Electrospinning of Poly(Hydroxybutyrate-co-hydroxyvalerate) Fibrous Scaffolds for Tissue Engineering Applications: Effects of Electrospinning Parameters and Solution Properties

Electrospinning, a technology capable of fabricating ultrafine fibers (microfibers and nanofibers), has been investigated by various research groups for the production of fibrous biopolymer membranes for potential medical applications. In this study, poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), a natural, biocompatible, and biodegradable polymer, was successfully electrospun to form nonwoven fibrous mats. The effects of different electrospinning parameters (solution feeding rate, applied voltage, working distance and needle size) and polymer solution properties (concentration, viscosity and conductivity) on fiber diameter and morphology were systematically studied and causes for these effects are discussed. The formation of beaded fibers was investigated and the mechanism presented. It was shown that by varying electrospinning parameters within the processing window that was determined in this study, the diameter of electrospun PHBV fibers could be adjusted from a few hundred nanometers to a few microns, which are in the desirable range for constructing “biomimicking” fibrous scaffolds for tissue engineering applications.     

Poly(Butylene Terephthalate)/Single Wall Carbon Nanotubes Composite Nanofibers by Electrospinning

Poly(buthylene terephthalate)(PBT)/single wall carbon nanotubes (SWCNTs) composite nanofibers were prepared by electrospinning. The effect of carbon nanotubes on the morphology, crystallization, and mechanical properties of the electrospun composite nanofibers were investigated by SEM, DSC, and tensile testing, respectively. SEM observations indicated that the presence of SWCNTs resulted in finer nanofibers for lower loading; however, a broader distribution, especially for the higher diameter ranges was found for nanofibers with higher amounts of carbon nanotubes. SWCNTs accelerated crystallization and acted as a nucleating agent; the degree of crystallinity increased with increasing content of SWCNTs, followed by a moderate decrease at higher content. Specific tensile strength and modulus of the PBT/SWCNTs composite nanofibers mats were higher than that of neat PBT nanofibers mat. However, the elongation at break of composite nanofibers mats was lower than that of the neat PBT nanofibers mat.     

Preparation of Chitosan/Polyvinyl Alcohol Electrospinning Nano-Membranes Using the Green Solvent,Plasma Acid

Abstract

In this paper, a green solvent for chitosan, plasma acid, was made and chitosan/plasma-acid solutions were prepared. An environmentally friendly chitosan/polyvinyl alcohol (PVA) nano-membrane was prepared via electrospinning due to the difficulty of electrospinning of pure chitosan/plasma-acid solutions. Two blending methods of chitosan with PVA were investigated. One way was to mix a chitosan/plasma-acid solution (1%) and a PVA/water solution (10%) with the volume ratios of 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 and 8:2, respectively. The results showed that fibrous nano-membranes could start to be formed at a chitosan/PVA mixing ratio of 7:3 up to the ratio of 2:8 with increasing PVA. The average fiber diameters increased with increased adding of PVA, ranging from 74.7?nm for the 7:3 ratio to 280.7?nm for the 2:8 ratio. The other way to prepare the chitosan/PVA solutions was to put PVA and chitosan powders into the plasma acid together. Fibrous nano-membranes could also be formed at 6% PVA and 10% PVA solution, both with 1% chitosan compositions. The average diameters of the resulting nano-fibers were 144.67?nm and 300.7?nm, respectively. The Fourier transform infrared (FTIR) spectroscopy results showed that the chitosan was bonded to the PVA by hydrogen bonds in the nano-membranes (6% PVA, 1% chitosan). It is noted that both of the two blending methods permitted obtaining chitosan/PVA nano-membranes. As indicated, the PVA in the solution had a large effect on the diameters of the nano-fibers. The first method permitted obtaining nano-fibers with smaller diameter. The maximum concentration of chitosan in the solution was 0.7% (7:3 ratio). The second method was simpler and permitted increasing the chitosan concentration in the solution to 1% for both the 6% and 10% concentrations of PVA.     

Production and Characterization of Zirconia (ZrO2) Ceramic Nanofibers by Using Electrospun Poly(Vinyl Alcohol)/Zirconium Acetate Nanofibers as a Precursor

Zirconia (ZrO₂) inorganic ceramic nanofibers were produced using electrospinning of the poly(vinyl alcohol)/zirconium acetate as a precursor followed by calcinating and sintering to decompose the polymer and turn the metal salt (zirconium acetate) into the metal oxide. Characterization of the nanofibers, including polymer thermal decomposition, chemical and crystal structure, phase transformations, and fiber morphology were investigated by simultaneous thermal analysis (STA), thermomechanical analysis (TMA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and field emission scanning electron microscopy (FESEM). The results showed that the polymer decomposition started at 250°C and zirconia nanofibers with different phases (tetragonal and monoclinic) were obtained by the calcination of the precursor nanofibers at various temperatures between 500°C and 1100°C. The initially crystallized zirconia phase, which formed at 500°C, was tetragonal and with increasing calcination temperature, zirconia nanofibers with increasing amount of monoclinic phase were formed. Consequently, at 1100°C, the tetragonal phase disappeared and was transformed to the monoclinic phase of the zirconia completely. Increasing the calcination temperature caused the fiber average diameter decrease and grain growth took place due to the removal of the polymer and organic groups; neighboring grains sintered to each other and formed fibers with a high aspect ratio. At 1100°C the grains size was about the same as the fiber diameter.     

Wettability Improvement of Poly (Butylene Terephthalate) Nanofibrous Mats Prepared via Electrospinning by Blending With Regenerated Silk Fibroin

Poly (butylene terephthalate) (PBT)/regenerated silk fibroin (RSF) blend electrospun nanofibrous mats were manufactured to combine the excellent mechanical behavior of PBT with the extraordinary hydrophilic property of RSF. A 1:1 mixture of trifluoroacetic acid (TFA) and dichloromethane (DCM) was adopted as the solvents for PBT and RSF with 20% (w/v) PBT and 16 wt% RSF solutions being mixed in various proportions for electrospinning. The morphology, crystallization, Fourier transform infrared (FTIR) spectra, surface roughness, contact angle, and wetting time of the electrospun blended materials were studied. When the weight ratio of RSF was larger than 50%, a water drop on the surface of the electrospun mat was completely permeated within 300 s or less. Besides the chemical influence of the amino and carboxy groups in RSF, the physical characteristics of the RSF in the blend electrospun mats, such as random coil structure, lower crystallinity, rougher surface than PBT, etc., were a partial reason for the improvement of wettability. The blend nanofibrous mats may be especially applicable in biomedical fields.     

pH-Sensitive Poly(Vinyl Alcohol)/Sodium Carboxymethylcellulose Hydrogel Beads for Drug Delivery

A series of pH-sensitive hydrogel beads were prepared composed of poly(vinyl alcohol) (PVA) and sodium carboxymethylcellulose (CMC) by using Fe³⁺ crosslinking and freeze-thawing (FT) cycle techniques. The mixed solution of CMC and PVA was firstly crosslinked with Fe³⁺ to form beads and then subjected to freezing-thawing cycles for further crosslinking. The formation of hydrogel was confirmed by Fourier transform infrared spectroscopy (FTIR). The gelling rate in ferric solution and the swelling and pH-senstive properties of the hydrogel beads were investigated. The encapsulation efficiency and in-vitro release properties of beads were also evaluated using Bovine serum albumin as model drug. The pH sensitivity and the release rate increased with increasing CMC content. These results suggest that the PVA/CMC hgdrogel beads should be useful as pH-sensitive drug delivery systems for bioactive agents.     

Manufacture and Characterization of Poly (butylene terephthalate) Nanofibers by Electrospinning

Poly (butylene terephthalate) (PBT) nanofiber mats were prepared by electrospinning, being directly deposited in the form of a random fibers web. The effect of changing processing parameters such as solution concentration and electrospinning voltage on the morphology of the electrospun PBT nanofibers was investigated with scanning electron microscopy (SEM). The electrospun fibers diameter increased with rising concentration and decreased by increasing the electrospinning voltage, thermal and mechanical properties of electrospun fibers were characterized by DSC and tensile testing, respectively.     

Characterization of Poly(Vinyl Alcohol) Membranes Cross-Linked by Aldehyde-Substituting Cyclotriphosphazene

A new type of cross-linker, based on cyclotriphosphazene with six aldehyde groups, was used for the cross-linking of poly(vinyl alcohol) membranes. FTIR-ATR analysis indicated that cyclophosphazene reacted with poly(vinyl alcohol) by forming C–O–C bonds. TGA and DTG analysis showed that cross-linking improved the thermal stability. The swelling degree and pervaporation properties of cross-linked PVA membranes were also characterized. With increasing cross-linker concentration, swelling degrees and flux decrease while separation factors increase. Compared with PVA membranes cross-linked by glutaraldehyde, PVA membranes cross-linked by cyclophosphazene exhibited better selectivity and permeation rate.     

Properties of Poly(Lactic Acid)/ Organo-Montmorillonite Nanocomposites Prepared by Solution Intercalation

Poly(lactic acid)/organo-montmorillonite (PLA/OMMT) nanocomposite films were prepared through solution intercalation using dichloromethane as solvent. X-ray diffraction indicated that organo-montmorillonite (OMMT) was well intercalated and the interlayer spacing d increased by 0.94–1.47 nm. Transmission Electron Microscopy showed that a majority of OMMT was fully exfoliated and uniformly dispersed in the PLA matrix at low filler loading, whereas more intercalated tactoids and aggregates of OMMT existed at high loading. The crystallinity of PLA was hardly changed with the addition of OMMT. Additionally, CO₂ permeability and water vapor transmission rate of the composite films were reduced with increasing content of OMMT. At 5 wt% OMMT loading, CO₂ permeability and water vapor transmission rate were reduced by 75.8% and 23.9%, respectively. The tensile strength (TS) and Young's modulus of the PLA/OMMT nanocomposites were first enhanced, and then decreased with increasing content of OMMT. Compared with pure PLA, a 83.8% increase in the Young's modulus and a 76.0% improvement in TS were obtained with the addition of 3 wt% OMMT.     

Thermal Stabilities of Poly(Vinyl Chloride)/Calcium Carbonate (PVC/CaCO3) Composites

Poly(vinyl chloride)/calcium carbonate (PVC/CaCO₃) composites with micrometer or nanometer CaCO₃ as fillers were prepared by the solution blending method. The thermogravimetric analysis (TGA) of the composite films conducted in N₂ atmosphere showed that the addition of the CaCO₃ fillers could improve their thermal stabilities. It was also found that the nanometer CaCO₃ filler provided better thermal stabilities than the micrometer fillers even with a smaller amount. The mechanism of the improvements was investigated by a facile chemical analysis developed to examine the thermal stabilizing effect of calcium carbonate particles with different sizes in PVC/CaCO₃ composites after the pyrolysis of the samples in an air atmosphere in an oven.     

Assessment of Compatibility in Polypropylene/Poly(lactic acid)/Ethylene Vinyl Alcohol Ternary Blends: Relating Experiments and Molecular Dynamics Simulation Results

Two systems of polypropylene (PP), poly(lactic acid) (PLA) and ethylene vinyl alcohol copolymer (EVOH) ternary blends having different compositions were extruded in a co-rotating twin screw extruder. The first system was PP/PLA (75/25) with various EVOH contents, the second one was PP/EVOH (75/25) having various PLA contents. The effects of composition on the morphology and the tensile and impact properties of the blends were investigated. There were increases in the tensile modulus and tensile strength with an increase in the EVOH and PLA contents in the first and second systems, respectively. A molecular dynamics (MD) simulation was used to investigate the compatibility between the components. Prediction of the miscibility of the blends was carried out by determining the interaction parameters (χ), mixing energies (ΔH_mix), phase diagrams and Gibbs free energies. The MD simulation showed a UCST behavior for the components. Moreover, the simulation results showed a compatibilizer effect for the EVOH component. The experimental values of the dynamic mechanical thermal analysis (DMTA) and mechanical properties were correlated to the MD results. There was a good correlation between the MD and DMTA results. The modulus values using the parallel and Davis models were near to the experimental ones. A good fitting to the mixture law with addition of EVOH confirmed a good compatibilzing effect of it between the PP and PLA components.     

Characterization of Nano-Structured Poly(D,L-lactic acid) Nonwoven Mats Obtained from Different Solutions by Electrospinning

Two different solvent mixtures, chloroform/dimethylformamide (DMF) and chloroform/ acetone, in 60/40 v/v concentrations, were used to electrospin poly(D,L-lactic acid) (PDLLA). The influence of solvent type, solution concentration, and processing conditions on the morphology and properties of the electrospun mats was studied. The nanofibers characterization was done by scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The smallest nanofibers’ diameters from both mixtures were obtained from solutions with 5 wt%/v PDLLA concentration using a 1.0 kV/cm electrical field. In general the nanofibers from the chloroform/DMF mixture had smaller diameters than the nanofibers from the chloroform/acetone mixture. However, the latter ones were porous, while the nanofibers from the chloroform/DMF mixtures were not. All the PDLLA nanofibers, independent of solvent mixture, had a very low amount of crystallinity and were composed of very small and imperfect α and β crystals.     

Preparation of Polycaprolactone Tissue Engineering Scaffolds by Improved Solvent Casting/Particulate Leaching Method

The classic solvent casting/particulate leaching method to fabricate PCL scaffolds was improved by using a centrifugal technology, a direct bonding process in preparing salt matrices and a technology of vacuum treatment under heating in the desolvation process. Series operations of preshaping, centrifuging, casting and desolvating were employed during the scaffold's manufacture. The scaffold's properties were characterized including micro‐structures, pore dimensions, porosity and hydrophilicity. The results show that centrifugal technology can improve the pore uniformity of scaffolds. In the bonding process, well‐interconnected porous structures were formed if water content was between 2～7%. The distribution of pore dimensions was from 10 to 80 μm, and the porosities were about 89%. Generally, the porosities formed by vacuum treatment at high temperature are greater than those formed by vacuum treatment at ambient temperature in the desolvation process. The fabricated porous PCL scaffolds with good elasticity and desired thickness could be a good choice for application in soft tissue engineering.     

Preparation and Characterization of Poly(Vinyl Alcohol) (PVA)/SiO2, PVA/Sulfosuccinic Acid (SSA) and PVA/SiO2/SSA Membranes: A Comparative Study

Abstract

New organic–inorganic nanocomposites based on PVA, SiO₂ and SSA were prepared in a single step using a solution casting method, with the aim to improve the thermomechanical properties and ionic conductivity of PVA membranes. The structure, morphology, and properties of these membranes were characterized by Raman spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), water uptake (Wu) measurements and ionic conductivity measurements. The SAXS/WAXS analysis showed that the silica deposited in the form of small nanoparticles (～ 10?nm) in the PVA composites and it also revealed an appreciable crystallinity of pristine PVA membrane and PVA/SiO₂ membranes (decreasing with increasing silica loading), and an amorphous structure of PVA/SSA and PVA/SSA/SiO₂ membranes with high SSA loadings. The thermal and mechanical stability of the nanocomposite membranes increased with the increasing silica loading, and silica also decreased the water uptake of membranes. As expected, the ionic conductivity increased with increasing content of the SSA crosslinker, which is a donor of the hydrophilic sulfonic groups. Some of the PVA/SSA/SiO₂ membranes had a good balance between stability in aqueous environment (water uptake), thermomechanical stability and ionic conductivity and could be potential candidates for proton exchange membranes (PEM) in fuel cells.     

Fabrication and Characterization of Ultrathin Graphene Oxide/Poly(Vinyl Alcohol) Composite Films via Layer-by-Layer Assembly

Novel multilayer ultrathin films comprised of graphene oxide (GO) and poly(vinyl alcohol) (PVA) were fabricated through a layer-by-layer (LBL) assembly technique. GO could self-assemble onto quartz substrates alternately with PVA via hydrogen-bonding interactions. X-ray diffraction, atomic force microscopy, and transmission electron microscopy analysis revealed that GO was exfoliated to monolayers. The ultrathin films, with PVA/GO multilayer structures fabricated by LBL assembly, were characterized by ultraviolet-visible spectroscopy and X-ray diffraction analysis, confirming that the assembly of the multilayer films was quantitative and reproducible.     

The Peculiar Temperature Response of Dynamic Rheological Behaviors of Poly (Vinyl Chloride)/trioctyl Trimellitate (100/70) System

The dynamic rheological behavior, application of time-temperature superposition (TTS) and the failure mechanism of TTS are studied for the poly(vinyl chloride) (PVC)/trioctyl trimellitate (TOTM) (100/70) system. The Arrhenius equation, Williams–Landel—Ferry (WLF) equation, mathematical non-linear fitting and manual shift are applied to TTS fitting. For the PVC/TOTM (100/70) system, none of those methods can give well-superimposed master curves with either single horizontal shift or two-dimensional (horizontal and vertical) shift. The failure reason is attributed to the thermorheological complexity of the PVC/TOTM (100/70) system. Curves of the storage modulus versus the frequency can be well fitted with an empirical equation (G′=G′₀+Kω ⁿ ) usually used to describe filled polymer systems, indicating the multilevel flowing unit characteristic in this system. With the increase of test temperature, the structure of the PVC/TOTM (100/70) system changes and an apparent transition appears in the rheological behavior. Differential scanning calorimetry (DSC) results reveal that for the PVC/TOTM (100/70) system there are microcrystallites present below 220°C, but above the rheological transition temperature (190°C) the bulk of the microcrystallites melted, which corresponds to the appearance of viscous flow participating in the rheological behavior. It verifies the fact that the gel networks crosslinked by microcrystallites dominate the rheological behavior below the transition temperature in the PVC/TOTM (100/70) system. The quantity of microcrystallites remaining in the melt determines the perfection of the physical gel networks. With the increase of test temperature, the microcrystallites melted gradually and the gel networks are broken up.     

La6WO12：Eu3+纳米荧光粉的合成及荧光纳米纤维膜的制备

采用Pechini法合成了La6WO12:Eu3+纳米荧光粉.分别用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TG-DTG)、反射光谱,荧光光谱和发光衰减曲线对样品进行了表征.该荧光粉可以被395nm的近紫外光有效激发,进而得到峰值波长位于615 nm(电偶极跃迁5D0→7F2)左右的红光发射.将该...     

Morphology and Properties of Poly(vinyl alcohol)/MMT Nanocomposite Prepared by Solid-state Shear Milling (S3M)

Poly(vinyl alcohol) (PVA)/montmorillonite (MMT) nanocomposites were prepared by combining solid-state shear milling (S³M) technology with melt intercalation. Compared with the composite obtained by simple melt intercalation, more MMT layers were exfoliated and apparently oriented along the injection molding direction in the nanocomposite prepared by combining S³M technology and melt intercalation, which greatly increased the orientation degree of MMT, resulting in the greater interactions between PVA and MMT layers. Simultaneously, this also promoted the orientation of PVA molecules and produced effective nucleation of the crystallization of PVA. Consequently, the thermal stability and mechanical properties of PVA were obviously improved. For instance, when the MMT content was 3 wt%, the tensile strength and modulus of the nanocomposite with MMT prepared by S³M were 98.9 MPa and 3.1 GPa, respectively, increasing by 52% and 63.2% compared with PVA.     

Study of enhanced red emission from Sm(Sal)3Phen ternary complexes in Poly Vinyl Alcohol film

In the present work, dinuclear complexes of salicylic acid (Sal) and 1,10-phenanthroline (Phen) were synthesized with different concentrations of Samarium ion (Sm³⁺) in Poly Vinyl Alcohol (PVA) polymer films and their structural and spectroscopic properties were investigated. Judd-Ofelt theory has been employed to estimate the several radiative parameters for SmCl₃ and Sm(Sal)₃Phen complex in PVA polymer film which are in fairly agreement between the experimental and the theoretical values supporting the J-O theory. Photoluminescence properties of the complex have been studied on 355 nm and 400 nm excitations in steady state as well as in time domain. On the basis of the UV-Vis absorption, FT-IR absorption, excitation, emission spectra and decay curves, spectroscopic properties of these films were studied and the photophysics involved was explained in terms of energy transfer and the RE encapsulation effect.     

Electro-Optical and Thermophysical Characterization of Poly (Tripropylene Glycol Di-Acrylate)/Liquid Crystal Composite Materials Prepared by Polymerization Induced Phase Separation

Abstract

This work examines the development and characterization of tripropylene glycol di-acrylate/liquid crystal E7 (TPGDA/LC E7) PDLCs composite materials (polymer-dispersed-liquid-crystals). These systems were produced by UV irradiation photopolymerization (PIPS) of a mixture of the monomer tripropylene glycol di-acrylate (TPGDA) and the liquid crystal E7 (LC E7, a mixture of three cyano-biphenyl and one cyano-terphenyl LCs), in the presence of 2?wt% (of the acrylate/E7 mixture) of a photoinitiator. Electro-optical, thermal and optical characterization was used to understand the effect of the LC concentration on the electro-optical and thermo-physical properties of these materials. Polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) studies were performed to observe the system morphology and to determine the transition temperatures of these materials, both as a function of their composition. The findings showed a slight variation of the nematic-isotropic transition temperature, T_NI, of the LC E7 and of the glass transition temperature, T_g, of the TPGDA polymeric matrix as a function of the mass percentage of the LC E7. A very good electro-optical response for the composition 30/70?wt % TPGDA/LC E7 was obtained.