Spherulitic Morphology Research Articles

Grating Harmony of Orderly-Banded Spherulites of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with Tunable Structures

A detailed investigation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) blended with poly(vinyl phenol) (PVPh) at a 90/10 weight ratio reveals the significant impact of PVPh on crystallization and spherulite morphology. Because PVPh remains in a rigid, glassy state during PHBV crystallization, it restricts molecular movement, leading to a more controlled and organized morphology of the PHBV lamellae. Advanced microscopic analysis highlights the morphological sensitivity to crystallization conditions, with SEM images showing cracks and diverse lamellae orientations. Etching and fracturing expose the interior 3D lamellae architecture, revealing distinct ridge and valley regions where vertically oriented lamellae beneath ridges transition to horizontal lamellae in valleys, resulting in double ring-banded spherulites. Advanced synchrotron-radiation microbeam X-ray techniques provide additional insights into the polymorphic forms and self-assembly behavior of lamellae. The investigation also examines order-induced photonic phenomena by considering that the orderly-banded spherulites can exhibit iridescence. This comprehensive study enhances our understanding of PHBV crystal assembly, underscoring the sophistication of polymer self-assembly at the microscopic level.

Origin of Au-Ag Mineralization in Sphalerite Ores from Data on Sphalerite Co-Crystallization with Ag and Au in Model Hydrothermal Systems

Abstract ––Au-Ag mineralization occurrences in sphalerite ores of hydrothermal genesis are paradoxical in view of the incompatibility of these elements in sphalerite. The formation of sphalerite with Au and Ag impurities under hydrothermal crystallization of ZnS at 450 °C and 1 kbar pressure was studied experimentally. Sn impurity was taken as a source of point defects in crystals modelling the interaction of Au and Ag with vacancies. The Ag solubility in low-Fe sphalerite is estimated as 3.8 ± 0.7 μg/g, Au ̶ ≤ 0.6 μg/g. The main forms of Ag and Au occurrence in sphalerite are the inclusions of (Ag, Au)xS phases with x varies mainly from 1.8 to 2.0, and Au varies from 0.01 to 0.75 a.p.f.u. The primary forms of the elements in ores might be microinclusions (Ag, Au) 1.8-2.1S or close to (Ag, Au)S at higher fS2. In presence of Sn, solubilities of Au and Ag become higher. The behavior of Au corresponds to the substitution reaction Sn4+ + Au+ + v‒ ↔ 2Zn2+ in the presence of two types of vacancy defects (v–) ‒ the “inherent” vacancies dependent on the crystallization conditions and the vacancies accompanying Sn4+ incorporation. Ag entrance is seemingly more dependent on fS2 conditions and does not correlate with Sn. The extra vacancies arise because of metastable crystallization under the conditions of oversaturation of growth medium. This is supported by the spherulite morphology of growth products and the admixture of wurtzite ZnS form. The distribution and cocrystallization coefficients show an increasing trend for both precious metals (PM), due to which Au changes from incompatible to the category of highly compatible elements in sphalerite. The geochemical environments favorable for the formation of imperfect mineral crystals are considered. Such crystals are capable to uptake PMs and other incompatible in “ideal” crystal elements because of their interaction with vacancies, both constitutional (inherent to the substance) and non-equilibrium defects, and surficial nano-sized formations (nonautonomous phases). The evolution of these initially “invisible” forms of PM under metamorphic processes and remobilization of ore substance may result in Au and Ag escape and aggregation into microparticles.

Morphological control for hollow rod crystals of a photochromic diarylethene on spherulites by surface properties of substrates.

Sublimation methods utilizing the surface properties of substrates can address the challenge of controlling hollow morphologies in rod crystals. Spherulites were formed on the hydrophilic surface of the (0001) planes of α-quartz and sapphire substrates by sublimation of 1,2-bis(3,5-dimethyl-2-thienyl)perfluorocyclopentene (1a). Various types of hollow morphologies, distinguished by the size and shape of their cross sections and by the presence or absence of branching structures, were formed separately on α-quartz and sapphire substrates. Such precise control of the hollow morphologies was attributed to the wettability of each substrate, leading to the formation of spherulites of 1a. In addition, it was indicated that the formation process of the surface morphologies of spherulites was associated with the hollow morphologies of rod crystals of 1a.

Crystallization-Controlled Structure and Thermal Properties of Biobased Poly(Ethylene2,5-Furandicarboxylate).

Crystallization-controlled structure and thermal properties of biobased poly(ethylene 2,5-furandicarboxylate) (PEF) were studied. The cold-crystallization temperature controlled the structure and thermal properties of the biobased PEF. The melting was complex and evidenced the presence of a significant fraction of less-stable crystals with a low melting temperature that linearly increased with Tc, which formed already during the early stages of crystallization, together with those melting at a higher temperature. Low Tc resulted in the α'-phase formation, less crystallinity, and greater content of the rigid amorphous phase. At high Tc, the α-phase formed, higher crystallinity developed, the rigid amorphous phase content was lower, and the melting temperature of the less-stable crystals was higher; however, slight polymer degradation could have occurred. The applied thermal treatment altered the thermal behavior of PEF by shifting the melting of the less stable crystals to a significantly higher temperature. SEM examination revealed a spherulitic morphology. A lamellar order was evidenced with an average long period and small average lamella thickness, the latter about 3-3.5 nm, only slightly increasing with Tc.

Strong Hydrogen Bonds Sustain Even-Odd Effects in Poly(ester amide)s with Long Alkyl Chain Length in the Backbone.

The number of methylene groups between strongly interacting functional groups within polymer repeating units induces even-odd effects on thermal and mechanical properties. However, detailed studies correlating the even-odd effect with structural changes are still lacking. In this work, we establish correlations between the structure and thermal properties of poly(ester amide)s containing long alkyl chain lengths. The even-odd effect impacts the thermal properties, including the melting temperature and crystallinity degree. It influences the spherulitic morphology of poly(ester amide)s, controlling the appearance of banding. We demonstrate that even-odd effects in poly(ester amides)s persist even with 27 CH2 groups within the repeating unit, an effect due to strong hydrogen bonds caused by the amide groups. Our X-ray studies reveal that the even-odd effect originates from changes in the crystalline structure of the materials. This work helps elucidate the role of strong intermolecular interactions (i.e., hydrogen bonding) on the even-odd effect in long-chain poly(ester amides).

Tunable crystallization behavior, memory effect, and thermo-mechanical properties of biobased polyamides PA5X

To reduce carbon dioxide emissions, the development of sustainable bio-based polyamides with performance advantages has become the focus of widespread attention. 1,5-Pentanediamine (PDA) is a renewable monomer produced by decarboxylation of lysine, which can be used as a sustainable alternative to traditional petroleum-based diamines and play a crucial role in the synthesis of bio-based polyamides. Herein, a series of bio-based aliphatic polyamides (PA5X) synthesized from PDA and aliphatic diacids with different methylene groups were successfully prepared via melt polycondensation. Their chemical structures were characterized, and the effects of diacid chain length on crystallization behavior, memory effect, and thermo-mechanical properties were emphatically investigated. The results show that the melting and crystallization temperatures of PA5X decrease with increasing diacid chain length. Meanwhile, the PA5X exhibits high thermal stability, with Td,5 % exceeding 380 °C. Unlike the even-even polyamide, the crystalline form of PA5X is γ-form, and the crystallization behavior and spherulitic morphology change significantly with diacid chain length, which is attributed to the complex entanglement effects. More particularly, the correlation between the diacid chain length and the melt memory effect is explored. PA56 with shorter methylene groups exhibits stronger melt memory effects due to the memory effects being directly affected by segmental chain interactions. Moreover, PA5X exhibits comparable or even superior tensile strength and ductility compared with hexamethylenediamine-based polyamide (PA6X) and reported fully bio-based PA11. This work provides a comprehensive investigation into the structure-property relationship of the bio-based polyamide PA5X, demonstrating great potential for application in high-performance eco-friendly materials.

Transcrystalline Mechanism of Banded Spherulites Development in Melt-Crystallized Semicrystalline Polymers.

The decades-long paradigm of continuous and perpetual lamellar twisting constituting banded spherulites has been found to be inconsistent with several recent studies showing discontinuity regions between consecutive bands, for which, however, no explanation has been found. The present research demonstrates, in three different semicrystalline polymers (HDPE, PEG10000 and Pluronic F-127), that sequential transcrystallinity is the predominant mechanism of banded spherulite formation, heterogeneously nucleated on intermittent self-shear-oriented amorphous layers excluded during the crystals' growth. It is hereby demonstrated that a transcrystalline layer can be nucleated on amorphous self-shear-oriented polymer chains in the melt, by a local melt flow in the bulk or in contact with any interface-even in contact with the interface with air, e.g., in contact with an entrapped air bubble or at the edges of the sample-or nucleated following the multiple directions and orientations induced by a turbulent flow. The bilateral excessive local exclusion of amorphous non-crystallizable material, following a short period of initial non-banded growth, is found to be the source of dislocations leading to spirally banded spherulites, through the transcrystalline layers' nucleation thereon. The present research reveals and demonstrates the sequential transcrystalline morphology of banded spherulites and the mechanism of its formation, which may lead to new insights in the understanding and design of polymer processing for specific applications.

Engineering the Crystalline Architecture for Enhanced Properties in Fast-Rate Processing of Poly(ether ether ketone) (PEEK) Nanocomposites.

Rapid cooling in fast-rate manufacturing processes such as additive manufacturing and stamp forming limits the development of crystallinity in semicrystalline polymer nanocomposites and, therefore, potential improvements in the mechanical performance. While the nucleation, chain mobility, and crystallization time from rapid cooling are known competing mechanisms in crystallization, herein we elucidate that the crystalline morphology and architecture also play a key role in tuning the mechanical performance. We explore how modifying the spherulite morphology via a cellulose nanocrystal (CNC) and graphene nanoplatelet (GNP) hybrid system in their pristine form can improve or preserve the mechanical properties of poly(ether ether ketone) (PEEK) nanocomposites under two extreme cooling rates (fast -460 °C/min and slow -0.7 °C/min). A scalable manufacturing methodology using water as the medium to disperse the powder system was developed, employing a CNC as a dispersing agent and stabilizer for PEEK and GNP. Despite the expected limited mechanical reinforcement due to thermal degradation, CNCs significantly impacted PEEK's crystalline architecture and mechanical performance, suggesting that surface interactions via lattice matching with PEEK's (200) crystallographic plane play a critical role in engineering the microstructure. In fast cooling, the CNC and CNC:GNP systems reduced the crystallinity, respectively, yet led to minimizing the reduction in the tensile strength and maintaining the tensile modulus at the Neat level in slow cooling. With slow cooling, crystallinity remained relatively unchanged; however, the addition of CNC:GNP improved the strength and modulus by ∼10% and ∼16%, respectively. These findings demonstrate that a hybrid nanomaterial system can tailor PEEK's crystalline microstructure, thus presenting a promising approach for enhancing the mechanical properties of PEEK nanocomposites in fast-rate processes.

An Algorithm for Modeling Thermoplastic Spherulite Growth Using Crystallization Kinetics.

Crystallization kinetics were used to develop a spherulite growth model, which can determine local crystalline distributions through an optimization algorithm. Kinetics were used to simulate spherulite homogeneous nucleation, growth, and heterogeneous nucleation in a domain discretized into voxels. From this, an overall crystallinity was found, and an algorithm was used to find crystallinities of individual spherulites based on volume. Then, local crystallinities within the spherulites were found based on distance relative to the nucleus. Results show validation of this model to differential scanning calorimetry data for polyether ether ketone at different cooldown rates, and to experimental microscopic images of spherulite morphologies. Application of this model to various cooldown rates and the effect on crystalline distributions are also shown. This model serves as a tool for predicting the resulting semi-crystalline microstructures of polymers for different manufacturing methods. These can then be directly converted into a multiscale thermomechanical model.

Robust superhydrophobic Poly(vinylidene fluoride) membranes with spherulitic surface morphology against wetting and scaling in membrane distillation

Membrane distillation (MD) offers a theoretically complete interception of salts, presenting a promising desalination pathway for freshwater supply. However, conventional hydrophobic membranes fail to desalinate water containing surfactants or supersaturated gypsum over prolonged periods. To address wetting and scaling challenges, we developed a superhydrophobization methodology for poly (vinylidene fluoride) membranes by in situ controlling spherulitic surface morphology through thermally induced phase separation. The major advantages of this one-step strategy lie in its fluorination-free, template-free, and nanoparticle-free. The as-prepared membranes exhibit a rough morphology and superhydrophobic characters with high air-trapping pockets. They demonstrate stable vapor fluxes and high salt rejections (>99 %) when used in desalination processes for saline water containing 0.6 mM sodium dodecyl sulfate, 0.03 mM cetyltrimethylammonium bromide, or gypsum solution with a saturation index of 1.1. Also, the outstanding anti-wetting and anti-scaling properties were demonstrated using synthetic shale gas wastewater. The formation of an air layer on the integrated spherulitic surface highlights the local kinetic barrier and slippery surface, effectively preventing the attachment of amphiphilic surfactants and mineral ions. Importantly, due to the membrane's structural integrity, the spherulitic surface displays high robustness and minimal impact from abrasion cycles and ultrasonication. This work exemplifies a facile strategy to engineer micro-/nano-spherulitic surface morphology for robust superhydrophobic membranes used in MD desalination.

Crystallization Behavior and Mechanical Property of Biodegradable Poly(butylene succinate-co-2-methyl succinate)/Cellulose Nanocrystals Composites.

Biodegradable poly(butylene succinate-co-2-methyl succinate) (PBSMS)/cellulose nanocrystals (CNC) composites were successfully prepared at low CNC loadings with the aims of improving crystallization and mechanical properties and extending the practical application of PBSMS. CNC is finely dispersed in the PBSMS matrix without obvious aggregations. The low content of CNC obviously promoted the crystallization behavior of PBSMS under different conditions. The spherulitic morphology study revealed that CNC, as an effective heterogeneous nucleating agent, provided more nucleation sites during the melt crystallization process. In addition, the nucleation effect of CNC was quantitatively evaluated by the following two parameters, i.e., nucleation activity and nucleation efficiency. The crystal structure and crystallization mechanism of PBSMS remained unchanged in the composites. In addition, as a reinforcing nanofiller, CNC significantly increased Young's modulus and the yield strength of PBSMS. The crystallization behavior and mechanical properties of PBSMS were significantly improved by the low content of CNC, which should be interesting and essential from the perspective of biodegradable polymer composites.

Structural Characteristics of Fibrillar Crystals in Uniaxially Stretched Isotactic Polypropylene Dominated by Temperature and Strain

AbstractThe spherulitic morphology of isotactic polypropylene can be transformed into the oriented fibrillar morphology through hot stretching processes with varying temperature (Ts) or altering strain (εt). The effects of Ts and εt on the structural characteristics of fibrillar crystals are comprehensively investigated with respect to crystal orientation, long periodic spacing, lamellar thickness (Lc), crystallinity (Xc), melting point, and chain relaxation behavior. Small‐angle X‐ray scattering patterns illustrate that the fibrillar crystals consist of alternated stacks of crystalline lamellae and amorphous layers. High Ts leads to a low orientation degree of lamellae, whereas large εt facilitates a high orientation level. The Xc and mean Lc are improved continuously with the increasing of Ts or εt, indicating a stretching‐enhanced crystallization behavior driven by the two factors. The endothermic profiles reveal that new chain‐folded lamellae with relatively thinner thickness form during the hot stretching process. The formation of thinner lamellae is dominated by the melting–recrystallization mechanism. This work would provide guidance for optimizing process conditions to manipulate the microstructure of hot‐stretched semicrystalline polymers.

Controlled reaction dynamics of cellulose: Revealing the dual morphology nanocrystals

Cellulose nanocrystals exhibit diverse morphology with embedded crystallinity derived from the ordered crystalline regimes of cellulose fibers. Acid hydrolysis parameters controls the morphology of nanocrystals and is the primary efficient route for the synthesis of cellulose nanocrystals. In this study, we explored the impact of temperature on the morphology engineering of cellulose nanocrystals derived from banana pseudostem by oxalic acid hydrolysis, an underexplored method. Confirmation of successful cellulose extraction was achieved through fibrous morphology observed in FESEM and TEM analyses. X-ray diffraction and Raman spectroscopy affirmed the presence of type II cellulose. Notably, for the first time, we report the derivation of toroidal and spherulitic sheet-like morphologies in cellulose nanocrystals synthesized by hydrothermal method from banana psuedostem. Our investigation revealed that cellulose hydrolysis at 120 °C yields nanocrystals characterized by toroidal and spherulitic sheet-like morphologies with excellent crystallinity, as confirmed by FESEM and TEM analyses, with average thicknesses of 13.70 nm and 18.05 nm, respectively. Interestingly, elevating the hydrolysis temperature to 180 °C led to the collapse of these structures into carbon dots, exhibiting notable cyan emission.

Effect of mechanical stretching and low amount of silica adding on gas transport properties of poly(butylene succinate-co-adipate) films

This work aimed at studying the influence of a post drawing process on the morphology and the gas permeability of a PBSA (Polybutylene succinate-co-adipate) film. Two films were studied, one of neat PBSA and one filled with 1%wt of silica. The influence of silica was also studied. Reference films of PBSA and PBSA + Si presented a spherulitic morphology despite a difference of spherulites sizes and long period. After stretching, this isotropic morphology changed to an oriented one, as shown by WAXS measurements. SAXS analysis revealed that stretching led to a lamellae organization in the stretching direction, with lamellae oriented perpendicular to the stretching direction. Thermal characterizations have shown that stretching did not modified the degree of crystallinity for both systems. The helium, carbon dioxide and oxygen permeability increased with stretching, mainly due to the orientation of crystalline lamellae, decreasing the diffusion path. Moreover, for PBSA + Si stretched films, small non-percolating voids were evidenced around the silica particles which could also make gas transport easier. Thus, for both systems, this increase in gas permeability happened in a different way.

Synthesis, crystallization behavior and mechanical property of biodegradable Poly(butylene succinate-co-2-methyl succinate) copolyesters

In this research, a series of biodegradable poly(butylene succinate-co-2-methyl succinate) (PBSMS) random copolyesters with butylene 2-methyl succinate (BMS) unit content from about 10 to 90 mol% were successfully synthesized. Both the homopolymers poly(butylene succinate) (PBS), poly(butylene 2-methyl succinate) (PBMS), and PBSMS copolyesters showed relatively high intrinsic viscosity values of over 0.8 dL/g. The basic thermal parameters, crystallization behavior, crystal structure, spherulitic morphology and growth rate, and mechanical properties of PBSMS copolyesters were extensively studied and compared with those of PBS. The incorporation of methyl group not only effectively increased the toughness of PBSMS copolyesters but also significantly restrained the crystallizability of these copolyesters, showing that PBSMS copolyesters with the BMS unit content higher than 50 mol% were amorphous. Among these copolyesters, PBSMS30 (BMS unit content = 30 mol%) exhibited the most outstanding mechanical properties, with a Young's modulus of 188.0 ± 19.1 MPa, a tensile strength of 19.1 ± 1.8 MPa, and an elongation at break of 714.5 ± 23.2 %. By randomly introducing methyl as a side group into the PBS main chain, the mechanical properties of PBSMS copolyesters have been significantly improved. From the perspective of structure and properties, this study should be interesting and crucial for the development and research of biodegradable polymers.

Preparation and Characterization of Soft-Hard Block Copolymer of 3,4-IP-b-s-1,2-PBD Using a Robust Iron-Based Catalyst System.

A series of well-defined diblock copolymers, namely, 3,4-polyisoprene-block-syndiotactic-1,2-polybutadiene (3,4-PI-b-s-1,2-PBD), with a soft-hard block sequence were synthesized via an in situ sequential polymerization process using a robust iron-based catalytic system Fe(acac)3/(isocyanoimino) triptenylphosphorane (IITP)/AliBu3. This catalyst exhibits vigorous activity and temperature tolerance, achieving a polymerization activity of 5.41 × 106 g mol(Fe)-1 h-1 at 70 °C with a [IP]/[Fe] ratio of 15,000. Moreover, the quasi-living polymerization characteristics of the catalyst were verified through kinetic experiments. The first-stage polymerization of isoprene (IP) is performed at 30 °C to give a soft 3,4-PI block, and then a quantitative amount of 1,3-butadiene was added in situ to the quasi-living polymerization system to produce a second hard s-1,2-PBD. The s-1,2-PBD segments in block copolymers display a rodlike morphology contrasting with the spherulitic morphology characteristic of s-1,2-PBD homopolymers. The precise tunability of the length of the soft and hard chain segments of these novel elastic materials with the feed ratio of IP and BD, endowing them with outstanding mechanical properties and excellent dynamic mechanical properties, which are expected to be promising high-performance rubber materials.

Melt-crystallization and self-nucleation of UHMWPE/bi-HDPE blends: The combined role of composition and molecular weight

Blends of bi-modal high-density polyethylene (bi-HDPE) and ultra-high molecular weight polyethylene (UHMWPE) with varying content (0–30 wt%.) and different molecular weights (MWs) (2.2, 3.5, and 4.5 M g/mol) of UHMWPE were prepared. The effect of UHMWPE content, MW, and their interplay on the microstructure, nucleation, and crystallization behavior of bi-HDPE was examined through rheology, scanning electron microscopy, and differential scanning calorimetry. The results revealed that UHMWPE serves as a partially miscible nucleating agent, effectively dispersing in the bi-HDPE matrix up to 5 wt%, thereby promoting the transition from randomly dispersed lamellae to a spherulitic morphology. The nucleating effect saturated when the UHMWPE content reached 10 wt%, leading to a diminished spherulitic structure. Beyond 10 wt% of UHMWPE, an anti-nucleation effect with segregated crystalline regions emerged. Isothermal kinetics analysis also revealed the highest crystallization rate at the optimum UHMWPE content of 5 wt%, where the critical nucleation energy barrier and fold-surface free energy were minimized. Apart from the UHMWPE content, signs of nucleation enhancement were slightly more pronounced in the bi-HDPE blend with the lowest molecular weight of UHMWPE. This phenomenon results from increased concentration fluctuations due to the larger interfacial area, as postulated from entanglement density measurements. For the first time, self-nucleation (SN) analysis revealed that the incorporation of 5 wt% of UHMWPE into bi-HDPE resulted in a wider Domain II width, indicating an increased memory effect. Notably, the crystalline memory was more pronounced in the blend containing UHMWPE with the MW of 2.2 M g/mol, exhibiting the super-nucleating effect with the highest nucleation efficiency of 218 %.

Mechanical, Thermal, and Physicochemical Properties of Filaments of Poly (Lactic Acid), Polyhydroxyalkanoates and Their Blend for Additive Manufacturing.

Polymeric blends are employed in the production of filaments for additive manufacturing to balance mechanical and processability properties. The mechanical and thermal properties of polymeric filaments made of poly (lactic acid) (PLA), polyhydroxyalkanoates (PHA), and its blend (PLA-PHA) are investigated herein and correlated to their measured structural and physicochemical properties. PLA exhibits the highest stiffness and tensile strength, but lower toughness. The mechanical properties of the PLA-PHA blend were similar to those of PLA, but with a significantly higher toughness. Despite the lower mechanical properties of neat PHA, incorporating a small amount (12 wt.%) of PHA into PLA significantly enhances toughness (approximately 50%) compared to pure PLA. The synergistic effect is attributed to the spherulitic morphology of blended PHA in PLA, promoting interactions between the amorphous regions of both polymers. Thermal stability is notably improved in the PLA-PHA blend, as determined by thermogravimetric analysis. The blend also exhibits lower cold crystallization and glass transition temperatures as compared to PLA, which is beneficial for additive manufacturing. Following additive manufacturing, X-ray photoelectron spectroscopic showed that the three filaments present an increase in C-C and C=O bonds associated with the loss of C-O bonds. The thermal process induces a slight increase in crystallinity in PHA due to chain reorganization. The study provides insights into the thermal and structural changes occurring during the melting process of additive manufacturing.

Enhanced Dielectric Constant of PVDF-HFP/BFO Composite Films for Ferroelectric Applications

We have developed multiferroic Bismuth ferrite (BiFeO3, BFO) incorporated Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer-ceramic composites through the solution casting method. The polymer-ceramic composites are fabricated by varying the composition of the BFO as a filler material ranging 5, 10, 15, 20, 25, 30, and 40 wt% into the PVDF-HFP polymer matrix. We have investigated the effect of BFO loading on the structural, morphological, spectroscopic, and dielectric properties by different characterization techniques. X-ray diffraction analysis indicates the presence of non-polar α- and polar β- phases of PVDF-HFP in the composites. Scanning electron microscope studies revealed the spherulite morphology and homogenous dispersion of BFO particles. The addition of BFO filler in PVDF-HFP matrix at various percentages has been studied to improve the polar β- phase of PVDF-HFP which may enhance ferroelectric properties. The dielectric studies at room temperature showed an increase in dielectric constant value from 9.5 (pure PVDF-HFP) to 21.08 (30% loaded BFO) at 100 Hz. It is also evident from the Fourier Transform- Infrared (FT-IR) spectra, that a maximum of 75.24% of β-fraction is observed for 30% loaded BFO composition. The enhanced properties of the fabricated materials suggest that they may be useful for polymer-ceramic capacitor applications. The results are discussed in detail.

Boosting the Biodegradation and Bioactivity of PBS‐DLS Copolymers via Incorporation of PEG

AbstractBiodegradable polymers play a crucial role in the development of materials for biomedical applications. This study investigates the enzymatic biodegradation, bioactivity, and cytotoxicity of poly(butylene succinate‐dilinoleic succinate) (PBS‐DLS) copolymers modified with poly(ethylene glycol) (PEG). Two copolymer variations with different segmental compositions (70 wt.% and 60 wt.% of hard segments) are synthesized. After modifying the copolymers with PEG, the presence of a lipase catalyst accelerated degradation after 20 days, evidenced by reduced residual content. Gel permeation chromatography analysis showed up to 40% decrease in molecular weight, while gravimetric analysis indicated a mass loss of up to 10%. Morphological examination revealed that the enzymatic breakdown, facilitated by hydrolase activity (boosted by the presence of PEG), resulted in surface erosion, holes, and changes in spherulitic morphology. Bioactivity studies demonstrated the formation of biomimetic calcium/phosphate (Ca/P) crystals. Copolymers with higher crystallinity (70 wt.% hard segments) favored tricalcium phosphate‐like crystal formation, while those with lower crystallinity (60 wt.% hard segments) are more susceptible to hydroxyapatite precipitation. In vitro cytotoxicity tests exhibited excellent cell viability and attachment for all copolymers. The ability to control degradation through PEG modification, along with their bioactivity and cell compatibility, positions them as promising candidates for diverse biomedical applications.