Hydrolytic degradation of ionically cross-linked polyphosphazene microspheres

The hydrolytic degradation of gel microspheres based on calcium cross-linked phosphazene polyelectrolytes, poly[di(carboxylatophenoxy)phosphazene] (PCPP) and poly[(carboxylatophenoxy) (glycinato)phosphazene] (PCGPP), was investigated. These microspheres are of importance as carriers in protein and cell encapsulation. Both PCPP and PCGPP ionotropic polyphosphazene hydrogels are degradable in an aqueous environment (pH 7.4, 37°C). The degradation rates can be increased by incorporation of hydrolysis sensitive glycinato groups as the pendant structures in the polymer (PCGPP). Hydrolysis of these polymer hydrogels led to low molecular weight (<1,000 Da) products. The erosion and molecular weight profiles varied also according to the molecular weight of the polyphosphazene constituting the gel beads. Another approach to affect the degradation rates consists of coating microspheres with poly-L -lysine. Ionotropic polyphosphazene hydrogels have potential as biodegradable devices for controlled drug delivery systems. © 1994 John Wiley & Sons, Inc.     

The production of polycarbosilane-derived porous carbon fibers

When a C-rich polycarbosilane (PCS) fiber is pyrolyzed in the presence of KOH, a porous carbon fiber was obtained after acid washing. During the process, silicon was almost completely eliminated and a large microporosity was formed. The porous carbon fibers have a surface area of 1100 m²/g and an average pore size of 2.80 nm. These materials are called “organic-carbide-derived carbons”.     

The production of carbon nanofibers and thin films on palladium catalysts from ethylene-oxygen mixtures

The characteristics of carbonaceous materials deposited in fuel rich ethylene-oxygen mixtures on three types of palladium: foil, sputtered film, and nanopowder, are reported. It was found that the form of palladium has a dramatic influence on the morphology of the deposited carbon. In particular, on sputtered film and powder, tight ‘weaves’ of sub-micron filaments formed quickly. In contrast, on foils under identical conditions, the dominant morphology is carbon thin films with basal planes oriented parallel to the substrate surface. Temperature, gas flow rate, reactant flow ratio (C₂H₄:O₂), and residence time (position) were found to influence both growth rate and type for all three forms of Pd. X-ray diffraction, high resolution transmission electron microscopy, temperature-programmed oxidation, and Raman spectroscopy were used to assess the crystallinity of the as-deposited carbon, and it was determined that transmission electron microscopy and X-ray diffraction were the most reliable methods for determining crystallinity. The dependence of growth on reactor position, and the fact that no growth was observed in the absence of oxygen support the postulate that the carbon deposition proceeds by combustion generated radical species.     

Effect of solvent on surface wettability of electrospun polyphosphazene nanofibers

Two kinds of biodegradable polymers, poly(ε‐caprolactone) (PCL) and poly[(alanino ethyl ester)_0.67 (glycino ethyl ester)_0.33 phosphazene] (PAGP), were electrospun by using four different solvents. All PCL nanofibrous mats had similar surface water contact angles independent of solvents. However, it was found that the water contact angles of PAGP nanofibrous mats were 102.2° ± 2.3°, 113.5° ± 2.2°, 115.8° ± 1.4°, and 119.1° ± 0.7°, respectively, when trifluoroethanol, chloroform, dichloromethane, and tetrahydrofuran were used as a solvent. This difference was supposed mainly due to phosphorous and nitrous atoms in PAGP being dragged to fiber surface with solvent evaporation during the solidification of nanofibers, because of the strong interaction between positive phosphorous atoms and electronegative atoms in solvents. This interaction was confirmed by Fourier Transform Infrared, and the accumulation of phosphorous and nitrous atoms in the solvent‐casting PAGP film surface was identified by X‐ray photoelectron spectrometry analysis. PCL samples did not show the solvent‐controlled surface wettability because it contained fewer polar atoms. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Direct synthesis of fullerene-intercalated porous carbon nanofibers by chemical vapor deposition

Hybrid structures combining fullerenes and carbon nanotubes have exhibited exciting properties. However, the low efficiency and complex process of such assembly restrict their practical applications. We report a single-step procedure to synthesize the fullerene-intercalated (including endohedral metallofullerene (Y@Cn)) porous carbon nanofibers (pCNFs) by chemical vapor deposition (CVD) using a Fe/Y catalyst on a copper substrate. Fullerenes were simultaneously synthesized with the pCNF growth during the CVD process. Instead of attaching them on the surface of the CNFs, the fullerenes were inserted in the graphitic interlayer spacing, inducing micro- and mesopores in CNFs. The growth mechanism of the fullerene-intercalated pCNFs was discussed.     

The production of porous glassy carbon membranes from swift heavy ion irradiated Kapton

A porous glassy carbon membrane was obtained by first producing ion tracks in a polymeric Kapton film by irradiation with high energy krypton or xenon ions. Pores are formed by selective chemical etching along the ion tracks, and then the film was converted to glassy carbon by heat treatment at 1000 °C under an inert atmosphere. The process yields a self-supported glassy carbon thin membrane. The density of the pores in the membrane depends on the ion irradiation fluence, and the length, diameter and shape of the pores could be controlled by the ion energy and etching procedure.     

Electrospun nanofibers from a porous hollow tube

Single electrospinning jets are known to have low production rates. A 0.1 m² nonwoven mat containing 1 g of 100 nm fibers may take several days to create from a single jet. Inexpensive methods of higher production rates are needed for laboratory research applications. In this paper we present experimental results of many simultaneous electrospinning jets from the surface of tube having a porous wall. The pores in the wall are small and resist the flow of the polymer. Holes drilled half way into the wall of the tube provide points of reduced flow resistance. A polymer solution of 15 wt% polyvinylpyrrolidone (PVP) in ethanol is pushed by low air pressure of 1-2 kPa through the tube wall at the drilled holes. On the outer surface of the tube polymer drops form at the locations of the drilled holes. The solution is charged from 40 to 60 kV to electrospin the polymer. Multiple polymer jets launch from the tube surface and form fibers. A 13 cm long tube with 20 holes can produce 0.3-0.5 g/h of nanofiber. Production rates can easily be scaled by increasing the tube length and the number of holes.     

聚丙烯腈基多孔碳纳米纤维的制备及其结构与性能研究

以聚丙烯腈(PAN)为碳源,聚乙烯吡咯烷酮(PVP)为造孔剂,采用静电纺丝法制备出PAN/PVP复合纳米纤维,经水洗处理以及预氧化和碳化处理制备出PAN基多孔碳纳米纤维,采用扫描电镜、傅里叶变换红外光谱仪、差示扫描量热仪以及X射线衍射仪对碳化前后纤维的形貌和结构进行了表征,采用比表面和孔径分布分析仪、电化学工作站对多孔碳纳米纤维的比表面积、孔径分布及电化学性质进行了研究。结果表明:在预氧化和碳化处理过程中PAN基多孔纳米纤维的结构发生了变化,形成了碳碳键的环状结构;随着PVP含量的增加,多孔碳纳米纤维的比表面积增大,比电容增大;当加入PVP的质量分数为20%时,PAN基多孔碳纳米纤维的比表面积和孔体积可以达到216.684 m2/g和0.102 m3/g,扫描速率为5 m V/s的条件下其比电容可达154.36 F/g,电极电阻为3.64Ω。     

Polyimide‐based porous hollow carbon nanofibers for supercapacitor electrode

Porous hollow carbon nanofibers (PHCNFs) using styrene‐acrylonitrile copolymer (SAN) solution as core and polyacrylic acid (PAA) as shell were manufactured by co‐axial electrospinning technique, taking polyvinyl pyrrolidone (PVP) as a pore inducer additive in the shell. The shell thickness of PHCNFs could be adjusted by controlling flow rates of core and shell fluids. The prepared PHCNFs showed excellent electrochemical properties with the high specific capacitance of 221 F g^?1 and superior cycling stability, remaining a capacitance retention of 95% after 5000 cycles under a scan rate of 0.1 V s^?1. In this system, hollow structures bring a 20% capacitance improvement, while the porous morphology brings a 47% capacitance improvement. The attractive performances exhibited by these sponge supercapacitors make them potentially promising candidates for future energy storage systems. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43397.     

Activated porous carbon nanofibers using Sn segregation for high-performance electrochemical capacitors

Activated porous carbon nanofibers (CNFs) with three different types of porous structures, which were controlled to contain 1, 4, and 8 wt% of Sn–poly(vinylpyrrolidone) (PVP) precursors in the core region and 7 wt% polyaniline (PAN)–PVP precursors in the shell region during electrospinning, were synthesized using a co-electrospinning technique with H₂-reduction. The formation mechanisms of activated porous CNF electrodes with the three different types of samples were demonstrated. The activated porous CNFs, for use as electrodes in high-performance electrochemical capacitors, have excellent capacitances (289.0 F/g at 10 mV/s), superior cycling stability, and high energy densities; these values are much better than those of the conventional CNFs. The improved capacitances of the activated porous CNFs are explained by the synergistic effect of the improved porous structures in the CNF electrodes and the formation of activated states on the CNF surfaces.     

Barnacle-like manganese oxide decorated porous carbon nanofibers for high-performance asymmetric supercapacitors

In this study, barnacle-like manganese oxide (MnO₂) decorated porous carbon nanofibers (PCNF) were synthesized using electrospinning and the chemical precipitation method for high-performance asymmetric supercapacitors. The porous structure of PCNF was acquired using poly(styrene-co-acrylonitrile) in the electrospinning solution. In order to obtain the optimized barnacle-like MnO₂ on PCNF (MnO₂-PCNF), the barnacle-like MnO₂ was synthesized using different synthetic times (namely, 1.5, 3.0, and 7.0 min) of the chemical precipitation. Among them, the optimized MnO₂-PCNF for 3.0 min exhibited the well-dispersed MnO₂ on the PCNF with the nano-size of 190–218 nm. The optimized MnO₂-PCNF showed the superior specific capacitance of 209.8 F g^?1 at 10 mV s^?1 and the excellent high-rate performance of 160.3 F g^?1 at 200 mV s^?1 with the capacitance retention of 98.7% at 100 mV s^?1 for 300 cycles. In addition, electrochemical performances of asymmetric cell (constructed activated carbon and MnO₂-PCNF) showed the high specific capacitance of 60.6 F g^?1 at the current density of 0.5 A g^?1, high-rate capacitance of 30.0 F g^?1 at the current density of 10 A g^?1, and the excellent energy density of 30.3–15.0 Wh kg^?1 in the power density range from 270 to 9000 W kg^?1. The enhanced electrochemical performance can be explained by the synergistic effects of barnacle-like MnO₂ nanoparticles with a high active area related to high specific capacitance and well-dispersed MnO₂ with a short ion diffusion length related to the excellent high-rate performance.     

Preparation of porous carbon nanofibers derived from graphene oxide/polyacrylonitrile composites as electrochemical electrode materials

Porous carbon nanofibers (CNFs) derived from graphene oxide (GO) were prepared from the carbonization of electrospun polyacrylonitrile nanofibers with up to 15 wt.% GO at 1200 °C, followed by a low-temperature activation. The activated CNFs with reduced GOs (r-GO) revealed a specific surface area and adsorption capacity of 631 m²/g and 191.2 F/g, respectively, which are significantly higher than those of pure CNFs (16 m²/g and 3.1 F/g). It is believed that rough interfaces between r-GO and CNFs introduce oxygen pathways during activation, help to produce large amounts of all types of pores compared to pure activated CNFs.     

Strong carbon nanofibers from electrospun polyacrylonitrile

Strong carbon nanofibers with diameters between 150 nm and 500 nm and lengths of the order of centimeters were realized from electrospun polyacrylonitrile (PAN). Their tensile strength reached a maximum at 1400 °C carbonization temperature, while the elastic modulus increased monotonically until 1700 °C. For most carbonization temperatures, both properties increased with reduced nanofiber diameter. The tensile strength and the elastic modulus, measured from individual nanofibers carbonized at 1400 °C, averaged 3.5 ± 0.6 GPa and 172 ± 40 GPa, respectively, while some nanofibers reached 2% ultimate strain and strengths over 4.5 GPa. The average tensile strength and elastic modulus of carbon nanofibers produced at 1400 °C were six and three times higher than in previous reports, respectively. These high mechanical property values were achieved for optimum electrospinning parameters yielding strong PAN nanofibers, and optimum stabilization and carbonization temperatures, which resulted in smooth carbon nanofiber surfaces and homogeneous nanofiber cross-sections, as opposed to a previously reported core–shell structure. Turbostratic carbon crystallites with average thickness increasing from 3 to 8 layers between 800 °C and 1700 °C improved the elastic modulus and the tensile strength but their large size, discontinuous form, and random orientation reduced the tensile strength at carbonization temperatures higher than 1400 °C.     

Physical and electrochemical studies of polyphenylsilane-derived porous carbon nanofibers produced via electrospinning

Polyacrylonitrile (PAN)/polyphenylsilane (PPS)-based composite carbon nanofibers (CCNFs) are prepared by one-step electrospinning and subsequent thermal treatment to produce organic-inorganic hybrid CCNFs. We investigate the electrochemical behavior and structural properties of these CCNF materials as a function the PAN/PPS ratio. The CCNFs show large specific surface area, high electrical conductivity and high thermal stability. In addition, the electrochemical performance of the organic–inorganic hybrid CCNF electrode is improved by the special porous structure and the silicon oxycarbide (Si–O–C)-related structure.     

Adsorption characteristics of benzene on electrospun‐derived porous carbon nanofibers

The adsorption properties of polyacrylonitrile (PAN) carbon nanofibers fabricated by using an electrospinning route were assessed for their applicability as a novel alternative adsorbent. Commercial fiber, A–10, was chosen for comparison. Nitrogen adsorption/desorption isotherms and gravimetric techniques were used to examine the porous structure, adsorption equilibrium, kinetics, and the energetic heterogeneity of the prepared adsorbent. The nitrogen adsorption and desorption isotherms showed that PAN carbon nanofibers are highly microporous with small amounts of mesoporous regions. The equilibrium data of benzene was obtained at three different temperatures (343.15, 383.15, and 423.15) K with pressures up to 4 kPa. The data correlated successfully with the Toth isotherm equation. In addition, by using this isotherm model, the adsorption affinity and isosteric enthalpy of adsorption were determined. The results of the isosteric enthalpy of adsorption and adsorption energy distribution tests/equations revealed that although PAN carbon nanofibers have a heterogeneous surface, they seem to be more homogeneous than commercial carbon fibers. Moreover, the mass transfer and thermal desorption results showed that shallow pores contained within PAN carbon nanofibers may be effective adsorbents for removing toxic compounds. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2454–2462, 2006     

Hydrolysis of Ca-deficient hydroxyapatite precursors in the presence of alanine-functionalized polyphosphazene nanofibers

Hard tissues are made of nanoapatite crystallites grown on a nanofibrous collagen matrix. The mechanical interlocking and the chemical bonding between both phases provide the unique properties of hard tissues. A biodegradable alanine-substituted polyphosphazene nanofibrous scaffold was prepared by an electrospinning technique. Scaffolds were loaded with precursors that form Ca-deficient hydroxyapatite upon hydrolysis in aqueous media. Composite scaffolds containing 30, 60, and 90 wt% were subjected to hydrolysis in a phosphate buffer solution for up to 10 days, and was followed by pH measurements, x-ray diffraction and scanning electron microscopy. Results showed a delayed conversion of the precursors into Ca-deficient apatite, which was proven to be attributed to the encapsulation of the precursors within the polymer nanofibrous scaffold and the slow introduction of water of hydrolysis to the precursors. This was accompanied by an increasing swelling of the nanofibers. An overall buffering effect took place within the system as a result of the degradation of the polymeric nanofibers, maintaining pH of the media within physiologic pH values.     

Synthesis of multi-branched porous carbon nanofibers and their application in electrochemical double-layer capacitors

Multi-branched carbon nanofibers with a porous structure have been synthesized on a Cu catalyst doped with Li, Na, or K. The products were characterized by field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and Raman spectroscopy. Using this new type of nanofiber as polarized electrodes, an electrochemical double-layer capacitor with a specific capacitance of ca. 297 F/g was obtained using 6 M KOH as the electrolyte.     

The production of a homogeneous and well-attached layer of carbon nanofibers on metal foils

Carbon nanofibers (CNFs) were deposited on metal foils including nickel (Ni), iron (Fe), cobalt (Co), stainless steel (Fe:Ni; 70:11 wt.%) and mumetal (Ni:Fe; 77:14 wt.%) by the decomposition of C₂H₄ at 600 °C. The effect of pretreatment and the addition of H₂ on the rate of carbon formation, as well the morphology and attachment of the resulting carbon layer were explored. Ni and mumetal show higher carbon deposition rates than the other metals, with stainless steel and Fe the least active. Pretreatment including an oxidation step normally leads to higher deposition rates, especially for Ni and mumetal. Enhanced formation of small Ni particles by in situ reduction of NiO, compared to formation using a Ni carbide, is probably responsible for higher carbon deposition rates after oxidation pretreatment. The addition of H₂ during the CNF growth leads to higher carbon deposition rates, especially for oxidized Ni and mumetal, thus enhancing the effect of the reduction of NiO. The diameters of CNFs grown on metal alloys are generally larger compared to those grown on pure metals. Homogenously deposited and well-attached layers of nanotubes are formed when the carbon deposition rate is as low as 0.1-1 mg cm⁻² h⁻¹, as mainly occurs on stainless steel.     

Bundle-like carbon nanofibers grown from methane decomposition

Bundle-like carbon nanofibers (CNFs) were prepared from methane decomposition over Ni nanoparticles supported by grooved SiC nanowires. In the bundle-like CNFs, several CNFs grow in a parallel mode and form a bundle of CNFs. Large loading of Ni and limited space of nanoscale grooves on the nanowires lead to aggregation of Ni nanoparticles in the nanoscale grooves. The aggregated Ni nanoparticles generate several CNFs, which close up each other and form the bundle-like CNFs. The bundle-like CNFs become curved due to the difference in growth rates of different CNFs.