Synthesis and liquid crystalline properties of new amide‐modified poly(1,4‐cyclohexanedimethylene terephthalate)

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     

Differential AC-chip calorimeter for glass transition measurements in ultrathin films

A differential AC-chip calorimeter capable of measuring the step in heat capacity at the glass transition in nanometer-thin films is described. Because of the differential setup, pJ/K sensitivity is achieved. Heat capacity can be measured for sample masses below 1 ng in broad temperature range as needed for the study of the glass transition in nanometer-thin polymeric films. Relative accuracy is sufficient to investigate the changes in heat capacity as the step at the glass transition of polystyrene. The step is about 25% of the total heat capacity of polystyrene. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the frequency range from 1 Hz to 1 kHz. The glass transition in thin polystyrene films (50–4 nm) was determined at well-defined experimental time scales. No thickness dependency of the glass transition temperature was observed within the error limits (±3 K)—neither at constant frequency (40 Hz) nor for the trace in the activation diagram (1 Hz–1 kHz). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2996–3005, 2006     

Design,synthesis, and characterization of main‐chain,aromatic polyesters based on 3,4‐ethylenedioxythiophene

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     

Formation and magnetic properties of Co–Fe-based bulk metallic glasses with supercooled liquid region

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.     

800nm激光泵浦掺Nd^3＋的氟化物玻璃光纤正向双程超荧光分析

从实验上探讨了掺Ｎｄ＾３＋的氟化物玻璃光纤正向双程超荧光基本特性，包括输入－输出特性、输出－带宽特性以及输出－波长（激发）特性。并给出了理论上的拟合公式，实验表明利用氟化物玻璃光纤有望获得性能优异的有应用前景的低相干度集成化光源。     

Superconductivity and normal state resistivity of Ba0.6K0.4BiO3: an optical phonon approach

We discuss the nature of the pairing mechanism and the physical properties associated with the normal as well as the superconducting state of cubic perovskites Ba_0.6K_0.4BiO₃using the strong coupling theory. An interaction potential which includes the Coulomb, electron–optical phonon and electron–plasmon interactions is developed to elucidate the superconducting state. A model dielectric function is constructed with these interactions fulfilling thef-sum rule. The screening parameter (μ^* = 0.26) infers the poor screening of charge carriers. The electron–optical phonon strength (λ) estimated as 0.98 is consistent with an attractive electron–electron interaction and supports the moderate to strong coupling theory. The superconducting transition temperature of Ba_0.6K_0.4BiO₃is then estimated as 32 K. Ziman's formula of resistivity is employed to analyse and compare this with the temperature-dependent resistivity of a single crystal. The estimated contribution from the electron–optical phonon together with the residual resistivity clearly infers a difference when a comparison is made with experimental data. The subtracted data infer a quadratic temperature dependence in the temperature domain (30 ≤ T ≤ 200 K). The quadratic temperature dependence of ρ [ = ρ_exp − (ρ₀ + ρ_e–ph)] is understood in terms of 3D electron–electron inelastic scattering. The presence of these el–el and el–ph interactions allows a coherent interpretation of the physical properties. Analysis reveals that a moderate to strong coupling exists in the Ba_0.6K_0.4BiO₃system and the coupling of electrons with the high-energy optical phonons of the oxygen breathing mode will be a reason for superconductivity. The implications of the above analysis are discussed.     

Thermal Analysis of the Conformational Disorder in SCLC Polymers with Rigid Backbone Glass transition studies

Bis [(ω-(4′-cyanobiphenyl)-4-yl)oxy-n-alkyl]norborn-5-ene-2,3-dicarboxylate was polymerised via ring opening metathesis polymerisation (ROMP). Two disubstituted polynorbornene derivatives both of cis configuration with different length of the side-chain were studied. Differential scanning calorimetry (DSC) was used to study the effect of thermal history on the assignment of the glass transition event associated with the biaxial orientation of a smectic phase. Glass transition temperatures, the change of isobaric specific heats at T_g and the enthalpies of isotropisation were calculated. The DSC traces only show the classic step-wise change in T_g in some cases, giving the evidence that the amorphous domains are constrained and highly restricted in movement due to the morphology developed as a result of the biaxial stretching. Based on the literature data of mono- and disubstituted polynorbornene derivatives and our calorimetric experiments, the shape of T_g dependence on number of (CH₂) units is interpreted. The origin of this shape is discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Formation of Amorphous AgI Aggregates Dominating Fast Ion Conductivity in AgI-based Glasses

Precise calorimetry was performed for (AgI)_x(AgPO₃)_1–x and (AgI)_x(Ag₂PO_3.5)_1–x glasses with very high AgI compositions (x0.75). The glasses showed -glass transitions due to the freezing-in of the rearrangement of conductive Ag⁺ ions. Magnitude of the associated heat-capacity jump increased with increasing the AgI composition in the respective glass systems, and was larger in the former system than in the latter when compared at the same AgI composition. All the results were well explained by the amorphous AgI aggregate model for the AgI-based fast ion conducting glasses, indicating the appropriateness of the model for the structure of the glasses with high AgI compositions. The formation of the hypothetical bulk amorphous AgI was also indicated in the glasses at the highest limit of AgI composition.This revised version was published online in November 2005 with corrections to the Cover Date.