Liquid-Phase Transport During Removal of Organic Binders in Injection-Molded Ceramics

A method has been developed for calculating hydraulic pressures induced by thermal expansion of liquid binders early in the removal cycle, when evaporative losses are negligible and fully saturated conditions prevail. Specific results were obtained for flat compacts containing a common wax binder, mixed with varying amounts of low-density polyethylne. In general, these results show how the risk of hydraulic fracture increases with heating rate and compact thickness. Although pressures are minimal when the binder consists entirely of wax, the continual addition of polyethylene eventually gives rise to unacceptable risk levels, even for relatively thin compacts. Binder removal at elevated temperatures is considered subsequently. In this case, vapor pressures eventually approach a critical level, thereby allowing mass removal by evaporation to overcome the effect of thermal expansion in maintaining full saturation. With the onset of void formation, the developing capillary pressure supersedes hydraulic pressure as the driving force in liquid transport. Besides representing capillary flow, the present formulation also accounts for thermal degradation of the binder during removal. The resulting system of equations was solved numerically for a variety of representative debinding conditions. Predictions for flat compact containing a balanced wax/polyethylene binder indicate that thermal degradation of the polyethylene can give rise to a marked improvement in debinding rates. It turns out, however, that this enhancement is far more effective in thinner compacts.     

Influence of silicon on the growth of barrier-type anodic films on titanium

Amorphous anodic titania, stabilised by incorporation of silicon species, is shown to grow to high voltages on sputter-deposited, single-phase Ti-Si alloys during anodizing at a constant current density in ammonium pentaborate electrolyte. The films comprise two main layers, with silicon species confined to the inner layers. An amorphous-to-crystalline transition occurs at ∼60 V on the Ti-6 at.% Si alloy, while the transition is suppressed to voltages above 140 V on alloys with 12 and 26 at.% silicon. The crystalline oxide, nucleated at a depth of ∼40% of the film thickness, is associated with the presence of a precursor of crystalline oxide in the pre-existing air-formed oxide. The modified structure of the air-formed oxide due to increased incorporation of silicon species suppresses the amorphous-to-crystalline transition until the onset of dielectric breakdown. The transport numbers of cations and anions during growth of the anodic oxides are independent of the concentration of silicon species in the inner layer, despite the marked change in the field strength.     

EFFECTS OF ASYMMETRIC TEMPERATURE PROFILES ON THERMAL CONVECTION DURING PHYSICAL VAPOR TRANSPORT OF Hg2Cl2

Asymmetric horizontal thermal profiles can change the flow field structure in the physical vapor transport (PVT)of Hg₂Cl₂. It is found that for the ratios of horizontal to vertical thermal Rayleigh numbers Ra_H/Ra ≥ 1·5, the convetive flow structure changes from multicellular to unicellular for the base parametric state of Ra = 2·79 × 10⁴, Pr = 0·91, Le=l·01. Pe = 4·60, Ar= 0·2 and C_r = 1·01. The unicellular flow structure obtained by increasing ∇*_H(Ra_H) is not likely to support the conjecture of the presence of unicellular convective mode in the laser Doppler velocimetry (LDV) experiments for PVT process of Hg₂Cl₂ (Kim el al., 1996). When the six parameters of Ra, Pr, Le, Pe, Ar and C_r are fixed, the dimensional maximum magnitude of the velocity vector |U|_max is proportional to √∇T*_H.     

An analytical framework for integrated maritime terminal scheduling problems with time windows

Container transport, an integral part of intercontinental trade, has steadily increased over the past few decades. The productivity of such a system, in part, hinges on the efficient allocation of terminal resources such that the container transit time is minimized. This study provides an analytical framework, which entails efficient scheduling of quay and yard cranes, to minimize the time spent by containers at a terminal. A mixed-integer programming model is developed to capture the two-stage multi-processor characteristic of the problem, where each crane has specific time window availability. A genetic algorithm equipped with a novel decoding procedure is developed. The mixed-integer model is tested on a number of problem instances of varying sizes to gain managerial insights.     

Gas transport properties of 6FDA-TAPOB hyperbranched polyimide membrane

Physical and gas transport properties of the hyperbranched polyimide prepared from a triamine, 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), and a dianhydride, 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), were investigated and compared with those of linear-type polyimides with similar chemical structures prepared from diamines, 1,4-bis(4-aminophenoxy)benzene (TPEQ) or 1,3-bis(4-aminophenoxy)benzene (TPER), and 6FDA. 6FDA-TAPOB hyperbranched polyimide exhibited a good thermal stability as well as linear-type analogues. Fractional free volume (FFV) value of 6FDA-TAPOB was higher than those of the linear-type analogues, indicating looser packing of molecular chains attributed to the characteristic hyperbranched structure. It was found that increased resistance to the segmental mobility decreases the gas diffusivity of 6FDA-TAPOB, in spite of the higher FFV value. However, 6FDA-TAPOB exhibited considerably high gas solubility, resulting in high gas permeability. It was suggested that low segmental mobility and unique size and distribution of free volume holes arising from the characteristic hyperbranched structure of 6FDA-TAPOB provide effective O₂/N₂ selectivity. It is concluded that the 6FDA-TAPOB hyperbranched polyimide has relatively high permeability and O₂/N₂ selectivity, and is expected to apply to a high-performance gas separation membrane.     

Separation of kinetics and mass-transfer in a batch alkoxylation reaction

The quantitative aspects of the role of interfacial mass-transfer and reaction kinetics in ethoxylation of lauryl alcohol were examined in a batch recirculation reactor. The liquid droplets falling through a gas column were obtained by utilizing a recirculation loop and a set of spray nozzles. The CO₂/NaOH reaction was employed to characterize the interfacial area. The alkoxylation reaction was studied at temperatures between 124°C and 171°C, at catalyst levels between 0.09 and 0.50 weight percent and at ethylene oxide partial pressures between 68 kPa and 204 kPa. A model was developed which permits the prediction of reactor performance at various operating conditions. The mass-transfer during free fall dominates the interfacial mass-transfer and the contributions during the drop formation and coalescence stages are small. The rate of ethylene oxide (EO) addition to lauryl alcohol was constant during the batch run, indicating similar activity for the unreacted lauryl alcohol and the lauryl alcohol ethoxylated to varying extents. The rate of ethoxylation is first-order in both catalyst and ethylene oxide concentrations. The liquid-phase reaction kinetics and interfacial mass-transfer occur in series, with kinetics dominating the overall ethoxylation rate. As expected, an increasing role of mass transfer is observed at higher temperatures, and/or higher catalyst concentrations where the kinetic rate becomes significantly high. The intrinsic activation energy for the ethoxylation of lauryl alcohol is 55.2 kJ/mole.     

Sorption,diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) in water–acetic acid mixtures

Sorption, diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) were investigated for water–acetic acid mixtures by using a gravimetric method at 30, 40, and 50°C. The membranes were characterized by X‐ray diffraction and Fourier transform infrared techniques. Concentration‐independent diffusion coefficients were obtained by applying Fick's relationship before completion of equilibrium sorption. Permeation coefficients were calculated from sorption and diffusion coefficients. Concentration profiles of liquids were computed considering the sheet geometry for the membrane by solving Fick's equation under suitable boundary conditions. Arrhenius activation parameters were computed for the transport processes. Experimental results and calculated quantities were discussed to understand membrane–solvent interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1139–1150, 2004     

Characterization of dilute and dense phase vertical upflow gas-solid transport based on average concentration and velocity data

Dilute, ‘dense phase 1’, and possibly a third regime-‘dense phase 2’, were observed in a vertical 0.02 m diameter pneumatic conveyor using 210 μm sand particles. The transitions were marked by the alterations in the trend of the measured average solids hold-up while varying the solids mass flowrate at constant air velocity. Hydrodynamic characteristics together with the transition criteria for the various transport modes were established. A novel regime diagram based on average gas velocities and solids mass flowrates was developed to identify the operating conditions for these regimes, as well as the limiting solids carrying capacities of the present conveyor. A probable cause of the dilute to dense phase transition is speculated upon.     

Application of orthogonal collocations to some transport phenomena problems in co-axial cylinders and spheres

Collocation methods are developed for the solution of some differential equation models for transport phenomena problems in one-and two-dimensions in co-axial annuli of spherical and cylindrical shapes. General formulae are developed to obtain orthogonal polynomials over an arbitrary interval using two types of weighting functions. The convergence and accuracy of the methods are demonstrated using two test problems, i.e., calculation of effectiveness factors in (a) a spherical pellet with peripherally deposited catalyst and (b) a Raschig ring type cylindrical catalyst pellet. Comparisons of results obtained from the present methods with analytic solutions for the first-order reactions indicate good agreement. Numerical solutions are also obtained for the second-and the third-order reactions for which analytic solutions are not available. Results obtained in terms of a new Thiele modulus involving the ratio of volume of peripherally deposited part of catalyst to exterior surface area indicate that this normalization brings effectiveness factor versus Thiele modulus curves close together for co-axial spherical and long cylindrical pellets, as it does for these geometries without the inner co-axial portion.     

Methodology to resolve the transport equation with the discrete ordinates code TORT into the IPEN/MB-01 reactor

Resolution of the steady-state Neutron Transport Equation in a nuclear pool reactor is usually achieved by means of two different numerical methods: Monte Carlo (stochastic) and Discrete Ordinates (deterministic). The Discrete Ordinates method solves the Neutron Transport Equation for a set of selected directions, obtaining a set of directional equations and solutions for each equation which are the angular flux. In order to deal with the energy dependence, an energy multi-group approximation is commonly performed, obtaining a set of equations depending on the number of energy groups. In addition, spatial discretization is also required and the problem is solved by sweeping the geometry mesh. However, special cross-sections are required due to the energy and directional discretization, thus a methodology based on NJOY99 code capabilities has been used. Finally, in order to demonstrate the capability of this method, the 3D discrete ordinates code TORT has been applied to resolve the IPEN/MB-01 reactor.