Structural Control of NiO–YSZ/LSCF–YSZ Dual‐Layer Hollow Fiber Membrane for Potential Syngas Production

The objective of this study was to fabricate dual‐layer hollow fiber as a microreactor for potential syngas production via phase inversion‐based co‐extrusion/cosintering process. As the main challenge of phase inversion is the difficulty to obtain defect‐free fiber, this work focuses on the effect of the fabrication parameters, that is, nonsolvent content, sintering temperature and outer‐layer extrusion rate, on the macrostructure of the produced hollow fiber. SEM images confirm that the addition of nonsolvent has successfully minimized the finger‐like formation. At high sintering temperature, more dense hollow fiber was formed while outer‐layer extrusion rate affects the outer layer thickness.     

Effects of Temperature on the Filtration Characteristics of a Dual‐Layer Granular Bed Filter

The effects of temperature on the filtration efficiency and pressure drop of a dual‐layer granular bed filter were investigated in a hot dual‐layer granular bed filter with experimental dust. Enhanced higher filtration efficiency was obtained with higher filtration temperature, and the removal efficiency of ultrafine dust was also at a high level. Simultaneously, the total pressure drop maintained at an acceptable range. The results demonstrate that the dual‐layer granular bed has excellent prospects for application to low‐temperature coal pyrolysis.     

Dual-layer hollow fibers for gas separation processes produced by quadruple spinning

A novel quadruple spinneret to produce dual-layer hollow fiber membranes by simultaneous spinning of two polymer solutions, using the dual precipitation bath technique is proposed. Hollow fibers aimed at gas separation processes were prepared in extrusion system specifically designed and built for this purpose. A polyurethane polymer was selected as the selective layer (outer-layer), while polyethersulfone was defined as the support (inner-layer). Activated carbon powder was added into the PU solution for further improvement of the transport properties. The hollow fibers showed good adhesion between the polymer layers and a defect-free selective layer. Representative results include a CO₂/N₂ selectivity of 43.     

Hollow Poly(3‐hydroxybutyrate) Fibers Produced by Melt Spinning

Native and nucleated PHB has been melt‐spun and the properties of the resulting fibers have been investigated. Biocompatible nucleating agents such as HAP and THY were compared to BN as a reference material. DSC was used to investigate the non‐isothermal crystallization kinetics as a function of processing temperature and cooling rate. It was found that particularly the choice of process temperature can ensure sufficient primary crystallization of native PHB: heating not higher than 10–15 K above the melting temperature induced a favorable crystallization behavior of native PHB. Thus, melt spinning at low process temperatures without additives was demonstrated to be the key to the formation of well‐defined hollow PHB fibers.

     

NI/NI‐YSZ Current Collector/Anode Dual Layer Hollow Fibers for Micro‐Tubular Solid Oxide Fuel Cells

A co‐extrusion technique was employed to fabricate a novel dual layer NiO/NiO‐YSZ hollow fiber (HF) precursor which was then co‐sintered at 1,400 °C and reduced at 700 °C to form, respectively, a meshed porous inner Ni current collector and outer Ni‐YSZ anode layers for SOFC applications. The inner thin and highly porous “mesh‐like” pure Ni layer of approximately 50 μm in thickness functions as a current collector in micro‐tubular solid oxide fuel cell (SOFC), aiming at highly efficient current collection with low fuel diffusion resistance, while the thicker outer Ni‐YSZ layer of 260 μm acts as an anode, providing also major mechanical strength to the dual‐layer HF. Achieved morphology consisted of short finger‐like voids originating from the inner lumen of the HF, and a sponge‐like structure filling most of the Ni‐YSZ anode layer, which is considered to be suitable macrostructure for anode SOFC system. The electrical conductivity of the meshed porous inner Ni layer is measured to be 77.5 × 10⁵ S m^–1. This result is significantly higher than previous reported results on single layer Ni‐YSZ HFs, which performs not only as a catalyst for the oxidation reaction, but also as a current collector. These results highlight the advantages of this novel dual‐layer HF design as a new and highly efficient way of collecting current from the lumen of micro‐tubular SOFC.     

Comparatively Thermal and Crystalline Study of Poly(methyl‐methacrylate)/Polyacrylonitrile Hybrids: Core–Shell Hollow Fibers,Porous Fibers,and Thin Films

The polyacrylonitrile/polymethyl‐methacrylate (PMMA/PAN) porous fibers, core–shell hollow fibers, and porous thin films are prepared by coaxial electrospinning, single electrospinning, and spin‐coating technologies, respectively. The different morphologies arising from different processes display great influences on their thermal and crystalline properties. The adding of PMMA causes porous structure due to the microphase‐separation structure of immiscible PMMA and PAN phases. The lower weight loss, higher degradation temperature, and glass‐transition temperatures of porous thin films than those of porous fibers and core–shell hollow fibers are obtained, evidencing that the polymer morphologies produced from the different process can efficiently influence their physical properties. The orthorhombic structure of PAN crystals are found in the PMMA/PAN porous thin films, but the rotational disorder PAN crystals due to intermolecular packing are observed in the PMMA/PAN porous fibers and core–shell hollow fibers, indicating that different processes cause different types of PAN crystals.

     

Improved Electrodes/Electrolyte Interfaces for Solid Oxide Fuel Cell by Using Dual‐Sized Powders in Electrolyte Slurry

The dense electrolyte film with the rough surfaces for solid oxide fuel cell (SOFC) was fabricated on NiO/yttria‐stabilized zirconia (YSZ) anode substrate by using dual‐sized YSZ powders without additional effort to roughen electrolyte film. The dual‐sized YSZ powders consisted of the fine YSZ powder and the coarse YSZ powder at different weight ratios. Incorporation of the coarse YSZ powder into the fine YSZ powder is in order to increase the surface roughness of electrolyte film, and the surface roughness obviously increased with the increase of coarse YSZ powder. The rough surfaces resulted in an enlargement of the electrochemical active area. It was found that electrode polarization was reduced evidently and cell electrochemical performance was enhanced, as the surface roughness increased. However, the excessive coarse YSZ powder was not beneficial for densification of electrolyte film and thus the open‐circuit voltage (OCV) was declined. The cell with 17 wt.% coarse YSZ powder in the electrolyte exhibited the best performance and the maximum power density was 1,930 mW cm^–2 at 800 °C.     

Dual‐layer PBI/P84 hollow fibers for pervaporation dehydration of acetone

Acetone dehydration via pervaporation is challenging, because acetone and water have close molecular sizes, and acetone has a much higher vapor pressure than water. Acetone is also a powerful solvent, which dissolves or swells most polymers. We have developed novel polybenzimidazole/BTDA‐TDI/MDI (PBI/P84) dual‐layer hollow fibers for pervaporation dehydration of acetone for industrial and biofuel separations. Both thermal and chemical crosslinking modifications were applied to the membranes to investigate their effectiveness to overcome acetone‐induced swelling. Thermal treatment can effectively enhance separation performance, but performance stability can only be achieved through the crosslinking modification of PBI. Crosslinking by p‐xylene dichloride followed by a thermal treatment above 250°C show significant effectiveness to improve and stabilize pervaporation performance. The fractional free volume of the PBI selective layer reduces from 3.27 to 1.98% and 1.33%, respectively, after thermal treatment and a combination of chemical/thermal crosslinking modifications characterized by positron annihilation spectroscopy. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Formation of defect‐free polyetherimide/PIM‐1 hollow fiber membranes for gas separation

Dual‐layer hollow fiber membranes were produced from blends of Ultem and polymer of intrinsic microporosity (PIM‐1) with enhanced gas permeance. The effects of spinning parameters (take‐up speed and air gap distance) on gas separation performance were investigated based on the pristine Ultem. Selected spinning conditions were further adopted for the blend system, achieving defect‐free and almost defect‐free hollow fibers. Adding PIM results in a higher fractional free volume, 50% increments in gas permeance were observed for Ultem/PIM‐1 (95/5) and more than 100% increments for Ultem/PIM‐1 (85/15). Both O₂/N₂ and CO₂/CH₄ selectivities remained the same for Ultem/PIM‐1 (95/5) and above 80% of their respective intrinsic values for Ultem/PIM‐1 (85/15). The selective layer thickness ranges from 70 to 120 nm, indicating the successful formation of ultrathin dense layers. Moreover, minimum amounts of the expensive material were consumed, that is, 0.88, 1.7, and 2.3 wt % PIM‐1 for Ultem/PIM‐1 (95/5), (90/10), and (85/15), respectively. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3848–3858, 2014     

Surface‐Treated Activated Carbon for Removal of Aromatic Compounds from Water

Modifications of commercial activated carbons by chemical treatment with HNO₃ or HCl and HF and the adsorption behavior of simple aromatic compounds (aniline, pyridine, phenol, and benzene) on activated carbon and modified activated carbon were investigated. The results show that the textural properties change a little after these modifications, but the surface acidity (mainly oxygen‐containing groups) of activated carbon modified with HNO₃ increases greatly. The effect of ash of activated carbon on adsorption of the organic compounds mentioned above is insignificant. However, addition of surface acidity (mainly surface oxygen‐containing groups) decreases the adsorption capacity of compounds significantly. The adsorption uptake of compounds on activated carbon with oxidation of HNO₃ is low possibly due to dispersive interaction, water cluster blocking, or competition between water and compounds adsorbed on activated carbon's surface because of hydrophilic increase of the activated carbon surface. The solubility of aromatic compounds in water has an important effect on the adsorption capacity of activated carbon. q_m and K_L (Langmuir adsorption parameters) for the aromatic compounds vary similarly.     

Rolling of 3D Printed Dual‐Layer Beam into a Cylinder by Ethanol Absorption

4D printing is an extension to 3D printing whereby a printed shape programmatically undergoes shape transformation through external stimulations. There is an increasing interest in this field because of its potential applications. However, many demonstrated shape transformations work on simple and limited geometrical shapes. In this work, the formation of a cylinder from a printed flat dual‐layer beam when exposed to ethanol is demonstrated. The newly formed cylinder retains its shape even when the ethanol is removed through the use of a locking mechanism. The proposed method can be used for building medical stents or various sensors and actuators that require cylindrical shapes.     

Sulfur Removal from Low‐Sulfur Gasoline and Diesel Fuel by Metal‐Organic Frameworks

Several materials in the class of metal‐organic frameworks (MOF) were investigated to determine their sorption characteristics for sulfur compounds from fuels. The materials were tested using different model oils and common fuels such as low‐sulfur gasoline or diesel fuel at room temperature and ambient pressure. Thiophene and tetrahydrothiophene (THT) were chosen as model substances. Total‐sulfur concentrations in the model oils ranged from 30 mg/kg (S from thiophene) to 9 mg/kg (S from tetrahydrothiophene) as determined by elementary analysis. Initial sulfur contents of 8 mg/kg and 10 mg/kg were identified for low‐sulfur gasoline and for diesel fuel, respectively, by analysis of the common liquid fuels. Most of the MOF materials examined were not suitable for use as sulfur adsorbers. However, a high efficiency for sulfur removal from fuels and model oils was noticed for a special copper‐containing MOF (copper benzene‐1,3,5‐tricarboxylate, Cu‐BTC‐MOF). By use of this material, 78 wt % of the sulfur content was removed from thiophene containing model oils and an even higher decrease of up to 86 wt % was obtained for THT‐based model oils. Moreover, the sulfur content of low‐sulfur gasoline was reduced to 6.5 mg/kg, which represented a decrease of more than 22 %. The sulfur level in diesel fuel was reduced by an extent of 13 wt %. Time‐resolved measurements demonstrated that the sulfur‐sorption mainly occurs in the first 60 min after contact with the adsorbent, so that the total time span of the desulfurization process can be limited to 1 h. Therefore, this material seems to be highly suitable for sulfur reduction in commercial fuels in order to meet regulatory requirements and demands for automotive exhaust catalysis‐systems or exhaust gas sensors.     

Synthesis of Novel Submicrometer‐Scale Flat Carbon Fibers and Application in the Electrooxidation of Methanol

Novel submicrometer‐scale flat carbon fibers (SFCF) have been synthesized by catalytic chemical vapor deposition of acetylene over an Ni‐Al layered double hydroxide (NiAl‐LDH) compound, and the electrochemical activity of Pt supported on as‐synthesized SFCF for methanol oxidation has been investigated. The materials were characterized by power X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, and cyclic voltammetry tests. The results reveal that the active crystal facets of the NiAl₂O₄ spinel phase derived from NiAl‐LDH can deposit carbon atoms to grow SFCF, and that the co‐growing Ni nanoparticles are not catalytically active for the formation of SFCF. Furthermore, after support with Pt, the resultant Pt/SFCF electrocatalyst shows much higher activity for methanol oxidation than the Pt/C one in both acid and alkaline media, which is attributed to the combined beneficial effects of the microstructure of the SFCF support, improved electrical conductivity originating from the NiAl₂O₄ spinel catalyst embedded in SFCF, and improved dispersion of Pt particles through exposed Ni nanoparticles adhering intimately to the SFCF.     

Engineering design of outer‐selective tribore hollow fiber membranes for forward osmosis and oil‐water separation

Outer‐selective thin‐film composite (TFC) hollow fiber membranes offer advantages like less fiber blockage in the feed stream and high packing density for industrial applications. However, outer‐selective TFC hollow fiber membranes are rarely commercially available due to the lack of effective ways to remove residual reactants from fiber's outer surface during interfacial polymerization and form a defect‐free polyamide film. A new simplified method to fabricate outer‐selective TFC membranes on tribore hollow fiber substrates is reported. Mechanically robust tribore hollow fiber substrates containing three circular‐sector channels were first prepared by spinning a P84/ethylene glycol mixed dope solution with delayed demixing at the fiber lumen. The thin wall tribore hollow fibers have a large pure water permeability up to 300 L m^?2 h^?1 bar^?1. Outer‐selective TFC tribore hollow fiber membranes were then fabricated by interfacial polymerization with the aid of vacuum sucking to ensure the TFC layer well‐attached to the substrate. Under forward osmosis studies, the TFC tribore hollow fiber membrane exhibits a good water flux and a small flux difference between active‐to‐draw (i.e., the active layer facing the draw solution) and active‐to‐feed (i.e., the active layer facing the feed solution) modes due to the small internal concentration polarization. A hyperbranched polyglycerol was further grafted on top of the newly developed TFC tribore hollow fiber membranes for oily wastewater treatment. The membrane displays low fouling propensity and can fully recover its water flux after a simple 20‐min water wash at 0.5 bar from its lumen side, which makes the membrane preferentially suitable for oil‐water separation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4491–4501, 2015     

Fabrication and Characterization of Electrospun Dopants/PS Composite Fibers with Porous and Hollow‐Porous Structures

Three different dopants are used to fabricate electrospun dopants/polystyrene (dopants/PS) composite fibers from PS solution and PS sol. The relative humidity and the influence of the dopants on the morphologies, diameter, porous structures, and dopant distribution of electrospun PS fibers are investigated. Compared to those obtained from PS solution, electrospun dopants/PS composite fibers from PS sol with hollow‐porous and multichannel hollow‐porous structures present significant advantages due to the multi‐stage degree of interfacial structure and diversity of the internal environment. In comparison to coaxial electrospun PS fibers, the electrospun dopants/PS composite fibers from PS sol obtained in one step have an improved yield and a simplified technological process simultaneously, leading to significant competitiveness in fields such as catalysis, fluidics gas storage, and sensing.

     

Elaboration of Ultra‐High Molecular Weight Polyethylene/Carbon Nanotubes Electrospun Composite Fibers

Micron‐sized fibers of UHMWPE reinforced with CNT were fabricated by the electrospinning process. Conditions for a metastable mutual solution of UHMWPE and CNTs were found at elevated temperature. These solutions were used for electrospining using a device having controlled temperature and gaseous environment around the electrospun liquid jet. The fabricated micron‐sized fibers exhibited the reinforcing CNTs as self‐organized nano‐ropes embedded within them. A post‐spinning drawing process enhanced the mechanical properties of the composite fibers to the level of 6.6 GPa strength and elongation at break of 6%. The CNT nano‐ropes form spontaneously in the liquid jet during electrospinning, and provide the reinforcement framework which is amenable for post‐drawing of the fibers for subsequent utilization as composite nanofibers. The experimental results exhibit the highest strength value reported to date for electrospun fibers.

     

Surface Modification of Carbon Fibers by Free Radical Graft‐Polymerization of 2‐Hydroxyethyl Methacrylate for High Mechanical Strength Fiber–Matrix Composites

Free radical polymerization of vinylic monomers in the presence of carbon fibers results in the grafting of polymers onto the carbon fiber surface. Graft polymers cannot be removed by intense washing with good polymer solvents. The density and size of these structures are successfully controlled by reaction conditions. Grafting of the carbon fiber surface with hydroxyethyl methacrylate allows for introducing functional groups suitable for the reaction with an epoxy‐based resin. The resulting fiber‐reinforced composites show enhanced mechanical properties compared to samples prepared from carbon fibers equipped with a standard sizing for epoxy resins. Thus, tensile strength increases by 10%, while interlaminar shear strength improves by 20%.     

A Control‐oriented Dynamic Model Adapted to Variant Steam‐to‐carbon Ratios for an SOFC with Exhaust Fuel Recirculation

The steam‐to‐carbon ratio (S/C) is a typical disturbance parameter in the operation of solid oxide fuel cell (SOFC) power generation system. A planar SOFC with a pre‐reformer and exhaust fuel recirculation system is investigated in this work. A lumped, nonlinear dynamic model is developed for the SOFC with consideration both of the spatial effect and the variant S/Cs. The dynamic model is deduced based on a fitting function so‐called Exponential Association Function, which is employed to describe the spatial distribution of state variables in SOFC. Three parameters of the fitting function are identified to integrate the spatial effect and S/C effect in the model. The parameters of Exponential Association Function are determined by function fitting on three‐dimensional numerical data at the sample operation points. Carbon formation activity is analysed using the simulation results and thermodynamic data. Dynamic simulation is implemented with the help of software MATLAB/SIMULINK. The results show that the developed model has good performance in predicting the responses of the state variables and catching the changes of S/C.     

Semianalytical solution for power‐law polymer solution flow in a converging annular spinneret

A semianalytical solution for a power‐law fluid flowing through a conical annulus was derived to estimate the velocity profile in the axial direction, the shear rate and the elongation rate within a spinneret during the spinning of hollow fiber membranes. The angle coefficient was introduced as a new parameter to account for the effect of radial flow and to modify the governing equation, which initially neglected the effect of radial flow. The results estimated from this semianalytical solution agreed more closely with computational fluid dynamics simulation results than those obtained from the approximate analytical solution in our previous study. By accurately predicting the velocity profile in the axial direction and the shear and elongation rates in a conical annulus, the solution derived in this study is expected to provide a reliable criterion for spinneret design to achieve a specified membrane morphology with a desired performance. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3489–3499, 2015