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Liquid Crystalline Polymers

Liquid Crystalline Polymers

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Published by Luu Khue

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Published by: Luu Khue on Mar 05, 2013
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LIQUID CRYSTALLINE POLYMERS© World Scientific Publishing Co. Pte. Ltd.http://www.worldscibooks.com/materialsci/5309.html
Chapter 1
Liquid Crystal States of Matter
1.1. LIQUID CRYSTAL STATES
As we know, there are three basic states of matter, solid, liquid, andgaseous states. These states of matter can be transformed into each otherat appropriate conditions. In the solid state (generally meaning the crys-talline state), the building blocks, such as atoms, or molecules, or clustersof molecules are packed closely and regularly, forming a crystal lattice. TheX-ray diffraction of the state shows many regular diffraction spots. Over95% of matter on the earth exist in the form of the crystalline state. Thetypes of crystal structure are enormous. The physical properties of crystalsare basically anisotropic. The crystals have a constant melting temperature(except for amorphous solids). Two different crystal planes make a con-stant angle. As the temperature of matter increases the thermal movementof atoms or molecules become so severe that the crystal lattice is dissolvedand fluidity appears. At this temperature, matter does not have a regu-lar shape and anisotropic properties any more. It becomes a liquid. In theliquid state, the atoms or molecules are no longer arranged in a regularorder, but they are still bonded to each other tightly, though not in thetightest packing. Compared with the crystal state, the volume change of a liquid is not great but the liquid does not have a regular shape and canflow. Because of gravity the surface of liquids is usually flat. Increasing thetemperature further up beyond the melting point, matter is transformedto the gaseous state. In the gaseous state, no short-range order exists. Theinteraction between the constituent molecules is extremely weak. Due tothermal excitation the molecules fill the container uniformly and hence the
1
 
LIQUID CRYSTALLINE POLYMERS© World Scientific Publishing Co. Pte. Ltd.http://www.worldscibooks.com/materialsci/5309.html
2
Liquid Crystalline Polymers
gas no longer has a flat surface. Generally, as the temperature increasesprogressively, matter at first appears in the form of a crystal solid, andthen a liquid and finally the gaseous state. Exceptionally, a few materialsmay be heated directly from the solid into the gas state, that is, by sublima-tion, such as for iodine. Conversely, some substances may be transformeddirectly from gas to solid, which is called sublimation as well. Water vaporcondensing to ice is an example of sublimation.As the understanding about the states of matter became deeper, peoplehad found that in addition to the above mentioned well-known three states,there exist other states of matter in nature, such as the plasma state, amor-phous solid, liquid crystal state, superconductor, neutron state, etc. Amongthem the liquid crystal state is the subject of this book.The liquid crystal state is a kind of state whose order is between thecrystal solid and isotropic liquid states. In the crystal state, there is a longrange order in position and orientation, while in the liquid state there areno long range ordering in either of them. Figure 1.1 is a comparison of thecrystal (a), the liquid crystal (b) and the liquid (c) states.The liquid crystal was once considered a rare state in the nature, but sofar over eighty thousand liquid crystalline compounds have actually beenfound, making them a great family of matter.The discovery of the liquid crystal state should be traced back to astory taking place one hundred years ago. Austria botanist F. Reinitzerobserved a peculiar phenomenon in 1888under a microscope (Reinitzer,1888), cholesteryl nonanoate melted into a cloudy liquid at 145
.
5
C; asthe temperature rose to 178
.
5
C, it suddenly became clear. When coolingdown, the substance briefly appeared violet-blue just before becoming an
Figure 1.1. The schematics of (a) crystal, (b) liquid crystal and (c) liquid.
 
LIQUID CRYSTALLINE POLYMERS© World Scientific Publishing Co. Pte. Ltd.http://www.worldscibooks.com/materialsci/5309.html
Liquid Crystal States of Matter 
3
opaque liquid, and then finally a white solid crystal. Reinitzer was puz-zled about what he observed: why were there two melting points betweenthe crystal (solid) and clear (liquid) states. He sent the sample togetherwith his observation to German physicist Otto Lehmann who later madedetailed observations by means of the polarizing microscope equipped witha heat stage. He at last concluded that cholesteryl nanonoate in the tem-perature range of 145
.
5
C and 178
.
5
C must be in a new state of matter.After a few years of hesitation, he finally named this state of matter, the
liquid crystal 
(Lehmann, 1900). Later somebody proposed that the term“mesogenic state” might be an appropriate nomenclature for the new state,because it may avoid possible confusion. In spite of this problem, peoplehave seemed to prefer the term liquid crystal due to its vivid descriptionand the term liquid crystal has since been widely adopted, while the termmesogen or mesogenic is now used for a compound that is able to showthe liquid crystal state. Contemporary knowledge tells us that cholesterylnanonate actually exhibits two liquid crystal phases in the temperaturerange of 178
.
5
C and 145
.
5
C. As the temperature decreases, the first bluecolor is that of the blue phase of the liquid crystal, and the second violet-blue color results from the cholesteric phase of the liquid crystal. More thantwenty liquid crystal phases have since been discovered. The blue phase andcholesteric phase are two of them.One enlightenment that can be drawn from the discovery of the liquidcrystal is that despite the fact that Reinitzer and Lehmann pursued dif-ferent fields and were in different countries, the cooperation between theminaugurated a new field of sciencethe liquid crystal. Actually the wholedevelopment of the field of the liquid crystal has demonstrated this type of cooperation.As early as 1850, a German scientist discovered, in fact, the possibilityof the liquid crystal when he found that natural fats exhibited two meltingpoints. With increasing temperature, the substance starts to become cloudyat around 52
C and is completely opaque at 58
C, and then becomes clearat 62
.
5
C. This observation should be the earliest record of the “discovery”of the liquid crystal. At around the same time, the cholesterol derivativeexhibited a striking color when it cooled from the isotropic liquid state.Unfortunately, these phenomena were not given enough attention or cor-rectly explained. The researchers themselves did not realize that they wereapproaching the entrance of a new field of science. Therefore, the discoveryof the liquid crystal should be attributed to Reinitzer and Lehmann.

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