Liquid crystal polymers, orientation

The liquid crystal polymers consist of rod-like molecules which, during shear, tend to orient in the direction of shear. Because of the molecular order the molecules flow past each other with comparative ease and the melts have a low viscosity. When the melt is cooled the molecules retain their orientation, giving self-reinforcing materials that are extremely strong in the direction of orientation. 

In Chapter 3 it was pointed out that certain rod-like polymers showed many of the attributes of liquid crystals in the melt. In particular, these molecules were oriented in shear to such an extent that interchain entanglement was small and the melts had a low viscosity. On cooling of the melt these rod-like molecules remained oriented, effectively self-reinforcing the polymer in the direction of flow. The essential differences in the properties of liquid crystal polymers... 

Liquid crystalline solutions as such have not yet found any commercial uses, but highly orientated liquid crystal polymer films are used to store information. The liquid crystal melt is held between two conductive glass plates and the side chains are oriented by an electric field to produce a transparent film. The electric field is turned off and the information inscribed on to the film using a laser. The laser has the effect of heating selected areas of the film above the nematic-isotropic transition temperature. These areas thus become isotropic and scatter light when the film is viewed. Such images remain stable below the glass transition temperature of the polymer. 

Electro-optic materials can be made using liquid crystal polymer combinations. In these applications, termed polymer-stabilized liquid crystals [83,86], the hquid crystal is not removed after polymerization of the monomer and the resulting polymer network stabilizes the liquid crystal orientation. 

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. 

A number of other characteristics are required in order to ensure a viable polymeric conductor. Chain orientation is needed to enhance the conducting properties of a polymeric material, especially the intermolecular conduction (i.e., conduction of current from one polymer molecule to another). This is a problem with many of the polymers that are amorphous and show poor orientation. For moderately crystalline or oriented polymers, there is the possibility of achieving the required orientation by mechanical stretching. Liquid crystal polymers would be especially advantageous for electrical conduction because of the high degree of chain orientation that can be achieved. A problem encountered with some doped polymers is a lack of stability. These materials are either oxidants or reductants relative to other compounds, especially water and oxygen. 

Applications. The polyamides have important applications. The very high degree of polymer orientation that is achieved when liquid crystalline solutions are extruded imparts exceptionally high strengths and moduli to polyamide libers and lilms. DuPont markets such polymers, e g. Kevlar, and Monsanto has a similar product, e.g.. X-500. which consists of polyamide and hydrazide-lype polymers. Liquid-crystal polymers arc also used in olccirnnpnc displays. 

Two types of liquid crystal polymers (LCP s) can be distinguished lyotropic and thermotropic. The first type is formed in a solution this is done when the polymer has such a high melting point (low AS, see 4.2), that it cannot be handled in the molten condition without being degraded. If this limitation is not present, then the orientation can be brought about in the melt in such a case we have a thermotropic LCP. 

A special category is formed by oriented polymers, which have considerably higher stiffnesses. The most obvious example is the textile fibre the orientation, frozen-in in a crystalline structure, raises E by a factor of 3 to 5. Extremely high orientations, as met in liquid-crystal polymers (LCP s) result in even higher E-values, namely 60 to 120 GPa ... 

Liquid polymers (at ambient temperature) are in general macromolecules with a relatively low molecular weight, many of them being in fact oligomers. Some liquid polymers are utilized as synthetic oils. Certain polymers can form liquid crystals in other words they can have an ordered structure while being in liquid state (either melted or in a solution). The orientation of certain polymeric molecules in liquid state such that the properties of the material are anisotropic is possible. Polymer liquid crystals have practical applications, and solution of liquid crystal polymers can be used for extruding fibers that have a highly crystalline structure after solvent elimination. 

Ordered polymer films made from poly benzthiazole (PBZT) and poly benzoxazole (PBO) can be used as substrates for multilayer printed circuit boards and advanced interconnects to fill the current need for high speed, high density packaging. Foster-Miller, Inc. has made thin substrates (0.002 in.) using biaxially oriented liquid crystal polymer films processed from nematic solutions. PBZT films were processed and laminated to make a substrate with dielectric constant of 2.8 at 1 MHz, and a controllable CTE of 3 to 7 ppm/°C. The films were evaluated for use in multilayer boards (MLBs) which require thin interconnect substrates with uniform controllable coefficient of thermal expansion (CTE), excellent dielectric properties, low moisture absorption, high temperature capability, and simple reliable processing methods. We found that ordered polymer films surpass the limitations of fiber reinforced resins and meet the requirements of future chip-to-chip interconnection. 

Fig. 15 Orientation of attachment of rod-like mesogenic groups to a central scaffold and mesophases formed for supermolecular systems, shown in comparison to the structures of side-chain liquid crystal polymers...

The mono-substituted PEIs melt from a saniditic layered structure into a normal nematic phase whereas the disubstituted presumably yield a biaxially oriented nematic melt. The disubstituted PEIs isotropise from the melt around 200 °C lower than the monosubstituted of equal chain length. As the second substituent should increase chain stiffness rather than reduce it, Kricheldorf suggests that interactions between temporarily coplanar aromatic n systems, particularly donor-acceptor interactions, can make an efficient contribution to the stabilisation of nematic phases. If this hypothesis is correct then a greater variety of non-linear monomers may be regarded as building blocks for liquid crystal polymers. 

The effects of molecular order on the gas transport mechanism in polymers are examined. Generally, orientation and crystallization of polymers improves the barrier properties of the material as a result of the increased packing efficiency of the polymer chains. Liquid crystal polymers (LCP) have a unique morphology with a high degree of molecular order. These relatively new materials have been found to exhibit excellent barrier properties. An overview of the solution and diffusion processes of small penetrants in oriented amorphous and semicrystalline polymers is followed by a closer examination of the transport properties of LCP s. 

We first give a concise review of the effects of orientation and crystallinity on the barrier properties of polymeric materials, paying particular attention to their effects on the solubility and diffusion coefficients. This will provide useful background for considering the transport properties of liquid crystal polymers which, because of their unique properties, may have some role to play in the quest for improved barrier polymers. 

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