Thermo‐oxidative stability of ionic liquids as lubricating fluids

Thermo‐oxidative stability of ionic liquids was evaluated by three bulk‐scale tests. The changes in chemical and physical properties such as viscosity, deposit formation, weight loss and TAN were obtained. The results are discussed in terms of chemical structure of ionic liquids. TFSI derivatives exhibit good thermo‐oxidative stability in comparison with BF4 derivatives. As chain length of alkyl group in imidazolium‐cationic moiety increases, the thermo‐oxidative stability of the molecule decreases. Water contaminant promotes the thermo‐oxidative degradation of ionic liquids. Reaction mechanism via radical intermediates is proposed herein. Copyright © 2007 John Wiley & Sons, Ltd.     

Utilization of NaCl for phillipsite synthesis from fly ash by hydrothermal treatment with microwave heating

The coal fly ash was treated hydrothermally with the mixture of NaOH aqueous solution and NaCl aqueous solution at 373 K, using the microwave heating and the conventional heating in order to clarify influences of the NaCl concentration in the hydrothermal solution on the growth rate and the crystalline phase of synthesized zeolites.As a result, it was found that phillipsite crystallinity of product powder increases with the additive NaCl concentration in the hydrothermal solution when the concentration of NaOH is so low as not to generate the zeolite from fly ash. On the other hand, in case that NaOH concentration is relatively high, the addition of NaCl to the hydrothermal solution using the conventional heating hardly affects phillipsite crystallinity of product powder; however, the generation of hydroxysodalite is enhanced by the microwave heating.Moreover, it was revealed that the necessary treatment time to complete the crystallization of phillipsite increases with increasing concentration of NaCl in the hydrothermal solution. This is because the substitution of NaCl for NaOH reduces the dissolution rate of aluminate and silicate ions from fly ash and the generation rate of the precursor aluminosilicate gel. However, this delay of the completion of the crystallization can be shortened by the microwave heating method.These experimental results concluded that the utilization of NaCl for the hydrothermal solution is effective in phillipsite synthesis from fly ash only when the NaOH concentration is relatively low in the hydrothermal solution and especially, when the microwave heating is used.     

Poly(L‐Lactide), 8. High‐Temperature Hydrolysis of Poly(L‐Lactide) Films with Different Crystallinities and Crystalline Thicknesses in Phosphate‐Buffered Solution

Poly(L ‐lactide) (PLLA) films having different crystallinities (X_c's) and crystalline thicknesses (L_c's) were prepared by annealing at different temperatures (T_a's) from the melt and their high‐temperature hydrolysis was investigated at 97°C in phosphate‐buffered solution. The changes in remaining weight, molecular weight distribution, and surface morphology of the PLLA films during hydrolysis revealed that their hydrolysis at the high temperature in phosphate‐buffered solution proceeds homogeneously along the film cross‐section mainly via the bulk erosion mechanism and that the hydrolysis takes place predominantly and randomly at the chains in the amorphous region. The remaining weight was higher for the PLLA films having high initial X_c when compared at the same hydrolysis time above 30 h. However, the difference in the hydrolysis rate between the initially amorphous and crystallized PLLA films at 97°C was smaller than that at 37°C, due to rapid crystallization of the initially amorphous PLLA film by exposure to crystallizable high temperature in phosphate‐buffered solution. The hydrolysis constant (k) values of the films at 97°C for the period of 0–8 h, 0.059–0.085 h^–1 (1.4–2.0 d^–1), were three orders of magnitude higher than those at 37°C for the period of 0–12 months, 2.2–3.4×10^–3 d^–1. The melting temperature (T_m) and X_c of the PLLA films decreased and increased, respectively, monotonously with hydrolysis time, excluding the initial increase in T_m for the PLLA films prepared at T_a = 100, 120, and 140°C in the first 8, 16, and 16 h, respectively. A specific peak that appeared at a low molecular weight around 1×10⁴ in the GPC spectra was ascribed to the component of one fold in the crystalline region. The relationship between T_m and L_c was found to be T_m (K) = 467·[1–1.61/L_c (nm)] for the PLLA films hydrolyzed at 97°C for 40 h.     

Formation of porous poly(ethylene‐co‐vinyl alcohol) membrane via thermally induced phase separation

Crystalline poly(ethylene‐co‐vinyl alcohol) (EVOH) membranes were prepared by a thermally induced phase separation (TIPS) process. The diluents used were 1,3‐propanediol and 1,3‐butanediol. The dynamic crystallization temperature was determined by DSC measurement. No structure was detected by an optical microscope in the temperature region higher than the crystallization temperature. This means that porous membrane structures were formed by solid–liquid phase separation (polymer crystallization) rather than by liquid–liquid phase separation. The EVOH/butanediol system showed a higher dynamic crystallization temperature and equilibrium melting temperature than those of the EVOH/propanediol system. SEM observation showed that the sizes of the crystalline particles in the membranes depended on the polymer concentration, cooling rate, and kinds of diluents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2449–2455, 2001     

Blends of aliphatic polyesters. II. Hydrolysis of solution-cast blends from poly(L-lactide) and poly(E-caprolactone) in phosphate-buffered solution

Blend films were prepared from poly(L -lactide) (PLLA) and poly(E-caprolactone) (PCL) with different PLLA contents [X_PLLA (w/w) = PLLA/(PCL + PLLA)] by the solution-casting method and their hydrolysis behaviors were investigated up to 20 months in a phosphate-buffered solution of pH 7.4 at 37°C by gel permeation chromatography, tensile testing, differential scanning calorimetry, and gravimetry. Polarizing microscopic observation and dynamic mechanical analysis revealed that PCL and PLLA were phase-separated in blend films before hydrolysis. The mass remaining, molecular weight, and tensile strength of the blend films with X_PLLA of 0.5 and 0.75 decreased more rapidly by hydrolysis than those of the nonblended PLLA, while the elongation at break of the blend film of X_PLLA = 0.25 decreased the slowest. The rate constant for hydrolysis (k) calculated from the M_n change during hydrolysis was higher for blend films of X_PLLA = 0.5 and 0.75 than those expected from k of nonblended PLLA and PCL. The melting temperature (T_m) of PLLA in the blend and nonblended films of X_PLLA = 0.5, 0.75, and 1 decreased from 179 to 161, 160, and 175°C upon hydrolysis for 20 months, respectively, while that for X_PLLA = 0.25 slightly increased from 176 to 177°C. On the other hand, T_m and the crystallinity of PCL was significantly increased by hydrolysis for 20 months, irrespective of X_PLLA. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 405–415, 1998     

A Metal-Oxide Surge Arrester model with active V-I characteristics

Generally a model of Metal Oxide Surge Arrester (MOSA) for numerical analysis uses a nonlinear resistance. But actual Voltage-Current (V-I) characteristics of MOSA have a hysteresis loop in the time domain like the i-Φ characteristic of a transformer and frequency dependency. The authors have investigated the relation between the actual V-I hysteresis characteristics obtained by some current waveforms and the static V-I characteristics. From the voltage difference between the above two characteristics, an equation was derived and a new model of MOSA was developed. This model consists of a nonlinear resistance representing the fundamental V-I characteristic, a linear inductance, and a voltage source that depends on the absorbed energy. The calculated results by the proposed model are compared with measurement results by using the waveform of standard impulse current, steep front current, and oscillated current. The accuracy of the model has been confirmed to be satisfactory. The model is expected to be useful to investigate insulation coordination of power systems. © 1997 Scripta Technica, Inc. Electr Eng Jpn, 121 (1): 35–42, 1997     

Enhanced crystallization of poly(L‐lactide‐co‐ε‐caprolactone) during storage at room temperature

Copolymer of L ‐lactide and ε‐caprolactone [P(LLA‐CL)] (50/50) was synthesized using stannous octoate and was stored at room temperature. The change in physical properties occurring during this storage at room temperature was investigated by differential scanning calorimetry (DSC), X‐ray diffractometry, polarizing optical microscopy, tensile and bending tests, and light absorbance measurements. It was concluded that the increase in mechanical properties and light absorbance during storage can be ascribed to gradual selective crystallization of the L ‐lactide sequence in P(LLA‐CL) at room temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 947–953, 2000     

Properties and morphology of poly(L‐lactide). III. Effects of initial crystallinity on long‐term in vitro hydrolysis of high molecular weight poly(L‐lactide) film in phosphate‐buffered solution

The effects of crystallinity (x_c) on the hydrolysis of high molecular weight poly(L ‐lactide) (PLLA) films in a phosphate‐buffered solution at 37°C was investigated by gel permeation chromatography, tensile testing, differential scanning calorimetry, scanning electron microscopy, and polarizing optical microscopy. The change in molecular weight distribution and surface morphology of the PLLA films after hydrolysis revealed that the hydrolysis of PLLA film in a phosphate‐buffered solution proceeded homogeneously along the film cross section, mainly via the bulk‐erosion mechanism. The induction period until the start of the decrease in mass remaining and the tensile strength became longer with a decrease in the initial x_c of the PLLA films. The rate of molecular weight reduction was higher as the initial x_c of the PLLA films increased when hydrolysis was carried out up to 24 months. Melting and glass transition temperatures of the PLLA films increased in the first 12 months of hydrolysis, while they decreased in another 24 months, irrespective of the initial x_c. The x_c value of the PLLA films increased monotonously by hydrolysis. The lamella disorientation in PLLA spherulites after hydrolysis implied that the hydrolysis of PLLA chains occurred predominantly in the amorphous region between the crystalline regions in the spherulites. The area of a specific molecular weight in GPC spectra at 36 months increased with increase in the initial x_c of the PLLA film, suggesting that the specific peak should be due to the component of one fold in the crystalline region. The reason for enhanced hydrolysis of PLLA films having higher initial crystallinities was discussed in terms of tie chains and terminal groups of PLLA. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1452–1464, 2000     

Iodine transfer dispersion polymerization (dispersion ITP) with CHI3 and reversible chain transfer catalyzed dispersion polymerization (dispersion RTCP) with GeI4 of styrene in supercritical carbon dioxide

Submicrometer-sized, polystyrene (PS) particles with controlled molecular weight distribution (MWD), were successfully obtained directly as powder state by iodine transfer dispersion polymerization (dispersion ITP) and reversible chain transfer catalyzed dispersion polymerization (dispersion RTCP) in supercritical carbon dioxide (scCO₂) for the first time. These dispersion polymerizations proceeded similarly reaching 80% conversion in 21 h. In the dispersion ITP, the number-average molecular weight (M_n) nonlinearly increased with the conversion, which were always higher than theoretical values, and the MWD at each conversion was comparatively narrow (M_w/M_n = 1.5–1.7) throughout polymerization. In the dispersion RTCP, M_n also nonlinearly increased with increasing conversion and M_w/M_n values were in the range of 1.3–1.5, which were lower than those of the dispersion ITP. In chain extension tests in bulk systems, the degrees of livingness of PS prepared by the dispersion ITP and the dispersion RTCP in scCO₂ systems were, respectively, estimated to be 56% and 48%. From these results, while more investigation is necessary, it was concluded that both polymerizations with scCO₂ proceeded in a partly controlled manner.     

Separation and enrichment of carbon dioxide by capillary membrane module with permeation of carrier solution

A novel facilitated transport membrane for gas separation using a capillary membrane module is proposed in which a carrier solution is forced to permeate the membrane. Both a feed gas and a carrier solution are supplied to the lumen side (high pressure side, feed side) of the capillary ultrafiltration membrane and flow upward. Most of the carrier solution which contains dissolved solute gas, CO₂ in the present case, permeates the membrane to the permeate side (low pressure side, shell side), where the solution liberates dissolved gas to form a lean solution. The lean solution is circulated to the lumen side. This type of capillary membrane module was applied to the separation of CO₂ from model flue gases consisting of CO₂ and N₂. Monoethanolamine (MEA), diethanolamine (DEA) and 2-amino-2-methyl-1-propanol (AMP) were used as carriers or absorbents of CO₂. The feed side pressure was atmospheric and the permeate side was evacuated at about 10 kPa. CO₂ in the feed gas was successfully concentrated from 5–15% to more than 98%. The CO₂ permeance was as high as 2.7×10⁻⁴ mol m⁻² s⁻¹ kPa⁻¹ (8.0×10⁻⁴ cm³ cm⁻² s⁻¹ cmHg⁻¹) when the CO₂ mole fraction in the feed was 0.1 and temperature was 333 K. The selectivity of CO₂ over N₂ was in the range from 430 to 1790. The membrane was very stable over a discontinuous one-month testing period.