L-lactide) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Influence of the PEG block as a diluted solvent

Isothermal crystallization kinetics and morphology of the poly(L-lactide) block in poly(L-lactide)poly(ethylene glycol) diblock copolymers were studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The results were compared with that of the PLLA homopolymer. The introduction of the PEG block accelerated the crystallization rate of the PLLA block and promoted to form ring-banded spherulites. The analysis of isothermal crystallization kinetics has shown that the PLLA homopolymer accorded with the Avrami equation. But the PLLA block of the diblock copolymers deviated from the Avrami equation, which resulted from increasing of the crystallization rate and occurring of the second crystallization process. The equilibrium melting temperature (T,,) of the PLLA block fell with its molecular weight decreasing. The conditions to obtain more regular ring-banded spherulites were below: the sample was the PLLA block of LA(5) EG(5); the crystallization temperature was about from 95 degrees C to 100 degrees C, which almost corresponded to regime II.

Nonisothermal crystallization behavior of the poly(ethylene glycol) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Effect of the poly(L-lactide) block length

The confined crystallization behavior, melting behavior, and nonisothermal crystallization kinetics of the poly(ethylene glycol) block (PEG) in poly(L-lactide)poly(ethylene glycol) (PLLA-PEG) diblock copolymers were investigated with wideangle X-ray diffraction and differential scanning calorimetry. The analysis showed that the nonisothermal crystallization behavior changed from fitting the Ozawa equation and the Avrami equation modified by Jeziorny to deviating from them with the molecular weight of the poly(L-lactide) (PLLA) block increasing. This resulted from the gradual strengthening of the confined effect, which was imposed by the crystallization of the PLLA block. The nucleation mechanism of the PEG block of PLLA15000-PEG5000 at a larger degree of supercooling was different from that of PLLA2500-PEG5000, PLLA5000-PEG5000, and PEG5000 (the numbers after PEG and PLLA denote the molecular weights of the PEG and PLLA blocks, respectively). They were homogeneous nucleation and heterogeneous nucleation, respectively.

Nonisothermal crystallization behavior of poly (L-lactide)-poly(ethylene glycol) dibloick copolymer

The nonisothermal crystallization behavior of poly (L-lactide)-poly(ethylene glycol) ( PLLA-PEG) diblock copolymer was studied by means of real-time WAXD, DSC and POM, and Ozawa equation was used to analyze the kinetics of PLLA-PEG under nonisothermal crystallization conditions. During the crystallization of the high-T-m block (PLLA), the low-T-m block (PEG) acts as a noncrystalline diluent, and the crystallization behavior of PLLA obeys the Ozawa theory. When the PEG block begins to crystallize, the PLLA phase is always partially solidified and the presence of the spherulitic microstructure of PLLA profoundly restricts its crystallization behavior, which results in that the overall crystallization process does not obey the Ozawa equation. Furthermore, the study of the crystalline morphology of PLLA-PEG at different cooling rates indicates that when the cooling rate is from low to high, the crystalline morphology undergoes a transformation from the ring-banded spherulites to the typical Maltese cross spherulites, which experiences the mixed crystalline morphologies of ring-banded and typical Maltese cross spherulites, and the spherulitic size becomes smaller.

Electrospun poly(L-lactide)-grafted hydroxyapatite/poly(L-lactide) nanocomposite fibers

Composite fibers composed of poly(L-lactide)-grafted hydroxyapatite (PLA-g-HAP) nanoparticles and polylactide (PLA) matrix were prepared by electro-spinning. Environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM) were employed to investigate the morphology of the composite fibers and the distribution of PLA-g-HAP nanoparticles in the fibers, respectively. At a low content (similar to 4 wt%) of PLA-g-HAP, the nanoparticles dispersed uniformly in the fibers and the composite fibrous mats exhibited higher strength properties, compared with the pristine PLA fiber mats and the simple hydroxyapatite/PLA blend fiber mats. But when the content of PLA-g-HAP further increased, the nanoparticles began to aggregate, which resulted in the deterioration of the mechanical properties of the composite fiber mats. The degradation behaviors of the composite fiber mats were closely related to the content of PLA-g-HAP. At a low PLA-g-HAP content, degradation may be delayed due to the reduction of autocatalytic degradation of PLA. When PLA-g-HAP content was high, degradation rate increased because of the enhanced wettability of the composite fibers and the escape of the nanoparticles from fiber surfaces during incubation.

Sugars-grafted aliphatic biodegradable poly(L-lactide-co-carbonate)s by click reaction and their specific interaction with lectin molecules

A novel biodegradable aliphatic poly(L-lactide-co-carbonate) bearing pendant acetylene groups was successfully prepared by ring-opening copolymerization of L-lactide (LA) with 5-methyl-5-propargyloxycarbonyl-1,3-dioxan-2-one (PC) in the presence of benzyl alcohol as initiator with ZnEt2 as catalyst in bulk at 100 degrees C and subsequently used for grafting 2-azidoethyl beta-D-glucopyranoside and 2-azidoethyl beta-lactoside by the typical "click reaction," that is Cu(I)-catalyzed cycloaddition of azide and alkyne. The density of acetylene groups in the copolymer can be tailored by the molar ratio of PC to LA during the copolymerization. The aliphatic copolymers grafted with sugars showed low cytotoxicity to L929 cells, improved hydrophilic properties and specific recognition and binding ability with lectins, that is Concanavalin A (Con A) and Ricinus communis agglutinin (RCA). Therefore, this kind of sugar-grafted copolymer could be a good candidate in variety of biomedical applications.

RGD peptide grafted biodegradable amphiphilic triblock copolymer poly(glutamic acid)-b-poly(L-lactide)-b-poly(glutamic acid): Synthesis and self-assembly

A novel amphiphilic biodegradable triblock copolymer (PGL-PLA-PGL) with polylactide (PLA) as hydrophobic middle block and poly(glutamic acid) (PGL) as hydrophilic lateral blocks was successfully synthesized by ring-opening polymerization (ROP) Of L-lactide (LA) and N-carboxy anhydride (NCA) consecutively and by subsequent catalytic hydrogenation. The results of cell experiment of PGL-PLA-PGL suggested that PGL could improve biocompatibility of polyester obviously. The copolymer could form micelles of spindly shape easily in aqueous solution. The pendant carboxyl groups of the triblock copolymer were further activated with N-hydroxysuccinimide and combined with a cell-adhesive peptide GRGI)SY Incorporation of the oligopeptide further enhanced the hydrophilicity and led to formation of spherical micelles. PGL-PLAPGL showed better cell adhesion and spreading ability than pure PLA and the GRGDSY-containing copolymer exhibited even further improvement in cell adhesion and spreading ability, indicating that the copolymer could find a promising application in drug delivery or tissue engineering.

Biodegradable poly(L-lactide)/poly(epsilon-caprolactone)-modified montmorillonite nanocomposites: Preparation and characterization

New nanocomposites were prepared by melt blending poly(L-lactide) (PLLA), poly(epsilon-caprolactone) (PCL), and organically modified montmorillonite (OMMT). The obtained nanocomposites showed enhanced tensile strength, modulus and elongation at break than that of PLLA/PCL blends. The dynamic mechanical analysis showed the increasing mechanical properties with temperature dependence of nanocomposites. Wide-angle X-ray diffraction analysis and transmission electron microscopy indicated that the material formed the nanostructure. Adding OMMT improved the thermal stability and crystalline abilities of nanocomposites. The morphology was investigated by environmental scanning electron microscopy, which showed that increasing content of OMMT reduces the domain size of phase-separated particles. The specific interaction between each polymer and OMMT was characterized by the Flory-Huggins interaction parameter, B, which was determined by the equilibrium melting point depression of nanocomposites. The final values of B showed that PLLA was more compatible with OMMT than PCL.

Surface-grafted silica linked with L-lactic acid oligomer: A novel nanofiller to improve the performance of biodegradable poly(L-lactide)

A new surface modification method by grafting L-lactic acid oligomer onto the surface silanol groups of silica nanoparticles has been developed. The surface-grafting reaction is confirmed by IR and Si-29 MAS NMR analyses. TEM and SEM results show that grafted SiO2 (g-SiO2) nanoparticles can be comparatively uniformly dispersed in chloroform or PLLA matrix, while the unmodified SiO2 nanoparticles tend to aggregate. The loading of g-SiO2 nanoparticles in poly(L-lactide) (PLLA) matrix greatly improves the toughness and tensile strength of this material. In contrast, the incorporation of un-grafted SiO2 nanoparticles into PLLA leads to the deterioration of its mechanical properties. DSC analysis shows that g-SiO2 nanoparticles can serve as a nucleating agent for the crystallization of PLLA in the composites. SEM characterization shows the tough characteristics and great interfacial combination strength for g-SiO2 (5wt%)/PLLA nanocomposites.

Effect of crystallization on the lamellar orientation in thin films of symmetric poly(styrene)-b-poly(L-lactide) diblock copolymer

The effect of crystallization on the lamellar orientation of poly( styrene)-b-poly(L-lactide) (PS-PLLA) semicrystalline diblock copolymer in thin films has been investigated by atomic force microscopy (AFM), transmission electronic microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). In the melt state, microphase separation leads to a symmetric wetting structure with PLLA blocks located at both polymer/substrate and polymer/air interfaces. The lamellar period is equal to the long period L in bulk determined by small-angle X-ray scattering (SAXS). Symmetric wetting structure formed in the melt state provides a model structure to study the crystallization of PLLA monolayer tethered on glassy (T-c < T-g,T-PS) or rubber (T-c > T-g,T-PS) PS substrate. In both cases, it is found that the crystallization of PLLA results in a "sandwich" structure with amorphous PS layer located at both folding surfaces. For T-c <= T-g,T- PS, the crystallization induces a transition of the lamellar orientation from parallel to perpendicular to substrate in between and front of the crystals. In addition, the depletion of materials around the crystals leads to the formation of holes of 1/2 L, leaving the adsorbed monolayer exposure at the bottom of the holes.

Eutectic crystallization of poly(l-lactic acid) and pentaerythrityl tetrabromide

Diluents (either low molecular weight compounds orother polymers) are known to modify the morphology, the rates of nucleation and growth of polymers 1- 4. Recentlybinary systems in which both the components crystallize simultaneously to give a eutectic solid have been studied with great interest. Carbonnei et al.

In vivo mineralization and osteogenesis of nanocomposite scaffold of poly (lactide-co-glycolide) and hydroxyapatite surface-grafted with poly(L-lactide)

Nanocomposite of hydroxyapatite (HAP) surface-grafted with poly(L-lactide) (PLLA) (g-HAP) shows a wide application for bone fixation materials due to its improved interface compatibility, mechanical property and biocompatibility in our previous study. In this paper, a 3-D porous scaffold of g-HAP/poly (lactide-co-glycolide) (PLGA) was fabricated using the solvent casting/particulate leaching method to investigate its applications in bone replacement and tissue engineering. The composite of un-grafted HAP/PLGA and neat PLGA were used as controls. Their in vivo mineralization and osteogenesis were investigated by intramuscular implantation and replacement for repairing radius defects of rabbits. After surface modification, more uniform distribution of g-HAP particles but a lower calcium exposure on the surface of g-HAP/PLGA was observed. Intramuscular implantation study showed that the scaffold of g-HAP/PLGA was more stable than that of PLGA, and exhibited similar mineralization and biodegradability to HAP/PLGA at the 12-20 weeks post-surgery.