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.

Impact response and parametric studies of reinforced concrete circular columns

This paper presents a detailed description of the influence of critical parameters that govern the vulnerability of columns under lateral impact loads. Numerical simulations are conducted by using the Finite Element program LS-DYNA, incorporating steel reinforcement, material models and strain rate effects. A simplified method based on impact pulse generated from full scale impact tests is used for impact reconstruction and effects of the various pulse loading parameters are investigated under low to medium velocity impacts. A constitutive material model which can simulate failures under tri-axial state of stresses is used for concrete. Confinement effects are also introduced to the numerical simulation and columns of Grade 30 to 50 concrete under pure axial loading are analysed in detail. This research confirmed that the vulnerability of the axially loaded columns can be mitigated by reducing the slenderness ratio and concrete grade, and by choosing the design option with a minimal amount of longitudinal steel. Additionally, it is evident that approximately a 50% increase in impact capacity can be gained for columns in medium rise buildings by enhancing the confinement effects alone. Results also indicated that the ductility as well as the mode of failure under impact can be changed with the volumetric ratio of lateral steel. Moreover, to increase the impact capacity of the vulnerable columns, a higher confining stress is required. The general provisions of current design codes do not sufficiently cover this aspect and hence this research will provide additional guidelines to overcome the inadequacies of code provisions.

Parametric building development during early design stage

Objectives The objectives of this project were two-fold: • Assess the ease with which current architectural CAD systems supported the use ofparametric descriptions in defining building shape, engineering system performance and cost at the early stages of building design; • Assess the feasibility of implementing a software decision support system that allowed designers to trade-off the characteristics and configuration of various engineering systems to move towards a “global optimum” rather than considering each system in isolation and expecting humans to weigh up all of the costs and benefits. The first stage of the project consisted of using four different CAD systems to define building shells (envelopes) with different usages. These models were then exported into a shared database using the IFC information exchange specifications. The second stage involved the implementation of small computer programs that were able to estimate relevant system parameters based on performance requirements and the constraints imposed by the other systems. These are presented in a unified user interface that extracts the appropriate building shape parameters from the shared database Note that the term parametric in this context refers to the relationships among and between all elements of the building model - not just geometric associations - which will enable the desired coordination.

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.

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.

Robot navigation in sensor space

This thesis investigates the problem of robot navigation using only landmark bearings. The proposed system allows a robot to move to a ground target location specified by the sensor values observed at this ground target posi- tion. The control actions are computed based on the difference between the current landmark bearings and the target landmark bearings. No Cartesian coordinates with respect to the ground are computed by the control system. The robot navigates using solely information from the bearing sensor space. Most existing robot navigation systems require a ground frame (2D Cartesian coordinate system) in order to navigate from a ground point A to a ground point B. The commonly used sensors such as laser range scanner, sonar, infrared, and vision do not directly provide the 2D ground coordi- nates of the robot. The existing systems use the sensor measurements to localise the robot with respect to a map, a set of 2D coordinates of the objects of interest. It is more natural to navigate between the points in the sensor space corresponding to A and B without requiring the Cartesian map and the localisation process. Research on animals has revealed how insects are able to exploit very limited computational and memory resources to successfully navigate to a desired destination without computing Cartesian positions. For example, a honeybee balances the left and right optical flows to navigate in a nar- row corridor. Unlike many other ants, Cataglyphis bicolor does not secrete pheromone trails in order to find its way home but instead uses the sun as a compass to keep track of its home direction vector. The home vector can be inaccurate, so the ant also uses landmark recognition. More precisely, it takes snapshots and compass headings of some landmarks. To return home, the ant tries to line up the landmarks exactly as they were before it started wandering. This thesis introduces a navigation method based on reflex actions in sensor space. The sensor vector is made of the bearings of some landmarks, and the reflex action is a gradient descent with respect to the distance in sensor space between the current sensor vector and the target sensor vec- tor. Our theoretical analysis shows that except for some fully characterized pathological cases, any point is reachable from any other point by reflex action in the bearing sensor space provided the environment contains three landmarks and is free of obstacles. The trajectories of a robot using reflex navigation, like other image- based visual control strategies, do not correspond necessarily to the shortest paths on the ground, because the sensor error is minimized, not the moving distance on the ground. However, we show that the use of a sequence of waypoints in sensor space can address this problem. In order to identify relevant waypoints, we train a Self Organising Map (SOM) from a set of observations uniformly distributed with respect to the ground. This SOM provides a sense of location to the robot, and allows a form of path planning in sensor space. The navigation proposed system is analysed theoretically, and evaluated both in simulation and with experiments on a real robot.

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)