Synthesis of zirconia nanoparticles on carbon nanotubes and their potential for enhancing the fracture toughness of alumina ceramics

Nanoparticles of zirconia (ZrO₂) were in situ synthesized on the surface of carbon nanotubes by means of liquid phase reactions and a proper heat treatment process. The size of the nanoparticles could be controlled by the amount of zirconium source materials in a solution and its reaction times. In this study, the size of the nanoparticles ranged from several nanometers to twenty nanometers. It was particularly noted that the synthesized zirconia possessed a cubic structure (c-phase) which generally existed as a stable form of zirconia crystals at high temperatures (above 2370 °C) as well as a form of zirconia that could be used for enhancing the fracture toughness of alumina ceramics. Experimental results showed that the mechanical properties of alumina ceramics mixed with in situ synthesized nanoparticles on the surface of carbon nanotubes were much better than that of pristine nanotubes or zirconia nanoparticles alone. The existence of the nanoparticles on the surface of nanotubes results in improving the dispersion and bonding properties of the nanotubes in alumina matrix environment. The fracture toughness of CNT/ZrO₂ alumina ceramics was also improved by the mechanism of bridging effect.     

Influence of the crystallinity of the iron catalysts on the formation of carbon nanotubes

In this work, carbon nanotubes and minor amount of Fe/C core-shell structure nanoparticles were simultaneously synthesized by catalytic pyrolysis of ferrocene. Through high-resolution TEM observation and ED characterization, the results showed that the well-crystallized iron nanoparticles could catalyze the formation of carbon nanotubes, while the amorphous iron nanoparticles could not catalyze the formation of carbon nanotubes but form the Fe/C core-shell nanoparticles.     

Activated carbon catalyzing the formation of carbon nanotubes

Activated carbon (AC), a common carbon material, is employed as catalyst to synthesize carbon nanotubes (CNTs) through chemical vapor deposition (CVD) and detonation-assisted CVD methods. The results show AC can effectively catalyze CNT formation. From the microscopic observations on morphologies and structures of the formed intermediates, it is found that carbon-catalyzed CNT formation follows particle-wire-tube stepwise evolution mechanism, in which carbon nanoparticles first assemble into wire-like nanostructures, then evolve into nanotubes via particle-particle coalescence and structural crystallization.     

钛酸盐中钠离子含量对其水热转化制备TiO_2纳米材料的影响

采用水热法制备了单晶TiO2纳米材料。用X射线衍射仪和透射电子显微镜对产物的晶相组成和形貌进行了表征。考查了钛酸盐中钠离子含量对其水热转化所得TiO2产物的相组成、形貌和尺寸的影响。当pH值为1,含有钠离子时,得到的是以菱形为主的直径为10nm左右的单晶锐钛矿纳米颗粒,不含钠离子时,得到的产物以单晶锐钛矿纳米颗粒为主,同时含有少量单晶金红石纳米棒。当pH值为4,含有钠离子时,得到的是具有高长径比的单晶锐钛矿纳米棒,宽为60nm左右,长为300～500nm左右,不含钠离子时,得到的是尺寸为20nm×60nm的短纳米棒。同时,探讨了钛酸盐中钠离子的影响机理。     

New synthesis of Cu2O and Cu nanoparticles on multi-wall carbon nanotubes

Cu₂O and Cu nanoparticles were deposited on the surface of multi-walled carbon nanotubes with a diameter range of 15–90 nm by the impregnate method. Multi-wall carbon nanotubes with a length of 200 μm and a diameter range of 70–110 nm were grown inside of quartz tubing by the spray pyrolysis method using ferrocene/benzene under argon flow. The nanotubes were then treated with nitric acid to clean the surface and generate carboxylic groups. The copper was impregnated on multi-walled carbon nanotubes using a xylene solution of copper(I) phenylacetylide as the precursor. Copper and cuprous oxide nanoparticles were obtained during thermal treatment.     

Synthesis of TiO2-based nanotube on Ti substrate by hydrothermal treatment

TiO2-based titanate nanotube film was directly synthesized by hydrothermal treatment of Ti substrate in NaOH solution. The prepared high aspect ratio nanotubes have diameter of 10 nm and pore size of 5 nm with length of several microns. The nanotubes show the same structure and component characteristics as the nanotubes prepared through hydrothermal treatment of TiO2. Other nanostructured titanate as oriented nanofiber film and translucent film were also prepared by adjusting the hydrothermal conditions. The formation mechanism of nanostructured titanate was discussed.     

Optimization of the chemical vapor deposition process for fabrication of carbon nanotube/Al composite powders

In order to optimize the chemical vapor deposition process for fabrication of carbon nanotube/Al composite powders, the effect of different reaction conditions (such as reaction temperature, reaction time, and reaction gas ratio) on the morphological and structural development of the powder and dispersion of CNTs in Al powder was investigated using transmission electron microscope. The results showed that low temperatures (500-550 °C) give rise to herringbone-type carbon nanofibers and high temperatures (600-630 °C) lead to multi-walled CNTs. Long reaction times broaden the CNT size distribution and increase the CNT yield. Appropriate nitrogen flow is preferred for CNT growth, but high and low nitrogen flow result in carbon nanospheres and CNTs with coarse surfaces, respectively. Above results show that appropriate parameters are effective in dispersing the nanotubes in the Al powder which simultaneously protects the nanotubes from damage.     

Hierarchical composites of carbon nanotubes on carbon fiber: Influence of growth condition on fiber tensile properties

Growing carbon nanotubes (CNT) on the surface of high performance carbon fibers (CF) provides a means to tailor the thermal, electrical and mechanical properties of the fiber–resin interface of a composite. However, many CNT growth processes require pretreatment of the fiber, deposition of an intermediate layer, or harsh growth conditions which can degrade tensile properties and limit the conduction between the fiber and the nanotubes. In this study, high density multi-wall carbon nanotubes were grown directly on two different polyacrylonitrile (PAN)-based carbon fibers (T650 and IM-7) using thermal Chemical Vapor Deposition (CVD). The influence of CVD growth conditions on the single-fiber tensile properties and CNT morphology was investigated. The mechanical properties of the resultant hybrid fibers were shown to depend on the carbon fiber used, the presence of a sizing (coating), the CNT growth temperature, growth time, and atmospheric conditions within the CVD chamber. The CNT density and alignment morphology was varied with growth temperature and precursor flow rate. Overall, it was concluded that a hybrid fiber with a well-adhered array of dense MWCNTs could be grown on the unsized T650 fiber with no significant degradation in tensile properties.     

Functionalization of gold-coated carbon nanotubes with self-assembled monolayers of thiolates

Multi-walled carbon nanotubes (CNT) were synthesized by chemical vapor deposition using Co–Fe as a catalyst and ethylene as a carbon source. Afterward, a simple method combining wet-chemistry and chemical reduction was used to prepare carbon nanotube/gold material (CNT/Au). Pristine nanotubes and CNT/Au were characterized by transmission electron microscopy micrographs. It appeared that gold formed nanoparticles on CNTs endings and their sidewalls. Further functionalization was carried out by using thiols of different chemical properties and molecule sizes. Thiols formed self-assembled monolayer on gold surface that led to formation of CNT/gold/thiol-functionalized material. The amounts of chemisorbed thiols were measured by elemental analysis and thermogravimetry.     

Synthesis of polycrystalline SnO2 nanotubes on carbon nanotube template for anode material of lithium-ion battery

Polycrystalline tin oxide nanotubes have been prepared by a layer-by-layer technique on carbon nanotubes template. Firstly, the surface of carbon nanotubes was modified by polyelectrolyte. Then, a uniform layer of tin oxide nanoparticles was formed on the positive charged surface of carbon nanotubes via a redox process. At last, the polycrystalline tin oxide nanotubes were synthesized after calcination at 650 °C in air for 3 h. The as-synthesized polycrystalline nanotubes with large surface area exhibit finer lithium storage capacity and cycling performance, which shows the potentially interesting application in lithium-ion battery.     

微波水热法合成钛酸钠盐纳米管

采用微波水热法合成了钛酸钠盐纳米管,考察了原料、反应时间、NaOH浓度等主要影响因素.在微波功率195W、NaOH浓度8—12mol/L、反应时间>70min条件下,得到了形貌均一的钛酸钠盐纳米管,并用TEM、XRD、BET、EDAX和N₂吸附/脱附等对产物进行了表征.研究表明,微波法制得的纳米管合成时间短、热稳定性高,其管壁塌陷温度高于500℃,比普通水热法合成的高100℃左右;所得样品在300℃以上煅烧,可转化为单晶钛酸纳盐纳米管.     

Nitrogen-doped TiO2 nanotubes with enhanced photocatalytic activity synthesized by a facile wet chemistry method

Nitrogen-doped TiO₂ nanotubes with enhanced photocatalytic activity were synthesized using titanate nanotubes as raw material by a facile wet chemistry method. The resulting nanotubes were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectroscopy, and UV-vis absorption spectroscopy, etc. The photocatalytic activity of nitrogen-doped TiO₂ nanotubes was evaluated by the decomposition of methylene blue under artificial solar light. And it was found that nitrogen-doped TiO₂ nanotubes exhibited much higher photocatalytic activity than undoped titanate nanotubes.     

Carbon nanotube based pressure sensor for flexible electronics

A pressure sensor was developed based on an arrangement of vertically aligned carbon nanotubes (VACNTs) supported by a polydimethylsiloxane (PDMS) matrix. The VACNTs embedded in the PDMS matrix were structurally flexible and provided repeated sensing operation due to the high elasticities of both the polymer and the carbon nanotubes (CNTs). The conductance increased in the presence of a loading pressure, which compressed the material and induced contact between neighboring CNTs, thereby producing a dense current path and better CNT/metal contacts. To achieve flexible functional electronics, VACNTs based pressure sensor was integrated with field-effect transistor, which is fabricated using sprayed semiconducting carbon nanotubes on plastic substrate.     

Hydrothermal processing of hydrogen titanate/anatase-titania nanotubes and their application as strong dye-adsorbents

The nanotubes of pure hydrogen titanate and anatase-titania have been synthesized via hydrothermal treatment of as-received anatase-titania particles. The formation mechanism of anatase-titania nanotubes via hydrothermal has been discussed in detail in view of the finger-prints produced by characterizing the intermediate and end products using various microscopic and spectroscopic techniques such as scanning electron microscope, high-resolution transmission electron microscope, X-ray diffraction, Brunauer, Emmett, and Teller specific surface-area measurement, Fourier transform infrared spectroscope, diffuse reflectance, photoluminescence, thermal gravimetric and differential thermal analyses. The obtained results strongly support the rollup mechanism, involving multiple nanosheets, for the formation of anatase-titania nanotubes with the formation of different intermediate hydrothermal products having various morphologies such as sodium titanate having aggregated rectangular block-like structures, hydrogen sodium titanate and pure hydrogen titanate having highly aggregated unresolved fine-structures containing nanotubes, and finally, the pure anatase-TiO2 nanotubes. It is demonstrated that, during the hydrothermal treatment, the nanotubes of pure hydrogen titanate are formed first coinciding with the stable solution-pH during washing, indicating the completion of ion-exchange process, and a drastic increase in the specific surface-area of the hydrothermal product. The anatase-titania nanotubes are then derived from the pure hydrogen titanate nanotubes via thermal treatment. The use of pure hydrogen titanate and anatase-titania nanotubes for an organic textile dye-removal, from an aqueous solution under the dark condition, via surface-adsorption mechanism has been demonstrated. It is shown that, the specific surface-area and the surface-charge govern the maximum dye-absorption capacity of the anatase-TiO2 nanotubes under the dark condition.     

Synthesis of flake-like MnO2/CNT composite nanotubes and their applications in electrochemical capacitors

MnO2/CNT composite nanotubes with nanometer-sized flake-like MnO2 on carbon nanotubes' surfaces have been synthesized through an easy and efficient solution-based method. Similarly, Mn3O4/CNT composite nanotubes have also been synthesized by using the same method but different heat treatment process. The structures and compositions of the two types of composite nanotubes are characterized by using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and nitrogen adsorption-desorption isotherms. Electrochemical measurements indicate that the MnO2/CNT composites nanotubes exhibit significantly enhanced supercapacitance performance compared with the Mn3O4/CNT composite nanotubes, the as-synthesized MnO2 nanoparticles and commercial MnO2. The possibilities of the enhanced properties are illustrated on the basis of analysis of XRD and X-ray photoelectron spectroscopy measurements. Our results presented here can give clear evidence of the superiority of nanocrystalline MnO2 to nanocrystalline Mn3O4 toward the applications as electrode materials in electrochemical capacitors.     

Influence of various plasma treatment on the properties of carbon nanotubes for composite applications

In present work, the effects of hydrogen and oxygen plasma treatments on the structural properties of carbon nanotubes (CNTs) synthesized by catalytic CVD (Chemical Vapor Deposition) have been systematically investigated. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy were used to characterize the microstructural changes of the CNTs. The oxygen plasma treatment resulted in that the nanoparticles were appeared at the surface of CNTs. At high r.f. power (300 Watt), the microstructure of CNT was changed from nanotube type to nano particles. Long plasma treatment time changed the CNT morphology dramatically. For hydrogen plasma, however, there was no change in microstructure of CNT From the Raman analysis, the crystallinity of CNT was deteriorated by the plasma treatment, regardless of plasma power, treatment time, and gas types. The CNTs treated in oxygen plasma for 90 min showed excellent dispersion properties in aqueous solution.     

Impact and after-impact properties of carbon fibre reinforced composites enhanced with multi-wall carbon nanotubes

The goal of the present study was to investigate the influence of multi-wall carbon nanotubes (MWCNTs) on the impact and after impact behaviour of carbon fiber reinforced polymer (CFRP) laminates. About 0.5% per weight MWCNTs were dispersed via a high shear device in the epoxy matrix (Bisphenol A) of carbon reinforced quasi-isotropic laminates. Subsequently, the modified CFRPs were subjected to low-energy impact and directly compared with unmodified laminates. In previous studies, the beneficial effect of the MWCNT inclusion to the fracture properties of CFRPs has been demonstrated. In terms of the CFRP impact performance, enhanced performance for the CNT doped specimens was observed for higher energy levels. However, the after-impact properties and more specifically compression after impact were improved for both the effective compression modulus and the compression strength. In addition, compression–compression fatigue after impact performance of the CNT modified laminates was also improved, by extending the fatigue life.     

Growth of carbon nanotubes on carbon fibre substrates to produce hybrid/phenolic composites with improved mechanical properties

Carbon nanotubes were grown by chemical vapor deposition (CVD) on different carbon fibre substrates namely, unidirectional (UD) carbon fibre tows, bi-directional (2D) carbon fibre cloth and three dimensional (3D) carbon fibre felt. These substrates were used as the reinforcement in phenolic resin matrix to develop hybrid CF–CNT composites. The growth morphology and other characteristics of the as grown tubes were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermal gravimetry (TGA) which confirmed a copious growth of multiwalled carbon nanotubes (MWNTs) on these substrates. The mechanical properties of the hybrid composites was found to increase with the increasing amount of deposited carbon nanotubes. The flexural strength (FS) improved by 20% for UD, 75% for 2D and 66% for 3D hybrid composites as compared to that prepared by neat reinforcements (without CNT growth) under identical conditions. Flexural modulus (FM) of these composites also improved by 28%, 54% and 46%, respectively.     

Studies on transformation of titanate nanotubes into nanoribbons

High aspect ratio titanate nanostructures were synthesized by simple hydrothermal treatment and the nature of two distinct morphologies, hollow nanotubes and titanate nanoribbons was explored as a function of hydrothermal processing conditions. The samples were characterized by means of SEM, XRD and TEM. The specific surface area of the final products was determined by Brunauer-Emmett-Teller (BET) method. It has been found that hydrothermal temperature and the treatment duration have a strong effect on the morphological control of the resulting products. Transformation of nanotubes into nanoribbons was observed with increase in the treatment temperature from 180 °C to 200 °C which became more dense with further increase in the temperature from 200 °C to 220 °C and treatment duration from 12 h to 24 h.     

The effect of carbon nanotubes microstructures on reinforcing properties of SWNTs/alumina composite

Alumina reinforced with 1 wt% single-wall carbon nanotubes (SWNTs) was fabricated by hot-pressing. The fracture toughness of SWNTs/Al₂O₃ composite reaches 6.40 ± 0.3 MPa m^1/2, which is twice as high as that of unreinforced alumina. Nanoindentation introduced controlled cracks and the damage were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SWNTs reinforcing mechanisms including CNT pullout, CNT fracture, CNT bridging and crack deflection were directly observed, and the relationship between carbon nanotubes microstructures in the matrix and mechanical properties was also discussed in detailed.