Carbon Nanofibers. Группа авторов
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It is possible to control the length of carbon nanofibers by controlling the rate of gas flow in the quartz tube (C). In addition, direction of fiber growth can also be controlled by adjusting the direction of gas flow. If adjusted properly, the variable parameters of the process can yield CNF with submicrometer diameters and lengths of a few to 100 μm.
Figure 1.8 A sketch of a typical CVD unit. A1 and A2 are two furnaces operating at two different temperatures. B1 and B2 are two quartz boats used for keeping precursor and catalyst respectively. CNF is grown on the boat B2 as well as over the entire area covering the furnace A2, C is the quartz tube in which growth of CNF takes place, D is ceramic tube over which heating wire is wrapped to create required temperature, E and F are gas valves and flow meter to regulate flow rate of gas. G is a gas bubbler to prevent backflow of gas into the quartz tube and allow the escape of unreacted gas into the atmosphere, H is the gas cylinder containing the carrier gas and K is precursor gas like methane or acetylene.
1.3.2 Precursors for CNF
Precursor for synthesizing CNF can be several types of hydrocarbons such as natural oils like mustard oil, pure fatty acids (liquid or solid), camphor, terpene oil, acetylene, ethylene, methane, natural gas, benzene, etc. Introduction of carbon monoxide (CO) into the gas flow can increase the carbon yield, hence yields a greater amount of CNF. It is also possible to use plant seed materials like mustard seed, stem of any plant, plant leaves, bamboo, rice straw, bagasse, etc. It is also possible to use some gasses directly like methane, acetylene, etc. When using solid materials like plant leaves, there is no need to use the furnace (Figure 1.8A1). These precursors can be kept directly in the boat (Figure 1.8B2) along with any catalyst (if needed). If gases like methane are to be used as a precursor then there is also no need to use the furnace (Figure 1.8A1). Gas from the cylinder (Figure 1.8K) can be sent to the furnace (Figure 1.8A2) where suitable catalyst is kept in the boat. The precursor gas can either be directly fed into the unit or is mixed with carrier gas in the required proportion.
1.3.3 Use of Catalyst in the Synthesis of CNF
There are variations in the type of catalyst used for the synthesis of CNF. There are some catalysts which are solid like ferrocene, cobaltocene, etc. These catalysts vaporize in the temperature range of 300 to 400 °C. Such catalysts are kept in a boat (Figure 1.8B1) in the furnace (Figure 1.8A1) along with the precursor like oil. The vapor of oil and the vapor of catalyst like ferrocene are carried with carrier gas to the furnace (Figure 1.8A2). Catalyst decomposes into its metal oxide and in-situ reaction takes place with the vapor of oil to produce CNF. These CNFs are collected in the boat (Figure 1.8B2).
Catalyst can be used either in the form of powder or as a thin film deposited on a substrate like quartz glass, alumina plate, or as a metal plate like nickel, iron metal, etc. Normally, after scratching a metal plate with diamond powder it is cleaned with water and dried with acetone, which is also used as a catalyst. Scratching the plate creates more roughness of the metal, which produces more surface states and surface area over which the reaction of vapor of precursor reacts more favorably with catalyst. The preferred size of catalyst particles should be in the range of 5–25 nm in diameter. Some examples of the role of different types of catalysts and their effect on the carbon nanomaterials produced are shown in Figure 1.4.
There is no hard and fast rule to suggest which type of catalyst will produce better CNF. Better CNF means the value of its diameter, length, surface area and surface states. Selection of catalyst and its type depends upon the type of precursor and size of catalyst powder, which can only be decided by carrying out some specific experiments. Powder or thin films of Fe/Ni, Ni, Co, Mn, Cu, V, Cr, Mo, Pd, MgO, and Al2O3 are used as catalyst. But most popular catalysts are powder or thin film of organometallic compounds of iron or nickel or cobalt. Details of the use of different catalysts are presented in Chapter 3 of this book.
1.3.4 Selection of Variable Parameters for Growth of CNF
Variable parameters of pyrolysis under the CVD units are: precursor (oil, solid materials like plant materials, camphor, etc.), temperature (Figure 1.8A1 and A2), type and size of catalyst (usually nickel, iron and cobalt), carrier gas (argon, nitrogen, etc.), reactive gas (hydrogen), and duration of pyrolysis. Due to the large number of variables, it becomes very time-consuming to reach a suitable condition to obtain the desired type of CNF.
It is advisable that one should adopt the Taguchi method, which can provide information of effective variables to produce the required type of CNF [1–3]. For example, with 4 variables (requires 24 experiments) one needs to carry out only 9 sets of experiments; whereas, with 6 variables (requires 720 experiments) one needs to carry out only 16 sets of experiments.
1.3.5 Epitaxial Growth of Aligned CNF
Afre et al. [8] have developed a CVD with spray techniques (Figure 1.9A) to get epitaxial growth of aligned, continuous (Figure 1.9B), catalyst-free carbon nanofiber from vapor of turpentine oil. Aligned CNF possesses properties like high mechanical strength, high directional electrical conductivity, and high thermal conductivity. The main difference between the CVD unit described in Figure 1.8 and 1.9 is the inclusion of a spray facility so that solution containing precursor and the catalyst sprays its liquid in the furnace like a cloud of material.
1.3.6 Mechanism of CNF Synthesis
There are different mechanisms suggested to explain the role of catalyst but none of them can explain why CNFs