UNIT I

Importance of nano scale: The nanoscopic scale usually refers to structures with a length scale applicable to nanotechnology, usually cited as 1-100 nanometers. The nanoscopic scale is (roughly speaking) a lower bound to the mesoscopic scale for most solids. For technical purposes, the nanoscopic scale is the size at which the expected fluctuations of the averaged properties (due to the motion and behavior of individual particles) can no longer be reduced to a size below some desirable threshold (often a few percent), and must be rigorously established within the context of any particular problem. The 'nanoscopic scale' is sometimes marked as the point where the properties of a material change; above this point, the properties of a material are caused by 'bulk' or 'volume' effects, namely which atoms are present, how they are bonded, and in what ratios. Below this point, the properties of a material change, and while the type of atoms present and their relative orientations are still important, 'surface area effects' (also referred to as quantum effects)become more apparent-these effects are due to the geometry of the material (how thick it is, how wide it is, etc), which, at these low dimensions, can have a drastic effect on quantized states, and thus the properties of a material

1. Introduction Zero dimensional nano structures are the three dimensional relatively equi axed materials having their largest dimension in between 0 to 100 nm. These are also called as nano particles or nano powders. Nano particles have created a high intrest in recent years by virtue of their unusual mechanical, electrical, optical and magnetic properties. Due to their special properties, nano particles are finding their wide applications in all fields of engineering, medicine like longer lasting medical implants of biocompatible nanostructured ceramic and carbides, biocompatible coating for medical applications, drug delivery, protection coatings, composite materials, anti fogging coatings for spectacles and car windows etc. Many techniques, including both top-down and bottom-up approaches, have been developed and applied for the synthesis of nanoparticles. This chapter deals with some of the common as well as some of the more obscure processes that have been employed in recent years with an emphasis on production of nano particles.

Processes for producing ultrafine powders There are two approaches to the synthesis of nanomaterials and the fabrication of nanostructures; viz top-down and bottom-up. Top down approach involves the breaking down of the bulk material into nano sized structures or particles. These techniques are an extension of those that have been used for producing micron- sized particles. An example of such a technique is high-energy wet ball milling. The alternative approach, which has the potential of creating less waste and hence the more economical, is the bottom- up. Bottom up approach refers to the build up of a material from the bottom: atom-by-atom, molecule-by-molecule, or cluster-by-cluster. Many of these techniques are still under development or are just beginning to be used for commercial production of nano powders. Characteristics of Nano particles that should posses by any fabrication technique: Getting merely a small size is not the only requirement. It should have i. Identical size of all particles (also called mono sized or with uniform size distribution. ii. iii. Identical shape or morphology. Identical chemical composition and crystal structure that are desired

among different particles and within individual particles, such as core and composition must be the same. iv.
2.Topdownappraoach: High-Energy ball milling: The milling of materials is of prime interest in the mineral, ceramic processing, and powder metallurgy industry. Typical objectives of the milling process include particle size reduction (comminution), solid-state alloying, mixing or blending, and particle shape changes. These industrial processes are mostly restricted to relatively hard, brittle materials which fracture, deform, and cold weld during the milling operation. While oxide-dispersion strengthened super alloys have been the primary application of mechanical attrition, the technique has been extended to produce a variety of nonequilibrium structures including nanocrystalline, amorphous and quasicrystalline materials. A variety of ball mills has been developed for different purposes including tumbler mills, attrition mills, shaker

Individually dispersed or mono dispersed i.e., no agglomeration.

mills, vibratory mills, planetary mills, etc. The basic process of mechanical attrition is illustrated in fig below.

Fig: Schematic representation of the principle of mechanical milling. Powders with typical particle diameters of about 50 m are placed together with a number of hardened steel or tungsten carbide (WC) coated balls in a sealed container which is shaken or violently agitated. The most effective ratio for the ball to powder masses is five to 10. High-energy milling forces can be obtained using high frequencies and small amplitudes of vibration. Shaker mills (e.g. SPEX model 8000) which are preferable for small batches of powder (approximately 10 cm3 is sufficient for research purposes) are highly energetic and reactions can take place one order of magnitude faster than with other types of mill. Since the kinetic energy of the balls is a function of their mass and velocity, dense materials (steel or tungsten carbide) are preferable to ceramic balls. During the continuous severe plastic deformation associated with mechanical attrition, a continuous refinement of the internal structure of the powder particles to nanometer scales occurs during high energy mechanical attrition. The temperature rise during this process is modest and is estimated to be less than or equal to 100 to 2000 C. The difficulty with top-down approaches is ensuring all the particles are broken down to the required particle size. Furthermore, for all nanocrystalline materials prepared by a variety of different synthesis routes, surface and interface contamination is a major concern. In particular, during mechanical attrition, contamination by the milling tools (Fe) and atmosphere (trace elements of O2, N2, in rare gases) can be a problem. By minimizing the milling time and using the purest, most ductile metal powders available, a thin coating of the milling tools by the respective powder material can be obtained which reduces Fe contamination tremendously. Atmospheric contamination can be minimized or

eliminated by sealing the vial with a flexible O ring after the powder has been loaded in an inert gas glove box. Small experimental ball mills can also be enclosed completely in an inert gas glove box. As a consequence, the contamination with Fe based wear debris can generally be reduced to less than 1-2 % and oxygen and nitrogen contamination to less than 300 ppm. However, milling of refractory metals in a shaker or planetary mill for extended periods of time (>30 h) can result in levels of Fe contamination of more than 10% if high vibrational or rotational frequencies are employed. On the other hand, contamination through the milling atmosphere can have a positive impact on the milling conditions if one wants to prepare metal or ceramic nanocomposites with one of the metallic elements being chemically highly reactive with the gas (or fluid) environment. On the other side, main advantage of topdown approach is high production rates of nano powders. 3. Bottom-up approach: 3.1 Wet Chemical Synthesis of nanomaterials (Sol-gel process): The sol-gel process, as the name implies, involves the evolution of inorganic networks through the formation of a colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid phase (gel). The precursors for synthesizing these colloids consist usually of a metal or metalloid element surrounded by various reactive ligands. The starting material is processed to form a dispersible oxide and forms a sol in contact with water or dilute acid. Removal of the liquid from the sol yields the gel, and the sol/gel transition controls the particle size and shape. Calcination of the gel produces the oxide. Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based precursors such as Si (OEt) 4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the sol-gel chemistry based on the hydrolysis and condensation of metal alkoxides M(OR)z can be described as follows: MOR + H2O MOH + ROH (hydrolysis) MOH+ROMM-O-M+ROH (condensation) Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is widely employed to prepare oxide materials. The sol-gel process can be characterized by a series of distinct steps. Step 1: Formation of different stable solutions of the alkoxide or solvated metal precursor (the sol).

Step 2: Gelation resulting from the formation of an oxide- or alcohol- bridged network (the gel) by a polycondensation or polyesterification reaction that results in a dramatic increase in the viscocity of the solution. Step 3: Aging of the gel (Syneresis), during which the polycondensation reactions continue until the gel transforms into a solid mass, accompanied by contraction of the gel network and expulsion of solvent from gel pores. Ostwald ripening (also referred to as coarsening, is the phenomenon by which smaller particles are consumed by larger particles during the growth process) and phase transformations may occur concurrently with syneresis. The aging process of gels can exceed 7 days and is critical to the prevention of cracks in gels that have been cast. Step 4: Drying of the gel, when water and other volatile liquids are removed from the gel network. This process is complicated due to fundamental changes in the structure of the gel. The drying process has itself been broken into four distinct steps: (i) the constant rate period, (ii) the critical point, (iii) the falling rate period, (iv)the second falling rate period. If isolated by thermal evaporation, the resulting monolith is termed a xerogel. If the solvent (such as water) is extracted under supercritical or near super critical conditions, the product is an aerogel. Step 5: Dehydration, during which surface- bound M-OH groups are removed, there by stabilizing the gel against rehydration. This is normally achieved by calcining the monolith at temperatures up to 8000C. Step 6: Densification and decomposition of the gels at high temperatures (T>8000C). The pores of the gel network are collapsed, and remaining organic species are volatilized. The typical steps that are involved in sol-gel processing are shown in the schematic diagram below.

Fig: Schematic representation of sol-gel process of synthesis of nanomaterials.

The interest in this synthesis method arises due to the possibility of synthesizing nonmetallic inorganic materials like glasses, glass ceramics or ceramic materials at very low temperatures compared to the high temperature process required by melting glass or firing ceramics. The major technical difficulties to overcome in developing a successful bottom-up approach is controlling the growth of the particles and then stopping the newly formed particles from agglomerating. Other technical issues are ensuring the reactions are complete so that no unwanted reactant is left on the product and completely removing any growth aids that may have been used in the process. Also production rates of nano powders are very very low by this process. The main advantage is one can get monosized nano particles by any bottom up approach. 3.2 Liquid solid reactions: Ultrafine particles are produced by precipitation from a solution, the process being dependent on the presence of the desired nuclei. For example, TiO2 powders have been produced with particle sizes in the range 70-300 nm from titanium tetraisopropoxide. The ZnS powders were produced by reaction of aqueous zinc salt solutions with thioacetamide (TAA). Precursor zinc salts were chloride, nitric acid solutions, or zinc salts with noncommon associated ligands (i.e., acetylacetonate,

trifluorocarbonsulfonate, and dithiocarbamate). The 0.05 M cation solutions were heated in a thermal bath maintained at 70 or 80 C in batches of 100 or 250 ml. Acid was added dropwise to bring it to a pH of 2. The reaction was started by adding the TAA to the zinc salt solution, with the molar ratio of TAA and zinc ions being set to an initial value of either 4 or 8. In intervals, aliquots were collected from the reacting solution 3.4. Chemical Vapour Condensation (CVC) Chemical vapor condensation (CVC) was developed in Germany in 1994. It involves pyrolysis of vapors of metal organic precursors in a reduced pressure atmosphere. Particles of ZrO2, Y2O3 and nanowhiskers have been produced by CVC method. As shown schematically in Figure, the evaporative source used in GPC is replaced by a hot wall reactor in the Chemical Vapour Condensation or the CVC process. The original idea of the novel CVC process which is schematically shown below where it was intended to adjust the parameter field during the synthesis in order to suppress film formation and enhance homogeneous nucleation of particles in the gas flow. It is readily found that the residence time of the precursor in the reactor determines if films or particles are formed. In a certain range of residence time

both particle and film formation can be obtained. Adjusting the residence time of the precursor molecules by changing the gas flow rate, the pressure difference between the precursor delivery system and the main chamber and the temperature of the hot wall reactor results in the prolific production of nanosized particles of metals and ceramics instead of thin films as in CVD processing. In the simplest form a metalorganic precursor is introduced into the hot zone of the reactor using mass flow controller. For instance, hexamethyldisilazane (CH3)3 Si NHSi (CH3)3 was used to produce SiCxNyOz powder by CVC technique. Besides the increased quantities in this Continuous process compared to GPC it has been demonstrated that a wider range of ceramics including nitrides and carbides can be synthesised. Additionally, more complex oxides such as BaTiO3 or composite structures can be formed as well. In addition to the formation of single phase nanoparticles by CVC of a single precursor the reactor allows the synthesis of 1. Mixtures of nanoparticles of two phases or doped nanoparticles by supplying two precursors at the front end of the reactor, and 2. Coated nanoparticles, i.e., n-ZrO2 coated with n-Al2 O3 or vice versa, by Supplying a second precursor at a second stage of the reactor. In this case nanoparticles which have been formed by homogeneous nucleation are coated by heterogeneous nucleation in a second stage of the reactor.

Fig: A schematic of a typical CVC reactor

Because CVC processing is continuous, the production capabilities are much larger than in GPC processing. Quantities in excess of 20 g/hr have been readily produced with a small scale laboratory reactor. A further expansion can be envisaged by simply enlarging the diameter of the hot wall reactor and the mass flow through the reactor. The microstructure of nanoparticles as well as the properties of materials obtained by CVC has been identical to GPC prepared powders. 3.5. Laser ablation: Laser ablation has been extensively used for the preparation of nanoparticles and particulate films. In this process a laser beam is used as the primary excitation source of ablation for generating clusters directly from a solid sample in a wide variety of applications. The possibility for preparing nanoparticulate web-like structures over large sample area is of particular interest in view of their novel properties that can be applied to new technological applications as shown by El-Shall and his collaborators. Laser vaporization cluster beams were introduced by smalley and coworkers to overcome the limitations of oven sources. In this method, a high energy pulsed laser with an intensity flux exceeding 107 W/cm3 is focused on a target containing the material to be made into clusters. The resulting plasma causes highly efficient vaporization since with current, pulsed lasers one can easily generate temperatures at the target material greater than

104 K.

This high temperature vaporizes all known

substances so quickly that the rest of the source can operate at room temperature. Typical yields are

1014-1015 atoms from a surface area of 0.01 cm2 in a 10-8 s pulse. The local atomic vapor density can
exceed 1018 atom/cm3 (equivalent to 100 Torr pressure) in the microseconds following the laser pulse. The hot metal vapor is entrained in a pulsed flow of carrier gas (typically He) and expanded through a nozzle into a vacuum. The cool, high-density helium flowing over the target serves as a buffer gas in which clusters of the target material form, thermalize to near room temperature and then cool to a few K in the subsequent supersonic expansion. A typical laser vaporization source is shown in figure below. In a recent investigation utilising a novel atomization system, (LINA-SPARK), LSA, based on laser spark atomization of solids has been developed that seems to be very versatile for different

materials. Briefly, the LSA is capable of evaporating material at a rate of about 20 g/s from a solid target under argon atmosphere. The small dimensions of the particles and the possibility to form thick films make the LSA quite an efficient tool for the production of ceramic particles and coatings and also an ablation source for analytical applications such as the coupling to induced coupled plasma emission spectrometry, ICP, the formation of the nanoparticles has been explained following a liquefaction process which generates an aerosol, followed by the cooling/solidification of the droplets which results in the formation of fog. The general dynamics of both the aerosol and the fog favours the aggregation process and micrometer-sized fractal-like particles are formed. The laser spark atomizer can be used to produce highly mesoporous thick films and the porosity can be modified by the carrier gas flow rate thus enabling for a control of the microstructure of the coatings which make these nanoparticulate thick films suitable candidates for application in membrane technology, catalysis and lithium ion batteries. ZrO2 and SnO2 nanoparticulate thick films were also synthesized successfully using this process with quite identical microstructure. Synthesis of other materials such as lithium manganate, silicon and carbon has also been carried out by this technique.

Role of Bottom-up and Top-Down approaches in Nano technology:

Figure: Schematic representation of the building up of Nanostructures.

There are two approaches for synthesis of nano materials and the fabrication of nano structures. Top down approach refers to slicing or successive cutting of a bulk material to get nano sized particle. Bottom up approach refers to the build up of a material from the bottom:

atom by atom, molecule by molecule or cluster by cluster. Both approaches play very important role in modern industry and most likely in nano technology as well. There are advantages and disadvantages in both approaches. Attrition or Milling is a typical top down method in making nano particles, where as the colloidal dispersion is a good example of bottom up approach in the synthesis of nano particles. The biggest problem with top down approach is the imperfection of surface structure and significant crystallographic damage to the processed patterns. These imperfections which in turn leads to extra challenges in the device design and fabrication. But this approach leads to the bulk production of nano material. Regardless of the defects produced by top down approach, they will continue to play an important role in the synthesis of nano structures. Though the bottom up approach oftenly referred in nanotechnology, it is not a newer concept. All the living beings in nature observe growth by this approach only and also it has been in industrial use for over a century. Examples include the production of salt and nitrate in chemical industry. Although the bottom up approach is nothing new, it plays an important role in the fabrication and processing of nano structures. There are several reasons for this and explained as below.When structures fall into a nanometer scale, there is a little chance for top down approach. All the tools we have possessed are too big to deal with such tiny subjects. Bottom up approach also promises a better chance to obtain nano structures with less defects, more homogeneous chemical composition. On the contrary, top down approach most likely introduces internal stress, in addition to surface defects and contaminations.