ion NEM Materials, 7 ul nt ; CATION OF ENGINEERING MATERIALS: wu ¥en engineetns materials are classified into following six groups: ot Composites yavanced materials COMPOSITES: , (June 2014 (5 Marks), 2015 (5 Marks); Dec. 2014 (5 Marks)} 63 Composites are combinations of two or more different materials with significantly sero physical or chemical Properties which remain separate and distinct at the macroscopic aT croscopic scale within the finished structure. Each of the various compore oti in ORE composite and maintains its characteristics structure and properties. Composite ide reals aF€ generally possesse stiffness, strength, high-temperature performance, corrosion mal ess, and conductivity. Analysis of these properties shows that they depend on stance, +. ~ pers of individual components, the shape, size and distribution of cis Pnponents, the orientation of components and the degree of bonding between compone sls involved can be organics, metals or ceramics which gives 2 wide range of rerious materi freedom. 62 CHARACTERISTICS OF COMPOSITES: (i) Composite materials are superior to all other known structural materials in specific strength and stiffness, high-temperature strength, fatigue strength and other properties. The desired combination of properties can be tailored in advance and realized in the manufacture ofa particular material. (ii) Composite materials are complex materials whose components differ strongly from each other in the properties, are mutually insoluble or only slightly soluble and divided by distinct boundaries. (ii) The principle of manufacture of composites has been borrowed from nature. Trunks and stems of plants and bones of man and animals are examples of natural composites. (iv) The properties of composites mainly depend on the physicomechanical properties of their components and the strength of bonds between them. A characteristic feature of composite materials is that the merits of their components are fully utilized. (¥) The base, or matrix, of composites, may consist of metals or alloys (metallic composites), polymers, carbon and ceramic materials (no metallic composites). (vi) The matrix is essentially the binding and shaping component in composites. Its properties determine to a large extent the process conditions for the manufacture of composite materials and the important operating characteristics, e.g., working temperature, fatigue re strength, resistance to environmental effects, density, and specific strength. Vii)Composites with combined matrix may be called multi-matrix, or multi-layer composites Multi-matrix composites can be characterized by a wider spectrum of useful properties. For example, use of titanium as an addition to aluminium may increase the strength of a Composite material in directions transverse to fibers.Is are uniformly Ce. « f composites and thus they are called strengthenera, py hardness, and clastic modulus. (viii) Fillers, ie., other component major part in the strengthening 0! should possess high values of strength, There are three main divislg CLASSIFICATION OF COMPOSITES: classification is shown in Fig. 6.1 d structural compos 6.3 Composite materials particle reinforced, fibre-reinforced and struct ——~ Composites ' | | Particle reinforced Fibre reinforced Structural | tool Dispersion Continuous Discontinuous Laminates Sand) e (short) panel | strenghened (aligned) Aligned Randomly orlented Fig. 6.1: Classification of Composites composites, usually consists of These are a special class of ese composites depend not only te materials. Properties of th but also on the geometrical design of various structural ” widely used are, sed of two-dimensional layers that have a preferred strength direction. These layers are stacked and cemented together according to the requirement. Materials used in their fabrication are metal sheets, cotton, paper, ~ woven glass fibers embedded in a plastic matrix, etc. Many laminar composites are” designed to increase corrosion resistance while retaining low cost, high strength or light weight. Safety glass is a laminate in which a layer of polymeric adhesive is placed between two pieces of glass and serves to retain the fragments when the glass is broken. Laminar composites are shown in Fig. 6.2. (a) Structural Composites: homogeneous and composit the properties of the constituents elements. Two classes of these composites (i) Laminar Composites: There are compo: Fig, 6.2: Laminar Composites 4 tures: These consist of thin layers of a facing material joined to alight Neither the filler material nor the facing material is strong te possesses both properties. The faces bear most of the i i) Sandwich struc! weight filler material. sd bot the composiNew Materials 0 yw + alo wwe 229 Joading ae al ‘ f ony raneverse bending atresges, 7 alloys, fiber-reinforced plastics, titaniun® steel a Plc face materials include Al- / steel, an junctions, It separates the faces and resists Plywood. The cote serves two rovides a certain de, «ts deformations i ra Fico. ‘Typical raaterials Gee Tigidity along Pane araes eee = : organic cement and balsa wood, +e are foamed polymers, Ses at inorgt . Sandwich struct 8, synthetic rubbers, ike roofs, floors, walls of buildings a ures are found in many applications 0 nd i skins, Sandwich structures are shown in Fig, gc) tO” Wins fuselage, and tail plane 4 Face sheet 7 >” 3: Sandwich Structures (b) Particle-Reinforced Composites: It consists of discrete particles of one material surrounded by a matrix of another material. Concrete is the best example of this type, consisting of sand and gravel particles surrounded by cement. The particle reinforced composites are, (i) Dispersion strengthened composites: These composites contain small amount of hard, brittle, small particle of oxides and carbides which can disperse throughout in a softer and ductile matrix. The strengthening occurs at the atomic level ie, mechanism of strengthening is similar to precipitation hardening in metals where matrix bears the major portion of an applied load. An example of dispersion strengthened materials includes sintered aluminum powder (SAP) where aluminium matrix is dispersed with extremely small flakes of alumina (Al,Os), thoria (ThO:) dispersed Ni-alloys (TD Ni- alloys) with high-temperature strength. Dispersion strengthened composites are shown in Fig, 6.4. Particles Fig. 6.4: Dispersion strengthened composites ; (ii) Particulate composites: These contain large amounts of comparatively coarse particles. These ornate are designed to produce unusual combinations of properties rather than to improve the strength. Particulate composites are used with all three material types: metals, polymers, and ceramics. Cermets contain hard ceramic particlesoo” Vipuite™ Material tech, 230 www 7 i lic matrix. An example of particulate composite materials inety tages tide (tae C0 ee ma oat & : ently rei icuy waters ach ie ere to ae ae Satbon by enhances toughness and sbrasion resistance of i rubber rs ty containing dispersed SiC particles are picelraesedl coon se en aie medium and finely dispersed Patticuta of gravel in addition to fine aggregate (sand) and water. tm paride improve (©) Fiber-Reinforced Composites: Most fiber-reinforced compos tes provide imp ¥€8 re I properties and strength-to-weight ratio, TX suppor. ie Sar fiber, rotects them from environments and handling and Prov ee shes while ber carries most ofthe load and imparts enhance Stiff te Sieaeee es of fiber-reinforced composites depend on the Properties ie mae a iH of applied load transmitted to the fibers by the matrix phase. The len, tate thei crintaten and volume fraction in addition to the cirection of externa} |, application affects the mechanical Properties of these composites Automobile fibers of nylon, rayon, aramid or steels in various numbers and orientations to rein, rubber and provide added strength and durability. Fiber-Reinforced C in Fig. 65. force ‘omposites are. MWg | " nn i Discontinuous and randomly orlented fibers fibers. (ii) Graphite: These are poy I ah Organic fiber with 31 ; th, ders! approximately one-half that of alumini 4 good oie ay meen &xpansion Coefficient. It ig flame tetardant and tra attractive for a numb mili er of milita, and temperature is not excessive, a anejon to New Materials ti ‘li Carbide: Thes, jy) Silicon \ 3 ‘oe CSE Material iv IS hay, wr ae sto wo materials generat, EME mod cH flaws. When these materials are sed ly fail ude a Of elasticity. 7, the failure of individual fiber and not the : fiber e peat i dlue to the Propagat neh gavanced Fiber Reinforced Composites eNtire assembiye etM of flaw one leads iS @ J pptications Tequiring exceptional * These - combinati Materials . superior TeeP and fatigue Tesistance, low Ons of strength, stir been devel = pration damping characteristics an ther = loped 88 and light A ; den Mal expansion, (ess 2S light wei repair in these materials. The advang wronmenta side f | sti bh W friction and w i ele ed composites ety ate other properties th ee i iN matrix . y ms a modulus of fibers of 8taphite, ara Posites: These Materials use hi service temperature of about ise a boron. These materials igh a i eas am ~ t heating. The typical applications of this tyre Pelymetric Matrix loses strength after rackets, golf clubs, and fishing poles, Sporting equipment such as tena (ii) Metal matrix composites (MMCs); temperatures up to 1250°C, where the a onaterials can be used for ti cont: for operating nditions Fequire high strength coupled with , these composites offer e temperature, a lower thermal exansion and nee i abrasion and wear. Alum: aluminium has been used in au (ii) Carbon-carbon composites: Graphite fibers in a carbon matrix offer the ity of heat resistant material that could operate at temperatures up to 33005, with aa that is 20 times that of conventional graphite and a density is 30% lighter. These materials withstand strength at high temperatures. The composite requires some form of a coating to protect it from oxidizing. Various coatings can be used for different temperature ranges. Applications of this materials include racing car disc brakes, aerospace turbines and jet engines components, rocket nozzles and surgical implants. (iv) Ceramic matrix composites (CMCs): These materials offer light weight, high- temperature strength and good dimensional and environmental stability. Glass matrix can operate at 1500°C temperature. The crystalline ceramics usually based on alumina, silicon carbide, silicon nitride, boron nitride or zirconia can be used for even hotter conditions. The fibers add additional strength, increase fracture toughness reg thermal shock resistance. Typical reinforcements include carbon fiber, glass fiber, fiber of various matrix materials and ceramic whiskers. S: 64 ADVANTAGES, LIMITATIONS AND APPLICATIONS OF COMPOSITE (0 Advanta ites: le with iges of Composites: , often comparable wi (@ Composites have high stiffness, strength, and toughness, Di" Cot ia II structure is lighter in weight @ compelling structural metal alloys. The overa ‘ght savings might be a comp devices such as airplanes or spacecraft these weight © ed t A fo gy aianiee. erties in different directions an this can i fferent prop! tresses are Somposites can re a ae In many structures eat the circumferential fe a more e jen instance, in closed-end press! ifferent directions; for "232 () (d) (e) (f) ® ava Vipul’s™ tateria) tony stresses are twice the axial stresses. Using composites, such a vessel can be ma as strong in the circumferential direction as in the axial. Composites have excellent fatigue resistance in comparison with metal alloys, Composites have relatively high levels of damping and furthermore, the damping often be tailored to desired levels by suitable formulation and processing. Composites can be excellent in applications involving sliding friction, with tribolo, properties approaching those of lubricated steel. Composites do not rust and resistance to this common form of enyiro, minen degradation may offer better life-cycle cost even if the original structure is initial more costly. Composites offer a lot of flexibility in processing and property control and this often leads to possibilities for part reduction and simpler manufacture. (2) Limitations of Composites: (a) (b) (c) (d) (e) Manufacturing of composites is quite labor intensive and there is a lack of establishe; design guidelines and data, information about fabrication costs and well- -developed quality control and inspection methods. It is difficult to predict the interfacial bond strength, the strength of the composite, is response to impacts and probable mode of failure. Defects can involve delaminations, voids, missing layers, fiber breakage and hard to detect improperly cured resin. Most composites have limited ability to be repaired if damaged, preventive maintenance procedures are not well established and recycling is difficult. Assembly operations with composites require the use of industrial adhesives. (3) Applications of Composites: (a) (b) ©) (d) Composites are suitable for Aerospace applications which required light weigtt stiffness and fatigue resistance. Sporting equipment such as golf club shafts, baseball bats, fishing rods and tenn’s rackets. Bicycle frames are also available in a variety of fibrous composites. Composites are useful in an automobile such as body panels, drive shafts, spring bumpers, oil pans, instrument panels and engine covers.EE EEE ELE TIS INE Cit a tistics of high-temperature materials are, e ability to withstand loading at an operating temperature close to its melting poing, ) Substantial resistance to mechanical degradation over extended periods of time. (c) Structural materials, the static properties of yield stress, ultimate tensile strength fracture toughness are also important and these must be maintained over time. (d) Tolerance of severe operating environments. For example, the hot gases generated fired electricity-generating turbine are highly corrosive due to the high sulfur | charge. In these cases, the high operating temperatures enhance the possibility of oxi Under such conditions, any surface degradation reduces component life. 6.7 NANO MATERIALS: [une 2014 (5 Marks), Dec. 2014 (6 Ma The discovery of fullerenes and carbon nanotubes has opened a new resear physics, chemistry and material science. Nanostructured materials may be defined materials whose structural element clusters, crystallites or molecules—have dime: to 100 nm range. Clusters of atoms consisting of typically hundreds of thousan nanometer (nm) scale are commonly called as nanoclusters. These small groups of general, go by different names such as nanoparticles, nanocrystals, quantum dots and boxes. Substantial work is being carried out in the domain of nanostructured mat:nanotubes in the Past one decade. The explosion in both academic and industrial interest in these materials Ver ce past decade arises from the remarkable variations in fundamental , optical an magnetic Properties that occur as one progresses from an ‘infinitely Srended soli a particle of material consisting of a countable number of atoms. tructured materials have led to new basic sci ; Naor Cum and long term. science phenomena and several applications for The number of products produced by nanotechnology or containing nanomaterials entering the market is increasing. Current applications include healthcare (is targeted drug delivery, regenerative medicine, and diagnostics), electronics, cosmetics, textiles, information ology and environmental protection. For example, nanosilver is appearing in a range of products, including washing machines, socks, food packaging, wound dressings and food supplements. Food supplements need especially close scrutiny. Carbon-based nanomaterials and nanostructures including fullerenes and nanotubes play an increasingly pervasive role in nanoscale science and technology. Carbon nanotubes are currently being studied in an effort to understand their novel structural, electronic and mechanical properties to explore their immense potential for many applications in nanoelectronics, and as actuators and sensors. Fullerenes and carbon nanotubes can be seen as curves pieces of graphite. Graphite is another polymorph of carbon. (1) Graphite: Graphite has a crystal structure distinctly different from that of diamond and is also more stable than diamond at ambient temperature and pressure. Graphite is formed by flat hexagonal layers of carbon atoms separated 3.35A. The C-C distance is 142A and the structure belongs to P 63 me space groups with lattice constants a = 2.46 A and c = 6.71 A, Graphite is highly anisotropic solid, structurally it's more interplane interplana spacing (3.35 A) is quite large compared to the in plane interatomic spacing (1.42 A). Physically its stiffness along the plane is quite large because of strong _ bonds and in the perpendicular direction, it is weak because of the Vander Waal’s force. The. graphite structure is composed of layers of hexagonally arranged carbon atoms; within the layers, each carbon atom is bonded to three coplanar neighbor atoms by strong covalent bonds. Other desirable properties of graphite include high strength and good chemical stability at elevated temperatures and in none oxidizing atmospheres, high thermal conductivity, low coefficient of thermal expansion and high resistance to thermal shock, high absorption of gases, and good machinability. Graphite is commonly used in heating elements for electric furnaces, as electrodes for ac welding, in metallurgical crucibles, in casting moulds for metal alloys and ceramics, for high temperature refractories and insulations, in rocket nozzles, in chemical reactor vessels, for electrical contacts, brushes and resistors, as electrodes in batteries, and in air purification devices. There are other layered materials which also can acquire curvature to generate new nanomaterials with novel applications. The other types of nanostructured materials which have been considered for applications in optoelectronic devices and quantum-optic devices are nanosized powders of silicon, silicon-nitride (SiN), silicon carbide (SiC) and their thin films. Some of these nanomaterials, e.g. SiC and SiN are also used as advanced ceramics with controlled microstructures because their strength and poushness increase when the grain size diminishes. The structure of Graphite is shown in ig. 6.6.ee Fig. 6.6: The structure of Graphite a holt lerenes: ist in discrete molecular form and consist of a hollow. ° a of ee eee a single molecule is denoted by C60. Each mo compesed of groups of carbon atoms that are bonded to one another to form bo (sixcarbon atom) and pentagon (five carbon atom) geometrical configurations molecule, is found to consist of 20 hexagons and 12 pentagons which are arrayed 5 no two pentagons share a common side; the molecular surface thus exhibits the symm, ‘soccer ball. Fullerenes are large, closed-cage, carbon clusters and have several special propertie were not found in any other compound before. Therefore, fullerenes in general form interesting class of compounds that surely will be used in future technologies applications. Before the first synthesis and detection of the smaller fullerenes C60 and C79 was generally accepted that these large spherical molecules were unstable. However, so; Russian scientists already had calculated that C60 in the gas phase was stable and had relatively large band gap. A structure of fullerenes is shown in Fig. 6.7. a One su ; Fig. 6.7: Structures of Fuller As is the case with numerous, mars i i , important Scientific di ies, fullerenes W' accidentally discovered, In 1985, Kroto liscoveries, evaporated carbon samples. Herewith, ful suley found strange results in mass spect ‘erenes were discovered and their stability inint The was proven. The search for other fulle gos PI of diferent shapes and sizes, such as llerenes had sated, There are many othe notube structure: With th i ; on Nanotube pues € Tevolutionary discovery of so-called fullerenes and @ * pon Tesearch fields in the dot i f main of carbon experienced an cat mous boom: Fullerenes are spherical molecules, the smallest of which composed of 60 ‘pon atoms that are arranged like the edges of the hexagons and pentagons on a football. a notubes can BE poate as a rolled-up tubular shell of the sgaphene sheet, which is made of benzene-type lexagonal tings of carbon atoms. The body of the tubular shell is thus nly made of hexagonal rings (in a sheet) of carbon atoms, whereas the ends are capped by half-dome shaped half-fullerene molecules. Due to their special one-dimensional form, they have interesting physical Properties like they have metallic or semiconducting electrical conductivity depending on the chirality’s of the carbon atoms in the tube. Nanotubes have a large geometric aspect ratio and they are the first nanocavities. This and other properties one _would like to use in different applications e.g. as an electrode material in super capacitors and hydrogen storage material for the fuel storage or as field emitters in flat panel displays. Carbon nanotubes may be classified into three different types: armchair, zigzag, and chiral nanotubes depending on how the two-dimensional graphene sheet is ‘rolled up’. The first of the three structural categories is zigzag, which is named after the pattern of hexagons as one move circumferentially around the body of the tubule. The second of these nanotube structures is termed armchair, which describes one of the two conformers of cyclohexane, 2 hexagon of carbon atoms, and describes the shape of the hexagons as one move around the body of the tubule. The third form is known as chiral and is believed to be the most commonly occurring SWNT. The name chiral means handedness and indicates that the tubes may twist in either direction. The geometry of the chiral SWCNT lies between that of the armchair and zigzag SWCNTs. It is shown in Fig. 6.8. Fig. 6.8: The Structure of Nanotubeshich are known jque nanostructures Which 7 renaslable ee ates generar per These Se ee i mechanic: . CNTs i in thei ible uses for nano-electronic and nanom arcdesticnmnduies of greater than 1 TPa (that of a diamond is Paae) and strength 104d times higher than the strongest steel at a fraction of the weight eee a ele current i i i wires. ound t carrying capacity 1000 times higher than copper s have an extremely large breaking strain which decreased with temperature. In the T-tigh i anotubes are me! binding model within the zone folding scheme, coe aan eee ar eae two-thirds are semiconducting depending on the! may induce oxidative stro jotubes that arise during the production process may on pulmonary inflammation. Studies collectively show that regardless Of the proce 5 i: ind amounts of metals they conta Ci anhich CNTs wore synthesized a ie mato ‘i epithelioid granulomas (micros, 4 CNTs were capable of producing inflammation, epith a ‘OScopie nodules), fibrosis, and biochemical toxicological changes in the lungs. ie needle-like fiber shape of CNTs, similar to asbestos fibers, raises fears that widespread use of carbon, Ranotubes may lead to mesothelioma, cancer of the lining of the lungs often caused by exposure to asbestos. Although further research is required, results presented today ¢| eatly demonstrate that under certain conditions, especially those involving chronic expos carbon nanotubes can pose a serious risk to human health. Therefore, their use has to assagg the whole life cycle of the product and its proper disposal. The unique properties of both the single-walled and multiwalled varieties of carbon nanotubes have led to several studies in modern physics, resulting in applications in 2 wide variety of materials and devices. CNTs’ small size with larger surface area, high sensitivi and fast response to gas molecules and good reversibility at room temperature enable them as gas molecule sensors, high electrical conductivity, and chemical stability make them good electron emitters, carbon nanotubes are also being considered for energy storage and production because of their small dimensions, a smooth surface topology, and perfect surface Pilsen they are also used in scanning probe tips or as a composite on airplane wings lages. NanoBuds: Carbon NanoBuds are a newly discovered material combining two previously discovered allotropes of carbon: carbon nanotubes and fullerenes. In this new material, fullerenes are covalently bonded to the outer sidewalls of the underlying nanotube instance, the mechanical Properties and the electrical conductivity of the NanoBuds are similar to those of corresponding carbon nanotubes, however, because of the higher facil of the atiached fullerene molecules, the hybrid material can be further pees ved th rou a fullerene chemistry, Additionally, the attached fullerene ee as mol lecular anchors to prevent slipping of the nanotubes in various 1p aterials, thus improving the composite’s mechanical Properties. It is shown inae Fig, 6.9: Different Structures of NanoBuds. (6) Carbon Nanofibers: Nanofibers consist of the graphite sheet completely arranged in various orientations. One of the most outstanding features of these structures presence of a plenty of sites which in turn make sites, with readiness accessible to chemical or physical interaction, ly adsorption. Carbon nanofibers change from 5 to several hundred microns in length and between 100-300 nm in diameter. From electronic microscopy studies, it was possible to define a sequence of the events leading to the formation of carbon nanofibers. Fig.6.8 shows schematically the key steps of the growth of the carbon nanofibers. When a hydrocarbon is adsorbed on a metal surface (A) and condition exist that favor the scission of a carbon-carbon bond in the molecules, then the resulting atomic species may dissolve in the particle (B), diffuse to the rear faces, and ultimately precipitate at the interface (C) to form a carbon nanostructure. The composition of the reactant gases and the reaction temperature control the degree of crystalline perfection of the deposited fiber (D) and is also dictate chemical nature of the catalyst particle. In this special case, a plate of graphite oriented itself in a “herringbone” classification. Surface science studies have revealed that certain faces prefer precipitation of the carbon in the form of the graphite. The choice of the catalyst, the relation of the hydrocarbon/hydrogen reactant mixture, and reaction conditions control the morphological qualities, the degree of crystallinity and the orientation of the precipitated graphite crystallites with regard to the fiber axis. It was pointed out that the distance between graphite is 0.34 nm separate from layers one of another one. This spacing can be increased by introducing selected groups between the layers, a process known as intercalation, thereby generating new types of sophisticated molecular sieves. Such unique structural conformations found in carbon nanofibers open Up numerous possibilities in the fabrication of new materials.5 Metal Catalyst Particio [] | Graphite Platelets —> }4—Interlayer Spacing Fig. 6.10: Schematic diagram of a Catalytically Grown Carbon Nanofiber Itis possible to make nanofibers, which will consist completely is, show double structure depending on crystallographic to the ori which exist in the metal-carbon interface. Over the past few performed a very comprehensive of plates of graph, entation of cataly years, many researchers evaluation of the potential of a number of luction of carbon nanostructures. From the da from some experiments, it appears that certain nickel- and iron-based alloys are amo; most effective catalysts for the reaction The “herringbone structures" of the carbon nanofiber are frequently found when catalysts are used in the nanofiber process, it has been found that it is possible to tail oe Fig. 6.11: High-resolution Electron Micro; nanofibers with their Staphite platelet gtaphs and schematic representation of Car! ts, (a) Perpendicular (b) Parallel to the fiberoe po «eg; Fullerenes and CNT are h [ ollow, ig nator elements and compounds Ine eine ere ert eo ete giro ee ar discharge with a metal 4 metal inside CNT might form a nanowire gang eorsea A difficulty with the m paaes inside the anode produces CNT filled with petal ee this wright affect the pvr od mentioned above is that the tubes are filled arta SF we use small amounts of ity properties. It is found that nanotubes could be fled MOT? od. Moreover, the selenium, sulfur, and germanium with the electric arc é © The tubes can be pees Si jremical techniques in which by nitric acid rreatments : en materials such as palladium, silver, gold pal i ured Sete molybdenum, tin, pes iamnt en i cadmium . interior. It is important to know that en zy Tes d 0 nave been nanotubes. Capillarity effects have also been cel eee elements inst ee ut ca tin, lead, bismuth, cesium, sulfur, and selenium Nanowires ave been used prepare ultimately interconnects in integrated circuits. gpeCiAL PROPERTIES OF CARBON NANOTUBES: Electronic, molecular and structural properties of carbon nanotubes are determined to a see exter py their nearly one-dimensional structure. The most important properties of carbon : e naterial and their molecular background are stated below. a Chemical Reactivity: The chemical reactivity of a Carbon Nanotubes (CNT) is, compared with a graphene sheet, as a direct result of the curvature of the CNT surface. Carbon nanotube reactivity is carectly related to the pi-orbital difference caused by an increased curvature. Therefore, 2 difference must be made between the sidewall and the end caps of a nanotube. For the same wesson, a smaller nano tube diameter results in increased reactivity. Covalent chemical “ocifcation of either sidewalls or end caps thas shown to be possible. For example, the solubility cECNTs in different solvents can be controlled this way. Though, direct investigation of chemical odifications on nanotube behavior is difficult as the crude nanotube samples are still not pure 65 enough. (2) Electrical Conductivity: ing on their chiral vector, carbon nanotubes with a small diameter are either semiconducting or metallic. The differences in conducting properties are caused by the molecular structure that results in a different band structure and thus a different band gap. The differences in conductivity can easily be derived from the graphene sheet properties. It was shown that a (n, m) nanotube ig metallic as accounts that: n=m oF (n-m) = 3i, where ‘isan integer and n and m are defining the ‘nanotube, The resistance to conduction is determined by quantum mechanical aspects and was proved to be independent of the nanotube length. (8) Optical Activity: ; Theoretical studies have revealed that the optical activity of chiral nanotubes disappears if the nanotubes become larger. Therefore, it is expected that other physical properties are influenced by these parameters 100 rare ofthe optical activity might result in oplc devices in ich CNTs play an important role. (4) Mechanical Strength: ok Carbon nanotubes have a very large Young modulus in their axial direction e Nanotube as a whole is very flexible because of the great length. Therefore, these compound's are Potentially suitable for applications in composite materials that need anisotropic properties.PRODUCTION METHODS OF CARBON NANOTUBES AND CARR, NANOFIBERS: (June 2015 ¢5 fibers, vapor grown carbon fi, Differ +6 of carbon nanotubes, carbon nano! p 0 : other types ore carbon nano structure materials can be Ea ale ries ane common techniques used nowadays are arc discharge, laser abla on veal vap ; eposi Economically feasible large-scale production and purification rechniq ave ee d by an arc discharge between tw, ns In th discharge, a vapor is create: ; ae e electrodes with or without P catalyst In the laser ablation technology a high achievernen, | beam, impose to a volume of the carbon, containing feedstock gas (methane or monoxide), Now laser ablation produces avery small amount of pure nanotubes, whi. discharge method produces in general large amounts of the impure material. CVD seer; to the most promising. 6.9 [ARGE: “n ae discharge method, initially used for producing C60 fullerenes, is common and perhaps easiest way to produce carbon nanotubes as it is rather undertake. However, it is a technique that produces a mixture of components an separating nanotubes from the soot and the catalytic metals present in the crude pro. ti method creates nanotubes through arc-vaporisation of two carbon rods placed end to on separated by approximately 1mm, in an enclosure that is usually filled with inert gas ( argon) at low pressure (between 50 and 700 mbar). Recent investigations have shown tha: also possible to create nanotubes with the arc method in liquid nitrogen. A direct current of 3) 100 A driven by approximately 20 V creates a high-temperature discharge between the ~ electrodes. The discharge vaporizes one of the carbon rods and forms a small rod shaped depo on the other rod. Producing nanotubes in high yield depends on the uniformity of the plasma and the temperature of the deposit form on the carbon electrode. be single walled tubes or multiple walled nanotubes. This method is relatively easy to impleme: and will produce yields of 30%.The nanotubes produced contain more impurities compared t other methods, and the consistency of the shape, wall, and lengths of the tubes are somew random. Depending on the exact technique, it is Possible to selectively grow SWNTs or MWNTS) which is shown in Fig. 6.12, na ‘ r discharge apparent 6:12. Two distinct methods of synthesis can be performed with the @er / _ Hellum atmosphere, %, 400 mbar Graphite anode Plasma Deposit Graphite cathode | © 10 pumps : DC current sources. Multiwel nenouthos Fig. 6.12: Experimental set-up of an Arc Discharge Apparatus synthesis of Single Wall Nanotube (SWNT): If SWNTs are preferable, the anode has to be doped withmetal catalysts, su + Ni, Yor Mo. A lot of elements and mixtures of elements have been tested by various it is noted that the results vary a lot, even though they use the same elements. This is not surprising as experimental conditions differ. The quantity and quality of the nanotubes obtained depend on various parameters such as the metal concentration, inert gas pressure, kind of gas, the current and system geometry. Usually, the diameter is in the range of 1.2 to14nm. A couple of ways to improve the process of arc discharge are stated below. (1) Inert Gas: The most common problems with SWNT synthesis are that the product contains 2 lot of metal catalyst, SWNTs have defects and purification is hard to perform. On the other hand, an advantage is that the diameter can slightly be controlled by changing thermal transfer and diffusion, and hence condensation of atomic carbon and metals between the plasma and the vicinity of the cathode can control nano tube diameter in the arc process. This was shown in an experiment in which different mixtures of inert gases were used. It appeared that argon, with a lower thermal conductivity and diffusion coefficient, gave SWNTs with a smaller diameter of approximately 1.2 nm. A linear fit of the average nanotube diameter showed a 0.2 nm diameter decrease pet 10 % increase in argon helium tatio when nickel/yttrium was used (C/Ni/Y was 94,8:4.2:1) as a catalyst. Optical Plasma Control: A second way of control is plasma control by changing the anode to cathode distance (ACD). The ACD is adjusted in order to obtain strongly visible vortices around the cathode. This enhances anode vaporization, which improves nanotubes formation. Combined with controlling the argon helium mixture, one can simultaneously control the macroscopic and microscopic parameters of the nanotubes formed. : With a nickel and yttrium catalyst (C/Ni/Y is 94,8:4.2:1) the optimum nanotube veld was found at a pressure of 660 mbar for pure helium and 100 mbar for pure argon. TNS nanotube diameter ranges from 1.27 to 1.37 nanometer. Quld give SWNT, , (3) Catalyat: Knowing, that chemical vapor enema ae eer for on aaa 4 diameter (0.6-1,2 nm, researchers tried the same catal paea ee met h ot ie : “ esult in nanotubes fe catalysts used appeared to resu os sized by CVD) 4,18 then ec es Bae relation of diameter of SWNTs synthe: y ond ag here seemed to be a cv ek ly lowered to a range of 0.6-1.2 nen wirh ey. he diameter can be controllably atalyst results dichange Use mixture of Co and Mo in high concertina cay aul result These diameters are considerably smaller than 1.2-1/ D il ta: gained from arc discharge. pts in developing etn : There 1s also progr 5 vement of Oxidation Resistance: h i uence CF the. ° eo the oxidation resistance of the SWNTs, yeni a for the nanotubes Present in nanotubes. A strong oxidation resistance is a Recent research fag to be uned for applications such as field emission disp ane ae ch has i that a modified are-discharge method using a bowl-like ca ig. 6.13), eg defects and gives cleaner nanotubes, 8 | a) (b) | | Anode ‘Anode | Arc plasma. Oo Cathode Cathode dic and thus improves the oxidation resistance. Fig. 6.13: Schematic drawings of the electrode set-uj The Raman spectrum of th formed are cleaner and less def , methods. The anode rod contained Ni /Ni/Y is 94.8:4.2:1). No information is given about the diameter size, Open Air Synthesis with Only a couple of years ago, researchers discovered that it was Possible to form MWNT; (5; 'ps for (a) the conventional and the new are discharge electrodes, fe newly synthesized nanotubes shows that the nano fective compared with those synthesized by conventiorWelding are torch Soot ~aa— tsolated Substrate _ £7ZAZza Water-cooled base electrode Fig. 6.14: Experimental set-up of the Torch arc method in open Air. In the soot, carbon nano horns (CNHs) and bundles of SWNT with an average diameter of 132 nm were found. However, the yield was much lower than for the conventional low- pressure arc discharge method. There are two reasons for this fact. At first, because of the open air, the lighter soot will escape into the atmosphere. Secondly, the carbon vapor might be oxidized and emitted as carbon dioxide gas. In order to improve the yield in this method, contrivances for collecting soot and development of an appropriate target are required. This method promises to be convenient and inexpensive once the conditions for higher yield are optimized. With a Ni/Y catalyst (Ni/Y is 3.6:0.8), SWNT bundles and CNHs are formed. In this case, the SWNTs have a diameter of approximately 1.32 nm.6.12 | BENEFITS OF NANOMATERIALS: / (1) Superior physical, mechanical and chemical properties due to extremely fing . size (1-100 nm). (2). Superior formability and potential super plasticity. (3) Possess high strength, toughness, and ductility. (4) Extremely large specific surface area. (5) Reduced thermal conductivity. (6) Dispersoids can be utilized to further increase strength. 6.13 APPLICATIONS OF NANOMATERIALS: Various applications of nanomaterials are: (1) Biomedical devices. (2) Drug delivery. (3) Flat panel displays. (4) High energy batteries. (5) Sensors. (6) Automobile components. (7) High power magnets. (8) Dielectrics. (9) Fuel cells. (10) Optical devices. (11) Cutting tools. (12) Cosmetics. (13) Aerospace components. 6.14 NANOCOMPOSITES: a A eee is a multiphase solid material where one of the phases has one, two a ensions ess than 100 nanometers (nm), or structures having nano-scale rep disiane v e different Phases that make up the material. In the broadest sense, inition can include Porous media, colloids, gels, and copolymers, but is more usually taken mean the solid combination of a bulk matrix and nano-dimensional phase(s) difering|0 nm for achieving superparamagnetism, mechanical strengthening or restricting, matrix on movement. Nanocomposites are found in nature, for example in the structure of the abalone shell qd bone. ‘The use of nanoparticle-rich materials long predates the understanding of the physical on vq chemical nature of these materials. Jose-Yacaman investigated the origin of the depth of color | ary the resistance to acids and bio-corrosion of Maya blue paint, attributing it to nanoparticle anism. From the mid-1950s nanoscale organo-clays have been used to control the flow of ymer solutions (e.g. as paint viscosities Fs) or the constitution of gels (e.g. 43 4 thickening Fipstance in cosmetics, keeping the preparations in homogeneous form). By the 1970s polymer/clay composites were the topic of textbooks, although the term “nanocomposites” was notin common use. In mechanical terms, nanocomposites differ from conventional composite materials due tothe exceptionally high surface to volume ratio of the reinforcing phase and/or its exceptionally high aspect ratio. The reinforcing material can be made up of particles (e.g. minerals), sheets (e.g- exfoliated clay stacks) or fibers (e.g. carbon nanotubes or electrospun fibers). The area of the interface between the matrix and reinforcement phase(s) is typically an order of magnitude ter than for conventional composite materials. The matrix material properties are significantly affected in the vicinity of the reinforcement. This large amount of reinforcement surface area means that a relatively small amount of nanoscale reinforcement can have an observable effect on the macro scale properties of the composite. For example, adding carbon nanotubes improves the electrical and therma conductivity. Other kinds of nano particulates may result in enhanced properties, dielectric, hea resistance or mechanical properties such as stiffness, strength, and resistance to wear an damage. In general, the nano reinforcement is dispersed into the matrix during processing. Th percentage by weight (called mass. fraction) of the nanoparticulate introduced can remain very lo\ on the order of 0.5% to 5%) due to the low filler percolation threshold, especially for the mo: ommonly used non-spherical, high aspect ratio fillers (e.g. nanometer-thin platelets, such < lays, or nanometer-diameter cylinders, such as carbon nanotubes). Applications of Nanocomposites: (a) Automotive - Maintaining Performance to Provide Added Value (b) Barrier - Nano Filler as Part of Formulation - (©) Flame Retardants - NanoFiller’s Latent Role: Self-Passivation & Reinforcement (d) CERF - Approach to “Engineered Materials” (e) Shape Memory - Impacting the “Dominate” Attribute of the Polymer () “DC” Electrical - NanoParticle Network and “Critical Junctions” (g) Dynamic Electrical - Network Responsivity (h) Dielectric - Field Distribution, Interfaces, and Charge Trapping6.20 | SMART MATERIALS Smart or intelligent materials form a Sroup of new and state-of-the art materials now being developed that will have a significant influence on many of our technologies. The adjective “smart” implies that these materials are able to sense changes in their environments and then respond to these changes in predetermined manners—traits that are also found in living organisms. In addition, the concept of smart materials is being extended to rather sophisticated systems that consist of both smart and traditional materials. The field of smart materials attempts to combine the sensor (that detects an input signal), actuator (that performs a responsive and adaptive function) and the control circuit on as oneunit. Actuators may be called to jon, natural inves ; ae * to change shay i : : 3 unit upon rpe, position, natu s | characteristics in response to changes in tempe: electric fields, and sacs ; Usually, four types of materials are commonly used for Seurc field when their dimensions are altered. The behaviour of maz sralogos to that of the piezoelectric ceramic materials, except that they ar ic fields. Also, electrorheological and magnetorheological fluids ~ dramatic changes in viscosity upon the application of electric and magnetic wepectively- “These are known as smart sensors, microsystem -nicroslectromechanical systems (MEMS). Materials /devices employed as sensors ir bers, piezcelectric materials (including some polymers), and MEMS. MEMS devices are small in size, light weight, low cost, reliable febrication technology. They generally consist of sensors that gather environmental informaton such aS pressure, temperature, acceleration etc, integrated electronics to process the datz collected and actuators to influence and control the environment in the desired manner. The MEMS technology involves a large number of materials. Silicon forms the backbone of these systems also due to its excellent mechanical properties as well as mature icrO- fabrication technology including lithography, etching, and bonding. Other maierials piezoelectric, piezoresistive, ferroelectric and other properties are widely used for sensing anc actuating functions in conjunction with silicon. The field of MEMS is expected to touch all aspects of our lives during this decade with revolution in aviation, pollution contol, and ind: i processes. 621 MODERN MATERIALS NEEDS There has been tremendous progress over the decades in the field of materials science and engineering, innovation of new technologies, and need for better performances of existing technologies demands much more from the materials field. More over it is evident that new materials/technologies are needed to be environmental friendly. Some typical needs, thus, of modern materials needs are listed in the following: * Engine efficiency increases at high temperatures: requires high temperature structural materials * Use of nuclear energy requires solving problem with residues, or advances in nuclear waste Processing. Hypersonic flight requires materials that are light, strong and resist high temperatures. Optical communications require optical fibers that absorb light negligibly. Civil construction - materials for unbreakable windows. Structures; materials that are strong like metals and resist corrosion like plastics. (MST) oF nchude optical having