Improving the surface properties of multi-walled carbon nanotubes after irradiation with gamma rays

The effects of gamma-irradiation on the modification of the surface and structure of multi-walled carbon nanotubes were studied. Gamma-irradiation affected the graphitization properties of functional groups, and decreased the diameter of multi-walled carbon nanotubes. The irradiated multi-walled carbon nanotubes with the absorbed dose of 100 kGy exhibited a larger specific surface area and microporous volume as compared with the other samples. The Raman spectroscopy and X-ray photoelectron spectroscopy showed that the interaction between the gamma-irradiation and the multi-walled carbon nanotubes with the absorbed dose of 150 kGy destroyed the nanostructure of carbons, leading to the formation of diamond-like structures and carbon oxides. In addition, gamma-irradiation with the absorbed dose of 100 kGy improved multi-walled carbon nanotubes graphitization and surface properties while at higher absorbed dose (150 kGy), it induced damaged structures (sp³ bonds and oxygen compositions).     

Core-shell structure and magnetic properties of magnetite magnetic fluids stabilized with dextran

The adsorption process of different dextran molecules onto the surface of in water dispersed magnetite nanoparticles has been investigated to optimize the preparation of magnetite magnetic fluids (MMFs). An average magnetite core size of 7.1 nm was found by X-ray diffraction and that of 8 nm was found by transmission electron microscopy for the samples prepared at 90 °C. An average hydrodynamic diameter of 25 nm was observed by scanning electron microscopy and that of 25-300 nm was obtained by photon correlation spectroscopy. The dextran was adsorbed by physical adsorption, a molecular weight of 20 kDa gave the best stability of these MMFs. The shell layer of the particles was weakly negatively charged in buffer solutions of pH values between 5.5 and 9.5. The particles seem to be mainly stabilized by sterical repulsion. The maximum available saturation magnetization of the MMFs was 3.5 kA/m.     

Self assembly of SiO2-encapsulated carbon microsphere composites

SiO₂ was firstly coated onto the surface of carbon microspheres (CMSs) using tetraethyl orthosilicate (TEOS) as precursor by Stöber method. Then SiO₂-encapsulated CMS (CMS@SiO₂) composites were self-assembled by vertical deposition, in which the effects of deposition temperature and suspension concentration on the quality of self-assembling film were investigated. Morphologies and structures of the samples were characterized by field emission scanning electron microscopy, Fourier transformation infrared spectrometry, X-ray diffraction and thermogravimetry. The results show that uniform CMS@SiO₂ composites with good mono-dispersion were prepared by St?ber method with 0.5 g of CMSs, 2 mL of TEOS, 30 mL of ammonia and 12 h of reaction time, the CMSs-based films with ordered and denser structure were prepared by vertical deposition using CMS@SiO₂ composites as monodipersion spheres under suspension concentration of 1 wt% and deposition temperature of 50 °C. The ultraviolet-visible absorption measurement shows that the absorbance of CMS@SiO₂ composite films grew steadily with increasing suspension concentration.     

Controlled deposition of covalently bonded tantalum oxide on carbon supports by solvent evaporation sol-gel process

A simple strategy for covalently attaching Ta₂O₅ particles onto functionalized graphitic carbon supports has been developed to fabricate hybrid nanocomposites. In this process, tantalum ethoxide was directly reacted with functional groups on the carbon surface to form covalent bonding, which caused the carbonyl stretches of the carbon supports to be blue-shifted to 50-70 cm⁻¹ after Ta₂O₅ particle deposition. Homogeneously deposited Ta₂O₅ particles on the carbon supports have been studied by X-ray diffraction (XRD), FT-IR spectroscopy, scanning electron microscopy (SEM), and transmission electron microscope (TEM).     

Densification mechanism of polyacrylonitrile-based carbon fiber during heat treatment

Polyacrylonitrile (PAN)-based carbon fibers were heat treated at various temperatures for varying durations to simulate the graphitization process in the manufacture of C/C composites. Densification of the resulting fibers was confirmed by density measurement. The composition and structure of the fibers were investigated by means of elemental analysis, X-ray diffraction and Raman spectroscopy. For specified isothermal heat treatment time, the structural parameters depended strongly on heat treatment temperature. The nitrogen content decreased with increased heat treatment temperature and extended time at constant temperature. Nitrogen loss was complete at temperatures above 1900 °C. The graphite crystallite size increased rapidly with increasing heat treatment temperature, and slowly with extended isothermal heat treatment time. At 2100 °C a more ordered graphitic structure appeared. Denitrogenation induced “puffing”, which made the fibers expand. Decrease in density in the heat treatment temperature range 1500-1900 °C originated from the abrupt evolution of nitrogen, and above 1900 °C the graphitization transition induced steadily increasing density. Densification of the carbon fibers was determined both by the rate of denitrogenation and the rearrangement of carbon atoms.     

Adsorption and decomposition of triethylsilane on Si(1 0 0)

The adsorption and decomposition of triethylsilane (TES) on Si(1 0 0) were studied using temperature programmed desorption (TPD), high resolution electron energy loss spectroscopy (HREELS), electron stimulated desorption (ESD), and X-ray photoelectron spectroscopy (XPS). TPD and HREELS data indicate that carbon is thermally removed from the TES-dosed Si(1 0 0) surface via a β-hydride elimination process. At high exposures, TPD data shows the presence of physisorbed TES on the surface. These species are characterized by desorption of TES fragments at 160 K. Non-thermal decomposition of TES was studied at 100 K by irradiating the surface with 600 eV electrons. ESD of mass 27 strongly suggests that a β-hydride elimination process is a channel for non-thermal desorption of ethylene. TPD data indicated that electron irradiation of physisorbed TES species resulted in decomposition of the parent molecule and deposition of methyl groups on the surface that desorbed thermally at about 900 K. Without electron irradiation, mass 15 was not detected in the TPD spectra, indicating that the production of methyl groups in the TPD spectra was a direct result of electron irradiation. XPS data also showed that following electron irradiation of TES adsorbed on Si(1 0 0), carbon was deposited on the surface and could not be removed thermally.     

Influence of high temperature annealing on the structure, hardness and tribological properties of diamond-like carbon and TiAlSiCN nanocomposite coatings

Diamond-like carbon (DLC) and TiAlSiCN nanocomposite coatings were synthesized and annealed at different temperatures in a vacuum environment. The microstructure, hardness and tribological properties of as-deposited and annealed DLC-TiAlSiCN nanocomposite coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Raman spectroscopy, nano-indentation and friction tests. The TEM results reveal that the as-deposited DLC-TiAlSiCN coating has a unique nanocomposite structure consisting of TiCN nanocrystals embedded in an amorphous matrix consisting of a-Si₃N₄, a-SiC, a-CN and DLC, and the structure changed little after annealing at 800 °C. However, XPS and Raman results show that an obvious graphitization of the DLC phase occurred during the annealing process and it worsened with annealing temperature. Because of the graphitization, the hardness of the DLC-TiAlSiCN coating after annealing at 800 °C decreased from 45 to 36 GPa. In addition, the DLC-TiAlSiCN coating after annealing at 800 °C has a similar friction coefficient to the as-deposited coating.     

Growth of Y-junction bamboo-shaped CNx nanotubes on GaAs substrate using single feedstock

Nitrogen-doped Y-junction bamboo-shaped carbon nanotubes were synthesized by chemical vapor deposition of monoethanolamine/ferrocene mixture on GaAs substrate at 950 °C. The use of monoethanolamine as the C/N feedstock simplifies the experimental arrangement by producing ammonia during the growth process. The structure, morphology and graphitization of as-grown nitrogen-doped carbon nanotubes (CN_x) were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy analysis. TEM analysis indicates that nanotubes have a bamboo-like structure. The nitrogen concentration on as-grown CN_x nanotube was found to be 7.8 at.% by X-ray photoelectron spectroscopy (XPS) analysis. XPS analysis also indicated that there are two different types of nitrogen atoms (pyridinic and graphitic) in these materials. The possible growth mechanism of formation of Y-junction CN_x nanotubes was briefly discussed. Field emission measurement suggested that as-grown CN_x nanotubes are excellent emitters with turn-on and threshold fields of 1.6 and 2.63 V/μm, respectively. The result indicated that monoethanolamine proves to be an advantageous precursor to synthesize Y-junction nitrogen-doped carbon nanotubes and such nanotubes might be an effective material to fabricate various field emission devices.     

Evaluation of residual iron in carbon nanotubes purified by acid treatments

A detailed analysis by X-ray photoelectron spectroscopy was carried out on multi-walled carbon nanotube (MWCNT) surfaces after non-oxidative and oxidative purification treatments in liquid-phase. The MWCNT were produced by pyrolysis of camphor and ferrocene, that provides a high yield but with high iron contamination (∼15% wt). The elimination and/or oxidation of iron nanoparticles were monitored by Fe2p and O1s core level. Oxygen-based functional groups attachment was also investigated by C1s fitting. The effectiveness of each treatment in iron removal was evaluated by thermogravimetric analysis (TGA) and atomic absorption spectroscopy (AAS). The integrity of the MWCNT structure was verified by Raman spectroscopy (RS) and transmission electron microscopy (TEM). A purity degree higher than 98% was achieved only with non-oxidative treatments using sonification process.     

Modification of multi-walled carbon nanotubes for electric double-layer capacitors: Tube opening and surface functionalization

Multi-walled carbon nanotubes (MWCNTs) obtained opening the closed ends and using surface functionalization by means of a combination of partial oxidation in air and chemical modifications are characterized systematically in 0.3 M H₂SO₄ between 0 and 1.0 V, and these nanotubes were planned to be used as electrode materials in electric double-layer capacitors (EDLCs). Opening of MWCNTs, clearly observed by means of transmission electron microscopy (TEM), can be easily achieved by the partial oxidation in air through a seven-step temperature program identified by thermogravimetric/differential thermal analyses (TG/DTA). An increase in 175% specific capacitance is obtained for the MWCNTs, partially oxidized in air and chemically modified in H₂SO₄+HNO₃. The temperature-programmed desorption (TPD) data showed that evolutions of CO and CO₂ are, respectively, promoted by the application of partial oxidation in air and chemical modification in H₂SO₄+HNO₃. The above increase in specific capacitance for modified MWCNTs is attributed to an obvious increase in the BET surface area (double-layer capacitance) and the density of oxygen-containing surface functional groups (pseudocapacitance).     

Field emission properties of electrophoretic deposition carbon nanotubes film

The field emission properties of electrophoretic deposition(EPD) carbon nanotubes (CNTs) film have been improved by depositing CNTs onto the titanium (Ti)-coated Si substrate, followed by vacuum annealing at 900 °C for 2 h, and the enhanced emission mechanism has been studied using X-ray diffraction (XRD), scanning electron microscope (SEM) and Raman spectroscopy. Field emission measurements showed that the threshold electric field was decreased and the emission current stability was improved compared to that of EPD CNTs film on bare Si substrate. XRD and Raman spectroscopy investigations revealed that vacuum annealing treatment not only decreased the structural defects of CNTs but made a titanium carbide interfacial layer formed between CNTs and substrate. The field emission enhancement could be attributed to the improved graphitization of CNTs and the improved contact properties between CNTs and substrate including electrical conductivity and adhesive strength due to the formed conductive titanium carbide.     

Auger electron spectroscopy depth profiling of Fe-oxide layers on electromagnetic sheets prepared by low temperature oxidation

Auger electron spectroscopy depth profiling was applied to characterize the Fe-oxide layers prepared by low temperature oxidation of Fe electromagnetic sheets produced on an industrial line for applications in the field of electrical motors. In addition the surface morphology, layer composition and layer structure were analysed by electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction techniques. We found that the oxide layers on Fe-sheets with good adhesion between the oxide layer and Fe-substrate, consist mainly of magnetite and to a smaller extent of haematite; the layers are typically thinner than 1 μm and the interface between the oxide layer and the Fe-substrate is relatively broad, i.e. up to 0.3 μm. On the contrary, a decrease of adhesion between the oxide layer and the Fe-substrate was found when the layer is thicker than 1 μm and the layer/substrate interface is narrow and contaminated by foreign elements.     

Selective growth of carbon nantoubes on SiO2/Si substrate

Three-step raising temperature process was employed to fabricate carbon nanotubes by pyrolysis of ferrocene/melamine mixtures on silica and single crystalline silicon wafers respectively. Then the morphologies, structures and compositions of obtained carbon nanotubes are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscope (EDX) and electron energy-loss spectroscopy (EELS). TEM and SEM observation shows that on silica substrate, high-oriented carbon nanotube can grow compactly to form continuous film on both frontal and cross-section surfaces, but on silicon substrate, only can form on cross-section surface. These carbon nanotubes have much irregular cup-like structure, and with outer diameter varying from 25 nm to 35 nm. At the top end of carbon nanotube there is a catalyst particle. EDX analysis reveals that the particle are iron cluster, and EELS spectrum indicates that the nanotube is composed of pure carbon. Finally, the effect of substrate surface roughness on the growth behavior of carbon nanotubes has been discussed.     

Influence of a controlled oxidation at moderate temperatures on the surface chemistry of nitinol wire

Commercial nitinol wire is oxidised at 480-530 °C/10 min in air. Surface morphology and chemistry is studied in detail using scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, Raman spectrometry and X-ray photoelectron spectroscopy. It is found that the main oxidation product at both temperatures is rutile containing a few at.% Ni. Beneath the rutile layer, there are titanium sub-oxides, showing characteristic maxima in depth profiles. Nickel in an oxidised state is present on the surface, whereas in a sub-surface region of scales, there is only metallic nickel. Thickness of the total oxide layers is 70 and 140 nm after oxidation at 480 and 530 °C, respectively. The preferential oxidation of titanium causes the formation of a Ni-enriched and Ti-depleted zone, suggesting the presence of Ni₃Ti phase. XRD reveals that the presence of cubic B2 NiTi phase in the base alloy is not affected by oxidation at 480-530 °C/10 min.     

Surface modification study of low energy electron beam irradiated polycarbonate film

The effect of low energy electron beam irradiation on polycarbonate (PC) film has been studied here. The PC film of thickness 20 μm was exposed by 10 keV electron beam with 100 nA/cm² current density. The irradiated film was characterized by mean of X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and residual gas analyzer (RGA). Formation of unsaturated bonds and partial graphitization of the surface layer are measured by XPS. Results of the AFM imaging shows electron implantation induce changes in surface morphology of the polymer film. The residual gas analyzer (RGA) spectrum of PC is recorded in situ during irradiation. The results show the change in cross-linking density of the polymer at the top surface.     

Stability of hydrogen-terminated vicinal Si(1 1 1) surface under ambient atmosphere

In this paper a comparative study of different wet-chemical etching procedures of vicinal Si(1 1 1) surface passivation is presented. The stability against oxidation under ambient atmosphere was studied by X-ray photoelectron spectroscopy and atomic force microscopy. The best results were achieved by the buffered HF etching and the final smoothing of the surface by hot (72 °C) NH₄F. The procedures consisting of a large number of etching steps were unsatisfactory, since the probability of contamination during each step was increasing. The passivated surface was stable against oxidation for at least 3 h under ambient atmosphere.     

Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO₃/H₂SO₄ (1/3 or 1/1), 8 M HCl or 8 M HNO₃ was carried out. The results showed that 8 M HNO₃ could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO₃/H₂SO₄ (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.     

The influence of treatment duration on multi-walled carbon nanotubes functionalized by H2SO4/HNO3 oxidation

Variation in the nature of multi-walled carbon nanotubes (MWCNTs) subjected to different degrees of oxidation was investigated. The microstructure was determined by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) methods, and the surface chemistry was evaluated in terms of the functional groups determined by X-ray photoelectron spectroscopy (XPS) and thermal analysis-mass spectroscopy (TA-MS). In addition, TGA was used to indicate the thermal stability of the nanotubes. Results demonstrate that the graphitic structure of nanotubes oxidized with a mild mixture of H₂SO₄/HNO₃ was preserved. Decrease in the degree of crystallinity started with widening of the C(0 0 2) XRD diffraction peak, followed by this peak shifting towards lower angles. The oxygen content increased with increasing treatment time. A defect peak incorporated in deconvolution of XPS C1s spectra was helpful for detecting the generation of defect sites. The predominant surface functionalities of the nanotubes have been changed from basic to acidic groups after treatment for one day. The samples oxidized for two days had the most abundant surface -COOH and the highest oxidation resistance. The oxidation mechanism of MWCNTs in mild H₂SO₄/HNO₃ mixture was proposed, which was a successive and iterative process, including the initial attack on active sites, and next the hexagon electrophilic attack generating new defects and introducing more oxygen, and then the tubes becoming thinner and shorter.     

Composition and morphology of fluorinated anodic oxides on InAs (1 1 1)A surface

The composition and morphology of fluorinated anodic oxide (FAO) films grown on InAs (1 1 1)A in alkaline aqueous (pH 11.5) and acid waterless (pH 1.5) electrolytes are studied by means of X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM) in order to reveal the passivation mechanism of fluorine on the FAO/InAs(1 1 1)A interface. The formation of the highest oxidation form of As⁺⁵ and passivation of defects in the FAO layers during the fluorination process explain the reduction of the density of surface states and unpinning of the Fermi level on the fluorinated AO/InAs(1 1 1)A interface.     

Effect of heat treatment on bioactivity of anodic titania films

Anodic oxidation could be employed to produce crystalline titania films on Ti6Al4 V surfaces for inducing apatite formation in simulated body fluid (SBF). In this work, the effect of further heat treatment on the bioactivity of anodic titania films was researched. The surface constitution, morphology, crystal structure and apatite-forming ability of titania films were characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results indicated the apatite formation on the Ti6Al4 V surfaces could be attributed to abundance of Ti-OH groups formed via anodic oxidation, but subsequent heat treatment would decrease the amount of surface hydroxyl (OH) groups and result in the loss of the apatite-forming ability.