Lecture 2

Nucleation and Growth

Importance - Nucleation and Growth

Precursor Solution/Vapor Formation of Nuclei Homogenous Heterogeneous

Important controlling Parameters: Selection of Precursors

Growth of Nuclei Ostwald Ripening Agglomeration

Purity of precursors
Precursor Concentration Mixing Sequence Reaction Temperature Reaction Time

Precipitation
1. Variation of Particle Size Distribution 2. Hard agglomeration 3. Nano size change to micron

SIZE is an important phenomenon for NANOMATERIALS

Monosize and Wide Size Distribution Nanoparticles!!

20nm

Titanium Carbide 84nm

Iron Oxide 5, 9, 12,16 and 22nm

T. Hyeon et al, Nature Materials, 3, 2004, 891-95 D. Sarkar et al, J American Ceramic Society, 92 [12], 2877 2882, 2009

Effect of Nucleation and Growth on particle size distribution

Particle Size Distribution

monosize Volume Fraction (%) narrow size wide size

Particle Size (nm)

= Shape , b = Scale, g = location, x = particle size and f(x) = Cumulative undersize

Cumulative undersize mass distribution gives the amount of particle smaller than the defined size.

D. Sarkar et al, J American Ceramic Society, 92 [12] 2877 2882, 2009

When Nucleation Start?

A Temperature

Liquid

Te Solid

B C D

Consider cooling a liquid into a solid through a eutectic point

Composition

at point A: solid is not stable so will not form at point B: solid and liquid are both stable so no driving force to solid at point C: liquid is unstable - will form solid at point D: liquid is unstable - will form solid

Beyond equilibrium => Need driving force to form solid Transformation to solid phase
Requires: 1. Nucleation of new phase 2. Growth of new phase

Nucleation
Nucleation, the first step First process is for microscopic clusters (nuclei) of atoms or ions to form Nuclei possess the beginnings of the structure of the crystal Only limited diffusion is necessary Thermodynamic driving force for crystallization must be present

Two Type: Homogeneous - random accumulation of mother molecules Heterogeneous -small particles present in the solution act as nuclei

Homogenous Nucleation
G1 G2 G 2 G 1 = - DG Solid particle The change in free energy is balanced by the energy gain of creating a new volume, and the energy cost due to creation of a new interface. When the overall change in free energy, DG is negative, nucleation is favored J/cc) In the classic case of a spherical cluster that liberates -Gv J/cc during formation, but which must pay the positive cost of J/cm2 of surface interfacing with the surrounding

Free Energy needed to form a cluster of radius r is ; DG = 4/3r3Gv + 4r2

or DG = 4/3r3Gv 4r2

First term shows the energy gain of creating a new volume Second term shows the energy loss due to surface tension of the new interface

Homogenous NucleationContd
Free energy to add molecules to this cluster, until the radius reaches Critical radius

2 Gv

r* =

dG Where, =0 dr

For Ti, DGv = 50J/cm3 and = 50mJ/m2

r* = 2nm (5-10times larger than single unit cell)

Addition of new molecules to clusters larger than this critical radius is no longer limited by nucleation, but perhaps by diffusion (i.e. the supply of molecules) or continuous growth of nuclei The free energy needed to form this critical radius can be found by

DG* =

163

3(Gv)2

which occurs at the maximum DG where dG / dr = 0

As the phase transformation becomes more and more favorable, the formation of a given volume of nucleus frees enough energy to form an increasingly large surface

Surface energy related to Gibbs free energy during nucleation !!

Heterogeneous Nucleation
Heterogeneous nucleation occurs much more often than homogeneous nucleation It forms at preferential sites such as phase boundaries or impurities like dust and requires less energy than homogeneous nucleation.

At such preferential sites, the effective surface energy is lower, thus diminished the free energy barrier and facilitating nucleation.
Surfaces promote nucleation because of wetting contact angles greater than zero between phases encourage particles to nucleate The free energy needed for heterogeneous nucleation is equal to the product of homogeneous nucleation and a function of the contact angle : Homo DGheterogeneous = DGhomogenous x f(q)

f(q) = + Cosq Cos3q

Hetero
DG r* r

Energy needed for heterogeneous nucleation is reduced Wetting angle determines the ease of nucleation by reducing the energy needed.

Nucleation and Growth Process

Formation of Nuclei
formation favor: high initial concentration or supersaturation low viscosity low critical energy barrier uniform nanoparticle size: same time formation abruptly high supersaturation

Growth of Nuclei
Growth processes then enlarge existing nuclei Smallest nuclei often redissolve Larger nuclei can get larger through diffusion and adsorption Thermodynamics favors the formation of larger nuclei

Growth Rate

Nucleation Rate

Strong overlap of growth and nucleation rates Nucleation rate is high Growth rate is high Both are high at the same temperature

Temperature

Rate

Growth Rate No overlap of growth and nucleation rates Nucleation rate is small Growth rate is small At any one temperature one of the two is zero

Nucleation Rate

Nucleation & Growth

Typical precipitation reaction:

Reactant 1 + Reactant 2

T, t Stabilizer

Product + By-product

Nucleation (critical size)

Agglomeration Primary particles Growth Crystallites Particles

Clusters

Precipitation
Precipitation has generally been shown to occur in four steps: (a) nucleation (b) crystal growth (c) agglomeration and (d) ripening of the solids (a) Nucleation: a nucleus is a fine particle on which the spontaneous formation or precipitation of a solid phase can take place in a supersaturated solution. Homogeneous nucleation occurs when the nuclei is formed from component ions of the precipitate; if foreign particles are the nuclei, heterogeneous nucleation occurs.

Precipitation.Contd
(b) Crystal growth: crystals form by the deposition of the precipitate constituent ions onto nuclei.
Crystal growth rate can be expressed as:

dC = kS (C C*) n dt
where

C* = saturation concentration (mole/L) C = actual concentration of limiting ion (mole/L) k = rate constant (Ln / time mg) S = surface area available for precipitation (mg/L of a given particle size) n = constant
When the diffusion rate of ions to the surface of the crystal controls the crystal growth rate, exponent n = 1; when other processes such as the reaction rate at the crystal surface are rate limiting, n 1

Precipitation.Contd
(c) Agglomeration : conversion of small particles into larger particles is enhance by agglomeration of particles to form larger particles, which is the continual growth until equilibrium is reached. The changes in crystal structure that take place over time are often called aging.
(d) Ostwald Ripening : A phenomenon called ripening may also take place whereby the crystal size of the precipitate increases. Growth of Protein Crystal
Day 6 Day 10 Day 13 Day 16

Ostwald ripening
Ostwald ripening is an observed phenomenon in solid (or liquid) solutions which describes the change of an inhomogeneous structure over time. The phenomenon was first described by Wilhelm Ostwald in 1896 It is a spontaneous process that occurs because larger crystals are more energetically favored than smaller crystals. While the formation of many small crystals is kinetically favored, (i.e. they nucleate more easily) large crystals are thermodynamically favored. Thus, from a standpoint of kinetics, it is easier to nucleate many small crystals. However, small crystals have a larger surface area to volume ratio than large crystals. Molecules on the surface are energetically less stable than the ones already well ordered and packed in the interior.

Large crystals, with their greater volume to surface area ratio, represent a lower energy state.
Thus, many small crystals will attain a lower energy state if transformed into large crystals and this is what we see in Ostwald ripening.

Conclusion
In a homogenous precipitation, a short single burst of nucleation occurs when the concentration of constituent species reaches critical supersaturation The nuclei so obtained are allowed to grow uniformly by diffusion of solutes from the solution to their surface until the final size is attained

To achieve monodispersity, these two stages must be separated and nucleation should be avoided during the period of growth (Curve I) Curve III represents self-sharpening growth process, i.e Ostwald ripening

Uniform particles can be obtained due to aggregation of much smaller subunits rather than continuous growth by diffusion (Curve II)