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A crystal dendrite is a crystal that develops with a typical multi-branching form. The name comes from the Greek word dendron (δενδρον) which means "tree", since the crystal's structure resembles that of a tree. These crystals can be synthesised by using a supercooled pure liquid, however they are also quite common in nature. The most common crystals in nature exhibit dendritic growth are snowflakes and frost on windows, but many minerals and
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
s can also be found in dendritic structures.


History


Maximum velocity principle

The first dendritic patterns were discovered in palaeontology and are often mistaken for fossils because of their appearance. The first theory for the creation of these patterns was published by Nash and Glicksman in 1974, they used a very mathematical method and derived a non-linear
integro-differential equation In mathematics, an integro-differential equation is an equation that involves both integrals and derivatives of a function. General first order linear equations The general first-order, linear (only with respect to the term involving deriva ...
for a classical needle growth. However they only found an inaccurate numerical solution close to the tip of the needle and they found that under a given growth condition, the tip velocity has a unique maximum value. This became known as the maximum velocity principle (MVP) but was ruled out by Glicksman and Nash themselves very quickly. In the following two years Glicksman improved the numerical methods used, but did not realise the non-linear integro-differential equation had no mathematical solutions making his results meaningless.


Marginal stability hypothesis

Four years later, in 1978,
Langer Langer is a surname originally of German origin. For the etymology, meaning, and pronunciation of the name, and for the Hiberno-English slang word, see Wiktionary. People with the family name Langer include: Academics and scientists *Alois Lange ...
and Müller-Krumbhaar proposed the marginal stability hypothesis (MSH). This hypothesis used a stability parameter σ which depended on the thermal diffusivity, the surface tension and the radius of the tip of the dendrite. They claimed a system would be unstable for small σ causing it to form dendrites. At the time however Langer and Müller-Krumbhaar were unable to obtain a stability criterion for certain growth systems which lead to the MSH theory being abandoned.


Microscopic solvability condition

A decade later several groups of researchers went back to the Nash-Glicksman problem and focused on simplified versions of it. Through this they found that the problem for isotropic surface tension had no solutions. This result meant that a system with a steady needle growth solution necessarily needed to have some type of anisotropic surface tension. This breakthrough lead to the microscopic solvability condition theory (MSC), however this theory still failed since although for isotropic surface tension there could not be a steady solution, it was experimentally shown that there were nearly steady solutions which the theory did not predict.


Macroscopic continuum model

Nowadays the best understanding for dendritic crystals comes in the form of the macroscopic continuum model which assumes that both the solid and the liquid parts of the system are continuous media and the interface is a surface. This model uses the microscopic structure of the material and uses the general understanding of nucleation to accurately predict how a dendrite will grow.


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 liquid-solid 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_ 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 \Delta T_m, which has the relation \Delta T_m \propto \frac 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 \gamma_(\theta) = \gamma_^0 + \epsilon \cos(4\theta) This gives rise to a surface stiffness \gamma_^0 - 15\epsilon \cos(4\theta)/math> where we note that this quantity is positive for all angles \theta when \epsilon < 1/15. In this case we speak of "weak anisotropy". For larger values of \epsilon, 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 The Wulff construction is a method to determine the equilibrium shape of a droplet or crystal of fixed volume inside a separate phase (usually its saturated solution or vapor). Energy minimization arguments are used to show that certain crystal pl ...
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^. We do however find stable parabolic growth, where the length grows with t and the width with \sqrt. 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 In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric pattern ...
, 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 \langle 100 \rangle 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 \langle 111 \rangle, even though it is a BCC latice.


Metal dendrites

For
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
s 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 Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
flows along fractures and bedding planes between layers of
limestone Limestone ( calcium carbonate ) is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals calcite and aragonite, which are different crystal forms of . Limestone forms w ...
and other rock types, depositing dendritic crystals as the solution flows through. A variety of manganese oxides and hydroxides are involved, including: * birnessite () *
coronadite Coronadite is a black monoclinic mineral containing a ternary oxide of lead and manganese in two oxidation states. The mineral was named after Francisco Vasquez de Coronado who was an explorer of southwest USA. The name was made up by Waldemar ...
() * cryptomelane () * hollandite () * romanechite () * todorokite () 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) is a materials science solidification experiment that researchers use on Space Shuttle missions to investigate dendritic growth in an environment where the effect of gravity ( convection in the liquid) can 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.


See also

*
Brownian tree In probability theory, the Brownian tree, or Aldous tree, or Continuum Random Tree (CRT) is a special case from random real trees which may be defined from a Brownian excursion. The Brownian tree was defined and studied by David Aldous in three ...
* Monocrystalline whisker * Patterns in nature * STS-87—Space Shuttle mission * Whisker (metallurgy)


References


External links


Mindat Manganese Dendrites










* ttps://www.manganese-dendrite.com/ All About Manganese Dendrites {{Authority control Crystals