Thermotropic liquid crystal physical properties

Liquid crystal polymers (LCP) are polymers that exhibit liquid crystal characteristics either in solution (lyotropic liquid crystal) or in the melt (thermotropic liquid crystal) [Ballauf, 1989 Finkelmann, 1987 Morgan et al., 1987]. We need to define the liquid crystal state before proceeding. Crystalline solids have three-dimensional, long-range ordering of molecules. The molecules are said to be ordered or oriented with respect to their centers of mass and their molecular axes. The physical properties (e.g., refractive index, electrical conductivity, coefficient of thermal expansion) of a wide variety of crystalline substances vary in different directions. Such substances are referred to as anisotropic substances. Substances that have the same properties in all directions are referred to as isotropic substances. For example, liquids that possess no long-range molecular order in any dimension are described as isotropic. 

Lyotropic liquid crystals are principally systems that are made up of amphiphiles and suitable solvents or liquids. In essence an amphiphilic molecule has a dichotomous structure which has two halves that have vastly different physical properties, in particular their ability to mix with various liquids. For example, a dichotomous material may be made up of a fluorinated part and a hydrocarbon part. In a fluorinated solvent environment the fluorinated part of the material will mix with the solvent whereas the hydrocarbon part will be rejected. This leads to microphase separation of the two systems, i.e., the hydrocarbon parts of the amphiphile stick together and the fluorinated parts and the fluorinated liquid stick together. The reverse is the case when mixing with a hydrocarbon solvent. When such systems have no bend or splay curvature, i.e., they have zero curvature, lamellar sheets can be formed. In the case of hydrocarbon/fluorocarbon systems, a mesophase is formed where there are sheets of fluorocarbon species separated from other such sheets by sheets of hydrocarbon. This phase is called the La phase. In the La phase the molecules are orientationally ordered but positionally disordered, and as a consequence the amphiphiles are arranged perpendicular to the lamellae. The La phase of lyotropics is therefore equivalent to the smectic A phase of thermotropic liquid crystals. 

Thermotropic liquid crystal polymers (LCI ) are of considerable current interest, because of their theoretical and technological aspects [1-3]. Evidently, a new class of polymers has been developed, combining anisotropic physical properties of the liquid crystalline state with diaracteristic polymer features. This unique combination promises new and interesting material properties with potential ai lications, for example in the field of high modulus fibers [4], storage technology, or non-linear optics [5]. 

The subject of liquid crystals has now grown to become an exciting interdisciplinary field of research with important practical applications. This book presents a systematic and self-contained treatment of the physics of the different types of thermotropic liquid crystals - the three classical types, nematic, cholesteric and smectic, composed of rod-shaped molecules, and the newly discovered discotic type composed of disc-shaped molecules. The coverage includes a description of the structures of these four main types and their polymorphic modifications, their thermodynamical, optical and mechanical properties and their behaviour under external fields. The basic principles underlying the major applications of liquid crystals in display technology (for example, the twisted and supertwisted nematic devices, the surface stabilized ferroelectric device, etc.) and in thermography are also discussed. 

A. Jakli, C. Bailey and J. Harden, Chapter 2, Physical properties of banana liquid crystals. In ed. A. Ramamoorthy, Thermotropic Liquid Crystals Recent Advances, Springer Publishers, 2007. 

For a thermotropic liquid crystal, its physical properties, such as birefringence, viscosity, dielectric anisotropy, and elastic constant, are all dependent on the operation temperature -except at different rates. Polymer-stabilized BPLC is no exception [45]. Figure 14.10 shows... 

A. Saupe, On molecular structure and physical properties of thermotropic liquid crystals. Mol. Cryst. Liq. Cryst. 7, 59-74 (1969). 

Aromatic thermotropic liquid crystal polyesters (Ar-TLCP s) and TLCP s containing aliphatic linkages can be compatibilized as binary-TLCP blends by transesterification. The morphology and physical properties of the resultant binary-TLCP blend are dependent on the blockiness, composition and viscosity ratios of the two TLCP components. Polycarbonate (PC) can also be blend compatibilized with either TLCP s or binary-TLCP blends, by transesterification of aliphatic linkages from the TLCP s into the PC. In this work, the degree of selective transesterification is quantified and its effect on TLCP blend compatibility is described... 

Kim Yun Seong, Kim Hun Seong, Lee Hwan Seung, and Youn Ryoun Jae. Internal strue-ture and physical properties of thermotropic liquid crystal polymer/poly(ethylene 2,6-naphthalate) composite fibers. Composites Part A. 40 no. 5 (2009) 607-612. 

The existence or nonexistence of mirror symmetry plays an important role in nature. The lack of mirror symmetry, called chirality, can be found in systems of all length scales, from elementary particles to macroscopic systems. Due to the collective behavior of the molecules in liquid crystals, molecular chirality has a particularly remarkable influence on the macroscopic physical properties of these systems. Probably, even the flrst observations of thermotropic liquid crystals by Planer (1861) and Reinitzer (1888) were due to the conspicuous selective reflection of the helical structure that occurs in chiral liquid crystals. Many physical properties of liquid crystals depend on chirality, e.g., certain linear and nonlinear optical properties, the occurrence of ferro-, ferri-, antiferro- and piezo-electric behavior, the electroclinic effect, and even the appearance of new phases. In addition, the majority of optical applications of liquid crystals is due to chiral structures, namely the ther-mochromic effect of cholesteric liquid crystals, the rotation of the plane of polarization in twisted nematic liquid crystal displays, and the ferroelectric and antiferroelectric switching of smectic liquid crystals. 

Pelzl, G. Weissflog, W. Mesophase behaviour at the borderline between calamitic and banana-shaped mesogens, in Thermotropic Liquid Crystals Recent Advances, A. Ramamoorthy, Ed. Springer, Dordrecht, 2007, pp. 1-58. JakU, A Bailey, C. Harden, J. Physical properties of banana liquid crystals, in Thermotropic Liquid Crystals Recent Advances, A. Ramamoorthy, Ed. Springer, Dordrecht, 2007, pp. 59-83, and references therein. 

Extensive experimental studies have been carried out about the structures, phase diagrams and physical properties of these thermotropic liquid crystals [68, 69]. 

Bandyopadhyay, J., S. Sinha Ray, and M. Bousmina. 2008. Viscoelastic properties of clay-containing nanocomposites of thermotropic liquid-crystal polymer. Macromolecular Chemistry and Physics 210 (2) (December 17) 161-171. doi 10.1002/macp.200800479. http //doi.wiley.eom/10.1002/macp.200800479. 

Thermotropic liquid crystals hold a dominant position in the field of the LCD however, researchers have also to pay attention to another type of liquid crystals, lyotropic liquid crystals, fi om the aspect of the life science field. Essential properties of cell membranes originate from their liquid crystalline behavior. The point of view of biophysics exists in the liquid crystal discovery time inferred from the monograph of Otto Lehmaim titled The liquid crystal and life flieory . In the experimental research of material science, the development of science cannot be expected without collaboration with a physicist, a physical chemist, and a synthetic chemist, as showing the history of research not only as that of liquid crystals but also of macromolecules and colloid science, among others. Because a considerable portion of a living organism (cell membrane, skin structure, etc.) is composed of liquid crystalline states, participation of researchers from many different fields is necessary for the bio-matter liquid crystal. I would hope to see the development of medical science, pharmacy, and foods by the full utilization of the potential of liquid crystal materials. 

The unique physical and chemical properties of liquid crystalline polymers make them attractive to chemists, physicists, electrical engineers, mechanical engineers and chemical engineers. We have limited ourselves here to a description of thermotropic liquid crystals—those prepared by heating certain polymers. 

It is very often the commercial interest in novel materials which stimulates the growth in their study and eventual exploitation. This is certainly true in the case of thermotropic liquid crystals and their application in electro-optic displays. Indeed, the production of high-strength, high-modulus fibres has seen a wealth of interest in lyotropic main chain polymers. The use of lyotropic side chain polymers has, by comparison, been less well publicized. This is not to say that there are no applications. Alkyl polyoxyethylene surfactants attached to polysiloxane polymers have found uses in many personal care products such as liquid soaps, shampoos, skin creams, and hair mousses. Unfortunately the physical properties of these and other similar materials have been closely guarded secrets and the amount of information available in the literature is low. The limited data which does exist, however, provides us with some interesting structure - behaviour relationships. 

In order to understand the basic principles of operation of the many different kinds of LCDs being developed and/or manufactured at the present time, it is necessary to briefly describe the liquid crystalline state and then define the physical properties of direct relevance to LCDs. First, the nematic, smectic and columnar liquid crystalline states will be described briefly. However, the rest of the monograph dealing with liquid crystals will concentrate on nematic liquid crystals and their physical properties, since the vast majority of LCDs manufactured operate using mixtures of thermotropic, non-amphiphilic rodlike organic compounds in the nematic state. 

Since their discovery in the nineteenth century [1], hquid crystals have fascinated scientists due to their unusual properties and their wide range of potential apphcations, especially in optoelectronics. LC systems can be divided into two categories thermotropic LC phases and lyotropic LC phases. Thermotropic LC systems result from anisotropic molecules or molecular parts (so called mesogens or mesogenic moieties, respectively), and form hquid crystalline phases between the soHd state and the isotropic hquid state, where they flow like liquids but possess some of the characteristic physical properties of crys-... 

Many cellulose derivatives form lyotropic liquid crystals in suitable solvents and several thermotropic cellulose derivatives have been reported (1-3) Cellulosic liquid crystalline systems reported prior to early 1982 have been tabulated (1). Since then, some new substituted cellulosic derivatives which form thermotropic cholesteric phases have been prepared (4), and much effort has been devoted to investigating the previously-reported systems. Anisotropic solutions of cellulose acetate and triacetate in tri-fluoroacetic acid have attracted the attention of several groups. Chiroptical properties (5,6), refractive index (7), phase boundaries (8), nuclear magnetic resonance spectra (9,10) and differential scanning calorimetry (11,12) have been reported for this system. However, trifluoroacetic acid causes degradation of cellulosic polymers this calls into question some of the physical measurements on these mesophases, because time is required for the mesophase solutions to achieve their equilibrium order. Mixtures of trifluoroacetic acid with chlorinated solvents have been employed to minimize this problem (13), and anisotropic solutions of cellulose acetate and triacetate in other solvents have been examined (14,15). The mesophase formed by (hydroxypropyl)cellulose (HPC) in water (16) is stable and easy to handle, and has thus attracted further attention (10,11,17-19), as has the thermotropic mesophase of HPC (20). Detailed studies of mesophase formation and chain rigidity for HPC in dimethyl acetamide (21) and for the benzoic acid ester of HPC in acetone and benzene (22) have been published. Anisotropic solutions of methylol cellulose in dimethyl sulfoxide (23) and of cellulose in dimethyl acetamide/ LiCl (24) were reported. Cellulose tricarbanilate in methyl ethyl ketone forms a liquid crystalline solution (25) with optical properties which are quite distinct from those of previously reported cholesteric cellulosic mesophases (26). 

Mesomorphic Phase. A phase consisting of anisometric molecules or particles that are aligned in one or two directions but randomly arranged in other directions. Such a phase is also commonly referred to as a liquid-crystalline phase or simply a liquid crystal. The mesomorphic phase is in the nematic state if the molecules are oriented in one direction, and in the smectic state if oriented in two directions. Mesomorphic phases are also sometimes distinguished on the basis of whether their physical properties are mostly determined by interactions with surfactant and solvent (lyotropic liquid crystals) or by temperature (thermotropic Uquid crystals). See also Neat Soap. 

Thennotropic and lyotropic liquid crystals share a common state of matter with many analogies in their structural and physical properties. However, these two fields of liquid crystal research are usually treated completely separately. This is partially due to historical reasons, but also to striking differences in some aspects of these two classes of liquid crystals. One of these differences is the occurrence of thermotropic phases which do not have a lyotropic counterpart A compelling example of this is the thermotropic ferroelectric SmC phase. Due to its unique chirality effects, i.e. ferroelectricity and a helical configuration of the tilt-direction, this phase attracted considerable scientific interest over the last decades. However, there are no reports found in literature about a SmC analog phase in lyotropic liquid crystals. 

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