1.1 Introduction Nanotechnology is the science of the extremely tiny. The prefix nano, derived from the Greek nanos signifying dwarf, is becoming increasingly common in scientific literature. "Nano" is now a popular label for much of modern science, and many nano- words have recently appeared in dictionaries, including: nanometer, nanoscale, nanoscience, nanotechnology, nanostructure, nanotube, nanowire, and nanorobot. Many words that are not yet widely recognized are used in respected publications, such as Science and Nature. These include nanoelectronics, nanocrystal, nanovalve, nanoantenna, nanocavity, nanoscaffolds, nanofibers, nanomagnet, nanoporous, nanoarrays, nanolithography, nanopatterning, nanoencapsulation, etc. Although the idea of nanotechnology: producing nanoscale objects and carrying out nanoscale manipulations, has been around for quite some time, the birth of the concept is usually linked to a speech by Richard Feynman at the December 1959 meeting of the American Physical Society where he asked, What would happen if we could arrange the atoms one by one the way we want them? The nanometer is a metric unit of length, and denotes one billionth of a meter or 10 -9 m. Nanotechnology refers broadly to a field of applied science and technology whose unifying theme is the control of matter on the atomic and molecular scale, normally 1 to 100 nanometers, and the fabrication of devices with critical dimensions that lie within that size range. It is a highly multidisciplinary field, drawing from field such as applied physics, materials science, interface and colloid science, device physics, supermolecular chemistry, self-replicating machines and robotics, chemical engineering, mechanical engineering, biological engineering and electrical engineering. Much speculation exists as to what may result from these lines of research. Nanotechnology can be seen as extension of existing science into the nanoscale, or as a recasting of existing sciences using a newer, more modern term. 1.2 Nano and Nature Nanomaterials can be natural or manmade. For example, nanoparticles are produced naturally by plants, algae and volcanic activity. They have also been created for thousands of years as products of cooking and burning, and more recently from vehicle exhausts. Some proteins in the body, which control things like flexing muscles and repairing cells, are nanosized. We can set out to make nanomaterials in a variety of different ways. Some nanomaterials can assemble themselves from their components. Carbon fragments, for example, can self- assemble into nanotubes in this way. Another approach used in the production of computer chips, is to etch nanomaterials from larger pieces of material. Increasingly, these two methods are converging, leading to exciting new production techniques. Fig.1.1 Powerful microscopes have been developed which allow researchers not only to look more closely at atoms and molecules, but also to pick them up and move them around to form basic nanostructures. 1.3 Background of nanotechnology Some nanotechnologies have example nano-sized particles of gold and silver have been us pigments (Fig 1.2) in stained glass since the 10 Fig.1.1 the scale of things nanometer and more Powerful microscopes have been developed which allow researchers not only to look more closely at atoms and molecules, but also to pick them up and move them around to form basic nanostructures. Background of nanotechnology Some nanotechnologies have been around for hundreds of years; for sized particles of gold and silver have been used as coloured ) in stained glass since the 10 th century AD. nanometer and more Powerful microscopes have been developed which allow researchers not only to look more closely at atoms and molecules, but also to pick them up and been around for hundreds of years; for ed as coloured Fig 1.2 Gold and silver coated nanoparticle The Lycurgus Cup (British Museum; AD fourth century) as shown in Figures is a Roman cup depicting triumph of Dionysus over Lycurgus. He is seen being dragged into the underworld by the Greek nymph Ambrosia, the cut-work design of the cup that shows the high levels of skill involved in its production. The glass of the cup is dichotic; in direct light it resembles jade with an opaque greenish-yellow tone, but light) it turns to a translucent ruby colour. X of silver-gold alloy, with a ratio of silver to gold of about 7:3, containing in addition about 10% copper. behaviour of the glass when the light shines from different directions. Many chemicals and chemical processes have nanoscale features. Chemists have been making polymers, large molecules made up of nano for many decades. Computer chips have nano surface, and nanotechnologies have enabled computers to be made smaller and faster over the last thirty years. Gold and silver coated nanoparticle The Lycurgus Cup (British Museum; AD fourth century) as shown in Figures is a Roman cup depicting figures, carved in deep relief, showing the triumph of Dionysus over Lycurgus. He is seen being dragged into the underworld by the Greek nymph Ambrosia, who is disguised as a vine. However it is not only work design of the cup that shows the high levels of skill involved in its production. The glass of the cup is dichotic; in direct light it resembles jade with an yellow tone, but when light shines through the glass (transmitted light) it turns to a translucent ruby colour. X-ray analysis has shown nanoparticles gold alloy, with a ratio of silver to gold of about 7:3, containing in . These nano particles are responsible for the differential behaviour of the glass when the light shines from different directions. Many chemicals and chemical processes have nanoscale features. Chemists have been making polymers, large molecules made up of nano-sized com for many decades. Computer chips have nano-sized features etched into their surface, and nanotechnologies have enabled computers to be made smaller and faster over the last thirty years. The Lycurgus Cup (British Museum; AD fourth century) as shown in above figures, carved in deep relief, showing the triumph of Dionysus over Lycurgus. He is seen being dragged into the underworld who is disguised as a vine. However it is not only work design of the cup that shows the high levels of skill involved in its production. The glass of the cup is dichotic; in direct light it resembles jade with an when light shines through the glass (transmitted ray analysis has shown nanoparticles gold alloy, with a ratio of silver to gold of about 7:3, containing in ticles are responsible for the differential behaviour of the glass when the light shines from different directions. Many chemicals and chemical processes have nanoscale features. Chemists sized components, sized features etched into their surface, and nanotechnologies have enabled computers to be made smaller and More recently, researchers have produced nano-sized wires and tubes. Nano wires have remarkable optical, electronic and magnetic properties, so it is hoped they will prove useful in storing computer data. Carbon nanotubes may lead to new building materials, being much stronger and lighter than steel. Nanoparticles - tiny particles with special properties have also found some areas of application. Nanoparticles of titanium dioxide have been added to some suntan lotions and cosmetics. These tiny particles are transparent on the skin and can absorb and reflect ultra-violet rays. In contrast to their use in cosmetics, where they are free to move around, nanoparticles can also be fixed into layers on surfaces, to give them new properties. 1.3.1 History In 1965, Gordon Moore, one of the founders of Intel Corporation, made the astounding prediction that the number of transistors that could be fit in a given area would double every 18 months for the next ten years. This it did and the phenomenon became known as Moore's Law. This trend has continued far past the predicted 10 years until this day, going from just over 2000 transistors in the original 4004 processors of 1971 to over 700,000,000 transistors in the Core 2. There has, of course, been a corresponding decrease in the size of individual electronic elements, going from millimetres in the 60's to hundreds of nanometres in modern circuitry. At the same time, the chemistry, biochemistry and molecular genetics communities have been moving in the other direction. Over much the same period, it has become possible to direct the synthesis, either in the test tube or in modified living organisms. Finally, the last quarter of a century has seen tremendous advances in our ability to control and manipulate light. We can generate light pulses as short as a few femtoseconds (1 fs = 10 15 s). Light too has a size and this size is also on the hundred nanometer scale. Thus now, at the beginning of a new century, three powerful technologies have met on a common scale the nanoscale with the promise of revolutionizing both the worlds of electronics and of biology. This new field, which we refer to as biomolecular nanotechnology, holds many possibilities from fundamental research in molecular biology and biophysics to applications in bio sensing, bio control, bioinformatics, genomics, medicine, computing, information storage and energy conversion. 1.3.1a) Historical background Humans have unwittingly employed nanotechnology for thousands of years, for example in making steel, paintings and in vulcanizing rubber. Each of these processes rely on the properties of stochastically formed atomic ensembles mere nanometers in size (Fig 1.3), and are distinguished from chemistry in that they don't rely on the properties of individual molecules. But the development of the body of concepts now subsumed under the term nanotechnology has been slower. The first mention of some of the distinguishing concepts in nanotechnology (but predating use of that name) was in 1867 by JAMES CLERK MAXWELL when he proposed as a thought experiment a tiny entity known as Maxwell's Demon able to handle individual molecules. Fig 1.3 Atomic ensembles of nanoparticle The first observations and size measurements of nano-particles was made during the first decade of the 20 th century. They are mostly associated with RICHARD ADOLF ZSIGMONDY who made a detailed study of gold sols and other nanomaterials with sizes down to 10 nm and less. He published a book in 1914. He used ultra microscope that employs the dark field method for seeing particles with sizes much less than light wavelength. Zsigmondy was also the first who used nanometer explicitly for characterizing particle size. He determined it as 1/1,000,000 of milli meter. He developed the first system classification based on particle size in the nanometer range. There have been many significant developments during the 20th century in characterizing nanomaterials and related phenomena, belonging to the field of interface and colloid science. In the 1920s, Irving Langmuir and Katharine B. Blodgett introduced the concept of a monolayer, a layer of material one molecule thick. Langmuir won a Nobel Prize in chemistry for his work. In the early 1950s, Derjaguin and Abrikosova conducted the first measurement of surface forces. The first use of the concepts found in 'nano-technology' (but pre-dating use of that name) was in "There's Plenty of Room at the Bottom," a talk given by physicist Richard Feynman at an American Physical Society meeting at Caltech on December 29, 1959. Feynman described a process by which the ability to manipulate individual atoms and molecules might be developed, using one set of precise tools to build and operate another proportionally smaller set, and so on down to the needed scale. In the course of this, he noted, scaling issues would arise from the changing magnitude of various physical phenomena: gravity would become less important, surface tension and Van der Waals attraction would become increasingly more significant, etc. This basic idea appeared plausible, and exponential assembly enhances it with parallelism to produce a useful quantity of end products. But I am not afraid to consider the final question as to whether, ultimately-- -in the great future---we can arrange the atoms the way we want; the very atoms, all the way down -Richard Feynman, There's Plenty of Room at the Bottom 1.4 Scientific revolutions and opportunities at the nanoscale With nanotechnology, a large set of materials and improved products rely on a change in the physical properties when the feature sizes are shrunk. Nanoparticles for example take advantage of their dramatically increased surface area to volume ratio. Their optical properties, e.g. fluorescence, become a function of the particle diameter. When brought into a bulk material, nanoparticles can strongly influence the mechanical properties of the material, like stiffness or elasticity. For example, traditional polymers can be reinforced by nanoparticles resulting in novel materials which can be used as lightweight replacements for metals. Therefore, an increasing societal benefit of such nanoparticles can be expected. Such nanotechnologically enhanced materials will enable a weight reduction accompanied by an increase in stability and an improved functionality. There are many applications of nano technology; few of them are listed below. Fig. 1.4 Applications of Nanotechnology 1.4.1 Medical application a) Medicine The biological and medical research communities have exploited the unique properties of nanomaterials for various applications (e.g., contrast agents for cell imaging and therapeutics for treating cancer). Terms such as nanotechnology, bionanotechnology hybrid field. Functionalities can be added to nanomaterials by interfacing them with biological molecules or structures. The size of nanomaterials is similar to that of most biological molecules and stru for both in vivo and in vitro biomedical research and applications. Thus far, the reduction accompanied by an increase in stability and an improved functionality. plications of nano technology; few of them are listed below. Fig. 1.4 Applications of Nanotechnology Medical application The biological and medical research communities have exploited the unique properties of nanomaterials for various applications (e.g., contrast agents for cell imaging and therapeutics for treating cancer). Terms such as chnology, and nanomedicine are used to describe this hybrid field. Functionalities can be added to nanomaterials by interfacing them with biological molecules or structures. The size of nanomaterials is similar to that of most biological molecules and structures; therefore, nanomaterials can be useful for both in vivo and in vitro biomedical research and applications. Thus far, the reduction accompanied by an increase in stability and an improved functionality. plications of nano technology; few of them are listed below. The biological and medical research communities have exploited the unique properties of nanomaterials for various applications (e.g., contrast agents for cell imaging and therapeutics for treating cancer). Terms such as biomedical are used to describe this hybrid field. Functionalities can be added to nanomaterials by interfacing them with biological molecules or structures. The size of nanomaterials is similar to that ctures; therefore, nanomaterials can be useful for both in vivo and in vitro biomedical research and applications. Thus far, the integration of nanomaterials with biology has led to the development of diagnostic devices, contrast agents, analytical tools, physical therapy applications, and drug delivery vehicles. Fig 1.5 Molecular imaging and therapy b) Diagnostics Nanotechnology-on-a-chip is one more dimension of lab-on-a-chip technology. Magnetic nanoparticles, bound to a suitable antibody, are used to label specific molecules, structures or microorganisms. Gold nanoparticles tagged with short segments of DNA can be used for detection of genetic sequence in a sample. Multicolor optical coding for biological assays has been achieved by embedding different-sized quantum dots into polymeric microbeads. Nanopore technology for analysis of nucleic acids converts strings of nucleotides directly into electronic signatures. c) Drug delivery The overall drug consumption and side-effects can be lowered significantly by depositing the active agent in the morbid region only and in no higher dose than needed. This highly selective approach reduces costs and human suffering. An example can be found in dendrimers and nanoporous materials. They could hold small drug molecules transporting them to the desired location. Another vision is based on small electromechanical systems; NEMS are being investigated for the active release of drugs. Some potentially important applications include cancer treatment with iron nanoparticles or gold shells. A targeted or personalized medicine reduces the drug consumption and treatment expenses resulting in an overall societal benefit by reducing the costs to the public health system. Nanotechnology is also opening up new opportunities in implantable delivery systems, which are often preferable to the use of injectable drugs, because the latter frequently display first-order kinetics (the blood concentration goes up rapidly, but drops exponentially over time). This rapid rise may cause difficulties with toxicity, and drug efficacy can diminish as the drug concentration falls below the targeted range. d) Tissue engineering 1) Nanotechnology can help to reproduce or to repair damaged tissue. Tissue engineering makes use of artificially stimulated cell proliferation by using suitable nanomaterial-based scaffolds and growth factors. Tissue engineering might replace todays conventional treatments like organ transplants or artificial implants. Advanced forms of tissue engineering may lead to life extension. 2) For patients with end-state organ failure, there may not be enough healthy cells for expansion and transplantation into the ECM (extracellular matrix). In this case, pluripotent stem cells are needed. One potential source for these cells is iPS (induced Pluripontent Stem cells); these are ordinary cells from the patients own body that are reprogrammed into a pluripotent state, and has the advantage of avoiding rejection (and the potentially life-threatening complications associated with immunosuppressive treatments). Another potential source of pluripotent cells is from embryos, but this has two disadvantages: 1) It requires that we solve the problem of cloning, which is technically very difficult (especially preventing abnormalities). 2) It requires the harvesting of embryos. Given that each one of us was once an embryo, this source is ethically problematic. 1.4.2 Chemistry and environment Chemical catalysis and filtration techniques are two prominent examples where nanotechnology already plays a role. The synthesis provides novel materials with tailored features and chemical properties: for example, nanoparticles with a distinct chemical surrounding (ligands), or specific optical properties. In this sense, chemistry is indeed a basic nanoscience. In a short-term perspective, chemistry will provide novel nanomaterials and in the long run, superior processes such as self-assembly will enable energy and time preserving strategies. In a sense, all chemical synthesis can be understood in terms of nanotechnology, because of its ability to manufacture certain molecules. Thus, chemistry forms a base for nanotechnology providing tailor-made molecules, polymers, etcetera, as well as clusters and nanoparticles. a) Catalysis Chemical catalysis benefits especially from nanoparticles, due to the extremely large surface to volume ratio. The application potential of nanoparticles in catalysis ranges from fuel cell to catalytic converters and photocatalytic devices. Catalysis is also important for the production of chemicals. Platinum nanoparticles are now being considered in the next generation of automotive catalytic converters because the very high surface area of nanoparticles could reduce the amount of platinum required. However, some concerns have been raised due to experiments demonstrating that they will spontaneously combust if methane is mixed with the ambient air. Ongoing research at the Centre National de la Recherche Scientifique (CNRS) in France may resolve their true usefulness for catalytic applications. Nanofiltration may come to be an important application, although future research must be careful to investigate possible toxicity. b) Filtration 1) A strong influence of nanochemistry on waste-water treatment, air purification and energy storage devices is to be expected. Mechanical or chemical methods can be used for effective filtration techniques. One class of filtration techniques is based on the use of membranes with suitable hole sizes, whereby the liquid is pressed through the membrane. Nanoporous membranes are suitable for a mechanical filtration with extremely small pores smaller than 10 nm (nanofiltration) and may be composed of nanotubes. Nanofiltration is mainly used for the removal of ions or the separation of different fluids. On a larger scale, the membrane filtration technique is named ultrafiltration, which works down to between 10 and 100 nm. One important field of application for ultrafiltration is medical purposes as can be found in renal dialysis. Magnetic nanoparticles offer an effective and reliable method to remove heavy metal contaminants from waste water by making use of magnetic separation techniques. Using nanoscale particles increases the efficiency to absorb the contaminants and is comparatively inexpensive compared to traditional precipitation and filtration methods. 2) Some water-treatment devices incorporating nanotechnology are already on the market, with more in development. Low-cost nanostructured separation membranes methods have been shown to be effective in producing potable water in a recent study. 1.4.3 Energy The most advanced nanotechnology projects related to energy are: storage, conversion, manufacturing improvements by reducing materials and process rates, energy saving (by better thermal insulation for example), and enhanced renewable energy sources. a) Reduction of energy consumption A reduction of energy consumption can be reached by better insulation systems, by the use of more efficient lighting or combustion systems, and by use of lighter and stronger materials in the transportation sector. Currently used light bulbs only convert approximately 5% of the electrical energy into light. Nanotechnological approaches like light-emitting diodes (LEDs) or quantum caged atoms (QCAs) could lead to a strong reduction of energy consumption for illumination. Increasing the efficiency of energy production 1) Today's best solar cells have layers of several different semiconductors stacked together to absorb light at different energies but they still only manage to use 40 percent of the Sun's energy. Commercially available solar cells have much lower efficiencies (15-20%). Nanotechnology could help increase the efficiency of light conversion by using nanostructures with a continuum of bandgaps. 2) The degree of efficiency of the internal combustion engine is about 30-40% at the moment. Nanotechnology could improve combustion by designing specific catalysts with maximized surface area. In 2005, scientists at the University of Toronto developed a spray-on nanoparticle substance that, when applied to a surface, instantly transforms it into a solar collector. 3) The use of more environmentally friendly energy systems An example for an environmentally friendly form of energy is the use of fuel cells powered by hydrogen, which is ideally produced by renewable energies. Probably the most prominent nanostructured material in fuel cells is the catalyst consisting of carbon supported noble metal particles with diameters of 1-5 nm. Suitable materials for hydrogen storage contain a large number of small nanosized pores. Therefore many nanostructured materials like nanotubes, zeolites or alanates are under investigation. Nanotechnology can contribute to the further reduction of combustion engine pollutants by nanoporous filters, which can clean the exhaust mechanically, by catalytic converters based on nanoscale noble metal particles or by catalytic coatings on cylinder walls and catalytic nanoparticles as additive for fuels. Fig. 1.6 Friendly energy systems 4) Recycling of batteries Because of the relatively low energy density of batteries the operating time is limited and a replacement or recharging is needed. The huge number of spent batteries and accumulators represent a disposal problem. The use of batteries with higher energy content or the use of rechargeable batteries or supercapacitors with higher rate of recharging using nanomaterials could be helpful for the battery disposal problem(Fig. 1.7). Fig 1.7 Recycling of batteries 1.4.4 Information and communication 1) Current high-technology production processes are based on traditional top down strategies, where nanotechnology has already been introduced silently. The critical length scale of integrated circuits is already at the nanoscale (50 nm and below) regarding the gate length of transistors in CPUs or DRAM devices. 2) Memory Storage Electronic memory designs in the past have largely relied on the formation of transistors. However, researches into crossbar switch based electronics have offered an alternative using reconfigurable interconnections between vertical and horizontal wiring arrays to create ultra high density memories. Two leaders in this area are Nantero which has developed a carbon nanotube based crossbar memory called Nano-RAM and Hewlett-Packard which has proposed the use of memristor material as a future replacement of Flash memory. 3) Novel semiconductor devices An example of such novel devices is based on spintronics.The dependence of the resistance of a material (due to the spin of the electrons) on an external field is called magnetoresistance. This effect can be significantly amplified (GMR - Giant Magneto-Resistance) for nanosized objects, for example when two ferromagnetic layers are separated by a nonmagnetic layer, which is several nanometers thick (e.g. Co-Cu-Co). The GMR effect has led to a strong increase in the data storage density of hard disks and made the gigabyte range possible. The so called tunneling magnetoresistance (TMR) is very similar to GMR and based on the spin dependent tunneling of electrons through adjacent ferromagnetic layers. Both GMR and TMR effects can be used to create a non-volatile main memory for computers, such as the so called magnetic random access memory or MRAM. In 1999, the ultimate CMOS transistor developed at the Laboratory for Electronics and Information Technology in Grenoble, France, tested the limits of the principles of the MOSFET transistor with a diameter of 18 nm (approximately 70 atoms placed side by side). This was almost one tenth the size of the smallest industrial transistor in 2003 (130 nm in 2003, 90 nm in 2004, 65 nm in 2005 and 45 nm in 2007). It enabled the theoretical integration of seven billion junctions on a 1 coin. However, the CMOS transistor, which was created in 1999, was not a simple research experiment to study how CMOS technology functions, but rather a demonstration of how this technology functions now that we ourselves are getting ever closer to working on a molecular scale. Today it would be impossible to master the coordinated assembly of a large number of these transistors on a circuit and it would also be impossible to create this on an industrial level. 4) Novel optoelectronic devices In the modern communication technology traditional analog electrical devices are increasingly replaced by optical or optoelectronic devices due to their enormous bandwidth and capacity, respectively. Two promising examples are photonic crystals and quantum dots. Photonic crystals are materials with a periodic variation in the refractive index with a lattice constant that is half the wavelength of the light used. They offer a selectable band gap for the propagation of a certain wavelength, thus they resemble a semiconductor, but for light or photons instead of electrons. Quantum dots are nanoscaled objects, which can be used, among many other things, for the construction of lasers. The advantage of a quantum dot laser over the traditional semiconductor laser is that their emitted wavelength depends on the diameter of the dot. Quantum dot lasers are cheaper and offer a higher beam quality than conventional laser diodes. 5) Displays The production of displays with low energy consumption could be accomplished using carbon nanotubes (CNT). Carbon nanotubes are electrically conductive and due to their small diameter of several nanometers, they can be used as field emitters with extremely high efficiency for field emission displays (FED). The principle of operation resembles that of the cathode ray tube, but on a much smaller length scale. Unlike a conventional flat panel display, which uses a power to illuminate its pixels, electronic paper reflects light like ordinary paper and is capable of holding text and images indefinitely without drawing electricity, while allowing the image to be chan flexible substrates an due to their paper displays are considered prime examples of the electronic paper category. Fig. 1.8 6) Quantum computers Entirely new approaches for computing exploit the laws of quantum mechanics for novel quantum computers, which enable the use of fast quantum algorithms. The Quantum computer has quantum bit memory space termed "Qubit" for several computations at the same time. This facility may improve the performance of the older systems. flat panel display, which uses a power-consuming backlight to illuminate its pixels, electronic paper reflects light like ordinary paper and is capable of holding text and images indefinitely without drawing electricity, while allowing the image to be changed later. Because they can be produced on thin, flexible substrates an due to their paper-like appearance (Fig. 1.8), electrophoretic displays are considered prime examples of the electronic paper category. Fig. 1.8 Electrophoretic displays Entirely new approaches for computing exploit the laws of quantum mechanics for novel quantum computers, which enable the use of fast quantum algorithms. The Quantum computer has quantum bit memory space termed "Qubit" for several e same time. This facility may improve the performance of the consuming backlight to illuminate its pixels, electronic paper reflects light like ordinary paper and is capable of holding text and images indefinitely without drawing electricity, while ged later. Because they can be produced on thin, , electrophoretic displays are considered prime examples of the electronic paper category. Entirely new approaches for computing exploit the laws of quantum mechanics for novel quantum computers, which enable the use of fast quantum algorithms. The Quantum computer has quantum bit memory space termed "Qubit" for several e same time. This facility may improve the performance of the 1.4.5 Heavy Industry 1) Aerospace Lighter and stronger materials will be of immense use to aircraft manufacturers, leading to increased performance. Spacecraft will also benefit, where weight is a major factor. Nanotechnology would help to reduce the size of equipment and thereby decrease fuel-consumption required to get it airborne. Hang gliders may be able to halve their weight while increasing their strength and toughness through the use of nanotech materials. Nanotech is lowering the mass of super capacitors that will increasingly be used to give power to assistive electrical motors for launching hang gliders off flatland to thermal- chasing altitudes. 2) Construction Nanotechnology has the potential to make construction faster, cheaper, safer, and more varied. Automation of nanotechnology construction can allow for the creation of structures from advanced homes to massive skyscrapers much more quickly and at much lower cost. 2) Refineries Using nanotech applications, refineries producing materials such as steel and aluminum will be able to remove any impurities in the materials they create. 3) Vehicle manufacturers Much like aerospace, lighter and stronger materials will be useful for creating vehicles that are both faster and safer. Combustion engines will also benefit from parts that are more hard-wearing and more heat-resistant. 1.4.6 Consumer goods Nanotechnology is already impacting the field of consumer goods, providing products with novel functions ranging from easy-to-clean to scratch-resistant. Modern textiles are wrinkle-resistant and stain-repellent; in the mid-term clothes will become smart, through embedded wearable electronics. Already in use are different nanoparticle improved products. Especially in the field of cosmetics, such novel products have a promising potential. 1) Foods Complex set of engineering and scientific challenges in the food and bio- processing industry for manufacturing high quality and safe food through efficient and sustainable means can be solved through nanotechnology. Bacteria identification and food quality monitoring using biosensors; intelligent, active, and smart food packaging systems; nanoencapsulation of bioactive food compounds are few examples of emerging applications of nanotechnology for the food industry Nanotechnology can be applied in the production, processing, safety and packaging of food. A nanocomposite coating process could improve food packaging by placing anti-microbial agents directly on the surface of the coated film. Nanocomposites could increase or decrease gas permeability of different fillers as is needed for different products. They can also improve the mechanical and heat-resistance properties and lower the oxygen transmission rate. Research is being performed to apply nanotechnology to the detection of chemical and biological substances for sensanges in foods. 1a) Nano-foods New consumer products Emerging Nanotechnologies (PEN), based on an inventory it has drawn up of 609 known or claimed nano-products. On PEN's list are three foods a brand of canola cooking oil called Canola Active Oil, a tea called Nanotea and a chocolate diet shake called Nanoceuticals Slim Shake Chocolate. According to company information posted on PEN's Web site, the canola oil, by Shemen Industries of Israel, contains an additive called "nanodrops" designed to carry vitamins, minerals and phytochemicals through the digestive system. The shake, according to U.S. manufacturer RBC Life Sciences Inc., uses cocoa infused "NanoClusters" to enhance the taste and health benefits of cocoa without the need for extra sugar. Household The most prominent application of nanotechnology in the household is self- cleaning or easy-to-clean surfaces on ceramics or glasses. Nanoceramic particles have improved the smoothness and heat resistance of common household equipment such as the flat iron. Optics The first sunglasses using protective and anti-reflective ultrathin polymer coatings are on the market. For optics, nanotechnology also offers scratch resistant surface coatings based on nanocomposites. Nano-optics could allow for an increase in precision of pupil repair and other types of laser eye surgery. Textiles The use of engineered nanofibers already makes clothes water- and stain-repellent or wrinkle-free. Textiles with a nanotechnological finish can be washed less frequently and at lower temperatures. Nanotechnology has been used to integrate tiny carbon particles membrane and guarantee full electrostatic charges for the wearer. Many other applications have been dev by research institutions such as the University. Fig. 1.9 Improved and new functionalities of textile by nanotechnology Cosmetics One field of application is in sunscreens. The traditional chemical UV protection approach suffers from its poor long nanoparticles such as titanium dioxide offer several advantages. Titanium oxide nanoparticles have a comparable UV protection property as the bulk material, but lose the cosmetically undesirable whitening as the particle size is decreased. 1.4.7 Agriculture Applications of nanotechnology have the potential to change the entire agriculture sector and food industry chain from production to conservation, processing, packaging, transportation, and even waste treatment. NanoScience concepts and Nanotechnology appl tiny carbon particles membrane and guarantee full-surface protection from electrostatic charges for the wearer. Many other applications have been dev by research institutions such as the Textiles Nanotechnology Laboratory oved and new functionalities of textile by nanotechnology One field of application is in sunscreens. The traditional chemical UV protection approach suffers from its poor long-term stability. A sunscreen based on mineral tanium dioxide offer several advantages. Titanium oxide nanoparticles have a comparable UV protection property as the bulk material, but lose the cosmetically undesirable whitening as the particle size is decreased. Applications of nanotechnology have the potential to change the entire agriculture sector and food industry chain from production to conservation, processing, packaging, transportation, and even waste treatment. NanoScience concepts and Nanotechnology applications have the potential to redesign the surface protection from electrostatic charges for the wearer. Many other applications have been developed Textiles Nanotechnology Laboratory at Cornell oved and new functionalities of textile by nanotechnology One field of application is in sunscreens. The traditional chemical UV protection term stability. A sunscreen based on mineral tanium dioxide offer several advantages. Titanium oxide nanoparticles have a comparable UV protection property as the bulk material, but lose the cosmetically undesirable whitening as the particle size is decreased. Applications of nanotechnology have the potential to change the entire agriculture sector and food industry chain from production to conservation, processing, packaging, transportation, and even waste treatment. NanoScience ications have the potential to redesign the production cycle, restructure the processing and conservation processes and redefine the food habits of the people. Major Challenges related to agriculture like low productivity in cultivable areas, large uncultivable areas, shrinkage of cultivable lands, wastage of inputs like water, fertilizers, pesticides, wastage of products and of course Food security for growing numbers can be addressed through various applications of nanotechnology. Nano scale Popularly, nano is also used as an adjective to describe objects, systems, or phenomena with characteristics arising from nanometer-scale structure. While micro has come to mean anything small, nano emphasizes the atomic granularity that produces the unique phenomena observed in nanoscience. While there are some exceptional examples, most of the exciting properties of nano begin to be apparent in systems smaller than 1000 nm, or 1 micrometer, 1 m. The particles with any dimension smaller than 1 micrometer as nanoparticles, and those somewhat larger as microparticles. Nanostructured materials did not first come into existence with the recent emergence of the field of nanotechnology. Many existing materials are structured on the micro- and nanometer scales, and many industrial processes that have been used for decades (e.g. polymer and steel manufacturing) exploit nanoscale phenomena. Fig. 1.10 Logarithmical length scale showing size of Nanomateria compared to biological components and definition of nano and micro sizes Moreover, many materials that seems smooth to the naked eye have an intricate structure on the scale of nanometers are not new. Recent advances in have fueled a boom in the study and industrial use of nano new vocabulary has emerged from this research, and its important terms and concepts are defined below. 1.1.1 Nanomaterials Nanomaterials are materials that have structural components smaller than 1 micrometer in at least one dimension. While the atomic and molecular building blocks (~0.2 nm) of matter are considered nanomaterials, examples such as bulk crystals with lattice spacing of nanometers but macroscopic dimensions overall, are commonly excluded. thmical length scale showing size of Nanomateria compared to biological components and definition of nano and micro sizes Moreover, many materials that seems smooth to the naked eye have an scale of nanometers. Thus in many ways nanomaterials are not new. Recent advances in synthesis and characterization tools, however, have fueled a boom in the study and industrial use of nano-structured materials. A new vocabulary has emerged from this research, and its important terms and omaterials are materials that have structural components smaller than 1 micrometer in at least one dimension. While the atomic and molecular building blocks (~0.2 nm) of matter are considered nanomaterials, examples such as bulk ng of nanometers but macroscopic dimensions overall, are thmical length scale showing size of Nanomaterials compared to biological components and definition of nano and micro sizes Moreover, many materials that seems smooth to the naked eye have an . Thus in many ways nanomaterials synthesis and characterization tools, however, structured materials. A new vocabulary has emerged from this research, and its important terms and omaterials are materials that have structural components smaller than 1 micrometer in at least one dimension. While the atomic and molecular building blocks (~0.2 nm) of matter are considered nanomaterials, examples such as bulk ng of nanometers but macroscopic dimensions overall, are 1.1.2 Nanoparticles Nanoparticles are particles with at least one dimension smaller than 1 micron and potentially as small as atomic and molecular length scales (~0.2 nm). Nanoparticles can have amorphous or crystalline form and their surfaces can act as carriers for liquid droplets or gases. To some degree, nanoparticulate matter should be considered a distinct state of matter, in addition to the solid, liquid, gaseous, and plasma states, due to its distinct properties (large surface area and quantum size effects). Examples of materials in crystalline nanoparticle form are fullerenes and carbon nanotubes, while traditional crystalline solid forms are graphite and diamond. Many authors limit the size of nanomaterials to 50 nm or 100 nm the choice of this upper limit being justified by the fact that some physical properties of nanoparticles approach those of bulk when their size reaches these values. However, this size threshold varies with material type and cannot be the basis for such a classification. A legitimate definition extends this upper size limit to 1 micron, the sub-micron range being classified as nano. Nanoparticulate matter refers to a collection of nanoparticles, emphasizing their collective behavior. Nanotechnology can be defined as the design, synthesis, and application of materials and devices whose size and shape have been engineered at the nanoscale. It exploits unique chemical, physical, electrical, and mechanical properties that emerge when matter is structured at the nanoscale. 1.6 Surfaces and dimensional space Two primary factors cause nanomaterials to behave significantly differently than bulk materials: surface effects (causing smooth properties scaling due to the fraction of atoms at the surface) and quantum effects (showing discontinuous behavior due to quantum confinement effects in materials with delocalized electrons). These factors affect the chemical reactivity of materials, as well as their mechanical, optical, electric, and magnetic properties. The fraction of the atoms at the surface in nanoparticles is increased compared to microparticles or bulk. Compared to microparticles, nanoparticles have a very large surface area and high particle number per unit mass. For illustration, one carbon microparticle with a diameter of 60 m has a mass of 0.3 g and a surface area of 0.01 mm 2 . The same mass of carbon in nanoparticulate form, with each particle having a diameter of 60 nm, has a surface area of 11.3 mm 2 and consists of 1 billion nanoparticles (Fig.1. 11 a). The ratio of surface area to volume (or mass) for a particle with a diameter of 60 nm is 1000 times larger than a particle with a diameter of 60 m (Fig. 1.11 b). As the material in nanoparticulate form presents a much larger surface area for chemical reactions, reactivity is enhanced roughly 1000-fold. While chemical reactivity generally increases with decreasing particle size, surface coatings and other modifications can have complicating effects, even reducing reactivity with decreasing particle size in some instances. The atoms situated at the surface have less neighbors than bulk atoms, resulting in lower binding energy per atom with decreasing particle size. A consequence of reduced binding energy per atom is a melting point reduction with particle radius, following the Gibbs-Thomson equation. For example, the melting temperature of 3 nm gold nanoparticles is more than 300 degrees lower than the melting temperature of bulk gold, as shown in Fig. 1.11c. 1.6.1 Generations Fig 1.12 Schamatic diagram of nanosystem development Fig. 1.11 Schamatic diagram of nanosystem development Schamatic diagram of nanosystem development 1.7 Evolution of band structures and Fermi surfaces 1.7.1 Electronic band structure of nano crystals and solids: Materials can be identified with appropriate structure and bonding. To understand different thermal, electronic, mechanical and magnetic properties it is necessary to know the electronic structure of solids. The electronic structure of nano materials would be different from atoms, molecules or solids. Nanomaterials are intermediate form of solids. They are too small to be considered as bulk three dimensional solids and too big to be considered as molecules. When two atoms are brought together there will be a change in the electronic structure. Addition of each atom would change the electronic structure till the number of atoms becomes too large. An alternative view of the electronic band structure of solids is to consider the electron waves in a periodic crystalline potential. The starting point for this approach is the DrudeLorentz free electron model for metals. In this model a metallic solid is considered as consisting of a close packed lattice of positive cations surrounded by an electron sea or cloud formed from the ionization of the outer shell (valence) electrons. We can then treat the valence electrons as if they were a gas inside a container and use classical kinetic gas theory. This works best for the electropositive metals of Groups I and II as well as aluminium (the so- called free electron metals) and can explain many of the fundamental properties of metals such as high electrical and thermal conductivities, optical opacity, reflectivity, ductility and alloying properties. However, a more realistic approach is to treat the free electrons in metals quantum mechanically and consider their wave-like properties. Here the free valence electrons are assumed to be constrained within a potential well which essentially stops them from leaving the metal (the particle-in-a-box model). The box boundary conditions require the wavefunctions to vanish at the edges of the crystal (or box). The allowed wavefunctions given by the Schrodinger equation then correspond to certain wavelengths as shown in Fig. 1.13. For a one- dimensional box of length L, the permitted wavelengths are E n represents solely kinetic energy since the potential energy is assumed to be zero within the box. Thus there is a parabolic relationship between E n and n, and therefore between E n and k since k depends directly on n as described above. The permitted energy levels on this parabola are discrete (i.e., quantized): however in principle the size of L for most metal crystals (ranging from microns to millimetres or even centimetres) means that the separation between levels is very small compared with the thermal energy k B T, and we can regard the energy distribution as almost continuous (quasi-continuous) so that the levels form a band of allowed energies as shown in Fig. 1.14. Fig 1.13 Energy level diagram also showing the form of some of the allowed wavefunctions for an electron confined to a one-dimensional potential well Note that as the electron becomes more localized (i.e., L decreases), the energy of a particular electron state (and more importantly the spacing between energy states) increases; this has important implications for bonding and also for reduced- dimensionality or quantum-confined systems which are discussed later. Fig 1.14 Schematic version of the parabolic relationship between the allowed electron wave vectors and their energy for electrons confined to a one- dimensional potential well. Shaped energy regions represent those occupied with electrons 1.6.1 Electronic conduction We may now observe that the series of allowed k values in equation extends up to the edges of the Brillouin zone, at k =/a. Since one of these endpoints may be mapped onto the other by a reciprocal lattice vector translation, the total number of allowed k values is precisely N. Recalling that each k state may be occupied by both a spin up and a spin down electron, the total number of states available is 2N per energy band. In three dimensions, this result is generalised to 2N states per band, where N is the number of unit cells in the crystal. Now, the total number of valence electrons in the crystal is z N, where z is the number of valence electrons per unit cell. This leads to two very different electronic configurations in a solid. If z is even, then one energy band is completely filled, with the next band being completely empty. Fig. 1.15 Electron energy band structure diagram and density of states of crystalline silicon The highest filled band is the valence band, and the next, empty band, is the conduction band. The electrons in the valence band cannot participate in electrical conduction, because there are no available states for them to move into consistent with the small increase in energy required by motion in response to an externally applied voltage: hence this configuration results in an insulator or, if the band gap is sufficiently small, a semiconductor. Alternatively, if z is odd, then the highest occupied energy band is only half full. In such a material, there are many vacant states immediately adjacent in energy to the highest occupied states, therefore electrical conduction occurs very efficiently and the material is a metal. Fig. 1.16 shows schematic energy diagrams for insulators, metals and semiconductors respectively. There is one further, special case which gives rise to metallic behaviour: namely, when the valence band is completely full (z is even), but the valence and conduction bands overlap in energy, such that there are vacant states immediately adjacent to the top of the valence band, just as in the case of a half- filled band. Such a material is called a semi-metal. Fig.1.16 Electron energy band diagram for insulator, semiconductor and conductor 1.10 Size and shapes Dimensionality and size dependent phenomena Nanoparticles are generally classified based on their dimensionality, morphology, composition, uniformity, and agglomeration. An important additional distinction should be made between nanostructured thin films or other fixed nanometer-scale objects (such as the circuits within computer microprocessors) and free nanoparticles. The motion of free nanoparticles is not constrained, and they can easily be released into the environment leading to human exposure that may pose a serious health risk. In contrast are the many objects containing nanostructured elements that are firmly attached to a larger object, where the fixed nanoparticles should pose no health risk when properly handled. An example of this important distinction is the material asbestos, which is perfectly safe in its primary state (basically a type of solid rock), but is a significant health hazard when mined or worked in such a way as to produce the carcinogenic nanometer- scale fibrous particles that become airborne (aerosol) and are therefore readily absorbed in the lungs. It is also very important to recognize that not all nanoparticles are toxic; toxicity depends on at least chemical composition and shape in addition to simply size and particle ageing. In fact, many types of nanoparticles seem to be non-toxic, others can be rendered non-toxic, while others appear to have beneficial health effects. An important lesson we are in the process of learning from nanoscience is that simple classifications of physical behavior (and therefore toxicity) are overly limiting and that we must study toxicology of each material and each morphology, in addition to particle ageing, to obtain accurate information to inform policy and regulatory processes. 1.10.1 Dimensionality As shape, or morphology of nanoparticles plays an important role in their toxicity, it is useful to classify them based on their number of dimensions. This is a generalization of the concept of aspect ratio. 1D nanomaterials - Materials with one dimension in the nanometer scale are typically thin films or surface coatings, and include the circuitry of computer chips and the antireflection and hard coatings on eyeglasses. Thin films have been developed and used for decades in various fields, such as electronics, chemistry, and engineering. Thin films can be deposited by various methods and can be grown controllably to be only one atom thick, a so-called monolayer. 2D nanomaterials - Two-dimensional nanomaterials have two dimensions in the nanometer scale. These include 2D nanostructured films, with nanostructures firmly attached to a substrate, or nanopore filters used for small particle separation and filtration. Free particles with a large aspect ratio, with dimensions in the nanoscale range, are also considered 2D nanomaterials. Asbestos fibers are an example of 2D nanoparticles. 3D nanomaterials - Materials that are nanoscaled in all three dimensions are considered 3D nanomaterials. These include thin films deposited under conditions that generate atomic-scale porosity, colloids, and free nanoparticles with various morphologies. 1.10.2. Nanoparticle morphology Morphological characteristics to be taken into account are: flatness, sphericity, and aspect ratio. A general classification exists between high- and low-aspect ratio particles (Fig1.17). High aspect ratio nanoparticles include nanotubes and nanowires, with various shapes, such as helices, zigzags, belts, or perhaps nanowires with diameter that varies with length. Small-aspect ratio morphologies include spherical, oval, cubic, prism, helical, or pillar. Collections of many particles exist as powders, suspension, or colloids. 1.10.3. Nanoparticle composition Nanoparticles can be composed of a single constituent material (Fig. 1.17) or be a composite of several materials. The nanoparticles found in nature are often agglomerations of materials with various compositions, while pure single- composition materials can be easily synthesized today by a variety of methods. 1.10.4. Nanoparticle uniformity and agglomeration Based on their chemistry and electro-magnetic properties, nanoparticles can exist as dispersed aerosols, as suspensions/colloids, or in an agglomerate state (Fig. 1.17). For example, magnetic nanoparticles tend to cluster, forming an agglomerate state, unless their surfaces are coated with a non-magnetic material. In an agglomerate state, nanoparticles may behave as larger particles, depending on the size of the agglomerate. Hence, it is evident that nanoparticle agglomeration, size and surface reactivity, along with shape and size, must be taken into account when deciding considering health and environmental regulation of new materials. Fig. 1.17 Classification of nanostructured materials from the point of view of nanostructure dimensions, morphology, composition, uniformity and agglomeration state. Nanotechnology is helping to considerably improve, even revolutionize, many technology and industry environmental science, medicine, homeland security, food safety, and transportation, among many others. Most benefits of nanotechnology depend on the fact that it is possible to tailor the essential structures of m nanoscale to achieve specific properties, thus greatly extending the well toolkits of materials science. Using nanotechnology, materials can effectively be made to be stronger, lighter, more durable, more reactive, more sieve electrical conductors, among many other traits. Classification of nanostructured materials from the point of view of nanostructure dimensions, morphology, composition, uniformity and Nanotechnology is helping to considerably improve, even revolutionize, many technology and industry sectors: information technology, energy, environmental science, medicine, homeland security, food safety, and transportation, among many others. Most benefits of nanotechnology depend on the fact that it is possible to tailor the essential structures of m nanoscale to achieve specific properties, thus greatly extending the well toolkits of materials science. Using nanotechnology, materials can effectively be made to be stronger, lighter, more durable, more reactive, more sieve electrical conductors, among many other traits. Classification of nanostructured materials from the point of view of nanostructure dimensions, morphology, composition, uniformity and Nanotechnology is helping to considerably improve, even revolutionize, sectors: information technology, energy, environmental science, medicine, homeland security, food safety, and transportation, among many others. Most benefits of nanotechnology depend on the fact that it is possible to tailor the essential structures of materials at the nanoscale to achieve specific properties, thus greatly extending the well-used toolkits of materials science. Using nanotechnology, materials can effectively be made to be stronger, lighter, more durable, more reactive, more sieve-like, or better
(Intelligent Systems, Control and Automation_ Science and Engineering 72) B. S. Goh, W. J. Leong, K. L. Teo (Auth.), Honglei Xu, Xiangyu Wang (Eds.)-Optimization and Control Methods in Industrial Engi