Equilibrium swelling measurements of network and semicrystalline polymers in supercritical carbon dioxide using high-pressure NMR

The extent of swelling of cross-linked poly(dimethylsiloxane) and linear low-density poly(ethylene) in supercritical CO2 has been investigated using high-pressure NMR spectroscopy and microscopy. Poly(dimethylsiloxane) was cross-linked to four different cross-link densities and swollen in supercritical CO2. The Flory-Huggins interaction parameter, x, was found to be 0.62 at 300 bar and 45 degrees C, indicating that supercritical CO2 is a relatively poor solvent compared to toluene or benzene. Linear low-density poly(ethylene) was shown to exhibit negligible swelling upon exposure to supercritical CO2 up to 300 bar. The effect Of CO2 pressure on the amorphous region of the poly(ethylene) was investigated by observing changes in the H-1 T-2 relaxation times of the polymer. These relaxation times decreased with increasing pressure, which was attributed to a decrease in mobility of the polymer chains as a result of compressive pressure.

Microhardness mapping and the hardness-yield strength relationship in high-pressure diecast magnesium alloy AZ91

Microhardness maps of cross-sections of high-pressure diecast test bars of AZ91 have been determined. Specimens with rectangular cross-sections, 1, 2 and 3 mm thick, or with a circular cross-section 6.4 mm in diameter, have been studied. The hardness is generally higher near the edges in all specimens, and more so near the corners of the rectangular specimens. The hardness at the center of the castings is generally lower, due to a coarser solidification microstructure and the concentration of porosity. The evidence confirms that the surface of the castings is harder than the core, but it does not support the concept of a skin with a sharp. and definable boundary. This harder layer is irregular in hardness and depth and is not equally hard on opposite sides of the casting. The mean hardness obtained by integrating the microhardness maps over the entire cross-section increased with decreasing thickness of the bars, and was found to be in good correlation with each bar's yield strength. (c) 2005 Elsevier B.V. All rights reserved.

The design of a high pressure solvent extraction process using liquid ammonia as solvent

The literature on the potential use of liquid ammonia as a solvent for the extraction of aromatic hydrocarbons from mixtures with paraffins, and the application of reflux, has been reviewed. Reference is made to extractors suited to this application. A pilot scale extraction plant was designed comprising a Scm. diameter by 12Scm. high, 50 stage Rotating Disc Contactor with 2 external settlers. Provision was made for operation with, or without, reflux at a pressure of 10 bar and ambient temperature. The solvent recovery unit consisted of an evaporator, compressor and condenser in a refrigeration cycle. Two systems were selected for study, Cumene-n-Heptane-Ammonia and Toluene-Methylcyclohexane-Ammonia. Equlibrium data for the first system was determined experimentally in a specially-designed, equilibrium bomb. A technique was developed to withdraw samples under pressure for analysis by chromatography and titration. The extraction plant was commissioned with a kerosine-water system; detailed operating procedures were developed based on a Hazard and Operability Study. Experimental runs were carried out with both ternary ammonia systems. With the system Toluene-Methylcyclohexane-Ammonia the extraction plant and the solvent recovery facility, operated satisfactorily, and safely,in accordance with the operating procedures. Experimental data gave reasonable agreement with theory. Recommendations are made for further work with plant.

Development of a novel magnetic resonance imaging contrast agent for pressure measurements using lipid-coated microbubbles

The aim of this study was to prepare gas-filled lipid-coated microbubbles as potential MRI contrast agents for imaging of fluid pressure. Air-filled microbubbles were produced with phospholipid 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) in the presence or absence of cholesterol and/or polyethylene-glycol distearate (PEG-distearate). Microbubbles were also prepared containing a fluorinated phospholipid, perfluoroalkylated glycerol-phosphatidylcholine, F-GPC shells encompassing perfluorohexane-saturated nitrogen gas. These microbubbles were evaluated in terms of physico-chemical characteristics such as size and stability. In parallel to these studies, DSPC microbubbles were also formulated containing nitrogen (N2) gas and compared to air-filled microbubbles. By preventing advection, signal drifts were used to assess their stability. DSPC microbubbles were found to have a drift of 20% signal change per bar of applied pressure in contrast to the F-GPC microbubbles which are considerably more stable with a lower drift of 5% signal change per bar of applied pressure. By increasing the pressure of the system and monitoring the MR signal intensity, the point at which the majority of the microbubbles have been damaged was determined. For the DSPC microbubbles this occurs at 1.3 bar whilst the F-GPC microbubbles withstand pressures up to 2.6 bar. For the comparison between air-filled and N2-filled microbubbles, the MRI sensitivity is assessed by cycling the pressure of the system and monitoring the MR signal intensity. It was found that the sensitivity exhibited by the N2-filled microbubbles remained constant, whilst the air-filled microbubbles demonstrated a continuous drop in sensitivity due to continuous bubble damage.

Robust spatially resolved pressure measurements using MRI with novel buoyant advection-free preparations of stable microbubbles in polysaccharide gels

MRI of fluids containing lipid coated microbubbles has been shown to be an effective toot for measuring the local fluid pressure. However, the intrinsically buoyant nature of these microbubbles precludes lengthy measurements due to their vertical migration under gravity and pressure-induced coalescence. A novel preparation is presented which is shown to minimize both these effects for at least 25 min. By using a 2% polysaccharide gel base with a small concentration of glycerol and 1,2-distearoyl-sn-glycero-3-phosphocholine coated gas microbubbles, MR measurements are made for pressures between 0.95 and 1.44 bar. The signal drifts due to migration and amalgamation are shown to be minimized for such an experiment whilst yielding very high NMR sensitivities up to 38% signal change per bar.

Three-dimensional fluid pressure mapping in porous media using magnetic resonance imaging with gas-filled liposomes

This paper presents and demonstrates a method for using magnetic resonance imaging to measure local pressure of a fluid saturating a porous medium. The method is tested both in a static system of packed silica gel and in saturated sintered glass cylinders experiencing fluid flow. The fluid used contains 3% gas in the form of 3-μm average diameter gas filled 1,2-distearoyl-sn-glycero-3-phosphocholine (C18:0, MW: 790.16) liposomes suspended in 5% glycerol and 0.5% Methyl cellulose with water. Preliminary studies at 2.35 T demonstrate relative magnetic resonance signal changes of 20% per bar in bulk fluid for an echo time TE=40 ms, and 6-10% in consolidated porous media for TE=10 ms, over the range 0.8-1.8 bar for a spatial resolution of 0.1 mm3 and a temporal resolution of 30 s. The stability of this solution with relation to applied pressure and methods for improving sensitivity are discussed. © 2007 Elsevier Inc. All rights reserved.

ANALYSIS OF HYPORHEIC FLOW INDUCED BY A BAR IN A GRAVEL STREAM: AN EXPERIMENTAL STUDY

Pipelines are one of the safest means to transport crude oil, but are not spill-free. This is of concern in North America, due to the large volumes of crude oil shipped by Canadian producers and the lengthy network of pipelines. Each pipeline crosses many rivers, supporting a wide variety of human activities, and rich aquatic life. However, there is a knowledge gap on the risks of contamination of river beds due to oil spills. This thesis addresses this knowledge gap by focussing on mechanisms that transport water (and contaminants) from the free surface flow to the bed sediments, and vice-versa. The work focuses on gravel rivers, in which bed sediments are sufficiently permeable that pressure gradients caused by the interactions of flow with topographic elements (gravel bars), or changes in direction induce exchanges of water between the free surface flow and the bed, known as hyporheic flows. The objectives of the thesis are: to present a new method to visualize and quantify hyporheic flows in laboratory experiments; to conduct a novel series of experiments on hyporheic flow induced by a gravel bar under different free surface flows. The new method to quantify hyporheic flows rests on injections of a solution of dye and water. The method yielded accurate flow lines, and reasonable estimates of the hyporheic flow velocities. The present series of experiments was carried out in a 11 m long, 0.39 m wide, and 0.41 m deep tilting flume. The gravel had a mean particle size of 7.7 mm. Different free surface flows were imposed by changing the flume slope and flow depth. Measured hyporheic flows were turbulent. Smaller free surface flow depths resulted in stronger hyporheic flows (higher velocities, and deeper dye penetration into the sediment). A significant finding is that different free surface flows (different velocities, Reynolds number, etc.) produce similar hyporheic flows as long as the downstream hydraulic gradients are similar. This suggests, that for a specified bar geometry, the characteristics of the hyporheic flows depend on the downstream hydraulic gradients, and not or only minimally on the internal dynamics of the free surface flow.

Nonlinear soil-structure interaction for buried pressure pipes under differential ground motion

Pipelines extend thousands of kilometers across wide geographic areas as a network to provide essential services for modern life. It is inevitable that pipelines must pass through unfavorable ground conditions, which are susceptible to natural disasters. This thesis investigates the behaviour of buried pressure pipelines experiencing ground distortions induced by normal faulting. A recent large database of physical modelling observations on buried pipes of different stiffness relative to the surrounding soil subjected to normal faults provided a unique opportunity to calibrate numerical tools. Three-dimensional finite element models were developed to enable the complex soil-structure interaction phenomena to be further understood, especially on the subjects of gap formation beneath the pipe and the trench effect associated with the interaction between backfill and native soils. Benchmarked numerical tools were then used to perform parametric analysis regarding project geometry, backfill material, relative pipe-soil stiffness and pipe diameter. Seismic loading produces a soil displacement profile that can be expressed by isoil, the distance between the peak curvature and the point of contraflexure. A simplified design framework based on this length scale (i.e., the Kappa method) was developed, which features estimates of longitudinal bending moments of buried pipes using a characteristic length, ipipe, the distance from peak to zero curvature. Recent studies indicated that empirical soil springs that were calibrated against rigid pipes are not suitable for analyzing flexible pipes, since they lead to excessive conservatism (for design). A large-scale split-box normal fault simulator was therefore assembled to produce experimental data for flexible PVC pipe responses to a normal fault. Digital image correlation (DIC) was employed to analyze the soil displacement field, and both optical fibres and conventional strain gauges were used to measure pipe strains. A refinement to the Kappa method was introduced to enable the calculation of axial strains as a function of pipe elongation induced by flexure and an approximation of the longitudinal ground deformations. A closed-form Winkler solution of flexural response was also derived to account for the distributed normal fault pattern. Finally, these two analytical solutions were evaluated against the pipe responses observed in the large-scale laboratory tests.

Comparison Of Postoperative Stability Of Three Rigid Internal Fixation Techniques After Sagittal Split Ramus Osteotomy For Mandibular Advancement.

The aim of this investigation was to compare the skeletal stability of three different rigid fixation methods after mandibular advancement. Fifty-five class II malocclusion patients treated with the use of bilateral sagittal split ramus osteotomy and mandibular advancement were selected for this retrospective study. Group 1 (n = 17) had miniplates with monocortical screws, Group 2 (n = 16) had bicortical screws and Group 3 (n = 22) had the osteotomy fixed by means of the hybrid technique. Cephalograms were taken preoperatively, 1 week within the postoperative care period, and 6 months after the orthognathic surgery. Linear and angular changes of the cephalometric landmarks of the chin region were measured at each period, and the changes at each cephalometric landmark were determined for the time gaps. Postoperative changes in the mandibular shape were analyzed to determine the stability of fixation methods. There was minimum difference in the relapse of the mandibular advancement among the three groups. Statistical analysis showed no significant difference in postoperative stability. However, a positive correlation between the amount of advancement and the amount of postoperative relapse was demonstrated by the linear multiple regression test (p < 0.05). It can be concluded that all techniques can be used to obtain stable postoperative results in mandibular advancement after 6 months.

Study Of The Homogeneity Of Drug Loaded In Polymeric Films Using Near-infrared Chemical Imaging And Split-plot Design.

Split-plot design (SPD) and near-infrared chemical imaging were used to study the homogeneity of the drug paracetamol loaded in films and prepared from mixtures of the biocompatible polymers hydroxypropyl methylcellulose, polyvinylpyrrolidone, and polyethyleneglycol. The study was split into two parts: a partial least-squares (PLS) model was developed for a pixel-to-pixel quantification of the drug loaded into films. Afterwards, a SPD was developed to study the influence of the polymeric composition of films and the two process conditions related to their preparation (percentage of the drug in the formulations and curing temperature) on the homogeneity of the drug dispersed in the polymeric matrix. Chemical images of each formulation of the SPD were obtained by pixel-to-pixel predictions of the drug using the PLS model of the first part, and macropixel analyses were performed for each image to obtain the y-responses (homogeneity parameter). The design was modeled using PLS regression, allowing only the most relevant factors to remain in the final model. The interpretation of the SPD was enhanced by utilizing the orthogonal PLS algorithm, where the y-orthogonal variations in the design were separated from the y-correlated variation.

Nebivolol Reduces Central Blood Pressure In Stage I Hypertensive Patients: Experimental Single Cohort Study.

Assessment of central blood pressure (BP) has grown substantially over recent years because evidence has shown that central BP is more relevant to cardiovascular outcomes than peripheral BP. Thus, different classes of antihypertensive drugs have different effects on central BP despite similar reductions in brachial BP. The aim of this study was to investigate the effect of nebivolol, a β-blocker with vasodilator properties, on the biochemical and hemodynamic parameters of hypertensive patients. Experimental single cohort study conducted in the outpatient clinic of a university hospital. Twenty-six patients were recruited. All of them underwent biochemical and hemodynamic evaluation (BP, heart rate (HR), central BP and augmentation index) before and after 3 months of using nebivolol. 88.5% of the patients were male; their mean age was 49.7 ± 9.3 years and most of them were overweight (29.6 ± 3.1 kg/m2) with large abdominal waist (102.1 ± 7.2 cm). There were significant decreases in peripheral systolic BP (P = 0.0020), diastolic BP (P = 0.0049), HR (P < 0.0001) and central BP (129.9 ± 12.3 versus 122.3 ± 10.3 mmHg; P = 0.0083) after treatment, in comparison with the baseline values. There was no statistical difference in the augmentation index or in the biochemical parameters, from before to after the treatment. Nebivolol use seems to be associated with significant reduction of central BP in stage I hypertensive patients, in addition to reductions in brachial systolic and diastolic BP.

Effects Of High Pressure Homogenization On The Activity, Stability, Kinetics And Three-dimensional Conformation Of A Glucose Oxidase Produced By Aspergillus Niger.

High pressure homogenization (HPH) is a non-thermal method, which has been employed to change the activity and stability of biotechnologically relevant enzymes. This work investigated how HPH affects the structural and functional characteristics of a glucose oxidase (GO) from Aspergillus niger. The enzyme was homogenized at 75 and 150 MPa and the effects were evaluated with respect to the enzyme activity, stability, kinetic parameters and molecular structure. The enzyme showed a pH-dependent response to the HPH treatment, with reduction or maintenance of activity at pH 4.5-6.0 and a remarkable activity increase (30-300%) at pH 6.5 in all tested temperatures (15, 50 and 75°C). The enzyme thermal tolerance was reduced due to HPH treatment and the storage for 24 h at high temperatures (50 and 75°C) also caused a reduction of activity. Interestingly, at lower temperatures (15°C) the activity levels were slightly higher than that observed for native enzyme or at least maintained. These effects of HPH treatment on function and stability of GO were further investigated by spectroscopic methods. Both fluorescence and circular dichroism revealed conformational changes in the molecular structure of the enzyme that might be associated with the distinct functional and stability behavior of GO.

Taurine Supplementation Reduces Blood Pressure And Prevents Endothelial Dysfunction And Oxidative Stress In Post-weaning Protein-restricted Rats.

Taurine is a sulfur-containing amino acid that exerts protective effects on vascular function and structure in several models of cardiovascular diseases through its antioxidant and anti-inflammatory properties. Early protein malnutrition reprograms the cardiovascular system and is linked to hypertension in adulthood. This study assessed the effects of taurine supplementation in vascular alterations induced by protein restriction in post-weaning rats. Weaned male Wistar rats were fed normal- (12%, NP) or low-protein (6%, LP) diets for 90 days. Half of the NP and LP rats concomitantly received 2.5% taurine supplementation in the drinking water (NPT and LPT, respectively). LP rats showed elevated systolic, diastolic and mean arterial blood pressure versus NP rats; taurine supplementation partially prevented this increase. There was a reduced relaxation response to acetylcholine in isolated thoracic aortic rings from the LP group that was reversed by superoxide dismutase (SOD) or apocynin incubation. Protein expression of p47phox NADPH oxidase subunit was enhanced, whereas extracellular (EC)-SOD and endothelial nitric oxide synthase phosphorylation at Ser 1177 (p-eNOS) were reduced in aortas from LP rats. Furthermore, ROS production was enhanced while acetylcholine-induced NO release was reduced in aortas from the LP group. Taurine supplementation improved the relaxation response to acetylcholine and eNOS-derived NO production, increased EC-SOD and p-eNOS protein expression, as well as reduced ROS generation and p47phox expression in the aortas from LPT rats. LP rats showed an increased aortic wall/lumen ratio and taurine prevented this remodeling through a reduction in wall media thickness. Our data indicate a protective role of taurine supplementation on the high blood pressure, endothelial dysfunction and vascular remodeling induced by post-weaning protein restriction. The beneficial vascular effect of taurine was associated with restoration of vascular redox homeostasis and improvement of NO bioavailability.

Onset Of Hypertension During Pregnancy Is Associated With Long-term Worse Blood Pressure Control And Adverse Cardiac Remodeling.

Up to 20% of women with hypertensive pregnancy disorders might persist with chronic hypertension. This study compared clinical and echocardiographic features between women whose hypertension began as hypertensive pregnancy disorders (PH group) and women whose diagnosis of hypertension did not occur during pregnancy (NPH group). Fifty PH and 100 NPH women were cross-sectionally evaluated by clinical, laboratory, and echocardiography analysis, and the groups were matched by duration of hypertension. PH exhibited lower age (46.6 ± 1.4 vs. 65.3 ± 1.1 years; P < .001), but higher systolic (159.8 ± 3.9 vs. 148.0 ± 2.5 mm Hg; P = .009) and diastolic (97.1 ± 2.4 vs. 80.9 ± 1.3 mm Hg; P < .001) blood pressure than NPH, although used more antihypertensive classes (3.4 ± 0.2 vs. 2.6 ± 0.1; P < .001). Furthermore, PH showed higher left ventricular wall thickness and increased prevalence of concentric hypertrophy than NPH after adjusting for age and blood pressure. In conclusion, this study showed that PH may exhibit worse blood pressure control and adverse left ventricular remodeling compared with NPH.

Unusual Erythrocyte Split Chimerism In Pregnancy After Allogeneic Stem Cell Transplantation.

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