Deep Raman Spectroscopy in the analytical forensic investigation of concealed substances

Deep Raman Spectroscopy is a domain within Raman spectroscopy consisting of techniques that facilitate the depth profiling of diffusely scattering media. Such variants include Time-Resolved Raman Spectroscopy (TRRS) and Spatially-Offset Raman Spectroscopy (SORS). A recent study has also demonstrated the integration of TRRS and SORS in the development of Time-Resolved Spatially-Offset Raman Spectroscopy (TR-SORS). This research demonstrates the application of specific deep Raman spectroscopic techniques to concealed samples commonly encountered in forensic and homeland security at various working distances. Additionally, the concepts behind these techniques are discussed at depth and prospective improvements to the individual techniques are investigated. Qualitative and quantitative analysis of samples based on spectral data acquired from SORS is performed with the aid of multivariate statistical techniques. By the end of this study, an objective comparison is made among the techniques within Deep Raman Spectroscopy based on their capabilities. The efficiency and quality of these techniques are determined based on the results procured which facilitates the understanding of the degree of selectivity for the deeper layer exhibited by the individual techniques relative to each other. TR-SORS was shown to exhibit an enhanced selectivity for the deeper layer relative to TRRS and SORS whilst providing spectral results with good signal-to-noise ratio. Conclusive results indicate that TR-SORS is a prospective deep Raman technique that offers higher selectivity towards deep layers and therefore enhances the non-invasive analysis of concealed substances from close range as well as standoff distances.

Design, modelling and measurement of hybrid powerplant for unmanned aerial vehicles (UAVs)

The success or effectiveness for any aircraft design is a function of many trade-offs. Over the last 100 years of aircraft design these trade-offs have been optimized and dominant aircraft design philosophies have emerged. Pilotless aircraft (or uninhabited airborne systems, UAS) present new challenges in the optimization of their configuration. Recent developments in battery and motor technology have seen an upsurge in the utility and performance of electric powered aircraft. Thus, the opportunity to explore hybrid-electric aircraft powerplant configurations is compelling. This thesis considers the design of such a configuration from an overall propulsive, and energy efficiency perspective. A prototype system was constructed using a representative small UAS internal combustion engine (10cc methanol two-stroke) and a 600W brushless Direct current (BLDC) motor. These components were chosen to be representative of those that would be found on typical small UAS. The system was tested on a dynamometer in a wind-tunnel and the results show an improvement in overall propulsive efficiency of 17% when compared to a non-hybrid powerplant. In this case, the improvement results from the utilization of a larger propeller that the hybrid solution allows, which shows that general efficiency improvements are possible using hybrid configurations for aircraft propulsion. Additionally this approach provides new improvements in operational and mission flexibility (such as the provision of self-starting) which are outlined in the thesis. Specifically, the opportunity to use the windmilling propeller for energy regeneration was explored. It was found (in the prototype configuration) that significant power (60W) is recoverable in a steep dive, and although the efficiency of regeneration is low, the capability can allow several options for improved mission viability. The thesis concludes with the general statement that a hybrid powerplant improves the overall mission effectiveness and propulsive efficiency of small UAS.

Vibrational spectroscopy of the phosphate mineral lazulite – (Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil

This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm-1 assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO2/4- units. Two Raman bands at 1102 and 1137 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm-1 are attributed to the m1 PO3/4- symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm-1 are assigned to the v3PO3/4- antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm-1 are assigned to the m4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm-1 are attributed to the m2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm-1 are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood.

Fabrication and characterisation of graphene oxide-epoxy nanocomposite

Adequate amount of graphene oxide (GO) was firstly prepared by oxidation of graphite and GO/epoxy nanocomposites were subsequently prepared by typical solution mixing technique. X-ray diffraction (XRD) pattern, X-ray photoelectron (XPS), Raman and Fourier transform infrared (FTIR) spectroscopy indicated the successful preparation of GO. Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) images of the graphite oxide showed that they consist of a large amount of graphene oxide platelets with a curled morphology containing of a thin wrinkled sheet like structure. AFM image of the exfoliated GO signified that the average thickness of GO sheets is ~1.0 nm which is very similar to GO monolayer. Mechanical properties of as prepared GO/epoxy nanocomposites were investigated. Significant improvements in both Young’s modulus and tensile strength were observed for the nanocomposites at very low level of GO loading. The Young’s modulus of the nanocomposites containing 0.5 wt% GO was 1.72 GPa, which was 35 % higher than that of the pure epoxy resin (1.28 GPa). The effective reinforcement of the GO based epoxy nanocomposites can be attributed to the good dispersion and the strong interfacial interactions between the GO sheets and the epoxy resin matrices.

Cerebral cortex activation mapping upon electrical muscle stimulation by 32-channel time-domain functional near-infrared spectroscopy

The application of different EMS current thresholds on muscle activates not only the muscle but also peripheral sensory axons that send proprioceptive and pain signals to the cerebral cortex. A 32-channel time-domain fNIRS instrument was employed to map regional cortical activities under varied EMS current intensities applied on the right wrist extensor muscle. Eight healthy volunteers underwent four EMS at different current thresholds based on their individual maximal tolerated intensity (MTI), i.e., 10 % < 50 % < 100 % < over 100 % MTI. Time courses of the absolute oxygenated and deoxygenated hemoglobin concentrations primarily over the bilateral sensorimotor cortical (SMC) regions were extrapolated, and cortical activation maps were determined by general linear model using the NIRS-SPM software. The stimulation-induced wrist extension paradigm significantly increased activation of the contralateral SMC region according to the EMS intensities, while the ipsilateral SMC region showed no significant changes. This could be due in part to a nociceptive response to the higher EMS current intensities and result also from increased sensorimotor integration in these cortical regions.

Investigation of ultra trace detection in functionalised-surface enhanced Raman spectroscopy (SERS)

We have developed an explanation for ultra trace detection found when using Au/Ag SERS nanoparticles linked to biochemical affinity tags, e.g. antibodies. The nanoparticle structure is not as usually assumed and the aggregated nanoparticles constitute hot spots that are indispensable for these very low levels of analyte detection, even more so when using a direct detection method.

Vibrational spectroscopy of the borate mineral olshanskyite Ca3[B(OH)4]4(OH)2

The mineral olshanskyite is one of many calcium borate minerals which has never been studied using vibrational spectroscopy. The mineral is unstable and decomposes upon exposure to an electron beam. This makes the elemental analysis using EDX techniques difficult. Both the Raman and infrared spectra show complexity due to the complexity of the structure. Intense Raman bands are found at 989, 1,003, 1,025 and 1,069 cm-1 with a shoulder at 961 cm-1 and are assigned to trigonal borate units. The Raman bands at 1,141, 1,206 and 1,365 cm-1 are assigned to OH in-plane bending of BOH units. A series of Raman bands are observed in the 2,900–3,621cm-1 spectral range and are assigned to the stretching vibrations of OH and water. This complexity is also reflected in the infrared spectra. Vibrational spectroscopy enables aspects of the structure of olshanskyite to be elucidated.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 2. -- A fourier-transform infrared spectroscopy study of methanol adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methanol adsorbed at 295 K on ZnO/SiO 2, on reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methanol on ZnO/SiO2 gave methoxy species on ZnO and SiO, in addition to both strongly and weakly physisorbed methanol on SiO2. The corresponding adsorption of methanol on reduced Cu/ZnO/SiO2 also gave methoxy species on Cu and a small amount of bridging formate. Reaction of methanol with a reoxidised Cu/ZnO/SiO2 catalyst resulted in an enhanced quantity of methoxy species on Cu. Heating adsorbed species on Cu/ZnO/SiO2 at 393 K led to the loss of methoxy groups on Cu and the concomitant formation of formate species on both ZnO and Cu. The comparable reaction on a reoxidised Cu/ZnO/SiO2 catalyst gave an increased amount of formate species on ZnO and this correlated with an increased quantity of methoxy groups lost from Cu. An explanation is given in terms of adsorption of formate and formaldehyde species at special sites located at the copper/zinc oxide interface.

A combined temperature-programmed reaction spectroscopy and Fourier-transform infrared spectroscopy study of CO2/H2 and CO/CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol-synthesis catalysts

The reaction of CO2 and H2 with ZnO/SiO2 catalyst at 295 K gave predominantly hydrogencarbonate on zinc oxide and a small quantity of formate was evolved after heating at 393 K. Elevation of the reaction temperature to 503 K enhanced the rate of formation of zinc formate species. Significantly these formate species decomposed at 573 K almost entirely to CO2 and H2. Even after exposure of CO2-H2 or CO-CO2-H2 mixtures to highly defected ZnO/SiO2 catalyst, the formate species produced still decomposed to give CO2 and H2. It was concluded that carboxylate species which were formed at oxygen anion vacancies on polar Zn planes were not significantly hydrogenated to formate. Consequently it was proposed that the non-polar planes on zinc oxide contained sites which were specific for the synthesis of methanol. The interaction of CO2 and H2 with reduced Cu/ZnO/SiO2 catalyst at 393 K gave copper formate species in addition to substantial quantities of formate created at interfacial sites between copper and zinc oxide. It was deduced that interfacial formate species were produced from the hydrogenation of interfacial bidentate carbonate structures. The relevance of interfacial formate species in the methanol synthesis reaction is discussed. Experiments concerning the reaction of CO2-H2 with physical mixtures of Cu/SiO2 and ZnO/SiO2 gave results which were simply characteristic of the individual components. By careful consideration of previous data a detailed proposal regarding the role of spillover hydrogen is outlined. Admission of CO to a gaseous CO2-H2 feedstock resulted in a considerably diminished amount of formate species on copper. This was ascribed to a combination of over-reduction of the surface and site-blockage.

A hybrid genetic algorithm for the minimum interconnection cut problem

In the real world there are many problems in network of networks (NoNs) that can be abstracted to a so-called minimum interconnection cut problem, which is fundamentally different from those classical minimum cut problems in graph theory. Thus, it is desirable to propose an efficient and effective algorithm for the minimum interconnection cut problem. In this paper we formulate the problem in graph theory, transform it into a multi-objective and multi-constraint combinatorial optimization problem, and propose a hybrid genetic algorithm (HGA) for the problem. The HGA is a penalty-based genetic algorithm (GA) that incorporates an effective heuristic procedure to locally optimize the individuals in the population of the GA. The HGA has been implemented and evaluated by experiments. Experimental results have shown that the HGA is effective and efficient.

Formation of polypyrrole and polythiophene within Cu2+- and H+-mordenite hosts studied by EPR and UV-VIS spectroscopy

The reactions of pyrrole and thiophene monomers in copper-exchanged mordenite have been investigated using EPR and UV–VIS absorption spectroscopy. The EPR spectra show a decrease in the intensity of the Cu2+ signal and the appearance of a radical signal due to the formation of oxidatively coupled oligomeric and/or polymeric species in the zeolite host. The reaction ceases when ca. 50% of the copper has reacted and differences in the form of the residual Cu2+ signal between the thiophene and pyrrole reactions suggest a greater degree of penetration of the reaction into the zeolite host for pyrrole, in agreement with previous XPS measurements. The EPR signal intensities show that the average length of the polymer chain that is associated with each radical centre is 15–20 and 5–7 monomer units for polypyrrole and polythiophene, respectively. The widths of the EPR signals suggest that these are at least partly due to small oligomers. The UV–VIS absorption spectra of the thiophene system show bands in three main regions: 2.8–3.0 eV (A), 2.3 eV (B) and 1.6–1.9 eV (D, E, F). Bands A and D–F occur in regions which have previously been observed for small oligomers, 4–6 monomer units in length. Band B is assigned to longer chain polythiophene molecules. We therefore conclude that the reaction between thiophene and copper-loaded mordenite produces a mixture of short oligomers together with some long chain polythiophene. The UV–VIS spectra of the pyrrole system show bands in the regions 3.6 eV (A), 2.7–3.0 eV (B, C) and 1.5–1.9 eV (D, F). Assignments of these bands are less certain than for the thiophene case because of the lack of literature data on the spectra of pyrrole oligomers.

Hybrid placemaking in the library : designing digital technology to enhance users’ on-site experience

This paper presents research findings and design strategies that illustrate how digital technology can be applied as a tool for hybrid placemaking in ways that would not be possible in purely digital or physical space. Digital technology has revolutionised the way people learn and gather new information. This trend has challenged the role of the library as a physical place, as well as the interplay of digital and physical aspects of the library. The paper provides an overview of how the penetration of digital technology into everyday life has affected the library as a place, both as designed by place makers, and, as perceived by library users. It then identifies a gap in current library research about the use of digital technology as a tool for placemaking, and reports results from a study of Gelatine – a custom built user check-in system that displays real-time user information on a set of public screens. Gelatine and its evaluation at The Edge, at State Library of Queensland illustrates how combining affordances of social, spatial and digital space can improve the connected learning experience among on-site visitors. Future design strategies involving gamifying the user experience in libraries are described based on Gelatine’s infrastructure. The presented design ideas and concepts are relevant for managers and designers of libraries as well as other informal, social learning environments.

Hybrid place : blurring the edge between the digital and physical layers of urban environments

The purpose of this paper is to investigate the edge condition between the digital layers and the physical layers of the city and how tangible expressions of the interrelationships between them to create and define new experiences of place, creating hybrid place. To date there has been discussion and investigation into understanding the importance of place, similarly into defining hybrid space. This paper explores principles of place and space to question how they can be applied into defining and proposing the notion of hybrid place in urban environments. The integration of media spaces into architecture provide infrastructure for the development of hybrid place. The physical boundaries of urban spaces become blurred through the integration of media such as computer technologies connecting the physical environment with the digital. Literature and case studies that reflect the current trends of use of technology by people in space and place within urban environments are examined.

Vibrational spectroscopy of the borate mineral pinnoite MgB2O(OH)6

There is a large number of boron containing minerals with water and/or hydroxyl units of which pinnoite MgB2O(OH)6 is one. Some discussion about the molecular structure of pinnoite exists in the literature. Whether water is involved in the structure is ill-determined. The molecular structure of pinnoite has been assessed by the combination of Raman and infrared spectroscopy. The Raman spectrum is characterized by an intense band at 900 cm−1 assigned to the BO stretching vibrational mode. A series of bands in the 1000–1320 cm−1 spectral range are attributed to BO antisymmetric stretching modes and in-plane bending modes. The infrared spectrum shows complexity in this spectral range. Multiple Raman OH stretching vibrations are found at 3179, 3399, 3554 and 3579 cm−1. The infrared spectrum shows a series of overlapping bands with bands identified at 3123, 3202, 3299, 3414, 3513 and 3594 cm−1. By using a Libowitzky type function, hydrogen bond distances were calculated. Two types of hydrogen bonds were identified based upon the hydrogen bond distance. It is important to understand the structure of pinnoite in order to form nanomaterials based upon the pinnoite structure.