NucleationHandout.

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Nucleation of Crystals
If a liquid is cooled below its melting point, we expect to see crystals form immediately, but that is not what happens. It is difficult for molecules in the liquid to organize themselves into the ordered arrangement of the solid; in fact, there is an energy barrier that inhibits the formation of a crystal. We will examine the nature of this barrier and see how nature overcomes it.

Free energy
To analyze the nucleation and growth of crystals, we need to know the energy of the liquid and solid phases. Einstein showed that the total energy of a mass m is m c2 , but most of that energy is not available in ordinary chemical reactions. We use the term free energy to describe the energy content of a material that we can change by adjusting the temperature or pressure, or by performing chemical reactions. The free energy per mole, G, of a crystal or liquid changes nearly linearly with temperature, T:
G = H - TS (1)

where H and S are called the enthalpy and entropy, respectively. Suppose that the free energy of the liquid is
GL = HL - T SL (2)

and that of the solid is

GS = HS - T SS (3)

The energy difference (Joules/mole) between the phases is

DG GS - GL = DH - T DS (4)

where DH = HS - HL (Joules/mole) and DS= SS - SL (Joules/molesC). At the melting point, Tm , the energies of the two phases are identical so
DH = Tm D S (5)

so eq. (4) can be written as

DG = HTm - T L DS (6)

This equation indicates that the energy difference between the liquid and the solid is zero at the melting point, and increases linearly as the temperature drops below that point.

Homogeneous nucleation
If pure liquid is cooled below its melting point, the liquid becomes unstable with respect to the solid; that is, if a crystal is thrown into the liquid, it will grow until all the liquid is transformed to solid. However, if no crystal is introduced, it is difficult for the liquid to nucleate (spontaneously form) a crystal. The problem is that the interface between the solid and the liquid has a high surface energy, because of the structural discontinuity between the solid and liquid phases:

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Figure 1

The molecules in the solid and liquid do not like to be in contact. The atoms on the solid surface are unhappy, because they have fewer neighbors on that side than in the underlying layer of solid. The atoms in the liquid adjacent to the solid are unhappy, because the attraction to the solid surface tries to tie them down. Consequently, there is an energy per unit area gCL associated with the creation of an interface between the crystal and the liquid, just as there is surface tension between a liquid and a vapor. Before analyzing the nucleation barrier, we should take a closer look at the nature of surface energy. The existence of surface tension is readily demonstrated by the soap film experiment, where a force T must be exerted per unit length of the moveable wire to increase the area of the film by dx. The work T dx is thus equal to the energy 2 g dx required to create new surface area.

Figure 2

The force/length or energy/area is called the surface tension or surface energy, g = T/2. It exists because the atoms or molecules at the exposed surface cannot satisfy their bonding requirements, so they are in a higher energy state than those in the interior.

Figure 3 The atom at the surface makes fewer bonds than the atom in the interior.

Therefore, it is necessary to do work to increase the area (i.e., to bring more atoms to the surface).
DGV = HTm - T L DSV

The energy gained by forming a unit volume of the crystal from the liquid is found from eq. (6) to be
(7)

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where DSV = DS VM (which is a negative quantity) and VM is the volume per mole of the crystal. If we form a spherical crystal with radius r in a liquid, the energy gain is
DGvol = 4p 3 r3 HTm - T L DSV (8)

However, the amount of energy that is consumed by creating the interface between the crystal and liquid is
DGsurf = 4 p r2 gCL (9)

so the total energy change is

DGtot = 4p 3 r3 HTm - T L DSV + 4 p r2 gCL (10)

When T < Tm , the first term in eq. (10) is negative and the second is positive. When r is small the second term dominates, as shown in Figure 4 (using values for water/ice, DSV = 1.2 106 Pa/C, gCL = 0.04 J m2 ):

DGtot 510
-18

210 -510
-18

-9

410

-9

610

-9

810

-9

110

-8

1.210

-8

r HmL

-110

-17

-1.510

-17

Figure 4

As a small crystal starts to form from the liquid, its energy actually increases along the curve in Figure 4, so it is more likely to melt away than to keep growing. If a fluctuation in energy allows a cluster of molecules to form a crystal large enough to pass the peak, then any further growth decreases the energy. Thus, the height of the peak in DGtot constitutes a barrier to the homogeneous nucleation of a crystal in a liquid. The critical radius, r*, is the size corresponding to the peak, which we can find by taking the derivative of eq. (10):

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d DGtot dr

r=r* = 0 = 4 p r2 HTm - T L DSV + 8 p r gCL

(11)

so
r* = HTm - T L DSV 2 gCL = HTm - T L DSV 2 gCL (12)

(This is a positive radius, since DSV <0.) Substituting eq. (12) into eq. (10) we obtain the magnitude of the energy barrier to homogeneous nucleation:
DGtot
homo

Hr* L =

HTm - T L DSV
2 2

3 16 p gCL

(13)

Equation (13) shows that homogeneous nucleation is impossible at the melting point, because the denominator is zero when T = Tm , so the barrier to nucleation is infinite. As the temperature drops, r* decreases, and eventually becomes small enough so that it only requires a few hundred molecules to make a cluster exceeding the critical size. For water, that happens only when T -38C! This has been experimentally verified by cooling extremely pure water to that temperature withou freezing. However, your refrigerator is much warmer than that, so how do ice cubes ever form? The answer is that crystals form by heterogeneous nucleation.

Heterogeneous nucleation
We have seen that the crystal/liquid interfacial energy constitutes a barrier to nucleation of a crystal. However, if a crystal is dropped into the liquid, there is no barrier to its continued growth (as long as it is already larger than the critical size). In fact, even if it is a crystal of a different substance, it may help nucleate growth from the liquid. Figure 5 shows a crystal forming on the surface of another solid material (the nucleating substrate). If the crystal structure of the substrate resembles that of the crystal forming on its surface, then the energy gSC of the interface between them may be low. In that case, the barrier to nucleation is reduced. This process (forming a crystal on the surface of another solid) is called heterogeneous nucleation.

SL CL

Crystal
SC

Liquid

Substrate

Figure 5

In the case of heterogeneous nucleation, there are 3 interfacial energies that must be considered: substrateliquid HgSL L, crystal-liquid HgCL L, and substrate-crystal HgSC L. Each one can be regarded as a force per unit area pulling on the line of contact between the three substances, so the relationship between them can be evaluated using a vector sum. The force gSL pulls the line to the left in the figure (i.e., it tries to extend the crystal over the substrate to reduce the crystal-substrate surface area). Similarly, the force gSC tends to pull the line to the right, reducing the crystalsubstrate surface area. Finally, there is a component of the crystal-liquid force, gCL cos(q), pulling parallel to gSC , which tends to reduce the crystal-liquid surface area. Thus, the force balance is
gSL = gSC + gCL cosHqL (14)

Eq. (14) is known as Young's equation. If the contact angle were zero, we could put a disc of crystal with radius r onto the surface of the substrate with no penalty in energy:

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Eq. (14) is known as Young's equation. If the contact angle were zero, we could put a disc of crystal with radius r onto the surface of the substrate with no penalty in energy:
Crystal r Substrate Liquid

Figure 6

Placing the crystal on the substrate eliminates an area of substrate-liquid interface equal to pr2 , while creating equal areas of crystal-liquid and crystal-substrate interface. Therefore, the resulting change in the energy of the system is
DG = p r2 HgSC + gCL - gSL L (15)

If the contact angle is zero, Young's equation indicates that DG is zero. Evidently, the presence of a substrate with a low contact angle will permit the formation of a crystal without raising the energy of the system; that is, it will reduce the energy barrier to nucleation. We now derive an explicit expression for the energy barrier when the crystal forms a spherical cap on the substrate, as in Figure 5. In the notation of Figure 7, the area of the crystal-liquid surface (which is a spherical cap) is A = 2pRh and the area of the substrate-crystal surface is pa2 . The energy change upon formation of the crystal is the elimination of the substrate-liquid energy, pa2 gSL , and the creation of crystal-substrate energy pa2 gSC plus crystal-liquid surface energy A gCL .
h

Rh R

Figure 7 The geometry of the spherical cap is described in terms of its height h, the radius of its base a, and the radius of curvature R. The area of the upper curved surface is A and the volume of the cap (with height h) is V. The dimensions are related by: a = R sin(q), h = R[1-cos(q)], A = 2p R h, V = p h2 H3 R - hL 3

Therefore, the total energy change on forming a nucleus is

DGtot = V HTm - T L DSV + A gCL + p a2 HgSC - gSL L (16)

or, since gSL = gSC + gCL cos(q),

DGtot = V HTm - T L DSV + A gCL - p a2 gCL cosHqL

(17)

The critical nucleus size is found by taking the derivative with respect to R,
d DGtot dR R=R* = 0 (18)

After some algebraic simpification, and making use of Young's equation, the critical radius is found to be
R* = HTm - T L DSV 2 gCL (19)

which is identical to the critical radius for homogeneous nucleation. The corresponding energy barrier to heterogeneous nucleation is

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which is identical to the critical radius for homogeneous nucleation. The corresponding energy barrier to heterogeneous nucleation is
DGtot HR* L =
het

HTm - T L

3 16 p gCL f HqL 2

2 DSV

= DGtot

homo

HR* L f HqL

(20)

where
f HqL =

2 - 3 cosHqL + cos3 HqL 4

(21)

Thus, the barrier is equal to that found for homogeneous nucleation multiplied by the function f(q). As shown in Figure 8, f is equal to 1 when the contact angle is q = p, so that the crystal does not touch the substrate; in that case, the substrate is ineffective and nucleation must occur homogeneously. As the contact angle decreases, so does the barrier to nucleation.

1 0.8 0.6 0.4 0.2 0 0 0.5 1 1.5 2 2.5 3 3.5

f ( )

Figure 8 The inserts show the shape of the heterogeneous nucleus. When the contact angle is high, the area of contact between the crystal and the substrate is small; in the limit when q = p, there is no contact at all, so the substrate does not facilitate nucleation. As the contact angle decreases, the crystal tends to form a large area of contact, because the crystal-substrate interfacial energy is small; in the limit q = 0, there is no barrier to formation of a nucleus.

The reason that ice crystals form so easily in the refrigerator is that there are bits of dust and dirt that act as substrates for heterogeneous nucleation. In fact, the most effective surfaces for nucleating ice are organic. The road surface freezes right at 0C, because there are proteins from decaying leaves, bacteria, and other substances that help to organize water molecules into an ice-like structure. The snow machines on ski slopes add a protein (made from a genetically engineered organism) to the water to facilitate nucleation, so that the droplets freeze before touching the ground (if the droplets were still liquid when then landed on the ground, the slope would become glazed with ice).

Nucleation in a solid
The preceding analyses described formation of a crystal within a liquid, where the only barrier to nucleation is the crystal-liquid interfacial energy. However, materials processing often involves nucleation of crystals within another crystalline material, and the resulting volume change produces strain energy. The total change in energy upon formation of a nucleus with volume V and area A is

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DGtot = V DGV + A gCC + DGstrain - DGdefects

(22)

where gCC is the crystal-crystal interfacial energy. The strain energy resulting from the formation of a crystal of phase b in a matrix of phase a is related to the volumetric strain, e. If the molar volumes are Va and V b , then e = (V b -Va )/Va and the strain energy is
DGstrain = 2 K b ma 3 K b + 4 ma e2 V b (23)

where K b and ma are the bulk and shear moduli of the phases, respectively. The strain energy raises the barrier to nucleation, so new crystals are most likely to form in a place where the strain is least; in particular, nucleation is favored at free surfaces and grain boundaries. In fact, there is an interfacial energy associated with grain boundaries, since the atomic packing is imperfect in the boundaries. If a crystal nucleates on a grain boundary, it eliminates that defect and thereby reduces the energy of the system. Therefore, the total energy balance contains a negative term that represents the energy gained by destroying defects.

Crystal Growth
If ice crystals and liquid water are mixed together at the melting point (0C or 32F), they are in equilibrium; that is, the energy difference between them is zero, as indicated by eq. (6). Therefore, the water doesn't freeze and the ice doesn't melt. However, on the molecular level the situation is not static: water molecules are bombarding the surface of the ice, and some attach to the surface of the crystal, while other molecules jump from the crystal into the liquid. This dynamic equilibrium is indicated in Figure 1, where a water molecule (gray) is about to attach to the crystal, while an ice molecule (yellow) is about to enter the liquid. At the melting point, the rates at which molecules are added to the surface of the crystal is exactly equal to the rate at which they leave. Molecules in ice spend most of their time vibrating back and forth, then only rarely make a jump away from the surface. As the temperature drops they vibrate more and more slowly, and jump less frequently. The movement of the liquid molecules slows down too, but not as much. Consequently, as the temperature drops below the melting point (or, freezing point), molecules begin to hop onto the surface faster than they hop off, and therefore the crystal begins to grow. It is possible to measure the rate of crystal growth by putting a crystal of ice in water at 0C, then dropping the temperature. In a microscope, the growth of the ice crystal can be seen and measured; the result for ice is shown in Figure 9. The growth rate, u, of ice is given by

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u Hcm sL = 0.16 D T

1.7

(24)

where DT is the amount (in degrees Celsius) by which the temperature is reduced below the melting point. For example, at -1C, ice grows at 0.16 cm/s (or 10 cm/minute); at -10C, it grows at 8 cm/s. High growth rates are characteristic of liquids, such as water or molten metals, that have very low viscosity. At the other extreme, liquids with a high degree of covalent bonding (such as the silicates used to make window glass) are very viscous at their melting points, so they crystallize slowly. Polymer melts also crystallize slowly, because it is difficult to align the long chains into a crystalline arrangement; the entanglement of the chains makes the liquids quite viscous. u HcmsL 8 6 4 2 T H C L

-8

-6

-4
Figure 9

-2