Application of the dry‐spinning method to produce poly(ε‐caprolactone) fibers containing bovine serum albumin laden gelatin nanoparticles

We designed and manufactured a polymeric system with combined hydrophilic–hydrophobic properties by loading gelatin nanoparticles (GNPs) containing bovine serum albumin (BSA) into poly(ε‐caprolactone) (PCL) fibers. Our ultimate goal was to create a device capable of carrying and releasing protein drugs. Such a system could find several biomedical applications, such as those in controlled release systems, surgical sutures, and bioactive scaffolds for tissue engineering. A two‐step desolvation method was used to produce GNPs, whereas PCL fibers were produced by a dry‐spinning method. The morphological, mechanical, and thermal properties of the produced system were investigated, and the distribution of nanoparticles both inside and on the surface of the fibers was examined. The effect of the particles on the biodegradability of the fibers was also evaluated. In vitro preliminary tests were performed to study the release of BSA from nanoparticle‐laden fibers and to compare this with its release from free nanoparticles. Our results indicate that the distribution of particles inside the fibers was quite homogeneous and only a few of them were present on the surface. The presence of the particles in the fibers did not affect the thermal properties of the PCL polymer matrix, although it created voids that affected the degradation characteristics so the PCL fibers favored faster erosion compared to the plain fibers. Preliminary results indicate that the release from GNP‐laden fibers occurred much more slowly compared to that in the free GNPs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44233.     

Fibers spinning from poly(trimethylsilylpropyne) solutions

This study for the first time directs in assessment of the necessary conditions for spinning fibers from poly[1-(trimethylsilyl)1-propyne], one of the best for gas separation. It includes a search of appropriate solvents, investigation of rheological properties of solutions, a preparation of dopes with reasonable polymer content and a choice of effective coagulants based on their solubility parameters in frames of wet fiber spinning. The fibers were obtained with diameter of 7 ± 1 μm and strength of up to 200 MPa. The morphology of the surface and core of the PTMSP fibers was distinctively different: dense skin and friable core. From the viewpoint of membrane properties, it looks like asymmetrical membrane. In addition, the hollow fibers we prepared by dry spinning method. Overall, the stable fiber spinning process from PTMSP solutions was developed for the first time, and monolith and hollow PTMSP fibers of good quality were obtained. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48511.     

Piezoelectric polymeric bicomponent fibers produced by melt spinning

Melt spinning of a novel piezoelectric bicomponent fiber, with poly(vinylidene fluoride) as the electroactive sheath component, has been demonstrated. An electrically conductive compound of carbon black (CB) and high density polyethylene was used as core material, working as an inner electrode. A force sensor consisting of a number of fibers embedded in a soft CB/polyolefin elastomer matrix was manufactured for characterization. The fibers showed a clear piezoelectric effect, with a voltage output (peak‐to‐peak) of up to 40 mV under lateral compression. This continuous all‐polymer piezoelectric fiber introduces new possibilities toward minimal single fiber sensors as well as large area sensors produced in standard industrial weaving machines. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt spinning of β‐phase poly(vinylidene fluoride) yarns with and without a conductive core

When poly(vinylidene fluoride) (PVDF) is to be used as a piezoelectric material, the processing must include the formation of polar β‐phase crystallites, as well as the application of electrically conducting charge collectors, that is, electrodes. In this article, results from the melt spinning of PVDF yarns and a novel bicomponent PVDF‐yarn with a conductive carbon black/polypropylene (CB/PP) core are presented. Melt spinning has been done under conditions typical for industrial large‐scale fiber production. The effects on the resulting crystalline structure of varying the spinning velocity, draw rate, and draw temperature are discussed. The results show that, for maximum α‐to‐β phase transformation, cold drawing should take place at a temperature between 70 and 90°C, and both the draw ratio and the draw rate should be as high as possible. It was observed that the cold drawing necessary to form β‐phase crystallinity simultaneously leads to a decrease in the core conductivity of the bicomponent yarns. In this work, the melt spinning of bicomponent fibers with high‐β‐phase PVDF in the sheath and a CB/PP core was successfully accomplished. The core material remained electrically conductive, paving the way for the use of a CB‐polymer compound as inner electrode in the melt spinning of piezoelectric bicomponent fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface hydrolysis of filaments based on poly(trimethylene terephthalate) spun at high spinning speeds

The surface alkaline hydrolysis of fibers made from poly(trimethylene terephthalate) (PTT) was studied after extruding the polymer at high spinning speeds from 2000 to 6000 m/min and heat setting in the range of temperatures from 100 to 180°C. Fiber weight loss increased with an increasing heat‐setting temperature but it was also dependent on the spinning speed. Some of the partially hydrolyzed fibers had a well‐developed, hydrophilic surface, and pore size in the range of 0.69 to 1.20 μm. The optimum reaction and morphological conditions for increasing porosity in PTT fibers depends on spinning speed and heat‐setting temperature. A temperature of 180°C is the upper limit for heat‐setting PTT filaments but seems to be the most effective for making porous fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1724–1730, 2004     

Effect of processing parameters of the continuous wet spinning system on the crystal phase of PVDF fibers

Poly(vinylidene difluoride) (PVDF) has been widely used in piezoelectric applications as films and nanofiber mats, but there are limited publications on piezoelectric wet‐spun fibers. In this work, PVDF fibers were prepared using the wet spinning method, and the processing parameters, including the drawing ratio and heat setting temperature, were controlled in the continuous wet spinning system to increase the β‐phase crystallinity of the fibers. In addition, the wet‐spun PVDF fibers were compressed by a rolling press to eliminate voids in the fibers. Then, the compressed PVDF fibers were poled to align the molecular dipoles. The crystal structures of the PVDF fibers were investigated using X‐ray diffraction and Fourier‐transform infrared spectroscopy. Single filament tensile tests were performed to measure the tensile strength of the fibers. The morphologies of the PVDF fibers with respect to the processing parameters were observed by scanning electron microscope (SEM) and polarization optical microscopy. The piezoelectric constant of the prepared PVDF fibers was then measured using a d₃₃ meter. The wet‐spun PVDF fibers showed the highest β‐phase and piezoelectric constants when the drawing ratio and heat setting temperature were 6 and 150 °C, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45712.     

Stereocomplex formation between enantiomeric poly(lactic acid). VIII. Complex fibers spun from mixed solution of poly(D-lactic acid) and poly(L-lactic acid)

To obtain poly(lactic acid) (PLA) complex fibers, spinning was performed by wet and dry methods from 5–10 g/dL chloroform solutions of poly(D-lactic acid) (PDLA) and poly(L-lactic), both with a viscosity-average molecular weight of 3 × 10⁵. The dope was extruded from a monohole nozzle into coagulation baths from ethanol and chloroform for wet spinning and into a drying column kept at 60°C for dry spinning. Scanning electron microscopic observation of the as-spun fibers showed that the surface of the wet-spun fiber had large basins with diameters of 50–100 μm and many pores with diameters from sub μm to 10 μm, whereas the surface of dry-spun fiber had a microporous structure with the pore diameter of 1–3 μm. The tensile strength of the wet-spun complex fiber was very low and could not be drawn at high temperatures, in contrast to the dry-spun fiber. The tensile strength of dry-spun complex fiber increased upon hot drawing and showed the tensile strength of 94 kg/mm² by drawing at 160°C to the draw ratio of 13. Differential scanning calorimetry revealed that the complex fibers contained both the stereocomplex crystallites (racemic crystallites) and the crystallites of the single polymers, PDLA and PLLA, regardless of the spinning methods. The ratio of the racemic crystallites to the single-polymer crystallites increased with the draw ratio of the complex fiber. © 1994 John Wiley & Sons, Inc.     

Application of response surface methodology to evaluate the effect of dry‐spinning parameters on poly (ε‐caprolactone) fiber properties

Poly (ε‐caprolactone) fibers were prepared by dry‐spinning method. The effect of processing parameters on linear density, mechanical, and morphological properties of fibers was investigated using the response surface methodology (RSM). This method allowed evaluating a quantitative relationship between polymer concentrations, spinning speed, and draw ratio on the properties of the fibers. Polynomial regression model was fitted to the experimental data to generate predicted response. The results were subjected to analysis of variance to determine significant parameters. It was found that all three parameters had significant effect on linear density of fibers. Combined effect of concentration and spinning speed was observed in which the linear density of fiber was more sensitive to changes in the solution concentration at lower spinning speed. Polymer concentration had the largest influence on the mechanical properties of fibers. An average cross‐sectional radius of fibers was affected by concentration and draw ratio in opposite manner. Among all three parameters, only polymer concentration had significant effect on circularity of fiber cross sections. By applying the RSM, it was possible to obtain a mathematical model that can be used to better define processing parameters to fabricate dry‐spun PCL fiber in a more rational manner. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42113.     

Melt electrospinning from poly(L‐lactide) rods coated with poly(ethylene‐co‐vinyl alcohol)

Rodlike poly(L ‐lactide) (PLLA) samples coated with poly(ethylene‐co‐vinyl alcohol) (EVOH) were made. Fibers were produced from these rodlike samples by using a melt electrospinning system equipped with a laser irradiating device, and the effects of EVOH content and the processing parameters of the melt electrospinning on fiber diameters were investigated. We also studied the fiber formation mechanism from the rods during the laser melt electrospinning process. The following conclusions were reached: (i) coating of EVOH on PLLA rods has a remarkable effect on decreasing fiber diameter from 3 μm to around 1 μm; (ii) increases in the electric field strength and temperature of spinning space decrease the average diameter of fibers produced from pure PLLA rods, and longer collector distance leads to lager PLLA fiber diameter; and (iii) the migration of PLLA component from the core to the surface of electrospun fibers takes place during the fiber formation process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melt‐electrospun fibers obtained from polypropylene/poly(ethylene‐co‐vinyl alcohol)/polypropylene three‐layer films

Production of polypropylene (PP) nanofibers below 1 μm in average diameter is difficult with conventional melt‐spinning. A nozzle‐free melt‐type electrospinning (M‐ESP) system with a line‐like CO₂ laser beam melting device were used to produce PP nanofibers. To achieve the purpose, core [poly(ethylene‐co‐vinyl alcohol) (EVOH)]–clad (PP) nanofibers (average diameter, 0.88 μm) were fabricated from PP/EVOH/PP three‐layer films using the M‐ESP. The core–clad structure was formed by a wrapping phenomenon caused by the difference in the melt flow rates (MFRs) of PP and EVOH melts. Hollow PP nanofibers were obtained from the core–clad nanofibers by extraction of EVOH. Nanofiber diameter and hollow wall thickness could be altered by changing the MFR of the PP melt. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46393.     

A facile method of preparing highly porous polylactide microfibers

Highly porous polylactide (PLA) microfibers with the diameter of about 14 µm are prepared by melt‐spinning and stretching core–sheath PLA fibers (CSF) and sequent treatment of ethyl acetate. The resultant pores are regular and elliptical. The average values of length of major axis and minor axis of elliptical pores are around 1 and 0.5 μm, respectively. This new and facile method can prepare porous PLA fibers on industrial scale, and nearly overcome all the shortcomings of melt‐spinning and stretching method. In addition, highly porous structure in partially oriented poly(l ‐lactide) yarn (POY) can be also formed by treating POY using ethyl acetate. The obtained pores are irregular. In addition, the formation mechanism of pore structure in CSF is different with the one in POY. The former is the separation of row‐nucleated lamellae induced by stretching while the latter is swelling and subsequent solvent‐induced crystallization. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45860.     

Influence of process parameters on the structure formation of man‐made cellulosic fibers from ionic liquid solution

The influence of dry‐jet wet spinning parameters on the production of man‐made cellulosic fibers from 13 wt % cellulose/1,5‐diazabicyclo[4.3.0]non‐5‐ene acetate solutions was investigated. The spinneret nozzle diameter, extrusion velocity, draw ratio, and coagulation bath temperature were the studied parameters. The production of highly oriented fibers was favored by selecting higher extrusion velocity and lower spinneret diameter. A spinneret size of 100 µm and a draw ratio of 6 were sufficient to highly orient the cellulose macromolecules and achieve tenacities above 40 cN/tex (600 MPa). Total orientation assessed via birefringence measurement, tenacity, and Young's modulus values reached a plateau at a draw of 6 and no further development in properties was observed. A temperature of the aqueous coagulation bath of 15 °C slightly promoted greater orientation of the fibers by hampering structural changes of the cellulose macromolecules in the nascent solid fibers. Furthermore, the determination of the elongational viscosity of the liquid thread via the measurement of radial force tensor was tested and showed promising results. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43718.     

Effect of protein‐loading on properties of wet‐spun poly(L,D‐lactide) multifilament fibers

Protein‐loaded multifilament fibers were fabricated by the wet‐spinning method. The polymers which were tested included poly(L,D ‐lactide) [P(L,D )LA], L/D ratio 96/4 and poly(L,DL ‐lactide) [P(L,DL )LA], L /DL ratio 70/30. The polymers were dissolved in dichloromethane and bovine serum albumin (BSA) was dissolved in water, respectively. The solutions were mixed together using a probe sonicator to form a polymer‐protein emulsion. This emulsion was extruded to an ethanol spin bath. The fibers possessed a distinct sheath‐core structure, where the inner core was porous and the outer sheath was smooth. The diameters of the filaments were in the range of 46 and 70 μm. The tenacity values of the filaments were between 7 and 17 MPa. In vitro drug release rate of the P(L,DL )LA 70/30 filament was faster than that of the P(L,D )LA 96/4 filament. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Temperature‐sensitive PVDF hollow fiber membrane fabricated at different air gap lengths

This article describes preparation of temperature‐sensitive poly(vinylidene fluoride) hollow fiber membranes using the dry‐wet spinning technique and investigates effects of air gap length on the structures and performances. In spinning these hollow fibers, N,N‐dimethyl formamide and poly(ethylene glycol) (10,000) were used as the solvent and pore‐forming agent, respectively. The prepared fiber membranes were characterized by scanning electron microscopy, pore size measurement, filtration experiments of pure water flux, and solutes with different molecular weights. The fiber membranes exhibit a quite asymmetric structures consisting of double skin layers situated on the fiber walls, two finger‐like layers near skin layers as well as macrovoids and sponge‐like structures at the center of the fiber cross‐sections. Remarkable changes of pure water flux and retention of solute are observed around 32°C, indicating an excellent temperature‐sensitive permeability. As the air gap length increases, the pore size of fiber membrane decreases, which results in decrease of pure water flux and allows small molecules to permeate through the fiber membrane. POLYM. ENG. SCI., 53:2519–2526, 2013. © 2013 Society of Plastics Engineers     

PEEKWC ultrafiltration hollow‐fiber membranes: Preparation,morphology, and transport properties

A series of hollow‐fiber membranes was produced by the dry–wet spinning method from PEEKWC, a modified poly(ether ether ketone) with good mechanical, thermal, and chemical resistance. The fibers were prepared under different spinning conditions, varying the following spinning parameters: polymer concentration in the spinning solution, height of the air gap, and bore fluid composition. The effect of these parameters on the water permeability, the rejection of macromolecules (using dextrane with an average molecular weight of 68,800 g/mol), and the morphology of the membranes was studied. The results were also correlated to the viscosity of the spinning solution and to the ternary polymer/solvent/nonsolvent phase diagram. The morphology of the cross section and internal and external surfaces of the hollow fibers were analyzed using scanning electron microscopy (SEM). All membranes were shown to have a fingerlike void structure and a skin layer, depending on the spinning conditions, varying from (apparently) dense to porous. Pore size measurements by the bubble‐point method showed maximum pore sizes ranging from 0.3 to 2 μm. Permeability varied from 300 to 1000 L/(h^?1 m^?2 bar) and rejection to the dextrane from 10 to 78%. The viscosity of polymer solutions was in the range of 0.2 to 3.5 Pa s. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 841–853, 2004     

Elemental sulfur‐based polymeric materials: Synthesis and characterization

New elemental sulfur‐based polymeric materials called poly(sulfur‐random‐divinylbenzene) [poly(S‐r‐DVB)] were synthesized by ring opening polymerization via inverse vulcanization technique in the presence of a mixture of o‐, m‐, and p‐diviniylbenzene (DVB) as a cross‐linker. A clear yellow/orange colored liquid was obtained from the elemental sulfur melted at 160 °C and then by adding various amounts of DVB to this liquid directly via a syringe at 200 °C viscous reddish brown polymeric materials were obtained. The copolymers are soluble in common solvents like tetrahydrofuran, dichloromethane, and chloroform, and they can be coated on any surface as a thin film by a spray coating technique. The characterization of the materials was performed by using nuclear magnetic resonance, fourier transform infrared, and Raman spectroscopies. The morphological properties were monitored via scanning electron microscope technique. Thermal analysis showed that an increase in the amount of DVB in the copolymers resulted in an increase in the thermal decomposition temperature. On the other hand, poly(S‐r‐DVB) copolymers exhibited good percent transmittance as 50% T between 1500 and 13,000 nm in electromagnetic radiation spectrum, which makes them good candidates to be amenable use in military and surveillance cameras. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43655.     

Investigation on the effect of spinning conditions on the properties of hollow fiber membrane for hemodialysis application

Polyethersulfone (PES) hollow fiber membranes were fabricated via the dry‐wet phase inversion spinning technique, aiming to produce an asymmetric, micro porous ultrafiltration hollow‐fiber specifically for hemodialysis membrane. The objective of this study is to investigate the effect of spinning conditions on the morphological and permeation properties of the fabricated membrane. Among the parameters that were studied in this work are air gap distance, dope extrusion rate, bore fluid flow rate, and the take‐up speed. The contact angle was measured to determine the hydrophilicity of the fibers. Membrane with sufficient hydrophilicity properties is desired for hemodialysis application to avoid fouling and increase its biocompatibility. The influences of the hollow fiber's morphology (i.e., diameter and wall thickness) on the performance of the membranes were evaluated by pure water flux and BSA rejection. The experimental results showed that the dope extrusion rate to bore fluid flow rate ratio should be maintained at 1:1 ratio to produce a perfectly rounded asymmetric hollow fiber membrane. Moreover, the flux of the hollow fiber spun at higher air gap distance had better flux than the one spun at lower air gap distance. Furthermore, spinning asymmetric hollow fiber membranes at high air gap distance helps to produce a thin and porous skin layer, leading to a better flux but a relatively low percentage of rejection for BSA separation. Findings from this study would serve as primary data which will be a useful guide for fabricating a high performance hemodialysis hollow fiber membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43633.     

Dry‐jet‐wet spun polyurethane fibers. I. Optimization of the spinning parameters

This study examined the spinning of polyurethane‐based elastomeric fibers with the dry‐jet‐wet spinning method. The three important spinning variables that were chosen were the coagulation bath ratio (dimethylformamide/water), the bath temperature, and the stretch ratio. A three‐variable factorial design method, proposed by Box and Behnken, was used to optimize these process parameters. The spinning process was further fine‐tuned by the variation of the stretch ratio and the dope solid content. The effect of the dry‐jet length on the fiber properties was also studied. The tenacity and elastic recovery properties of the fibers were found to be optimum at a bath ratio (dimethylformamide/water) of 60 : 40, a bath temperature of 15°C, and a stretch ratio of 2.5. The density and sonic modulus were measured to determine the effect of varying the process variables on structural parameters such as the density and orientation. The surface morphological features, as revealed by scanning electron microscopy, were correlated to the fiber properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of sulfuric acid bath on morphological structure and mechanical properties of poly(p‐phenylene‐1,3,4‐oxadiazole) fibers

Poly(p‐phenylene‐1,3,4‐oxadiazoles) (p‐PODs) spinning solution was prepared by one‐step polycondensation, and p‐POD fibers were obtained by wet spinning method using dilute sulfuric acid as coagulation bath. The morphology and mechanical properties of p‐POD fibers under different coagulating conditions, such as bath concentration and temperature, were qualitatively and quantitatively studied by microscopes, ultrasonic orientation measurement, WAXD, and other traditional methods. The microscopic observation indicated that the p‐POD fibers were of three‐layer structure which consisted of outer skin, inner skin, and the core. The skin‐core structure and surface feature of the fibers were greatly affected by the coagulating conditions. At the same time, the results of WAXD and ultrasonic orientation measurement demonstrated that the crystallinity and orientation of the fibers also varied with the change of bath conditions. The tests of mechanical properties showed that the tensile strength, elongation at break, and maximum draw ratio of the p‐POD fibers were determined by their solid‐phase structures, which were largely influenced by coagulation conditions. According to the structure analysis and the mechanical tests, the optimal coagulation parameters were chosen to obtain p‐POD fibers with denser and more regular structure and better mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel electrospun nanofibers incorporating polymeric prodrugs of ketoprofen: Preparation,characterization, and in vitro sustained release

A facile and efficient protocol for the preparation of nanofibers incorporating polymeric ketoprofen prodrugs and polyvinylpyrrolidone was developed. Polymeric ketoprofen prodrugs were constructed by a two‐step chemo‐enzymatic synthetic route, and nanofibers prepared by electrospinning from dimethylformamide/ethanol (1 : 1, v/v) solutions. The morphological characteristics of the fibers were influenced by the concentration of active agent in the spinning solution; average diameters varied from 196 to 370 nm. In vitro release studies indicated that the ketoprofen release rate from the electrospun fibers was significantly higher than that from the pure polymeric prodrugs. Cumulative drug release from the electrospun fibers reached 40–70% after 3 h and 75–100% after 12 h, while the pure polymeric prodrug released only 7–9% of the active agent over 12 h. Functional nanofibers incorporating polymeric prodrugs therefore comprise potentially effective drug delivery systems for sustained release. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1570–1577, 2013