Morphological characteristics and thermal,rheological, and mechanical properties of cellulose nanocrystals-containing biodegradable poly(lactic acid)/poly(ε-caprolactone) blend composites

This work investigates the effect of cellulose nanocrystal (CN) loading on the properties of polylactide / poly(ε-caprolactone) (PLA/PCL) (70/30) blend processed in a twin-screw extruder as a potential material that can be utilized in various applications where biodegradation is highly desired. The morphological analysis revealed a reduction in droplet size of dispersed PCL phase upon addition of CN at low concentrations (1 and 2 wt %) with maximum reduction at 2 wt % which led to maximum improvement in mechanical properties. The reinforcing effect of CN in increasing the DMA storage modulus of the prepared systems was noticed when CN concentration was increased. Further, CN enhanced the crystallization of PCL, whereas the cold crystallization of PLA remained the same with CN addition. Both melt strength and viscosity of PLA improved with the incorporation of PCL and CN. In general, a green composite material with improved properties was successfully prepared using an environmentally friendly filler material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48665.     

DSC studies of poly(vinyl chloride)/poly(ε-caprolactone)/poly(ε-caprolactone)-b-poly(dimethylsiloxane) blends

Poly(vinyl chloride)/poly(ε-caprolactone)/poly(ε-caprolactone)-b-poly(dimethylsiloxane) [PVC/PCL/(PCL-b-PDMS)] blends were prepared by solvent casting from tetrahydrofuran. The content of PVC was kept constant (60 wt%); the PCL and PCL-b-PDMS contents were varied by replacing different amounts of PCL [0–20 wt% from the PVC/PCL (60/40) blend] with PCL-b-PDMS copolymer having different molecular weights of the PCL blocks. The thermal properties of prepared blends were investigated by differential scanning calorimetry in order to analyse miscibility (through glass transition temperature) and crystallinity. Differential scanning calorimetry analyses show that the PVC/PCL/PCL-b-PDMS blends are multi-phase materials which contain a PVC plasticized with PCL phase, a block copolymer PCL-b-PDMS phase (with crystalline and amorphous PCL and PDMS domains) and a PCL phase (preponderantly crystalline).     

Enzymatic degradation,electronic, and thermal properties of graphite- and graphene oxide-filled biodegradable polylactide/poly(ε-caprolactone) blend composites

Commodity polymers are the most widely used materials for electronic packaging applications. However, they are nondegradable and causing serious environmental damage. Addressing this challenge, the relative effects of graphite (G) and graphene oxide (GO) dispersion on the enzymatic degradation, electronic properties, thermal degradation, and crystallization behavior of enzyme degradable polylactide/poly(ε-caprolactone) blend composites is investigated. Owing to the oxygenated surface functionalities and excellent thermal conductivity arising from the carbon structure, the randomly dispersed GO particles do not provide electrical pathways and facilitate large enhancements in the electrical resistivity (126%) and thermal conductivity (72%) of the blend composites. However, while the G particles enhanced the thermal conductivity of the composites, they had little effect on enzymatic degradation. Furthermore, they reduced the electrical resistivity, particularly at high concentration (0.25 wt % G), as a result of the conducting delocalized electrons in the G structure and due to network formation. We also find that the energy required to initiate and propagate the thermal degradation process for GO-filled blend composites is relatively lower than that of G-filled blend composite. However, the former composites show higher crystallization rate coefficients value than that of G-filled composites and the neat blend, thereby providing better crystallization ability and miscibility with the matrix. In summary, the GO-filled blend composites are observed to show potential for use in sustainable materials for thermal management applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47387.     

Multilayer biopolymer/poly(ε-caprolactone)/polycation nanoparticles

Combining two or more materials for carrier construction is one of the topical approaches to avoid/diminish deficiencies and to increase functionality in delivery systems for bioactive compounds. In this context, here, multilayered nanoparticles comprising both natural (atelocollagen—AteCol; hyaluronic acid derivative—HA) and synthetic [poly(ε-caprolactone)—PCL; polyethylenimine—PEI; poly(l-lysine)—PLL] polymers were prepared and characterized. The combination of a modified double-emulsion method with polymer modification reactions allowed improvement of the polymer particle’s functionality. Fourier transform infrared spectroscopy (FTIR), UV–Vis spectroscopy, fluorescence spectroscopy, dynamic light scattering, transmission/scanning electron microscopy and fluorescence microscopy investigations confirmed the obtention of the envisaged nanomaterials with the expected composition and structure. The double-layered biopolymer/PCL-based nanoparticles formed in a first synthesis step could be successfully coated with PEI and PLL. The gel electrophoresis assay attested the DNA packing ability of the formed nano-vehicles involving surface grafting of the former biopolymer/PCL-based nanoparticles in the case of both cationic polymers, for N/P ratios of 10 (PEI coating) and 3.5 (PLL coating), respectively. According to the FTIR registration, the protein’s native form was preserved. Considering the advantage of biocompatibility and high versatility (controlled size, tuned chemistry and biodegradation rate) some of the resulted nanomaterials may appear as potential candidates for biomedical uses (i.e., drug/gene delivery and tissue engineering).     

Poly(ε-caprolactone)/poly(m-anthranilic acid) and poly(ε-caprolactone)/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) electrospun nanofibers: Characterization,antioxidant, and electrochemical properties

Conducting polymers are widely used in many biomedical applications, but their non-degradability and non-biocompatibility limit their widespread use in applications. For this reason, many studies have been carried out on the developing degradable, biocompatible, and electrically conductive polymers. In this study, mixtures of conductive polymers (poly(m-antranilic acid) (P3ANA) and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS)) with biocompatible and biodegradable poly(ε-caprolactone) (PCL) were prepared. Their nanofibers were obtained by electrospinning and their antioxidant properties were investigated by 2,2′-azino-bis-3-ethylbenzthiazoline-6-sulfonic acid (ABTS) and copper ion reducing antioxidant capacity (CUPRAC) assays. Electrochemical properties were also investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The highest antioxidant activity was obtained from PCL/P3ANA3 electrospun nanofiber containing 10% (of PCL w/w) P3ANA with 93 and 614 μg TE/mg values for ABTS and CUPRAC assays, respectively. This nanofiber was found to be non-toxic according to 2,5-diphenyl-2H-tetrazolium bromide (MTT) analysis. PCL/PEDOT:PSS electrospun nanofiber has the highest maximum anodic current value of 0.08 mA. The maximum anodic current value of PCL/P3ANA3 nanofiber with the highest amount of P3ANA is also higher than other PCL/P3ANA nanofibers. These nanofibers were characterized by FT-IR, UV–vis., XRD and TGA and their surface morphologies were examined by scanning electron microscopy (SEM).     

Structures and mechanical properties of electrospun cellulose nanofibers/poly(ε-caprolactone) composites

Poly(ε-caprolactone) (PCL) is one of the ecofriendly biodegradable polymers with excellent moldability but with rather low mechanical properties especially for the industrial and biomedical use. In this research, to overcome the problem, the two types of cellulose nanofibers, the cellulose acetate nanofibers (CA-NF) and the cellulose nanofibers (C-NF), were composited into PCL for the enhancement of the mechanical properties of PCL. CA-NF were prepared by electrospinning and converted into C-NF afterward by deacetylation. It was found that the Young's modulus of the CA-NF/PCL composite at the fiber concentration of 35 wt% significantly increased by ~3 times as compared with that of neat PCL, whereas C-NF/PCL of the same fiber concentration also increased by ~4.5 times. It was also found that the Young's moduli of CA-NF/PCL nearly reached the theoretical values calculated by the equation suggested by Tsai, but that the Young's moduli of C-NF/PCL could not reach the theoretical values. It indicates that CA-NF possessed better compatibility with PCL than C-NF, agreeing well with the fracture-surface analyses of the two composites by the scanning electron microscopy.     

Effects of processing conditions on hybrid filler selective localization,rheological, and thermal properties of poly(ε-caprolactone)/poly(lactic acid) blends

In this study, the effects of processing conditions through different mixing sequences were used to analyze the factors, which could influence the hybrid filler selective localization in an immiscible polymer blend and how localization can influence the rheological and thermal properties. Different selective localizations were observed depending on the mixing sequence used when the hybrid filler was added. Notably, nanoparticles can interact with each other, which favor a synergy between them and alters, besides the localization, the dispersion state, or can interact with one polymer phase, and also alter the nanoparticles' selective localization. An improvement in rheological properties was observed in the hybrid nanocomposite in which there was interaction between the nanoparticles, favoring the hexagonal boron nitride exfoliation. On the other hand, for the storage modulus and degree of crystallinity, the sharpest increase occurred in the hybrid nanocomposite in which the nanoparticles could interact preferably with one polymer phase. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48711.     

Nucleation,crystallization, self-nucleation and thermal fractionation of cyclic and linear poly(ε-caprolactone)s

A series of low polydispersity cyclic PCL samples (C-PCLs), as well as their linear analogs (L-PCLs), were synthesized by click chemistry in a number average molecular weight (M_n) range of 2–22 kg/mol. They were investigated by Polarized Light Optical Microscopy (PLOM) and Differential Scanning Calorimetry (DSC). The nucleation and overall crystallization kinetics were studied, as well as their self-nucleation behavior and SSA (Successive Self-nucleation and Annealing) thermal fractionation. Cyclic PCLs were found to nucleate and crystallize faster than linear PCLs due to: (a) faster diffusion of C-PCL chains and (b) larger supercoolings of C-PCLs at any given crystallization temperature, as compared to L-PCLs. A bell shape curve was obtained when the overall crystallization rate was examined as a function of M_n, this effect is probably due to a competition between nucleation and diffusion. It was found for the first time, that since cyclic molecules have lower entanglement densities, they can quickly recover their pseudo-equilibrium compact coil conformations upon melting and therefore exhibit much smaller crystalline memory effects than their linear counterparts of identical chain lengths. SSA revealed that C-PCLs are more sensitive to annealing than L-PCLs because their ring topology and limited lamellar chain folding facilitates crystal thickening.     

Effect of poly(ε-caprolactone) and titanium (IV) dioxide content on the UV and hydrolytic degradation of poly(lactic acid)/poly(ε-caprolactone) blends

The effect of accelerated weathering degradation on the properties of poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) blends and PLA/PCL/titanium (IV) dioxide (TiO₂) nanocomposites are presented in this paper. The results show that both polymers are susceptible to weathering degradation, but their degradation rates are different and are also influenced by the presence of TiO₂ in the samples. Visual, microscopic and atomic force microsocpy observations of the surface after accelerated weathering tests confirmed that degradation occurred faster in the PLA/PCL blends than in the PLA/PCL/TiO₂ nanocomposites. The X-ray diffraction results showed the degradation of PCL in the disappearance of its characteristic peaks over weathering time, and also confirmed that PLA lost its amorphous character and developed crystals from the shorter chains formed as a result of degradative chain scission. It was further observed that the presence of TiO₂ retarded the degradation of both PLA and PCL. These results were supported by the differential scanning calorimetry results. The thermogravimetric analysis results confirmed that that PLA and PCL respectively influenced each other's thermal degradation, and that TiO₂ played a role in the thermal degradation of both PLA and PCL. The tensile properties of both PLA/PCL and PLA/PCL/TiO₂ were significantly reduced through weathering exposure and the incorporation of TiO₂.     

Compatibilizing capability of poly(β-hydroxybutyrate-,co-ε-caprolactone) in the blend of poly(β-hydroxybutyrate) and poly(ε-caprolactone)

In order to increase the miscibility in the blend of poly(β-hydroxybutyrate) [PHB] and poly(ε-caprolactone) [PCL], PHB/PCL copolyesters were used as compatibilizers. These PHB/PCL copolyesters were synthesized by transesterification in solution phase. The melting point [T_m] depression, which was not observed in PHB/PCL blend without compatibilizer, was observed when PHB/PCL copolyesters as compatibilizers were added to the PHB/PCL blend system. As the amount of compatibilizer added to the blend increased, the crystallization temperature [T_c] of PCL in the blend increased and T_c of PHB in the blend decreased. The difference in T_c between PHB and PCL was gradually reduced. When the sequence length of PHB block and PCL block in the PHB/PCL copolyester increased, the miscibility of the blend increased. This is evidenced by the depression in the T_m of PHB and PCL in the blend and by the decrease in the difference of T_c between PHB and PCL. From the polarizing optical micrographs, the phase separation in PHB/PCL blend was observed. However, in the presence of PHB/PCL copolyester, the spherulite of PHB grows in equilibrium with one phase melt. Received: 27 July 1998/Revised version: 12 October 1998/Accepted: 4 November 1998     

Physical properties and biodegradation of acrylic acid grafted poly(ε-caprolactone)/chitosan blends

We blended films of acrylic acid grafted polycaprolactone (PCLgAA) and citosan (CS) with different compositions from aqueous acetic acid solution. DSC measurements showed that the melting temperatures and enthalpies of the blends decreased with increasing CS content. From FTIR results, we observe that the amino groups of CS form covalent bonds with the carboxylic groups of PCLgAA in addition to hydrogen bonds between the constituents in the blends. Though the crystal structure of the PCLgAA component was not changed, as proved by WAXD results, blending CS suppressed the crystallinity of the blends. Furthermore, the ductility of CS was increased during tensile testing in PCLgAA/CS blends due to enhanced affinity between the two components. However, PCLgAA/CS blends show greater resistance than PCL/CS blends to biodegradation in an enzymatic environment.     

Synthesis and self-assembly of a new amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) block copolymer

New amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) (PNVCL-b-PCL) block copolymers were synthesized by ring-opening polymerization of ε-caprolactone with hydroxy-terminated poly(N-vinylcaprolactam) (PNVCL-OH) as a macroinitiator. The structures of the polymers were confirmed by IR, ¹H NMR and GPC. The critical micelle concentrations of copolymer in aqueous solution measured by the fluorescence probe technique reduced with the increasing of the proportion of hydrophobic parts, so did the diameter and distribution of the micelles determined by dynamic light scattering. The shape observed by transmission electron microscopy (TEM) demonstrated that the micelles are spherical. On the other hand, the UV–vis measurement showed that polymers exhibit a reproducible temperature-responsive behavior with a lower critical solution temperature (LCST). The LCST of PNVCL-OH can be adjusted by controlling the molecular weights, and that of copolymers can be adjusted by controlling the compositions and the concentration. Variable temperature TEM measurements demonstrated that LCST transition was the result of transition of individual micelles to larger aggregates.     

In vitro degradation of poly(l-lactide)/poly(ε-caprolactone) blend reinforced with MWCNTs

The physical and mechanical properties of poly(l-lactide)/poly(??-caprolactone) (PLLA/PCL) blends reinforced with multiwalled carbon nanotubes (MWCNTs) before and after in vitro degradation were investigated. Because of brittleness, PLLA needs to be plasticized by PCL as a soft polymer. The MWCNTs are used to balance the stiffness and the flexibility of PLLA/PCL blends. The results showed that with incremental increase in concentration of MWCNTs in composites, the agglomerate points of MWCNTs were increased. The physical and mechanical properties of prepared PLLA/PCL blends and MWCNT/PLLA/PCL nanocomposites were characterized. The X-ray diffraction analysis of the prepared blends and composites showed that MWCNTs, as heterogeneous nucleation points, increased the lamella size and therefore the crystallinity of PLLA/PCL. The mechanical strength of blends was decreased with incremental increase in PCL weight ratio. The mechanical behavior of composites showed large strain after yielding and high elastic strain characteristics. The tensile tests results showed that the tensile modulus and tensile strength are significantly increased with increasing the concentration of MWCNTs in composites, while, the elongation-at-break was decreased. The in vitro degradation rate of polymer blends in phosphate buffer solution (PBS) increased with higher weight ratio of PCL in the blend. The in vitro degradation rate of nanocomposites in PBS increased about 65% when the concentration of MWCNTs increased up to 3% (by weight). The results showed that the degradation kinetics of nanocomposites for scaffolds can be engineered by varying the contents of MWCNTs.     

Rheological properties of poly(ε-caprolactone) and poly(styrene-co-acrylonitrile) blends

Summary Rheological properties of poly(-caprolactone) (PCL) and Poly (styrene-co-acrylonitrile) (SAN) blends were examined as a function of the acrylonitrile (AN) content in SAN, to systematically understand the correlation between the interaction parameter and the theological properties of miscible polymer blends. When the plateau modulus (G _N ⁰) and zero shear viscosity ( ₀) of the PCL/SAN blends are plotted against the AN content in SAN, a minimum is observed. Qualitatively, the results obtained parallel the variation of the interchain interaction with the AN content. The negative deviation ofG _N ⁰ and ₀ from linearity seems to be attributed to the increase in the entanglement molecular weight between dissimilar chains which results from the chain extension caused by interchain interaction.     

Fabrication and characterization of poly(ε-caprolactone)/gelatin nanofibrous scaffolds for retinal tissue engineering

Different ratios of poly(ε-caprolactone) (PCL) and gelatinwere used to fabricate scaffolds for regeneration of retinal pigment epithelium (RPE) layer. Physical and chemical characterizations were performed and the behavior of human RPE cells on the scaffolds was evaluated subsequently. An increase in gelatin content in the scaffold enhanced hydrophilicity, RPE cell attachment, proliferation, and spreading over PCL scaffolds. Granular and cytoplasmic expressions of RPE65 and Cytokeratin 8/18 markers confirmed the presence of RPE cells. It was believed that PCL/gelatin scaffolds could be used as substrates to replace RPE extracellular matrix to facilitate regeneration of RPE layer in retinal diseases.     

Tetracycline hydrochloride-containing poly (ε-caprolactone)/poly lactic acid scaffold for bone tissue engineering application: in vitro and in vivo study

In the current study, tetracycline hydrochloride (TCH), an antibiotic against most of the medically relevant bacteria, was incorporated into poly (ε-caprolactone)/poly lactic acid solution in order to develop a composite scaffold with both antibacterial and osteoinductive properties for the repair of infected bone defects. The composite scaffolds were produced from poly (ε-caprolactone) (PCL) and poly lactic acid (PLA) solution (1:1 (w/w)) incorporated with 3, 5, and 10% (w/w) of TCH by thermally induced phase separation technique. The scaffolds were evaluated regarding their morphology, wettability, porosity, degradation, mechanical properties, and cellular response. The scaffold containing 10% of TCH (PCL/PLA/TCH10%) was chosen as the optimum scaffold for further investigation in a rat femoral defect model. The study showed that after eight weeks, the bone formation was relatively higher in PCL/PLA/TCH10%-treated group with completely filled defect when compared with control (PCL/PLA scaffold without TCH). Histopathological evaluation showed that the defect in PCL/PLA/TCH10%-treated group was fully replaced by new bone and connective tissue. Our results provide evidence supporting the possible applicability of TCH-containing scaffolds for successful bone regeneration.     

Preparation and the controlled release effect study of graphene oxide-modified poly(ε-caprolactone)

Functionalized graphene oxide-modified poly(ε-caprolactone) composites ((graphene oxide)GO/PCL) were successfully synthesized by Steglich esterification for drug applications of controlled release. Lomefloxacin (LMF) was selected as a model drug to investigate its controlled release properties. The controlled release effect of the LMF-contained pills of the GO/PCL and polylactic acid blend was evaluated. In contrast to the pure PCL, GO/PCL could effectively adjust the time of drug release and release the drug at a constant rate, achieving the controlled release requirements. Furthermore, different additive amounts of graphene oxide have different effects on adjusting the time of controlled release, while the best result obtained under the ratio is 4% GO/PCL as carrier of drug. Thus, high-quality drug carrier materials are obtained which are more suitable for clinical use. Exploring the optimum addition of graphene oxide is very significant for the development of GO/PCL carrier material.     

Disclosing the role of surface and bulk erosion on the viscoelastic behavior of biodegradable poly(ε-caprolactone)/poly(lactic acid)/hydroxyapatite nanocomposites

In this study, biodegradable polymer blends and their nanocomposites were prepared using poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) as blending components and hydroxyapatite (HA) nanoparticles as reinforcement. X-ray diffraction spectra showed that the presence of HA nanoparticles enhanced the intensity of the peaks (100) and (200) corresponding to the PCL's crystalline planes. The transmission electron microscopy images confirmed the high tendency of HA nanoparticles to locate in the PLA phase. The water uptake values of samples measured at pH 4 were more than those measured at other pH values. The weight loss behavior of blends in acidic medium was completely different from that in basic and neutral media. The Williams–Landel–Ferry equation and time–temperature superposition principle were applied to the creep compliance of the samples and their master curves were determined at reference temperature of 30 °C, and the mechanical properties of samples were predicted in other conditions. The effect of pH on the creep–recovery response of studied samples was analyzed. From this analysis, it could be found that at pH 4, the creep stain increased, while, at pH 7, there was no a significant change in the viscoelastic property. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47151.     

Polymer blending or fiber blending: A comparative study using chitosan and poly(ε-caprolactone) electrospun fibers

Nonwoven membranes of poly(ε-caprolactone) (PCL) and chitosan (CS) were produced according to the two methods: by blending the polymers in solution followed by electrospinning – polymer blending method – and by simultaneous deposition of fibers electrospun from separate solutions – fiber blending (FB) method. The two production methods were compared by assessing fiber morphology, mass loss, swelling degree, water contact angle, and mechanical properties of the resulting electrospun membranes. Furthermore, the adhesion, proliferation, and morphology of human dermal fibroblasts on the eight types of scaffold produced were evaluated to assess if the blending method used would influence cell–scaffold interaction. Cell adhesion to the different scaffolds lied in the interval 40–60%, with the CS scaffold presenting the lowest value. Interestingly, cell proliferation was the same when comparing polymer blending and FB scaffolds having 3:1 or 1:3 PCL/CS ratios but very different when the ratio was 1:1 – the FB scaffold sustained a proliferation rate double that of the polymer blending scaffold. This work shows that, when blending polymers to improve the properties of a scaffold for tissue engineering or 3D cell culture, their spatial distribution may considerably affect scaffold's properties and should be considered as another parameter requiring optimization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47191.     

Rheologically determined phase diagram of poly(ε-caprolactone)/poly(styrene-co-acrylonitrile) blends: Role of ramp rate in dynamic measurements

The phase behavior of poly(ε-caprolactone) (PCL)/poly(styrene-co-acrylonitrile) (SAN) blends, with a lower critical solution temperature (LCST)-type phase diagram over a virtual upper critical solution temperature (UCST) one, was investigated through thermal analysis and dynamic rheological measurements as a function of ramp rate. The LCST phase diagram was detected rheologically from the observed slope changes in the dynamic temperature ramps of storage modulus (G′). The determined phase transition points along with the spinodal temperatures, which are estimated based on the theoretical approach of Ajji and Choplin's mean field theory, shift to higher temperatures by reducing the ramp rate. The detected shifts show a composition dependency. Far away from the critical point, the phase transition temperatures of PCL/SAN blends change more noticeably, which originates from the smaller magnitude of concentration fluctuations in the metastable region and the stronger competition between the phase dissolution and cooling rate. The Flory–Huggins interaction parameter (χ) was appropriately adjusted into the LCST phase boundary as a function of temperature and composition. The results confirmed that the adjusted χ has higher temperature dependency at larger ramp rate of the dynamic measurements. The experimentally combined LCST and UCST phase behavior were also verified by the compressible regular solution model. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47750.