The present article describes an equilibrium theory for determining binary phase diagrams of various crystalline-amorphous polymer blends by taking into account the contributions from both liquid-liquid phase separation between the constituents and solid-liquid phase transition of the crystalline component. An analytical expression for determining a crystal-amorphous interaction parameter is deduced based on the solid-liquid transition, involving the solidus and liquidus lines in conjunction with the coexistence curve of an upper critical solution temperature type. Of particular importance is that the crystalline-amorphous interaction parameter can be determined directly from the melting point depression data. The present analysis is therefore different from the conventional Flory-Huggins interaction parameter, which is associated with the liquid-liquid phase separation. The validity of the present theory is tested with the experimental phase diagrams of blends of poly(ethylene oxide)/diacrylate and poly(vinyl alcohol)/cellulose.
To elucidate induced smectic A and smectic B phases in binary nematic liquid crystal mixtures, a generalized thermodynamic model has been developed in the framework of a combined Flory-Huggins free energy for isotropic mixing, Maier-Saupe free energy for orientational ordering, McMillan free energy for smectic ordering, Chandrasekhar-Clark free energy for hexagonal ordering, and phase field free energy for crystal solidification. Although nematic constituents have no smectic phase, the complexation between these constituent liquid crystal molecules in their mixture resulted in a more stable ordered phase such as smectic A or B phases. Various phase transitions of crystal-smectic, smectic-nematic, and nematic-isotropic phases have been determined by minimizing the above combined free energies with respect to each order parameter of these mesophases. By changing the strengths of anisotropic interaction and hexagonal interaction parameters, the present model captures the induced smectic A or smectic B phases of the binary nematic mixtures. Of particular importance is the fact that the calculated phase diagrams show remarkable agreement with the experimental phase diagrams of binary nematic liquid crystal mixtures involving induced smectic A or induced smectic B phase.
Eutectic behavior and the induced crystalline phase in mixtures of hexagonal columnar liquid crystal, 2, 3, 6, 7, 10, 11-hexakis-(pentyloxy) triphenylene (HPTP)/reactive mesogenic diacrylate monomer, 4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1, 4-phenylene ester (RM257) have been investigated both experimentally and theoretically. To determine the theoretical phase boundaries, we combined the free energy of Flory-Huggins free energy for liquid-liquid demixing, Maier-Saupe free energy of nematic ordering, and Chandrasekhar-Clark free energy of hexagonal ordering. The calculated phase diagram of the HPTP/RM257 blend is essentially of a eutectic type that consists of isotropic (I), nematic (N), and hexagonal columnar (Col(h)) regions, and nematic + isotropic (N+I), hexagonal columnar + isotropic (Col(h)+I), and hexagonal columnar + nematic (Col(h)+N) coexistence regions, bound by the liquidus and solidus lines. Of particular interest is the formation of an induced crystalline phase (Cr(in)) in the intermediate compositions of the HPTP/RM257 mixtures, exhibiting Cr(2) (RM257) + Cr(in) in the RM257-rich and Cr(in) + Cr(1) (HPTP) in the HPTP-rich regions.
The phase diagram of a mixture consisting of hyperbranched polyester (HBPEAc-COOH) and eutectic nematic liquid crystals (E7) has been established experimentally by means of differential scanning calorimetry and polarized optical microscopy subjected to prolonged annealing. The observed phase diagram is an upper azeotrope, exhibiting the coexistence of nematic + isotropic phase in the vicinity of 90 approximately 110 degrees C above the clearing temperature of neat E7 (60 degrees C). With decreasing temperature, a focal-conic fan shaped texture develops in the composition range of 63 approximately 93 wt % of the annealed E7/HBPEAc-COOH blends, suggestive of induced smectic phase in the mixture. Wide angle X-ray diffraction (WAXD) technique revealed the existence of higher order mesophase(s).
Uniaxially cracked indium tin oxide (ITO) on a polyethylene terephthalate (PET) substrate and its application in replacing photolithography to make stripe ITO electrodes were developed. An ITO coated PET (ITO/PET) film uniformly and controllably rolled and uniaxially cracked. This procedure produced fine, parallel cracks in the ITO separated by 5~10 microns. The crack separation and electrical isolation of the resulting long and thin ITO electrodes was enhanced by etching with dilute hydrogen chloride (HCl) or by uniaxially stretching. Heating and stretching proves the most effective, producing a crack width of about 0.05 microns and a differential conductivity (measured parallel and perpendicular to the cracks) in the resulting films greater than two orders of magnitude. A polymer dispersed liquid crystal (PDLC) shutter was prepared using the cracked ITO/PET film as one substrate. The addressed lines were defined by the contact electrode. The sharpness of the line edges increased as the drive frequency was increased. This PDLC prototype demonstrated how photolithographic etching of ITO or printing of conducting polymer could be replaced by controlled cracking of ITO to produce the line electrodes required for flexible, passive matrix displays and in related flexible electronic applications.
Uniformly uni-axially aligned electrodes are formed by uniaxially cracking an indium tin oxide, ITO, film vacuum deposited on a polyester substrate. The cracks are produced by bending the film around a small radius of curvature, producing narrow, parallel cracks in the ITO separated by 5-10 μm. The cracks are enhanced by etching or uniaxial stretching. Heating and stretching is the most effective, producing a crack width of about 0.05 μm and a differential conductivity (measured parallel and perpendicular to the cracks) several orders of magnitude or greater. A passive matrix bistable cholesteric display is fabricated using top and bottom substrates with perpendicularly aligned electrodes. The addressed lines on each substrate are defined by the contact electrode, which contacts multiple cracked ITO lines. Because of the small dimension of the cracks (much less than the thickness of the active layer) they are not visible in the display. The separation between the contact electrodes must be great than 20 μm in order to include at least one crack and electrically isolate each individual line. The resulting display demonstrates how controlled cracking of ITO can replace photolithographic etching of ITO or printing of conducting polymers to produce the line electrodes required for flexible, passive matrix displays and related electronic applications. Un-axially cracking can be easily integrated into a roll-to-roll manufacturing process.
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