Growth of carbon nanofiber coatings on nickel thin films on fused silica by catalytic thermal chemical vapor deposition: On the use of titanium, titanium-tungsten and tantalum as adhesion layers

Coatings of carbon nanofiber (CNF) layers were synthesized on fused silica substrates using a catalytic thermal chemical vapor deposition process (C-TCVD). The effects of various adhesion layers-titanium, titanium-tungsten and tantalum-under the nickel thin film on the attachment of carbon nanofibers and their morphological properties are presented. The diameter and the thicknesses of the CNF-coatings were analyzed by scanning electron microscopy, whereas the microstructure and crystallinity of the synthesized carbon nanofibers were investigated by transmission electron microscopy and Raman spectroscopy, respectively. Specific surface areas of CNF-coatings were determined with nitrogen adsorption-desorption isotherm measurements.Using C-TCVD of ethylene at 700 °C (1 h), well-attached, entangled, quasi-crystalline platelet carbon nanofibers were synthesized with tip-type growth mode on 25 nm thick nickel films with an adhesion layer of 10 nm Ta or Ti-W. The thickness of CNF-coating was ~ 3.5 μm, and the diameter of the fibers depended on the composition of the metallic thin film stack: 20-50 nm for Ni/Ta and 80-125 nm for Ni/Ti-W. The ultimate goal is the integration of these CNF-coatings as catalyst support in microfluidic devices, for which it is important to control CNF-coating characteristics such as fiber diameter, layer thickness, specific surface area and adhesion to the surface.     

Improvement of water/resin wettability of graphite using carbon black nano particles coating via ink media

Carbon coated graphite with high resin and water wettability characteristics could expand the refractory and carbon–carbon composites application in different fields. Improvement of water and resin wettability of graphite using carbon black coating via ink media is reported. Present method is based on preparing colloidal disperion of carbon black in ink followed by adding proper amount of graphite to the mixture which was dried and heat treated at 250 °C afterwards. The results showed that by controlling the amount of carbon black in ink and optimizing the process, a uniform coating with a thickness of 50 nm could be developed on the graphite surface.The wettability was evaluated by measuring contact angle and the microstructure of samples was characterized by optic microscope (OM) and scanning electron microscope (SEM). Also Raman spectroscopy was employed to support the results. The microstructure of coating was found to be uniform composed of carbon black nanoparticles. It was also demonstrated that the coating that could enhance the phenolic resin wettability was well. We also showed the coating could be applied on other ceramic particles such as MgO.     

Properties of composite films of titania nanofibers and Safranin O dye

Titania (TiO₂) nanofibers and composite thin films of titania nanofibers and Safranin O dye (SAF) were studied. TiO₂ nanofibers were prepared by electrospinning technique from titanium tetra-isopropoxide precursor solution in ethanol. Surface topology of the nanofibers was observed using scanning electron microscopy (SEM), their crystal structure was studied by X-ray diffraction (XRD) and the chemical composition by X-ray photoelectron spectroscopy (XPS). Properties of the TiO₂ nanofibers were studied in dependence on the values of relative air humidity in the range from 15% to 55%. It was necessary to maintain the relative humidity lower than 30% during electrospinning in order to obtain high quality nanofiber films. The average minimum diameter of the as-prepared TiO₂ nanofibers was found to be around 100 nm. Nanofiber diameter diminishes to about 50 nm after annealing at 420 °C for 1 h. The as-prepared titania nanofiber films were completely amorphous while anatase crystal phase was detected in the films after annealing. In order to prepare the composite films, solution of SAF dye with poly(vinylpyrrolidone) in ethanol/water was dropped off on the prepared titania nanofibers surface. Opto-electrical properties of SAF dye and the resulting nanocomposite films were studied by UV–Vis spectroscopy and current–voltage characteristics. Safranin O is characterized by two strong absorption peaks; one at 274 nm and a wide band with splitting between 420 nm and 600 nm. The optical energy band gap of titania nanofibers was estimated from the UV–Vis measurements to be 3.4 eV. The charge transport in the composite films is influenced by the space charge limited currents due to the very high resistance of the materials.     

Preparation of platinum-iridium nanoparticles on titania nanotubes by MOCVD and their catalytic evaluation

Pt based catalysts are commonly used in several industrial processes involving hydrogenation and dehydrogenation reactions. New deposition methods as well as support materials are being investigated to generate new catalysts with superior catalytic activity. In this work, platinum-iridium (Pt-Ir) nanoparticles of about 5 nm in size were supported on titania (TiO₂) nanotubes by metal organic chemical vapor deposition (MOCVD). The TiO₂ nanotubes were prepared by an alkali hydrothermal method using sodium hydroxide solution at 100 °C, during 64.8 ks. Pt-Ir nanoparticles were obtained by controlling the MOCVD conditions at 400 °C and 66.6 kPa.Textural properties and particle size were investigated by nitrogen physisorption (BET method), X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy. Catalytic activity was measured in cyclohexene disproportion as the test molecule for hydrogenation/dehydrogenation reactions. The TiO₂ nanotubes exhibit a considerable high surface area of about 425,000 m²/kg, however, after calcination at 400 °C their nanotubular morphology was partially transformed. In spite of this change, the 5 nm Pt-Ir nanoparticles supported on TiO₂ nanotubes were more active in the cyclohexene disproportion reaction than conventional Pt-Ir/alumina catalysts in the whole range of temperatures investigated (50–250 °C). Hydrogenation reactions (high selectivity to cyclohexane) predominate at temperatures below 150 °C.     

Electrospinning of carbon nanofiber supported Fe/Co/Ni ternary alloy nanoparticles

Polyacrylonitrile (PAN)-based carbon nanofiber supported Fe/Co/Ni ternary alloy nanoparticles were prepared by using the electrospinning technique for potential fuel cell applications. The solution was prepared by adding pre-solved catalytic precursor into PAN/DMF solution. The effect of PAN and catalyst precursor concentration on solution properties (viscosity and conductivity) and heat stabilization temperature has been investigated. Electrospun nanofibers were characterized by field emission scanning electron microscope, transmission electron microscope, energy dispersive spectrometer and X-ray diffractometer. It has been found that ternary nanoparticle size is in the range of 5–115 nm (average: 20 nm) and is a crystal alloy of Fe, Co and Ni. Also, TEM results demonstrate that in some regions metal nanoparticles tend to agglomerate into larger particles mainly due to the non-uniform distribution of nanoparticles in as-spun condition. PAN-derived carbon nanofiber mean diameter was measured as 200 nm by varying from 40 nm to 420 nm.     

Synthesis and hydrogen storage of carbon nanofibers

Carbon nanofibers were synthesized by catalytic decomposition of methane using Ni–MgO catalyst and hydrogen adsorption experiments were carried out by a Sievert’s apparatus under 120 bar at 25 °C. Hydrogen adsorption capacity was elevated up to 1.4 wt.% after heat treatment at 1200 °C in N₂ atmosphere. CO and CO₂ were detected by gas chromatography (GC) during heat treatment which promoted active surface suitable for hydrogen adsorption of carbon nanofibers. High resolution transmission electron microscopy (HRTEM) and XRD analysis revealed that the structure of carbon nanofibers was durable after hydrogen uptake even at high pressures.     

Preparation of helical carbon and graphite films using morphology-retaining carbonization

Helical carbon and graphite films were prepared from iodine-doped helical polyacetylene (H-PA) film using currently developing morphology-retaining carbonization. It was found from scanning electron microscopy (SEM) observations that the hierarchical helical morphology of the H-PA film remains unchanged even after the carbonization at 800 °C. Besides, the weight loss of the film due to the carbonization was very small, which was only a few percent to the weight of the film before doping. Furthermore, the graphite film prepared by the subsequent heating at 2600 °C still retained the same morphology as those in the original H-PA film and in the helical carbon film prepared at 800 °C. X-ray diffraction (XRD) and Raman scattering measurements were then pursued. The results showed that graphitic crystallization proceeds in the carbon film through the heat treatment at 2600 °C. Transmission electron microscopy (TEM) image of a single helical graphitic fibril was also observed by ultrasonicating the graphite film in ethanol. Carbonization of the H-PA films by way of iodine doping was found to afford helical carbon and graphite films, where spiral morphologies and even helical fibril structures were completely preserved.     

Microstructure transformation of carbon nanofibers during graphitization

The microstructures of vapor-grown carbon nanofibers（CNFs） before and after graphitization process were analyzed by high resolution transmission electron microscopy（HRTEM）, Raman spectroscopy, X-ray diffractometry（XRD）, near-edge-X-ray absorption fine structure spectroscopy（NEXAFS） and thermogravimetric analysis（TGA）. The results indicate that although non-graphitized CNFs have the characteristics of higher disorder, a transformation is found in the inner layer of tube wall where graphite sheets become stiff, which demonstrates the characteristics of higher graphitization of graphitized CNFs. The defects in outer tube wall disappear because the amorphous carbon changes to perfect crystalline carbon after annealing treatment at about 2 800 ℃. TGA analysis in air indicates that graphitized CNFs have excellent oxidation resistance up to 857 ℃. And the graphitization mechanism including four stages was also proposed.     

Synthesis of VN nanopowders by thermal nitridation of the precursor and their characterization

Vanadium nitride (VN) nanopowders can be synthesized by thermal nitridation of the precursor of ammonium vanadate (NH₄VO₃) and nanometer carbon black. The products were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the single phase VN powders can be synthesized at 1100 °C for 1 h, and the powders show good dispersion and are mainly composed of uniformly sized spherical particles with a mean diameter of 50 nm. The surface of the specimen mainly consists of V, N, O and C four species elements, the peak core at 397.24 eV corresponds to N 1s of VN. The O 1s peaks with the binding energies of 530.40 eV and 532.15 eV are ascribed to vanadium pentoxide (V⁵⁺) and H₂O (OH⁻), and the contents are very little. The C 1s profile is a single symmetric peak, which mainly comes from the polluted carbon used for the correction of the XPS measurement.     

Structural properties of carbon prepared from aligned polyacetylene thin films

Aligned polyacetylene (PA) thin films consisting of fibrils of about 100 nm in diameter were carbonized at 1000 °C in a vacuum or in an argon gas. Structures and morphologies of the carbons prepared from the aligned PA thin films were investigated using Raman spectroscopy, X-ray measurements, and scanning and transmission electron microscopes. The carbonization gave rise to a char of amount of 20% in weight of the PA film. The char was found to contain nanorods of about 10 nm in width. Morphology of the carbon nanorod reflected that of the aligned PA thin film. Subsequently, the char was graphitized by further heating at 2600 °C.     

Raman study of polyaniline nanofibers prepared by interfacial polymerization

Polyaniline nanofibers were synthesized by interfacial polymerization of aniline. Polyaniline so formed was studied using transmission electron microscopy, scanning electron microscopy, UV–vis and Raman spectroscopy. TEM of polymer dispersion shows the presence of fibers having diameter around 30–80 nm. Strikingly different Raman spectra were observed from the polyaniline film, which were related to two dissimilar areas on the film. SEM of polyaniline films shows fibrous as well as flake like structures scattered in fiber matrix. Raman spectra of the films heat treated from 25 °C to 300 °C were taken to study the structural variations induced by the change of temperature at these two regions. Many applications of polymer films are dependent on the homogeneity of the systems. In this work we intend to employ Raman Spectroscopy as an indispensable tool for looking into the non-uniformities of the polyaniline films.     

Bimetallic nanoalloys: Preparation, characterization and their catalytic activity

Bimetallic nanoalloys (BMNAs) of 3d-series (Ni–Cu, Ni–Co and Ni–Zn) were prepared by hydrazine reduction of respective metal chloride in ethylene glycol at 60 °C. These were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) and particle size was found to be in the order of 34, 43 and 30 nm, respectively. The thermolysis of ammonium perchlorate (AP) and AP-HTPB composite solid propellants was found to be catalyzed with BMNAs and burning rate was found to be enhanced considerably. TG and ignition delay studies demonstrated that higher temperature decomposition (HTD) of AP is enhanced enormously by these additives and Ni–Co nanoalloy is the best catalyst.     

Nanocrystalline spherical iron–nickel (Fe–Ni) alloy particles prepared by ultrasonic spray pyrolysis and hydrogen reduction (USP-HR)

FeCl₂ and NiCl₂ were used for synthesis of nanocrystalline spherical Fe–Ni alloy particles by ultrasonic spray pyrolysis and hydrogen reduction (USP-HR). Spherical ultrafine Fe–Ni particles were obtained by USP of aqueous solutions of iron–nickel chloride followed by thermal decomposition of generated aerosols in hydrogen atmosphere. Particle sizes of the produced Fe–Ni particles can be controlled by the change of the concentration of an initial solution. The effect of the precursor solution in the range of 0.05, 0.1, 0.2 and 0.4 M on the morphology and crystallite size of the Fe–Ni alloy particles are investigated under the conditions of 1.5 h running time, 900 °C reduction temperature, and 1.0 L/min H₂ volumetric flow rate. X-ray diffraction (XRD) studies and Scherrer crystallite size calculations show that the crystalline size was nearly 28 nm. Energy dispersive spectroscopy (EDS) was performed to determine the chemical composition of the particles. Transmission electron microscope (TEM) was used to confirm the crystalline size, that was determined using XRD results. Scanning electron microscopy (SEM) observations reveal that the precursor solution strongly influences the particle size of the synthesized Fe–Ni alloy particles. Spherical nanocrystalline Fe–Ni alloy particles in the range of 80 and 878 nm were obtained at 900 °C.     

An investigation on the stabilization of special polyacrylonitrile nanofibers as carbon or activated carbon nanofiber precursor

This paper reports the effect of the conditions of stabilization process on the properties of special polyacrylonitrile nanofibers (SAF) with an average diameter of 467 nm. Stabilization constitutes an important pretreatment for the production of either carbon fibers or activated carbon fibers. It was found that the higher the stabilization temperature, the lower the initial induction time and the total reaction time. Extent of reaction increases with both treatment time and temperature of stabilization process. Crystallinity index and crystal size of stabilized nanofibers decreases as a result of stabilization. Special polyacrylonitrile nanofibers containing itaconic acid shows a higher capability for stabilization process. Potassium permanganate as a catalyst leaves a positive effect on the extent of reaction of stabilization. The diameter of nanofibers decreases by about 20% as a result of stabilization at 250 °C. Thermally stabilized nanofiber shows a wider exothermic peak with a lower height.     

Low-temperature synthesis and characterization of ZnO quantum dots

ZnO quantum dots (QDs) were fabricated at low temperature of 200 °C through thermal decomposition method with slight introduction of sodium dodecyl sulfate (SDS). The morphology, structure and optical properties were investigated by the methods of X-ray diffraction (XRD), transmission electron microscope (TEM), photoluminescence (PL) and Raman spectrum, respectively. The XRD results showed the as-synthesized ZnO QDs had hexagonal wurtzite structure and the average grain size estimated from Scherrer formula was 7.5 nm which had a good agreement with TEM result. And it is evident that the introduction of SDS can actually decrease the grain size to form ZnO QDs. The Raman results also indicated that the ZnO QDs keep the overall crystal structure of the bulk ZnO. Both spatial confinement within the dot boundaries and phonon localization by defects were the mainly reason for the only few cm⁻¹ redshift of the Raman scatter peaks. The room-temperature photoluminescence reveals that the as-prepared ZnO QDs exhibit an ultraviolet emission at 380 nm and a broad deep level emission band in the range of 420–700 nm in wavelength, which testified the Raman and XRD results that the as-synthesized ZnO QDs had defects. Moreover, the growth mechanism of ZnO QDs was also discussed in the article.     

Enhanced photocatalytic properties of ultra-long nanofiber synthesized from pure titanium powders

Using Ti powder as reagent,ultra-long TiO2 nanofibers were prepared via hydrothermal method in NaOH solution.The samples were char-acterized respectively by means of field emission scanning electron microscopy (FESEM),transmission electron microscopy (TEM) with selected area electron diffraction (SAED),and X-ray diffraction (XRD).The diameter and the length of the ultra-long TiO2 nanofiber were ～100 nm and >200μm,respectively.The ultra-long TiO2 nanofibers were anatase after heat treatment at 450 ?C for 1 h.Moreover,the optical properties of the products were investigated by UV-visible light absorption spectrum.Furthermore,methyl orange was used as a target molecule to estimate the photocatalytic activity of the specimens.Under the same testing conditions,the photocatalytic activity of the ultra-long TiO2 nanofibers was higher than that of P25.Direct electrical pathway and improved light-harvesting efficiency were crucial for the superior photocatalytic activity of the ultra-long TiO2 nanofibers.     

Effects of catalyst precursors on carbon nanowires by using ethanol catalytic combustion technique

Iron nitrate, nickel nitrate and cobalt nitrate were used as catalyst precursors to study their effects on carbon nanowires synthesized by ethanol catalytic combustion （ECC） process. The as-grown carbon nanowires were characterized by means of scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. The results show that relatively uniform nanowires will be formed when the catalyst precursor is iron nitrate; while helical structure or disordered structure will be formed when the catalyst precursor is nickel nitrate or cobalt nitrate. precursor     

Phase transition, structure and luminescence of Eu:YAG nanophosphors by co-precipitation method

The methods to synthesize Eu:YAG phosphor by co-precipitation method and solid-state synthesis were compared. The dynamic aspects of the phase transition of Eu:YAG precursor synthesized by co-precipitation method were studied by using X-ray diffraction, infrared and Raman spectroscopy. The results showed that the precursor transformed to pure-YAG phase at the sintering temperature of 900 °C without intermediate phases present. Transmission electron microscope for the precursor powders sintered at 900–1200 °C showed that the powders were well-dispersed and had average size about 50–100 nm.The fluorescence spectra showed that the Eu:YAG phosphors had strong photoluminescence. The luminescence properties of the sintered powders depend on the sintering temperature were also analyzed.     

Hexagonal diamond formation on steel substrates by negative bias microwave plasma enhanced chemical vapor deposition

This paper reports for the first time the synthesis of hexagonal diamond thin films on high-speed steel substrates by multi-mode microwave plasma enhanced chemical vapor deposition. Before deposition of the films, the substrate surface was treated by scratching with diamond powder. The deposited films were characterized by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy. The XRD patterns of (100) and (101) planes and the Raman peaks at ~ 1317-1322 cm^− 1 were observed, confirming the formation of hexagonal diamond phase in the prepared films. The effects of voltage bias on the phase formation, microstructure and hardness of the films were also studied by setting the voltage to 0, − 70, − 150 and − 190 V. The highest hardness of 23.8 GPa was found in the film having clusters of size about 550 nm deposited under a bias voltage of − 150 V. These clusters were built up of grains of size about 14 nm.     

Thermal behavior of the amorphous precursors of the ZrO2–GaO1.5 system

The amorphous precursors of the ZrO₂–GaO_1.5 system on the ZrO₂-rich side of the concentration range were prepared by co-precipitation from aqueous solutions of the corresponding salts. Thermal behavior of the amorphous precursors was monitored using differential thermal analysis (DTA), X-ray powder diffraction (XRD), Raman spectroscopy and field emission scanning electron microscopy (FE-SEM). Crystallization temperature of the amorphous precursors rose with an increase in the GaO_1.5 content, from 405 °C (0 mol% GaO_1.5) to 720 °C (50 mol% GaO_1.5). The results of Rietveld refinements indicated that the maximum solubility of Ga³⁺ ions in the ZrO₂ lattice (43 mol%) occurred in the metastable products obtained after crystallization of the amorphous precursors. Further thermal treatment caused a decrease of the solubility limits, which became negligible after calcination at 1100 °C. The results of Raman spectroscopy showed that the incorporation of Ga³⁺ ions partially stabilized the tetragonal polymorph of ZrO₂, but could not stabilize its cubic polymorph. The incorporation of Ga³⁺ ions caused a linear decrease in the unit-cell volume of the ZrO₂-type solid solutions, but the rate of the decrease turned out to be smaller than the rate obtained after the incorporation of bigger Fe³⁺ ions.