Nanofibrous alumina structures fabricated using high-yield alternating current electrospinning

Nanofibrous alumina (Al₂O₃) structures were fabricated from the precursor aluminum nitrate/polyvinylpyrrolidone (PVP) nanofibers prepared using a free-surface alternating current (AC) electrospinning method. Precursor nanofibers were generated at rates up to 6.4 g/h and collected as 100–300 µm thick sheets suitable for direct conversion into the nanofibrous alumina structures. The effects of process conditions and annealing temperature on the nanofiber diameter, morphology, shrinking behavior and crystalline phase formation were investigated by Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, and X-ray diffraction (XRD). Textural properties of Al₂O₃ fibrous sheets composed of micro-/meso-porous nanocrystalline γ-alumina nanofibers with 260±90 nm diameters after the calcination at temperatures in the range from 700 °C to 1000 °C were determined from N₂ adsorption/desorption isotherms. Preliminary air permeability and apparent air flow resistance studies of single sheet and multilayer nanofibrous alumina membranes were performed and compared with other porous alumina membrane structures for the evaluation of their possible usage in gas filtration, separation, and other applications.     

Synthesis and characterization of electrospun aluminum doped Li1.6Mn1.6O4 spinel

Three dimensional porous Li_1.6Al_0.6MnO₄ (LAMO) nanofibers were successfully prepared for the first time, via a facile electrospinning homogenous solution of lithium acetate, manganese nitrate and aluminum nitrate in polyvinyl alcohol and polyvinylpyrolidone solution followed by calcination of the as-spun nanofibers at 500, 700 and 900 °C. The processing parameters were; voltage 25 kV, flow rate 0.7 ml/h, the distance between the needle and collector 10 cm and the inner diameter of the needle 0.499 mm. X-ray diffraction of the samples prepared by using electrospinning and sol–gel revealed that Li_1.6Al_0.6MnO₄ phase was formed at; 500 °C and 700 °C, respectively. Field Emission Scanning Electron Microscopy revealed that the electrospun nanofibers at 700 °C were fabricated with diameter 250 nm, and the single fiber composed of 30 nm LAMO grains. On the other hand, samples calcined at 700 °C, prepared by sol–gel, show coalescence of the fine grains of LAMO in the form of microspheres with an average diameter of 1 µm and each microsphere is composed of fine crystals of LAMO. The characteristics of the prepared spinel make them promising for use in lithium adsorption from polluted effluents.     

Carbon nanotubes and carbon nanofibers fabricated on tubular porous Al2O3 substrates

Carbon nanotubes and carbon nanofibers were grown at different temperatures on porous ceramic Al₂O₃ substrates with single channel geometry by means of a chemical vapor deposition technique using methane as carbon source and palladium as catalyst. Time-resolved in-situ Fourier transformed infrared spectroscopy was used for the investigation of methane decomposition for characterizing the catalyst’s performance. With increasing synthesis temperature, a structural transition from carbon nanofibers to carbon nanotubes was observed. At a synthesis temperature of 700 °C, solely carbon nanofibers were found, whereas at 800 °C a mixture of two types of bamboo-shaped carbon nanofibers were obtained, suggesting a structural transition. A synthesis temperature to 850 °C results in bamboo-shaped multi-walled carbon nanofibers and multi-walled carbon nanotubes. The carbon products and the observed structural transition were characterized by means of field emission scanning electron microscopy, high-resolution transmission electron microscopy, thermal gravimetric analysis, and Raman spectroscopy.     

Preparation and characterisation of mixed matrix Al2O3- and TiO2-based ceramic membranes prepared using polymeric synthesis route

Al₂O₃- and TiO₂-based ceramic membranes prepared using polymeric synthesis route were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and gas permeability tests. The influence of the final calcination temperature and the systematic investigation of the properties of the membranes are provided. The calcination temperature affected morphological, structural and chemical properties, as well as the gas permeability of the ceramic membranes. XRD analysis revealed rhombohedral and tetragonal structures of Al₂O₃ and TiO₂-based ceramic, respectively, prepared at calcination temperatures of 1100 and 1200 °C. The TiO₂-based ceramic matrix calcined at temperatures of 1100 and 1200 °C exhibited a well-defined crystalline microstructure with the grains increasing in size as a function of temperature. FTIR analysis revealed that phosphorus additives in orthoclase clay tend to form phosphonate groups during the calcination process. The decomposition of organic source was not fulfilled as tested at calcination temperatures of 1000, 1100 and 1200 °C.     

Microstructure and mechanical properties of ceramics obtained from chemically co-precipitated Al2O3-GdAlO3 nano-powders with eutectic composition

An efficient and flexible chemical co-precipitation method has been used to synthesize nanoscale Al₂O₃-GdAlO₃ powders with eutectic composition. The as-synthesized powders exhibit a highly dispersive and homogeneous distribution with an average particle size of 50 nm. The phase transition in the resulting powders strongly depends upon the calcination temperature. GdAlO₃ undergoes complete crystallization after calcination at 1050 °C, however, the diffraction peaks of α-Al₂O₃ are found at a relatively high calcination temperature of at least 1300 °C. The fully-densified Al₂O₃-GdAlO₃ ceramic with eutectic composition obtained by hot pressing the nanoscale powders at 1500 °C exhibits a room temperature flexural strength of 556 MPa, a Vickers hardness of 17.3 GPa and a fracture toughness of 7.5 MPa m^1/2. The high temperature flexural strength of the as-sintered Al₂O₃-GdAlO₃ ceramic is measured to be 515 MPa after bending tests at 1000 °C.     

Encapsulation of CoS nanoparticles in PAN electrospun nanofibers: Effective and reusable catalyst for ammonia borane hydrolysis and dyes photodegradation

In this study, the effective cobalt sulfide NPs were successfully encapsulated inside polyacrylonitrile (PAN) electrospun nanofibers. Typically, the solid NPs were in-situ synthesized by addition of ammonium sulfide drops to PAN/cobalt acetate solution. Electrospinning of the obtained colloid led to obtain good morphology polymeric nanofibers containing CoS NPs. Complete sheathing of the active nanoparticles did not affect their catalytic activity as the prepared mats revealed high performance toward hydrogen release from ammonia borane hydrolysis. Moreover, as a photocatalyst, a mat containing 2 wt% CoS could catalyze oxidation of methylene blue dye to be completely eliminated within 15 min. Furthermore, the introduced nanofibers photocatalytically enhanced complete degradation of the methyl red dye within relatively short time. The experimental results indicated that the optimum CoS content is 2 wt%, more increase in the concentration of the solid NPs leads to particles aggregation and consequently decrease the surface area. Beside the good activity obtained, the introduced immobilization strategy is considered an acceptable methodology to overcome the secondary pollution of the nanostructural photocatalysts because of the easy separation feasibility.     

Synthesis of mullite nanofibres by electrospinning of solutions containing different proportions of polyvinyl butyral

In this paper, the synthesis of continuous mullite (3Al₂O₃·2SiO₂) nanofibres by combination of the sol–gel and electrospinning technique is reported. To find out the optimum viscosity of the electrospinning solution for obtaining the high quality mullite nanofibers, solutions containing different amounts of polyvinyl butyral (PVB, 0–8 wt%) and the precursor sol were prepared for the electrospinning process. The precursor sol was made by using proper amounts of aluminium isopropoxide (AIP), hydrated aluminium nitrate (AN) and tetraethylorthosilicate (TEOS). Crystal phase, microstructure and thermal decomposition behaviour of the electrospun mullite nanofibres were investigated by conventional methods of analysis. The optimal amount of PVB in the electrospinning polymeric solutions was found to be between 4 and 6 wt% and the mullite nanofibres obtained as such were pure, smooth and uniform with diameter sizes of 85–130 nm after calcination at 1200 °C.     

TEM investigations of wear mechanism of Al2O3 and Si3N4 compacts with GLPs additions

Extended lifetime of ceramic cutting plates is ever more desired. One way of approaching it entails sintering precursor materials with graphene-like nanoplatelets (GLPs) acting as solid lubricants. Therefore, Al₂O₃ and Si₃N₄ ceramic powders with addition of GLPs of grade 3 (fine) or grade 4 (coarse) were Spark Plasma Sintered. It is found that the 0.15 wt% GLPs addition of both grades allows to keep hardness practically at the same level as GLPs-free compacts (~16 GPa). Only larger GLPs additions (2 wt%) caused its evident decrease (down to 14−15 GPa). The ball-on-disc test revealed that only Al₂O₃+0.15 wt% GLPs(3) shows a 50% reduction in wear rate. The post mechanical test examination by SEM confirmed that Al₂O₃ compacts with small GLPs showed smooth wear track, as opposed to those having a Si₃N₄ matrix with large meandering cavities. TEM observations revealed that the wear damage caused by the ball was restricted to ~2 µm deep sub-surface areas, while, carbon is found to transfer from the GLPs agglomerates into tribo-film. The present experiments showed, that ceramic sinters with small addition of GLPs platelets could exhibit lower wear than GLPs-free ones and therefore show a potential for application as cutting plates.     

Preparation of porous Al2TiO5-Mullite ceramic by starch consolidation casting and its corrosion resistance characterization

Stabilized Al₂TiO₅ (AT)-mullite (M) porous ceramics were fabricated by starch consolidation casting using corn starch as curing agent and their microstructure, mechanical properties, pore size distribution and corrosion resistance were examined. Results showed that AT-M porous ceramic with the flexural strength of 11.5 MPa, apparent porosity of about 54.7% and pore size distribution in the range of 1–15 µm could be obtained with 10 wt% corn starch addition. Corrosion resistance results showed mass losses in hot H₂SO₄ solution and NaOH solution for 10 h to decreased from 1.03% to 0.36% and 4.39–2% when the calcination temperature increased from 1400 °C to 1450 °C, which proved these AT-M porous ceramics to possess an excellent corrosion resistance in acidic condition when calcined at 1450 °C.     

Synthesis and electrochemical properties of nickel oxide/carbon nanofiber composites

The electrospinning of polyacrylonitrile (PAN) with a polyaniline and graphene sol–gel mixture produced uniform, smooth fibers with an average diameter of 0.3 μm. These electrospun fibers were stabilized for 2 h at 200 °C and then carbonized at 800 °C for 5 h. Composites were prepared by depositing Ni(OH)₂ on the carbon nanofibers (CNFs) and calcining them at different temperatures. The composites were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The effect of the calcination temperatures on the electrochemical properties was studied using cyclic voltammetry and electrochemical impedance spectroscopy. The specific capacitance (SC) was found to be highest (738 F g⁻¹) at a calcination temperature of 400 °C. The charge transfer resistance (R_p) decreased as the calcination temperature was increased. However, the electrical double layer capacitance (EDLC) increased with an increase in the calcination temperature. The EDLC increased from 0.144 F g⁻¹ at a calcination temperature of 100 °C to 485 F g⁻¹ at a calcination temperature of 500 °C.     

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.     

Chemically reduced electrospun polyacrilonitrile–carbon nanotube nanofibers hydrogels as electrode material for bioelectrochemical applications

Nanosized fibers containing carbon nanotube (CNT) were produced by electrospinning from a DMF solution containing CNT and polyacrilonitrile (PAN). The resulting fibers form a felt like fiber tissue that was used as an electrode. The nitrile groups of these fibers were chemically reduced to amines groups that were protonated at pH 5. The resulting positively charged nanofibers swell in aqueous solutions increasing the exposed surface of CNT and facilitating the diffusion of small molecules and ions to the conducting CNTs. The electrochemical behavior and the morphology of as prepared and reduced nanofibers were characterized by cyclic voltammetry and scanning electron microscopy (SEM) respectively. In addition, the influence of the reduction process determining the amount of amino groups, was investigated. The biofunctionalization of the nanofiber tissue electrodes was carried out by activation of the amino groups via incubation in glutaraldehyde vapor. Then, an enzyme model, polyphenol oxidase (PPO), was chemically grafted onto the nanofiber surface. The efficient covalent binding of PPO onto PAN–NH₂–CNT electrodes (1 × 1 cm size), was exemplified through the electro-enzymatic detection of catechol. The resulting sensitivity and maximum current values at saturated catechol concentration are 118 mA mol⁻¹ L and 10.66 μA respectively, with a detection limit of 0.9 μmol L⁻¹.     

Ag-doped M2O3 nanoflakes as effective catalyst for lignin liquefaction in supercritical methanol medium

Solid biomasses can be exploited as an effective source of energy if they can be converted into liquid and gaseous fuels. In this study, highly crystalline Ag–Mn₂O₃ nanoflakes are introduced as effective catalyst for cracking of lignin into alcohols in supercritical methanol medium. The introduced catalyst was synthesized by a sol–gel process. Typically, mixing of manganese acetate, silver nitrate and citric acid solutions led to form a continuous gel when the pH was kept at 7. Drying, grinding and calcination (at 600 °C) of the obtained gel resulted in producing Ag-Mn₂O₃ nanoflakes. The utilized XRD, SEM, FE-SEM and TEM analyses affirmed the concluded structure and morphology. The introduced inorganic nanostructure could successfully catalyze degradation of lignin into liquid alcohols when the solid biomass was catalytically treated in an autoclave reactor in presence of methanol at 180 °C. The experimental results indicated that maximum lignin dissolution of 42.5 wt% can be obtained when the catalyst content is kept at 17 wt% and treatment time of 2 h. Overall, the present study opens new avenue for the stable ceramic catalysts for solid biowastes conversion into valuable products.     

High-power properties of piezoelectric hard materials sintered at low temperature for multilayer ceramic actuators

0.05Pb(Mn_1/3Sb_2/3)O₃–0.05Pb(Al_1/2Nb_1/2)O₃–0.9Pb(Zr_0.48Ti_0.52)O₃ (PMS–PAN–PZT) high power piezoelectric system with both La₂O₃ as a hardener and CuO as a low sintering agent had been synthesized at 900 °C for 2 h. When La₂O₃ doping of the main composition went over 0.5 wt%, the mixed tetragonal and rhombohedral perovskite structure changed to pure rhombohedral perovskite structure. In case of the CuO, 1.0 and 1.5 wt% CuO content significantly improved the sinterability of the PMS–PAN–PZT system processed at 900 °C for 2 h. When La₂O₃ and CuO co-doped in PMS–PAN–PZT ceramics, piezoelectric constants (d₃₃), quality factor (Q_m), electromechanical coupling factor (k_p) and dielectric constant (${\epsilon }_3^{\text{T}}/{\epsilon }_0$) of the piezoelectric ceramics sintered at 900 °C for 2 h were optimized, such as 336 pC/N, 841, 60%, and 1358, respectively. New developed piezoelectric materials are promising for high power multilayer ceramic actuators.     

Utilization of recycled paper processing residues and clay of different sources for the production of porous anorthite ceramics

Production of porous anorthite ceramics from mixtures of paper processing residues and three different clays are investigated. Suitability of three different clays such as enriched clay, commercial clay and fireclay for manufacturing of anorthite based lightweight refractory bricks was studied. Porous character to the ceramic was provided by addition of paper processing residues (PPR). Samples with 30–40 wt% PPR fired at 1200–1400 °C contained anorthite (CaO·Al₂O₃·2SiO₂) as major phase and some minor secondary phases such as mullite (3Al₂O₃·2SiO₂) or gehlenite (2CaO·Al₂O₃·SiO₂), depending on the calcite to clay ratio. Anorthite formation for all clay types was quite successful in samples with 30–40 wt% of paper residues fired at 1300 °C. A higher firing temperature of 1400 °C was needed for the fireclay added samples to produce a well sintered product with large pores. Gehlenite phase occurred mostly at lower temperatures and in samples containing higher amount of calcium (50 wt% PPR). Compressive strength of compacted and fired pellets consisting of mainly anorthite ranged from 8 to 43 MPa.     

Carbon nanofiber-supported palladium nanoparticles as potential recyclable catalysts for the Heck reaction

5 wt% Pd catalysts supported on platelet carbon nanofibers has been prepared by incipient wetness impregnation. Both the calcination and the reduction temperature have a significant effect on the dispersion of palladium and it was found that about 3 nm sized Pd nanoparticles can be obtained at a calcination and reduction temperature of 250 °C and 150 °C, respectively. Pd catalysts have been applied to catalyze Heck reactions of various activated and non-activated aryl substrates. The activity increased exponentially with a decrease in Pd particle size. The high surface area, mesoporous structure of carbon nanofiber and highly dispersed palladium species on carbon nanofibers makes up one of the most active and reusable heterogeneous catalysts for Heck coupling reactions. Pd nanoparticles supported on platelet CNFs appear to be an excellent catalyst due to high activity, low sensitivity towards oxygen, almost no or low issues with leaching and high stability in multi-cycles.     

Fabrication of electronspun porous CeO2 nanofibers with large surface area for pollutants removal

The porous CeO₂ nanofibers with diameter of 100–140 nm were successfully synthesized by single-capillary electrospinning of a Ce(NO₃)₃·6H₂O/PVP precursor solution, followed by calcination. The preparation parameters, including solution parameters and process parameters, affecting the spinnability and the morphology of nanofibers were investigated and discussed systematically. And the effects of different calcination temperatures on the microstructure CeO₂ nanofibers were also studied. A plausible mechanism was proposed to explain the formation process of the CeO₂ nanofibers. The N₂ adsorption-desorption isotherm analysis showed that the specific surface area and average pore size of the nanofibers were 195.75 g/m² and 2.4 nm, respectively. Moreover, as absorbent, the porous CeO₂ nanofibers adsorbed the MO effectively. The adsorption experiment indicated that the adsorption process can be divided into two stages, including quick adsorption and gradual adsorption. And the adsorption capacities were not only determined by the specific surface area, but closely related to the pore size. Finally, the adsorption data were modeled by the pseudo-first-order and pseudo-second-order kinetics equations. The results showed that the pseudo-second order kinetics could best describe the adsorption of MO onto the porous CeO₂ nanofibers.     

Comparison of the homemade and commercial graphene in heightening mechanical properties of Al2O3 ceramic

Graphene has been successfully fabricated by a novel method, using graphite powder and NMP (N-Methyl Pyrrolidone) as the raw materials based on the principles of liquidoid exfoliation and mechanical milling. SEM, TEM and Raman spectrum were utilized to characterize the morphology of the homemade graphene, illustrating the few defects and rare layers were endowed in this study. Afterwards, the homemade and commercial graphene were doped into Al₂O₃ powder with the mass ratio of 0%, 1%, 2%, and 3% to reinforce the mechanical properties of the matrix. The composites were processed at 1600 °C, pressure of 30 MPa and soaking time of 1 h by vacuum hot pressing. The test results illustrated the bending strength and fracture toughness tended to be intensive at first and subdued afterwards, achieving the optimal performance of 625.4±18.2 MPa and 6.07±0.22 MPa m^1/2 at 2 wt% prepared graphene additive, and the commercial grapheme owned the best heighten effect in 3 wt% graphene/Al₂O₃ composites. Compared to the blank Al₂O₃ sintered samples, the graphene/Al₂O₃ specimens (both prepared and commercial additive) behaved evident increase in mechanical properties, even upon 30% enhanced in fracture toughness and bending strength generally by the prepared grapheme. Moreover, the prepared graphene had better improvement effect than commercial graphene in enhancing mechanical properties of Al₂O₃ ceramic.     

Selective epoxidation of styrene with air catalyzed by CoOx and CoOx/SiO2 without any reductant

Cobalt oxide (CoOx) prepared by a direct calcination of cobalt nitrate was considerably active for the epoxidation of styrene with air in DMF under mild conditions. A substrate conversion of 75.8 mol% with an epoxide selectivity of 82.1% was achieved at 353 K over 10 mg of cobalt oxide catalyst. Once CoOx was loaded on the support SiO₂ through a simple procedure consisting of wet impregnation, drying and calcination, the as-prepared catalyst presented higher catalytic activity and epoxide selectivity than cobalt oxide itself. Over the optimized catalyst CoOx/SiO₂ (1.0 wt% Co), 85.7 mol% of styrene was effectively converted at 363 K within 4 h, with a high epoxide selectivity up to 86.0%. The results showed that many factors influenced the performance of the catalyst, such as the Co loading, the support, the temperature and the atmosphere, etc. The leaching of cobalt from the catalyst CoOx/SiO₂ was negligible, indicating the applicability of the catalyst CoOx/SiO₂ as a true heterogeneous catalyst. The control test and UV–vis spectra revealed a synergic interaction among solvent, oxygen and substrate over CoOx/SiO₂.     

Preparation of Pt-loaded TiO2 nanofibers by electrospinning and their application for WGS reactions

Preparation of Pt-loaded TiO₂ nanofibers and their catalytic performance for water gas shift (WGS) reactions have been explained in this work. The Pt-loaded TiO₂ nanofibers were obtained by electrospinning poly-ethylene oxide (PEO) aqueous solutions containing Ti(OH)_n slurry and Pt nanoparticles at room temperature, followed by calcination at 773 K for 4 h. The calcined nanofibers were rougher than the nanofibers of PEO/Ti(OH)_n/Pt due to the PEO degradation and oxidation of Ti(OH)_n to TiO₂. Diameters of the Pt-loaded TiO₂ nanofibers ranged between 200 and 900 nm. Catalytic activity of the Pt-loaded TiO₂ nanofibers for water gas shift (WGS) reactions was evaluated and it was observed that their activity was 5–7 times higher than that of a bulk catalyst. Such improvement is attributed to the larger surface area of the nanofiber catalyst compared to that of the bulk catalyst. To the best of our knowledge, this is the first demonstration of a synthesis of Pt-loaded TiO₂ nanofibers from a Ti(OH)_n nanoparticle slurry using electrospinning and its application to WGS reactions.