Polypyrrole composite membrane with high permeability prepared by interfacial polymerization

Novel polypyrrole (PPy)/polydimethylsiloxane (PDMS) composite membrane was prepared by interfacial polymerization to make a very effective gas separation membrane. We found that Polymerized PPy films as thin as ～200 nm could be chemically synthesized as freestanding membranes by using the interfacial polymerization technique. Additionally, we show that difference morphology of PPys films was obtained by controlling polymerization rate and more dense films were formed at low polymerization rate. Wide X-ray diffraction study showed the d spacing value of the PPy film decreased from 4.89 å to 3.67 å by the rate of polymerization decreases. According to d spacing value decrease, selectivity of a PPy composite membrane was increased dramatically and permeability was reduced gradually. This high selectivity was derived from d spacing closed to the kinetic diameter of nitrogen. These results indicated that the permeability is controlled by the diffusion coefficient, reflecting the packed structure of the PPy film. The highest selectivity value of composite membrane that was prepared by interfacial polymerization was O₂/N₂=17.2 and permeability for O₂ was 40.2 barrer.     

A PRACTICAL METHOD FOR RECTIFYING INTERFACIAL TENSION DATA TO PREDICT THE SHAPE OF INTERFACES IN AN IMMISCIBLE LIQUID/LIQUID/GAS SYSTEM

The shape of interfaces formed by the contact of two liquid phases, immiscible with each other, and a gaseous phase can be predicted on the condition that the tension to work at each interface is known with a sufficient accuracy. In general, interfacial tension data available are not so accurate, however, as to be useful as they are in predicting the shape of interfaces, particularly when the spreading coefficient of either liquid (liquid 1) on the other (liquid 2) has a negative value of a small magnitude. Presented in this note is a simple method to rectify the interfacial tension data, with the aid of a measurement of the radius of a lens of liquid 1 of a known volume placed on the horizontal surface of liquid 2, and thereby make them usable for predicting interfacial geometries. The method is tested by applying it to benzene/water and n-pentane/water systems.     

Shear-induced interactions in blends of HMMPE containing a small amount of thermotropic copolyester HBA/HQ/SA

Shear-induced interactions between high molecular mass polyethylene (HMMPE) melt and a thermotropic liquid crystalline copolyester, HBA/HQ/SA (TLCP) were investigated using large amplitude oscillatory shear and capillary shear. Polarized optical microscopy (POM) observations show that the mono-domain nematic TLCP droplets embedded inside a HMMPE melt may be readily elongated using large amplitude oscillatory shear. The HMMPE melt adjacent to the elongated TLCP filament was observed to crystallize faster than that in the matrix away from the interface. TEM analysis on the 1 wt% TLCP/HMMPE blend quenched after capillary shear shows that there are strong interfacial interactions between the elongated TLCP filament and the HMMPE matrix. Long range PE lamellae orientational order up to 2 μm away from the TLCP filament surface were observed, with all the lamellae surface normal parallel to the TLCP fiber. Additionally, a strong interfacial compatibility between the TLCP filament and the HMMPE matrix with an interfacial thickness of ∼30 nm has also been observed. The enhanced interfacial compatibility is attributed to the -CH₂- group interactions due to chain alignment in both components at their interface. These results provide a fundamental insight to other TLCP containing thermoplastics where compatibilities may be present due to segmental interactions.     

Influence of aggregates on chloride diffusion coefficient into mortar

In order to determine the influence of aggregates on chloride ion ingress, mortar specimens were cast with different aggregate size distribution and the same aggregate volume content. One side of the specimen was in contact with alkaline solution containing sodium chloride. The process of chloride ingress is due to diffusion. The effect of the interfacial transition zone (ITZ) around aggregate and of the tortuosity due to aggregates have been taken into account for interpreting the experimental data obtained. These two competing effects have been quantified by using the theory of composite materials. It appears that the diffusion coefficient varies as a function of the ITZ volume content and of the tortuosity.     

THE ROLE OF INTERFACIAL PHENOMENA IN A LIQUID-LIQUID REACTION SYSTEM: EXTRACTION OF PROPANOIC ACID BY TRIOCTYLAMINE

The kinetics of extraction of propanoic acid from water to isobulanol by reaction with trioctylamine have been investigated. Mass transfer was modelled by extending the approach used in absorption with chemical reaction, as it is usually done for liquid-liquid reactions. The presence of the amine, however, gave rise to phenomena that cause this method to fail, producing inconsistent results. In order to explain these data, the presence of relevant interfacial phenomena must be supposed.     

Interfacial shear strength of C/C composites

Fiber-bundle push-out, single-fiber push-in, and single-fiber push-out tests were conducted in order to examine the applicability of these methods for determining the interfacial shear strength of carbon-carbon composites. The fiber-bundle push-out test resulted mostly in fractures along the fiber/matrix interface but created a small amount of fractures in the matrix. Hence, the evaluated strength was regarded as an approximate value. In order to precisely evaluate the interfacial strength, push-in and push-out tests for a single fiber were performed using a micro-Vickers indentation tester. In these tests, the load has to be placed within a target fiber, and the indentation should not extend to the matrix. This condition restricted the load that could be applied to a carbon fiber. Within this limit, a single carbon fiber could not be pushed-in. For the sake of load reduction, single-fiber push-out tests were conducted using thin specimens. The thickness appropriate for a single-fiber push-out specimen was estimated based on the interfacial shear strength obtained by the bundle push-out tests. Below this thickness, single-fiber push-out tests could be successfully performed.     

Interfacial tension measurement between immiscible polymers: improved deformed drop retraction method

This paper describes an improvement of the technique to measure interfacial tension in immiscible polymer blends. Our method is based on the droplet retraction method, in which one relates the kinetics of relaxation of a deformed droplet to the interfacial tension between the matrix and droplet. Previously, the problem with this technique has been the difficulty in preparing axisymmetric ellipsoidal droplets. In our work, we demonstrate that perfect axisymmetric ellipsoidal droplets are produced at a later stage of relaxation of short imbedded fibers. With this technique, we utilize the strengths of both the deformed droplet method and the imbedded fiber retraction method while overcoming their shortcomings. The interfacial tension value thus obtained was compared to that by conventional methods. Additionally, the effect of confinement by external walls on the interfacial tension measurement was studied. Confinement affects interfacial tension measurement when the gap between the walls is less than two times the equilibrium drop size.     

Interfacial polymerization of pyrrole and in situ synthesis of polypyrrole/silver nanocomposites

We present a new synthetic approach leading to the formation of polypyrrole architectures in submicron level and to silver/polypyrrole nanocomposites via an interfacial polymerization in a water/chloroform interface. The oxidizing agent was either Ag(I) or Fe(III). In the first case, silver nanoparticles resulted. The mean diameter of the polypyrrole structures is in the range of 200-300 nm according to the addition or not of various surfactants. The progress of the reaction was studied by UV-visible spectroscopy, which also revealed the formation of a polaron band during the growth of the oligomers. The crystal structure of the polymers was examined by X ray diffractometry and all samples appeared to be amorphous, while the samples were further characterized by thermogravimetric analysis and FT-IR spectroscopy.     

Effects of the boundary layer and interfacial reaction on the time lag in supported liquid membranes

A mathematical model is proposed to describe the effects of boundary layer resistance and interfacial reaction on the time lag in supported liquid membranes for metal ion separation. The model shows that the presence of boundary layer resistance and interfacial reaction delays the time-lag, compared with the limiting case that rapid equilibrium at the interfaces and negligible boundary layer resistance are assumed. Calculated result describes the expected trend and the model equation allows one to predict the lumped parameters which represent the ratios of the diffusion time in the membrane to the characteristic time for boundary layer transfer and interfacial reactions.     

Electrochemical performance of gel-cast NiO-SDC composite anodes in low-temperature SOFCs

NiO-Ce_0.8Sm_0.2O_1.9 (SDC) composites were synthesized using gel-casting technique. The electrochemical performance of the gel-cast (GC) Ni-SDC cermet as anode was investigated contrast with that fabricated from traditional mechanical mixing (MM) technique using fuel cells with about 35 μm-thick SDC electrolyte and Sm_0.5Sr_0.5CoO₃-SDC cathode. Maximum power density of the cell with GC anode achieved 491 mW cm⁻² at 600 °C, over 100 mW cm⁻² larger than that with MM anode, inferring high catalytic activity of the GC anode. Impedance measurements on the fuel cell at open circuit showed that the anodic interfacial polarization resistance of the GC anode was 0.1 Ω cm² lower than that of the MM anode. Long-term stability of the cell with GC anode in hydrogen was also performed, which showed that it can stabilize at least 7 days.