Solubilities of Benzene Derivatives in Supercritical Carbon Dioxide

The solubilities of benzene derivatives in supercritical carbon dioxide was determined by the saturation method over the pressure range (9.5 to 14.5) MPa. The solubilities were determined at (308 and 313) K for 1-chloro-2,4-dinitrobenzene and (308, 318, and 328) K for m-dinitrobenzene. At 308K, the solubility (in mole fraction) of 1-chloro-2,4-dinitrobenzene varied from (2.83 to 5.88).10(-3) while the solubility of m-dinitrobenzene increased from (2.05 to 5.54).10(-3) as the pressure increased from (9.5 to 14.5) MPa. However, the solubilities of both compounds decreased with increasing temperature. Models based on the solubility parameter and semiempirical models such as the Mendez-Santiago-Teja model, the Gordillo model, and the association model, were used to correlate the experimental solubility data for the benzene derivatives.

Effect of Short Duration of Load increment on the Compressibility of Soils

This study concerns the effect of duration of load increment (up to 24 h) on the consolidation properties of expansive black cotton soil (liquid limit = 81%) and nonexpansive kaolinite (liquid limit = 49%). It indicates that the amount and rate of compression are not noticeably affected by the duration of loading for a standard sample of 25 mm in height and 76.2 mm in diameter with double drainage. Hence, the compression index and coefficient of consolidation can be obtained with reasonable accuracy even if the duration of each load increment is as short as 4 h. The secondary compression coefficient (C-alpha epsilon) for kaolinite can be obtained for any pressure range with 1/2 h of loading, which, however, requires 4 h for black cotton soil. This is because primary consolidation is completed early in the case of kaolinite. The paper proves that the conventional consolidation test can be carried out with much shorter duration of loading (less than 4 h) than the standard specification of 24 h or more even for remolded fine-grained soils.

Solubilities of resorcinol and pyrocatechol and their mixture in supercritical carbon dioxide

The equilibrium solubilities of dihydroxy benzene isomers (resorcinol and pyrocatechol) and its mixture were experimentally determined at different temperatures (308, 318, 328, and 338 K) in the pressure range of 9.8-16.2 MPa. In the ternary system, the solubilities of pyrocatechol increased while the solubilities of resorcinol decreased relative to their binary solubilities. A new association model was developed based on the concept of formation of solvate complex molecules to correlate the solubility of the solid for mixed solids in supercritical carbon dioxide (SCCO(2)). The model equation relates the solubility of solute in terms of the cosolute composition, temperature, pressure and density of SCCO(2). The proposed model correlated the solubilities of sixteen solid systems taken from the literature and current experimental data with an average absolute relative deviation (AARD) of around 4%. (C) 2011 Elsevier B.V. All rights reserved.

A new semi-empirical model for correlating the solubilities of solids in supercritical carbon dioxide with cosolvents

The equilibrium solubilities of the solids in supercritical carbon dioxide (SCCO(2)) are considerably enhanced in the presence of cosolvents. The solubilities of m-dinitrobenzene at 308 and 318 K over a pressure range of 9.5-14.5 MPa in the presence of 1.13-2.17 mol% methanol as cosolvent were determined. The average increase in the solubilities in the presence of methanol compared to that obtained in the absence of methanol was around 35%. A new semi-empirical equation in terms of temperature, pressure, density of SCCO(2) and cosolvent composition comprising of 7 adjustable parameters was developed. The proposed model was used to correlate the solubility of the solids in SCCO(2) for the 44 systems available in the literature along with current data. The average absolute relative deviation of the experimental data from the model equation was 3.58%, which is better than the existing models. (C) 2011 Elsevier B.V. All rights reserved.

Reactive pulsed laser deposition and characterization of niobium nitride thin films

We present a systematic study to explore the effect of important process variables on the composition and structure of niobium nitride thin films synthesized by Reactive Pulsed Laser Deposition (RPLD) technique through ablation of high purity niobium target in the presence of low pressure nitrogen gas. Secondary Ion Mass Spectrometry has been used in a unique way to study and fix gas pressure, substrate temperature and laser fluence, in order to obtain optimized conditions for one variable in single experimental run. The x-ray diffraction and electron microscopic characterization have been complemented by proton elastic backscattering spectroscopy and x-ray photoelectron spectroscopy to understand the incorporation of oxygen and associated non-stoichiometry in the metal to nitrogen ratio. The present study demonstrates that RPLD can be used for obtaining thin film architectures using non-equilibrium processing. Finally the optimized NbN thin films were characterized for their hardness using nano-indentation technique and found to be similar to 30 GPa at the deposition pressure of 8 Pa. (C) 2011 Elsevier B.V. All rights reserved.

Mixture solubilities of nitrobenzoic acid isomers in supercritical carbon dioxide

The ternary solubilities of solid isomers of nitrobenzoic acid (NBA) were experimentally determined at 308, 318 and 328K over a pressure range of 12-18 MPa in supercritical carbon dioxide (SCCO2). Compared to its binary solubility, the ternary solubilities of m-NBA increased at 308 K while it decreased at 328 K. However, the ternary solubilities of p-NBA increased at all temperatures and pressures except at 13 MPa and 328K. A new model was developed by applying solution model and activity coefficient model for the ternary solubilities of pharmaceutical and non-pharmaceutical solid mixtures in terms of temperature, density and cosolute composition. The model equation involves four temperature independent constraint-free parameters. The model equation correlates the ternary solubilities of seven pharmaceutical solid mixtures along with current data with an average AARD around 9.5% and sixteen non-pharmaceutical solid mixtures with 9% AARD. (C) 2012 Elsevier B.V. All rights reserved.

Measurement and correlation of quaternary solubilities of dihydroxybenzene isomers in supercritical carbon dioxide

The equilibrium quaternary solubilities of dihydroxybenzene (resorcinol + pyrocatechol + hydroquinone + SCCO2) isomers were experimentally determined at 308, 318 and 328K over a pressure range of 9.8-15.7 MPa by using a saturation method. The effects of temperature, pressure and the components on each other have been thoroughly investigated. The selectivity of SCCO2 for ternary (resorcinol + pyrocatechol + SCCO2) and quaternary systems was discussed. A new model equation for quaternary solubilities of solids has been developed by accounting for non-idealities by combining the solution model with Wilson activity coefficient model. The model equation has five adjustable parameters and correlates the quaternary solubilities of current data along with two other quaternary data reported in the literature. (C) 2012 Elsevier B.V. All rights reserved.

Experimental determination and activity coefficient based models for mixture solubilities of nitrophenol isomers in supercritical carbon dioxide

The experimental solubilities of the mixture of nitrophenol (m- and p-) isomers were determined at 308, 318 and 328 K over a pressure range of 10-17.55 MPa. Compared to the binary solubilities, the ternary solubilities of m-nitrophenol increased at 308, 318 and 328 K. The ternary solubilities of p-nitrophenol increased at 308 K, while the ternary solubilities decreased at lower pressures and increased at higher pressure at 318 and 328 K. The solubilities of the solid mixtures in supercritical carbon dioxide (SCCO2) were correlated with solution models by incorporating the non-idealities using activity coefficient based models. The Wilson and NRTL activity coefficient models were applied to determine the nature of the interactions between the molecules. The equation developed by using the NRTL model has three parameters and correlates mixture solubilities of solid solutes in terms of temperature and cosolute composition. The equation derived from the Wilson model contains five parameters and correlates solubilities in terms of temperature, density and cosolute composition. These two new equations developed in this work were used to correlate the solubilities of 25 binary solid mixtures including the current data. The average AARDs of the model equations derived using the NRTL and Wilson models for the solid mixtures were found to be 7% and 4%, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Solubilities of n-Butyl Esters in Supercritical Carbon Dioxide

The solubilities of butyl stearate and butyl laurate were determined in the temperature range of 308 K to 323 K and 313 K to 328 K, respectively, at pressures of 10 MPa to 16 MPa. The solubility of butyl laurate was higher than that of butyl stearate by almost an order in magnitude. Retrograde behavior was observed throughout the investigated pressure range. Semiempirical models such as Mendez-Teja, Chrastil, and other density-based models were used to correlate the experimental data of our work as well as several other liquid solutes.

DESIGN OF AN EXPERIMENTAL TEST FACILITY FOR SUPERCRITICAL CO2 BRAYTON CYCLE

A supercritical CO2 test facility is currently being developed at Indian Institute of Science, Bangalore, India to analyze the performance of a closed loop Brayton cycle for concentrated solar power (CSP) generation. The loop has been designed for an external heat input of 20 kW a pressure range of 75-135 bar, flow rate of 11 kg/min, and a maximum cycle temperature of 525 degrees C. The operation of the loop and the various parametric tests planned to be performed are discussed in this paper The paper addresses various aspects of the loop design with emphasis on design of various components such as regenerator and expansion device. The regenerator design is critical due to sharp property variations in CO2 occurring during the heat exchange process between the hot and cold streams. Two types of heat exchanger configurations 1) tube-in-tube (TITHE) and 2) printed circuit heat exchanger (PCHE) are analyzed and compared. A PCHE is found to be similar to 5 times compact compared to a TITHE for identical heat transfer and pressure drops. The expansion device is being custom designed to achieve the desired pressure drop for a range of operating temperatures. It is found that capillary of 5.5 mm inner diameter and similar to 2 meter length is sufficient to achieve a pressure drop from 130 to 75 bar at a maximum cycle temperature of 525 degrees C.

Temperature measurement of reflected shock wave by using chemical indicator

This report describes a new method for measuring the temperature of the gas behind the reflected shock wave in shock tube, corresponding to the reservoir temperature of a shock tunnel, based on the chemical reaction of small amount of CF4 premixed in the test gas. The final product C2F4 is used as the temperature indicator, which is sampled and detected by a gas chromatography in the experiment. The detected concentration of C2F4 is correlated to the temperature of the reflected shock wave with the initial pressure P-1 and test time tau as parameters in the temperature range 3 300 K < T < 5 600 K, pressure range 5 kPa < P1 <12 kPa and tau similar or equal to 0.4 ms.

Shock tube study of JP-10 ignition delay time

JP-10 (exo-tetrahydrodicyclopentadiene, C10H16) ignition delay times were measured in a preheated shock tube. The vapor pressures of the JP-10 were measured directly by using a high-precision vacuum gauge, to remedy the difficulty in determining the gaseous concentrations of heavy hydrocarbon fuel arising from the adsorption on the wall in shock tube experiments. The whole variation of pressure and emission of the OH or CH radicals were observed in the ignition process by a pressure transducer and a photomultiplier with a monochromator. The emission of the OH or CH radicals was used to identify the time to ignition. Experiments were performed over the pressure range of 151-556 kPa, temperature range of 1000-2100 K, fuel concentrations of 0.1%-0.55% mole fraction, and stoichiometric ratios of 0.25, 0.5, 1.0 and 2.0. The experimental results show that for the lower and higher temperature ranges, there are different dependency relationships of the ignition time on the temperature and the concentrations of JP-10 and oxygen.

Thermal cracking of aviation kerosene for scramjet applications

Thermal cracking of China No.3 aviation kerosene was studied experimentally and analytically under supercritical conditions relevant to regenerative cooling system for Mach-6 scramjet applications. A two-stage heated tube system with cracked products collection/analysis was used and it can achieve a fuel temperature range of 700-1100 K, a pressure range of 3.5-4.5 MPa and a residence time of approximately 0.5-1.3 s. Compositions of the cracked gaseous products and mass flow rate of the kerosene flow at varied temperatures and pressures were obtained experimentally. A one-step lumped model was developed with the cracked mixtures grouped into three categories: unreacted kerosene, gaseous products and residuals including liquid products and carbon deposits. Based on the model, fuel conversion on the mass basis, the reaction rate and the residence time were estimated as functions of temperature. Meanwhile, a sonic nozzle was used for the control of the mass flow rate of the cracked kerosene, and correlation of the mass flow rate gives a good agreement with the measurements.

Heat Transfer of Aviation Kerosene at Supercritical Conditions

The heat transfer characteristics of China no. 3 kerosene were investigated experimentally and analytically under conditions relevant to a regenerative cooling system for scramjet applications. A test facility developed for the present study can handle kerosene in a temperature range of 300-1000 K, a pressure range of 2.6-5 MPa, and a mass How rate range of 10-100 g/s. In addition, the test section was uniquely designed such that both the wall temperature and the bulk fuel temperature were measured at the same location along the flowpath. The measured temperature distributions were then used to analytically deduce the local heat transfer characteristics. A 10-component kerosene surrogate was proposed and employed to calculate the fuel thermodynamic and transport properties that were required in the heat transfer analysis. Results revealed drastic changes in the fuel flow properties and heat transfer characteristics when kerosene approached its critical state. Convective heat transfer enhancement was also found as kerosene became supercritical. The heat transfer correlation in the relatively low-fuel-temperature region yielded a similar result to other commonly used jet fuels, such as JP-7 and JP-8, at compressed liquid states. In the high-fuel-temperature region, near and beyond the critical temperature, heat transfer enhancement was observed; hence, the associated correlation showed a more significant Reynolds number dependency.

A small arc-heated plasma testing facility for thermal protection materials

Experimental research on a 150 kW arc-heated plasma testing facility was conducted. Stable plasma jets with different gas compositions, temperatures and velocities were obtained at chamber pressure between 400 Pa – 100 kPa. Stagnation ablation experiments were conducted on samples of typical super alloys used for thermal protection systems. The microstructure and hardness of alloys before and after ablation were compared.