Effect of platinum salt concentration on the electrospinning of polyacrylonitrile/platinum acetylacetonate solution

The preparation and characterization of electrospun polyacrylonitrile (PAN)/platinum(II) acetylacetonate composite nanofibers were investigated. The solution properties, such as viscosity, surface tension, and conductivity, of Pt‐acetylacetonate‐added PAN solutions in N,N‐dimethylformamide were measured, and their influences on the resulting fiber structure were also determined. At low Pt salt concentrations, the addition of Pt salt increased the fiber diameter but did not change the fiber diameter distribution. However, the fiber diameter decreased, and the fiber diameter distribution became broader when the Pt salt concentration went beyond a critical value. The structure of the electrospun fibers was determined by the formation of polymer–salt– solvent interactions, which changed the balance among the viscosity, surface tension, and conductivity of the solutions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of novel ultrafine fibers based on DNA and poly(ethylene oxide) by electrospinning from aqueous solutions

Novel DNA/Polyethyleneoxide (PEO) electrospun fibers were obtained from aqueous solution. Key solution properties related to electrospinning: conductivity, surface tension and viscosity were determined. The ionic conductivity of the solution increased significantly with the addition of DNA and only slightly with increasing amounts of PEO; the surface tension decreased with the addition of PEO; the viscosity increased with the addition of either DNA or PEO. It was found that solutions containing both DNA and PEO had ideal properties for electrospinning. The use of these solutions resulted in the formation of ultrafine fibrous mats with fiber diameters of 50–250 nm. It was also found that the average diameter of electrospun fibers decreased with decreased feed rate, increased tip-to-collector distance and increase in the potential employed during electrospinning.     

Electrospinning of cellulose nanofibers from ionic liquids: The effect of different cosolvents

Cellulose was electrospun with various concentrations of ionic liquid and cosolvent. Three different cosolvents were used in this study; dimethylacetamide (DMAc), dimethyl formamide (DMF), and dimethyl sulfoxide (DMSO). The cosolvents were added to modify the viscosity, electrical conductivity, and surface tension of the solutions. The solubility of cellulose in ionic liquids is highly affected by changes in solvent properties on the molecular level in the binary solvent systems. The difference in molecular structure of the cosolvents and the interactions between cosolvent and ionic liquid can explain the difference in dissolution power of the cosolvents. Scanning electron microscope (SEM) was used to characterize electrospun cellulose fibers. For the systems tested the importance of having a rather high viscosity and high surface tension, and some degree of shear thinning to produce fibers is shown. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Imidazolium‐organic solvent–alkali metal salt mixtures as nonflammable electrolytes incorporated into PVDF–PEG polymer electrolyte

A mixture of flammable organic solvent, alkali metal salt, and nonflammable room temperature ionic liquid has been used as a new type of electrolyte. A novel microporous polymer electrolyte based on poly(vinylidene fluoride), i.e., PVDF, and poly(ethylene glycol), i.e., PEG, was prepared by a simple phase‐inversion technique. The mixed electrolyte was observed to be nonflammable at ionic liquid contents of 60 vol % or greater. The viscosity (range, 0.98–30.5 mPa s) and conductivity (range, 9.9 to 22.25 mS cm^?1) of the mixed electrolyte were discussed. The porosity, solution uptake, and conductivity mechanism of polymer membranes also were discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Electrospinning pure protein solutions in core–shell fibers

Electrospinning of protein‐loaded fibers faces many challenges, e.g. burst release owing to segregation of the protein on the fiber surface, loss of activity due to electrospinning conditions, limitation of loading capacity etc. Core–shell electrospinning provides an effective way to electrospin fibers wherein the core can be loaded with bioactive molecules in friendly conditions of a compatible polymer solution, thereby protecting the molecules from the electrostatic field and organic solvent of shell solutions. The shell polymer, after the electrospinning, acts as a barrier to control the release of the loaded molecules. However, the limitation of loading capacity still remains due the prerequisite of using an additional polymer as additive to achieve the minimum viscosity of the core solution required for viscous drag by the shell solution being drawn by the electrostatic force. The work reported here aims to alleviate the need of a polymer additive by using aqueous protein solutions of very high concentration. High concentrations of protein solutions were successfully electrospun as the core of the protein–poly(lactide‐co‐glycolic acid) core–shell fibers. A partitioning effect was seen in the controlled release of hydrophilic proteins as they were retained in the aqueous core for longer times. Using lysozyme as a model protein, it was shown that the activity is significantly retained after electrospinning, compared with electrospinning in monolithic fibers. Moreover, the lysozyme activity was also comparable with the lysozyme released from core–shell fibers spun using poly(vinyl acetate) as additive in the core. Copyright © 2012 Society of Chemical Industry     

添加不同物质的聚乙烯醇/海藻酸钠静电纺丝研究

分别添加少量NaCl、乙酸、表面活性剂十二烷基硫酸钠(SDS),研究少量添加物对海藻酸钠/聚乙烯醇(PVA)溶液性质和静电纺纤维的影响,并初步探讨了溶液静电纺丝机制。结果表明:NaCl改变了溶液的电导率和黏度,乙酸降低了溶液的黏度、提高了溶剂挥发性,SDS降低了溶液的表面张力;适量的添加物可使纤维形貌得到改善;添加物对电纺纤维化学结构无本质影响;无机盐离子加剧了纤维拉伸作用,结晶性有所提高;处于泰勒锥处液滴表面受到静电排斥力、表面张力、同种聚合物分子间的氢键作用力、不同聚合物分子间的氢键作用力以及聚合物同水等溶剂形成的氢键作用力。     

Synthesis and characterization of novel crosslinked polyurethane–acrylate electrolyte

Flexible, transparent, and crosslinked polymer films were synthesized by polymerization of PEG‐modified urethane acrylate using a simple method. A series of novel solid polymer electrolytes and gel electrolytes were prepared based on this type of polymer film. To understand the interactions among salt, solvent, and polymer, the swelling behaviors of the crosslinked polymer in pure propylene carbonate (PC) and liquid electrolyte solutions (LiClO₄/PC) were investigated. The results showed that the swelling rate in the electrolyte solution containing moderate LiClO₄ was greater than that in pure PC. Thermogravimetric analysis (TGA) also supported the interaction between the solvent and polymer. The morphology and crystallinity of the crosslinked polymer and polymer electrolytes were studied using atomic force microscopy (AFM) and wide‐angle X‐ray diffraction (WAXD) spectroscopy. The effects of the content of the electrolyte solution on the ionic conductivity of gel electrolytes were explored. The dependence of the conductivity on the amount of the electrolyte solution was nonlinear. With a different content of the plasticizer, the ionic conduction pathway of the polymer electrolytes would be changed. The best ionic conductivity of the gel electrolytes, which should have good mechanical properties, was 4 × 10^r?3 S cm^?1 at 25°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 340–348, 2003     

The influence of the solvent upon the low shear viscosity of styrene–acrylonitrile copolymer solutions

This paper describes the results of an experimental investigation concerning the effect of polymer–solvent thermodynamics on low-shear viscosity of copolymer soltions. Thermodynamic parameters and low-shear solution viscosities were measured for solutions of polystyrene homopolymer and styrene–acrylonitrile copolymers in four solvents: benzene, dioxane, methyl ethyl ketone, and dimethylformamide. The thermodynamic quality of a solvent for a polymer is characterized by free-energy-of-mixing parameters. These quantities are: the Flory-Huggins thermodynamic interaction parameter χ, the second virial coefficient (from light scattering), the intrinsic viscosity, and the polymer expansion factor. The thermodynamic interaction between a solvent and a polymer in solution influences the rheological behavior of the system. At low concentrations of polymer in solvent, the low-shear solution viscosity is larger in a good solvent than in a poor solvent. In solutions of higher concentration, the reverse may be true and the viscosity is often significantly larger in a poor solvent than in a good one. These results are not predicted quantitatively by existing theory. The parameters in existing viscosity correlation techniques are found to be solvent dependent. The so-called entanglement concentrations for polymer solutions are not unique for a particular polymer but are related to the free energy of mixing polymer with solvent.     

Electrospinning of polycaprolactone nanofibers using H2O as benign additive in polycaprolactone/glacial acetic acid solution

Considerable efforts have been devoted to the production of polycaprolactone (PCL) nanofibrous structures by electrospinning. However, some toxic solvents have often been used to achieve bead‐free nanofibers. At present, a benign solvent such as glacial acetic acid (GAC) only leads to beaded or microscale fibers. Therefore a study is done to extend the electrospinnability of the PCL/GAC system by the addition of H₂O. The solution properties of conductivity, viscosity, and surface tension were altered by the addition of H₂O, especially increasing the conductivity and viscosity. These properties essential to electrospinning could remain stable for 6 h when the H₂O content was less than or equal to 9 vol %. Then ultrafine PCL fibers with diameters from 188 to 200 nm, 10 times smaller than when dissolved in pure GAC, were electrospun from solutions of PCL with concentrations in the range of 17 to 20 wt % with H₂O content at 9 vol %. Finally, the crystallinity and crystallite size of the resulting fibers were smaller than that of raw PCL pellets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45578.     

Conducting rubberlike copolymer–carbon fiber composites

Electrically conductive rubberlike copolymer–carbon fiber composites have been prepared by either a solution method or a concentrated emulsion method. In the former procedure, carbon fibers were introduced with stirring in a copolymer–toluene solution, and the polymer–fiber composites were precipitated by extracting the solvent with methanol. In the latter procedure, a pastelike concentrated emulsion of copolymer–toluene solution in an aqueous solution of sodium dodecylsulfate (SDS) was first formed, and the carbon fibers were mechanically blended with the concentrated emulsion. The polymer–carbon fiber composites were precipitated by extracting the toluene and water with methanol. Four kinds of rubberlike copolymers have been used: styrene/ethylene–butylene/styrene triblock copolymer (SES), styrene/butadiene/styrene triblock copolymer (SBS), ethylene/propene/ethylene triblock copolymer (EPE), and ethylene/vinylacetate copolymer (EVA). Short (L = 0.1 mm)- and medium (L = 5 mm)-length carbon fibers were employed. The composites were hot-pressed in a Laboratory Press to form a sheet. The effects of the two methodologies on the electrical conductivity and mechanical properties of the sheets were investigated by changing the type of polymer, the size of the carbon fibers, the volume fraction of the carbon fibers in the composites, and the hot-pressing temperature. Composites with electrical conductivities in the range of 5–14 S/cm, tensile strengths in the range of 10–17 MPa, and elongations at break point larger than 200% were obtained. The conductivities of the composites prepared with the short fibers were by two orders of magnitude smaller than those prepared with medium-size fibers. © 1994 John Wiley & Sons, Inc.     

Surfactant interactions with P(AM–AA–BPAM) hydrophobically modified polyelectrolytes

The interactions of hydrophobically modified polyelectrolytes poly(acrylamide–sodium acrylic acid–N‐(4‐butyl)phenylacrylamide [P(AM‐AA‐BPAM)] with anionic (sodium dodecyl sulfate), cationic (cetyl trimethylammonium bromide), and nonionic (tetradecyldimethyl‐aminoxid) surfactants were studied via solution rheology, surface tension, and atomic force microscopy measurements. Viscosity measurements indicated that the intermolecular association of the polymer was greatly enhanced by the interaction with the surfactants, especially the oppositely charged surfactants with both a hydrophobic association and an electrostatic attraction. The greatest viscosity increase was realized with the addition of such oppositely charged surfactants. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2664–2671, 2003     

Influence of solution properties on the roller electrospinning of poly(vinyl alcohol)

In recent years, nanofiber production via electrospinning has gained importance because of superior properties of submicron fibers. In this study, the effect of molecular weight, concentration of solution, electric conductivity, surface tension and solution viscosity of the polymer solution on the roller electrospinning of PVA nanofibers was investigated. One nonspinnable and two spinnable polymer species were studied. The effect of polymer concentration and solution viscosity on the electrospinning process throughput, fiber diameters and quality of nanofiber layers was measured. According to the results there is a significant difference in rheological behavior of nonspinnable and spinnable polymer solutions. Electric conductivity and surface tension of the solutions did not influence both throughput and fiber diameter significantly. Whereas molecular weight has an important effect on the spinnability, concentration of the solutions has not. On the contrary, concentration influences the process throughput considerably and properties of nanofibers and nanofiber layers to some extent. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Solution properties of a hyamine based on N,N‐dimethyl diallyl ammonium chloride–acrylamide copolymer

A hyamine based on N,N‐dimethyl diallyl ammonium chloride–acrylamide copolymer was successfully synthesized in this study. Solution properties of this hyamine including electrical conductivity and viscosity behavior were studied in detail, and effects of temperature and counter ion concentration on electrical conductivity of the solution were also discussed. It was found that a solution of hyamine in water showed a typical viscosity behavior of polyelectrolytes, which followed the Fuoss equation. With the increase of ion radius (cationic ion or anionic ion), or with the increase of salt concentration, the shrinkage degree of the polymer chain increased, with a concomitant decrease in reduced viscosity and intrinsic viscosity and an increase of Huggins constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 765–771, 2003     

Sulfonated polyisobutylene telechelic ionomers. XIII. Viscosity behavior in nonpolar solvents and nonpolar–polar solvent mixtures

The effect of molecular variables upon the dilute solution viscosity of sulfonated polyisobutylene telechelic ionomers has been studied in both nonpolar solvents and nonpolar–polar solvent mixtures. In nonpolar solvents, association of the terminal salt groups results in an increase in viscosity and gelation at very low concentrations. The concentration at which gelation occurs was found to be dependent upon molecular variables such as architecture, molecular weight, neutralizing cation, extent of neutralization, and the type of solvent. Addition of a small amount of a more polar cosolvent tends to break up ionic associations between polymer chains and thus reduces viscosity. Finally, such solutions with a small amount of polar cosolvent may display dramatic increases in viscosity with increasing temperature due to a dynamic equilibrium between the ionic groups on the polymer chain, the nonpolar solvent, and the polar cosolvent. The results of this work suggest that these ionomers may potentially be useful as viscosity modifiers or “thermal thickeners” in some applications.     

Modeling of fiber–polymer coupling for suspensions of mono‐modal fibers

The rheology of suspensions of fibers in polymer solutions is strongly dependent on fiber–fiber and fiber–polymer interactions. To model these interactions and their dependence on the flow and suspension properties, the steady shear viscosity of glass fibers in a polyethylene oxide polymer solution are measured for different fiber volume fractions and aspect‐ratios. The measurements are conducted for well characterized fiber samples that have a uniform and well defined aspect‐ratio and for moderate volume fractions. The results of the experimental study are used to correlate the polymer–fiber coupling factor and the fiber–fiber interaction coefficient using a mathematical model based on a modified FENE‐P (finitely extensible nonlinear elastic) constitutive equation. It was found that both parameters are strongly dependent on the characteristics of the suspension, but also depend on the flow shear rate that determines the degree of fiber orientation. In general, fiber–fiber and polymer–fiber interactions increase with both the aspect‐ratio and the volume fraction and are more important when the fibers are not fully oriented. POLYM. COMPOS., 27:82–91, 2006. © 2005 Society of Plastics Engineers     

Effect of composition on the solution rheology of stearyl methacrylate‐co‐styrene‐co‐vinyl pyrrolidinone in paraffinic base oil

The rheological behavior of dilute and semi‐dilute solutions of stearyl methacrylate‐co‐styrene‐co‐vinyl pyrrolidinone copolymers (SMA‐S‐VP) was investigated over a wide range of temperatures (20–140°C) under steady shear (0.1–5000 s^?1) and dynamic conditions (0.01–500 rad/s). The solvent used was polyalpha olefin, PAO4 (C20‐C40 fraction), a fully synthetic paraffinic oil normally used as base oil for lubricant oil formulations. The investigation focuses on the effect of the polar comonomer segment content, of the copolymer, on the viscosity‐temperature relationship of the solution. This information provides insight into the effect of polymer microstructure on the viscosity index (VI) behavior of the lubricant. Copolymers with different ratios of stearyl methacrylate, styrene and vinyl pyrrolidinone were synthesized by solution radical polymerization. The microstructure and molecular weight of the copolymers were evaluated by nuclear magnetic resonance spectroscopy (NMR). The molecular weight and polydispersity of the polymers were determined using GPC. The polymer solutions exhibit non‐Newtonian behavior, which is more evident at lower temperatures and higher concentrations. The temperature‐concentration superposition principle developed by Ferry (1) was applied to steady shear data and the resulting master curve was fitted to the Carreau model. A modified Fedors equation for intrinsic viscosity calculation, at low and moderate polymer solution concentrations, was used. The results confirm that the viscosity index improver properties (VII) of the copolymer are superior when the VP content is low. The polymer‐solvent interactions and solvency power of PAO4 were analyzed using an Arrhenius expression. The results show that at low VP content, PAO4 is a better solvent for the copolymer. Polym. Eng. Sci. 44:736–748, 2004. © 2004 Society of Plastics Engineers.     

Effects of filler–filler and polymer–filler interactions on rheological and mechanical properties of HDPE–wood composites

High‐density polyethylene (HDPE)–wood composite samples were prepared using a twin‐screw extruder. Improved filler–filler interaction was achieved by increasing the wood content, whereas improved polymer–filler interaction was obtained by adding the compatibilizer and increasing the melt index of HDPE, respectively. Then, effects of filler–filler and polymer–filler interactions on dynamic rheological and mechanical properties of the composites were investigated. The results demonstrated that enhanced filler–filler interaction induced the agglomeration of wood particles, which increased the storage modulus and complex viscosity of composites and decreased their tensile strength, elongation at break, and notched impact strength because of the stress concentration. Stronger polymer–filler interaction resulted in higher storage modulus and complex viscosity and increased the tensile and impact strengths due to good stress transfer. The main reasons for the results were analyzed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

溶剂及溶液中无机盐对电纺纤维的影响

采用二甲基乙酰胺(DMAc)与丙酮的混合溶剂,对醋酸纤维素(SCA)电纺过程中溶液性质对纤维直径及形态的影响进行研究。不同的溶液性质具体表现为不同的溶度参数、黏度、表面张力、挥发度等,而纤维直径的细化是以上参数共同作用的结果。而本文中,由于丙酮对溶液的挥发度起了决定性作用,使电纺纤维的直径的改变受其影响最大。当DMAc∶丙酮的混合比为20∶80时,纤维表面会充满凹陷的小孔。另外,无机盐的加入也会导致溶液黏度、表面张力呈先下降后上升的趋势,电导率和电荷密度随之上升。在其他条件一定时,SCA/LiCl体系的纤维直径要小于SCA/CaCl2体系;无机盐含量超过2%时,纤维直径会有一定程度的增加。     

Solvent-dependent adsorption of phenolic resin onto silica substrate

The solution impregnation route is commonly exploited to prepare polymer-based composites. However, the adsorption of polymer components is complicated, which is the result of interactions between reinforcement, solvent and polymer. In this study, the adsorption of phenolic resin onto silica substrate from different solvents was investigated by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, UV-visible absorption spectroscopy and thermogravimetric analysis (TGA). Isotherms for phenolic resin adsorption from solvents onto silica substrate have been examined as a function of phenolic resin content in different solvents. The viscosity and surface tension were measured for the solution systems before and after adsorption. Hydrogen bonding interaction was considered to be operative in the resin–solvent–silica system. The adsorption of phenolic resin is dependent on its relative affinity for the solvent on one hand and for the silica surface on the other. UV-visible absorption spectroscopy results suggested that phenolic resin forms hydrogen bonds with the solvent, which competes with the hydrogen-bonding adsorption mechanism for phenolic resin occurring on silica surface. This hydrogen bonding in solution along with the competitive adsorption of solvent onto silica surface suppresses the adsorption of phenolic resin and such suppression is unfavorable in a solution impregnation process.