Effect of high-pressure vapor on the microstructure and mechanical properties of TiO2 continuous fibers

During the preparation of TiO₂ continuous fibers, the organic ligands of the precursor fibers are severely decomposed and generated a large amount of gas, which can reduce the fiber matrix strength. Tt is necessary to choose a suitable treatment strategy to avoid this and obtain high-quality TiO₂ continuous fibers. In this study, flexible continuous TiO₂ fibers with a diameter of about 30 μm were prepared using a high-pressure vapor pretreatment method. The high-pressure vapor pretreatment caused precursor hydrolysis, which promoted the decomposition of the organic ligands in a mild way and prevented fiber fracture caused by the violent oxidative decomposition. The crystallization temperature decreased by 120 °C because of the synergistic effects of vapor and pressure. The hydrolysis of the precursor and the reduction in the crystallization temperature were conducive to the formation of compact fibers with high strength. However, the presence of water vapor caused the fibers to undergo the dissolution-precipitation process simultaneously, forming a large number of defects, which was harmful to its strength. The sample 1501 composed of anatase and rutile showed the highest average tensile strength of 385 MPa because it had fewer defects than the other samples. Although the highest average tensile strength is lower than the reported value of 800 MPa, the method is easy to implement and solves the problem of organics decomposition, which is helpful for industrial preparation.     

Tribological performance of SiC coating for carbon/carbon composites at elevated temperatures

SiC coating was deposited on carbon/carbon (C/C) composites by chemical vapor deposition (CVD). The effects of elevated temperatures on tribological performance of SiC coating were investigated. The related microstructure and wear mechanism were analyzed. The results show that the as-deposited SiC coating consists of uniformity of β-SiC phase. The mild abrasive and slight adhesive wear were the main wear mechanisms at room temperature, and the SiC coating presented the maximum friction coefficient and the minimum wear rate. Slight oxidation of debris was occurred when the temperature rose to 300?°C. As the temperature was above 600?°C, dense oxide film formed on the worn surface. The silica tribo-film replaced the mechanical fracture and dominated the frication process. However, the aggravation of oxidation at elevated temperatures was responsible for the decrease of friction coefficient and the deterioration of wear rate. The SiC coating presented the minimum friction coefficient and the maximum wear rate when the temperature was 800?°C.     

Controlled Synthesis of Monolayer Graphene Toward Transparent Flexible Conductive Film Application

We demonstrate the synthesis of monolayer graphene using thermal chemical vapor deposition and successive transfer onto arbitrary substrates toward transparent flexible conductive film application. We used electron-beam-deposited Ni thin film as a synthetic catalyst and introduced a gas mixture consisting of methane and hydrogen. To optimize the synthesis condition, we investigated the effects of synthetic temperature and cooling rate in the ranges of 850–1,000°C and 2–8°C/min, respectively. It was found that a cooling rate of 4°C/min after 1,000°C synthesis is the most effective condition for monolayer graphene production. We also successfully transferred as-synthesized graphene films to arbitrary substrates such as silicon-dioxide-coated wafers, glass, and polyethylene terephthalate sheets to develop transparent, flexible, and conductive film application.     

Oxidation protection of carbon fibers by coating with alumina and/or titania using atomic layer deposition

Alumina and titania coatings were deposited by atomic layer deposition onto carbon fibers at temperatures of 200 °C or below and reduced pressure. The coatings were smooth, uniform and conformed to the fiber surface. Thermogravimetric analysis (TGA) revealed that the coatings improved the oxidation resistance of the carbon fibers: the oxidation onset temperature of uncoated fibers and fibers coated with 66 nm of alumina was 630 °C. For fibers coated with 20 nm of titania it was 550 °C. Double layer coatings by 50 nm of alumina followed by 13 nm of titania yielded an oxidation onset temperature of 660 °C, while changing the order of the layers, i.e., coating fibers first with 20 nm of titania followed by 30 nm of alumina yielded an oxidation onset temperature of 750 °C. These TGA results were confirmed by a set of additional oxidation experiments conducted at a fixed temperature of 550 °C using a tube furnace in air. In this latter set of additional experiments, the times needed for a complete oxidation of the above mentioned samples were 8 h, 12 h, 10 h, 13 h, and 30 h, respectively.     

Synthesis and characterization of calcium zirconate nanofibers produced by electrospinning

Calcium zirconate fibers were produced by electrospinning and characterized in this work. The solution was prepared from zirconium and calcium salts, using polyvinyl-pyrrolidone (PVP) as processing aid. The decomposition of the organic fraction and crystallization of calcium zirconate were followed by thermogravimetry and differential scanning calorimetry (TG/DSC). Raman Spectroscopy was used to measure the vibrational modes in the green as well as in the calcined fibers. The final phase composition was studied by means of X-ray diffraction (XRD). The fiber morphology was investigated by confocal laser scanning microscopy (CLS) and scanning electron microscopy (SEM). The formation reaction of calcium zirconate was observed at about 740 °C. Highly crystalline fibers were obtained already at 800 °C, but the crystallinity and calcium zirconate yield improved when the temperature was increased to 1000 °C.     

Structure of composite materials based on aluminum and coreless silicon carbide fibres

The kinetics of the reaction on the matrix—fibre interface in composite materials based on aluminum and silicon carbide fibres was investigated at temperatures of 700, 800, and 900°C. It was found that the fibres treated at high temperature have important stability in aluminum melt due to the reduced concentration of free carbon in them and the formation of a barrier layer of β-SiC on the surface of the fibres. However, because of their poor mechanical properties, it is not expedient to use them for reinforcement of aluminum. The fibres treated at low temperature are totally suitable for strengthening aluminum but require the minimum contact time with the melt or protective coatings. Moscow State Institute of Steel and Alloys (Engineering University); All-Russian Scientific-Research Institute of Polymer Fibres, Mytishchi. Translated fromKhimicheskie Volokna, No. 6, pp. 42–46, November–December, 1999.     

Comparative study of interphase evolution in polysiloxane resin-derived matrix containing carbon micro and nanofibers during thermal treatment

The work presents the results of research on composite materials made of silicon-containing polymer-derived ceramic matrix composites (PDC-Cs) and nanocomposites (PDC-NCs). Carbon micro and nanofibers (CFs and CNFs) were used as reinforcements. The interactions between carbon micro and nanofibers and polysiloxane matrix, as well as interphase evolution mechanism in composite samples during their heating to 1000 °C were studied. CF/resin and CNF/resin composites were prepared via liquid precursor infiltration process of unidirectionally aligned fibers. After heating to 700 °C–800 °C, decomposition of the resin in the presence of CNFs led to the formation of fiber/organic-inorganic composites with pseudo-plastic properties and improved oxidation resistance compared to as-prepared fiber/resin composites. The most favourable mechanical properties and oxidation resistance were obtained for composites and nanocomposites containing the maximum amount of carbon nanoparticles precipitated in the SiOC matrix during the heat treatment at 800 °C. The precipitated carbon phase improves fiber/matrix adhesion of composites.     

Comparison of vapor adsorption characteristics of acetone and toluene based on polarity in activated carbon fixed-bed reactor

Adsorption characteristics according to polarity of acetone and toluene vapors on coconut based activated carbon were investigated by using a fixed bed reactor. Single vapor and binary vapor adsorption of acetone and toluene were conducted. In the single vapor system, the equilibrium adsorption capacity of toluene vapor on activated carbon was five times higher than that of acetone vapor because of polarity difference between adsorbent and adsorbate. The breakthrough curve of acetone vapor in the binary vapor was quite different from that of single acetone vapor. Acetone adsorbed in the binary vapor was substituted with toluene due to the affinity difference during adsorption process and its outlet concentration increased to 1.6 times than inlet concentration. The temperature changes in activated carbon bed during adsorption of acetone vapor and toluene vapor occurred in the time ranges of 10–30 min. The temperature change for acetone vapor adsorption was about 3 °C; however, that for toluene vapor adsorption was increased to 33 °C maximally.     

Borate treatment of carbon fibers and carbon/carbon composites for improved oxidation resistance

Carbon fibers and carbon/carbon composites have been treated with borate additives and then cured at 500–600°C to produce a continuous film of boron oxide on all exposed surfaces.This treatment has been found to be highly effective in retarding oxidation of the carbonaceous substrate for extended periods in flowing air at temperatures up to 1000°C. At higher temperatures, and in the presence of water vapor, borate species were appreciably volatile and the oxidation protection provided by the coatings was less effective.     

Comparative study of the structure and microstructure of PAN-based nano- and micro-carbon fibers

The work presents results on the manufacture and comparative assessment of the structure and microstructure parameters of polyacrylonitrile polymer (PAN)-based carbon nano- and micro-fibers. Using the same polymer solution, PAN nano- and microfibers were obtained. The PAN nanofibers were obtained by electrospinning, and microfibers were spun using the conventional solution-spinning method. The PAN-based fiber precursors were annealed to 1000 °C, 2000 °C and to 2800 °C. Using X-ray diffraction and Raman spectroscopy, the structural and microstructural parameters of both types of carbon fibers were examined. The morphology of PAN nanofibers and carbon nanofibers (CNF) were studied by SEM. Both types of ex-PAN carbon fibers (nano and micro) have similar the c-axis spacing (d₀₀₂) values and crystallite sizes after heat treatment to 2000 °C presenting turbostratic structure. HR-TEM images of low temperature CNF show uniform microstructure with the misoriented small carbon crystallites along the fiber axis. The ratio of the integrated intensities of the D and G peaks for carbon nanofibers after heat treatment at 2000 °C was distinctly higher in comparison to carbon microfibers (CF). After additional annealing the fibers to 2800 °C a better structural ordering show CNF. The crystallite sizes (L_c, L_a) in CNF were distinctly higher in comparison to the crystallites in CF. CF consist of two carbon components, whereas CNF contain three carbon components varying in structural and microstructural parameters. One of carbon phases in CNF was found to have the interlayer spacing close to graphite, i.e. d₀₀₂=0.335 nm.     

Growth of carbon nanotubes on the surface of carbon fiber using Fe–Ni bimetallic catalyst at low temperature

This article provides a method for growing carbon nanotubes(CNTs) on carbon fibers(CFs) using iron and nickel as catalysts at low temperatures. This series of experiments was conducted in a vacuum chemical vapor deposition(CVD)furnace. It is found that Fe–Ni catalysts, which have a certain thickness and can be better combined with resins when manufacturing composite materials, are more ideal for the growth of CNTs than single metal catalysts. At the same time, it is proved that the CVD process worked best at 450 °C. The mechanical property test proved the reinforcing effect of CNTs on carbon fiber, the single-filament tensile strength of CFs obtained by using Fe–Ni catalyst at 450 °C was 11% higher than that of Desized CFs. The bonding strength of carbon fiber and resin has also been significantly improved. When synthesized at low temperature, CNTs exhibited a hollow multi-wall structure.     

Preparation of mesoporous activated carbon fibers by catalytic gasification

A commercial activated carbon fiber with micropores, CH700-20 (Kuraray), was reformed to a mesoporous one by catalytic gasification. The catalytic gasification was composed of two steps: CO₂ pretreatment and air oxidation. Cobalt was used as the catalyst and gasification was performed in the temperature range of 500–700 °C. BET surface area and pore volume of catalytically modified carbon fiber were analyzed by N₂ adsorption. BET surface area of the original CH700-20 was 1,711 m²/g, and the mesopore volume percentage was 11.9%. After catalytic gasification, BET surface area was similar to the original CH700-20, while mesopore volume percentage increased up to 56%. The average pore size of mesopores was 3–4 nm in diameter. The average size of mesopores could be controlled with nanometer resolution by varying the temperature and time of activation.     

Interfacial bonding and optical transmission for transparent fiberglass/poly(methyl methacrylate) composites

Evidence is presented relating the interfacial bonding strength and the optical transmission of transparent glass fiber reinforced PMMA composites. The temperature dependent (20° to 50°C) optical transmission of composites that contained uncoated 13 μm glass fibers and 13 μm glass fibers coated with divinyltetramethyl disilazane or 3-(trimethoxysilyl)propyl methacrylate was found to decrease in the same order as the bond strength of the PMMA/glass fiber interface, namely, trimethoxy silane coated fiber, disilazane coated fiber, and uncoated fiber. SEM photographs showed similar fracture surfaces, clean fiber pull-out, and no apparent bonding of the glass fiber to the PMMA for the composites containing uncoated and disilazane coated fiber, whereas, the composite containing trimethoxy silane coated fiber showed virtually no clean fiber pullout. Additional evidence for differences in the bonding strength is seen in the degradation (penetration of water and fiber whitening) on aging at 23°C in air or water for composites containing uncoated fiber (most degradation), disilazane coated fiber (slight degradation), and trimethoxy silane coated fiber (no degradation). The optical transmission between 20° and 30°C at 600 to 800 nm for the composite containing trimethoxy silane coated fiber decreased the least with increasing temperature (from ∼85% to 70%) while the composite containing uncoated fiber decreased the most (from ∼85% to 32%).     

Catalytic reduction of nitric oxide by methane over CaO catalyst

The selective catalytic reduction of nitric oxide by methane was studied over CaO catalyst in a bubbling fluidized bed in the temperature range of 800–900 °C, in which NO cannot be reduced by CH₄ without CaO catalyst. The nitric oxide conversion was found to depend on oxygen and CH₄ feed concentration, and also on temperature. In addition, the presence of water vapors in the flue gas enhanced the NO reduction admirably well in the absence of O₂. But water vapor has an inhibiting effect on the reaction while O₂ is present in the flue gas. The addition of CO₂ poisoned the CaO catalyst and exhibited a detrimental effect on NO conversion at the working temperature range, 800–900 °C. However, with a temperature rise to 900 °C the CO₂ poisoning effect on NO reduction was weakened. The mechanism was studied and discussed according to the references in the paper. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

In Situ Gas–Solid Reaction and Oxidation Resistance of Silicon Carbide Coating on Carbon Fibers

Silicon carbide (SiC) coating on carbon fibers was realized based on in situ low‐temperature gas–solid reaction processing in which carbon reacted with Si vapor at the temperature of 1200°C–1300°C. X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), and energy‐dispersive spectroscopy (EDS) analysis showed that the SiC coating was uniform and crystallized by beta‐SiC. The oxidation resistant properties of the SiC‐coated carbon fibers were significantly improved according to isothermal oxidation measurement. The initial oxidation temperature of the SiC‐coated carbon fibers was about 200°C higher than that of the raw carbon fibers. The SiC‐coating carbon fibers treated at 1250°C possessed higher antioxidant property than the one treated at 1300°C.     

Synthesis of a silicon carbide coating on carbon fibers by deposition of a layer of pyrolytic carbon and reacting it with silicon monoxide

A method for preparing a SiC coating on carbon fibers is presented. The SiC coating was generated from the reaction of silicon monoxide (SiO) with a pyrolytic carbon (PyC) layer deposited on the fibers. The influence of holding time on the microstructure of the SiC layer was discussed. The oxidation behaviors of the uncoated and SiC coated carbon fibers were compared. The formation mechanism of the SiC coating was evaluated. With increased reaction time, the SiC coating becomes thicker and its surface becomes rough. The oxidation resistance of the carbon fiber was improved by the SiC coating. The initial oxidation temperature of the SiC coated carbon fiber is about 200 °C higher than that of the uncoated carbon fiber. The growth of the SiC coating is mainly attributed to the indirect reactions of SiO with PyC in the SiO/SiC/C system, in which silicon is considered a critical intermediate product.     

Oxidation protection of C/C composites with a multilayer coating of SiC and Si + SiC + SiC nanowires

An oxidation protective Si–SiC coating with randomly oriented SiC nanowires was prepared on the SiC-coated carbon/carbon (C/C) composites by a two-step technique. First, a porous network of SiC nanowires was produced using chemical vapor deposition. This material was subjected to pack cementation to infiltrate the porous layer with a mixture of Si and SiC. The nanowires in the coating could efficiently suppress the cracking of the coating by various toughening mechanisms including nanowire pullout, nanowire bridging, microcrack deflection and good interaction between nanowire/matrix interface. The results of thermogravimetric analysis and thermal shock showed that the coating had excellent oxidation protection for C/C composites between room temperature and 1500 °C. These results were confirmed by two additional oxidation experiments conducted at temperature of 900 and 1400 °C, which demonstrated that the coating could efficiently protect C/C composites from oxidation at 900 °C for more than 313 h or at 1400 °C for more than 112 h.     

Carbon nanotube wires for high-temperature performance

We developed carbon nanotube wires (CNWs) and monitored in situ their electrical properties at high temperature conditions for the first time. The dominant type of CNTs present in the material and packing density of thereof proved to have a dominant effect on the thermal stability of CNWs. Furthermore, we showed that kinetics of CNW oxidation plays an important role and slow heating rates or prolonged heating times are essential for the proper determination of thermal stability of CNTs. To enhance the stability at high temperatures, we applied SiC coating onto the CNWs, what allowed a 300 °C improvement to the operational window, eventually reaching 700 °C in the long-haul. Correlation of the change in electrical properties with thermogravimetric response showed that the loss of electrical percolation takes place at 100 °C lower temperature than the last observed weight loss in CNTs content. Finally, we demonstrated feasibility of SiC-coated CNWs under high temperature conditions, by creating a heating device out of them. The presence of SiC layer gave rise to a significant improvement to the thermal stability of the CNT heaters, which now offer unprecedented range of operation reaching 700 °C, as compared to 400 °C when uncoated.     

Preparation and characterization of sol–gel Al2O3/Ni–P composite coatings on carbon steel

Ceramic films have been applied to improve the resistance against high temperature oxidation of carbon steels. Alumina film was prepared on carbon steel surface by a dip coating technique. Electroless Ni–P plating film has been pre-deposited as an intermediate layer to improve the adherence of the film to carbon steel substrate. The oxidation kinetics of coated sample was investigated by measuring weight gain at 800 °C for 100 h. The surface and cross-section morphology of samples before and after oxidation were characterized by scanning electron microscopy (SEM). The composition and element distribution at the interface of the coated samples were analyzed by energy dispersive spectroscopy (EDS) and EMAX.The results show that the composite coating is uniform. The alumina coating adhesion strength to the substrate is up to 20 ± 2 N in scratch test because the alumina film presents interdiffusion of nickel and aluminum during heat treatment. The oxidation resistance test indicates higher oxidation resistance of as-coated carbon steel comparing to uncoated ones.     

Dynamic oxidation resistance and residual mechanical strength of ZrB2-CrSi2-SiC-Si/SiC coated C/C composites

To improve oxidation resistance of carbon/carbon (C/C) composites, a multiphase double-layer ZrB₂-CrSi₂-SiC-Si/SiC coating was prepared on the surface of C/C composites by pack cementation. Thermogravimetry analysis showed that the as-prepared coating could provide effective oxidative protection for C/C composites from room temperature to 1490 °C. After thermal cycling between 1500 °C and room temperature, the fracture behaviors of the as-prepared specimens changed and their residual flexural strengths decreased as thermal cycles increased. The specimen after 20 thermal cycles presented pseudo-plastic fracture characteristics and relatively high residual flexural strength (83.1%), while the specimen after 30 thermal cycles failed catastrophically without fiber pullout due to the severe oxidation damage of C/C substrate especially the brittleness of the reinforcement fibers.