Description of the thermodynamic properties and fluid-phase behavior of aqueous solutions of linear,branched, and cyclic amines

The SAFT-γ Mie group-contribution equation of state is used to represent the fluid-phase behavior of aqueous solutions of a variety of linear, branched, and cyclic amines. New group interactions are developed in order to model the mixtures of interest, including the like and unlike interactions between alkyl primary, secondary, and tertiary amine groups (NH₂, NH, N), cyclic secondary and tertiary amine groups (cNH, cN), and cyclic methine-amine groups (cCHNH, cCHN) with water (H₂O). The group-interaction parameters are estimated from appropriate experimental thermodynamic data for pure amines and selected mixtures. By taking advantage of the group-contribution nature of the method, one can describe the fluid-phase behavior of mixtures of molecules comprising those groups over broad ranges of temperature, pressure, and composition. A number of aqueous solutions of amines are studied including linear, branched aliphatic, and cyclic amines. Liquid–liquid equilibria (LLE) bounded by lower critical solution temperatures (LCSTs) have been reported experimentally and are reproduced here with the SAFT-γ Mie approach. The main feature of the approach is the ability not only to represent accurately the experimental data employed in the parameter estimation, but also to predict the vapor–liquid, liquid–liquid, and vapor–liquid–liquid equilibria, and LCSTs with the same set of parameters. Pure compound and binary phase diagrams of diverse types of amines and their aqueous solutions are assessed in order to demonstrate the main features of the thermodynamic and fluid-phase behavior.     

Optimization of waste quail eggshells as biocomposites for polyaniline in ammonia gas detection

A simple, cost-effective, and novel chemical sensor for ammonia (NH₃) gas detection was developed from polyaniline (PANI)/quail eggshell (QES) composites. QES is a natural waste enriched in calcium carbonate. In this work, pure PANI was synthesized from chemical oxidation method and PANI/QES composites were prepared from physical mixing of QES with the synthesized PANI at different mass ratio. A series of complementary techniques including Fourier transform infrared and ultraviolet-visible spectrometers, scanning electron microscope with energy dispersive detection coupled with mapping, thermogravimetric analysis, and X-ray diffractometer were used to characterize the physicochemical and textural properties of the biocomposites. From the results, PANI/QES composite with a mass ratio of 1 exhibited the lowest NH₃ detection limit of 5.24 ppm with a linear correlation coefficient (R²) of close to unity (0.9932) between the signal and NH₃ gas concentration. As a whole, the PANI/QES biocomposites synthesized from this work exhibited excellent selectivity toward NH₃ gas even in the presence of other gas impurities, such as acetone, ethanol, and hexane. For the sensor reusability, the PANI/QES biocomposites can be reused in the application of NH₃ gas detection for at least 4 cycles.     

On stochastic comparisons of finite mixtures for some semiparametric families of distributions

In this paper, we consider the classical finite mixture model, which is an effective tool for modeling lifetime distributions for random samples from heterogeneous populations. We discuss new results on stochastic comparison for two finite mixtures when each of them is drawn from one of the following semiparametric families, i.e., proportional hazards, accelerated lifetime and proportional reversed hazards.     

An overlapping domain decomposition dual reciprocity method

We present a domain decomposition boundary integral equation method for two-dimensional partial differential equations. The overlapping Schwarz method is employed to improve the dual reciprocity boundary element method. The resulting algorithm turns out to be more accurate than a non-overlapping approach previously proposed. Some numerical results showing the improved accuracy and efficiency of the methods are given.     

Ice-slurry production using direct contact heat transfer

An ice slurry generation system was developed using direct contact heat transfer between water and the coolant, Fluroinert FC-84. The location of the coolant nozzle is an important design consideration to avoid clogging due to freezing of water. An ice fraction of up to about 40 percent was obtained with the nozzle located at the bottom of the ice slurry tank and the jet directed upwards into the water. Two simplified model were developed to extract the heat transfer coefficient between the coolant drops and the water. The first model requires as input the average drop diameter and the residence time while the second model uses the measured drop diameter distribution. The estimated heat transfer coefficients are much smaller than those computed using single-sphere correlations.     

A generalized equation for the prediction of melting temperatures of homopolymers and copolymers

A generalized equation was derived to calculate the melting temperatures of homopolymers and copolymers. The Gibbs‐Thomson equation for homopolymers and a modified application to copolymers were derived using the proposed equation. The melting temperature T_m⁰ in the Flory equation corresponds to the melting temperature T_m^C,∞ of copolymer crystals with stems of infinite length. Also, T_m^C,n*, the melting temperature for copolymer crystals with stems containing the maximum possible number of structural units, n*, should be used instead of T_m⁰ as the basis of supercooling in crystallization. The proposed equation shows good agreement with experimental data for α‐alkene‐ethylene homogeneous copolymers.     

On the kinetics of the autoxidation of fats: influence of pro‐oxidants,antioxidants and synergists

The influence of minor amounts of pro‐ and anti‐oxidants on the kinetics of the autoxidation of fat has been evaluated. The reaction rates of oxygen with the substrates were found to follow the same basic equation, hitherto established for pure substrates. There is evidence that the surface of the reaction vessel also acts as a reaction catalyst and its effect is proportional to the area of glass in contact with lipids. Oxidation is enhanced by trace metal ions as well as by surface‐active compounds (e.g. hydroperoxides and sterols). Antioxidants such as α‐tocopherol and butylated hydroxyanisole inhibit the oxidation by delaying the start of oxygen consumption (the induction period) while retarders like amino acids only decrease the rate of oxidation. Thus pro‐ and anti‐ oxidants affect either the start or the rate of oxygen consumption. The empirical formula dx/dt = k [O₂] (1‐x/n) f′(t) was found applicable to the different stages of oxidation.     

Evaluation of simple dynamic models and controllers for hydraulic and nozzle pressure in injection molding

Simple pseudo-steady state relations between the hydraulic and nozzle pressures of an injection molding machine were presented and verified experimentally. A simulation study was performed to evaluate the performance of simple controllers using dynamic models developed for the hydraulic and nozzle pressures. The controllers chosen were the discrete proportional, proportional-integral (PI), and proportional-integral-derivative (PID) types, tuned according to the ITAE criterion. The control of hydraulic pressure simulation showed that the PI controller had the best overall performance, whereas the result of nozzle pressure control loop simulation showed that the PID controller performance was better than that of the PI controller. All the controllers, in both loops, gave responses that were about an order of magnitude more rapid than the open loop response.     

A New Variable Diffusion Drying Model for the Second Falling Rate Period of Paddy Dried in a Rapid Bin Dryer

The objectives of this article is to propose a new drying model for the second falling rate period known as the variable diffusion controlled period that follows after the first falling rate period and to propose a new method to determine the second critical moisture content that separates these two periods. Experimental work on paddy drying at minimum fluidization velocity was carried out in a rapid bin dryer. The effects of operating temperatures (60-120°C) and bed depths (2-6 cm) on the paddy drying characteristics were investigated. It was found that the normalized drying rate of paddy was proportional to the normalized moisture content in the first falling rate period but in the second falling rate period, the normalized drying rate of the material varies exponentially with the normalized moisture content. The different relationship between the normalized drying rate and the normalized moisture content in the first and second falling rate periods indicate that two different mechanism of moisture transport are at work. The new exponential model of the second falling rate period and the linear model of the first falling rate period were found to fit the experimental data very well. Derivation from variable diffusion equation shows that the linear model is the result of constant diffusion coefficient whereas the new exponential model is the result of linear diffusion coefficient. This also implies that the first falling rate period is a constant diffusion controlled period and the second falling rate period is a variable diffusion controlled period. In addition, drying kinetics data of a drying process that fits the exponential model over a very slow drying period will show that the drying process is under the effect of a linear diffusion coefficient. It was also found that the proposed new method to determine the second critical moisture content that distinguishes between the first and second falling rate periods by using a sudden change in the value of the drying rate gradient to a much lower value at that point is more rigorous and yet simpler than the method of determining the specific location of the receding drying boundary since it is based on the behavior of the actual drying kinetic data.