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The Birth Of Liquid Crystals

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The Birth Of Liquid Crystals

Liquid crystals (LCs) are a state of matter that has properties between those of a conventional liquid and those of a solid crystal. For instance, an LC may flow like a liquid, but its molecules may be oriented in a crystal-like way. There are many different types of LC phases, which can be distinguished by their different optical properties (such as birefringence). When viewed under a microscope using a polarized light source, different liquid crystal phases will appear to have distinct textures. The contrasting areas in the textures correspond to domains where the LC molecules are oriented in different directions. Within a domain, however, the molecules are well ordered. LC materials may not always be in an LC phase (just as water may turn into ice or steam).

Liquid crystals can be divided into thermotropic, lyotropic and metallotropic phases. Thermotropic and lyotropic LCs consist of organic molecules. Thermotropic LCs exhibit a phase transition into the LC phase as temperature is changed. Lyotropic LCs exhibit phase transitions as a function of both temperature and concentration of the LC molecules in a solvent (typically water). Metallotropic LCs are composed of both organic and inorganic molecules; their LC transition depends not only on temperature and concentration, but also on the inorganic-organic composition ratio.

Examples of liquid crystals can be found both in the natural world and in technological applications. Most modern electronic displays are liquid crystal based. Lyotropic liquid-crystalline phases are abundant in living systems. For example, many proteins and cell membranes are LCs. Other well-known LC examples are solutions of soap and various related detergents, as well as tobacco mosaic virus.

In 1888, Austrian botanical physiologist Friedrich Reinitzer, working at the Charles University in Prague, examined the physico-chemical properties of various derivatives of cholesterol, which are now known as cholesteric liquid crystals. Previously, other researchers had observed distinct color effects when cooling cholesterol derivatives just above the freezing point, but had not associated it with a new phenomenon. Reinitzer perceived that color changes in a derivative cholesteryl benzoate were not the most peculiar feature. He found that cholesteryl benzoate does not melt in the same manner as other compounds, but has two melting points. At 145.5 Â°C (293.9 Â°F) it melts into a cloudy liquid, and at 178.5 Â°C (353.3 Â°F) it melts again and the cloudy liquid becomes clear. The phenomenon is reversible. Seeking help from a physicist, on March 14, 1888, he wrote to Otto Lehmann, at that time a Privatdozent in Aachen. They exchanged letters and samples. Lehmann examined the intermediate cloudy fluid, and reported seeing crystallites. Reinitzer's Viennese colleague von Zepharovich also indicated that the intermediate "fluid" was crystalline. The exchange of letters with Lehmann ended on April 24, with many questions unanswered. Reinitzer presented his results, with credits to Lehmann and von Zepharovich, at a meeting of the Vienna Chemical Society on May 3, 1888.

By that time, Reinitzer had discovered and described three important features of cholesteric liquid crystals (the name coined by Georges Friedel in 1922): the existence of two melting points, the reflection of circularly polarized light, and the ability to rotate the polarization direction of light.

After his accidental discovery, Reinitzer did not pursue studying liquid crystals further. The research was continued by Lehmann, who realized that he had encountered a new phenomenon and was in a position to investigate it: In his postdoctoral years he had acquired expertise in crystallography and microscopy. Lehmann started a systematic study, first of cholesteryl benzoate, and then of related compounds which exhibited the double-melting phenomenon. He was able to make observations in polarized light, and his microscope was equipped with a hot stage (sample holder equipped with a heater) enabling high temperature observations. The intermediate cloudy phase clearly sustained flow, but other features, particularly the signature under a microscope, convinced Lehmann that he was dealing with a solid. By the end of August 1889 he had published his results in the Zeitschrift für Physikalische Chemie.

Lehmann's work was continued and significantly expanded by the German chemist Daniel Vorländer, who from the beginning of 20th century till his retirement in 1935, had synthesized most of the liquid crystals known. However, liquid crystals were not popular among scientists and the material remained a pure scientific curiosity for about 80 years.

Chemical structure of N-(4-Methoxybenzylidene)-4-butylaniline (MBBA) molecule

In 1969, Hans Kelker succeeded in synthesizing a substance that had a nematic phase at room temperature, MBBA, which is one of the most popular subjects of liquid crystal research . The next step to commercialization of liquid crystal displays was the synthesis of further chemically stable substances (cyanobiphenyls) with low melting temperatures by George Gray.

In 1991, when liquid crystal displays were already well established, Pierre-Gilles de Gennes received the Nobel Prize in physics "for discovering that methods developed for studying order phenomena in simple systems can be generalized to more complex forms of matter, in particular to liquid crystals and polymers".

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