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61.
Bryan B. Sauer Richard Beckerbauer Lixiao Wang 《Journal of Polymer Science.Polymer Physics》1993,31(12):1861-1872
The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main Tg, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that Tg is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc. 相似文献
62.
Kelly A. Burke Sona Sivakova Blayne M. McKenzie Patrick T. Mather Stuart J. Rowan 《Journal of polymer science. Part A, Polymer chemistry》2006,44(17):5049-5059
We report herein studies on the liquid crystalline behavior of a series of supramolecular materials that contain different ratios of two complementary symmetrically-substituted alkoxy-bis(phenylethynyl)benzene AA- and BB-type monomers. One monomer has thymine units placed at either end of the rigid mesogenic core, while the other has N6-(4-methoxybenzoyl)-adenine units placed on the ends. Differential scanning calorimetric and polarized optical microscopy studies have been carried out on these systems. These studies show that the material's behavior is strongly dependent on its thermal history. As a result, the materials can exhibit, on heating, either a liquid crystalline phase, a crystalline phase, or the coexistence of crystalline and liquid crystalline regions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5049–5059, 2006 相似文献
63.
P. Deepa K. Divya M. Jayakannan 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):42-52
New series of cycloaliphatic poly(ester‐amide)s, poly(1,4‐cyclohexanedimethyleneterephthalate‐co‐1,3‐cyclohexanedimethylene terephthalamide), were synthesized through solution polymerization route. The compositions of ester/amide units in the copolymers were varied from 0 to 100% by varying the amount of 1,4‐cyclohexanedimethanol and 1,3‐cyclohexanebis(methylamine) in the feed. The structures of the polymers were confirmed by NMR and FTIR, and the molecular weights were determined by inherent viscosity. The composition analysis by NMR reveals that the reactivity of the diamine toward the acid chlorides is lowered than that of diol, which results in the formation of more ester content in the poly (ester‐amides). The thermal analysis indicate that the new poly(ester‐amide)s having less than 10 mol % of amide linkages are thermotropic liquid crystalline from 200 to 250 °C and a thread like nematic phases are observed under the polarizing microscope. WXRD studies suggest that the liquid crystalline domains promote the nucleation process in the polyester chains and increases the percent crystallinity of the poly(ester‐amide)s. The glass transition temperature of the copolymers initially increases with increase in amide units because of the presence of nematic phases and subsequently follows the Flory–Fox behavior. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 42–52, 2006 相似文献
64.
David Ribera Marta Giamberini Angels Serra Ana Mantecn 《Journal of polymer science. Part A, Polymer chemistry》2006,44(21):6270-6286
We reacted various dimeric, liquid‐crystalline epoxy–imine monomers, differing in the length of the central aliphatic spacer or the dipolar moments, with heptanedioic acid. The resulting systems showed a liquid‐crystalline phase in some cases, depending on the dimer and on the reaction conditions. The systems were characterized with respect to their mesomorphic properties and then were submitted to dynamic mechanical thermal analysis in both fixed‐frequency and frequency‐sweep modes in the shear sandwich configuration. The arrangement in the liquid‐crystalline phase seemed to be mainly affected both by the polarization of the mesogen and by the reaction temperature, which favored the liquid‐crystalline arrangement when it was lying in the range of stability of the dimer mesophase. In agreement with other recent literature data, dynamic mechanical thermal analysis results suggested that the presence of the mesogen directly incorporated into the main chain increased the lifetimes of the elastic modes both in the isotropic phase and in the liquid‐crystalline phase with respect to side‐chain liquid‐crystalline elastomers and that the time–temperature superposition principle did not hold through the liquid‐crystalline‐to‐isotropic transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:6270–6286, 2006 相似文献
65.
Lourdes Callau Marta Giamberini Jos Antonio Reina Ana Mantecn 《Journal of polymer science. Part A, Polymer chemistry》2006,44(6):1877-1889
The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P4 and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and 1H and 13C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C2 mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006 相似文献
66.
A series of new thermoplastic polyesters based on 3,4‐ethylenedioxythiophene (EDOT) with flexible aliphatic spacers have been synthesized and characterized for the first time. The thermal properties of these polyesters based on EDOT are comparable to those of conventional polyesters based on the 1,4‐phenyl unit, indicating that EDOT is a viable replacement for the phenyl units. The glass‐transition and melting‐transition temperatures decrease monotonically with an increase in the spacer length. Theoretical calculations have revealed that the core angle for EDOT is comparable to that of unsubstituted thiophene and hence should be compatible with the formation of the mesophase. This has been confirmed experimentally by the synthesis of a main‐chain, thermotropic, liquid‐crystalline polyester based on EDOT that exhibits fluid birefringence. In fact, this is the first report in which a main‐chain, liquid‐crystalline polymer based on 3,4‐disubstituted thiophene has been successfully designed and synthesized. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3479–3486, 2006 相似文献
67.
Peng Chen Jun Chen Baoqing Zhang Jun Zhang Jiasong He 《Journal of Polymer Science.Polymer Physics》2006,44(6):1020-1030
Polycarbonate (PC) was melt blended with small amount of liquid‐crystalline polymer (LCP) and various contents of glass beads (GB) having different diameters. The rheological measurements indicated that the GB addition increased the viscosity ratio and seemed unfavorable to the LCP fibrillation. However, the morphological observation showed that the LCP fibrillation was promoted by the GB addition and varied with the GB packing. With the increased GB packing by increasing the GB content and/or decreasing the GB diameter, LCP deformed from spheres and ellipsoids into stretched ellipsoids at lower shear rates and into long fibrils at higher shear rates. Although higher content of smaller GB jammed into the larger LCP droplets and inhibited the LCP fibrillation, very long LCP fibrils formed at higher shear rates at a high enough packing of GB. The relationship between GB packing and LCP fibrillation revealed two kinds of hydrodynamic effects of GB promoting the LCP fibrillation: at lower GB packing, the shear flow was enhanced by the high local shear between GB, in quantity; and for a high enough GB packing, the shear flow was changed, in quality, into elongational flow, which was more effective for the LCP fibrillation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1020–1030, 2006 相似文献
68.
We perform an analysis of the pattern formation for a moving sheet of inviscid fluid. The sheet, which is assumed to have an infinite horizontal extent, moves at some prescribed velocity into a passive surrounding gas. The sheet’s thickness is assumed much smaller than the horizontal scale of the fluid motion. By considering a system that is symmetric with respect to the horizontal planes, long scale asymptotics are used to reduce the full governing equations in three dimensions to a set of three coupled nonlinear partial differential equations for the horizontal components of the velocity field and the height of the interface profile. The interfacial conditions consisting of the kinematic and normal stress balance are incorporated into these evolution equations. Investigations are carried out as function of the sole dimensionless parameter, namely the Weber number. A small amplitude stability analysis around the planar gas–liquid interface reveals that wave patterns in the form of traveling plane waves occur subcritically, and are therefore unstable. The reduced evolution equations are solved numerically for fixed values of the Weber number. Since the reduced system of equations is homogeneous, the wave motion is generated by initial conditions. Five initial conditions have been imposed: one-dimensional rolls, two-dimensional squares, two-dimensional hexagons, two-dimensional ridges, and smooth peaks. The ensuing evolution of the liquid sheet’s shape and corresponding flow fields are described by illustrations of the changes in the sheet’s morphology with time. 相似文献
69.
A new Co–Fe-based ferromagnetic bulk metallic glass (BMG) was synthesized by copper mould casting method. The thermal stability and crystallization processes were investigated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The soft magnetic behavior was studied by DC magnetic measurements. The high glass formation ability was interpreted in terms of the effective suppression of nucleation and growth of the intermetallic compounds which appear in the multicomponent system during solidification. The high thermal stability indicates that the new Co–Fe-based BMG could be used as high-temperature magnetic material. The low coercivity which was as low as 8 A/m for the as-cast sample was found in the Co–Fe-based metallic glass cylinder with a diameter of 1.5 mm. 相似文献
70.
Applying a Lindemann like criterion obtained previously by Kierfeld et al. [J. Kierfeld, T. Nattermann, T. Hwa, Phys. Rev. B 55 (1997) 626], we estimate the magnetic field and temperature for a high-Tc superconductor, at which a topologically ordered vortex glass phase becomes unstable with respect to a disorder-induced formation of dislocations. The employed criterion is shown to be equivalent to a conventional phenomenological Lindemann criterion including the values for the numerical factors, i.e., for the Lindemann number. The positional correlation length of the topologically ordered vortex glass is calculated. 相似文献