Igneous differentiation

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Igneous_differentiation

 

This article is largely based on an article in the out-of-copyright Encyclopædia Britannica Eleventh Edition, which was produced in 1911. It should be brought up to date to reflect subsequent history or scholarship (including the references, if any). When you have completed the review, replace this notice with a simple note on this article's talk page.

In geology, igneous differentiation, or magmatic differentiation, is an umbrella term for the various processes by which magmas undergo bulk chemical change during the partial melting process, cooling, emplacement, or eruption.

Definitions

Primary melts

When a rock melts to form a liquid, the liquid is known as a primary melt. Primary melts have not undergone any differentiation and represent the starting composition of a magma. In nature, primary melts are rarely seen. Some leucosomes of migmatites are examples of primary melts. Primary melts derived from the mantle are especially important and are known as primitive melts or primitive magmas. By finding the primitive magma composition of a magma series, it is possible to model the composition of the rock from which a melt was formed, which is important because we have little direct evidence of the Earth's mantle.

Parental melts

Where it is impossible to find the primitive or primary magma composition, it is often useful to attempt to identify a parental melt. A parental melt is a magma composition from which the observed range of magma chemistries has been derived by the processes of igneous differentiation. It need not be a primitive melt.

For instance, a series of basalt lava flows is assumed to be related to one another. A composition from which they could reasonably be produced by fractional crystallization is termed a parental melt. To prove this, fractional crystallization models would be produced to test the hypothesis that they share a common parental melt. 

Cumulate rocks

Fractional crystallization and accumulation of crystals formed during the differentiation process of a magmatic event are known as cumulate rocks, and those parts are the first which crystallize out of the magma. Identifying whether a rock is a cumulate or not is crucial for understanding if it can be modelled back to a primary melt or a primitive melt, and identifying whether the magma has dropped out cumulate minerals is equally important even for rocks which carry no phenocrysts.

Underlying causes of differentiation

The primary cause of change in the composition of a magma is cooling, which is an inevitable consequence of the magma being created and migrating from the site of partial melting into an area of lower stress - generally a cooler volume of the crust.

Cooling causes the magma to begin to crystallize minerals from the melt or liquid portion of the magma. Most magmas are a mixture of liquid rock (melt) and crystalline minerals (phenocrysts). 

Contamination is another cause of magma differentiation. Contamination can be caused by assimilation of wall rocks, mixing of two or more magmas or even by replenishment of the magma chamber with fresh, hot magma.

The whole gamut of mechanisms for differentiation has been referred to as the FARM process, which stands for Fractional crystallization, Assimilation, Replenishment and Magma mixing.

Fractional crystallization of igneous rocks

Fractional crystallization is the removal and segregation from a melt of mineral precipitates, which changes the composition of the melt. This is one of the most important geochemical and physical processes operating within the Earth's crust and mantle.

Fractional crystallization in silicate melts (magmas) is a very complex process compared to chemical systems in the laboratory because it is affected by a wide variety of phenomena. Prime amongst these are the composition, temperature, and pressure of a magma during its cooling.

The composition of a magma is the primary control on which mineral is crystallized as the melt cools down past the liquidus. For instance in mafic and ultramafic melts, the MgO and SiO₂ contents determine whether forsterite olivine is precipitated or whether enstatite pyroxene is precipitated.

Two magmas of similar composition and temperature at different pressure may crystallize different minerals. An example is high-pressure and high-temperature fractional crystallization of granites to produce single-feldspar granite, and low-pressure low-temperature conditions which produce two-feldspar granites.

The partial pressure of volatile phases in silicate melts is also of prime importance, especially in near-solidus crystallization of granites. 

Assimilation

Assimilation is a popular mechanism for explaining the felsification of ultramafic and mafic magmas as they rise through the crust. Assimilation assumes that a hot primitive melt intruding into a cooler, felsic crust will melt the crust and mix with the resulting melt. This then alters the composition of the primitive magma. Also pre-existing mafic host rocks can be assimilated, with little effect on the bulk magma chemistry.

 

Effects of this kind are to be expected, and have been clearly proven in many places. There is, however, a general reluctance to admit that they are of great importance. The nature and succession of the rock types do not as a rule show any relation to the sedimentary or other materials which may be supposed to have been dissolved; and where solution is known to have gone on the products are usually of abnormal character and easily distinguishable from the common rock types.

Replenishment

When a melt undergoes cooling along the liquid line of descent, the results are limited to the production of a homogeneous solid body of intrusive rock, with uniform mineralogy and composition, or a partially differentiated cumulate mass with layers, compositional zones and so on. This behaviour is fairly predictable and easy enough to prove with geochemical investigations. In such cases, a magma chamber will form a close approximation of the ideal Bowen's reaction series. However, most magmatic systems are polyphase events, with several pulses of magmatism. In such a case, the liquid line of descent is interrupted by the injection of a fresh batch of hot, undifferentiated magma. This can cause extreme fractional crystallisation because of three main effects:

• Additional heat provides additional energy to allow more vigorous convection, allows resorption of existing mineral phases back into the melt, and can cause a higher-temperature form of a mineral or other higher-temperature minerals to begin precipitating
• Fresh magma changes the composition of the melt, changing the chemistry of the phases which are being precipitated. For instance, plagioclase conforms to the liquid line of descent by forming initial anorthite which, if removed, changes the equilibrium mineral composition to oligoclase or albite. Replenishment of the magma can see this trend reversed, so that more anorthite is precipitated atop cumulate layers of albite.
• Fresh magma destabilises minerals which are precipitating as solid solution series or on a eutectic; a change in composition and temperature can cause extremely rapid crystallisation of certain mineral phases which are undergoing a eutectic crystallisation phase.

Magma mixing

Magma mixing is the process by which two magmas meet, comingle, and form a magma of a composition somewhere between the two end-member magmas. 

Magma mixing is a common process in volcanic magma chambers, which are open-system chambers where magmas enter the chamber, undergo some form of assimilation, fractional crystallisation and partial melt extraction (via eruption of lava), and are replenished.

Magma mixing also tends to occur at deeper levels in the crust and is considered one of the primary mechanisms for forming intermediate rocks such as monzonite and andesite. Here, due to heat transfer and increased volatile flux from subduction, the silicic crust melts to form a felsic magma (essentially granitic in composition). These granitic melts are known as an underplate. Basaltic primary melts formed in the mantle beneath the crust rise and mingle with the underplate magmas, the result being part-way between basalt and rhyolite; literally an 'intermediate' composition. 

Other mechanisms of differentiation

Interface entrapment Convection in a large magma chamber is subject to the interplay of forces generated by thermal convection and the resistance offered by friction, viscosity and drag on the magma offered by the walls of the magma chamber. Often near the margins of a magma chamber which is convecting, cooler and more viscous layers form concentrically from the outside in, defined by breaks in viscosity and temperature. This forms laminar flow, which separates several domains of the magma chamber which can begin to differentiate separately.

Flow banding is the result of a process of fractional crystallization which occurs by convection, if the crystals which are caught in the flow-banded margins are removed from the melt. The friction and viscosity of the magma causes phenocrysts and xenoliths within the magma or lava to slow down near the interface and become trapped in a viscous layer. This can change the composition of the melt in large intrusions, leading to differentiation.

Partial melt extraction
With reference to the definitions, above, a magma chamber will tend to cool down and crystallize minerals according to the liquid line of descent. When this occurs, especially in conjunction with zonation and crystal accumulation, and the melt portion is removed, this can change the composition of a magma chamber. In fact, this is basically fractional crystallization, except in this case we are observing a magma chamber which is the remnant left behind from which a daughter melt has been extracted.

If such a magma chamber continues to cool, the minerals it forms and its overall composition will not match a sample liquid line of descent or a parental magma composition. 

Typical behaviours of magma chambers

It is worth reiterating that magma chambers are not usually static single entities. The typical magma chamber is formed from a series of injections of melt and magma, and most are also subject to some form of partial melt extraction.

Granite magmas are generally much more viscous than mafic magmas and are usually more homogeneous in composition. This is generally considered to be caused by the viscosity of the magma, which is orders of magnitude higher than mafic magmas. The higher viscosity means that, when melted, a granitic magma will tend to move in a larger concerted mass and be emplaced as a larger mass because it is less fluid and able to move. This is why granites tend to occur as large plutons, and mafic rocks as dikes and sills.

Granites are cooler and are therefore less able to melt and assimilate country rocks. Wholesale contamination is therefore minor and unusual, although mixing of granitic and basaltic melts is not unknown where basalt is injected into granitic magma chambers.

Mafic magmas are more liable to flow, and are therefore more likely to undergo periodic replenishment of a magma chamber. Because they are more fluid, crystal precipitation occurs much more rapidly, resulting in greater changes by fractional crystallisation. Higher temperatures also allow mafic magmas to assimilate wall rocks more readily and therefore contamination is more common and better developed. 

Dissolved gases

All igneous magmas contain dissolved gases (water, carbonic acid, hydrogen sulfide, chlorine, fluorine, boric acid, etc.). Of these water is the principal, and was formerly believed to have percolated downwards from the Earth's surface to the heated rocks below, but is now generally admitted to be an integral part of the magma. Many peculiarities of the structure of the plutonic rocks as contrasted with the lavas may reasonably be accounted for by the operation of these gases, which were unable to escape as the deep-seated masses slowly cooled, while they were promptly given up by the superficial effusions. The acid plutonic or intrusive rocks have never been reproduced by laboratory experiments, and the only successful attempts to obtain their minerals artificially have been those in which special provision was made for the retention of the "mineralizing" gases in the crucibles or sealed tubes employed. These gases often do not enter into the composition of the rock-forming minerals, for most of these are free from water, carbonic acid, etc. Hence as crystallization goes on the residual melt must contain an ever-increasing proportion of volatile constituents. It is conceivable that in the final stages the still uncrystallized part of the magma has more resemblance to a solution of mineral matter in superheated steam than to a dry igneous fusion. Quartz, for example, is the last mineral to form in a granite. It bears much of the stamp of the quartz which we know has been deposited from aqueous solution in veins, etc. It is at the same time the most infusible of all the common minerals of rocks. Its late formation shows that in this case it arose at comparatively low temperatures and points clearly to the special importance of the gases of the magma as determining the sequence of crystallization.

When solidification is nearly complete the gases can no longer be retained in the rock and make their escape through fissures towards the surface. They are powerful agents in attacking the minerals of the rocks which they traverse, and instances of their operation are found in the kaolinization of granites, tourmalinization and formation of greisen, deposition of quartz veins, and the group of changes known as propylitization. These "pneumatolytic" processes are of the first importance in the genesis of many ore deposits. They are a real part of the history of the magma itself and constitute the terminal phases of the volcanic sequence.

Quantifying igneous differentiation

There are several methods of directly measuring and quantifying igneous differentiation processes;

• Whole rock geochemistry of representative samples, to track changes and evolution of the magma systems
  • Using the above, calculating normative mineralogy and investigating trends
• Trace element geochemistry
• Isotope geochemistry
  • Investigating the contamination of magma systems by wall rock assimilation using radiogenic isotopes

In all cases, the primary and most valuable method for identifying magma differentiation processes is mapping the exposed rocks, tracking mineralogical changes within the igneous rocks and describing field relationships and textural evidence for magma differentiation.

Crystallization

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Crystallization

Crystallization
Concepts
Crystallization · Crystal growth Recrystallization · Seed crystal Protocrystalline · Single crystal
Methods and technology
Boules Bridgman–Stockbarger technique Crystal bar process Czochralski process Epitaxy Flux method Fractional crystallization Fractional freezing Hydrothermal synthesis Kyropoulos process Laser-heated pedestal growth Micro-pulling-down Shaping processes in crystal growth Skull crucible Verneuil process Zone melting
Fundamentals
Nucleation · Crystal Crystal structure · Solid

Crystallization or crystallisation is the (natural or artificial) process by which a solid forms, where the atoms or molecules are highly organized into a structure known as a crystal. Some of the ways by which crystals form are precipitating from a solution, freezing, or more rarely deposition directly from a gas. Attributes of the resulting crystal depend largely on factors such as temperature, air pressure, and in the case of liquid crystals, time of fluid evaporation.

Crystallization occurs in two major steps. The first is nucleation, the appearance of a crystalline phase from either a supercooled liquid or a supersaturated solvent. The second step is known as crystal growth, which is the increase in the size of particles and leads to a crystal state. An important feature of this step is that loose particles form layers at the crystal's surface lodge themselves into open inconsistencies such as pores, cracks, etc.

The majority of minerals and organic molecules crystallize easily, and the resulting crystals are generally of good quality, i.e. without visible defects. However, larger biochemical particles, like proteins, are often difficult to crystallize. The ease with which molecules will crystallize strongly depends on the intensity of either atomic forces (in the case of mineral substances), intermolecular forces (organic and biochemical substances) or intramolecular forces (biochemical substances).

Crystallization is also a chemical solid–liquid separation technique, in which mass transfer of a solute from the liquid solution to a pure solid crystalline phase occurs. In chemical engineering, crystallization occurs in a crystallizer. Crystallization is therefore related to precipitation, although the result is not amorphous or disordered, but a crystal.

Process

The crystallization process consists of two major events, nucleation and crystal growth which are driven by thermodynamic properties as well as chemical properties. In crystallization Nucleation is the step where the solute molecules or atoms dispersed in the solvent start to gather into clusters, on the microscopic scale (elevating solute concentration in a small region), that become stable under the current operating conditions. These stable clusters constitute the nuclei. Therefore, the clusters need to reach a critical size in order to become stable nuclei. Such critical size is dictated by many different factors (temperature, supersaturation, etc.). It is at the stage of nucleation that the atoms or molecules arrange in a defined and periodic manner that defines the crystal structure — note that "crystal structure" is a special term that refers to the relative arrangement of the atoms or molecules, not the macroscopic properties of the crystal (size and shape), although those are a result of the internal crystal structure.

The crystal growth is the subsequent size increase of the nuclei that succeed in achieving the critical cluster size. Crystal growth is a dynamic process occurring in equilibrium where solute molecules or atoms precipitate out of solution, and dissolve back into solution. Supersaturation is one of the driving forces of crystallization, as the solubility of a species is an equilibrium process quantified by K_sp. Depending upon the conditions, either nucleation or growth may be predominant over the other, dictating crystal size.

Many compounds have the ability to crystallize with some having different crystal structures, a phenomenon called polymorphism. Certain polymorphs may be metastable, meaning that although it is not in thermodynamic equilibrium, it is kinetically stable and requires some input of energy to initiate a transformation to the equilibrium phase. Each polymorph is in fact a different thermodynamic solid state and crystal polymorphs of the same compound exhibit different physical properties, such as dissolution rate, shape (angles between facets and facet growth rates), melting point, etc. For this reason, polymorphism is of major importance in industrial manufacture of crystalline products. Additionally, crystal phases can sometimes be interconverted by varying factors such as temperature, such as in the transformation of anatase to rutile phases of titanium dioxide.

In nature

Snowflakes are a very well-known example, where subtle differences in crystal growth conditions result in different geometries.

Crystallized honey

There are many examples of natural process that involve crystallization.

Geological time scale process examples include:

• Natural (mineral) crystal formation (see also gemstone);
• Stalactite/stalagmite, rings formation.

Human time scale process examples include:

• Snow flakes formation;
• Honey crystallization (nearly all types of honey crystallize).

 

Methods

Crystal formation can be divided into two types, where the first type of crystals are composed of a cation and anion, also known as a salt, such as sodium acetate. The second type of crystals are composed of uncharged species, for example menthol.

Crystal formation can be achieved by various methods, such as: cooling, evaporation, addition of a second solvent to reduce the solubility of the solute (technique known as antisolvent or drown-out), solvent layering, sublimation, changing the cation or anion, as well as other methods.

The formation of a supersaturated solution does not guarantee crystal formation, and often a seed crystal or scratching the glass is required to form nucleation sites.

A typical laboratory technique for crystal formation is to dissolve the solid in a solution in which it is partially soluble, usually at high temperatures to obtain supersaturation. The hot mixture is then filtered to remove any insoluble impurities. The filtrate is allowed to slowly cool. Crystals that form are then filtered and washed with a solvent in which they are not soluble, but is miscible with the mother liquor. The process is then repeated to increase the purity in a technique known as recrystallization.

For biological molecules in which the solvent channels continue to be present to retain the three dimensional structure intact, microbatch crystallization under oil and vapor diffusion methods have been the common methods.

Typical equipment

Equipment for the main industrial processes for crystallization.

1. Tank crystallizers. Tank crystallization is an old method still used in some specialized cases. Saturated solutions, in tank crystallization, are allowed to cool in open tanks. After a period of time the mother liquor is drained and the crystals removed. Nucleation and size of crystals are difficult to control. Typically, labor costs are very high.

 

Thermodynamic view

Low-temperature SEM magnification series for a snow crystal. The crystals are captured, stored, and sputter-coated with platinum at cryo-temperatures for imaging.

The crystallization process appears to violate the second principle of thermodynamics. Whereas most processes that yield more orderly results are achieved by applying heat, crystals usually form at lower temperatures—especially by supercooling. However, due to the release of the heat of fusion during crystallization, the entropy of the universe increases, thus this principle remains unaltered.

The molecules within a pure, perfect crystal, when heated by an external source, will become liquid. This occurs at a sharply defined temperature (different for each type of crystal). As it liquifies, the complicated architecture of the crystal collapses. Melting occurs because the entropy (S) gain in the system by spatial randomization of the molecules has overcome the enthalpy (H) loss due to breaking the crystal packing forces:

${\displaystyle T(S_{\text{liquid}}-S_{\text{solid}})>H_{\text{liquid}}-H_{\text{solid}},}$

${\displaystyle G_{\text{liquid}}$

Regarding crystals, there are no exceptions to this rule. Similarly, when the molten crystal is cooled, the molecules will return to their crystalline form once the temperature falls beyond the turning point. This is because the thermal randomization of the surroundings compensates for the loss of entropy that results from the reordering of molecules within the system. Such liquids that crystallize on cooling are the exception rather than the rule.

The nature of a crystallization process is governed by both thermodynamic and kinetic factors, which can make it highly variable and difficult to control. Factors such as impurity level, mixing regime, vessel design, and cooling profile can have a major impact on the size, number, and shape of crystals produced.

Dynamics

As mentioned above, a crystal is formed following a well-defined pattern, or structure, dictated by forces acting at the molecular level. As a consequence, during its formation process the crystal is in an environment where the solute concentration reaches a certain critical value, before changing status. Solid formation, impossible below the solubility threshold at the given temperature and pressure conditions, may then take place at a concentration higher than the theoretical solubility level. The difference between the actual value of the solute concentration at the crystallization limit and the theoretical (static) solubility threshold is called supersaturation and is a fundamental factor in crystallization.

Nucleation

Nucleation is the initiation of a phase change in a small region, such as the formation of a solid crystal from a liquid solution. It is a consequence of rapid local fluctuations on a molecular scale in a homogeneous phase that is in a state of metastable equilibrium. Total nucleation is the sum effect of two categories of nucleation – primary and secondary.

Primary nucleation

Primary nucleation is the initial formation of a crystal where there are no other crystals present or where, if there are crystals present in the system, they do not have any influence on the process. This can occur in two conditions. The first is homogeneous nucleation, which is nucleation that is not influenced in any way by solids. These solids include the walls of the crystallizer vessel and particles of any foreign substance. The second category, then, is heterogeneous nucleation. This occurs when solid particles of foreign substances cause an increase in the rate of nucleation that would otherwise not be seen without the existence of these foreign particles. Homogeneous nucleation rarely occurs in practice due to the high energy necessary to begin nucleation without a solid surface to catalyse the nucleation.

Primary nucleation (both homogeneous and heterogeneous) has been modelled with the following:

${\displaystyle B={\dfrac {dN}{dt}}=k_{n}(c-c^{*})^{n},}$

where

B is the number of nuclei formed per unit volume per unit time,

N is the number of nuclei per unit volume,

k_n is a rate constant,

c is the instantaneous solute concentration,

c^* is the solute concentration at saturation,

(c − c^*) is also known as supersaturation,

n is an empirical exponent that can be as large as 10, but generally ranges between 3 and 4.

Secondary nucleation

Secondary nucleation is the formation of nuclei attributable to the influence of the existing microscopic crystals in the magma. Simply put, secondary nucleation is when crystal growth is initiated with contact of other existing crystals or "seeds". The first type of known secondary crystallization is attributable to fluid shear, the other due to collisions between already existing crystals with either a solid surface of the crystallizer or with other crystals themselves. Fluid-shear nucleation occurs when liquid travels across a crystal at a high speed, sweeping away nuclei that would otherwise be incorporated into a crystal, causing the swept-away nuclei to become new crystals. Contact nucleation has been found to be the most effective and common method for nucleation. The benefits include the following:

• Low kinetic order and rate-proportional to supersaturation, allowing easy control without unstable operation.
• Occurs at low supersaturation, where growth rate is optimal for good quality.
• Low necessary energy at which crystals strike avoids the breaking of existing crystals into new crystals.
• The quantitative fundamentals have already been isolated and are being incorporated into practice.

The following model, although somewhat simplified, is often used to model secondary nucleation:

${\displaystyle B={\dfrac {dN}{dt}}=k_{1}M_{T}^{j}(c-c^{*})^{b},}$

where

k₁ is a rate constant,

M_T is the suspension density,

j is an empirical exponent that can range up to 1.5, but is generally 1,

b is an empirical exponent that can range up to 5, but is generally 2.

Crystal growth

 

Growth

Once the first small crystal, the nucleus, forms it acts as a convergence point (if unstable due to supersaturation) for molecules of solute touching – or adjacent to – the crystal so that it increases its own dimension in successive layers. The pattern of growth resembles the rings of an onion, as shown in the picture, where each colour indicates the same mass of solute; this mass creates increasingly thin layers due to the increasing surface area of the growing crystal. The supersaturated solute mass the original nucleus may capture in a time unit is called the growth rate expressed in kg/(m²*h), and is a constant specific to the process. Growth rate is influenced by several physical factors, such as surface tension of solution, pressure, temperature, relative crystal velocity in the solution, Reynolds number, and so forth.

The main values to control are therefore:

• Supersaturation value, as an index of the quantity of solute available for the growth of the crystal;
• Total crystal surface in unit fluid mass, as an index of the capability of the solute to fix onto the crystal;
• Retention time, as an index of the probability of a molecule of solute to come into contact with an existing crystal;
• Flow pattern, again as an index of the probability of a molecule of solute to come into contact with an existing crystal (higher in laminar flow, lower in turbulent flow, but the reverse applies to the probability of contact).

The first value is a consequence of the physical characteristics of the solution, while the others define a difference between a well- and poorly designed crystallizer.

Size distribution

The appearance and size range of a crystalline product is extremely important in crystallization. If further processing of the crystals is desired, large crystals with uniform size are important for washing, filtering, transportation, and storage, because large crystals are easier to filter out of a solution than small crystals. Also, larger crystals have a smaller surface area to volume ratio, leading to a higher purity. This higher purity is due to less retention of mother liquor which contains impurities, and a smaller loss of yield when the crystals are washed to remove the mother liquor. In special cases, for example during drug manufacturing in the pharmaceutical industry, small crystal sizes are often desired to improve drug dissolution rate and bio-availability. The theoretical crystal size distribution can be estimated as a function of operating conditions with a fairly complicated mathematical process called population balance theory (using population balance equations).

Main crystallization processes

Some of the important factors influencing solubility are:

• Concentration
• Temperature
• Solvent mixture composition
• Polarity
• Ionic strength

So one may identify two main families of crystallization processes:

• Cooling crystallization
• Evaporative crystallization

This division is not really clear-cut, since hybrid systems exist, where cooling is performed through evaporation, thus obtaining at the same time a concentration of the solution.

A crystallization process often referred to in chemical engineering is the fractional crystallization. This is not a different process, rather a special application of one (or both) of the above.

Cooling crystallization

Application

Most chemical compounds, dissolved in most solvents, show the so-called direct solubility that is, the solubility threshold increases with temperature.

Solubility of the system Na₂SO₄ – H₂O

So, whenever the conditions are favorable, crystal formation results from simply cooling the solution. Here cooling is a relative term: austenite crystals in a steel form well above 1000 °C. An example of this crystallization process is the production of Glauber's salt, a crystalline form of sodium sulfate. In the diagram, where equilibrium temperature is on the x-axis and equilibrium concentration (as mass percent of solute in saturated solution) in y-axis, it is clear that sulfate solubility quickly decreases below 32.5 °C. Assuming a saturated solution at 30 °C, by cooling it to 0 °C (note that this is possible thanks to the freezing-point depression), the precipitation of a mass of sulfate occurs corresponding to the change in solubility from 29% (equilibrium value at 30 °C) to approximately 4.5% (at 0 °C) – actually a larger crystal mass is precipitated, since sulfate entrains hydration water, and this has the side effect of increasing the final concentration.

There are limitations in the use of cooling crystallization:

• Many solutes precipitate in hydrate form at low temperatures: in the previous example this is acceptable, and even useful, but it may be detrimental when, for example, the mass of water of hydration to reach a stable hydrate crystallization form is more than the available water: a single block of hydrate solute will be formed – this occurs in the case of calcium chloride);
• Maximum supersaturation will take place in the coldest points. These may be the heat exchanger tubes which are sensitive to scaling, and heat exchange may be greatly reduced or discontinued;
• A decrease in temperature usually implies an increase of the viscosity of a solution. Too high a viscosity may give hydraulic problems, and the laminar flow thus created may affect the crystallization dynamics.
• It is not applicable to compounds having reverse solubility, a term to indicate that solubility increases with temperature decrease (an example occurs with sodium sulfate where solubility is reversed above 32.5 °C).

 

Cooling crystallizers

Vertical cooling crystallizer in a beet sugar factory

The simplest cooling crystallizers are tanks provided with a mixer for internal circulation, where temperature decrease is obtained by heat exchange with an intermediate fluid circulating in a jacket. These simple machines are used in batch processes, as in processing of pharmaceuticals and are prone to scaling. Batch processes normally provide a relatively variable quality of the product along with the batch.

The Swenson-Walker crystallizer is a model, specifically conceived by Swenson Co. around 1920, having a semicylindric horizontal hollow trough in which a hollow screw conveyor or some hollow discs, in which a refrigerating fluid is circulated, plunge during rotation on a longitudinal axis. The refrigerating fluid is sometimes also circulated in a jacket around the trough. Crystals precipitate on the cold surfaces of the screw/discs, from which they are removed by scrapers and settle on the bottom of the trough. The screw, if provided, pushes the slurry towards a discharge port.

A common practice is to cool the solutions by flash evaporation: when a liquid at a given T₀ temperature is transferred in a chamber at a pressure P₁ such that the liquid saturation temperature T₁ at P₁ is lower than T₀, the liquid will release heat according to the temperature difference and a quantity of solvent, whose total latent heat of vaporization equals the difference in enthalpy. In simple words, the liquid is cooled by evaporating a part of it.

In the sugar industry, vertical cooling crystallizers are used to exhaust the molasses in the last crystallization stage downstream of vacuum pans, prior to centrifugation. The massecuite enters the crystallizers at the top, and cooling water is pumped through pipes in counterflow.

Evaporative crystallization

Another option is to obtain, at an approximately constant temperature, the precipitation of the crystals by increasing the solute concentration above the solubility threshold. To obtain this, the solute/solvent mass ratio is increased using the technique of evaporation. This process is insensitive to change in temperature (as long as hydration state remains unchanged).

All considerations on control of crystallization parameters are the same as for the cooling models.

Evaporative crystallizers

Most industrial crystallizers are of the evaporative type, such as the very large sodium chloride and sucrose units, whose production accounts for more than 50% of the total world production of crystals. The most common type is the forced circulation (FC) model. A pumping device (a pump or an axial flow mixer) keeps the crystal slurry in homogeneous suspension throughout the tank, including the exchange surfaces; by controlling pump flow, control of the contact time of the crystal mass with the supersaturated solution is achieved, together with reasonable velocities at the exchange surfaces. The Oslo, mentioned above, is a refining of the evaporative forced circulation crystallizer, now equipped with a large crystals settling zone to increase the retention time (usually low in the FC) and to roughly separate heavy slurry zones from clear liquid. Evaporative crystallizers tend to yield larger average crystal size and narrows the crystal size distribution curve.

DTB crystallizer

DTB Crystallizer

Schematic of DTB

Whichever the form of the crystallizer, to achieve an effective process control it is important to control the retention time and the crystal mass, to obtain the optimum conditions in terms of crystal specific surface and the fastest possible growth. This is achieved by a separation – to put it simply – of the crystals from the liquid mass, in order to manage the two flows in a different way. The practical way is to perform a gravity settling to be able to extract (and possibly recycle separately) the (almost) clear liquid, while managing the mass flow around the crystallizer to obtain a precise slurry density elsewhere. A typical example is the DTB (Draft Tube and Baffle) crystallizer, an idea of Richard Chisum Bennett (a Swenson engineer and later President of Swenson) at the end of the 1950s. The DTB crystallizer (see images) has an internal circulator, typically an axial flow mixer – yellow – pushing upwards in a draft tube while outside the crystallizer there is a settling area in an annulus; in it the exhaust solution moves upwards at a very low velocity, so that large crystals settle – and return to the main circulation – while only the fines, below a given grain size are extracted and eventually destroyed by increasing or decreasing temperature, thus creating additional supersaturation. A quasi-perfect control of all parameters is achieved as DTF crystallizers offer superior control over crystal size and characteristics. This crystallizer, and the derivative models (Krystal, CSC, etc.) could be the ultimate solution if not for a major limitation in the evaporative capacity, due to the limited diameter of the vapour head and the relatively low external circulation not allowing large amounts of energy to be supplied to the system.

Fulgurite

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Fulgurite

 

Fulgurite

Typical broken fulgurite sections.

Fulgurites (from the Latin fulgur, meaning "lightning") are natural tubes, clumps, or masses of sintered, vitrified, and/or fused soil, sand, rock, organic debris and other sediments that sometimes form when lightning discharges into ground. Fulgurites are classified as a variety of the mineraloid lechatelierite. When lightning strikes a grounding substrate, upwards of 100 million volts (100 MV) are rapidly discharged into the ground. This charge propagates into and rapidly vaporizes and melts silica-rich quartzose sand, mixed soil, clay, or other sediments. This results in the formation of hollow, branching assemblages of glassy, tubes, crusts, and vesicular masses. Because of the high temperature differential between the core of a fulgurite and the surrounding soil, many fulgurites show evidence of progressive crystallization: in addition to glasses, many are partially protocrystalline or microcrystalline. Fulgurites have no fixed composition because their chemical composition is determined by the physical and chemical properties of whatever material is being struck by lightning. 

Fulgurites are homologous to Lichtenberg figures, which are the branching patterns produced on surfaces of insulators during dielectric breakdown by high-voltage discharges, such as lightning.

Description

Fulgurites are formed when lightning strikes the ground, fusing and vitrifying mineral grains. The primary SiO₂ phase in common tube fulgurites is lechatelierite, an amorphous silica glass. Because their groundmass is generally amorphous in structure, fulgurites are classified as mineraloids. 

Material properties (color, surface texture) of fulgurites vary widely, depending on bulk composition, interface dynamics, and trace elements. Most natural fulgurites fall on a spectrum from colorless (transparent), to white, to black. Iron oxide is a common impurity that can result in deep brownish-green coloration. Lechatelierite similar to fulgurites can also be produced via controlled (or uncontrolled) arcing of artificial electricity into a medium. Downed high voltage power lines have produced brightly-colored lechatelierites, due to copper or other materials from the power lines themselves. Brightly-colored lechatelierites resembling fulgurites are usually synthetic and reflect the incorporation of synthetic materials. However, lightning can strike man-made objects, resulting in colored fulgurites. 

The interior of Type I (sand) fulgurites normally is smooth or lined with fine bubbles, while their exteriors are coated with rough sedimentary particles or small rocks. Other types or fulgurites are usually vesicular, and may lack an open central tube; their exteriors can be porous or smooth. Branching fulgurites display fractal-like self-similarity and structural scale invariance as a macroscopic or microscopic network of root-like branches, and can display this texture without central channels or obvious divergence from morphology of context or target (e.g. sheet-like melt, rock fulgurites). Fulgurites are usually fragile, making the field collection of large specimens difficult. 

Fulgurites can exceed tens of centimeters in diameter and can penetrate deep into the subsoil, sometimes occurring as far as 15 m (49 ft) below the surface that was struck.  Or they may form directly on sedimentary surfaces. One of the longest fulgurites to have been found in modern times was a little over 4.9 m (16 ft) in length, and was found in northern Florida. The Yale University Peabody Museum of Natural History displays one of the longest known preserved fulgurites, approximately 4 m (13 ft) in length. Charles Darwin in The Voyage of the Beagle recorded that tubes such as these found in Drigg, Cumberland, UK reached a length of 9.1 m (30 ft). The Winans Lake fulgurite[s] (Winans Lake, Livingston County, Michigan), extended discontinuously throughout a 30 m range, and arguably includes the largest reported fulgurite mass ever recovered and described: its largest section extending approximately 16 ft (4.88 m) in length by 1 ft in diameter (30 cm).

Peak temperatures within a lightning channel exceed 30,000 K, with sufficient pressure to produce planar deformation features in SiO₂, a kind of polymorphism. This is also known colloquially as shocked quartz.

Classification

Fulgurites have been classified by Pasek et al. (2012) into five types related to the type of sediment in which the fulgurite formed, as follows:

• Type I - sand fulgurites with tubaceous structure; their central axial void may be collapsed
• Type II - soil fulgurites; these are glass-rich, and form in a wide range of sediment compositions, including clay-rich soils, silt-rich soils, gravel-rich soils, and loessoid; these may be tubaceous, branching, vesicular, irregular/slaggy, or may display a combination of these structures, and can produce exogenic fulgurites (droplet fulgurites)
• Type III - caliche or calcic sediment fulgurites, having thick, often surficially glazed granular walls with calcium-rich vitreous groundmass with little or no lechatelierite glass; their shapes are variable, with multiple narrow central channels common, and can span the entire range of morphological and structural variation for fulguritic objects
• Type IV - rock fulgurites, which are either crusts on minimally altered rocks, networks of tunneling within rocks, vesicular outgassed rocks (often glazed by a silicide-rich and/or metal oxide crust), or completely vitrified and dense rock material and masses of these forms with little sedimentary groundmass
• Type V - [droplet] fulgurites (exogenic fulgurites), which show evidence of ejection (e.g. spheroidal, filamentous, or aerodynamic), related by composition to Type II and Type IV fulgurites

Significance

Paleoenvironmental indicator

The presence of fulgurites in an area can be used to estimate the frequency of lightning over a period of time, which can help to understand past regional climates. Paleolightning is the study of various indicators of past lightning strikes, primarily in the form of fulgurites and lightning-induced remanent magnetization (LIRM) signatures.

Place in planetary processes and the geologic record

Many high-pressure, high-temperature materials have been observed in fulgurites. Many of these minerals and compounds are also known to be formed by synthetic or meteoritic sources such as nuclear weapon tests, hypervelocity impacts, and cosmic dust. Shocked quartz was first described in fulgurites in 1980. Other materials, including highly reduced silicon-metal alloys (silicides), the fullerene allotropes C₆₀ (buckminsterfullerene) and C₇₀, as well as high-pressure polymorphs of SiO₂, have since been identified in fulgurites.

Reduced phosphorus as phosphides and phosphites has been identified through quantitative analyses of a representative sample of 10 fulgurites recovered from most continents, in the form of schreibersite (Fe₃P, (Fe,Ni)₃P), and titanium(III) phosphide (TiP). Many of these reduced compounds are otherwise rare on Earth due to the presence of oxygen in Earth's atmosphere, which creates oxidizing surface conditions. 

In material culture

An object initially believed to be a fulgurite was found within the contents of the ash altar at the temple of Lykaian Zeus at Mount Lykaion in Greece. However, after nearly two decades, the "fulgurite" has not yet been analyzed or confirmed to be a fulgurite, and it has not been described in any peer-reviewed publications. The two published reports of the excavations at Mt. Lykaion notably omit any references to, or description of, a "fulgurite."

Fulgurites are popular among hobbyists and collectors of natural specimens.