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Some crystalline substances retain one- or two-dimensional long-range molecular order above the crystalline melting point Such substances are then described as being in the liquid crystal state They show the ow behavior of isotropic liquids but appear to possess some kind of long-range molecular order greater than the isotropic liquid state but less than the true crystal state Heating a thermotropic liquid crystal eventually results in its transformation to the liquid state at some temperature, Tlc;i , referred to as the liquid crystal isotropic phase transformation temperature for thermotropic liquid crystals Our understanding of lyotropic liquid crystals follows in a similar manner The action of solvent on a crystalline substance disrupts the lattice structure and most compounds pass into solution However, some compounds yield liquid crystal solutions that possess long-range ordering intermediate between solutions and crystal.



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(kz,n)2

The lyotropic liquid crystal can pass into the solution state by the addition of more solvent and/or heating to a higher temperature Thermotropic and lyotropic liquid crystals, both turbid in appearance, become clear when they pass itno the liquid and solution states, respectively Liquid crystal behavior is due chie y to molecular rigidity that excludes more than one molecule occupying a particular volume, rather than intermolecular attractive forces The requirement for a substance to exhibit liquid crystal behavior is molecular shape anisotropy, which is not affected by conformational changes Some biological molecules (eg, tobacco mosaic virus, polypeptides, and cellulose) are liquid crystals because of their rigid helical rod conformations This is not the case for synthetic polymers The typical polymer liquid crystal is a rigid-rod molecule (Theoretical studies indicate the molecular length must exceed the diameter by a factor greater than 6 [Flory and Ronca, 1979].





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) Other anisotropic molecular shapes (eg, disks) also show liquid crystal behavior but these are much more rare for polymers Polymer liquid crystals typically show either smectic or nematic liquid crystal behavior These are shown in Fig 2-20, where each line ( ) represents a polymer molecule There is a parallel arrangement of the long molecular axes in both nematic and smectic liquid crystals Smectic liquid crystals are more ordered than nematic liquid crystals as a result of differences in the orientation of their molecular chain ends Molecular chain ends are coterminal (ie, lined up next to each other) in smectics but are out of register (ie, have no particular orientation) in nematics Another difference between smectic and nematic liquid crystals is that smectics are layered while nematics are seldom layered.

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(A third type of liquid crystal, cholesteric, involves nematic packing in planes with the molecular axes in each plane turned at an angle relative to those in the next plane, but is rarely observed in polymers) Smectic liquid crystals, being more ordered, are more viscous than nematics (everything else being equal) Microscopic observations are of prime importance in distinguishing nematic and smectic structures [Demus and Richter, 1978]..

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Jk; + k~ to Kl/7r and kz to w == kzl/7r, we can rewrite the second term inside the braces on the right-hand side of (2.203) as

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Fig. 2-20 Molecular ordering in nematic and smectic liquid crystals compared to liquid. After Brown and Crooker [1983] (by permission of American Chemical Society, Washington, DC).

Vv + w 2 '

Rigid-rod liquid crystal polymer molecules result from having rigid groups either within the polymer chain or as side groups on the polymer chain. These two types of LC polymers, referred to as main-chain and side-chain LC polymers, respectively, are depicted in Fig. 2-21. The rigid groups are referred to as mesogens or mesogenic groups. The mesogens are shown as rigid-rod groups, but other shapes (e.g., disks) are also possible. The collection of mesogenic units results in a molecule that is a rigid rod with molecular shape anisotropy and liquid crystal behavior. Liquid crystal behavior in polymers has practical consequences. Liquid crystal melts or solutions have lower viscosities than melts or solutions of random-coil polymers and are easier to process. More importantly, the extension and orientation of polymer chains during processing yields highly crystalline products with high modulus and high strength. The moduli and strengths of chain-extended LC polymers is considerably higher than those of

(2.205)

the chain-folded crystalline polymers formed from non-LC polymers. LC polymers also have signi cantly increased crystalline melting temperatures as a result of the extended-chain morphology. Thus, the synthetic guidelines are the same for synthesis of heat-resistant and LC polymers build rigid polymer chains. Poly(1,4-oxybenzoyl) (LII) [IUPAC: poly(oxy-1,4-phenylenecarbonyl), obtained by selfreaction of p-hydroxybenzoic acid, and the various aramids (Sec. 2-8f) were among the rst LC polymers studied. The experience in commercializing poly(1,4-oxybenzoyl) and the

where again v == (Kl/7r)2. Thus, introducing the cutoff, we can rewrite (2.203) as Pcas(x,y) =

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