An infrared spectroscopic study of the some Autunite minerals

A series of selected autunites with phosphate as the anion have been studied using infrared spectroscopy. Each autunite mineral has its own characteristic spectrum. The spectra for different autunites with the same composition are different. It is proposed that this difference is due to the structure of water and hydrated cations in the interlayer region between the uranyl phosphate sheets. This structure is different for different autunites. The position of the water hydroxyl stretching bands is related to the strength of the hydrogen bonds as determined by hydrogen bond distance. The highly ordered structure of water is also observed in the water HOH bending modes where a high wavenumber bands are observed. The phosphate and uranyl stretching vibrations overlap and are obtained by curve resolution.

Thermal treatment of weddellite—a Raman and infrared emission spectroscopic study

Thermal transformations of natural calcium oxalate dihydrate known in mineralogy as weddellite have been undertaken using a combination of Raman microscopy and infrared emission spectroscopy. The vibrational spectroscopic data was complimented with high resolution thermogravimetric analysis combined with evolved gas mass spectrometry. TG–MS identified three mass loss steps at 114, 422 and 592 °C. In the first mass loss step water is evolved only, in the second and third steps carbon dioxide is evolved. The combination of Raman microscopy and a thermal stage clearly identifies the changes in the molecular structure with thermal treatment. Weddellite is the phase in the temperature range up to the pre-dehydration temperature of 97 °C. At this temperature, the phase formed is whewellite (calcium oxalate monohydrate) and above 114 °C the phase is the anhydrous calcium oxalate. Above 422 °C, calcium carbonate is formed. Infrared emission spectroscopy shows that this mineral decomposes at around 650 °C. Changes in the position and intensity of the C=O and C---C stretching vibrations in the Raman spectra indicate the temperature range at which these phase changes occur.

Passive solar systems for heating, daylighting and ventilation for rooms without an equator-facing facade

Spaces without northerly orientations have an impact on the ‘energy behaviour’ of a building. This paper outlines possible energy savings and better performance achieved by different zenithal solar passive strategies (skylights, roof monitors and clerestory roof windows) and element arrangements across the roof in zones of cold to temperate climates typical of the central and central-southern Argentina. Analyses were undertaken considering daylighting, thermal and ventilation performances of the different strategies. The results indicate that heating,ventilation and lighting loads in spaces without an equator-facing facade can be significantly reduced by implementing solar passive strategies. In the thermal aspect, the solar saving fraction reached for the different strategies were averaged 43.16% for clerestories, 41.4% for roof monitors and 38.86% for skylights for a glass area of 9% to the floor area. The results also indicate average illuminance levels above 500 lux for the different clerestory and monitor arrangements, uniformity ratios of 0.66–0.82 for the most distributed arrangements and day-lighting factors between 11.78 and 20.30% for clear sky conditions, depending on the strategy. In addition, minimum air changes rates of 4 were reached for the most extreme conditions.

Passive control of a bi-ventricular assist device : an experimental and numerical investigation

For the last two decades heart disease has been the highest single cause of death for the human population. With an alarming number of patients requiring heart transplant, and donations not able to satisfy the demand, treatment looks to mechanical alternatives. Rotary Ventricular Assist Devices, VADs, are miniature pumps which can be implanted alongside the heart to assist its pumping function. These constant flow devices are smaller, more efficient and promise a longer operational life than more traditional pulsatile VADs. The development of rotary VADs has focused on single pumps assisting the left ventricle only to supply blood for the body. In many patients however, failure of both ventricles demands that an additional pulsatile device be used to support the failing right ventricle. This condition renders them hospital bound while they wait for an unlikely heart donation. Reported attempts to use two rotary pumps to support both ventricles concurrently have warned of inherent haemodynamic instability. Poor balancing of the pumps’ flow rates quickly leads to vascular congestion increasing the risk of oedema and ventricular ‘suckdown’ occluding the inlet to the pump. This thesis introduces a novel Bi-Ventricular Assist Device (BiVAD) configuration where the pump outputs are passively balanced by vascular pressure. The BiVAD consists of two rotary pumps straddling the mechanical passive controller. Fluctuations in vascular pressure induce small deflections within both pumps adjusting their outputs allowing them to maintain arterial pressure. To optimise the passive controller’s interaction with the circulation, the controller’s dynamic response is optimised with a spring, mass, damper arrangement. This two part study presents a comprehensive assessment of the prototype’s ‘viability’ as a support device. Its ‘viability’ was considered based on its sensitivity to pathogenic haemodynamics and the ability of the passive response to maintain healthy circulation. The first part of the study is an experimental investigation where a prototype device was designed and built, and then tested in a pulsatile mock circulation loop. The BiVAD was subjected to a range of haemodynamic imbalances as well as a dynamic analysis to assess the functionality of the mechanical damper. The second part introduces the development of a numerical program to simulate human circulation supported by the passively controlled BiVAD. Both investigations showed that the prototype was able to mimic the native baroreceptor response. Simulating hypertension, poor flow balancing and subsequent ventricular failure during BiVAD support allowed the passive controller’s response to be assessed. Triggered by the resulting pressure imbalance, the controller responded by passively adjusting the VAD outputs in order to maintain healthy arterial pressures. This baroreceptor-like response demonstrated the inherent stability of the auto regulating BiVAD prototype. Simulating pulmonary hypertension in the more observable numerical model, however, revealed a serious issue with the passive response. The subsequent decrease in venous return into the left heart went unnoticed by the passive controller. Meanwhile the coupled nature of the passive response not only decreased RVAD output to reduce pulmonary arterial pressure, but it also increased LVAD output. Consequently, the LVAD increased fluid evacuation from the left ventricle, LV, and so actually accelerated the onset of LV collapse. It was concluded that despite the inherently stable baroreceptor-like response of the passive controller, its lack of sensitivity to venous return made it unviable in its present configuration. The study revealed a number of other important findings. Perhaps the most significant was that the reduced pulse experienced during constant flow support unbalanced the ratio of effective resistances of both vascular circuits. Even during steady rotary support therefore, the resulting ventricle volume imbalance increased the likelihood of suckdown. Additionally, mechanical damping of the passive controller’s response successfully filtered out pressure fluctuations from residual ventricular function. Finally, the importance of recognising inertial contributions to blood flow in the atria and ventricles in a numerical simulation were highlighted. This thesis documents the first attempt to create a fully auto regulated rotary cardiac assist device. Initial results encourage development of an inlet configuration sensitive to low flow such as collapsible inlet cannulae. Combining this with the existing baroreceptor-like response of the passive controller will render a highly stable passively controlled BiVAD configuration. The prototype controller’s passive interaction with the vasculature is a significant step towards a highly stable new generation of artificial heart.

A comparative study – regulatory requirements on subdivisions for increasing passive cooling

This is the third in a series of reports planned for this project. The aim of this research is to conduct a comparative study of current legislation or guidelines at the federal, state and local government levels to confirm if any natural ventilation criteria are required at the subdivision development stage of planning. It also seeks to discover if there are any other incentives, statutory planning or development principles that encourage developers to orient subdivision lots to maximize natural ventilation for the dwellings. Findings from the research in this report are intended to contribute to the discussion on the development of an enhanced lot rating methodology for sustainable subdivisions as documented in other reports in this series.

Infrared and infrared emission spectroscopy of gallium oxide α-GaO(OH) nanostructures

Infrared spectroscopy has been used to study nano to micro sized gallium oxyhydroxide α-GaO(OH), prepared using a low temperature hydrothermal route. Rod-like α-GaO(OH) crystals with average length of ~2.5 μm and width of 1.5 μm were prepared when the initial molar ratio of Ga to OH was 1:3. β-Ga2O3 nano and micro-rods were prepared through the calcination of α-GaO(OH) The initial morphology of α-GaO(OH) is retained in the β-Ga2O3 nanorods. The combination of infrared and infrared emission spectroscopy complimented with dynamic thermal analysis were used to characterise the α-GaO(OH) nanotubes and the formation of β-Ga2O3 nanorods. Bands at around 2903 and 2836 cm-1 are assigned to the -OH stretching vibration of α-GaO(OH) nanorods. Infrared bands at around 952 and 1026 cm-1 are assigned to the Ga-OH deformation modes of α-GaO(OH). A significant number of bands are observed in the 620 to 725 cm-1 region and are assigned to GaO stretching vibrations.

A comparative study : regulatory requirements on subdivisions for increasing passive cooling

A major project in the Sustainable Built Assets core area is the Sustainable Sub-divisions – Ventilation Project that is the second stage of a planned series of research projects focusing on sustainable sub-divisions. The initial project, Sustainable Sub-divisions: Energy focused on energy efficiency and examined the link between dwelling energy efficiency and sub-divisional layout. In addition, the potential for on site electricity generation, especially in medium and high-density developments, was also examined. That project recommended that an existing lot-rating methodology be adapted for use in SEQ through the inclusion of sub divisional appropriate ventilation data. Acquiring that data is the object of this project. The Sustainable Sub-divisions; Ventilation Project will produce a series of reports. The first report (Report 2002-077-B-01) summarised the results from an industry workshop and interviews that were conducted to ascertain the current attitudes and methodologies used in contemporary sub-division design in South East Queensland. The second report (Report 2002-077-B-02) described how the project is being delivered as outlined in the Project Agreement. It included the selection of the case study dwellings and monitoring equipment and data management process. This third report (Report 2002-077-B-03) provides an analysis and review of the approaches recommended by leading experts, government bodies and professional organizations throughout Australia that aim to increase the potential for passive cooling and heating at the subdivision stage. This data will inform issues discussed on the development of the enhanced lot-rating methodology in other reports of this series. The final report, due in June 2007, will detail the analysis of data for winter 2006 and summer 2007, leading to the development and delivery of the enhanced lot-rating methodology.

EPR, UV-visible and near infrared spectroscopic characterization of dolomite

Dolomite mineral samples having white and light green colours of Indian origin have been characterized by EPR, optical and NIR spectroscopy. The optical spectrum exhibits a number of electronic bands due to presence of Fe(III) ions in the mineral. From EPR studies, the parameters of g for Fe(III) and g, A and D for Mn(II) are evaluated and the data confirm that the ions are in distorted octahedron. Optical absorption studies reveal that Fe(III) is in distorted octahedron. The bands in NIR spectra are due to the overtones and combinations of water molecules. Thus EPR and optical absorption spectral studies have proven useful for the study of the chemistry of dolomite.

Diffuse reflectance near infrared spectroscopy can distinguish normal from enzymatically digested cartilage

A non-destructive, diffuse reflectance near infrared spectroscopy (DR-NIRS)approach is considered as a potential tool for determining the component-level structural properties of articular cartilage. To this end, DR-NIRS was applied in vitro to detect structural changes, using principal component analysis as the statistical basis for characterization. The results show that this technique, particularly with first-derivative pretreatment, can distinguish normal, intact cartilage from enzymatically digested cartilage. Further, this paper establishes that the use of DR-NIRS enables the probing of the full depth of the uncalcified cartilage matrix, potentially allowing the assessment of degenerative changes in joint tissue, independent of the site of initiation of the osteoarthritic process.

Near-infrared spectroscopic studies of human scalp hair in a forensic context

Human hair is a relatively inert biopolymer and can survive through natural disasters. It is also found as trace evidence at crime scenes. Previous studies by FTIRMicrospectroscopy and – Attenuated Total Reflectance (ATR) successfully showed that hairs can be matched and discriminated on the basis of gender, race and hair treatment, when interpreted by chemometrics. However, these spectroscopic techniques are difficult to operate at- or on-field. On the other hand, some near infrared spectroscopic (NIRS) instruments equipped with an optical probe, are portable and thus, facilitate the on- or at –field measurements for potential application directly at a crime or disaster scene. This thesis is focused on bulk hair samples, which are free of their roots, and thus, independent of potential DNA contribution for identification. It explores the building of a profile of an individual with the use of the NIRS technique on the basis of information on gender, race and treated hair, i.e. variables which can match and discriminate individuals. The complex spectra collected may be compared and interpreted with the use of chemometrics. These methods can then be used as protocol for further investigations. Water is a common substance present at forensic scenes e.g. at home in a bath, in the swimming pool; it is also common outdoors in the sea, river, dam, puddles and especially during DVI incidents at the seashore after a tsunami. For this reason, the matching and discrimination of bulk hair samples after the water immersion treatment was also explored. Through this research, it was found that Near Infrared Spectroscopy, with the use of an optical probe, has successfully matched and discriminated bulk hair samples to build a profile for the possible application to a crime or disaster scene. Through the interpretation of Chemometrics, such characteristics included Gender and Race. A novel approach was to measure the spectra not only in the usual NIR range (4000 – 7500 cm-1) but also in the Visible NIR (7500 – 12800 cm-1). This proved to be particularly useful in exploring the discrimination of differently coloured hair, e.g. naturally coloured, bleached or dyed. The NIR region is sensitive to molecular vibrations of the hair fibre structure as well as that of the dyes and damage from bleaching. But the Visible NIR region preferentially responds to the natural colourants, the melanin, which involves electronic transitions. This approach was shown to provide improved discrimination between dyed and untreated hair. This thesis is an extensive study of the application of NIRS with the aid of chemometrics, for matching and discrimination of bulk human scalp hair. The work not only indicates the strong potential of this technique in this field but also breaks new ground with the exploration of the use of the NIR and Visible NIR ranges for spectral sampling. It also develops methods for measuring spectra from hair which has been immersed in different water media (sea, river and dam)

The structure of selected magnesium carbonate minerals : a near infrared and mid-infrared spectroscopic study

The approach to remove green house gases by pumping liquid CO2 several kilometres below the ground implies that many carbonate containing minerals will be formed. Among these minerals the formation of dypingite and artinite are possible; thus necessitating a study of such minerals. Two carbonate bearing minerals dypingite and artinite with a hydrotalcite related formulae have been characterised by a combination of infrared and near-infrared spectroscopy. The infrared spectra of both minerals are characterised by OH and water stretching vibrations. Both the first and second fundamental overtones of these bands are observed in the NIR spectra in the 7030 to 7235 cm-1 and 10490 to 10570 cm-1. Intense (CO3)2- symmetric and antisymmetric stretching vibrations confirm the distortion of the carbonate anion. The position of the water bending vibration indicates water is strongly hydrogen bonded to the carbonate anion in the mineral structure. Split NIR bands at around 8675 and 11100 cm-1 indicates that some replacement of magnesium ions by ferrous ions in the mineral structure has occurred.

Near infrared spectroscopy of stearic acid adsorbed on montmorillonite

The adsorption of stearic acid on both sodium montmorillonites and calcium montmorillonites has been studied by near infrared spectroscopy complimented with infrared spectroscopy. Upon adsorption of stearic acid on Ca-Mt additional near infrared bands are observed at 8236 cm-1 and is assigned to an interaction of stearic acid with the water of hydration. Upon adsorption of the stearic acid on Na-Mt, the NIR bands are now observed at 5671, 5778, 5848 and 5912 cm-1 and are assigned to the overtone and combination bands of the CH fundamentals. Additional bands at 4177, 4250, 4324, 4337, 4689 and 4809 cm-1 are attributed to CH combination bands resulting from the adsorption of the stearic acid. Stearic acid is used as a model molecule for adsorption studies. The application of near infrared spectroscopy to the study of this adsorption proved most useful.