High-Temperature, High-Pressure Viscosities and Densities of n-Hexadecane, 2,2,4,4,6,8,8-Heptamethylnonane, and Squalane Measured Using a Universal Calibration for a Rolling-Ball Viscometer/Densimeter

The development of reference correlations for viscous fluids is predicated on the availability of accurate viscosity data, especially at high pressure, high temperature (HPHT) conditions. The rolling ball viscometer (RBV) is a facile technique for obtaining such HPHT viscosity data. A new, universal RBV calibration methodology is described and applied over a broad T-p region and for a wide range of viscosities. The new calibration equation is used to obtain viscosities for n-hexadecane (HXD), 2,2,4,4,6,8,8-heptamethylnonane (HMN), and 2,6,10,15,19,23-hexamethyltetracosane (squalane) from 298 – 530 K and pressures to 250 MPa. The available literature data base for HMN is expanded to 520 K and 175 MPa and for squalane to 525 K and 250 MPa. The combined expanded uncertainties are 0.6% and 2.5% for the densities and viscosities, respectively, each with a coverage factor, k = 2. The reliability of the viscosity data is validated by comparison of HXD and squalane viscosities to accepted reference correlations and HMN viscosities to available literature data. The necessity of this new calibration approach is confirmed by the large deviations observed between HXD, HMN, and squalane viscosities determined using the new, universal RBV calibration equation and viscosities determined using a quadratic polynomial calibration equation. HXD, HMN, and squalane densities are predicted with the Perturbed Chain Statistical Associating Fluid Theory using pure component parameters calculated with a previously reported group contribution (GC) method. HXD, HMN, and squalane viscosities are compared to Free Volume Theory (FVT) predictions using FVT parameters calculated from a literature correlation for nalkanes. Although the FVT predictions for HXD, a normal alkane, result in an average absolute percent deviation (∆AAD) of 3.8%, predictions for HMN and squalane, two branched alkanes, are four to 13 times larger. The fit of the FVT model for the branched alkanes is dramatically improved if the FVT parameters are allowed to vary with temperature

Hydrogen peroxide filled poly(methyl methacrylate) microcapsules: potential oxygen delivery materials

This paper describes the synthesis of H2O2–H2O filled poly(methyl methacrylate) (PMMA) microcapsules as potential candidates for controlled O2 delivery. The microcapsules are prepared by a water-in-oil solvent emulsion and evaporation method. The results of this study describe the effect of process parameters on the characteristics of the microcapsules and on their in vitro performance. The size of the microcapsules, as determined from scanning electron microscopy, ranges from ∼5 to 30 μm and the size distribution is narrow. The microcapsules exhibit an internal morphology with entrapped H2O2–H2O droplets randomly distributed in the PMMA continuous phase. In vitro release studies of 4.5 wt% H2O2-loaded microcapsules show that ∼70% of the H2O2 releases in 24 h. This corresponds to a total O2 production of ∼12 cc/gram of dry microcapsules. Shelf-life studies show that the microcapsules retain ∼84 wt% of the initially loaded H2O2 after nine months storage at 2–8 °C, which is an attractive feature for clinical applications

Fluid properties at high pressures and temperatures: Experimental and modelling challenges

Thermophysical properties impact many aspects of the chemical process industries. Here three example areas, primarily in the energy sector, are highlighted to provide context for the experimental and modelling challenges associated with obtaining fluid property data at high pressures and temperatures (HPHT). These three areas include the recovery of petroleum reserves in ultra-deep reservoirs, the use of lubricants to reduce frictional losses in the automotive industries, and the use of high-pressure, common rail diesel fuel delivery to reduce soot emissions for greener environments. The accurate knowledge of thermodynamic and transport properties in these three focused areas minimizes associated operating uncertainties and accelerates safe, reliable, and robust process and product development

Interfacial tension of isomers n-hexadecane and 2,2,4,4,6,8,8-heptamethylnonane at high pressures and temperatures

Highly branched alkanes exhibit enhanced free volume relative to their straight chain analogs leading to increased solubility of sparingly soluble gases, such as N2, as well as lower hydrocarbon-gas interfacial tension (IFT) values. In this study high-pressure, high-temperature (HPHT) IFT data are reported for two C16 isomers, hexadecane (HXD) and heptamethylnonane (HMN), with N2 from ~298 to 573 K and pressures to 100 MPa. The IFT data are modeled with Density Gradient Theory (DGT) in conjunction with the Perturbed-Chain, Statistical Associating Fluid Theory equation of state (EoS) with pure component parameters calculated with three different group contribution (GC) methods. One GC method (B-GC) is developed from a database of high-pressure density data and the other two GC methods (S-GC and T-GC) are developed from a large database of pure component vapor pressure and saturated liquid density data. DGT calculations incorporating the B-GC method reasonably represent the IFT for both HXD + N2 and HMN + N2 at low temperatures, but result in significant deviations from experimental IFT values at high temperatures. The S-GC method provides improved IFT predictions relative to the B-GC method at high temperatures, but S-GC predictions are inferior to those obtained using the T-GC method. The superior performance of the T-GC method is attributed to the use of second order GC parameters and to the ability of this method to more correctly predict EoS parameters for both normal and branched alkanes

General method for prediction of thermal conductivity for well-characterized hydrocarbon mixtures and fuels up to extreme conditions using entropy scaling

A general and efficient technique is developed to predict the thermal conductivity of well-characterized hydrocarbon mixtures, rocket propellant (RP) fuels, and jet fuels up to high temperatures and high pressures (HTHP). The technique is based upon entropy scaling using the group contribution method coupled with the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) equation of state. The mixture number averaged molecular weight and hydrogen to carbon ratio are used to define a single pseudo-component to represent the compounds in a well-characterized hydrocarbon mixture or fuel. With these two input parameters, thermal conductivity predictions are less accurate when the mixture contains significant amounts of iso-alkanes, but the predictions improve when a single thermal conductivity data point at a reference condition is used to fit one model parameter. For eleven binary mixtures and three ternary mixtures at conditions from 288 to 360 K and up to 4,500 bar, thermal conductivities are predicted with mean absolute percent deviations (MAPDs) of 16.0 and 3.0% using the two-parameter and three-parameter models, respectively. Thermal conductivities are predicted for three RP fuels and three jet fuels at conditions from 293 to 598 K and up to 700 bar with MAPDs of 14.3 and 2.0% using the two-parameter and three-parameter models, respectively

Factorial analysis of variables affecting bone stress adjacent to mini-implants used for molar distalization by direct anchorage—A finite element study

OBJECTIVE: The aim of this study was to investigate the stresses on mini-implant, cortical bone, and cancellous bone for maxillary molar distalization using an orthodontic implant in a finite element model for different angulations and depths of insertion. METHODS: A three-dimensional finite element method was used to simulate overall orthodontic tooth movements by using ANSYS software. The maxillary bone and the molars were reproduced using CT scan images and conversion of the same into STL file was done. Finite element model was generated and the effect of forces was studied on the model for different depths and angulations of mini-implant insertions. The distalization force was exerted by an open-coil spring and the direct skeletal anchorage was provided by a mini-implant. Mini-implants were placed in depths of 5 mm, 7 mm, and 9 mm inside the bone and insertion angles of 30°, 60°, and 90°. Stresses on mini-implant and extent of stress on the surrounding bone were assessed by the software. RESULTS: 1. Least stress was found when the mini-implant was inserted at an angle of 30°, as it is nearer to the stronger cortical bone. 2. As the length of the mini-implant increases, accompanied by the increase in the depth of insertion, a decrease in stress in the mini-implant, cortical bone, and cancellous bone was noticed. CONCLUSION: An increase in the insertion angle from 30° to 90° increases the stresses on both the implant and the cortical bone. A higher depth of thread in the bone helps in reducing the stress on the implant, cortical bone, and cancellous bone. This helps in improving the primary stability of the mini-implant and its life

Phase Behavior and Densities of Propylene + Hexane Binary Mixtures to 585 K and 70 MPa

In this study, we report phase behavior data for propylene + hexane mixtures at temperatures of 295 to 468 K and pressures to 5.5 MPa and high-pressure mixture density data at temperatures of 295 to 584 K and pressures to 70 MPa. Both the phase behavior and density data are simultaneously determined using a variable volume, high-pressure view cell that is coupled with a linear variable differential transformer. The phase behavior and mixture density data are modeled with the Soave–Redlich–Kwong (SRK), Peng–Robinson (PR), modified Sanchez–Lacombe (MSL), and perturbed-chain statistical associating fluid theory (PC-SAFT) equations of state (EoS). The PC-SAFT and MSL EoS provide the best fit of the phase behavior data with a nonzero value of 0.028 for <i>k</i>_<i>ij</i>. Likewise, the PC-SAFT EoS provides the best fit of the high-pressure mixture density data, though the PC-SAFT equation slightly overpredicts the solution density and the calculated densities are relatively insensitive to changes in <i>k</i>_<i>ij</i> from zero to 0.028