High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

Ultra high-pressure homogenized emulsions stabilized by sodium caseinate: effects of protein concentration and pressure on emulsions structure and stability

Microstructure, physical properties and oxidative stability of emulsions treated by colloid mill (CM), conventional homogenization (CH, 15 MPa) and ultra-high-pressure homogenization (UHPH, 100–300 MPa) by using different concentrations of 1, 3 and 5 g/100 g of sodium caseinate (SC), were evaluated. The application of UHPH treatment at 200 and 300 MPa resulted in emulsions that were highly stable to creaming and oxidation, especially when the protein content increased from 1 to 3 and 5 g/100 g. Further, increasing the protein content to 3 and 5 g/100 g in UHPH emulsions tended to change the rheological behavior from Newtonian to shear thinning. CH emulsions containing 1 g/100 g of protein exhibited Newtonian flow behavior with lower tendencies to creaming compared to those formulated with 3 or 5 g/100 g. This study has proved that UHPH processing at pressures (200–300 MPa) and in the presence of sufficient amount of sodium caseinate (5 g/100 g), produces emulsions with oil droplets in nano-/submicron scale with a narrow size distribution and high physical and oxidative stabilities, compared to CM and CH treatments.

Pharmacology of the Human Saphenous Vein

Nowadays, the great saphenous vein is the vascular conduit that is most frequently employed in coronary and peripheral revascularization surgery. It is known that saphenous vein bypass grafts have shorter patency than arterial ones, partly because the wall of the normal saphenous vein has different structural and functional characteristics. The features of this vein can be affected by the large distention pressures it is submitted to during its preparation and insertion into the arterial system. Indeed, a vein graft is subjected to considerable changes in hemodynamic forces upon implantation into the arterial circulation, since it is transplanted from a non-pulsatile, low-pressure, low-flow environment with minimal shear stress to a high-pressure system with pulsatile flow, where it undergoes cyclic strain and elevated shear. These changes can be responsible for functional and morphological alterations in the vessel wall, culminating in intima hyperproliferation and atherosclerotic degeneration, which contribute to early graft thrombosis. This review has followed a predetermined strategy for updating information on the human saphenous vein (HSV). Besides presenting the aspects relative to the basic pharmacology, this text also includes surgical aspects concerning HSV harvesting, the possible effects of the major groups of cardiovascular drugs on the HSV, and finally the interference of major cardiovascular diseases in the vascular reactivity of the HSV.

Paineilmajärjestelmän ja -hankinnan kehittäminen sementtitehtaalla

Työn tavoitteena oli kartoittaa Lappeenrannan sementtitehtaan paineilmajärjestelmä, tehdä järjestelmän kehittämissuunnitelma ja arvioida suunnitelman mukaisen investoinnin kannattavuus investointilaskelmilla. Kartoituksesta selviää paineilman hankinnan toteutus, järjestelmään kuuluvien laitteiden selvitys ja energiankulutus sekä jakeluverkon ja paineilman käytön kartoitus. Kartoituksen ja aineiston pohjalta laadittiin suunnitelma järjestelmän kehittämiseksi. Aineistoa kerättiin haastattelemalla laitetoimittajia sekä muiden sementtitehtaiden johtoa. Paineilman käyttöä tehostettiin ja tehtaan matalapaine- eli kuumailmaverkon osalta tehtiin suunnitelmat sen täydellisestä uusimisesta. Tehtaan korkeapaine- eli yleisilmaverkkoon päätettiin olla investoimatta työssä esiteltävien käytännön syiden vuoksi. Investoinnin taloudellinen kannattavuus arvioitiin työhön rakennetulla investointilaskentamallilla. Sen avulla laskettiin investoinnin kannattavuus annuiteettimenetelmällä. Laskelmien tulokseen liittyvä epävarmuus arvioitiin myös malliin rakennetulla herkkyysanalyysillä. Lisäksi mallilla vertailtiin investoinnin eri hankintavaihtoehtojen kannattavuutta. Investointi osoittautui kannattavaksi.

Combinación de sistemas de flujo de baja y alta presion para la determinacion de Mg, Ca y Sr en salmueras por espectrofotometria de absorcion atomica con llama

This article describes the combination of low- and high-pressure flow systems for the determination of Magnesium, Calcium and Strontium by flame atomic absorption spectrometry (FAAS). In the low-pressure system a short C-18 RP column (length 0,5 cm) was utilized for the preconcentration/matrix separation step, xylenol orange was used as chelating agent and tetrabutylamonium acetate for ion pair formation. The hydraulic high pressure nebulization (HHPN) was used for sample transport and sample introduction in the high pressure system. The repeatabilities and detection limits for Mg, Ca and Sr were determined and compared with those obtained by pneumatic nebulization (PN). The results show that the detection limits obtained using the HHPN for Mg, Ca and Sr are between 1.5 to 2 times better than those obtained by PN when the signal transient was measured in area. The system presented a sampling frequency of 130 h-1 for direct determination of Mg, Ca or Sr in samples of saturated sodium chloride used in the production of chlorine and sodium hydroxide.

Rainfall Climatology over Middle East Region and its Variability

A better understanding of the rainfall climatology of the Middle East region identifying the mechanisms responsible for the rain producing systems is essential for effective utilization of the water resources over the arid region. A comprehensive analysis on the rainfall climatology of the Middle East region is carried out to bring out the spatial and temporal variation of rainfall and mechanisms responsible for the rain events. The study was carried out utilizing rainfall, OLR, wind and humidity data sets procured from TRMM, NOAA and NCEP-NCAR. Climatology of annual rainfall brings out two areas of alarmingly low rainfall in the Middle East region: one in Egypt, Jordan and adjoining areas and the other in the southern part of Saudi Arabia. Daily rainfall analysis indicates that northern region gets rainfall mainly during winter and spring associated with the passage of Mediterranean low pressure systems whereas rain over the southern region is caused mainly by the monsoon organized convection, cross equatorial flow and remnants of low pressure systems associated with the monsoon during the summer season. Thermodynamic structure of the atmosphere reveals that the region does not have frequent local convection due to insufficient moisture content. The sinking motion associated with the sub tropic high pressure system and subsidence associated with the Walker circulation are responsible for maintaining warm and dry air over the region.

Effect of different methods of cutting fluid application on turning of a difficult-to-machine steel (SAE EV-8)

In this study, different methods of cutting fluid application are used in turning of a difficult-to-machine steel (SAE EV-8). Initially, a semisynthetic cutting fluid was applied using a conventional method (i.e. overhead flood cooling), minimum quantity of cutting fluid, and pulverization. A lubricant of vegetable oil (minimum quantity of lubricant) was also applied using the minimum quantity method. Thereafter, a cutting fluid jet under high pressure (3.0 MPa) was singly applied in the following regions: chip-tool interface, top surface of the chip (between workpiece and chip) and tool-workpiece contact. Moreover, two other methods were used: an interflow between conventional application and chip-tool interface jet (combined method) and, finally, three jets simultaneously applied. In order to carry out these tests, it was necessary to set up a high-pressure system using a piston pump for generating a cutting fluid jet, a venturi for fluid application (minimum quantity of cutting fluid and minimum quantity of lubricant) and a nozzle for cutting fluid pulverization. The output variables analyzed included tool life, surface roughness, cutting tool temperature, cutting force, chip form, chip compression rate and machined specimen microstructure. Among the results, it can be observed that the tool life increases and the cutting force decreases with the application of cutting fluid jet, mainly when it is directed to the chip-tool interface. Excluding the methods involving jet fluid, the conventional method seems to be more efficient than other methods of low pressure, such as minimum quantity of volume and pulverization, when considering just the cutting tool wear. © 2013 IMechE.

Different methods of cutting fluid application on turning of a difficult-to-machine steel

Different methods of cutting fluid application are used on turning of a difficult-tomachine steel (SAE EV-8). A semi-synthetic cutting fluid was applied using a conventional method, minimum quantity of cutting fluid (MQCF), and pulverization. By the minimum quantity method was also applied a lubricant of vegetable oil (MQL). Thereafter, a cutting fluid jet under high pressure (3.0 MPa) was singly applied in the following regions: chip-tool interface; top surface of the chip; and tool-workpiece contact. Two other methods were used: an interflow between conventional application and chip-tool interface jet and, finally, three jets simultaneously applied. In order to carry out these tests, it was necessary to set up a high pressure system using a piston pump for generating a cutting fluid jet, a Venturi for fluid application (MQCF and MQL), and a nozzle for cutting fluid pulverization. The output variables analyzed included tool life, surface roughness, cutting tool temperature, cutting force, chip form, chip compression rate and machined specimen microstructure. It can be observed that the tool life increases and the cutting force decreases with the application of cutting fluid jet, mainly when it is directed to the chip-tool interface. Excluding the methods involving jet fluid, the conventional method seems to be more efficient than other methods of low pressure. © (2013) Trans Tech Publications, Switzerland.

Solar forcing of North Atlantic surface temperature and salinity over the past millennium

There were several centennial-scale fluctuations in the climate and oceanography of the North Atlantic region over the past 1,000 years, including a period of relative cooling from about AD 1450 to 1850 known as the Little Ice Age1. These variations may be linked to changes in solar irradiance, amplified through feedbacks including the Atlantic meridional overturning circulation2. Changes in the return limb of the Atlantic meridional overturning circulation are reflected in water properties at the base of the mixed layer south of Iceland. Here we reconstruct thermocline temperature and salinity in this region from AD 818 to 1780 using paired δ18O and Mg/Ca ratio measurements of foraminifer shells from a subdecadally resolved marine sediment core. The reconstructed centennial-scale variations in hydrography correlate with variability in total solar irradiance. We find a similar correlation in a simulation of climate over the past 1,000 years. We infer that the hydrographic changes probably reflect variability in the strength of the subpolar gyre associated with changes in atmospheric circulation. Specifically, in the simulation, low solar irradiance promotes the development of frequent and persistent atmospheric blocking events, in which a quasi-stationary high-pressure system in the eastern North Atlantic modifies the flow of the westerly winds. We conclude that this process could have contributed to the consecutive cold winters documented in Europe during the Little Ice Age.

Geochemistry and paleontology of sediment core GeoB3359-3

A geochemical and paleontological reconstruction of paleoproductivity, upwelling intensity and sea surface temperature (SST) off central Chile at 35°S (GeoB3359-3) reveals marked changes from the Last Glacial Maximum (LGM) through the Early Holocene. Surface-water productivity was determined by the interaction between the atmospheric (the Southern Westerlies) and oceanographic (the Antarctic Circumpolar Current, ACC) systems from the LGM through early Termination I (TI). The northward shift of the climate zones during the LGM brought the ACC, as the main macronutrient source, closer to the GeoB3359-3, SST lowered, and surface water productivity and accumulation rates of biogenic components enhanced. With the poleward return of the Southern Westerlies and the ACC, the subtropical high-pressure system became the dominant atmospheric component southward till 35°S during the late TI and Early Holocene and caused surface water productivity to increase through enhanced upwelling.

A late Quaternary planktonic foraminifer faunal record of rapid climatic changes of sediment core GIK17938-2

A high-resolution planktonic foraminifer record from a core recovered from the South China Sea (SCS) (Sonne 17938-2: 19°47.2'N, 117° 32.3E; 2840 m; Delta t c. 250-1000 years) shows rapid millennial-scale changes in the western Pacific marginal sea climate during the last 30,000 years. The SCS is the largest western Pacific marginal sea off the southeast Asian continent, the area today dominated by seasonal monsoon changes. Quantitative analyses of planktonic foraminifer faunal abundance data frorn the core indicate large downcore variations in the relative abundances of the dominant taxa since about 30,000 years ago in the isotope stage 3. Further analyses indicate that the abundance of G. inflata, a good indicator species for cold SST (~13°-19°C) and deep MLD (~100-125 m) waters shows abrupt shifts. During stages 2 and 3, the abundance record of G. infiata tends to be punctuated by quasi-periodie short intervals (~2000-3000 yrs) where its abundance reaches 15% or greater, superimposed on generally low (5-10%) background values. This pattern suggests an instability of surface ocean conditions of the SCS during the past 30,000 years. The abrupt abundance changes of G. infiata correlate well with similar climatic changes observed from a GISP2 ice core 8180, and North Atlantic core DSDP 609 N. pachyderma (s.) and lithic grain abundances during 'Heinrich evcnts'. These results suggest that the millennial-scale variability of climate is not peculiar to the Atlantic region. Apparently, the rapid SCS climatic changes during Heinrich events are driven by effective mechanisms, of particularly the effects of shifts in the latitudinal position of the Siberia High Pressure System.

Differences into HT and HTO concentrations in air into the Western Mediterranean Basin and Continental Europe and Safety Related Issues.

Real time Tritium concentrations in air in two chemical forms, HT and HTO, coming from an ITER-like fusion reactor as source were coupled the European Centre Medium Range Weather Forecast (ECMWF) numerical model with the Lagrangian Atmospheric-particle dispersion model FLEXPART. This tool was analyzed in nominal tritium discharge operational reference and selected incidental conditions affecting the Western Mediterranean Basin during 45 days during summer 2010 together with surface “wind observations” or weather data based in real hourly observations of wind direction and velocity providing a real approximation of the tritium behavior after the release to the atmosphere from a fusion reactor. From comparison with NORMTRI - a code using climatologically sequences as input - over the same area, the real time results have demonstrated an apparent overestimation of the corresponding climatologically sequence of Tritium concentrations in air outputs, at several distances from the reactor. For this purpose two development patterns were established. The first one was following a cyclonic circulation over the Mediterranean Sea and the second one was based on the plume delivered over the Interior of the Iberian Peninsula and Continental Europe by another stabilized circulation corresponding to a High Pressure System. One of the important remaining activities defined then, was the qualification tool. In order to validate the model of ECMWF/FLEXPART we have developed of a new complete data base of tritium concentrations for the months from November 2010 to March 2011 and defined a new set of four patterns of HT transport in air, in each case using real boundary conditions: stationary to the North, stationary to the South, fast and very fast displacement. Finally the differences corresponding to those four early patterns (each one in assessments 1 and 2) has been analyzed in terms of the tuning of safety related issues and taking into account the primary phase o- - f tritium modeling, from its discharge to the atmosphere to the deposition on the ground, will affect to the complete tritium environmental pathway altering the chronic dose by absorption, reemission and ingestion both from elemental tritium, HT and from the oxide of tritium, HTO

Investigation into possible causes of elevated ozone concentrations in Miami, Florida

Ozone readings which exceeded the National Ambient Air Quality Standard of 120 ppbv were recorded in Miami, Florida during 1978 and 1980. Similar elevated concentrations of ozone extended across upper Florida and into the Southeastern portion of the United States. It is concluded that tropospheric transport of ozone into the Miami area occurs. This conclusion is supported by lead analyses of atmospheric samples taken in Miami and by isentropic trajectories. Six case studies are presented. In all cases transport of ozone into Florida appears to occur. In only four of the cases does this result in elevated ozone levels in Miami. In one case lower Florida was experiencing an oceanic influx of air and low ozone concentrations. In the other case Miami was experiencing a stagnation and high ozone concentrations apparently generated locally. The long range transport of ozone across the Southeastern United States appears to result from circulation within a weather pattern characterized by a stagnant high pressure system over the Southeastern United States.

Age determination of sediment core GIK16523-1

High-resolution studies of a planktonic foraminifer core record from the South China Sea (SCS) (31KL: 18°45.4'N, 115°52.4'E, water depth 3360 m) reveal changes driven by ice-volume forcings in the climate of the East Asian monsoon in the western Pacific marginal sea during the late Quaternary. The analyses of planktonic foraminifer faunal abundance data from the core indicate significant variations in the relative abundances of the dominant taxa over the past 100,000 years since the isotope stage 5. The transfer function estimates of faunal sea surface temperatures (SST) correlate well with a long-term (104-105 years) trend of global glaciation. About 65,000 years ago, there was an observable change in the mode of SST variability as many low-latitude records have shown. These findings suggest that the SCS surface circulation and the East Asian winter monsoon systems are mainly driven by variations in global glaciation levels. The association of surface ocean cooling in the SCS with global climatic events suggests that fluctuations in the strength of the East Asian winter monsoon may be linked to shifts in the latitudinal position of the westerly winds and the Siberian high-pressure system.

Characterization of Non-linear Polymer Properties to Predict Process Induced Warpage and Residual Stress of Electronic Packages

Nonlinear thermo-mechanical properties of advanced polymers are crucial to accurate prediction of the process induced warpage and residual stress of electronics packages. The Fiber Bragg grating (FBG) sensor based method is advanced and implemented to determine temperature and time dependent nonlinear properties. The FBG sensor is embedded in the center of the cylindrical specimen, which deforms together with the specimen. The strains of the specimen at different loading conditions are monitored by the FBG sensor. Two main sources of the warpage are considered: curing induced warpage and coefficient of thermal expansion (CTE) mismatch induced warpage. The effective chemical shrinkage and the equilibrium modulus are needed for the curing induced warpage prediction. Considering various polymeric materials used in microelectronic packages, unique curing setups and procedures are developed for elastomers (extremely low modulus, medium viscosity, room temperature curing), underfill materials (medium modulus, low viscosity, high temperature curing), and epoxy molding compound (EMC: high modulus, high viscosity, high temperature pressure curing), most notably, (1) zero-constraint mold for elastomers; (2) a two-stage curing procedure for underfill materials and (3) an air-cylinder based novel setup for EMC. For the CTE mismatch induced warpage, the temperature dependent CTE and the comprehensive viscoelastic properties are measured. The cured cylindrical specimen with a FBG sensor embedded in the center is further used for viscoelastic property measurements. A uni-axial compressive loading is applied to the specimen to measure the time dependent Young’s modulus. The test is repeated from room temperature to the reflow temperature to capture the time-temperature dependent Young’s modulus. A separate high pressure system is developed for the bulk modulus measurement. The time temperature dependent bulk modulus is measured at the same temperatures as the Young’s modulus. The master curve of the Young’s modulus and bulk modulus of the EMC is created and a single set of the shift factors is determined from the time temperature superposition. The supplementary experiments are conducted to verify the validity of the assumptions associated with the linear viscoelasticity. The measured time-temperature dependent properties are further verified by a shadow moiré and Twyman/Green test.