Dendrite (crystal)

Dendrite formation

Dendrite formation starts with some nucleation, i.e. the first appearance of solid growth, in the supercooled liquid. This formation will at first grow spherically until this shape is no longer stable. This instability has two causes: anisotropy in the surface energy of the solid/liquid interface and the attachment kinetics of particles to crystallographic planes when they have formed.

On the solid-liquid interface, we can define a surface energy, ${\gamma }_{sl}$, which is the excess energy at the liquid-solid interface to accommodate the structural changes at the interface.

For a spherical interface, the Gibbs–Thomson equation then gives a melting point depression compared to a flat interface $\mathrm{\Delta }{T}_m$, which has the relation

$${\displaystyle \mathrm{\Delta }{T}_m\propto \frac{{\gamma }_{sl}}{r}}$$

where $r$ is the radius of the sphere. This curvature undercooling, the effective lowering of the melting point at the interface, sustains the spherical shape for small radii.

However, anisotropy in the surface energy implies that the interface will deform to find the energetically most favourable shape. For cubic symmetry in 2D we can express this anisotropy int the surface energy as

$${\displaystyle {\gamma }_{sl}(\theta )={\gamma }_{sl}^0[1+ϵ\cos (4\theta )].}$$

This gives rise to a surface stiffness

$${\displaystyle {\gamma }_{sl}^0[1-15ϵ\cos (4\theta )]}$$

where we note that this quantity is positive for all angles $\theta$ when $ϵ<1/15$. In this case we speak of "weak anisotropy". For larger values of $ϵ$, the "strong anisotropy" causes the surface stiffness to be negative for some $\theta$. This means that these orientations cannot appear, leading to so-called 'faceted' crystals, i.e. the interface would be a crystallographic plane inhibiting growth along this part of the interface due to attachment kinetics.

Wulff construction

For both above and below the critical anisotropy the Wulff construction provides a method to determine the shape of the crystal. In principle, we can understand the deformation as an attempt by the system to minimise the area with the highest effective surface energy.

Growth velocity

Taking into account attachment kinetics, we can derive that both for spherical growth and for flat surface growth, the growth velocity decreases with time by $t^{-1/2}$. We do however find stable parabolic growth, where the length grows with $t$ and the width with $\sqrt{t}$. Therefore, growth mainly takes place at the tip the parabolic interface, which draws out longer and longer. Eventually, the sides of this parabolic tip will also exhibit instabilities giving a dendrite its characteristic shape.

Preferred growth direction

When dendrites start to grow with tips in different directions, they display their underlying crystal structure, as this structure causes the anisotropy in surface energy. For instance, a dendrite growing with BCC crystal structure will have a preferred growth direction along the $⟨100⟩$ directions. The table below gives an overview of preferred crystallographic directions for dendritic growth. Note that when the strain energy minimisation effect dominates over surface energy minimisation, one might find a different growth direction, such as with Cr, which has as a preferred growth direction $⟨111⟩$, even though it is a BCC latice.

Metal dendrites

For metals the process of forming dendrites is very similar to other crystals, but the kinetics of attachment play a much smaller role. This is because the interface is atomically rough; because of the small difference in structure between the liquid and the solid state, the transition from liquid to solid is somewhat gradual and one observes some interface thickness. Consequently, the surface energy will become nearly isotropic. For this reason, one would not expect faceted crystals as found for atomically smooth interfaces observed in crystals of more complex molecules.

Mineralogy and paleontology

In paleontology, dendritic mineral crystal forms are often mistaken for fossils. These pseudofossils form as naturally occurring fissures in the rock are filled by percolating mineral solutions. They form when water rich in manganese and iron flows along fractures and bedding planes between layers of limestone and other rock types, depositing dendritic crystals as the solution flows through. A variety of manganese oxides and hydroxides are involved, including:

• birnessite (Na
  ₄Mn
  ₁₄O
  ₂₇•9H
  ₂O)
• coronadite (PbMn
  ₈O
  ₁₆)
• cryptomelane (KMn
  ₈O
  ₁₆)
• hollandite (BaMn
  ₈O
  ₁₆)
• romanechite ((Ba,H
  ₂O)Mn
  ₅O
  ₁₀)
• todorokite ((Ba,Mn,Mg,Ca,K,Na)
  ₂Mn
  ₃O
  ₁₂•3H
  ₂O) and others.

A three-dimensional form of dendrite develops in fissures in quartz, forming moss agate

NASA microgravity experiment

The Isothermal Dendritic Growth Experiment (IDGE) was a materials science solidification experiment that researchers used on Space Shuttle missions to investigate dendritic growth in an environment where the effect of gravity (convection in the liquid) could be excluded. The experimental results indicated that at lower supercooling (up to 1.3 K), these convective effects are indeed significant. Compared to the growth in microgravity, the tip velocity during dendritic growth under normal gravity was found to be up to several times greater.