Molecular insight into toughening induced by core-shell structure formation in starch-blended bioplastic composites.

Binary and ternary blends with poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and thermoplastic starch (TPS) were prepared by a melt process to produce biodegradable biomass plastics with both economical and good mechanical properties. The mechanical and structural properties of each blend were evaluated. Molecular dynamics (MD) simulations were also conducted to examine the mechanisms underlying the mechanical and structural properties. PLA/PBS/TPS blends showed improved mechanical properties compared with PLA/TPS blends. The PLA/PBS/TPS blends with a TPS ratio of 25-40 wt% showed higher impact strength than PLA/PBS blends. Morphology observations showed that in the PLA/PBS/TPS blends, a structure similar to that of core-shell particles with TPS as the embedding phase and PBS as the coating phase was formed, and that the trends in morphology and impact strength changes were consistent. The MD simulations suggested that PBS and TPS tightly adhered to each other in a stable structure at a specific intermolecular distance. From these results, it is clear that PLA/PBS/TPS blends are toughened by the formation of a core-shell structure in which the TPS core and the PBS shell adhered well together and stress concentration and energy absorption occurred in the vicinity of the core-shell structure.

Development of poly(butylene adipate-co-butylene succinate-co-ethylene adipate-co-ethylene succinate) (PBEAS) net twine as biodegradable fishing gear.

Nylon fishing nets have excellent strength and durability, but when lost at sea, their insufficient decomposition destroys habitats and spawning grounds, and pollutes the marine environment. This led to the development of poly(butylene succinate) (PBS) resin for biodegradable fishing gear based on aliphatic fibers. Prompted by the low stiffness and elastic recovery of PBS, we introduced two additional components into the molecular structure of PBS: adipic acid and ethylene glycol. These two new components were combined with succinic acid and 1,4-butanediol, the existing components of PBS, to synthesize poly(butylene adipate-co-butylene succinate-co-ethylene adipate-co-ethylene succinate) (PBEAS) resin via esterification and polycondensation reactions of a quaternary aliphatic copolyester. Although the molecular weight and molecular weight distribution of PBEAS are similar to those of PBS, it has excellent tensile strength, stiffness, elastic recovery, and biodegradability, with a low melting point for good production efficiency. These improvements are expected to allow PBEAS resin to be applied to gill nets for fish that require high stiffness, thereby expanding the use of biodegradable fishing gear.

Highly Tunable Piezoresistive Behavior of Carbon Nanotube-Containing Conductive Polymer Blend Composites Prepared from Two Polymers Exhibiting Crystallization-Induced Phase Separation.

Conductive polymer composites (CPCs) are suitable as piezoresistive-sensing materials. When using CPCs for strain sensing, it is still a big challenge to simultaneously improve the piezoresistive sensitivity and linearity along with the electrical conductivity and mechanical properties. Here, highly tunable piezoresistive behavior is reported for multiwalled carbon nanotube (CNT)-filled CPCs based on blends of two semicrystalline polymers poly(vinylidene fluoride) (PVDF) and poly(butylene succinate) (PBS), which are miscible in the melt. When cooling the homogeneous mixture of the blend components, successive crystallization of PVDF and PBS occurs, creating complex crystalline structures in a mixed amorphous phase. The morphology of the blend matrix, the crystallinity of the blend components, and the dispersion and location of the CNTs in the blend depend on the CNT content and the blend composition. Compared with PVDF/CNT composites, the substitution of 10 to 50 wt % PVDF by PBS in the composites shifts the electrical percolation concentration Φc from 0.79 wt % to filler contents as low as 0.50 wt % while improving the stretchability. The piezoresistive behavior is highly tunable by changing the PVDF/PBS ratio. The ternary composites with matrix compositions of PVDF (90 wt %)/PBS (10 wt %) and PVDF (50 wt %)/PBS (50 wt %) show either higher piezoresistive sensitivity or linearity, respectively, caused by the differences in the microstructure of the CPCs. For example, the crystallinity of PBS in the ternary composites increased from 19.8% to 52.0% as the PBS content increased from 10 wt % to 50 wt %, which is connected with altered CNT distribution and conductive network structure and substantial improvement of the linearity of the electrical response to strains up to >20%. Our findings highly contribute to the understanding of the piezoresistive properties of CPCs based on two semicrystalline polymers and are important for future studies to tune the piezoresistive behavior to achieve simultaneously improved sensitivity and linearity.

Architectured helically coiled scaffolds from elastomeric poly(butylene succinate) (PBS) copolyester via wet electrospinning.

Electrospinning is one of the most investigated methods used to produce polymeric fiber scaffolds that mimic the morphology of native extracellular matrix. These structures have been extensively studied in the context of scaffolds for tissue regeneration. However, the compactness of materials obtained by traditional electrospinning, collected as two-dimensional non-woven scaffolds, can limit cell infiltration and tissue ingrowth. In addition, for applications in smooth muscle tissue engineering, highly elastic scaffolds capable of withstanding cyclic mechanical strains without suffering significant permanent deformations are preferred. In order to address these challenges, we report the fabrication of microscale 3D helically coiled scaffolds (referred as 3D-HCS) by wet-electrospinning method, a modification of the traditional electrospinning process in which a coagulation bath (non-solvent system for the electrospun material) is used as the collector. The present study, for the first time, successfully demonstrates the feasibility of using this method to produce various architectures of 3D helically coiled scaffolds (HCS) from segmented copolyester of poly (butylene succinate-co-dilinoleic succinate) (PBS-DLS), a thermoplastic elastomer. We examined the role of process parameters and propose a mechanism for the HCS formation. Fabricated 3D-HCS showed high specific surface area, high porosity, and good elasticity. Further, the marked increase in cell proliferation on 3D-HCS confirmed the suitability of these materials as scaffolds for soft tissue engineering.

Properties of Biodegradable Films Based on Poly(butylene Succinate) (PBS) and Poly(butylene Adipate-co-Terephthalate) (PBAT) Blends †,‡.

Compression molded biodegradable films based on poly(butylene succinate) (PBS) and poly(butylene adipate-co-terephthalate) (PBAT) at varying weights were prepared, and their relevant properties for packaging applications are here reported. The melt rheology of the blends was first studied, and the binary PBS/PBAT blends exhibited marked shear thinning and complex thermoreological behavior, due to the formation of a co-continuous morphology in the 50 wt% blend. The films were characterized by infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), mechanical tensile tests, scanning electron microscopy (SEM), and oxygen and water vapor permeability. PBS crystallization was inhibited in the blends with higher contents of PBAT, and FTIR and SEM analysis suggested that limited interactions occur between the two polymer phases. The films showed increasing stiffness as the PBS percentage increased; further, a sharp decrease in elongation at break was noticed for the films containing percentages of PBS greater than 25 wt%. Gas permeability decreased with increasing PBS content, indicating that the barrier properties of PBS can be tuned by blending with PBAT. The results obtained point out that the blend containing 25 wt% PBS is a good compromise between elastic modulus (135 MPa) and deformation at break (390%) values. Overall, PBS/PBAT blends represent an alternative for packaging films, as they combine biodegradability, good barrier properties and reasonable mechanical behavior.

Fabrication of bimodal open-porous poly (butylene succinate)/cellulose nanocrystals composite scaffolds for tissue engineering application.

The design of porous tissue engineering scaffold with multiscale open-pore architecture (i.e., bimodal structure) promotes cell attachment and growth, which facilitates nutrient and oxygen diffusion. In this study, a porous poly (butylene succinate) (PBS)/cellulose nanocrystals (CNCs) composite scaffold with a well-defined controllable bimodal open-pore interconnected structure was successfully fabricated. The bimodal open-porous scaffold architecture was designed by synergistic control of temperature variation and a two-step depressurization in a supercritical carbon dioxide (Sc-CO2) foaming process. The microstructure and properties of the bimodal open-porous PBS/CNCs scaffold, such as morphology, open porosity, hydrophilic and degradation performance, and mechanical compression properties, were analyzed. In the experiments, the scaffold with unimodal pore structure was used for comparison. The results showed that the bimodal open-porous PBS5 scaffold displayed a well-defined bimodal open-pore structure composed of large pore (~68.9 µm in diameter) and small pore (~11.0 µm in diameter), with a high open porosity (~95.2%). In addition, the scaffolds exhibited good mechanical compressive properties (compressive strength of 2.76 MPa at 50% strain), hydrophilicity (water contact angle of 71.7 °C) and in vitro degradation rate. Moreover, in vitro biocompatibility was determined with NIH-3T3 fibroblast cells using MTT assay and live/dead cell viability assay. Results indicated that the obtained bimodal open-porous scaffolds had a good biocompatibility and the viability of cells grown on the scaffolds reached up to 98% after 7th day of culture. Therefore, our work provides new insights into the use of biodegradable polymeric composite scaffolds with bimodal open-pore structure and balanced properties in tissue engineering.

Preparation of PBS/PLLA/HAP Composites by the Solution Casting Method: Mechanical Properties and Biocompatibility.

The use of biodegradable polymeric scaffolds for tissue regeneration is becoming a common practice in the clinic. Therefore, an inclined trend is developing with regards to improving the mechanical properties of these scaffolds. Here, we aim to improve the mechanical properties of poly (butylene succinate) (PBS)/poly (l-lactic acid) (PLLA) blends by incorporating hydroxyapatite nanoparticles (HAP) in the blends to form composites. PBS/PLLA = 100/0, 95/5, 90/10, 85/15, and 0/100 wt% blends, along-with the loadings of a few mg of HAPs, were prepared using the solution casting method. A scanning electron microscope showed the voids and droplets, indicating the immiscibility of blends. Due to this immiscibility, the tensile strength values of the blends were found to be in between that of pure PBS (42.85 MPa) and pure PLLA (31.39 MPa). HAPs act as a compatibilizer by incorporating themselves in the voids and spaces caused by the immiscibility, thus increasing the overall tensile strength of the resulting composite to a certain extent, e.g., the tensile strength of PBS/PLLA = 95/5 loaded with 50 mg HAPs was found to be 51.16 MPa. The structural analysis employing the X-ray diffraction (XRD) patterns confirmed the formation of polymer blends and composites. The contact angle analysis showed that the addition of HAPs increased the hydrophilicity of the resulting composites. Selective samples were investigated based on mechanical properties to see if the blends and composites are biocompatible. The obtained results showed that all of the samples with better mechanical properties demonstrated good biocompatibility. This indicates the effectiveness of scaffolds for tissue regeneration.

Microfibrillar polymeric ocular inserts for triamcinolone acetonide delivery.

Despite eye drops generally represent the most convenient, simple and patient-friendly formulations to treat ocular diseases, they suffer from poor retention on the ocular surface and low drug bioavailability leading to the necessity of prolonged and continuous treatment over time. Therefore, ocular insert could represent an innovative way to benefit from ocular topical administration while minimizing all the relevant limitation related to this route of administration. Polymeric non-erodible mucoadhesive ocular inserts should be comfortable and should rapidly adhere on the ocular surface, remain in situ for prolonged period, assure a reproducible and controlled drug release as well as act as transcorneal absorption promoters. In this study, a well-known aliphatic polyester, poly(1,4-butylene succinate) (PBS), was used as starting material to produce hydrophobic microfibrillar scaffolds by means of electrospinning technique. Plasma-assisted chemical surface functionalization of the PBS scaffolds with appropriate biopolymers (inulin, α,ß-poly(N-2-hydroxyethyl)-D,L-aspartamide, heparin) was carried out to confer to the final ocular inserts ad hoc properties as wettability, mucoadhesion and cytocompatibility on human corneal epithelial cells, by improving surface hydrophilicity without modifying the bulk properties of the material. The lipophilic drug triamcinolone acetonide was loaded into the obtained ocular insert and release studies were carried out to demonstrate the ability of drug loaded inserts to release the active until 30 days.

Fabrication of Poly(butylene succinate)/Carbon Black Nanocomposite Foams with Good Electrical Conductivity and High Strength by a Supercritical CO2 Foaming Process.

Lightweight, high-strength and electrically conductive poly(butylene succinate) (PBS)/ carbon black (CB) nanocomposite foams with a density of 0.107-0.344 g/cm3 were successfully fabricated by a solid-state supercritical CO2 (ScCO2) foaming process. The morphology, thermal and dynamic mechanical properties, and rheological behavior of the PBS/CB nanocomposites were studied. The results indicate that the CB nanofiller was well dispersed in the PBS matrix and the presence of a proper CB nanofiller can accelerate the rate of crystallization, improve the thermal stability, enhance the stiffness, and increase the complex viscosity of PBS/CB nanocomposites. These improved properties were found to play an important role in the foaming process. The results from foaming experiments showed that the PBS/CB nanocomposite foams had a much smaller cell size, a higher cell density, and a more uniform cell morphology as compared to neat PBS foams. Furthermore, the PBS/CB nanocomposite foams also possessed low density (0.107-0.344 g/cm3), good electrical conductivity (~0.45 S/cm at 1.87 vol % CB loading), and improved compressive strength (108% increase), which enables them to be used as lightweight and high-strength functional materials.

The Effect of Varying Almond Shell Flour (ASF) Loading in Composites with Poly(Butylene Succinate (PBS) Matrix Compatibilized with Maleinized Linseed Oil (MLO).

In this work poly(butylene succinate) (PBS) composites with varying loads of almond shell flour (ASF) in the 10⁻50 wt % were manufactured by extrusion and subsequent injection molding thus showing the feasibility of these combined manufacturing processes for composites up to 50 wt % ASF. A vegetable oil-derived compatibilizer, maleinized linseed oil (MLO), was used in PBS/ASF composites with a constant ASF to MLO (wt/wt) ratio of 10.0:1.5. Mechanical properties of PBS/ASF/MLO composites were obtained by standard tensile, hardness, and impact tests. The morphology of these composites was studied by field emission scanning electron microscopy-FESEM) and the main thermal properties were obtained by differential scanning calorimetry (DSC), dynamical mechanical-thermal analysis (DMTA), thermomechanical analysis (TMA), and thermogravimetry (TGA). As the ASF loading increased, a decrease in maximum tensile strength could be detected due to the presence of ASF filler and a plasticization effect provided by MLO which also provided a compatibilization effect due to the interaction of succinic anhydride polar groups contained in MLO with hydroxyl groups in both PBS (hydroxyl terminal groups) and ASF (hydroxyl groups in cellulose). FESEM study reveals a positive contribution of MLO to embed ASF particles into the PBS matrix, thus leading to balanced mechanical properties. Varying ASF loading on PBS composites represents an environmentally-friendly solution to broaden PBS uses at the industrial level while the use of MLO contributes to overcome or minimize the lack of interaction between the hydrophobic PBS matrix and the highly hydrophilic ASF filler.

Enzymatic Degradation of Poly(butylene succinate) Copolyesters Synthesized with the Use of Candida antarctica Lipase B.

Biodegradable polymers are an active area of investigation, particularly ones that can be produced from sustainable, biobased monomers, such as copolymers of poly(butylene succinate) (PBS). In this study, we examine the enzymatic degradation of poly(butylene succinate-dilinoleic succinate) (PBS-DLS) copolymers obtained by "green" enzymatic synthesis using lipase B from Candida antarctica (CALB). The copolymers differed in their hard to soft segments ratio, from 70:30 to 50:50 wt %. Enzymatic degradation was carried out on electrospun membranes (scaffolds) and compression-moulded films using lipase from Pseudomomas cepacia. Poly(ε-caprolactone) (PCL) was used as a reference aliphatic polyester. The degradation process was monitored gravimetrically via water uptake and mass loss. After 24 days, approx. 40% mass loss was observed for fibrous materials prepared from the PBS-DLS 70:30 copolymer, as compared to approx. 10% mass loss for PBS-DLS 50:50. Infrared spectroscopy (FTIR) and size exclusion chromatography (SEC) analysis were used to examine changes in chemical structure. Differential scanning calorimetry (DSC) and scanning light microscopy (LSM) revealed changes in degree of crystallinity, and changes in surface morphology, consistent with a surface erosion mechanism. We conclude that the obtained copolymers are suitable for tissue engineering applications thanks to tuneable degradation and lack of acidification during breakdown.

A Facile Fabrication of High Toughness Poly(lactic Acid) via Reactive Extrusion with Poly(butylene Succinate) and Ethylene-Methyl Acrylate-Glycidyl Methacrylate.

As is an excellent bio-based polymer material, poly(lactic acid) (PLA)'s brittle nature greatly restricts its extensive applications. Herein, poly(butylene succinate) (PBS) was introduced to toughening PLA by melt blending using a self-made triple screw extruder through in situ reactive with ethylene-methyl acrylate-glycidyl methacrylate (EGMA). The effect of EGMA concentrations on the mechanical properties, morphology, interfacial compatibility of PLA/PBS blends were studied. Fourier transform infrared (FT-IR) results demonstrated that the epoxy group of EGMA reacts with the hydroxyl groups of PLA and PBS, which proved the occurrence of interfacial reactions among the tri-component. The significantly improved compatibility between PLA and PBS after EGMA incorporation was made evident by scanning electron microscope (SEM) characterization results. Meanwhile, the contact angle test predicted that the EGMA was selectively localized at the interface between PLA and PBS, and the result was verified by morphological analysis of cryofracture and etched samples. The EGMA improves the compatibility of PLA/PBS blends, and consequently leads to a significantly increased toughness with the elongation at break occurring 83 times more when 10 wt % EGMA was introduced than neat PLA, while impact strength also enhanced by twentyfold. Ultimately, the toughening mechanism of PLA based polymers was established based on the above analysis, exploring a new way for the extensive application for degradable material.

Shape Memory Properties of PBS-Silica Hybrids.

A series of novel Si-O-Si crosslinked organic/inorganic hybrid semi-crystalline polymers with shape memory properties was prepared from alkoxysilane-terminated poly(butylene succinate) (PBS) by water-induced silane crosslinking under organic solvent-free and catalyst-free conditions. The hydrolyzation and condensation of alkoxysilane end groups allowed for the generation of silica-like crosslinking points between the polymeric chains, acting not only as chemical net-points, but also as inorganic filler for a reinforcement effect. The resulting networks were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic-mechanical analysis (DMA) and tensile and shape memory tests to gain insight into the relationship between the polymeric structure, the morphology and the properties. By controlling the molecular weight of the PBS precursor, a fine tuning of the crosslinking density and the inorganic content of the resulting network was possible, leading to different thermal, mechanical and shape memory properties. Thanks to their suitable morphology consisting of crystalline domains, which represent the molecular switches between the temporary and permanent shapes, and chemical net-points, which permit the shape recovery, the synthesized materials showed good shape memory characteristics, being able to fix a significant portion of the applied strain in a temporary shape and to restore their original shape above their melting temperature.

Mechanical properties and crystallization behavior of hydroxyapatite/poly(butylenes succinate) composites.

Biodegradable synthetic polymers have attracted much attention nowadays, and more and more researches have been done on biodegradable polymers due to their excellent mechanical properties, biocompatibility, and biodegradability. In this work, hydroxyapatite (HA) particles were melt-mixing with poly (butylenes succinate) (PBS) to prepare the material, which could be used in the biomedical industry. To develop high-performance PBS for cryogenic engineering applications, it is necessary to investigate the cryogenic mechanical properties and crystallization behavior of HA/PBS composites. Cryogenic mechanical behaviors of the composites were studied in terms of tensile and impact strength at the glass transition temperature (-30°C) and compared to their corresponding behaviors at room temperature. With the increase of HA content, the crystallization of HA/PBS composites decreased and crystallization onset temperature shifted to a lower temperature. The diameter of spherulites increased at first and decreased with a further HA content. At the same time, the crystallization rate became slow when the HA content was no more than 15wt% and increased when HA content reached 20wt%. In all, the results we obtained demonstrate that HA/PBS composites reveal a better tensile strength at -30°C in contrast to the strength at room temperature. HA particles with different amount affect the crystallization of PBS in different ways.