An in situ Raman study of the intercalation of supercapacitor-type electrolyte into microcrystalline graphite

An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et₄N⁺) and tetrafluoroborate (BF₄⁻) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et₄N⁺ into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li⁺. For the positive electrode, BF₄⁻ was shown to intercalate above +4.3 V versus Li/Li⁺. The characteristic G-band doublet peak (E_2g2(i) (1578 cm⁻¹) and E_2g2(b) (1600 cm⁻¹)) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm⁻¹) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm⁻¹) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM).     

Synthesis and luminescence properties of new blue‐light‐emitting polyconjugated poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene} polymers and copolymers

Three new soluble polyconjugated polymers, all of which emitted blue light in photoluminescence and electroluminescence, were synthesized, and their luminescence properties were studied. The polymers were poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene}, poly((9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)vinylene‐1,4‐phenylene]}) [P(DOF‐PVP)], and poly([N‐(2‐ethyl) hexylcarbazole‐3,6‐diyl]‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)]vinylene‐1,4‐phenylene}). The last two polymers had alternating sequences of the two structural units. Among the three polymers, P(DOF‐PVP) performed best in the light‐emitting diode devices of indium–tin oxide/poly(ethylenedioxythiophene) doped with poly(styrene sulfonate) (30 nm)/polymer (150 nm)/Li:Al (100 nm). This might have been correlated with the balance in and magnitude of the mobility of the charge carriers, that is, positive holes and electrons, and also the electronic structure, that is, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels, of the polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 307–317, 2006     

Piezo- and pyroelectricity in polymer blends of poly(vinylidene fluoride)/poly(methyl methacrylate)

Compatible polymer blends of poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) can be used as suitable model systems for investigating the relationship between the physico-chemical structure of polymers and their piezo- and pyroelectric activity. The structure of PVDF/PMMA blends can be varied over a very wide range which can lead to a strong influence on the piezo- and pyroelectric activity and the corresponding coefficients d₃₁ and g₃. The values of d₃₁ and g₃ were found to vary over nearly five decades whereas the normalized coefficients $\text{d}{}_{31}\text{P}$ and $\text{g}{}_3\text{P}$ remain largely unaffected. This emphasizes the importance of the molecular processes causing the macroscopic polarization P during the poling procedure. For a given polarization P and a given temperature T the properties of the polymer matrix, however, are far less important for the values obtained for d₃₁ and g₃. The experimental results were compared with theoretical predictions based on models which were recently developed by Tashiro et al., Broadhurst et al. and by Mopsik et al.. Considering the appropriate scope of each model a good agreement between theory and experiment is observed and general contradictions have not been found.     

Encapsulation mechanism of N2 molecules into the central hollow of carbon nitride multiwalled nanofibers

Nitrogen molecules have been encapsulated into the central hollows of vertically aligned carbon nitride (CN) multiwalled nanofibers by dc plasma-enhanced chemical vapor deposition with C₂H₂, NH₃, and N₂ gases on a Ni/TiN/Si(1 0 0) substrate at 650 °C. X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectra showed the existence of nitrogen molecules in CN nanofibers. Elemental mapping images with electron energy loss spectroscopy of the CN nanofiber and catalyst metal, and optical emission spectroscopy spectra of the plasma showed the distribution of nitrogen atoms and molecules in the CN nanofiber, catalyst metal, and gaseous precursor, respectively. These studies showed that atomic nitrogen diffused into the catalytic metal particle because of the concentration gradient and then saturated at the bottom of the particle. Saturated nitrogen atom participated in the formation of the CN nanofiber wall but most of nitrogen was trapped in the central hollow of the nanofiber as molecules.     

Developmental variations in plasma leptin,leptin soluble receptor and their molar ratio in healthy infants

Background  

Leptin and its soluble receptor (sOB-R) are important to regulation of body composition but there are no data on the developmental variations in these plasma variables and their relationship with body composition measurements,     

Experimental analysis of bubble mode in a plate-type absorber

An experimental analysis of ammonia-water absorption was performed in a plate-type absorber. The flow of water and ammonia gas was performed in the bubble mode. The experiments were made to examine the effects of solution flow rate and gas flow rate on the performance of the absorber. It was found that the increase of solution flow rate rarely affected the mass transfer, but improved the heat transfer. As the gas flow rate increased, slugging occurred in the bubble mode and influenced the thermal boundary layer. Finally, the results were converted into dimensionless numbers to elucidate physical phenomena and plotted as Sherwood number versus Reynolds number for mass transfer performance and Nusselt number versus Reynolds number for heat transfer performance.     

Monomer concentration effect on the phase behavior of poly(propyl acrylate) and poly(propyl methacrylate) with supercritical CO2 and C2H4

Experimental cloud-point data to temperature of 186 °C and pressure of ~2,500 bar are presented for ternary mixtures of poly(propyl acrylate)(PPA)-CO₂-propyl acrylate (PA) PPA-C₂H₄-PA and poly(propyl methacrylate) (PPMA)-CO₂-propyl methacrylate (PMA) systems. Cloud-point pressures of PPA-CO₂-PA system were measured in the temperature range of 32 °C to 175 dgC and to pressures as high as 2,070 bar with PA concentrations of 0.0, 5.0, 11.7 and 30.4 wt%. Adding 34.1 wt% PA to the PPA-CO₂ mixture significantly changes the phase behavior. This system changes the pressure-temperature slope of the phase behavior curves from U-LCST region to LCST region as the PA concentration increases. Cloud-point data to 170 °C and 1,400 bar are presented for PPA-C₂H₄-PA mixtures and with PA concentration of 0.0, 5.7, 15.5 and 22.2 wt%. The cloud-point curve of PPA-C₂H₄ system shows relatively flat at 730 bar for temperatures between 41 and 150 °C. With 15.5 and 22.2 wt% PA the cloud-point curve exhibits a positive slope that extends to 35 °C and ~180 bar. Also, the ternary PPMA-CO2-PMA system was measured below 186 °C and 2,484 bar, and with cosolvent of 5.2-20.1 wt%. PPMA does not dissolve in pure CO₂ to 233 °C and 2,500 bar. Also, when 41.5 wt% PMA is added to the PPMA-CO₂ solution, the cloud-point curve shows the typical appearance of a lower critical solution temperature (LCST) boundary.     

Power Smoothing of a Variable-speed Wind Turbine Generator

This paper presents a power-smoothing scheme of a variable-speed wind turbine generator (VSWTG) that employs separate control gains for the over-frequency section (OFS) and under-frequency section (UFS). In the proposed scheme, an additional proportional control loop based on the system frequency deviation operating in conjunction with maximum power point tracking operation is used. In the OFS, to improve the energy-storing capability, the scheme suggests the gain of the frequency deviation control loop, which is set to be monotonously decreasing with the rotor speed while being significantly larger than that in the UFS. In the UFS, to improve the energy-releasing capability while preventing over-deceleration, the gain of the frequency deviation control loop is set to be a linear function of the rotor speed. The simulation results under continuously varying wind speeds with different wind patterns and wind speeds clearly demonstrate that the proposed scheme significantly mitigates the output power fluctuations of a VSWTG. The proposed scheme keeps the frequency within a narrow range, thereby reducing the required primary frequency control reserve for regulating the frequency under normal operations.

     

Chemiresistor sensor using elastomer-functionalized carbon nanotube nanocomposites for the detection of gasoline spills

Two types of multi-walled carbon nanotube (MWNT)-based elastomer nanocomposites are used as a sensor material for the detection of gasoline spills by applying the interdigitated electrode (IDE) device. MWNT-g-polyisoprene (PI) and Si-MWNT/natural rubber (NR) are prepared by applying “grafting-from” and “grafting-to” process, respectively. When compared based on the identical condition of gasoline sensing test, the maximum response value to the exposure of gasoline is 17.5 for MWNT-g-PI sensor and 12.9 for Si-MWNT/NR sensor, which reach the maximum in less than 3 min. The MWNT-g-PI sensor selectively detects gasoline, and its response is completely reversible. It shows that the longer chain length of PI brings about the larger response of MWNT-g-PI sensor to gasoline. The sensitivity of MWNT-g-PI sensor highly depends on both how much gasoline is exposed to the sensor and what bias voltage is applied to the IDE device. The IDE sensor using MWNT-g-PI nanocomposites effectively detects gasoline spills.     

Temperature and grain size dependence of superplasticity in a Zn−0.3wt.%Al alloy

The superplastic deformation behavior of quasi-single phase Zn-0.3 wt. %Al was investigated. A series of load relaxation and tensile tests was conducted at various temperatures ranging from RT (20 °C) to 200 °C. The recently proposed internal variable theory of structural superplasticity was applied. The flow curves obtained from load relaxation tests were shown to consist of contributions from interface sliding (IS) and accommodating plastic deformation. In the case of quasi-single phase Zn-0.3 wt.% Al alloy with an average agrain size of 1 μm, the IS behavior could be described as a viscous flow process characterized by a power index of M_g=0.5. A large elongation of about 1400% was obtained at room temperature and the strain rate sensitivity parameter was about 0.4. Although relatively large-grained (10 μm) single phase alloy showed a high value of strain rate sensitivity comparable to that of fine-grained alloy at very low strain rate range, IS was not expected from the analysis based on the internal variable theory of structural superplasticity at room temperature. As the temperature increased above 100 °C, however, the contribution from IS was observed at a very low strain rate range. A high elongation of ∼400% was obtained in a specimen of 10-μm-grain-size at 200 °C under a strain rate of 2×10⁻⁴/sec. Jointly appointed at Center for Advanced Aerospace Materials (CAAM)