Crystallization

Crystallization 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.

Crystallization
Process-of-Crystallization-200px
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

Process

Time-lapse of growth of a citric acid crystal. The video covers an area of 2.0 by 1.5 mm and was captured over 7.2 min.

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 Ksp. 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. 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.

In nature

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

There are many examples of natural process that involve crystallization.

Geological time scale process examples include:

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.[1]

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[2] crystallization under oil and vapor diffusion[3] 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

LT-SEM snow crystal magnification series-3
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:

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:[4]

where

B is the number of nuclei formed per unit volume per unit time,
N is the number of nuclei per unit volume,
kn is a rate constant,
c is the instantaneous solute concentration,
c* is the solute concentration at saturation,
(cc*) 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.[5] Simply put, secondary nucleation is when crystal growth is initiated with contact of other existing crystals or "seeds".[6] 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:[5]

  • 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:[4]

where

k1 is a rate constant,
MT 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
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. 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

Kristalizacija

Some of the important factors influencing solubility are:

  • Concentration
  • Temperature
  • 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.

Solubilita Na2SO4
Solubility of the system Na2SO4 – H2O

So, whenever the conditions are favourable, 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

1-cooling-crystallizer-schladen
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 product along 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 (see evaporator). 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.[7]

DTB crystallizer

DTB Xls
DTB Crystallizer
DTB 2
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.[8] 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.

See also

References

  1. ^ Lin, Yibin (2008). "An Extensive Study of Protein Phase Diagram Modification:Increasing Macromolecular Crystallizability by Temperature Screening". Crystal Growth & Design. 8 (12): 4277. doi:10.1021/cg800698p.
  2. ^ Chayen, Blow (1992). "Microbatch crystallization under oil — a new technique allowing many small-volume crystallization trials". Journal of Crystal Growth. 122 (1–4): 176–180. Bibcode:1992JCrGr.122..176C. doi:10.1016/0022-0248(92)90241-A.
  3. ^ Benvenuti, Mangani (2007). "Crystallization of soluble proteins in vapor diffusion for x-ray crystallography". Nature Protocols. 2: 1663. doi:10.1038/nprot.2007.198.
  4. ^ a b Tavare, N. S. (1995). Industrial Crystallization. Plenum Press, New York.
  5. ^ a b McCabe & Smith (2000). Unit Operations of Chemical Engineering. McGraw-Hill, New York.
  6. ^ "Crystallization". www.reciprocalnet.org. Archived from the original on 2016-11-27. Retrieved 2017-01-03.
  7. ^ "Submerge Circulating Crystallizers - Thermal Kinetics Engineering, PLLC". Thermal Kinetics Engineering, PLLC. Retrieved 2017-01-03.
  8. ^ "Draft Tube Baffle (DTB) Crystallizer - Swenson Technology". Swenson Technology. Archived from the original on 2016-09-25. Retrieved 2017-01-03.

Further reading

  • A. Mersmann, Crystallization Technology Handbook (2001) CRC; 2nd ed. ISBN 0-8247-0528-9
  • Tine Arkenbout-de Vroome, Melt Crystallization Technology (1995) CRC ISBN 1-56676-181-6
  • "Small Molecule Crystallization" (PDF) at Illinois Institute of Technology website
  • Glynn P.D. and Reardon E.J. (1990) "Solid-solution aqueous-solution equilibria: thermodynamic theory and representation". Amer. J. Sci. 290, 164–201.
  • Geankoplis, C.J. (2003) "Transport Processes and Separation Process Principles". 4th Ed. Prentice-Hall Inc.
  • S.J. Jancic, P.A.M. Grootscholten: “Industrial Crystallization”, Textbook, Delft University Press and Reidel Publishing Company, Delft, The Netherlands, 1984.

External links

Acta Crystallographica

Acta Crystallographica is a series of peer-reviewed scientific journals, with articles centred on crystallography, published by the International Union of Crystallography (IUCr). Originally established in 1948 as a single journal called Acta Crystallographica, there are now six independent Acta Crystallographica titles:

Acta Crystallographica Section A: Foundations and AdvancesActa Crystallographica Section B: Structural Science, Crystal Engineering and MaterialsActa Crystallographica Section C: Structural ChemistryActa Crystallographica Section D: Structural BiologyActa Crystallographica Section E: Crystallographic CommunicationsActa Crystallographica Section F: Structural Biology CommunicationsActa Crystallographica has been noted for the high quality of the papers that it produces, as well as the large impact that its papers have had on the field of crystallography. The current six journals form part of the journal portfolio of the IUCr, which is completed by the Journal of Applied Crystallography, the Journal of Synchrotron Radiation, the open-access IUCrJ and the open-access data publication IUCr Data.

Andesite

For the extinct cephalopod genus, see Andesites.

Andesite ( or ) is an extrusive igneous, volcanic rock, of intermediate composition, with aphanitic to porphyritic texture. In a general sense, it is the intermediate type between basalt and rhyolite, and ranges from 57 to 63% silicon dioxide (SiO2) as illustrated in TAS diagrams. The mineral assemblage is typically dominated by plagioclase plus pyroxene or hornblende. Magnetite, zircon, apatite, ilmenite, biotite, and garnet are common accessory minerals. Alkali feldspar may be present in minor amounts. The quartz-feldspar abundances in andesite and other volcanic rocks are illustrated in QAPF diagrams.

Classification of andesites may be refined according to the most abundant phenocryst. Example: hornblende-phyric andesite, if hornblende is the principal accessory mineral.

Andesite can be considered as the extrusive equivalent of plutonic diorite. Characteristic of subduction zones, andesite represents the dominant rock type in island arcs. The average composition of the continental crust is andesitic. Along with basalts they are a major component of the Martian crust. The name andesite is derived from the Andes mountain range.

Angrite

Angrites are a rare group of achondrites consisting mostly of the mineral augite with some olivine, anorthite and troilite. The group is named for the Angra dos Reis meteorite.

Angrites are basaltic rocks, often having porosity, with vesicle diameters of up to 2.5 centimetres (0.98 in).

They are the oldest igneous rocks, with crystallization ages of around 4.55 billion years.

Calcium oxalate

Calcium oxalate (in archaic terminology, oxalate of lime) is a calcium salt of oxalate with the chemical formula CaC2O4(H2O)x, where x varies from 1 to 3. All forms are colorless or white. The monohydrate occurs naturally as the mineral whewellite, forming envelope-shaped crystals, known in plants as raphides. The rarer dihydrate (mineral: weddellite) and trihydrate (mineral: caoxite) are also recognized. Calcium oxalates are a major constituent of human kidney stones. Calcium oxalate is also found in beerstone, a scale that forms on containers used in breweries.

Chiral resolution

Chiral resolution in stereochemistry is a process for the separation of racemic compounds into their enantiomers. It is an important tool in the production of optically active drugs. Other terms with the same meaning are optical resolution and mechanical resolution.

One disadvantage of chiral resolution of racemates compared to direct asymmetric synthesis of one of the enantiomers is that only 50% of a desired enantiomer is obtained. Several methods exist.

Crystal

A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macroscopic single crystals are usually identifiable by their geometrical shape, consisting of flat faces with specific, characteristic orientations. The scientific study of crystals and crystal formation is known as crystallography. The process of crystal formation via mechanisms of crystal growth is called crystallization or solidification.

The word crystal derives from the Ancient Greek word κρύσταλλος (krustallos), meaning both "ice" and "rock crystal", from κρύος (kruos), "icy cold, frost".Examples of large crystals include snowflakes, diamonds, and table salt. Most inorganic solids are not crystals but polycrystals, i.e. many microscopic crystals fused together into a single solid. Examples of polycrystals include most metals, rocks, ceramics, and ice. A third category of solids is amorphous solids, where the atoms have no periodic structure whatsoever. Examples of amorphous solids include glass, wax, and many plastics.

Despite the name, lead crystal, crystal glass, and related products are not crystals, but rather types of glass, i.e. amorphous solids.

Crystals are often used in pseudoscientific practices such as crystal therapy, and, along with gemstones, are sometimes associated with spellwork in Wiccan beliefs and related religious movements.

Crystallization of polymers

Crystallization of polymers is a process associated with partial alignment of their molecular chains. These chains fold together and form ordered regions called lamellae, which compose larger spheroidal structures named spherulites. Polymers can crystallize upon cooling from the melt, mechanical stretching or solvent evaporation. Crystallization affects optical, mechanical, thermal and chemical properties of the polymer. The degree of crystallinity is estimated by different analytical methods and it typically ranges between 10 and 80%, thus crystallized polymers are often called "semi-crystalline". The properties of semi-crystalline polymers are determined not only by the degree of crystallinity, but also by the size and orientation of the molecular chains.

Fractional crystallization (chemistry)

In chemistry, fractional crystallization is a method of refining substances based on differences in solubility. It fractionates via differences in crystallization (forming of crystals). If a mixture of two or more substances in solution are allowed to crystallize, for example by allowing the temperature of the solution to decrease or increase, the precipitate will contain more of the least soluble substance. The proportion of components in the precipitate will depend on their solubility products. If the solubility products are very similar, a cascade process will be needed to effectuate a complete separation.

This technique is often used in chemical engineering to obtain very pure substances, or to recover saleable products from waste solutions.

Fractional crystallization (geology)

Fractional crystallization, or crystal fractionation, is one of the most important geochemical and physical processes operating within the Earth's crust and mantle. It is important in the formation of igneous rocks because it is one of the main processes of magmatic differentiation. Fractional crystallization is also important in the formation of sedimentary evaporite rocks.

Freezing

Freezing is a phase transition in which a liquid turns into a solid when its temperature is lowered below its freezing point. In contrast, solidification is a similar process where a liquid turns into a solid, not by lowering its temperature, but by increasing the pressure that it is under. Despite this technical distinction, the two processes are very similar and the two terms are often used interchangeably.

For most substances, the melting and freezing points are the same temperature; however, certain substances possess differing solid–liquid transition temperatures. For example, agar displays a hysteresis in its melting point and freezing point. It melts at 85 °C (185 °F) and solidifies from 32 °C to 40 °C (89.6 °F to 104 °F).

Igneous petrology

Igneous petrology is the study of igneous rocks—those that are formed from magma. As a branch of geology, igneous petrology is closely related to volcanology, tectonophysics, and petrology in general. The modern study of igneous rocks utilizes a number of techniques, some of them developed in the fields of chemistry, physics, or other earth sciences. Petrography, crystallography, and isotopic studies are common methods used in igneous petrology.

Igneous rock

Igneous rock (derived from the Latin word ignis meaning fire), or magmatic rock, is one of the three main rock types, the others being sedimentary and metamorphic. Igneous rock is formed through the cooling and solidification of magma or lava. The magma can be derived from partial melts of existing rocks in either a planet's mantle or crust. Typically, the melting is caused by one or more of three processes: an increase in temperature, a decrease in pressure, or a change in composition. Solidification into rock occurs either below the surface as intrusive rocks or on the surface as extrusive rocks. Igneous rock may form with crystallization to form granular, crystalline rocks, or without crystallization to form natural glasses. Igneous rocks occur in a wide range of geological settings: shields, platforms, orogens, basins, large igneous provinces, extended crust and oceanic crust.

Magma

Magma (from Ancient Greek μάγμα (mágma) meaning "thick unguent") is the molten or semi-molten natural material from which all igneous rocks are formed. Magma is found beneath the surface of the Earth, and evidence of magmatism has also been discovered on other terrestrial planets and some natural satellites. Besides molten rock, magma may also contain suspended crystals and gas bubbles. Magma is produced by melting of the mantle and/or the crust at various tectonic settings, including subduction zones, continental rift zones, mid-ocean ridges and hotspots. Mantle and crustal melts migrate upwards through the crust where they are thought to be stored in magma chambers or trans-crustal crystal-rich mush zones. During their storage in the crust, magma compositions may be modified by fractional crystallization, contamination with crustal melts, magma mixing, and degassing. Following their ascent through the crust, magmas may feed a volcano or solidify underground to form an intrusion (e.g., an igneous dike or a sill). While the study of magma has historically relied on observing magma in the form of lava flows, magma has been encountered in situ three times during geothermal drilling projects—twice in Iceland (see Magma usage for energy production), and once in Hawaii.

Melting point

The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends on pressure and is usually specified at a standard pressure such as 1 atmosphere or 100 kPa.

When considered as the temperature of the reverse change from liquid to solid, it is referred to as the freezing point or crystallization point. Because of the ability of some substances to supercool, the freezing point is not considered as a characteristic property of a substance. When the "characteristic freezing point" of a substance is determined, in fact the actual methodology is almost always "the principle of observing the disappearance rather than the formation of ice", that is, the melting point.

Protein crystallization

Protein crystallization is the process of formation of a protein crystal. In the process, proteins will dissolve in an aqueous environment, and sample solution to reach the supersaturated state. Different methods are used to reach that state. Such as, Vapor diffusion, Microbatch, Microdialysis, Free-interface diffusion, etc. In additional, some parameters including pH, temperature, ionic strength in the crystallization solution and other factors could influence the yield of crystallization as well. These crystals can then be used in structural biology to study the molecular structure of the protein, or for various industrial or biotechnological purposes.

Based on the crystals, the determination of protein structure can be achieved traditionally by utilizing X-Ray Diffraction (XRD). Alternatively, cryo-electron microscopy (cryo-EM) and nuclear magnetic resonance (NMR) could also be used for protein structure determination. The structural of proteins is significant to the structural analysis in biochemistry and translational medicine. Meanwhile, the protein structure is essential for the development of targeted therapy in modern drug advancement.

STS-73

STS-73 was a Space Shuttle program mission, during October–November 1995, on board the space shuttle Columbia. The mission was the second mission for the United States Microgravity Laboratory. The crew, who spent 16 days in space, were broken up into 2 teams, the red team and the blue team. The mission also included several Detailed Test Objectives or DTO's.

Scientific research on the International Space Station

Scientific research on the International Space Station is a collection of experiments that require one or more of the unusual conditions present in low Earth orbit. The primary fields of research include human research, space medicine, life sciences, physical sciences, astronomy and meteorology.The 2005 NASA Authorization Act designated the American segment of the International Space Station as a national laboratory with the goal of increasing the use of the ISS by other federal agencies and the private sector.Research on the ISS improves knowledge about the effects of long-term space exposure on the human body. Subjects currently under study include muscle atrophy, bone loss, and fluid shift. The data will be used to determine whether space colonisation and lengthy human spaceflight are feasible. As of 2006, data on bone loss and muscular atrophy suggest that there would be a significant risk of fractures and movement problems if astronauts landed on a planet after a lengthy interplanetary cruise (such as the six-month journey time required to fly to Mars).

Large scale medical studies are conducted aboard the ISS via the National Space Biomedical Research Institute (NSBRI). Prominent among these is the Advanced Diagnostic Ultrasound in Microgravity study in which astronauts (including former ISS Commanders Leroy Chiao and Gennady Padalka) perform ultrasound scans under the guidance of remote experts. The study considers the diagnosis and treatment of medical conditions in space. Usually, there is no physician on board the ISS, and diagnosis of medical conditions is a challenge. It is anticipated that remotely guided ultrasound scans will have application on Earth in emergency and rural care situations where access to a trained physician is difficult.Researchers are investigating the effect of the station's near-weightless environment on the evolution, development, growth and internal processes of plants and animals. In response to some of this data, NASA wants to investigate microgravity's effects on the growth of three-dimensional, human-like tissues, and the unusual protein crystals that can be formed in space.The investigation of the physics of fluids in microgravity will allow researchers to model the behaviour of fluids better. Because fluids can be almost completely combined in microgravity, physicists investigate fluids that do not mix well on Earth. In addition, an examination of reactions that are slowed by low gravity and temperatures will give scientists a deeper understanding of superconductivity.The study of materials science is an important ISS research activity, with the objective of reaping economic benefits through the improvement of techniques used on the ground. Other areas of interest include the effect of the low gravity environment on combustion, through the study of the efficiency of burning and control of emissions and pollutants. These findings may improve our knowledge about energy production, and lead to economic and environmental benefits. Future plans are for the researchers aboard the ISS to examine aerosols, ozone, water vapour, and oxides in Earth's atmosphere, as well as cosmic rays, cosmic dust, antimatter, and dark matter in the universe.

Supersaturation

Supersaturation is a solution that contains more of the dissolved material than could be dissolved by the solvent under normal circumstances. It can also refer to a vapor of a compound that has a higher (partial) pressure than the vapor pressure of that compound.

Water of crystallization

In chemistry, water of crystallization or water of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.

Upon crystallization from water or moist solvents, many compounds incorporate water molecules in their crystalline frameworks. Water of crystallization can generally be removed by heating a sample but the crystalline properties are often lost. For example, in the case of sodium chloride, the dihydrate is unstable at room temperature.

Compared to inorganic salts, proteins crystallize with large amounts of water in the crystal lattice. A water content of 50% is not uncommon for proteins.

Chirality types
Chiral molecules
Analysis
Chiral resolution
Reactions
Processes
Devices
Multiphase
systems
Concepts

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