SYNTHESIS OF NANOPARTICLES BY CHEMICAL ROUTES

NITIN GUPTA CH9249 PRAG KOHLI CH9250 PARUL OHRI CH9251 PRIYAL KHURANA CH9255 PUNEY KIRTI CH9256

CLASSIFICATION OF PREPARATION METHODS

In terms of phase of medium for preparationGas phase Liquid phase Aerosol phase Solid phase

In terms of method of "monomer" preparation Physical Chemical Bulk

CHEMICAL METHODS
Reverse Microemulsions Method. Sol-gel Technique.

Mechanochemical Synthesis.
Precipitation of Solutions. Chemical synthesis of preceramic polymers.

REVERSE MICRO EMULSION OR MICELLE METHOD

It is one of the recent promising routes to nanocrystalline materials. Surfactants dissolved in organic solvents form spherical aggregates called reverse micelles. In the presence of water, the polar head groups of surfactant molecules organize themselves around small water pools ,leading to dispersion of aqueous phase in the continuous oil phase. Reverse micelles are used to prepare nanoparticles by using a water solution of reactive precursors that can be converted to insoluble nanoparticles.

Nanoparticle synthesis inside the micelles can be achieved by various methods including hydrolysis of reactive precursors and precipitation reactions of metal salts. Solvent removal and subsequent calcinations leads to final product.

Surfactants like pentadecaoxyethylene nonyl phenyl ether(TNP-35), poly nonyl phenol ether(NP5) etc are used

Parameters affecting the particle size distribution are: Concentration of precursor in the micelle. Mass of aqueous phase in the microemulsion.

ADVANTAGES OF THIS METHOD AREPreparation of very small particles Ability to control the particle size.

DISADVANTAGES ARELow production yields. Need to use large amounts of liquids.

SOL GEL METHOD

The sol- gel process is a wet-chemical technique (also known as chemical solution deposition) is widely used in the fields of material science .

Such methods are primarily used for the fabrication of materials (typically a metal oxide) starting from a chemical solution (sol, short for solution) which 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 hydrolysis and polycondensation reactions to form either a network "elastic solid or colloidal suspension (or dispersion) a system composed of discrete

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.

Thus, the sol 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 many waysSEDIMENTATION CENTRIFUGATION 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.

Afterwards, a thermal treatment, or firing process, is often necessary in order to favour 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 ---

1.Densification is often achieved at a much lower temperature. 2. The sol-gel approach is a cheap and low-temperature technique that allows for the fine control of the products chemical composition.

PRECIPITATION FROM SOLUTION (WET CHEMICAL SYNTHESIS)

It is one of the conventional methods for preparing nanoparticles of metal oxide ceramics. The process involves dissolving a salt precursor usually a chloride, oxychloride or nitrate , eg-AlCl3 to make Al2O3. The corresponding metal hydroxides usually form and precipitate in water on addition of a base such as sodium hydroxide or ammonium hydroxide. The resulting chloride salts are then washed away and hydroxide is calcined after filtration and washing to obtain the final oxide powder.

The method is useful in preparing ceramic composites of different oxides by co-precipitation of corresponding hydroxides in same solution.

Disadvantage of this method is the difficulty in controlling the particle size distribution. Fast and uncontrolled precipitation often takes place, resulting in large particles.

CHEMICAL SYNTHESIS OF PRECERAMIC POLYMERS

This method involves the use of molecular precursors that facilitate the synthesis of nanomaterials containing phase of desired composition.

Using chemical reactions to prepare the preceramic polymer overcomes the limitation of low production yields of physical methods.

This method is useful in preparing non-oxide ceramics such as silicon carbide and silicon nitride.

Metal carbides and metal nitrides are obtained by pyrolysis of polymers containing appropriate metal like silver or aluminium and carbon or nitrogen(preceramic polymers).

5. MECHANO-CHEMICAL METHODS
In conventional chemical synthesis or chemosynthesis, reactive molecules encounter one another through random thermal motion in a liquid or vapor.

The particle morphology of Al2O3-20 wt.%ZrO2 sprayable feedstocks after first calcination. (a) Morphology of feedstock and (b) high resolution of feedstock.

In a hypothesized process of mechanosynthesis, reactive molecules would be attached to molecular mechanical systems, and their encounters would result from mechanical motions bringing them together in planned sequences, positions, and orientations. Nano sized particles of less than 100 nm in diameter have significant potential for a number of applications including super plastically formed high-strength structural ceramics, optical materials and ion conductors.Most of the unique properties of nanoparticles require not only nano-sized particles,but also particles dispersed without agglomeration. A relatively new solid state process named mechanochemical treatment has been applied for the synthesis of nanopowders ie powders with particles in nano metersize range.In general,mechanochemical treatment has been recognised as a powerful technique for the synthesis of a wide range of materials,which may be otherwise difficult to prepare by a conventional high temprature treatment.Mechanochemical treatment is a non-equilibrium solid-state process in which the final product retainsb a v finetypically nanocrystalline or amorphous structure. Therefore such powders may be used as a precursor for later solidstate reactions.It has been realized that that the use of,for instance,hydrated oxides or hydroxides relieves mechanochemical reactions.such a novel approach,mild mechanochemical synthesis based on reactions of solid acids,bases,hydrated compounds,basic and acidic salts is known as soft mechanochemistry.

It is envisioned that mechanosynthesis would avoid unwanted reactions by keeping potential reactants apart, and would strongly favor desired reactions by holding reactants together in optimal orientations for many molecular vibration cycles.

Mechanochemicalsynthesis of alumina nanoparticles: Formation mechanism and phase transformation

XRD patterns of (a) the stoichiometric AlCl3/CaO initial powder mixture, (b) after 5 hour milling, (c) after 50 hour milling, (d) the as-milled sample calcined at 250, (e) the as-milled sample calcined at 300 C and (f) HR-TEM image of the 5 hour milled initial powder mixture (inset: FFT images of the amorphous AlCl3 and crystalline CaO phases).

Mechanochemical synthesis involves mechanical activation of solid state displacement reactions. The process is used to make nanoparticles of ceramics like Al2O3 and ZrO2.

Zirconium Oxide (ZrO2) Nanopowder / Nanoparticles

It involves the milling of precursor powders to form a nanoscale composite structure that react during milling and subsequent heating.

Nanosized alumina powders were synthesized by mechanochemical treatment of stoichiometric mixture of anhydrous AlCl3 and CaO.

E.g.- nanoparticles of Al2O3 are prepared by milling AlCl3 with CaO powder. A nanocomposite of CaO particles embedded within AlCl3 matrix is obtained. Subsequent heating at 573K led to nanoparticles of -Al2O3 within a CaCl2 matrix . The by-product CaCl2 can be removed by washing.

AlCl3
On milling

CaO powder

nanocomposite of CaO particles embedded within AlCl3 matrix Heat (573K) by-product CaCl2 can be removed by washing. nanoparticles of Al2O3 within a CaCl2 matrix