Exploring the effects of non-solvent concentration, jet-stretching and hot-drawing on microstructure formation of poly(acrylonitrile) fibers during wet-spinning

The simultaneous effects of non-solvent concentration in the spinning dope, jet-stretching and hot-drawing on porosity, morphology development and mechanical properties of wet-spun poly(acrylonitrile) fibers were studied. Addition of non-solvent to the spinning dope increased dope viscosity, the entanglement density of the polymeric solution and the number of entanglements per chain. Drawability of the as-spun fiber depended on the number of entanglements per polymer chain. Therefore, addition of non-solvent improved or spoiled drawability of the wet-spun fibers based on the concentration of the initial spinning dope. Hot-drawing and jet-stretching did not affect the fraction of nanovoids but shifted their size distribution towards smaller values. However, hot-drawing was more effective in reducing the overall porosity of the fibers in comparison with jet-stretching. Fiber tenacity increased when overall porosity decreased. Finally, strength-diameter correlation showed good agreement with the Griffith’s theory.     

Designing index of void structure and tensile properties in wet‐spun polyacrylonitrile (PAN) fiber. I. Effect of dope polymer or nonsolvent concentration

An index Xη^?1 with numerator calculated solely from solubility parameters and denominator measured by on‐line viscosity of the fiber precursor in coagulation medium was defined as an indicator of the fiber structure and tensile properties. The Xη^?1 values of wet‐spun and wound polyacrylonitrile fibers from their dimethylformamide solutions with different polymer concentrations (series A) or nonsolvent concentrations in 10 vol % polymer solutions (series B) into water with draw ratio of one were determined and compared with the corresponding fiber structure and tensile properties. The Xη^?1 value of about 0.8 × 10⁶ s^?1 led to finger‐like structure with overall fiber porosity of 82 vol %. By reducing Xη^?1 through dope polymer concentration enhancement to 20 vol %, overall fiber porosity decreased to 62 vol % via substitution of some micrometer voids with dense polymer ligament. Accordingly, strong fiber modulus and elongation at break enhancement were observed due to structural defect reduction and cohesive energy density increment. On the other hand, dope nonsolvent concentration increment from 0 to 5 vol % at 10 vol % polymer concentration showed minute overall fiber porosity decrement via Xη^?1 increment through micrometer void substitution with nanometer ones (nuclei). Therefore, mild fiber modulus and elongation at break improvements were detected due to defect size reduction which magnifies mechanical properties improvements. Curve fitting of the Wang's second order modulus‐porosity correlation to the as‐spun fibers modulus‐porosity data verified the solid–liquid phase separation through nuclei growth‐resistance as the main governing morphological evolution mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Anisotropy of the elastic modulus for hybrid composites reinforced by short fibers and particles with respect to material porosity

Hybrid composites reinforced by short fibers and particles (HCRSFPs) have been widely used in many fields, and more and more scholars are paying attention to hybrid composites. In this study, the elastic moduli of HCRSFPs in arbitrarily chosen directions were investigated with respect to their porosities. A material model was built with the assumption of a compound of particles and polymer matrix containing voids as an effective matrix, and the HCRSFPs were treated as the compound of short fibers and the effective matrix. With consideration of the three‐dimensional spatial orientation distribution and the length distribution of the short fibers, the laminate analog approach and the Halpin–Tsai model were used to predict the elastic moduli of the HCRSFPs. Numerical examples and analyses showed that the fiber orientation distribution, reinforcement volume fraction, and porosity had great effects on the elastic moduli of the HCRSFPs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43708.     

Porosity and pore size determination in polysulfone hollow fibers

Average pore sizes and effective porosity of microporous polysulfone hollow fibers were determined by the gas permeability method. Surface structure and porosity were determined by scanning electron microscopy. The values of effective porosity ε/q² (porosity/tortuosity factor) are approximately one order of magnitude lower than those reported previously for flat sheet porous membrane. These lower values are a direct outcome of a higher polymer concentration in the spinning dope. Correlations between the wall void volume, equivalent pore size, and hydraulic permeabilities of the hollow fibers have been determined. Rather low values of ε/q² have been calculated compared to those of the void volume; these effective porosity values indicate either a very high tortuosity factor or a large number of “dead end” pores. Exposure of the fibers to elevated temperature (110°C) for a short period of time drastically reduces the surface pore size and narrows the pore size distributions, whereas overall fiber dimensions are reduced only by 1%, and 85% of the fiber's hydraulic permeability is retained. The scanning electron microscopy study reveals the formation of a relatively dense skin in some spun fibers. For such “skinned” fibers, kinetic (permeability) evaluation of static structure such as mean pore size is not realistic and is further generalized to the term “equivalent pore size.”     

Effect of spinning conditions on the mechanical properties of PA6/MWNTs nanofiber filaments

Carbon nanotube (CNT ) reinforced composite materials is a hot research issue now , but CNT/polymer composite nano-scale fibers still cannot be obtained readily, not mention to successfully prepare continuous CNTs/polymer composite nano-scale fiber filaments manufactured by electrospinning. In this paper, continuous filaments constructed of nano-scale PA6/MWNTs fibers in single-axis orientation were obtained by an improved wet-electrospinning technique. The effects of the concentrations of MWNTs, spinning speed and post-drawing on the mechanical properties of PA6/MWNTs nanofiber filaments were studied. The results show that when the concentrations of MWNTs is below 0.8 wt%, the increase of MWNTs content enhances the Young’s modules and breaking stress but reduces the breaking strain, while the breaking stress decreases when the MWNTs concentration exceeds 0.8 wt%. The Young’s modules and breaking stress increased as the spinning speed raised at the range of 1.8–9.0 m/min, but declined when the speed exceeded 9.0 m/min. The mechanical properties of the as-spun filaments can be improved by either dry or wet post-drawing, and the breaking stress of the wet post-drawn filaments was improved 2.64 times while that of the dry post-drawn filaments 2.28 times.     

Hollow Fiber Ultrafiltration Membranes from Poly(Vinyl Chloride): Preparation,Morphologies, and Properties

Hollow fiber poly(vinyl chloride) membranes were prepared by using the dry/wet spinning method. Cross-section, internal, and external surfaces of the hollow fibers structure were studied by SEM. The pore size and pore size distribution of the hollow fibers were measured by a PMI capillary flow porometer. UF experiments of pure water and aqueous solution of PVP K-90 were carried out. The effect of the PVC concentration on the hollow fibers mechanical properties was also investigated. It was found that the PVC fibers cross-sectional structure was affected by the polymer concentration in the dope solution. In particular, reduction of macrovoids size was observed when increasing PVC concentration from 15 to 19 wt%. The pore size distribution of the PVC hollow fibers was controlled by adjusting the PVC concentration. Indeed, an increase of PVC concentration up to 19 wt% leads to fibers with sharp pore size distribution (the 99% of pores is about 0.15 µm).The pure water permeation flux decreased from 162 to 128 (l/m² · h · bar), while the solute separation performance increased from 82 to 97.5%, when increasing the PVC concentration. The elongation at break, the tensile strength, and the Young's modulus of the PVC hollow fibers were improved with PVC concentration in dope solution.     

高压静电场纺丝法制备羟丙基甲基纤维素邻苯二甲酸酯超细纤维

通过高压静电场纺丝法制备了羟丙基甲基纤维素邻苯二甲酸酯(HPMCP)的超细纤维,并详细研究了溶液浓度、纺丝电压及混合溶剂的配比对纤维形态和直径的影响。当混合溶剂中的无水乙醇与二氯甲烷为1∶1(V/V)时,在纺丝电压为30kV的条件下,HPMCP可纺丝的浓度范围为7%～16%(wt)。溶液浓度为7%时,电纺得到珠状纤维;浓度大于8%时,得到表面光滑的圆柱状纤维。随着纺丝溶液浓度的增大,所得纤维的平均直径逐渐增大。在HPMCP溶液浓度(8%)和溶剂组成(无水乙醇/二氯甲烷=1∶1)保持一定时,随着纺丝电压的增大,所得纤维的平均直径呈下降的趋势。而在纺丝浓度和电压一定的情况下,随着混合溶剂中二氯甲烷体积分数的增大,所得纤维的平均直径先增大后减小,无水乙醇与二氯甲烷体积比为1∶1和1∶2时,所得纤维的直径分布相对集中。     

Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐co‐HFP) hollow fiber membranes prepared from PVDF‐co‐HFP/PEG‐600Mw/DMAC solution for membrane distillation

Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐co‐HFP) hollow fiber membranes were prepared by using the phase inversion method. The effect of polyethylene glycol (PEG‐600Mw) with different concentrations (i.e., 0, 5, 7, 10, 12, 15, 18, and 20 wt %) as a pore former on the preparation and characterization of PVDF‐co‐HFP hollow fibers was investigated. The hollow fiber membranes were characterized using scanning electron microscopy, atomic force microscopy, and porosity measurement. It was found that there is no significant effect of the PEG concentration on the dimensions of the hollow fibers, whereas the porosity of the hollow fibers increases with increase of PEG concentration. The cross‐sectional structure changed from a sponge‐like structure of the hollow fiber prepared from pure PVDF‐co‐HFP to a finger‐like structure with small sponge‐like layer in the middle of the cross section with increase of PEG concentration. A remarkable undescribed shape of the nodules with different sizes in the outer surfaces, which are denoted as “twisted rope nodules,” was observed. The mean surface roughness of the hollow fiber membranes decreased with an increase of PEG concentration in the polymer solution. The mean pore size of the hollow fibers gradually increased from 99.12 to 368.91 nm with increase of PEG concentration in polymer solution. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermodynamic study of non-solvent/dimethyl sulfoxide/polyacrylonitrile ternary systems: effects of the non-solvent species

In order to investigate the effects of the non-solvent species on the formation mechanism of polyacrylonitrile (PAN) fiber in wet spinning, theoretical ternary phase diagrams of water/DMSO/PAN and ethanol/DMSO/PAN systems were constructed based on the extended Flory–Huggins theory. The cloud-points of dilute PAN solutions of the two systems were determined by titration method and those of concentrated PAN solutions from Boom’s linearized cloud-point correlation. Binary interaction parameters were calculated and optimized to construct the theoretical phase diagram. The obtained diagrams were used to investigate the effects of the non-solvent species on the formation of PAN fibers. If the non-solvent water is replaced with ethanol, the meta-stable two-phase region in the ternary phase diagram increases. This favors the de-mixing of the filament via nucleation and growth mechanism during the coagulation process, resulting in homogenous dense PAN fibers with low porosity.     

In situ gradient nano-scale fibril formation during polypropylene (PP)/polystyrene (PS) composite fine fiber processing

The nano-scale dispersed fibrils with gradient distribution in PP/PS composite fine fibers were observed by in situ formation during its melt spinning process. The morphology development of polyblends, from granule to as-spun fiber as well as drawn fiber with various PS content from 2 to 8 wt% were investigated. The morphology conversion of PS dispersed phase from ellipse to gradient nano-scale fibril along the radial direction of as-spun composite fibers took palace at 4 wt% by weight of PS component, suggesting the presence of break-up in fiber center and the limited coalescence, especially in 8 wt% PS as-spun composite fibers. This morphology diversity was attributed to the radial variation of parameters including temperature, viscosity, axial velocity and stress in spinning path and was in good agreement with the droplet deformation criteria based on the reduced capillary number. In addition, the post hot-drawing process slightly influence the size and distribution of PS phase in cross-section of composite drawn fibers, while the rheological properties of PP, PS and polyblends were found to be correlated to the morphology of PP/PS composites.     

Effect of alumina fiber content on pore structure and properties of porous ceramics

Porous Al₂O₃ ceramics with different contents of alumina fibers were prepared by gel-casting process. The effects of Al₂O₃ fiber content on pore size distribution, porosity, compressive strength, and load-displacement behavior of the ceramic materials were investigated. Initial results showed that with the increase of Al₂O₃ fiber content, the pore size and porosity of the material is increased, and the compressive strength is decreased. However, upon increasing the fiber content from 50 wt% to 67 wt%, the performance of the samples changed greatly. The compressive strength of the material increased, while the porosity remained unchanged, the pore size increased greatly, and the shape of the load displacement curve changed. It showed that when the fiber content increased from 50 wt% to 67 wt%, the loading body in the fiber-reinforced porous ceramics changed from particles to fibers.     

Ultraporous 3D polymer meshes by low‐temperature electrospinning: Use of ice crystals as a removable void template

While electrospinning provides an excellent preparation method for the manufacturing of polymer fibers with defined diameter, controlling the overall porosity of the resulting fiber assemblies has remained elusive, particularly at higher porosities. In this study, the use of a low‐temperature fiber collection device in air with controlled humidity allowed the simultaneous deposition of polymer fibers and ice particles from condensing humidity. The ice particles were intimately embedded within the polymer fibers and served as a pore template thus defining the mesh porosity after drying of the collected fiber assemblies. The amount of water condensation therefore contributes to the control of the mean interfiber distance and the resulting porosity. This simple and well accessible use of ice crystals as void templates gives access to the preparation of biodegradable tissue engineering scaffolds with an up to four times higher porosity if compared to conventional fiber electrospinning. The successful application of low‐temperature electrospinning using polyesters or polyurethanes suggests a broad, material independent applicability of the process for the preparation of highly porous polymer structures. POLYM. ENG. SCI., 47:2020–2026, 2007. © 2007 Society of Plastics Engineers     

Short fiber reinforced thermoplastics. I. Rheological properties of glass fiber reinforced Noryl

An experimental study on the flow behavior of glass fiber reinforced Noryl (a commercial poly(phenyleneoxide)/polystyrene blend) using a capillary rheometer is described. The effect of fiber concentration on shear viscosity and die swell was studied at various temperatures. Breakage of glass fibers during flow through the rheometer is discussed; it was found that the average fiber length (about 230 μm) was not significiantly altered, except at the highest shear rate (575 s⁻¹) studied. The incorporation of short fibers into thermoplastic polymer melts increases their viscosity without changing the basic rheological character-shear rate dependency. No discernible viscosity changes were measured by incorporating 10 weight percent fibers, and upon further increase of fiber concentration from 20 to 30 weight percent no appreciable increase in viscosity was noted. It is shown that short glass fibers cause a large reduction in extrudate swell. The presence of voids and fiber orientation contribute to the decrease of the die swell, an effect greater than expected from volumetric considerations alone.     

热拉伸过程中PE–UHMW/PE–HD共混纤维的晶体结构演变

将超高分子量聚乙烯(PE–UHMW)与高密度聚乙烯(PE–HD)按照质量比为6︰4进行共混熔融纺丝,并对初生丝进行高倍热拉伸制得PE–UHMW/PE–HD共混纤维。利用广角X射线衍射、差示扫描量热、声速取向试验等方法研究了PE–UHMW/PE–HD共混纤维在热拉伸过程中的晶体结构演变过程。研究显示,随着热拉伸过程的进行,纤维的分子链沿纤维的轴向取向度逐渐增加,熔融峰温度逐渐升高,结晶度逐渐增加;沿径向的晶粒尺寸逐渐减小,而沿轴向的晶粒尺寸逐渐增加,即形成了更细长的晶粒;晶体的取向度逐渐增加。当拉伸倍数由1增大至6时,上述现象变化显著,当拉伸倍数由9增至15时,上述现象变化缓慢。与PE–HD共混后的纤维结晶度、晶体取向度和分子链取向度更高,晶粒更加细长。     

Effect of the addition of a fugitive salt on electrospinnability of poly(?-caprolactone)

Described in this paper is a novel study focused on producing bead-free ultrafine fibers, with narrow fiber diameter distribution, from Poly(?-caprolactone) (PCL) via electrospinning. High quality product is achieved with the use of a new solvent system that involves an acid-base reaction to produce weak salt complexes, which serve to increase the conductivity of the polymer solution. Additionally, the salt formed dissociates easily and evaporates along with the solvent during the spinning process because its respective acid-base components are volatile at room temperature. This results into the formation of pure PCL nanofibers of ultrafine dimensions. Glacial acetic acid was used as the solvent for the polymer and the organic base pyridine was used to initiate the formation of salt complexes in the solution. Pyridine was added at six different levels to vary the conductivity and examine the latter's effect on fiber morphology. Along with the pyridine content, the polymer concentration was also varied to determine how the two interacted in influencing the size of the fiber and the quality of the structure obtained. It was found that bead-free fibers of sizes lying well within the nano range (140-340 nm) could be produced using the conducting solvent system. Two interesting effects were noted. For a given polymer concentration, the mean fiber diameter increased with increase in pyridine amount. And, lower the polymer concentration, higher was the amount of pyridine required to produce bead-free nanofibers. The combination of these effects along with the fact that the reproducibility of the results was high provided a means of producing fibers with predictable sizes.     

Hollow fibers for seawater desalination from blends of PVDF with different molecular weights: Morphology,properties and VMD performance

In this work, different PVDF grades were used for producing hollow fibers for application in seawater desalination by membrane distillation (MD). In particular, PVDF Solef^® homopolymers, with increasing molecular weight and different crystallinity, were used, also in blend, for preparing polymeric dopes. The effect of PVDF molecular weight on the dope viscosity was investigated. Then, a group of six polymeric dopes, having the same additive composition and the same viscosity (about 7000 mPa s), but containing different PVDF types was selected. Spinning experiments were carried out under the same conditions to highlight the effect of PVDF type on the produced hollow fibers’ morphology and properties. It was evidenced that polymer concentration plays a major role in determining the final membrane morphology; in particular, the formation of macrovoids is more affected by polymer concentration than dope viscosity. Fibers’ mechanical properties, porosity and pore size were found to be also strongly affected by polymer concentration. Finally, the produced hollow fibers were tested in a membrane distillation unit working under vacuum (VMD). Tests were carried out both feeding pure water and synthetic seawater. It was found that VMD performance, both in terms of flux (J) and solute separation factor (α), being connected to fibers’ morphology and porosity, is also clearly dependent on polymer concentration.     

Process Optimization and Empirical Modeling for Electrospun Poly(D,L‐lactide) Fibers using Response Surface Methodology

Summary: Ultrafine fibers were spun from poly(D ,L ‐lactide) (PDLA) solution using a homemade electrospinning set‐up. Fibers with diameter ranging from 350 to 1 900 nm were obtained. Morphologies of fibers and distribution of fiber diameters were investigated varying concentration and applied voltage by scanning electron microscopy (SEM). Average fiber diameter and distribution were determined from about 100 measurements of the random fibers with an image analyzer (SemAfore 5.0, JEOL). A more systematic understanding of process parameters of the electrospinning was obtained and a quantitative relationship between electrospinning parameters and average fiber diameter was established by response surface methodology (RSM). It was concluded that the concentration of polymer solution played an important role in the diameter of fibers and standard deviation of fiber diameter. Lower concentration tended to facilitate the formation of bead‐on‐string structures. Fiber diameter tended to increase with polymer concentration and decrease with applied voltage. Fibers with lower variation in diameter can be obtained at lower concentration regardless of applied voltage. Fibers with uniform diameter and lower variation in diameter can be obtained at higher concentration and higher applied voltage. Process conditions for electrospinning of PDLA could be chosen according to the model in this study.

Contour plots of average fiber diameter as a function of concentration and applied voltage.     

In-situ preparation of macroporous network of silicalite-1 nanocrystallites

Large macroporous networks of silicalite-1 nanocrystallites have been produced from the in-situ hydrolysis of tetraethoxysilane (TEOS) in the presence of concentrated solutions of both molecular (tetrapropylammonium) and polymeric (monodispersed polystyrene beads, ∼400 nm) templating agents followed by hydrothermal and calcination treatments. The morphology of these solids has been characterized using SEM, HREM, XRD, ²⁹Si MAS-NMR, nitrogen adsorption–desorption and mercury intrusion techniques. It consists in a somewhat regular array of nanocrystals (∼100 nm) of silicalite-1 (pore size is ca. 6 nm) organized around interconnected macropores of narrow size distribution (330 ± 30 nm). As silicalite-1 crystals are grown into macropores’ walls, a secondary network of mesoscopic voids is formed between the crystallites (25 ± 15 nm). Two out of these three levels of porosity are narrow distributed.     

Characterization of Poly (Methyl Acrylate) Grafted Bleached Sulfite Pulp Fibers using AFM,AEM, EDS and STEM

Abstract

Sulfite pulp fibers were grafted by poly (methyl acrylate) at a low‐consistency (1% pulp consistency) and medium‐consistency (10% pulp consistency). It is of fundamental interest to determine the distribution of the polymer chains obtained at different fiber concentrations during grafting. In this study, modern analytical tools such as atomic force microscope (AFM), energy dispersive spectrometer (EDS), and scanning transmission electron microscope (STEM) were used for investigating the distribution of the polymer chains in the fiber matrix. AFM images in tapping mode showed that the fiber surface was covered with in‐situ generated polymers. The X‐ray mapping of Na in the cross‐section of the hydrolyzed grafted fibers by using EDS in combination with Na line scans by STEM showed that the distribution of poly (methyl acrylate) was affected by the pulp consistency during grafting; at a medium‐consistency condition the outer region of the fiber structure had a higher polymer concentration than the inner region. On the other hand, at a low‐consistency condition, grafting occurred uniformly across the fiber wall structure.     

Nano and submicrometric fibers of poly(D,L‐lactide) obtained by solution blow spinning: Process and solution variables

Nano and submicrometric fibers of poly(D ,L ‐lactide) (PDLLA or PLA) were spun from solutions using a solution blow spinning (SBS) apparatus. Fiber morphology and diameter were investigated by scanning electron microscopy as a function of polymer concentration, feed rate, and air pressure. A more systematic understanding of the SBS process parameters was obtained, and a quantitative relationship between these parameters and average fiber diameter was established by design of experiments and response surface methodology. It was observed that polymer concentration played an important role in fiber diameter, which ranges from 70 to 2000 nm, and its distribution. Lower polymer concentration tended to increase the formation of bead‐on‐string structures, whereas smooth fibers were formed at higher concentrations. Fiber diameter tended to increase with polymer concentration and decrease with feed rate. Based on these results, optimal conditions could be obtained for solution‐blow spun fibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.