CHAPTER 1 OVER VIEW OF NANOSCIENCE AND TECHNOLOGY: The prefix nano in the word nano science mean a billionth

h (1 x 10-9). Nano science deals with various structures of matter having dimensions of the order of a billionth of a meter. While the word nanotechnology ids relatively new, the existence of functional devices and structures of nanometer dimensions is not new, and in fact such structures have existed on earth as long as life itself. Nanotechnology, shortened to "nanotech", is the study of the controlling of matter on an atomic and molecular scale. Generally nanotechnology deals with structures sized between 1 to 100 nanometer in at least one dimension, and involves developing materials or devices within that size. Nanotechnology is very diverse, ranging from extensions of conventional device physics to completely new approaches based upon molecular self-assembly, from developing new materials with dimensions on the nanoscale to investigating whether we can directly control matter on the atomic scale. There has been much debate on the future implications of nanotechnology. Nanotechnology may be able to create many new materials and devices with a vast range of applications, such as in medicine, electronics, biomaterials and energy production. On the other hand, nanotechnology raises many of the same issues as with any introduction of new technology, including concerns about the toxicity and environmental impact of nanomaterials, and their potential effects on global economics, as well as speculation

about various doomsday scenarios. These concerns have led to a debate among advocacy groups and governments on whether special regulation of nanotechnology is warranted. TYPES OF NANOMATERIALS Most current nanomaterials could be organized into four types: Carbon Based Materials Metal Based Materials Dendrimers Composites

CARBON BASED MATERIALS These nanomaterials are composed mostly of carbon, most commonly taking the form of a hollow spheres, ellipsoids, or tubes. Spherical and ellipsoidal carbon nanomaterials are referred to as fullerenes, while cylindrical ones are called nanotubes. These particles have many potential applications, including improved films and coatings, stronger and lighter materials, and applications in electronics. METAL BASED MATERIALS These nanomaterials include quantum dots, nanogold, nanosilver and metal oxides, such as titanium dioxide. A quantum dot is a closely packed semiconductor crystal comprised of hundreds or thousands of atoms, and whose size is on the order of a few nanometers to a few hundred nanometers. Changing the size of quantum dots changes their optical properties.

DENDRIMERS These nanomaterials are nanosized polymers built from branched units. The surface of a dendrimer has numerous chain ends, which can be tailored to perform specific chemical functions. This property could also be useful for catalysis. Also, because threedimensional dendrimers contain interior cavities into which other molecules could be placed, they may be useful for drug delivery. COMPOSITES Composites combine nanoparticles with other nanoparticles or with larger, bulk-type materials. Nanoparticles, such as nanosized clays, are already being added to products ranging from auto parts to packaging materials, to enhance mechanical, thermal, barrier, and flame-retardant properties. Unique Properties The unique properties of these various types of intentionally produced nanomaterials give them novel electrical, catalytic, magnetic, mechanical, thermal, or imaging features that are highly desirable for applications in commercial, medical, military, and environmental sectors. These materials may also find their way into more complex nanostructures and systems. As new uses for materials with these special properties are identified, the number of products containing such nanomaterials and their possible applications continues to grow.

BOTTOM-UP APPROACHES These seek to arrange smaller components into more complex assemblies. DNA nanotechnology utilizes the specificity of WatsonCrick base pairing to construct well-defined structures out of DNA and other nucleic acids. Approaches from the field of "classical" chemical synthesis also aim at designing molecules with well-defined shape (e.g. bis-peptides). More generally, molecular self-assembly seeks to use concepts of supramolecular chemistry, and molecular recognition in particular, to cause single-molecule components to automatically arrange themselves into some useful conformation Functional approaches These seek to develop components of a desired functionality without regard to how they might be assembled. Molecular electronics seeks to develop molecules with useful electronic properties. These could then be used as single-molecule components in a nanoelectronic device. For an example see rotaxane. Synthetic chemical methods can also be used to create synthetic molecular motors, such as in a so-called nanocar. Biomimetic approaches

 Bionics or biomimicry seeks to apply biological methods and systems found in nature, to the study and design of engineering systems and modern technology. Biomineralization is one example of the systems studied. chnology, including use of viruses. Speculative These subfields seek to anticipate what inventions nanotechnology might yield, or attempt to propose an agenda along which inquiry might progress. These often take a bigpicture view of nanotechnology, with more emphasis on its societal implications than the details of how such inventions could actually be created. Molecular nanotechnology is a proposed approach which involves manipulating single molecules in finely controlled, deterministic ways. This is more theoretical than the other subfields and is beyond current capabilities. Nanorobotics centers on self-sufficient machines of some functionality operating at the nanoscale. There are hopes for applying nanorobots in medicine, but it may not be easy to do such a thing because of several drawbacks of such devices. Nevertheless, progress on innovative materials and methodologies has been demonstrated with some patents granted about new nanomanufacturing devices for future commercial applications, which also progressively helps in the development towards nanorobots with the use of embedded nanobioelectronics concepts. Productive nanosystems are "systems of nanosystems" which will be complex nanosystems that produce atomically precise parts for other nanosystems, not necessarily using novel nanoscale-emergent properties, but well-understood fundamentals of manufacturing. Because of the discrete (i.e. atomic) nature of matter and the possibility of

exponential logy and femtotechnology have been coined in analogy to it, although these are only used rarely and informally. Growth, this stage is seen as an the basis of another industrial revolution. Mihail Roco, one of the architects of the USA's National Nanotechnology Initiative, has proposed four states of nanotechnology that seem to parallel the technical progress of the Industrial Revolution, progressing from passive nanostructures to active nanodevices to complex nanomachines and ultimately to productive nanosystems. Programmable matter seeks to design materials whose properties can be easily, reversibly and externally controlled though a fusion of information science and materials science. Due to the popularity and media exposure of the term nanotechnology, the words picotechno. TOP DOWN APPROACHES These seek to create smaller devices by using larger ones to direct their assembly. Many technologies that descended from conventional solid-state silicon methods for fabricating microprocessors are now capable of creating features smaller than 100 nm, falling under the definition of nanotechnology. Giant magneto rsistance-based hard drives already on the market fit this description, as do atomic layer deposition (ALD) techniques. Peter Gruenberg and Albert Fert received the Nobel Prize in Physics in 2007 for their discovery of Giant magneto rsistance and contributions to the field of spintronics.

 Solid-state

techniques

can

also

be

used NEMS,

to

create which

devices are

known related

as nanoelectromechanical

systems or

to microelectromechanical systems or MEMS. Atomic force microscope tips can be used as a nanoscale "write head" to deposit a chemical upon a surface in a desired pattern in a process called dip pen nanolithography. This fits into the larger subfield of nanolithography. Focused ion beams can directly remove material, or even deposit material when suitable pre-cursor gasses are applied at the same time. For example, this technique is used routinely to create sub-100 nm sections of material for analysis in Transmission electron microscopy. TOOLS AND TECHNIQUES: Scanning Tunneling Microscope (STM) are two early versions of scanning probes that launched nanotechnology. There are other types of scanning probe microscopy, all flowing from the ideas of the scanning confocal microscope developed by Marvin Minsky in 1961 and the scanning acoustic microscope (SAM) developed by Calvin Quate and coworkers in the 1970s, that made it possible to see structures at the nanoscale. The tip of a scanning probe can also be used to manipulate nanostructures (a process called positional assembly). Feature-oriented scanning-positioning methodology suggested by Rostislav Lapshin appears to be a promising way to implement these nanomanipulations in automatic mode. However, this is still a slow process because of low scanning velocity of the microscope.

Various techniques of nanolithography such as optical lithography, X-ray lithography dip pen nanolithography, electron beam lithography or nanoimprint lithography were also developed. Lithography is a top-down fabrication technique where a bulk material is reduced in size to nanoscale pattern. Another group of nanotechnological techniques include those used for fabrication of nanowires, those used in semiconductor fabrication such as deep ultraviolet lithography, electron beam lithography, focused ion beam machining, and nanoimprint. Lithography, atomic layer deposition, and molecular vapor deposition, and further including molecular self-assembly techniques such as those employing di-block copolymers. However, all of these techniques preceded the nanotech era, and are extensions in the development of scientific advancements rather than techniques which were devised with the sole purpose of creating nanotechnology and which were results of nanotechnology research. The top-down approach anticipates nanodevices that must be built piece by piece in stages, much as manufactured items are made. Scanning probe microscopy is an important technique both for characterization and synthesis of nanomaterials. Atomic force microscopes and scanning tunneling microscopes can be used to look at surfaces and to move atoms around. By designing different tips for these microscopes, they can be used for carving out structures on surfaces and to help guide self-assembling structures. By using, for example, feature-oriented scanningpositioning approach, atoms can be moved around on a surface with scanning probe microscopy techniques. At present, it is expensive and time-consuming for mass production but very suitable for laboratory experimentation.

In contrast, bottom-up techniques build or grow larger structures atom by atom or molecule by molecule. These techniques include chemical synthesis, self-assembly and positional

assembly. Dual polarization interferometry is one tool suitable for characterization of self assembled thin films. Another variation of the bottom-up approach is molecular beam epitaxy or MBE. Researchers at Bell Telephone Laboratories like John R. Arthur. Alfred Y. Cho and Art C. Gossard developed and implemented MBE as a research tool in the late 1960s and 1970s. Samples made by MBE were key to the discovery of the fractional quantum Hall effect for which the 1998 Nobel Prize in Physics was awarded. MBE allows scientists to lay down atomically precise layers of atoms and, in the process, build up complex structures. Important for research on semiconductors, MBE is also widely used to make samples and devices for the newly emerging field of spintronics. However, new therapeutic products, based on responsive nanomaterials, such as the ultra deformable, stress-sensitive Transfer some vesicles, are under development and already approved for human use in some countries.

Review Questions:
1. What is Nanotechnology give its significance in science and technology? 2. Explain carbon based nano particles and metal based nano particles mention its applications? 3. Briefly discuss dentrimers and composite nano materials? 4. What are the approaches to synthesis the nano particles in science and technology? Explain the bottom - up approach? Give its merits 5. Explain the top - down approach? Give its merits. 6. Briefly discuss the tool and techniques of analysis of nano particles?

NANOMATERIALS AND SYNTHESIS METHODS

CHEMICAL VAPOUR DEPOSITION (CVD) Chemical vapor deposition (CVD) is a chemical process used to produce high-purity, highperformance solid materials. The process is often used in the semiconductor industry to produce thin films. In a typical CVD process, the wafer (substrate) is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposit. Frequently, volatile by-products are also produced, which are removed by gas flow through the reaction chamber. Chemical vapour deposition or CVD is a generic name for a group of processes that involve depositing a solid material from a gaseous phase and is similar in some respects to physical vapour deposition (PVD). Types of CVD Processes:
o

Classified by operating pressure Atmospheric pressure CVD (APCVD) - CVD processes at atmospheric pressure.

Low-pressure CVD (LPCVD) - CVD processes at subatmospheric pressures[1]. Reduced pressures tend to reduce unwanted gas-phase reactions and improve film uniformity across the wafer. Most modern CVD processes are either LPCVD or UHVCVD.
o

o Ultrahigh vacuum CVD (UHVCVD) - CVD processes at a very low pressure, typically below 106 Pa Classified by physical characteristics of vapor o Aerosol assisted CVD (AACVD) - A CVD process in which the precursors are transported to the substrate by means of a liquid/gas aerosol, which can be generated ultrasonically. This technique is suitable for use with non-volatile precursors. o Direct liquid injection CVD (DLICVD) - A CVD process in which the precursors are in liquid form, the precursor vapors are transported to the substrate as in classical CVD process. This technique is suitable for use on liquid or solid precursors. High growth rates can be reached using this technique.

A CVD apparatus will consist of several basic components:

Gas delivery system For the supply of precursors to the reactor chamber Reactor chamber Chamber within which deposition takes place Substrate loading mechanism A system for introducing and removing substrates, mandrels etc Energy source Provide the energy/heat that is required to get the precursors to react/decompose. Vacuum system A system for removal of all other gaseous species other than those required for the reaction/deposition. Exhaust system System for removal of volatile by-products from the reaction chamber. Exhaust treatment systems In some instances, exhaust gases may not be suitable for release into the atmosphere and may require treatment or conversion to safe/harmless compounds. Process control equipment Gauges, controls etc to monitor process parameters such as pressure, temperature and time. Alarms and safety devices would also be included in this category. Substances commonly deposited for ICs: The CVD processes often used for integrated circuits (ICs). Particular materials are deposited best under particular conditions. Polysilicon: Polycrystalline silicon is deposited from silane (SiH4), using the following reaction: SiH4 Si + 2 H2 This reaction is usually performed in LPCVD systems, Polysilicon may be grown directly with doping, if gases such as phosphine, arsine or diborane are added to the CVD chamber. Diborane increases the growth rate, but arsine and phosphine decrease it. Silicon dioxide: Silicon dioxide (usually called simply "oxide" in the semiconductor industry) may be deposited by several different processes. Common source gases include silane and oxygen, dichlorosilane (SiCl2H2) and nitrous oxide (N2O), or tetraethylorthosilicate (TEOS; Si(OC2H5)4). The reactions are as follows: SiH4 + O2 SiO2 + 2 H2 SiCl2H2 + 2 N2O SiO2 + 2 N2 + 2 HCl Si(OC2H5)4 SiO2 + byproducts

The choice of source gas depends on the thermal stability of the substrate. . Any of these reactions may be used in LPCVD. CVD oxide invariably has lower quality than thermal oxide, but thermal oxidation can only be used in the earliest stages of IC manufacturing.

Silicon nitride: Silicon nitride is often used as an insulator and chemical barrier in manufacturing ICs. The following two reactions deposit nitride from the gas phase: 3 SiH4 + 4 NH3 Si3N4 + 12 H2 3 SiCl2H2 + 4 NH3 Si3N4 + 6 HCl + 6 H2

Silicon nitride deposited by LPCVD contains up to 8% hydrogen. However, it has higher resistivity and dielectric strength than most insulators commonly available in microfabrication (1016 cm and 10 MV/cm, respectively). Another two reactions may be used in plasma to deposit SiNH: 2 SiH4 + N2 2 SiNH + 3 H2 SiH4 + NH3 SiNH + 3 H2 These films have much less tensile stress, but worse electrical properties (resistivity 10 6 to 1015 cm, and dielectric strength 1 to 5 MV/cm).[4] Applications : It is used to produce synthetic diamonds. It is used in micro-fabrication. Making graphene on a large scale.

SOLVO-THERMAL SYNTHESIS

Definition : A chemical reaction in a closed system in the presence of a solvent (aqueous and non aqueous solution) at a temperature higher than that of the boiling point of such a solvent.

Main parameters governing Solvo-thermal processes are:

The parameters that govern the Solvo-thermal reactions. The selection of the solvent plays a key role through the control of the chemical mechanisms leading to the target- material. The preparation of Cu7Te4 using CuCl2, H2O and tellurium as reagents and ethylenediamine as solvent. Using the same experimental conditions but changing only the nature of the solvent (benzene or diethylamine),tellurium did not react with copper chloride. Compare to non polar solvent as benzene, ethylenediamine is a polarizing solvent such a property being able to increase the solubility of the reagents. In addition its complexing properties can play an important role in the reaction mechanisms. The complexing properties of the solvent can lead to the intermediate formation of stable complexes systems(M(en)32+). Such a complex-cation can act as a template due to its octahedral geometry and can be incorporated into the structure of the final material. This type of solvo-thermal reactions has led to the synthesis of Sb(III) and Sb(V) thioantimonates [Mn(en)3]2Sb2S5 and [Ni(en)3(Hen)]SbS4.The formation of complex-cationsis important as an intermediate step during the solvothermal reaction mechanisms. Solvothermal preparation of the semiconductor material CuInSe2. The starting products were CuCl2, InCl3 and Se. The solvent was either ethylenediamine (en) or diethylamine. The selected experimental conditions were 180C and the resulting autogeneous pressure. The propose reaction mechanisms involve four steps:

The nucleophilic attack by amine could activate selenium to form Se2 in a similar way that sulphur is activated by amine to S2- [22, 23]. The formation of the Cu(en)2+complex (Cu+ resulting from the in situreduction of Cu2+)seems to play are important role in controlling the nucleation and growth of CuInSe2nano-whiskers.By replacing Ethylenediamine by ethylamine as solvent, the reactivity is lowered and the resulting morphology consists on spherical particles of CuInSe2. Consequently the nature of the solvent can act on the reactivity and the morphology of the resulting crystallites.The physico-chemical properties of the selected solvent play an important role for the orienting the structural form of the final material. The oxidation-reduction properties of thesolvothermalmedium during the reaction can be induced by the nature ofthe solvent or the composition of the mixed solvents and by the use of additives.

Thermodynamical parameters The parameters include are temperature, pressure and the reaction time. Thesolvothermal reactions are mainlydevelopedin mild temperature conditions : (T<400 C). Temperatureand pressure improving in the major cases thesolubility, the increase of such parameters induces anenhancement of the precursors-concentration into thesolvent and then favours the growing process (in particularin the preparation of micro or nanocrystallites). The brief analysis of the main factors governing solvothermalreactions underlines that the nature of the selectedsolvent plays a key-role, in particular for controlling thechemical mechanisms involved in thesolvothermalreactions. Reactions involved insolvothermalprocesses

Solvothermal reactions involve in situ different reactiontypesas mentioned through the analysis of the chemicalfactors governing such processes. In particular, itis possible in a first approach to classify the reactions in approximately are 5 types: (i) oxidation- reduction (ii) hydrolysis (iii) thermolysis (iv) complex-formation (v) metathesis reactions. The development of these different reactions implies to control carefully the chemistry in nonaqueous solventsand consequently to get more information concerning thephysico-chemical properties of such solvents. Main applications of Solvothermal processes Solvothermal reactionshave been developed in differentscientific domains: The synthesis of novel materials (design of materialswith specific structures and properties). The processingof functional materials (an emergingroute in Synthesis Chemistry. The crystal growth at low-temperature (a way to singlecrystals of low-temperature forms or with a low densityof defects). The preparation of micro- or nanocrystallites welldefine in size and morphology (as precursors of finestructured ceramics, catalyst, elements ofnano-devices). The low- temperature sintering ( preparation of ceramics from metastable structural forms, low temperature forms or amorphous materials). The thin films deposition ( with the development of low-temperature processes).

Solvothermal synthesis of novel materials Roy has described the challenge for synthesizing newmaterials to specification. Hydro- and Solvothermaltechnologies beingable to bring some new synthesis routes in mild conditions , such a synthesis routes appear promisingfor developing functional materials.

Geo-inspired materials The structure of natural materials can be a source of inspiration for the conception of novel materials.Phyllosilicates

is a large class of geomaterials characterized by layeredstructures. In most cases OH groups participate to such structures and consequently are a limitation of the thermal stabilityin the reaction (anionic vacancies). When the concentration of anionicvacancies increases the structure is decomposed. In order toimpede such a phenomenon, the objective was to prepare anew class of layered oxides free of OH groups but alwaysisostructuralof the naturalphyllosilicates.

Comparison of two preparation processes tested for stabilizingphyllosiloxidesfrom a Sol-gel starting step

The two-steps process has been developed. The first consistedon a Sol-gel process [using as precursors Si(O2CH5)4, Al(OC4Hg)3, Mg(OC2H5)2 and KOCH3]. The second was asolvothermal treatment of the resulting gel (50<P<100MPa, 650<T<750 C) using the 2-methoxy-ethanol assolvent. The resulting material with the composition K(Mg2Al)Si4O12 is isostructural to the micaphlogopiteKMg3(Si3Al)O10(OH)2. Such a new layeredoxide (called phyllosiloxide) has been characterized through different techniques (XRD, TEM, RMN) andhas been tested as an interphase in ceramic-matrix composite. Solvo-thermal processes open the route to a novel class of bidimensional oxides derived from natural phyllosilicates.

Materials with light elements These class of materials presents a strong interest, thestrong chemical bonding inducing specific physico-chemicalproperties as hardnest, insulating, optical properties.In themain cases the weak reactivity of the precursors requiresfor the synthesis severe pressure and temperatureconditions. Due to the enhancement of the reactivity observed forsolvothermal reactions, during these last fifty years, such processes were investigated for preparing in particular: diamond, c-BN and C3N4. Hydrothermal synthesis of diamond Due to its large variety ofphysico- chemical properties that diamond has, during the last 50 years, requires a greatattention for developing new synthesis routes in mildtemperature-pressure conditions. The conventional route that was industrially developed for preparingdiamond involved a fluxassisted conversion from graphite as reagent and a metallic flux as solvent Yamada et al. have underlined the role of water in theMg2SiO4graphite system in the diamond formationunder hightemperatures-high pressures conditions. The The flux-assisted conversion route using metallic systems as solvents require severe P, T conditions and being probably different than the natural process developed in the crust of the earth, many researchers have tried to reproduce the nucleation and the growth of natural diamonds. Different routes have been explored. (i)The decomposition of minerals (ii) The investigation of different systems Involving transition metal-carbon or carbide and water asNiNaOHC, NiCH2O, SiCH2O (iii) The hydrothermal decomposition of chlorinated hydrocarbon.

The potentialities of Solvothermal reactions for preparingnanostructures well characterized in size, morphologyand architecture have been strongly investigated in different materials families as oxides halogenides, chalcogenides,nitrides, carbides, phosphides, metallicsandintermetallics APPLICATIONS OF SOLVOTHERMAL PROCESSES . Solvothermal reactions are used for preparing carbonitrides as bulk-material. Appear as most promising route for the synthesis of materials with light elements due to the strong interest of such materials for industrial applications. To stabilize the hybrid materials which are characterized byinorganic skeleton with the participation oforganic molecules.

 For preparing novel hybrid materials with open framework. for preparing nanostructured chalcogenidesin particularsulphides or tellurides due to their large domain of applications (for example Cu2SnS3). For the stabilization of novel molecular clusters.

CONCLUSION Solvothermal reactions appear to be important for either the synthesis of novel materials, the preparation of nanostructured particles for nanotechnologies or the elaborationof bioinspired materials for applications in Biosciences . Due to the large variety of solvents or mixedsolvents able to be used and the different induced reactions types versus the nature of the reagents and the chemical composition of the solvent, solvothermal processes will be important for developing original industrial processes in mild temperature and pressure conditions as for example the transformation of biomass as a renewable organic resource .

SOL GEL TECHNIQUE

The sol-gel process, also known as chemical solution deposition, is a wet-chemical technique widely used in the fields of material science and ceramic engineering. Such methods are used primarily for the fabrication of materials (typically a metal oxide) starting from a chemical solution (or sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers. Typical precursors are metal alkoxides and metal chlorides, which undergo various forms of hydrolysis and polycondensation reactions. INTRODUCTION In this chemical procedure, the sol (or solution) gradually evolves towards the formation of a gel-like diphasic system containing both a liquid phase and solid phase whose morphologies range from discrete particles to continuous polymer networks. In the case of the colloid, the volume fraction of particles (or particle density) may be so low that a significant amount of fluid may need to be removed initially for the gel-like properties to be recognized. This can be accomplished in any number of ways. The simplest method is to allow time for sedimentation to occur, and then pour off the remaining liquid. Centrifugation can also be used to accelerate the process of phase separation. Removal of the remaining liquid (solvent) phase requires a drying process, which is typically accompanied by a significant amount of shrinkage and densification. The rate at which the solvent can be removed is ultimately determined by the distribution of porosity in the gel. The ultimate microstructure of the final component will clearly be strongly influenced by changes imposed upon the structural template during this phase of processing. Afterwards, a thermal treatment, or firing process, is often necessary in order to favor further polycondensation and enhance mechanical properties and structural stability via final sintering densification and grain growth. One of the distinct advantages of using this methodology as opposed

to the more traditional processing techniques is that densification is often achieved at a much lower temperature. The precursor sol can be either deposited on a substrate to form a thin film (e.g. by dip coating or spin coating), cast into suitable container with the desired shape (e.g., to obtain monolithic ceramics, glasses, fibers, membranes, aero gels) or used to synthesize powders (e.g. microsphere,nanosphere). The sol-gel approach is a cheap and low-temperature technique that allows for the fine control of the products chemical composition. Even small quantities of dopants, such as organic dyes and rare earth elements, can be introduced in the sol and end up uniformly dispersed in the final product. It can be used in ceramics processing and manufacturing as an investment casting material or as a means of producing very thin films of metal oxides for various purposes. Sol-gel derived materials have diverse applications in optics, electronics, energy, space, sensors, medicine (controlled drug release), reactive material and separation (chromatography) technology. The interest in sol-gel processing can be traced back in the mid-1880s with the observation that the hydrolysis of tetraethyl orthosilicate under acidic conditions led to formation of SiO 2 in the form of fibers and monoliths. Particles and polymers The term colloid is used primarily to describe a broad range of solid-liquid (and/or liquid-liquid) mixtures, all of which contain distinct solid (and/or liquid) particles which are dispersed to various degrees in a liquid medium. The term is specific to the size of the individual particles, which are larger than atomic dimensions but small enough to exhibit Brownian motion. If the particles are large enough, then their dynamic behavior in any given period of time in suspension would be governed by forces of gravity and sedimentation. But if they are small enough to be colloids, then their irregular motion in suspension can be attributed to the collective bombardment of a myriad of thermally agitated molecules in the liquid suspending medium. Under certain chemical conditions (typically in base-catalyzed sols), the particles may grow to sufficient size to become colloids, which are affected both by sedimentation and forces of gravity. Under certain chemical conditions (typically in acid-catalyzed sols), the interparticle forces have sufficient strength to cause considerable aggregation and/or flocculation prior to their growth. The formation of a more open continuous network of low density polymers exhibits certain advantages with regard to physical properties in the formation of high performance glass and glass/ceramic components in 2 and 3 dimensions.

In either case (discrete particles or continuous polymer network) the sol evolves then towards the formation of an inorganic network containing a liquid phase (gel). Formation of a metal oxide involves connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore generating metal-oxo or metal-hydroxo polymers in solution. In both cases (discrete particles or continuous polymer network), the drying process serves to remove the liquid phase from the gel, yielding a micro-porous amorphous glass or micro-crystalline

ceramic. Subsequent thermal treatment (firing) may be performed in order to favor further polycondensation and enhance mechanical properties. Polymerization Metal alkoxides are members of the family of organometallic compounds, which are organic compounds which have one or more metal atoms in the molecule. Metal alkoxides (R-O-M) are like alcohols (R-OH) with a metal atom, M, replacing the hydrogen H in the hydroxyl group. They constitute the class of chemical precursors most widely used in sol-gel synthesis. The formation of a metal oxide involves connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore generating metal-oxo or metal-hydroxo polymers in solution. A well studied alkoxide is silicon tetraethoxide, or tetraethyl orthosilicate (TEOS). The chemical formula for TEOS is given by: Si(OC2H5)4, or Si(OR)4 where the alkyl group R = C2H5. Alkoxides are ideal chemical precursors for sol-gel synthesis because they react readily with water. The reaction is called hydrolysis, because a hydroxyl ion becomes attached to the silicon atom as follows: Si(OR)4 + H2O HO-Si(OR)3 + R-OH Depending on the amount of water and catalyst present, hydrolysis may proceed to completion, so that all of the OR groups are replaced by OH groups, as follows: Si(OR)4 + 4 H2O Si(OH)4 + 4 R-OH Any intermediate species [(OR) 2Si-(OH) 2] or [(OR) 3Si-(OH)] would be considered the result of partial hydrolysis. In addition, two partially hydrolyzed molecules can link together in a condensation reaction to form a siloxane [SiOSi] bond: (OR)3Si-OH + HOSi-(OR)3 [(OR)3SiOSi(OR)3] + H-O-H Or (OR)3Si-OR + HOSi-(OR)3 [(OR)3SiOSi(OR)3] + R-OH Thus, polymerization is associated with the formation of a 1, 2, or 3- dimensional network of siloxane [SiOSi] bonds accompanied by the production of H-O-H and R-O-H species. Condensation liberates a small molecule, such as water or alcohol. This type of reaction can continue to build layer and layer containing molecules by process of polymerization.

Synthesis of silver silica nanocomposite by sol gel: The sol gel process involves the evolution of inorganic networks through the formation of a colloidal suspension (sol) and gelation of a sol to form a network in a continuous liquid phase (gel).Silver containing silica thin coatings were developed by the sol gel method and deposited on the optically transparent sodium glass microscope slides. Precursors used for silver and silica networks were silver nitrate (AgNO3) and tetraethylorthosilicate (TEOS) respectively. Dipping solution was prepared by dissolving calculated amount of AgNO3 in ethanol by stirring under gentle heating conditions in a conical flask. This solution was taken inside a moisture controlled glove box for addition of TEOS, as TEOS is moisture sensitive. A calculated TEOS was added drop by drop under stirring conditions. The flask containing this solution was brought out of the glove box and distilled water was added in to the resultant solution according to the molar ratio H2O/TEOS=4 for hydrolysis and later for condensation. A few drops of HNO3 ware added under stirring conditions to adjust the pH of the solution to 3. The pH was measured by dipping the probe of pH meter in to the solution. A slight

rise in temperature was observed in the solution when the drops of nitric acid were added. This resultant homogeneous solution was poured in to a two-neck flask for heating at 343k for 2hrs under reflux conditions. A Teflon coated stirred bar was put in to the flask containing sol. A coil condenser was fixed at one of the necks of the flask and tap water eas flown through it to maintain refluxing conditions. The flask was placed at the heater plate equipped with the temperature controller and magnetic stirrer. After completion of the heating process, the solution was cooled down to room temperature.The microscope sodium glass slides were cleaned with ethanol and dried. The prepared sol was coated on the slides by dip coating method and dried at room temperature. The samples were heated in an oxidizing air environment at a heating rate of 5k per minute at 3 temperatures 673k, 773k, and 873k for 30minutes each in the furnace. Oxidation process removed the organic impurities from the composite coatings. Subsequently, the already oxidized samples were further treated in reductive environment of pure hydrogen for 120 minutes at 673k, 773k, and 873k. Reduction of these samples resulted in to formation of silver nanoparticles in the amorphous silica network. Heating rate and dilution rate were kept same for all the samples processed at different temperatures. The reduced samples containing embedded silver nanoparticles in the silica matrix were transparent and yellow in colour. The samples were characterized by XRD, SEM and UV-Visible spectroscopy.

AgNO3+ ethanol of sol under and refluxing

addition of TEOS Under stirring in glave box

Addition of HNO3 to adjust pH=3

heating strring

Dip coating of XRD, SEM, UV Sol on Na glass characterization Slides sample

oxidation of sample in furnace in air environment

Reduction of already oxidized samples in Hydrogen of

Applications: 1. Protective Coating: The applications for sol-gel derived products are numerous. One of the largest applications areas is thin films, which can be produced on a piece of substrate by spin coating or dip coating. Protective and decorative coatings, electro-optic components can be applied to glass, metal and other types of substrates with these methods. Cast In to a mold and with further drying and heat treatment, dense ceramic or glass articles with novel properties can be formed that cannot be created by other method. Other coating methods include spraying, electrophoresis, inkjet printing and roll coating. 2. Thin Films And Fibers: With the viscosity of sol adjusted to a proper range, both optical and refractory ceramic fibers can be drawn which are used for the fiber optic sensors and thermal insulation respectively. Thus many ceramic materials both glassy and crystalline have found used in various forms from bulk solid state components to high surface ared forms such as thin films, coatings and fibers 3. Nanoscale Powder: Ultra fine and uniform ceramic powders can be formed by precipitation. These powders of single and multiple component compositions can be used in dental and biomedical applications; composite powders are used as agrochemicals and herbicides. One of more important applications of sol- gel processing is to carryout zeolite synthesis. 4. Opto-Mechanical: Macroscopic optical elements and active optical components can be made via sol-gel route.

Carbon Nanotubes Polymer Nanocomposites: Topic Description, Properties, Potential Applications. This section provides a general description about carbon nanotubes through next pages: -Carbon Nanotubes Topic Description (this page) -Carbon Nanotubes Structure -Carbon Nanotubes Properties and applications -Carbon Nanotubes Synthesis Methods Carbon Nanotubes Topic Description In the technological field of polymer nanocomposites, new potential applications may be obtain using carbon nanotubes as reinforced nanofibers and to impart unique electrical and thermal properties to the polymer matrix. Due to its typical structure with high aspect ratio and anisotropic structure, carbon nanotubes show characteristic electrical and thermal properties.

After verification of extraordinary mechanical properties of carbon nanotubes and its electrical conductivity and thermal properties, great excitement arise among researcher considering potential applications. So far, in contrast of layered silicate polymer nanocomposites, applications of carbon nanotubes have been hindered mainly to production and synthesis problems. In fact Carbon Nanotubes are now available commercially in limited quantities. Currently, production of Carbon Nanotubes with specific dimensions and physical properties is not be achieved. For this reasons in the last decades many research program has been developed in order to produce and to effective use of carbon nanotubes capacity. Potential applications go beyond mechanical reinforzed nanomaterials from antistatic film packaging to every applications in which are motivated well established electrical, optical and thermal properties of carbon nanotubes.

Carbon Nanotubes structure

Carbon Nanotubes has been fortuitously discovered in 1991 by Sumio Iijima found out it between secondary products during fullerene synthesis. In fact, Carbon nanotubes are fullerene-related structures which consist of graphene cylinders closed at either end with a sort of emi-fullerene. Two category of carbon nanotubes are usually considered: Single walled nanotubes (SWNT); Multi walled nanotubes ( MWNT):concentric single walled nanotubes;

In the figures, at left Single walled Carbon Nanotubes whereas at right double walled carbon nanotubes with and without interaction between tubes. Actually Carbon Nanotubes structure has imperfections that deform the structure (e.g octagonal or pentagonal rings). Range of Single Walled carbon nanotubes diameter is from 1 nm to 10 nm, but the greater

number of nanotubes are about 2 nm. Nanotubes are characterized of high length/diameter ratio (10e4 10e5) gives typical great properties of this nanostructured materials. Typical parameters of carbon nanotubes are: diameter and helicities characterized by the rolling vectors (n,m) see the figure:

From left (n,0) nanotubes, (n,n) nanotubes (n,m) nanotubes. Between the tubes of multi walled carbon nanotubes there are weak interaction (lip-lip interaction) seem stabilize growth of nanotubes during synthesis process. Diameter is greater than single walled nanotubes as far as decine of nm. Structure of multi walled carbon nanotubes has more imperfection than single walled carbon nanotubes. For this reason single walled carbon nanotubes are considered products more valuable than multi walled carbon nanotubes and very difficult to synthetize. Carbon Nanotubes properties and applications: Depending on their structure carbon nanotubes show Properties listed below: Mechanical Properties: High Youngs Modulus; High tensile and compressive strength; Flexible; Conductive properties: High current density per area cross-section Variable electrical conductivity High heat conductivity Anisotropic thermal conductivity Superconductivity under certain conditions Field Emission Properties Chemical-Biochemical properties: High specific surface area Naturally accepted material in the body

Absorption properties (capillarity) Depending on previous properties following list of potential (and real) application is reported: Polymers Reinforced composites; Flame retardant filler; Conductive polymers; Advanced high strength polymers; Energy Battery electrodes Hydrogen storage for fuel cells Membranes fuel cells Solar cells

Nanoelectronics X-ray device Interacting light element Data storage (memory) Field emission display Medical applications Drug delivery system Artificial muscles Other applications Membranes separation Chemical Catalysis Sensors

There are three main synthesis methods:

[Obviously there are other tecnniques. Reaserch centers are working hard in order to obtain sustainable (low cost) carbon nanotubes] Arc-discharge The carbon nanotubes were produced using an arc discharge evaporation method similar to that

used for the fullerene synthesis. The carbon needles, ranging from 4 to 30 nm in diameter and up to 1 mm in length, were grown on the negative end of the carbon electrode used for the direct current arc-discharge evaporation of carbon in an argon-filled vessel. Laser ablation [Smalley 1996] With this method can produced high yields (>70%) of SWNT, laser-vaporization of graphite rods with small amounts of Ni and Co at 1200 C. The Nanotube grows until too many catalyst atoms aggregate on the end of the nanotube. The large particles either detach or become over-coated with sufficient carbon to poison the catalysis. This allows the tube to terminate with a fullerenelike tip or with a catalyst particle.

Chemical Vapour Deposition (CVD) This method is capable of controlling growth direction on a substrate and synthesising a large quantity of nanotubes. In this process a mixture of hydrocarbon gas, acetylene, methane or ethylene and nitrogen was introduced into the reaction chamber. During the reaction, nanotubes were formed on the substrate by the decomposition of the hydrocarbon at temperatures 700900 C and atmospheric pressure. Discussion Both arc-discharge and laser-ablation techniques have the advantage of high (>70%) yields of SWNT and the drawback that they rely on evaporation of carbon atoms from solid targets at temperatures >3000 C makes difficult the purification and application of the samples. Chemical Vapour Deposition has two main advantages: the nanotubes are obtained at much lower temperature, although this is at the cost of lower quality, and the catalyst can be deposited on a substrate, which allows for the formation of novel structures.

Clay/Polymer Nanocomposites: Brief Outline SUMMARY:nanocomposite and nanomaterial as nanotechnology example In the field of nanotechnology, the synthesis and applications of polymer nanocomposites are an important and strategical field of nanomaterial science. Polymer nanocomposites respresent a new class of material alternative to conventional filled polymers. In this new class of material, nanosized inorganic filler (at least one dimension) are dispersed in polymer matrix offering tremendous improvement in performance properties of the polymer.

Typically smectite-type clays are used as fillers. Montmorillonite and hectorite layered structure are dispersed in polymer matrix. According with the bonding scenariuos between polymer chain and silicate layer, new material shows excellent mechanical properties compared to neat polymer: superior mechanical characteristics higher tensile strength (40% increase), heat resistance and chemical resistance. Its worthwhile to note these results are achieved with only 0.1-10 %vol. addition clay nanosized. Its clear that polymer/clay nanocomposites are a typical example of nanotechnology: embedding nanoclay structure in polymer matrix we obtain a new class of materials. Unlike to other nanotechnologies this material has an immediately applications and commercial development.

Polymer nanocomposites history. The true start of polymer nanocomposites history is in 1990 when Toyota first used clay/nylon6 nanocomposites for Toyata car in order to produce timing belt covers. After that other automotive application was implemented: -Mitsubishis GDI cover clay/nylon-6 nanocomposites engines; -General Motors clay/polyolefin nanocomposites step assistant GMC Safari and Chevrolet Astro vans. The potential applications go beyond automotive industry. One of the most promising is drink packaging application considering increased barrier properties of polymer clay nanocomposites. Its easy understand the commercial and technical importance of this field. back to top FABRICATION TECHNIQUES: polymer clay nanocomposites In order to disperse clay layers into polymer matrix its very important considering polymerclay compatibility. This means to provide organophilic character to the clay by a pretreatment in order to successful formation of polymer-clay nanocomposite. In the case of hydrophilic polymers and silicate layers pretreatment is not necessary. Most polymers are hydrophobic and are not compatible with hydrophilic clays. Pretreatment involved only clays in order to obtain organic compatibility. Organophilic clay can be formed from normally hydrophilic clay by means amino acids, organic ammonium salts,

or tetra organic phosphonium solution. Well established methods are: -Solution induced intercalation; -In situ polimerization; -Melt processing; Solution induced intercalation method consists to solubilize polymer in an organic solvent, then the clay is dispersed in the obtained solution and subsequently either the solvent is evaporated or the polymer precipitated. This approach leads to poor clay dispersion, besides other problem like: high costs of solvents required, large amount of solvent needs to be used to achieve appreciable filler dispersion, technical phase separation problem, health and safety problem. Solvent route technique is used in the case of water-soluble polymers for clear reasons. In situ polimerization consists to disperse clay layers into matrix by polimerization, mixing the silicate layers with the monomer, in conjunction with the polymerization initiator and/or the catalyst.

In the third technique the silicates layers are directly dispersed into the polymers during the melt. In order to use this method, the silicates should need to be previously surface treated through the organo-modification like previously mentioned. DISCUSSION When one talking about nanocomposites, underlining extraordinary improvements of material properties. In reality, mechanical properties in the best clay/polymer nanocomposites are much lower than conventional fiber reinforced composites. Only in the low filler range 4% nanocomposites show better mechanical performance. To obtain higher performance we have to add more filler, but, great physical-technological problem occurs. Increasing reinforcing load increase the surface area of the silicate-filler, leading to insufficient polymer molecules to wet enormous clay surface. The main advantage of nanosized filler become high hurdle to overcome. Several difficulties facing clay-polymer nanotechnology especially fabrication problem: -Difficulty in application to thermosetting polymers; -Thermally instability of organoclay. Clearly, the major difficulties of the development of clay/polymer nanocomposites are caused to the poor understanding the primary mechanisms of nano-world. Considering significant progress in the development of clay-polymer nanocomposites has been made over the past last decade probably is not so long the way from the end of tunnel!!

Metal/Polymer Nanocomposites: Brief Outline SUMMARY: Metal polymer nanocomposite and nanomaterial as nanotechnology example. Modern technology continuously need new materials with special combination of properties. Many efforts have been made in the last decades using novel nanotechnology and nanoscience knowledge in order to obtain nanomaterials with determined functionalty. Metal-polymer nanocomposites are a typical example: using nano-particles (nanostructured metal) as additives in polymer matrix. Nano-sized metals has different properties from bulk metals originating from nanocrystals size. Nanocrystals measure a few nanometers containing few hundred atoms. In this way, nanomaterials shows unique properties (electronic, magnetic, structural) depending on nano-size structure. Physical and chemical properties of metal nanoparticles... The specific-size dependence of these properties becomes evident when they:

no longer follow classical physical laws but rather are described by quantum mechanical ones; are dominated by particular interface effects; exhibit properties due to a limited number of constituents, since the usual term "material";

refers to an almost infinite number of constituents (e.g. atoms, molecules) displaying an averaged statistical behavior.

Moreover, embedded metal nanoparticles, profoundly affect polymer typical mechanical and physical properties (glass transition, crystallinity etc.) open a wide range of potential applications (barrier properties, mechanical and fire resistance). In this way, metal-polymer nanocomposites may be applicated for a number of technological applications such as optical devices, optical sensors, light color filters. Metal Polymer Nanocomposite Synthesis... Very important are nanoparticles size and shape in order to obtain predefined properties of nanomaterials. At present two different techniques can be use to obtain metal-polymer nanocomposites: -Ex-Situ synthesis method; -In-Situ synthesis method. In the in-situ tecnique nanoparticles are generated inside polymer matrix by decomposition of metal precursors. First, monomer is polymerized in solution containing metal ions chemical species, then metal nanoparticles are obtain reducing metal ions through chemically, thermally or photolysis methods. In the ex-situ tecnique first nanoparticles are produced by chemical methods then are distributed into a polymer solution or monomer solution to polymerize. Other type of tecniques have been studied in order to obtain optimal properties controlling size and shape of nanaparticles in matrix or polimeric film (e.g Vapor deposition cryochemical synthesis). Many research plans have been implemented worldwide lead to large a large amount of literature reference about that. Nanotechnology Metal Polymer Nanocomposites Future Opportunities Goal is produce engineered nanomaterials can be potentially used for a variety of diverse application: optical devices, filter color, sensors, polizares, magnetic data storage nano-system and more over. COMMERCIAL NANOCOMPOSITES AND NANOCLAYS Commercial polymer nanocomposites Product Characteristics Applications automotive parts (e.g. timingbelt cover, engine cover, barrier, Producer Bayer Honeywell Polymer RTP Company Toyota Nylon Nanocomposites improved modulus, strength, heat distort temperature, barrier

properties Polyolefin nanocomposites stiffer, stronger, less brittle, lighter, more easily recycled, improved flame retardancy

fuel line), packaging , barrier film step-assist for GMC Safari and chevrolet Astro vans, heavy-duty electrical enclosure

Motors Ube Unitika Basell, Blackhawk Automotive, Plastics Inc, General Motors, Gitto Global Corporation, Southern Clay Products Mitsubishi Gas Chemical Company Bayer

M9

High barrier properties Juice or beer bottles, multi-layer films, containers Doubling of stiffness, high gloss and clarity, reduced oxygen transmission rate, improved barrier properties Barrier films, paper coating

Durethan KU2-2601 (nylon 6)

Aegis NC (nylon 6/barrier nylon)

doubling of stiffness, medium barrier bottles Honeywell Polymer higher heat distort and films temperature, improved clarity Highly reduced oxygen High barrier beer transmission rate, bottles improved clarity improved temperature resistance and stiffness, very good impact properties automotive furniture appliance Honeywell Polymer

Aegis TM OX

Forte nanocomposite

Noble Polymer

Commercial nanoclay Product Nanomers Closite Characteristics microfine powder Organophilic Applications nylon, epoxy, unsaturated polyester, engineering resins Additives, enhance flexural and tensile modulus, barrier properties and flame retardance of thermoplastics Additives to enhance mechanical, flame retardant and barrier properties of thermoset and thermoplastics Producer Nanocor Southern Clay Products

Bentone

With a broad range of polarity

Elementis Specialties

Masterbatches pellet

thermoplastic olefin and urethane, styreneethylene butylene-styrene, Ethylene Vinyl Acetate Thermoplastics and thermosets electric and electronic, medical and healthcare, adhesive, building and construction materials

PolyOne Corporation, Clariant Corporation, RTP Company Sud-Chemie

Nanofil

Improve the mechanical, thermal and barrier properties additive, enhance mechanical barrier properties, thermal stability and flame resistance nanopigments, e.g. blue, red, green, yellow, high UV-stability

Planomers

TNO

PlanoColors

decorative coloring, UV-stable TNO coloring, heavy metal free coloring

PlanoCoatings additive, excellent transparent packaging TNO transparency and improved materials, protective coatings, barrier properties transparent barrier coatings