The various liquid-crystal phases (called
mesophases together with
plastic crystal phases) can be characterized by the type of ordering. One can distinguish positional order (whether molecules are arranged in any sort of ordered lattice) and orientational order (whether molecules are mostly pointing in the same direction). Liquid crystals are characterized by orientational order, but only partial or completely absent positional order. In contrast, materials with positional order but no orientational order are known as
plastic crystals. Most thermotropic LCs will have an
isotropic phase at high temperature: heating will eventually drive them into a conventional liquid phase characterized by random and isotropic molecular ordering and
fluid-like flow behavior. Under other conditions (for instance, lower temperature), a LC might inhabit one or more phases with significant
anisotropic orientational structure and short-range orientational order while still having an ability to flow. The ordering of liquid crystals extends up to the entire domain size, which may be on the order of micrometers, but usually not to the macroscopic scale as often occurs in classical
crystalline solids. However some techniques, such as the use of boundaries or an applied
electric field, can be used to enforce a single ordered domain in a macroscopic liquid crystal sample. The orientational ordering in a liquid crystal might extend along only one
dimension, with the material being essentially disordered in the other two directions.
Thermotropic liquid crystals Thermotropic phases are those that occur in a certain temperature range. If the temperature rise is too high, thermal motion will destroy the delicate cooperative ordering of the LC phase, pushing the material into a conventional isotropic liquid phase. At too low temperature, most LC materials will form a conventional crystal.
Nematic phase . The black color corresponds to isotropic medium. The simplest liquid crystal phase is the nematic. In a nematic phase, (rod-like) organic molecules lack a crystalline positional order, but do self-align with their long axes roughly parallel. The molecules are free to flow and their center of mass positions are randomly distributed as in a liquid, but their orientation is constrained to form a long-range directional order. The word
nematic comes from the
Greek (''''), which means "thread". This term originates from the
disclinations: thread-like
topological defects observed in nematic phases. Nematics also exhibit so-called "hedgehog"
topological defects. In two dimensions, there are topological defects with
topological charges and . Due to hydrodynamics, the defect moves considerably faster than the defect. When placed close to each other, the defects attract; upon collision, they annihilate. Most nematic phases are uniaxial: they have one axis (called a directrix) that is longer and preferred, with the other two being equivalent (can be approximated as cylinders or rods). However, some liquid crystals are
biaxial nematic, meaning that in addition to orienting their long axis, they also orient along a secondary axis. Nematic crystals have fluidity similar to that of ordinary (isotropic) liquids but they can be easily aligned by an external magnetic or electric field. Aligned nematics have the optical properties of uniaxial crystals and this makes them extremely useful in
liquid-crystal displays (LCD). Nematic phases are also known in non-molecular systems: at high magnetic fields, electrons flow in
bundles or stripes to create an "electronic nematic" form of matter.
Smectic phases The smectic phases, which are found at lower temperatures than the nematic, form well-defined layers that can slide over one another in a manner similar to that of soap. The word "smectic" originates from the Latin word "smecticus", meaning cleaning, or having soap-like properties. The smectics are thus positionally ordered along one direction. In the Smectic A phase, the molecules are oriented along the layer normal, while in the Smectic C phase they are tilted away from it. These phases are liquid-like within the layers. There are many different smectic phases, all characterized by different types and degrees of positional and orientational order. One example of smectic LCs is
p,p'-dinonylazobenzene.
Chiral phases or twisted nematics The
chiral nematic phase exhibits
chirality (handedness). This phase is often called the
cholesteric phase because it was first observed for
cholesterol derivatives. Only
chiral molecules can give rise to such a phase. This phase exhibits a twisting of the molecules perpendicular to the director, with the molecular axis parallel to the director. The finite twist angle between adjacent molecules is due to their asymmetric packing, which results in longer-range chiral order. In the smectic C* phase (an asterisk denotes a chiral phase), the molecules have positional ordering in a layered structure (as in the other smectic phases), with the molecules tilted by a finite angle with respect to the layer normal. The chirality induces a finite azimuthal twist from one layer to the next, producing a spiral twisting of the molecular axis along the layer normal, hence they are also called
twisted nematics.
Blue phases Blue phases are liquid crystal phases that appear in the temperature range between a
chiral nematic phase and an
isotropic liquid phase. Blue phases have a regular three-dimensional cubic structure of defects with
lattice periods of several hundred nanometers, and thus they exhibit selective
Bragg reflections in the wavelength range of visible light corresponding to the
cubic lattice. It was theoretically predicted in 1981 that these phases can possess icosahedral symmetry similar to
quasicrystals. Although blue phases are of interest for fast light modulators or tunable
photonic crystals, they exist in a very narrow temperature range, usually less than a few
kelvins. Recently the stabilization of blue phases over a temperature range of more than 60 K including room temperature (260–326 K) has been demonstrated. Blue phases stabilized at room temperature allow electro-optical switching with response times of the order of 10−4 s. In May 2008, the first
blue phase mode LCD panel had been developed. Blue phase crystals, being a periodic cubic structure with a bandgap in the visible wavelength range, can be considered as
3D photonic crystals. Producing ideal blue phase crystals in large volumes is still problematic, since the produced crystals are usually polycrystalline (platelet structure) or the single crystal size is limited (in the micrometer range). Recently, blue phases obtained as ideal 3D photonic crystals in large volumes have been stabilized and produced with different controlled crystal lattice orientations.
Discotic phases Disk-shaped LC molecules can orient themselves in a layer-like fashion known as the discotic nematic phase. If the disks pack into stacks, the phase is called a
discotic columnar. The columns themselves may be organized into rectangular or hexagonal arrays. Chiral discotic phases, similar to the chiral nematic phase, are also known.
Conic phases Conic LC molecules, like in discotics, can form columnar phases. Other phases, such as nonpolar nematic, polar nematic, stringbean, donut and onion phases, have been predicted. Conic phases, except nonpolar nematic, are polar phases.
Lyotropic liquid crystals (left) and
micelle (right). A
lyotropic liquid crystal consists of two or more components that exhibit liquid-crystalline properties in certain concentration ranges. In the
lyotropic phases,
solvent molecules fill the space around the compounds to provide
fluidity to the system. In contrast to thermotropic liquid crystals, these lyotropics have another degree of freedom of concentration that enables them to induce a variety of different phases. A compound that has two immiscible
hydrophilic and
hydrophobic parts within the same molecule is called an
amphiphilic molecule. Many amphiphilic molecules show lyotropic liquid-crystalline phase sequences depending on the volume balances between the hydrophilic part and hydrophobic part. These structures are formed through the micro-phase segregation of two incompatible components on a nanometer scale. Soap is an everyday example of a lyotropic liquid crystal. The content of water or other solvent molecules changes the self-assembled structures. At very low amphiphile concentration, the molecules will be dispersed randomly without any ordering. At slightly higher (but still low) concentration, amphiphilic molecules will spontaneously assemble into
micelles or
vesicles. This is done so as to 'hide' the hydrophobic tail of the amphiphile inside the micelle core, exposing a hydrophilic (water-soluble) surface to aqueous solution. These spherical objects do not order themselves in solution, however. At higher concentration, the assemblies will become ordered. A typical phase is a hexagonal columnar phase, where the amphiphiles form long cylinders (again with a hydrophilic surface) that arrange themselves into a roughly hexagonal lattice. This is called the middle soap phase. At still higher concentration, a lamellar phase (neat soap phase) may form, wherein extended sheets of amphiphiles are separated by thin layers of water. For some systems, a cubic (also called viscous isotropic) phase may exist between the hexagonal and lamellar phases, wherein spheres are formed that create a dense cubic lattice. These spheres may also be connected to one another, forming a bicontinuous cubic phase. The objects created by amphiphiles are usually spherical (as in the case of micelles), but may also be disc-like (bicelles), rod-like, or biaxial (all three micelle axes are distinct). These anisotropic self-assembled nano-structures can then order themselves in much the same way as thermotropic liquid crystals do, forming large-scale versions of all the thermotropic phases (such as a nematic phase of rod-shaped micelles). For some systems, at high concentrations, inverse phases are observed. That is, one may generate an inverse hexagonal columnar phase (columns of water encapsulated by amphiphiles) or an inverse micellar phase (a bulk liquid crystal sample with spherical water cavities). A generic progression of phases, going from low to high amphiphile concentration, is: • Discontinuous cubic phase (
micellar cubic phase) •
Hexagonal phase (hexagonal columnar phase) (middle phase) •
Lamellar phase • Bicontinuous
cubic phase • Reverse hexagonal columnar phase • Inverse cubic phase (Inverse micellar phase) Even within the same phases, their self-assembled structures are tunable by the concentration: for example, in lamellar phases, the layer distances increase with the solvent volume. Since lyotropic liquid crystals rely on a subtle balance of intermolecular interactions, it is more difficult to analyze their structures and properties than those of thermotropic liquid crystals. Similar phases and characteristics can be observed in immiscible diblock
copolymers.
Metallotropic liquid crystals Liquid crystal phases can also be based on low-melting inorganic phases like
ZnCl2 that have a structure formed of linked tetrahedra and easily form glasses. The addition of long chain soap-like molecules leads to a series of new phases that show a variety of liquid crystalline behavior both as a function of the inorganic-organic composition ratio and of temperature. This class of materials has been named metallotropic.
Laboratory analysis of mesophases Thermotropic
mesophases are detected and characterized by two major methods, the original method was use of thermal optical microscopy, in which a small sample of the material was placed between two crossed polarizers; the sample was then heated and cooled. As the isotropic phase would not significantly affect the polarization of the light, it would appear very dark, whereas the crystal and liquid crystal phases will both polarize the light in a uniform way, leading to brightness and color gradients. This method allows for the characterization of the particular phase, as the different phases are defined by their particular order, which must be observed. The second method,
differential scanning calorimetry (DSC), allows for more precise determination of phase transitions and transition enthalpies. In DSC, a small sample is heated in a way that generates a very precise change in temperature with respect to time. During phase transitions, the heat flow required to maintain this heating or cooling rate will change. These changes can be observed and attributed to various phase transitions, such as key liquid crystal transitions. Lyotropic mesophases are analyzed in a similar fashion, though these experiments are somewhat more complex, as the concentration of mesogen is a key factor. These experiments are run at various concentrations of
mesogen in order to analyze that impact. ==Biological liquid crystals==