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    Nano Materials

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    Chapter 8: NANOMATERIALS 509 yOMATERIALS 3 » materials xan materials are materials with dimensions and tolerances in the range of 100 nm to vey can Be metals, ceramics, polymeric materials, or composite materials. vials are biological, inorganic or organic structures that, due to their small size, properties different from those observed in bulk materials. Nanomaterials vary hape and composition. In other words, nanomaterials represent a new class of ‘smaller length scales (< 100 nm) impart enhanced or altered properties 0 N nique yy vid ly ins mate where eve ‘anomaterials specially help to improve products and applications. For example, they jprigher stability in sports equipments. They are used for UV protection in sun blockers hgo used in self-cleaning surfaces and fire protection ey 3 NANOSCIENC! £ AND NANO-TECHNOLOGY spose Nanoscience the study of the one dimension roug! is defined as fundamental principles of molecules and nanostructures ( ‘nly between 1 nm to 100 nm).” with at least and biological nanostructures, way of creating novel chemical ow to organize these new ties and finally learning about h complex functional structures and devices. Nanoscience is a new cedestanding theit proper seteractres into larger and more c internal and external constraints® towards a I design strategy to impact processes and device technologies at nanoscale. constraints are studied in internal constraints. Interfacial and died in external constraints. The constraints can be entropic, transitions or relaxations. tyjectves and Aims of Nanoscience Nanoscience is the study and research of éndamental nanomaterial Inter and Intramolecular fimensional constraints are stu chalpic organizational, mobility, Aanotechnology Nanotechnology can be defined as : “The application of science and scien! commercial objective”. tific knowledge, at the nanoscale, for industrial or Or “The engineering of functional systems at the molecular scale”. Or “The design, characterization, production, systems by controlled manipulation of size and shape at the nanometer scale (atomic, praia ‘and supramolecular scale) that produces structures, devices and systems with pe nts rnovel/superior function oF P ‘tance. The permissible Limit of variation in dimension- Gntualats, Restriction, ti Scanned with CamScanner Sere. TRY oF ENGINEERING CHEMIS XTBOOK ir g10 are ad molecules are in the 1 nm to 100 of atoms ‘Can we call these atomic or mo 1" Typical sizes see Learn fou them for fans 1° in, ‘ technologies ? Expat were neither observing size cause chemists : Bec ‘anostructure into some useful ion. No. Solution. plications of these ni were suggesting aPI 4 METHODS FOR THE PREPARATION OF NANOMATERIALS 41) Top-down Approach In this method small features® are created on large substrates’ by repeated pattern transfer steps involving lithographic methods. This method is used in themicroelectronics? industry, 42) Bottom-up Approach This method starts with very small units, often individual molecules or atoms and assembles these building-block units into larger hierarchical" and controlled structures. Generally, a special and unique method is used to prepare a new class of nanomaterial. Fig. 1 Illustration of oi For example, Preparation offi @ be made by vaporizing carbon within a inocomposites can be made by si then mixing it with polymer melts. atures, Characteristic, attribute, property, quality, . Substrates. Material substance or its surface, 8. Lithography. (reek. lithos = stone ; graphein »: to write), Itisa method ‘smooth surface. The image i mie ‘mage is made of a polymer coating or oil or fat or Scanned with CamScanner v OE, ha Top-down Approach spats approach, we Begin with "8 NANOMATERIALS 511 mich, we start with atoms or and build up to nonostructures ‘Tanger acale, then reduced 4 In ti anger scale, then reduced to nanoscale. | my lecul wn approach is | This approach is aaa (BIBW and not suitable for large | Th large scale is approach is suitable for prokicion t pproach appre productic Mechanical grinding, * Ion implantation 5 PROPERTIES OF NANOMATERIALS Nanoparticles are unique This is because the physical behaviour of particles changes from classical physics!” to quantum physics"? with decreasing particle size to < 100 nm. A nanoparticle with a radius of 2.5 nm and a density of 5 g/cm? has a surface area of 240 m2/g when assuming a spherical shape. However, the surface of a nanoparticle is never naked!” The particles are always agglomerated’ due to high energetic adhesive forces close to the surface, & Size effects. Only by varying the particle size of the material, properties like melting- point, solubility, colour, transparency, and catalytic behaviour changes & Composition effects. Different physical and chemical behaviour of the material is observed by varying the particle compositions. © Surface effects. Properties like dispersibility, conductivity, catalytic behaviour and optical properties alter with different surface properties of the nanoparticle. | Thus, the principal factors which cause the properties of nanomaterials 10 differ significantly from other materials are: (i) Small particle sizes <100 nm. Consider a material that exhibits ordered electronic spin on the surface but disordered electronic spin in the interior ofthe particle, ‘As the particle is reduced in Siiaabembneins 2 ‘sical Physics, Newtons laws of motion, wave theory of ght are applicable, B. uantum physics. Blackbody radiation, photoelectric effect etc. ate applicable 14 Waked. Uncovered. 'S. dggomerat. Latin “agglomerare” = to form into a ball or cust, Scanned with CamScanner ces as compared t0 those in the i eases a qerial completely Composed of orties derived from the. incre wes. A mat In nanometer sized particles or pe, ; in bounda: sed rel urface or grain vai {ip The increas he molecules oF HOP grain » particle OF es or ion at the surfac he concentration of molecules oF igng 17 i rge’” in the nanometer f the pose, the radius 0! eto the total molecul supp Then, the ratio of molecu! eof the grain decreases t! Thus as the sepend ant properties that emer “s. The size-depende of this increased ratio. boundary increé are in part a result a semiconductor is p1 (iii) Quantum size effects. The energy gap in sa result of of the square of the size. This effect is 2 aede too small to be comparable to the wavelength of the electron, Accordingly, instead of continuous energy bands such as that of bulk discrete energy states exist, the difference of which give rise to absorption of Sharacteristic of the composition and size of the nanoparticle. is) Size-distribution. Nanomaterials that have a wide particle size distribution unique properties, but these properties are a statistical result of the ensemble’? of ing present in the distribution. To exploit” the unique size-dependent properties, the must be composed of monodisperse” or nearly monodisperse nanoparticles, (0) Specific surface feature. When specific surface feature is responsible properties of the material, both size and the particular surface features must b observe unique properties. In crystalline materials, the place where two faces come together is kno piace where three or more faces come together is known as point. These edges the location for pronounced catalytic activity. Crystalline nanoparticles will contain enormous edges and points. r activity can be tuned mit i - or maximized through the selection of composition Bee 16, Grain. Small, hard, dry , 1, dry spheres (like seeds), 17 Emer. inate oer. , . Quantum confine 19, Ensemble, 4 Itincreates the spacing between energy levels as the ‘5#0up or unit of complementary parts that and decree fom, with the same size, shape, or mas. Scanned with CamScanner Chapter 8 ; NANOMATERIALS 513 y NANOTUBES (CNT) are about 0.4 nm in or multi-walled carbon eter 7 aia MWCNT). ibes (' anol root They own exceptionally high tensile strength. y Ci insulatit semicon i i 1 (a phi ie Fe ee coats sepbeer ee a ciy They possess large surface area {o) They show good properties in electron emission. ic) They are reported to be thermally stable in a vacuum up to 2800°C. they exhibit excellentelecticaland:mechanicalpropertes. They have capacity to electric current 1000 times better than copper wites:) carry an applications {i) Recently, carbon nanotubes were used as needles to bring active agents into living cells, This process could be applied as a new way to a therapy” against cancer. (i The excellent electrical conductivity, heat transmission capacity, heat stability, low density and high strength makes them candidates for use as fillers in composite materials for various applications like : (a) Polymer LED, (b) Ultra- resistant materials for use as reinforcement fibers, (c) Electrical-energy storage applications. 7 FULLERENES Fullerenes are a class of cage**-like carbon compounds composed of fused, pentagonal and/or hexagonal sp? carbon rings. Properties (i They are insoluble in water. (i) They exhibit excellent tribological” properties like excellent tensile strength, and highest packing density. (iii) They possess cage like structure. (io) They are impenetrable”® to all elements under normal circumstances. @ Fullerenes can be used as filers. Scanned with CamScanner CHEMISTRY aud. ayes -.. smal ligands to the carbon Cage Or 3 (i) By the attachment vant me potentially et pe rt 7 ets Me tantharice metals inside the cag llerene 0) igo eee om ay ) fy i pane ‘sto be useful at fighting the HIV” virus that io) They have B_ NANO-NETALS sulk nanostructured metals ; tals can be either nanopowders or b Nano-metals © ters of noble metals (AB, Aus Pt, Pd), A ae i tructured metals and powders (like Ti, TAL, Mg-ni, (i) Bulk nanos! uct . alloy, etc). Properties a Nanopowders possess high specific surface areas. They exhibit soft nl high effective permeabilities) and new deforn pended in a fluid or another material, the most it faces of the particle to the properties of the rial activity, which could be used as a c (like high magnetizations at When the nanopowders are sus is the high contribution of surf embedded in. This results in a high mate of ions for antibacterial? properties Applications Nano-metals have an enormous potential for applications in following secto Construction ® Catalysis @ Electronics ® Energy storage # Environment protection ® Information Technology ® Power transmission ® Medicine ® Telecommunications 9 BIOLOGICAL NANOMATERIALS Biological nanomaterials are materials of biological origi a ; origin that technological applications. These materials mainly consist of biological mo chosen or designed for a certain application that relies on a nanoscale featur Examples. Proteins, nucleic acids, lipids, hormones, vitamins ete. Deliver. Carry, transport, hand over, 28. Tracer. Discover, detect. 29. = sry cet Ne abl of eng damaged ox harmed or affected or disturbed. ). HIV. The human immunodet ae +, RSet virus isa virus that gradually attacks a dete elt and may develop rao dete oe st sage of . Antibacterial. Toi © illo slow down the growth of bacteria, Scanned with CamScanner Chapter 8 NANOMATERIALS 515 ogi nanomaterials exhibit Bw . Self-assembling™ properties and (ji) fo) Specific molecular recognition t esters | sical nanomaterials are very useful for the fol | piolog” lowing, application | e Drug delivery ® Specific filtration _ ‘ | © Arrays (chips) for lange scale protein or DNA screening? | 2 Motors © Actuators®* © Me 40 ANOWIRES a | >-wire is cluster of carbon atom : $$ vpon nano-wire is cluster of carbon atoms, which f 7 cai is carbon chain behaves like a nanowire. nm © icin sf tow coches stom gic {) Carbon nanowires are very strong. (i), They have useful electrical properties. (ii) Their diameter is smaller than the width of an electron’s wai () Nanowires can be used to develop a new class of solid state air-conditioners and power generators. refrigerators, | (i) Nanowires could be used in nanoelectronics, as microscopic machine parts (ii) Carbon nanowires could be used in ultra-strong fibers, as friction-free bearing: 27, and in space shuttle nose cones. | 141 SMART MATERIALS | “smart materials have the ability to sense changes in their environments and then they respond to these changes in pre-determined” manners (like living organisms).” re 1B. Stl-assembling, A process in which a disordered system of pre-existing components forms an organized structure or Juttem as a consequence of specific interactions among the components themselves, without external direction. “Mk Specitic molecular recognition. The specific interaction between two or more molecules (exhibiting molecular ‘omplementarity) through non-covalent bonding such as hydrogen bonding, van der Waals forces etc. ‘DMA screening, The process of (a) analyzing DNA samples to detect the ‘sherited disorder, (b) assessment of an individual's genetic makeup to Scanned with CamScanner 516 4 TEXTBOOK OF ENGINEERING CHEMISTRY Example : The Piezoelectric materials produce an electric field when mechanical force. Piezoelectric sensors are inserted into the blades of helicopters, To to, blade stresses and deformations ; feedback signals from these sensors are fed into a on ™%itor controlled adaptive device, which generates noise-canceling antinoise. Thus, this smart. ™PUer used in helicopters to reduce aero-dynamic cockpit noise that is created by the rotating rotor etal Limitations : (i) High cost. (ii) Poor availability. mes, 12 SMART MATERIALS ALLOYS Smart materials have the ability to sense external environmental stimuli (temper light, stress, humidity, and electric and magnetic fields) and respond to them by hanging their appearance, structure, functions or properties (electrical, mechanicly, Systems that use smart materials consist of sensors and actuators. The sensor detects a change in the environment, and the actuator component Performs a specific function ora response, Shape-memory alloys and piezoelectric ceramics are example of smart materials, Piezoelectric mates expand and contract in response to an applied electric field (or voltage). A change in an external electric field produces a mechanical response in these same materials. Example : Lead zirconium titanate (PZT). ‘Applications 1. The piezoelectric material is used to sense and reduce undesirable vibrations of a component through their actuator response. Once a vibrations is detected, a current is applied to generate a mechanical ‘Tesponse that counters the effect of the vibrations. Piezoelectric material is used to make devices such as spark generators for gas grils They are also used in sensors that can detect under-water objects like submarines and fishes. 2. Microelectromechanical systems (MEMs)” use smart materials and devices to sense, communicate, and actuate. These systems are used in micropumps, locking systems, sensors, mirrors and motors. 3. Magnetorheological or MR fluids are also smart materials used im suspension systems of automobiles. They respond to magnetic fields. mie _—_——— a 5 anical systems (MEMS). They integrate mechanical and electrical from micrometers to millimeters. Scanned with CamScanner Chapter 8 | NANOMATERIALS 517 RSPECTIVES rruRE PERSPECTIVES 9 some smart Materials A jnanoscience, the term smart material refers toa np specific task, per potorefractive polymers? have structures which contai ike metals. they are of major interest as informatioy exceed in comparison to Presently availabl of the new and futuristic applications of nano-technology are summarized below : ny material engineered at the nanoscale to in mobile electronic charges, Nn storage devices because their storage le magnetic storage structures, ost a 3.2. Sensors sensors are capable of responding in a xntodetect. They indicate the presence of aa amounts that are present. recognizable way to the presence of something we Particular molecules or biological structures, as well {p Natural Nanoscale Sensors Molecular recognition is the fundamental mechanism behind a dog's sense of smell or behind the pheromones® (the sex attractants). Complementary shapes within the sensing structure of the dog's nose or the insect's receptors recognize (a) the shape of the signal molecules, and (b) the distribution of electronic charge on their surfaces. ae Molecular Aa recognition structure ig, 2 Illustration of molecular recognition in natural sensors. i of the flower or leaf In the biological world, the specific molecular sensors in the structure set sere the presence of tian then aceasta __ lower or leaf to move in a particular direction, to face the sun eosey. Scanned with CamScanner rs ‘518 A TEXTBOOK OF ENGINEERING CHEMISTRY (if) Synthetic Nanoscale Sensors According to what they sense, the synthetic sensors can be classified into following , (@) Electromagnetic sensors. They are sensors for electromagnetic radiation. For j nanoscale photosensor is responsible for the art and science of traditional silver photography, ae the light energy (photons) cause a chemical reaction among the silver ions that are held jp it, emulsion on the film surface. The silver ions come together to form nanoscale silver clusters y® ‘grow large enough to scatter and capture the light, thereby appearing | black on the surface. Tha the change in properties with size is at work here that is so essential to nanotechnology. : sensors in photographic film are molecular/atomic, and the sensing Process consists of irreversible change in the clustering of the silver atoms. (b) Biosensors. Biosensors are either natural sensors that are part of life or they are a for biological entities like proteins, drugs, glucose etc. For example, colorimetric nanosensors use the change in color of metallic nanodots to detec molecules. First gold or silver nanodots are attached to the single strands of DNAM that ar. complementary to the analyte. Then it is introduced into a solution to be tested. If the analyte ig @® + NZ Nanodot | 1 Single strand of DNA — > a po (Target) 2 Hybridization | _~ SO Analyte & Formation of as RON double strand Scanned with CamScanner Chapter 8; NANOMATERIALS 519 it will hybridize with the test DNA and form a double strand. It causes the gold a eres to come closer together and change color. They can be read by simply looking at a em : eer DNA sensing is very important area in which nanoscience can improve medicine. The | chip concept is one of the most important application of DNA sensing. In it, several wong, Sensors are included on a chip for instant recognition of viral or bacterial DNA ated with several different diseases found in the body. Such chips can also be used to sense » of natural or artificial toxic species in water supplies. ee ons (0) Electronic Noses. Biological nose work using molecular recognition and then send a earl signal tothe brain In the electronic (or artificial) nose, an electrically conducting polymer Fes the nasal membrane. The polymer is spread between electrodes. When the molecules to be {nelled land on the polymer, the conductivity properties in particular regions will change in a srt ge way that is specific to any given analyte. These sensors are commercially available for toxic gs detection, air quality monitoring, food inspection and standardization, and disease analysis. 13.3 Biomedical Applications |All fundamental life processes take place the nanoscale. Developments in nanoscale siomedicine have the following potential applications : ( Drugs Nanosize molecular drugs are individual molecules that work by interacting specifically with biological targets like DNA or proteins within the body. Neurotransmitter molecules are the molecular couriers that carry messages between synapses in the brain. Too high or too low concentration of neurotransmitter molecules causes depression‘”. The smart nanoscale development of antidepressants is focussed on increasing this concentration of neurotransmitters. It is done by modifying their binding properties either by blocking or decreasing the destruction of neurotransmitter molecules, One of the crucial impacts of nanoscience and nanotechnology will be in facilitating development of new drugs with fewer side | effects and more beneficial behaviour. (i) Drug delivery For any good result of a medical treatment (therapeutic effectiveness), it is important that the drug molecules must reach the specific places in the body where they are needed and where they will do the most good and effective. Thus, successful drug delivery requires maximizing Siovailablity both over a period of time and at specified places in the body. be Nanoscience and nanotechnology are very useful in improving drug delivery. For example, Scanned with CamScanner 520 A TEXTBOOK OF ENGINEERING CHEMISTRY is swallowed as part of a tablet. Within the specific place in the body, as the Polymeric stru opens up, the enclosed drug is released. This method has the potential to continuously deliver, drug smoothly over an extended period of time. Polymer () Encapsulated drug (ii) Release of enclosed molecules within nanoscale drug as the polymeric cavities inside polymeric structure structure opens up. Fig. 4 Illustration of drug delivery using polymeric membranes having nanoscale cavities, Example 2_ Write the places in the body where the following drug molecules are effective : (@) Anticancer drugs, (b) Anti-inflammatories*®, and (c) Antidepressants, Solution. (a) At tumor sites, (b) At sites of stress, and (c) In the brain, Example 3 Is it appropriate to increase the amount of drug for increasing bioavailability ? Solution. No. For example, in chemotherapy™, the drugs used are actually somewhat toxic, and increasing the amount used could adversely affect or even kill a patient (iif) Photodynamic Therapy molecular dot particle. The energy from the light will heat the nanodot. The heat from excited nanodot is released only where the particles are and where the light is shined so it is directed therapy. With some particular molecular dots, light produces chemically reactive excited owyge" molecules. These oxygen molecules will chemically react and therefore destroy tumors next to them These are termed as photodynamic therapy because () they are promoted by photons of light and (i) they depend on the excited state dynamics of the nanodots or molecules involved. Example 4 Why photodynamic therapy is attractive unlike traditional chemotherapy ? Solution. It is directed and does not leave a toxic trail of highly aggressive and Chapter 8 : NANOMATERIALS 521 What kind of molecules can be used in photod, mple 5 lynamic therapy ? a ion. Molecules should have a mult olution. multicomponent . The radiation either heats or provides chemically reactive onygen eee es composite structures like: molecule/nanoparticle/biologial Peep i Molecule/Nanoparticle/Biological recognition agent (Multi-component quantum stricture) oa Tumor Otome | hy (radiation) Aes Tumor Molecule/Hot nanoparticle/Bound target species ve dito? tpepy rea fig, 5 Illustration of composite structure of molecule used in photodynamic therapy. (iv) Protein Engineering Protein engineering is one of the nanostructure schemes that is based on nanobio~ technology. It is the science of making proteins and then utilizing them in synthetic foods or in Rr ids. These long chains then ‘A protein consists of a long chain made from 20 amino acids. These long

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