An apparent kinetic model for the carbonation of calcium oxide by carbon dioxide

For the apparent kinetics of the carbonation reaction of calcium oxide by carbon dioxide, as a kind of noncatalytic gas–solid reaction, a model equation has been proposed as follows: X=kbt/(b+t), where X is the conversion of CaO; k, a kinetic rate constant (time⁻¹); b, a constant (time) equivalent to the time taken to attain half the ultimate conversion of CaO, and t, the time. As a result of analyses for some literature-reported data of CaO-carbonation conversion, it has been found that the rate of the carbonation can be well represented by dX/dt=k(1−X/X_u)², where X_u is the ultimate conversion of CaO, which is given by the product of two parametric constants, k and b. The constants k and b in the two rate control regimes of CaO-carbonation, chemical reaction control and diffusion control, have been determined as functions of temperature, respectively. The activation energy in the carbonation of surface CaO with CO₂ is estimated to about 72 kJ/mol regardless of the sources of CaO, however, that in the diffusion control regime appears differently as 102.5 (mesoporous CaO) or 189.3 kJ/mol (commercial-available CaO), possibly due to the morphological differences of the two CaO samples. From a practical point of view, the simple model equation proposed in this study deserves attention in that the CaO-carbonation behavior at working temperatures higher than 700 °C could be closely predicted.     

Feasibility of Sludge Ozonation for Stabilization and Conditioning

A pilot-scale sludge treatment plant was built to investigate the feasibility of ozonation processes for waste activated sludge treatment. Ozonation of wastewater sludge resulted in mass reduction by mineralization as well as by supernatant and filtrate recycle. Another advantage of sludge ozonation is a significant improvement of settleability and dewaterability. Experimental results showed that mass reduction of 70% and volume reduction of 85% compared with the control sludge was achieved through the sludge ozonation at a dose of 0.5?gO₃/gDS. It is also interesting to note that the filterability deteriorates up to ozone dose of 0.2?gO₃/gDS and then improves considerably at a higher ozone dose. The filterability could be improved by chemical conditioning even at a low ozone dose. The economic feasibility by cost analysis reveals that ozonation processes can be more economical than other alternative processes for sludge treatment and disposal at small-sized wastewater treatment plants.     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Amelioration of mechanical brittleness in hyperbranched polymer. 1. Macroscopic evaluation by dynamic viscoelastic relaxation

Hyperbranched poly(ether ketone)-b-linear poly(ether ketone)-b-hyperbranched poly(ether ketone) (HLHPEK) triblock copolymers with two different block compositions were prepared as an approach to improve the mechanical brittleness of hyperbranched poly(ether ketone) (HPEK). From the time-temperature superposition of dynamic shear moduli, G′(ω) and G″(ω), of HPEK and two HLHPEKs, it was investigated that the junction points between G′(ω) and G″(ω) shifted to the higher frequencies and the rubbery plateau region spread wider over the reduced frequency axis as the linear blocks were introduced and their compositions were increased. Such changes in viscoelastic response were consequences of increase in the amount of chain entanglements additionally formed by the linear blocks. In order to verify the effect of the linear block incorporation on amelioration of the mechanical brittleness, the degree of brittleness and its improvement were evaluated from the temperature dependence of the shift factors, a_Ts, experimentally obtained during the superposition of the dynamic moduli and of the average viscoelastic relaxation times, τ_HNs, determined with empirical Havriliak-Negami distribution function. From the nonlinear curve fittings of the a_Ts and the τ_HNs by the Vogel-Tamman-Fulcher equation, the degree of brittleness for HPEK and HLHPEK triblock copolymers were quantified as values of the material parameter D, an indicative of deviation from the linear Arrhenius behavior and a measure of fragility of the given material. The tendency of increasing D values with the linear block compositions confirmed substantial improvement of the mechanical brittleness in the HLHPEK triblock copolymers compared to HPEK. Therefore, the approach to copolymerize HPEK with its chemically analogous linear counterpart was verified to be an effective strategy to impart molecular entanglements and hence ameliorate the mechanical brittleness on the basis of macroscopic rheological evaluation.     

Microwave Dielectric Properties of (1−x)(Na1/2Nd1/2)TiO3−xLa(Mg1/2Ti1/2)O3 via Ordering and Far IR Reflectivity Spectra

Microwave dielectric properties of (1− x )(Na_1/2Nd_1/2)TiO₃(NNT)− x La(Mg_1/2Ti_1/2)O₃(LMT) system have been investigated with focus on structural ordering and far IR reflectivity spectra. A single perovskite phase was found to exist with various superlattice reflections over the entire compositional range. 1:1 ordering observed in the (111) reflection of X-ray diffraction patterns was found to progress significantly in the specimens above x =0.8. The ordering characteristics that presumably related to B-site Mg/Ti ordering were assumed to affect favorably the quality factor at microwave frequencies. The increase of the quality factor also could be explained in terms of the decrease of lattice anharmonicity with LMT by analysis of far IR reflectivity spectra. As expected from the values of pure NNT and LMT, the dielectric constant and the temperature coefficient of frequency tended to gradually decrease with increasing LMT content.     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.     

An Experimental Study of Fatigue Strength for Adhesively Bonded Tubular Single Lap Joints

In this paper, manufacturing technology of the tubular single lap adhesive joint was studied to obtain reliable and optimal joint quality. In addition, a surface preparation method and a bonding process for the joint were devised. The effect of the adhesive thickness and the adherend roughness on the fatigue strength of the joint was experimentally investigated. From experiments, it has been found that the fatigue strength of the joint increased as the adhesive thickness decreased and the optimal arithmetic surface roughness of the adherends was about 2 μm.     

Preparation of microporous chlorinated poly(vinyl chloride) membrane in fabric and the characterization of their pore sizes and pore‐size distributions

Chlorinated poly(vinyl chloride) (CPVC)/poly(vinyl pyrrolidone) (PVP) membranes were prepared by using the solvent system tetrahydrofuran (THF)/n‐butyl alcohol (n‐BA) to investigate the possibility of pore size and pore‐size distribution control. The coagulation of CPVC/PVP solution was induced by the exposure to water vapor at 25 (±0.5)°C. The average pore diameter, d_p, and the size distribution of pores on the surface of the membrane were quantified through the image analyzer from the images visualized by field emission scanning electron microscope (FE‐SEM). Surface pore size and distribution of the prepared CPVC/PVP membrane were strongly affected by the relative humidity (RH) in the environment and the content of PVP used as an additive. Particularly, in the case of CPVC membrane without PVP, the mean pore size was 0.15–0.2 μm, depending on the RH. The pore distribution became broad with the increase of the RH. The membranes had open pores as confirmed by the hydraulic permeation experiment. In addition, the water flux and membrane resistance (R_m) were greatly affected by the composition of polymer solution and the RH. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1195–1202, 2002     

Latent catalyst effects in halogen‐free epoxy molding compounds for semiconductor encapsulation

Latent catalyst effects were investigated to improve the physical properties of halogen‐free epoxy molding compounds (EMCs) for semiconductor encapsulation. In this study, biphenyl‐type resins were used as the epoxy and hardener resin for halogen‐free EMCs to obtain high flame‐retardant properties and high filler contents. Latent catalyst effects were examined with two kinds of EMC compositions, halogen‐free EMCs and conventional EMC compositions. We used triphenylphosphine‐benzoquinone salt (TPP‐BQ) as a latent catalyst. Spiral flow and gel time were measured to investigate the change in moldability with the latent catalyst. We measured package fail, moisture absorption, and delamination for reliability evaluation and flexural strength, flexural modulus, and adhesion for mechanical properties to examine latent catalyst effects. An improvement in moldability, reliability, and the mechanical properties were observed in two types of halogen‐free EMCs with TPP‐BQ as a latent catalyst. These phenomena were seen in conventional EMCs, including o‐cresol novolac epoxy resin. The cure kinetics of these systems were investigated by differential scanning calorimetry with an isothermal approach to explain these phenomena. The results indicate that the improvement in moldability in halogen‐free EMCs with TPP‐BQ was due to the low conversion rate of this system, and the increase in mechanical properties was attributed to the high conversion of curing reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2287–2299, 2005     

CO hydrogenation over potassium-promoted Fe/carbon catalysts

The effects of potassium on the catalytic behavior in CO hydrogenation over K-promoted Fe/carbon catalysts having low K/Fe ratios were investigated. Even though the doses of potassium were low the promotional effects were pronounced, especially on the olefin-to-paraffin ratio, and theC ₃ toC ₄ olefin selectivities of the K-promoted catalysts were as high as 51 to 66 mol%. Over the catalysts having no or low potassium content the olefin-to-paraffin ratio and the ratio of the CO₂ formation rate to the rate of CO conversion to hydrocarbons remained roughly the same regardless of temperature, while over the K-promoted catalysts having higher potassium content they increased with temperature. Formation of significant amounts of filamentous carbon was observed in the K-promoted catalysts; however, the carbon deposition did not appear to affect the inherent activity and selectivity of the K-promoted catalysts.