Origin of Melt Memory Effects in Poly(ethylene oxide): The Crucial Role of Entanglements.

The melt memory effect on crystallization is an intriguing phenomenon displayed by semicrystalline polymers, as opposed to low molar mass molecules. It concerns the effect of melt temperature on nucleation upon recrystallization. Typically, polymer crystals must be considerably superheated to erase the effect of previous morphology on the subsequent crystallization, avoiding an acceleration of the process. Despite being known for decades, its origin is still not fully understood. Investigating model poly(ethylene oxide) covering a wide range of molar mass, it is demonstrated that melt memory originates from topological constraints among the chains, i.e., entanglements, for PEO in which weak intermolecular interactions are present due to the ether groups. In fact, no memory is observed for samples below the critical molar mass for the formation of entanglements (about 1 kg mol-1). The increase in molar mass raises the number of entanglements and induces the formation of folded chains crystals, both factors leading to a topologically complex amorphous phase, enhancing the melt memory effect. The molecular origin of the melt memory effect in polymers with weak intermolecular interactions is thus ascribed to a slower isotropization in the melt of the chain segments originally contained in the crystals, due to the presence of entanglements among the chains. This study defines the distinction between small molecules and polymers from the point of view of melt memory.

Disappearance of Melt Memory Effect with Comonomer Incorporation in Isodimorphic Random Copolyesters.

Melt memory effects in polymer crystallization have attracted much attention in the past few years. Although progress has been made in understanding how the chemical structure of polymers can affect melt memory, there are still some knowledge gaps. In this work, we study how incorporating a second comonomer unit that is partially included in the crystalline unit cell affects the melt memory effect of the major component in a random isodimorphic copolymer for the first time. This second comonomer unit depresses the melting temperature of the homopolymer, reduces the crystallinity, and distorts the crystalline unit cell. However, its effect on the stability of self-nuclei and the production of melt memory has not been studied so far. To this aim, we have selected poly[(butylene succinate)-ran-(ε-caprolactone)] random copolyesters PBS-ran-PCL that are isodimorphic, i.e., they exhibit a pseudoeutectic point. This point separates the formation of BS-rich crystals from CL-rich crystals as a function of composition. The results reveal that the melt memory effect of these isodimorphic copolymers is strongly reduced with the incorporation of even very small amounts of comonomer unit (i.e., 1 molar %). This indicates that the incorporation of a second comonomer unit in the polymer chain disrupts the intermolecular interactions present between the chain segments in the crystal lattice of the major component and reduces the capacity of the material to produce self-nuclei. This reduction is more drastic for copolymers in which the second comonomer unit is mostly rejected from the crystalline phase. Contrary to olefin-based copolymers, for copolyesters, the second comonomer unit eases the process to reach an isotropic melt state upon melting. This work reveals the impact of introducing comonomer units on the melt memory effect in isodimorphic random copolyesters.

Seasonal Molecular Difference in Fibrillar Collagen Extracts Derived from the Marine Sponge Chondrosia reniformis (Nardo, 1847) and Their Impact on Its Derived Biomaterials.

Chondrosia reniformis (Nardo, 1847) is a marine sponge of high biotechnological interest both for its natural compound content and for its peculiar collagen, which is suitable for the production of innovative biomaterials in the form, for instance, of 2D membranes and hydrogels, exploitable in the fields of tissue engineering and regenerative medicine. In this study, the molecular and chemical-physical properties of fibrillar collagen extracted from specimens collected in different seasons are studied to evaluate the possible impact of sea temperature on them. Collagen fibrils were extracted from sponges harvested by the Sdot Yam coast (Israel) during winter (sea temperature: 17 °C) and during summer (sea temperature: 27 °C). The total AA composition of the two different collagens was evaluated, together with their thermal stability and glycosylation level. The results showed a lower lysyl-hydroxylation level, lower thermal stability, and lower protein glycosylation level in fibrils extracted from 17 °C animals compared to those from 27 °C animals, while no differences were noticed in the GAGs content. Membranes obtained with fibrils deriving from 17 °C samples showed a higher stiffness if compared to the 27 °C ones. The lower mechanical properties shown by 27 °C fibrils are suggestive of some unknown molecular changes in collagen fibrils, perhaps related to the creeping behavior of C. reniformis during summer. Overall, the differences in collagen properties gain relevance as they can guide the intended use of the biomaterial.

Cu3As: Uncommon Crystallographic Features, Low-Temperature Phase Transitions, Thermodynamic and Physical Properties.

The formation and crystal structure of the binary Cu3As phase have been re-investigated. Some physical properties were then measured on both single crystal and polycrystalline bulk. Cu3As melts congruently at 835 °C. At room temperature (RT), this compound has been found to crystallize in the hexagonal Cu3P prototype (hP24, P63cm) with lattice parameters: a = 7.1393(1) Å and c = 7.3113(1) Å, rather than in the anti HoH3-type (hP24, P-3c1) as indicated in literature. A small compositional range of 74.0-75.5 at.% Cu (26.0-24.5 at.% As) was found for samples synthesized at 300 and 400 °C; a corresponding slight understoichiometry is found in one out of the four Cu atomic sites, leading to the final refined composition Cu2.882(1)As. The present results disprove a change in the crystal structure above RT actually reported in the phase diagram (from γ' to γ on heating). Instead, below RT, at T = 243 K (-30 °C), a first-order structural transition to a trigonal low-temperature superstructure, LT-Cu3-xAs (hP72, P-3c1) has been found. The LT polymorph is metrically related to the RT one, having the c lattice parameter three times larger: a = 7.110(2) Å and c = 21.879(4) Å. Both the high- and low-temperature polymorphs are characterized by the presence of a tridimensional (3D) uncommon and rigid Cu sublattice of the lonsdaleite type (Cu atoms tetrahedrally bonded), which remains almost unaffected by the structural change(s), and characteristic layers of triangular 'Cu3As'-units (each hosting one As atom at the center, interconnected each other by sharing the three vertices). The first-order transition is then followed by an additional structural change when lowering the temperature, which induces doubling of also the lattice parameter a. Differential scanning calorimetry nicely detects the first low-temperature structural change occurring at T = 243 K, with an associated enthalpy difference, ΔH(TR), of approximately 2 J/g (0.53 kJ/mol). Low-temperature electrical resistivity shows a typical metallic behavior; clear anomalies are detected in correspondence to the solid-state transformations. The Seebeck coefficient, measured as a function of temperature, highlights a conduction of n-type. The temperature dependence of the magnetic susceptibility displays an overall constant diamagnetic response.

Synthesis of symmetric bis-α-ketoamides from renewable starting materials and comparative study of their nucleating efficiency in PLLA.

An efficient and smart synthesis of bis-α-ketoamides has been disclosed. The desired products have been obtained through a Passerini multicomponent reaction using biobased aldehydes, acetic acid and bis-isocyanides (prepared from the corresponding biobased diamides), followed by a deprotection/oxidation step. The effect of the synthesized compounds on the crystallization behavior of poly(l-lactide) (PLLA) has been investigated by differential scanning calorimetry (DSC) in non-isothermal conditions. Among all the synthesized compounds, only a few are able to meaningfully enhance the nucleation of PLLA, as confirmed by a shift of the polymer crystallization peak temperature towards higher values. With the research of active polymer nucleating agents being mostly empirical, the combinatorial synthetic approach proposed herein, coupled with the possibility of a small scale mixing procedure, can potentially represent a useful strategy for the discovery of new efficient biobased polymer additives.

Synergy of Fiber Surface Chemistry and Flow: Multi-Phase Transcrystallization in Fiber-Reinforced Thermoplastics.

Fiber-reinforced polymer composites are largely employed for their improved strength with respect to unfilled matrices. Considering semi-crystalline materials under relevant processing conditions, the applied pressure and flow induce shear stresses at the fiber-polymer interface. These stresses may strongly enhance the nucleation ability of the fiber surface with respect to the quiescent case. It is thus possible to assume that the fiber features are no longer of importance and that crystallization is dominated by the effect of flow. However, by making use of an advanced experimental technique, i.e., polarization-modulated synchrotron infrared microspectroscopy (PM-SIRMS), we are able to show that the opposite is true for the industrially relevant case of isotactic polypropylene (iPP). With PM-SIRMS, the local chain orientation is measured with micron-size spatial resolution. This orientation can be related to the polymer nucleation density along the fiber surface. For various combinations of an iPP matrix and fiber, the degree of orientation in the cylindrical layer that develops during flow correlates well with the differences in nucleation density found in quiescent conditions. This result shows that the morphological development during processing of polymer composites is not solely determined by the flow field, nor by the nucleating ability of the fiber surface alone, but rather by a synergistic combination of the two. In addition, using finite element modeling, it is demonstrated that, under the experimentally applied flow conditions, the interphase structure formation is mostly dominated by the rheological characteristics of the material rather than perturbations in experimental conditions, such as shear rate, layer thickness, and temperature. This once again highlights the importance of matrix-filler interplay during flow and, thus, of material selection in the design of hybrid and lightweight composite technologies.

Effect of the TrFE Content on the Crystallization and SSA Thermal Fractionation of P(VDF-co-TrFE) Copolymers.

In this contribution, we study the effect of trifluoro ethylene (TrFE) comonomer content (samples with 80/20, 75/25, and 70/30 VDF/TrFE molar ratios were used) on the crystallization in P(VDF-co-TrFE) in comparison with a PVDF (Poly(vinylidene fluoride)) homopolymer. Employing Polarized Light Optical Microscopy (PLOM), the growth rates of spherulites or axialites were determined. Differential Scanning Calorimetry (DSC) was used to determine overall crystallization rates, self-nucleation, and Successive Self-nucleation and Annealing (SSA) thermal fractionation. The ferroelectric character of the samples was explored by polarization measurements. The results indicate that TrFE inclusion can limit the overall crystallization of the copolymer samples, especially for the ones with 20 and 25% TrFE. Self-nucleation measurements in PVDF indicate that the homopolymer can be self-nucleated, exhibiting the classic three Domains. However, the increased nucleation capacity in the copolymers provokes the absence of the self-nucleation Domain II. The PVDF displays a monomodal distribution of thermal fractions after SSA, but the P(VDF-co-TrFE) copolymers do not experience thermal fractionation, apparently due to TrFE incorporation in the PVDF crystals. Finally, the maximum and remnant polarization increases with increasing TrFE content up to a maximum of 25% TrFE content, after which it starts to decrease due to the lower dipole moment of the TrFE defect inclusion within the PVDF crystals.

The Role of Molar Mass in Achieving Isotropy and Inter-Layer Strength in Mat-Ex Printed Polylactic Acid.

There has been extensive research in the field of material-extrusion (Mat-Ex) 3D printing to improve the inter-layer bonding process. Much research focusses on how various printing conditions may be detrimental to weld strength; many different feedstocks have been investigated along with various additives to improve strength. Surprisingly, there has been little attention directed toward how fundamental molecular properties of the feedstock, in particular the average molar mass of the polymer, may contribute to microstructure of the weld. Here we showed that weld strength increases with decreasing average molar mass, contrary to common observations in specimens processed in more traditional ways, e.g., by compression molding. Using a combination of synchrotron infra-red polarisation modulation microspectroscopy measurements and continuum modelling, we demonstrated how residual molecular anisotropy in the weld region leads to poor strength and how it can be eradicated by decreasing the relaxation time of the polymer. This is achieved more effectively by reducing the molar mass than by the usual approach of attempting to govern the temperature in this hard to control non-isothermal process. Thus, we propose that molar mass of the polymer feedstock should be considered as a key control parameter for achieving high weld strength in Mat-Ex.

Surface Roughness Enhances Self-Nucleation of High-Density Polyethylene Droplets Dispersed within Immiscible Blends.

Highly linear or high-density polyethylenes (HDPEs) have an intrinsically high nucleation density compared to other polyolefins. Enhancing their nucleation density by self-nucleation is therefore difficult, leading to a narrow self-nucleation Domain (i.e., the so-called Domain II or the temperature Domain where self-nuclei can be injected into the material without the occurrence of annealing). In this work, we report that when HDPE is blended (up to 50%) with immiscible matrices, such as atactic polystyrene (PS) or Nylon 6, its self-nucleation capacity can be greatly increased. In addition, temperatures higher than the equilibrium melting temperature of the HDPE phase are needed to erase the significantly enhanced crystalline memory in the blends. Morphological evidence gathered by Scanning and Transmission Electron Microscopies (SEM and TEM) indicates that these unexpected results can be explained by the modification of the interface between blend components. The filling of the solid HDPE surface asperities by the low viscosity polystyrene during heating to the self-nucleation temperature, or the crystallization of the matrix in the case of Nylon 6, enhances the interface roughness between the two polymers in the blends. Such rougher interfaces can remarkably increase the self-nucleation capacity of the HDPE phase via surface nucleation.

Potential Biomedical Applications of Collagen Filaments derived from the Marine Demosponges Ircinia oros (Schmidt, 1864) and Sarcotragus foetidus (Schmidt, 1862).

Collagen filaments derived from the two marine demosponges Ircinia oros and Sarcotragus foetidus were for the first time isolated, biochemically characterised and tested for their potential use in regenerative medicine. SDS-PAGE of isolated filaments revealed a main collagen subunit band of 130 kDa in both of the samples under study. DSC analysis on 2D membranes produced with collagenous sponge filaments showed higher thermal stability than commercial mammalian-derived collagen membranes. Dynamic mechanical and thermal analysis attested that the membranes obtained from filaments of S. foetidus were more resistant and stable at the rising temperature, compared to the ones derived from filaments of I. oros. Moreover, the former has higher stability in saline and in collagenase solutions and evident antioxidant activity. Conversely, their water binding capacity results were lower than that of membranes obtained from I. oros. Adhesion and proliferation tests using L929 fibroblasts and HaCaT keratinocytes resulted in a remarkable biocompatibility of both developed membrane models, and gene expression analysis showed an evident up-regulation of ECM-related genes. Finally, membranes from I. oros significantly increased type I collagen gene expression and its release in the culture medium. The findings here reported strongly suggest the biotechnological potential of these collagenous structures of poriferan origin as scaffolds for wound healing.

Crystallization of a Self-Assembling Nucleator in Poly(l-lactide) Melt.

In the present work, crystallization of a soluble nucleator N, N', N″-tricyclohexyl-1,3,5-benzenetricarboxylamide (TMC-328) in a poly(l-lactic acid) (PLLA) matrix has been studied at different temperatures. Based on the change in solubility with temperature, different levels of supersaturation of TMC-328 in a PLLA matrix can be obtained. This nucleator presents a fibrous structure produced via self-assembling and develops into an interconnected network when the temperature is lowered. The TMC-328 crystal nuclei density is quantified via optical microscopy, using the average distance of the adjacent fibrillar structure, which shows a steady decrease with the decrease in temperature. The crystallization rates of TMC-328 were assessed through rheological measurements of network formation. Both fibrils' density and crystallization kinetics display a power law dependence on supersaturation. For the first time, the solid-melt interfacial energy, the size of the critical nucleus, and the number of molecules making up the critical nucleus of the nucleator TMC-328 in the PLLA matrix have been determined by adopting the classical nucleation theory. The subsequent crystallization of PLLA induced by this nucleator was investigated as a function of the fibrils' spatial density. The crystallization rate of PLLA is enhanced with the increase in the TMC-328 fibrils' density because of the availability of a larger nucleating surface. The self-assembled fibril of TMC-328 can serve as shish to form a hybrid shish-kebab structure after the crystallization of PLLA, regardless of the number of nucleation sites.

Crystallization and Morphology of Triple Crystalline Polyethylene-b-poly(ethylene oxide)-b-poly(ε-caprolactone) PE-b-PEO-b-PCL Triblock Terpolymers.

The morphology and crystallization behavior of two triblock terpolymers of polymethylene, equivalent to polyethylene (PE), poly (ethylene oxide) (PEO), and poly (ε-caprolactone) (PCL) are studied: PE227.1-b-PEO4615.1-b-PCL3210.4 (T1) and PE379.5-b-PEO348.8-b-PCL297.6 (T2) (superscripts give number average molecular weights in kg/mol and subscripts composition in wt %). The three blocks are potentially crystallizable, and the triple crystalline nature of the samples is investigated. Polyhomologation (C1 polymerization), ring-opening polymerization, and catalyst-switch strategies were combined to synthesize the triblock terpolymers. In addition, the corresponding PE-b-PEO diblock copolymers and PE homopolymers were also analyzed. The crystallization sequence of the blocks was determined via three independent but complementary techniques: differential scanning calorimetry (DSC), in situ SAXS/WAXS (small angle X-ray scattering/wide angle X-ray scattering), and polarized light optical microscopy (PLOM). The two terpolymers (T1 and T2) are weakly phase segregated in the melt according to SAXS. DSC and WAXS results demonstrate that in both triblock terpolymers the crystallization process starts with the PE block, continues with the PCL block, and ends with the PEO block. Hence triple crystalline materials are obtained. The crystallization of the PCL and the PEO block is coincident (i.e., it overlaps); however, WAXS and PLOM experiments can identify both transitions. In addition, PLOM shows a spherulitic morphology for the PE homopolymer and the T1 precursor diblock copolymer, while the other systems appear as non-spherulitic or microspherulitic at the last stage of the crystallization process. The complicated crystallization of tricrystalline triblock terpolymers can only be fully grasped when DSC, WAXS, and PLOM experiments are combined. This knowledge is fundamental to tailor the properties of these complex but fascinating materials.

The Blending of Poly(glycolic acid) with Polycaprolactone and Poly(l-lactide): Promising Combinations.

Poly(glycolic acid) (PGA) holds unique properties, including high gas barrier properties, high tensile strength, high resistance to common organic solvents, high heat distortion temperature, high stiffness, as well as fast biodegradability and compostability. Nevertheless, this polymer has not been exploited at a large scale due to its relatively high production cost. As such, the combination of PGA with other bioplastics on one hand could reduce the material final cost and on the other disclose new properties while maintaining its "green" features. With this in mind, in this work, PGA was combined with two of the most widely applied bioplastics, namely poly(l-lactide) (PLLA) and poycaprolactone (PCL), using the melt blending technique, which is an easily scalable method. FE-SEM measurements demonstrated the formation of PGA domains whose dimensions depended on the polymer matrix and which turned out to decrease by diminishing the PGA content in the mixture. Although there was scarce compatibility between the blend components, interestingly, PGA was found to affect both the thermal properties and the degradation behavior of the polymer matrices. In particular, concerning the latter property, the presence of PGA in the blends turned out to accelerate the hydrolysis process, particularly in the case of the PLLA-based systems.

Sequential Crystallization and Multicrystalline Morphology in PE-b-PEO-b-PCL-b-PLLA Tetrablock Quarterpolymers.

We investigate for the first time the morphology and crystallization of two novel tetrablock quarterpolymers of polyethylene (PE), poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA) with four potentially crystallizable blocks: PE18 7.1 -b-PEO37 15.1 -b-PCL26 10.4 -b-PLLA19 7.6 (Q1) and PE29 9.5 -b-PEO26 8.8 -b-PCL23 7.6 -b-PLLA22 7.3 (Q2) (superscripts give number average molecular weights in kg/mol, and subscripts give the composition in wt %). Their synthesis was performed by a combination of polyhomologation (C1 polymerization) and ring-opening polymerization techniques using a ″catalyst-switch″ strategy, either ″organocatalyst/metal catalyst switch″ (Q1 sample, 96% isotactic tetrads) or ″organocatalyst/organocatalyst switch″ (Q2 sample, 84% isotactic tetrads). Their corresponding precursors-triblock terpolymers PE-b-PEO-b-PCL, diblock copolymers PE-b-PEO, and PE homopolymers-were also studied. Cooling and heating rates from the melt at 20 °C/min were employed for most experiments: differential scanning calorimetry (DSC), polarized light optical microscopy (PLOM), in situ small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS), and atomic force microscopy (AFM). The direct comparison of the results obtained with these different techniques allows the precise identification of the crystallization sequence of the blocks upon cooling from the melt. SAXS indicated that Q1 is melt miscible, while Q2 is weakly segregated in the melt but breaks out during crystallization. According to WAXS and DSC results, the blocks follow a sequence as they crystallize: PLLA first, then PE, then PCL, and finally PEO in the case of the Q1 quarterpolymer; in Q2, the PLLA block is not able to crystallize due to its low isotacticity. Although the temperatures at which the PEO and PCL blocks and the PE and PLLA blocks crystallize overlap, the analysis of the intensity changes measured by WAXS and PLOM experiments allows identifying each of the crystallization processes. The quarterpolymer Q1 remarkably self-assembles during crystallization into tetracrystalline banded spherulites, where four types of different lamellae coexist. Nanostructural features arising upon sequential crystallization are found to have a relevant impact on the mechanical properties. Nanoindentation measurements show that storage modulus and hardness of the Q1 quarterpolymer significantly deviate from those of the stiff PE and PLLA blocks, approaching typical values of compliant PEO and PCL. Results are mainly attributed to the low crystallinity of the PE and PLLA blocks. Moreover, the Q2 copolymer exhibits inferior mechanical properties than Q1, and this can be related to the PE block within Q1 that has thinner crystal lamellae according to its much lower melting point.

Fused Deposition Modeling of Polyamides: Crystallization and Weld Formation.

International newspapers and experts have called 3D printing the industrial revolution of this century. Among all its available variants, the fused deposition modeling (FDM) technique is of greater interest since its application is possible using simple desktop printers. FDM is a complex process, characterized by a large number of parameters that influence the quality and final properties of the product. In particular, in the case of semicrystalline polymers, which afford better mechanical properties than amorphous ones, it is necessary to understand the crystallization kinetics as the processing conditions vary, in order to be able to develop models that allow having a better control over the process and consequently on the final properties of the material. In this work it was proposed to study the crystallization kinetics of two different polyamides used for FDM 3D printing and to link it to the microstructure and properties obtained during FDM. The kinetics are studied both in isothermal and fast cooling conditions, thanks to a home-built device which allows mimicking the quenching experienced during filament deposition. The temperature history of a single filament is then determined by mean of a micro-thermocouple and the final crystallinity of the sample printed in a variety of conditions is assessed by differential scanning calorimetry. It is found that the applied processing conditions always allowed for the achievement of the maximum crystallinity, although in one condition the polyamide mesomorphic phase possibly develops. Despite the degree of crystallinity is not a strong function of printing variables, the weld strength of adjacent layers shows remarkable variations. In particular, a decrease of its value with printing speed is observed, linked to the probable development of molecular anisotropy under the more extreme printing conditions.

Melt Memory Effects in Poly(Butylene Succinate) Studied by Differential Fast Scanning Calorimetry.

It is widely accepted that melt memory effect on polymer crystallization depends on thermal history of the material, however a systematic study of the different parameters involved in the process has been neglected, so far. In this work, poly(butylene succinate) has been selected to analyze the effect of short times and high cooling/heating rates that are relevant from an industrial point of view by taking advantage of fast scanning calorimetry (FSC). The FSC experiments reveal that the width of melt memory temperature range is reduced with the time spent at the self-nucleation temperature (Ts), since annealing of crystals occurs at higher temperatures. The effectiveness of self-nuclei to crystallize the sample is addressed by increasing the cooling rate from Ts temperature. The effect of previous standard state on melt memory is analyzed by (a) changing the cooling/heating rate and (b) applying successive self-nucleation and annealing (SSA) technique, observing a strong correlation between melting enthalpy or crystallinity degree and the extent of melt memory. The acquired knowledge can be extended to other semicrystalline polymers to control accurately the melt memory effect and therefore, the time needed to process the material and its final performance.

Renewable and Tough Poly(l-lactic acid)/Polyurethane Blends Prepared by Dynamic Vulcanization.

Melt blending of homopolymers is an effective way to achieve an attractive combination of polymer properties. Dynamic vulcanization of fatty-acid-based polyester polyol with glycerol and poly(l-lactic acid) (PLLA) in the presence of hexamethylene diisocyanate (HDI) was performed with the aim of toughening PLLA. The dynamic vulcanization in an internal mixer led to the formation of a PLLA/PU biobased blend. Melt torque, Fourier transform infrared (FTIR), and gel fraction analysis demonstrated the successful formation of cross-linked polyurethane (PU) inside the PLLA matrix. Scanning electron microscopy (SEM) analysis showed that the PLLA/PU blends exhibit a sea-island morphology. Gel fraction analysis revealed that a rubbery phase was formed inside the PLLA matrix, which was insoluble in chloroform. FTIR analysis of the insoluble part shows the appearance of an absorption band centered at 1758 cm-1, related to the crystalline carbonyl vibration of the PLLA component, thus suggesting the partial involvement of PLLA chains in the cross-linking reaction. The overall content of the PU phase in the blends significantly affected the mechanical properties, thermal stability, and crystallization behavior of the materials. The overall crystallization rate of PLLA was noticeably decreased by the incorporation of PU. At the same time, polarized light optical microscopy (PLOM) analysis revealed that the presence of the PU rubbery phase inside the PLLA matrix promoted PLLA nucleation. With the formation of the PU network, the impact strength showed a remarkable increase while Young's modulus correspondingly decreased. The blends showed slightly reduced thermal stability compared to the neat PLLA.

Effect of the Crystallization Conditions on the Exclusion/Inclusion Balance in Biodegradable Poly(butylene succinate-ran-butylene adipate) Copolymers.

Biomedical applications of polymers require precise control of the solid-state structure, which is of particular interest for biodegradable copolymers. In this work, we evaluated the influence of crystallization conditions on the comonomer exclusion/inclusion balance of biodegradable poly(butylene succinate-ran-butylene adipate) (PBSA) isodimorphic random copolymers. Regardless of the crystallization conditions, the copolymers retain their isodimorphic character, displaying a pseudo-eutectic behavior with crystallization in the entire composition range. This illustrates the thermodynamic nature of the isodimorphic behavior for PBSA random copolymers. However, depending on the composition, the crystallization conditions affect the exclusion/inclusion balance of the comonomers. Fast cooling favors butylene adipate (BA) inclusion inside the poly(butylene succinate) (PBS) crystals, whereas isothermal crystallization strongly limits it. PBA-rich compositions behave differently. Both fast and slow crystallization formed the ß-phase, whereas BS unit inclusion is favored independently of the cooling conditions. During successive self-nucleation and annealing, the BA inclusion is intermediate between non-isothermal and isothermal conditions, while the crystalline structure of the PBA phase changes from the ß-phase to the more stable α-phase. We propose a simple crystallographic model to explain the changes in the unit cell dimension of the copolymers.

Polymorphism and Multiple Melting Behavior of Bio-Based Poly(propylene 2,5-furandicarboxylate).

Furandicarboxylate-based polyesters are considered an interesting class of bio-based polymers due to their improved properties with respect to the petrol-based terephthalate homologs. An in-depth analysis of the crystal structure of poly(propylene 2,5-furandicarboxylate) (PPF), after maximum possible removal of the catalyst, was carried out. The study disclosed that purified PPF presents two different crystalline phases after crystallization from the melt. Crystallizations at temperatures lower than 120 °C lead to growth of a single crystal form (ß-form), whereas two different crystal forms (α and ß) were found to coexist at higher Tcs. This behavior is opposite to that previously observed for unpurified PPF. The possibility that the catalyst nucleates the α-phase, which therefore becomes the kinetically favored modification at low crystallization temperatures in the presence of a higher amount of catalyst residue, has been considered as a feasible explanation. Two concomitantly different spherulitic morphologies were observed and connected to the ß- and α-phase, respectively. The association between polymorphism and melting behavior was studied. The origin of the peaks that compose the multiple melting endotherm recorded at conventional heating rates was determined by combined wide-angle X-ray scattering, differential scanning calorimetry, fast scanning chip calorimetry, and polarized light optical microscopy measurements. The higher thermal stability of the α-crystals in comparison with the ß-form was thus demonstrated.

Regioselective Photooxidation of Citronellol: A Way to Monomers for Functionalized Bio-Polyesters.

Dye-sensitized photooxygenation reaction of bio-based double bond-containing substrates is proposed as sustainable functionalization of terpenes and terpenoids to transform them into polyoxygenated compounds to be employed for the synthesis of new bio-based polyesters. As proof of concept, citronellol 1 has been regioselectively converted into diol 4 using singlet oxygen (1O2), a traceless reagent that can be generated from air, visible light and zeolite supported-photosensitizer (Thionine-NaY). With our synthetic approach, diol 4 has been obtained in two-steps, with good regioselectivity, using green reagents such as light and air, and finally a solvent-free oxidation step. From this compound, a citronellol-based copolyester of poly(butylene succinate) (PBS) has been synthesized and fully characterized. The results obtained evidence that the proposed copolymerization of PBS with the citronellol-based building blocks allows to obtain a more flexible and functionalizable material, by exploiting a largely available natural molecule modified through a green synthetic path.