Effects of Poly(ϵ-caprolactone) on Structure and Properties of Poly(lactic acid)/Poly(ϵ-caprolactone) Meltblown Nonwoven

To obtain flexile poly(lactic acid)-based melt-blown nonwoven filtration material, poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven with various components were melt-spun by melt-blown processing in the Melt-blown Experiment Line. The 3 wt.% tributyl citrate to poly(?-caprolactone) was added in the composites as compatibilizer. The effect of poly(?-caprolactone) on the structure, morphology, mechanical and filtration properties of poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven was reported. Scanning electron microscopy micrographs revealed good dispersion of the additive in the fiber webs. The crystallinity of melt-blown webs with poly(?-caprolactone) was more than that of poly(lactic acid) alone. The tensile strength, ductility and air permeability of poly(lactic acid) melt-blown nonwovens were enhanced significantly. The input of poly(?-caprolactone) increased the diameter of fibers and decreased the filtration efficiency of poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven.     

Effect of Surface Modification of Nano-Hydroxyapatite Particles on In Vitro Biocompatibility of Poly (ϵ-Caprolactone)–Matrix Composite Biomaterials

Three silane coupling agents were employed to modify the surfaces of nano-hydroxyapatite particles. Alamar Blue activity and alkaline phosphatase assay on the surfaces of the modified n-HA/PCL composites were carefully examined. The results showed that the KH792 silane modification had positively impact in interaction between bone marrow cells, and it suggested this KH792 modified composite was basically biocompatible with bone cells of rats.     

Scale of Homogeneous Mixing in Miscible Blends of Organosolv Lignin Esters with Poly(ϵ-caprolactone)

Abstract

Organosolv lignin (OSL) esters (side-chain carbon number, n = 3, 4, and 5) have been demonstrated to be miscible with poly(?-caprolactone) (PCL) on a scale (20–30 nm) for detecting glass transition temperature (T _g) by differential scanning calorimetry (Polym. J. 2009, 41(3), 219–227). Further precise quantification of homogeneity was conducted for the OSL propionate (OSL-Pr, n = 3)/PCL and OSL butyrate (OSL-Bu, n = 4)/PCL blends by means of dynamic mechanical analysis (DMA) and solid-state nuclear magnetic resonance (NMR). DMA revealed a composition-dependent T _g for these blend samples, which implies the attainment of an intimate mixing of the ingredients on a scale of ≤15 nm. From the measurements of proton spin-lattice relaxation times (T _1ρ ^H) using solid-state NMR, the blends were estimated to be substantially homogeneous on a scale of ～6 nm. But the equalization of the T _1ρ ^H for the components of OSL-Pr/PCL was not remarkable; that is, the constituents of OSL-Pr/PCL were relatively imperfectly miscible with each other.     

New Epoxy-Anhydride Thermosets Modified with Multiarm Stars with Hyperbranched Polyester Cores and Poly(ϵ-caprolactone) Arms

Multiarm star polymers with hyperbranched aromatic or aromatic-aliphatic cores and poly(?-caprolactone) arms have been used as toughness modifiers in epoxy-anhydride formulations catalyzed by benzyldimethylamine. The curing process has been studied by dynamic scanning calorimetry, demonstrating little influence of the mobility of the reactive species and the hydroxyl content on the kinetics of this process. The obtained materials were characterized by thermal and mechanical tests and the microstructure by electron microscopy. Homogeneous thermosets have been obtained with a remarkable increase in impact strength without compromising glass transition temperature, thermal stability or hardness.     

Crystallisation of nanohybrids of poly(ϵ-caprolactone) and hydrotalcites containing antimicrobial species

Abstract

New composites of poly(?-caprolactone) containing Zn/Al hydrotalcites [layer double hydroxide (LDH)] and ‘active’ antimicrobial anions (benzoate, dichlorobenzoate, o-hydroxybenzoate and p-hydroxybenzoate) prepared with two different techniques have been characterised through differential scanning calorimetry and dynamic mechanical analysis. The method of preparation of the samples has a strong influence on the dispersion of the nanolayers within the polymeric matrix, and, in turn, on the crystallisation kinetics: in fact, the samples prepared by high energy ball milling crystallise much faster than those prepared by casting. The different ‘active’ anions strongly affect the value of the LDH interlamellar distance, which, in turn, affects their capacity of dispersion in the polymer. As a consequence of the different kinds of dispersion, the sample containing benzoate LDH or dichlorobenzoate LDH crystallises faster than that containing p-hydroxybenzoate LDH. Such results are of great importance in the definition of processing and use conditions of such materials of potential interest in food ‘active’ packaging.     

Functionalized Multi-Walled Carbon Nanotubes with Vitamin C Structures: Characterization and Fabrication of Thiazole Containing Poly(amide–imide)-based Composites

The functionalization of multi-walled carbon nanotubes by ascorbic acid (vitamin C) was carried out. Then, functionalized multi-walled carbon nanotubes were dispersed throughout a poly(amide–imide) matrix by ex situ technique with 5, 10, and 15% loading by weight. The composite hybrid films were prepared by a solvent casting method. It was found that the functionalization of multi-walled carbon nanotubes could improve their dispersion and interfacial adhesion to the poly(amide–imide) matrix as proved by field emission scanning and transmission electron microscopy techniques. The modulus, tensile strength, and the thermal stability of the composites were improved in spite of excellent multi-walled carbon nanotube dispersion in the matrix.     

Enhancing the grafting amount of Poly(ε-caprolactone) on MgO nanoparticles by modifying with ethylene glycol for improving mechanical properties of Poly(ε-caprolactone)

A new surface modification method to improve the graft polymerization of ε-caprolactone (CL) on MgO surface was developed. The MgO nanoparticles were first modified with ethylene glycol (EG), and then used for initiating graft polymerization of CL. The modified MgO nanoparticles were attested by fourier transform infrared spectroscopy, thermal gravimetric analysis and dispersion stability test. The results showed that EG was successfully grafted onto the MgO surface, the hydroxyl group of the grafted EG initiated the graft polymerization of CL onto the MgO surface in the presence of stannous octanoate. The PCL grafting amount (11.13%) on MgO modified with EG (MgO-EG) is much higher than that of unmodified MgO (3.95%). MgO-EG-PCL with 11.13 wt% of grafted PCL exhibited the most excellent dispersibility in chloroform. The MgO-EG-PCL/PCL composites exhibited the most significant improvement, tensile strength and the elongation at break of PCL increased from 15.64 to 19.58 MPa and from 272.34% to 420.73%, respectively.     

Preparation of Chloride Salt of Octa (Aminopropylsilsesquioxane) Filled Low-κ Epoxy Composites with Improved Thermal Stability and Low Water Absorption

ABSTRACT

Herein, a kind of low-κ epoxy composites with excellent comprehensive properties were prepared by introducing chloride salt of octa (aminopropylsilsesquioxane). The dielectric constant (10⁶ Hz) of the composite was decreased by 0.94 when the fillers loading was only 3 wt%. The thermal stability and shore hardness were both improved, and the water adsorption was reduced. The improved properties of the composites were mainly attributed to the intrinsic cage-like structure of the filler and its good dispersion in the matrix. Moreover, the strong interface interaction between the filler and matrix also played an important role.     

Preparation and Properties of α-Cellulose Short Fiber-Reinforced Poly(lactic Acid) Composites

The objective of this study is to fabricate the PLA/α-cellulose composites and to investigate the effect of α-cellulose short fibers on the toughness improvement of PLA. To homogeneously disperse the polar α-cellulose in the non-polar PLA matrix, the as-received α-cellulose was subjected to surface modification using stearic acid to impart the hydrophobic characteristics to the short fibers. The α-cellulose fibers dispersed more homogeneously in PLA through this modification, and consequently, the fiber pull-out and longer micro-crack length could improve the toughness and damping property of the resulting PLA composites. The inclusion of α-cellulose short fibers considerably decreased the spherulite dimension of the PLA/α-cellulose composites to accommodate larger deformation through grain boundary sliding. The PLA/α-cellulose composite improved its toughness by three times that of the neat PLA with low α-cellulose content (～4 wt.%), and maintained its transparency.     

Fabrication and sustained release properties of poly(ε-caprolactone) electrospun fibers loaded with layered double hydroxide nanoparticles intercalated with amoxicillin

Amoxicillin (AMOX) was intercalated in layered double hydroxide (LDH) nanoparticles by coprecipitation. LDH intercalated with AMOX (LDH/AMOX) was successfully encapsulated at different concentrations into poly(ε-caprolactone) (PCL) by the electrospinning technique. Mats of non-woven PCL fibers loaded with LDH/AMOX were obtained and characterized in terms of morphology and in vitro release. The fibrous structure of a pristine PCL sample was composed of individual, uniform, and randomly oriented fibers with an average diameter ranging around 0.8 μm. The addition of LDH/AMOX at different concentrations caused a slight increase of the average diameter and the presence of rare beads possibly due to clusters of the nano-hybrid on the surface of the microfibers.The release curves present a sustained release behavior, although an initial rapid drug release was found. The initial high-rate drug release period was followed by a second step in which the release is slow, extending for long time. The comparison of the release curves showed that the release of AMOX protected into the clay is slower than the release of the drug alone.     

Temperature-Responsive Poly(?-caprolactone) Cell Culture Platform with Dynamically Tunable Nano-Roughness and Elasticity for Control of Myoblast Morphology

We developed a dynamic cell culture platform with dynamically tunable nano-roughness and elasticity. Temperature-responsive poly(ɛ-caprolactone) (PCL) films were successfully prepared by crosslinking linear and tetra-branched PCL macromonomers. By optimizing the mixing ratios, the crystal-amorphous transition temperature (T_m) of the crosslinked film was adjusted to the biological relevant temperature (~33 °C). While the crosslinked films are relatively stiff (50 MPa) below the T_m, they suddenly become soft (1 MPa) above the T_m. Correspondingly, roughness of the surface was decreased from 63.4–12.4 nm. It is noted that the surface wettability was independent of temperature. To investigate the role of dynamic surface roughness and elasticity on cell adhesion, cells were seeded on PCL films at 32 °C. Interestingly, spread myoblasts on the film became rounded when temperature was suddenly increased to 37 °C, while significant changes in cell morphology were not observed for fibroblasts. These results indicate that cells can sense dynamic changes in the surrounding environment but the sensitivity depends on cell types.     

Composites of Poly(Keto-Sulfide)–Epoxy Resin Systems and Their Thermal and Mechanical Properties

A novel matrix resin system, poly(keto-sulfide)–epoxy resin, has been developed. The poly(keto-sulfide)s (PKS), based on various ketones, formaldehyde, and sodium hydrogen sulfide (NaSH), were prepared by the reported process. These (PKS) having terminal thiol (–SH) groups were used for curing commercial epoxy resin (i.e., diglycidyl ether of bisphenol A – DGEBA), to fabricate crosslinked epoxy-poly(keto-sulfide) resin glass fiber-reinforced composites (GRC). Various epoxy/hardener (PKS) mixing ratios were used, and the curing of epoxy-PKS has been monitored using differential scanning calorimetry (DSC) in dynamic mode. Based on DSC parameters the GRC of epoxy-PKS were prepared and characterized by thermal and mechanical methods. The variation in resin/hardener ratio led to variations in thermal and mechanical properties.     

Poly(ε-caprolactone) diol functionalized with a cinnamoyl group and its UV-triggered in-plane alignment

Stimuli-sensitive biomaterials can present variable and tailored functions under specific external stimuli, thus showing potential for application in various biosciences. Significant efforts have focused on the utilization of light as a stimulus in biomedical applications because of its unique advantages, especially the precise control over its position, movement, and non-contact irradiation. This article highlights the preparation of a photo-reactive oligomer composed of biodegradable moieties and its UV-triggered in-plane molecular orientation, implicating its surface as a potential molecular alignment layer. We focus especially on the alignment of nematic liquid crystalline (LC) molecules on the biodegradable layer with molecular orientation, because they are promising candidates for sensing and interfacial applications.     

Poly(Vinylpyrrolidone)-Embedded Bismuth Ferrite—Poly(Vinylidene Fluoride-co-Hexafluoropropylene) Composites with Enhanced Dielectric Properties

The dielectric properties of poly(vinylpyrrolidone) (PVP)-modified bismuth ferrite (BFO) particles in the poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP) matrix were prepared through solution casting techniques. The composites showed enhanced dielectric constant (90) and reduced dielectric loss (<0.5) at 40?wt% of PVP-modified BFO particles. The dielectric constant of the resultant composites with PVP-modified BFO was much higher as compared to that of unmodified BFO-P(VDF-HFP) composites. The maximum remnant polarization reached (2Pr?～?1.12?µC?cm^?2) in the PVP-modified BFO-P(VDF-HFP) composites. The demonstrated approach might provide a route for using PVP-modified BFO particles to enhance the dielectric and ferroelectric performance of the composites.     

Kinetics of Phase Separation in Poly(ɛ-caprolactone)/Poly(ethylene glycol) Blends

The poly(ɛ-caprolactone)/poly(ethylene glycol) (PCL/PEG) blends reveal a miscibility window of upper critical solution temperature (UCST) character. The kinetics of liquid–liquid phase separation (LLPS) for the blends of PCL/PEG is investigated by time-resolved small angle light scattering (TRSALS). The time evolution of scattering profile is analyzed by linear Cahn–Hilliard theory for early stage of spinodal decomposition (SD). The evolution of the maximum intensity I_m(t) and the corresponding wavenumber q_m(t) obey the power-law scheme (I_m(t)∼t^β and q_m(t)∼t^−α). A relation of β=3α in late stage is obtained almost the same scaling exponents with β≅1 and α≅1/3 for various quenching depths. The α≅1/3 implied that a coarsening mechanism at the late stage of phase separation may proceed with Ostwald ripening or Brownian coalescence process. Besides, the intermediate and late stages of SD can be scaled into a universal from represented well by Furukawa’s structure factor. The percolation to cluster transition is accompanied with α∼0.13→1/3 from intermediate to late stage of SD for the off-critical mixture of PCL/PEG (4/6) blend. In this study, the experimental result demonstrates that the crystallization is a viable mechanism to lock phase-separated structure of the blends. The competition between phase separation and crystallization has been suggested to determine the final morphology.     

Bulk Synthesis of Monodisperse and Highly Biocompatible Poly(ɛ-caprolactone)-diol by Transesterification Side-Reactions

Ring-opening polymerization of ε-caprolactone was performed at 130°C, under partial vacuum in the presence of stannous octoate as the catalyst and 1,4-butanediol as the initiator. After the termination of polymerization by deionized water, a hydroxyl group formed at the end of the polymer chains. Structure of the synthetic poly(ε-caprolactone)-diols (PCL-diol), molecular weight, polydispersity index, and Cell viability were evaluated. Very narrow distribution in the molecular weight obtained for PCL-diols is due to a new method for synthesis. It was shown that by the increase in PCL-diols, the compatibility of human mesenchymal stem cells grew up.     

Fabrication of highly porous poly (ε-caprolactone) microfibers via electrospinning

Highly porous Poly (ε-caprolactone; PCL) microfibers were successfully fabricated by collecting the fibers into a water bath during electrospinning. The morphology of the fibers collected with and without the water bath was investigated. We observed that altering the pH of the water bath affected both the fiber diameter and the size of pores on the fibers. Acidic or basic condition was found to be more favorable than neutral conditions for the formation of well-porous fibers. The morphology and pore size of the microfibers were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The average diameter of the fibers and the pore size on the surface of the microfibers were found to be 12–14.5 and 0.3–0.7 μm, respectively. The crystallinity and thermal properties of the PCL mats were investigated by DSC. This highly porous nature of the microfibers makes PCL less crystalline and increases the surface to volume ratio of the mat. Therefore, the PCL mat obtained by water bath electrospinning may be more effective for tissue scaffolds and drug delivery than the mat obtained without water bath.     

Kinetic investigation and regularities during the synthesis of Poly(ε-caprolactam-co-ε-caprolactone) and Poly(ε-caprolactam-co-δ-valerolactone) biodegradable copolymers

Summary Large diversity of tailor-made poly[(ε-caprolactam)-co-(ε-caprolactone)] P[(CLA)-co-(CLO)] and poly[(ε-caprolactam)-co-(δ-valerolactone)] P[(CLA)-co-(VLO)] copolymers have been obtained via activated anionic polymerization of ε-caprolactam (CLA) with sodium caprolactam (NaCL) as a basic initiator. In the present study several poly(ε-caprolactones) (PCLOs) and poly(δ-valerolactone) polyols were employed as effective bifunctional polymeric activators (PACs) and suitable comonomers of CLA. The obtained poly(esteramides) PEAS were isolated and their structure was confirmed by the ¹H NMR and FTIR spectroscopy. The influence of the molecular weight and type of the PACs, the CLA/PAC ratio and polymerization conditions on the conversion, intrinsic viscosity and polymerization kinetic was explored. The results demonstrated that the use of the PACs reduces the polymerization time to several minutes and polymerization process proceeds without induction period at low energy of activation and high yield of copolymers. Evaluation of the PACs activity and the activation energy confirmed that the PACs are highly active compounds efficient to CLA features modification.     

Development and Assessment of Electrospun Poly(ε-caprolactone)–Poly(vinylalcohol) Blend Nanofibers for Pest Control in Stored Products

l-Carvone is a constituent of essential oil consisting of monoterpene ketone that possesses various medicinal properties. In this context, the present study focuses on the fabrication and assessment of electrospun poly(ε-caprolactone)–poly(vinylalcohol blend nanofibers imbibed with l-Carvone (5%, w/v) that served as a suitable polymeric carrier to preserve the antimicrobial and antioxidant activities of l-Carvone for a longer period of time. The fumigant potential of l-Carvone and C-PP fibers were assessed toward saw-toothed beetle, a major pest found in stored products. The prepared fragrant C-PP fibers displayed a promising potential formulation for the control of stored product pest such as saw-toothed beetle.     

Miscibility of Poly(Ethylene-co-Vinylalcohol)/Poly(δ-Valerolactone) Blend and Tissue Engineering Scaffold Fabrication Using Naphthalene as Porogen

Herein, various poly(ethylene-co-vinylalcohol)/poly(δ-valerolactone) blends were prepared at different ratios by solvent casting for use in tissue engineering. The miscibility of these polymers was studied in detail using differential scanning calorimetry, Fourier-transform infra-red spectroscopy, and X-ray diffraction. The Avrami model have been applied for determining the isothermal crystallization kinetics of poly(ethylene-co-vinyl alcohol), poly(δ-valerolactone) and their blend with equal compositions, in which the Avrami parameters, the maximum crystallization time and the half-time were deducted. Cell adhesion and cell proliferation of the resultant materials were examined by an (3-(4, 5-dimethylthiazolyl-2)-2, 5-diphenyltetrazolium bromide)MTT assay; the blend containing equal amounts of the two polymers showed the best performance. Micropores and their connections were formed by using a new porogen under vacuum at temperatures slightly less than the glass transition temperature. The produced micropores and their interconnections were studied using scanning electron microscopy.