A laser induced breakdown spectroscopy quantitative analysis method based on the robust least squares support vector machine regression model

Data fluctuation in multiple measurements of Laser Induced Breakdown Spectroscopy (LIBS) greatly affects the accuracy of quantitative analysis. A new LIBS quantitative analysis method based on the Robust Least Squares Support Vector Machine (RLS-SVM) regression model is proposed. The usual way to enhance the analysis accuracy is to improve the quality and consistency of the emission signal, such as by averaging the spectral signals or spectrum standardization over a number of laser shots. The proposed method focuses more on how to enhance the robustness of the quantitative analysis regression model. The proposed RLS-SVM regression model originates from the Weighted Least Squares Support Vector Machine (WLS-SVM) but has an improved segmented weighting function and residual error calculation according to the statistical distribution of measured spectral data. Through the improved segmented weighting function, the information on the spectral data in the normal distribution will be retained in the regression model while the information on the outliers will be restrained or removed. Copper elemental concentration analysis experiments of 16 certified standard brass samples were carried out. The average value of relative standard deviation obtained from the RLS-SVM model was 3.06% and the root mean square error was 1.537%. The experimental results showed that the proposed method achieved better prediction accuracy and better modeling robustness compared with the quantitative analysis methods based on Partial Least Squares (PLS) regression, standard Support Vector Machine (SVM) and WLS-SVM. It was also demonstrated that the improved weighting function had better comprehensive performance in model robustness and convergence speed, compared with the four known weighting functions.

Improved response time of laser etched polymer optical fiber Bragg grating humidity sensor

The humidity sensor made of polymer optical fiber Bragg grating (POFBG) responds to the water content change in fiber induced by the change of environmental condition. The response time strongly depends on fiber size as the water change is a diffusion process. The ultra short laser pulses have been providing an effective micro fabrication method to achieve spatial localized modification in materials. In this work we used the excimer laser to create different microstructures (slot, D-shape) in POFBG to improve its performance. A significant improvement in the response time has been achieved in a laser etched D-shaped POFBG humidity sensor.

Determining the change of Brillouin frequency shift by using the similarity matching method

We have proposed a similarity matching method (SMM) to obtain the change of Brillouin frequency shift (BFS), in which the change of BFS can be determined from the frequency difference between detecting spectrum and selected reference spectrum by comparing their similarity. We have also compared three similarity measures in the simulation, which has shown that the correlation coefficient is more accurate to determine the change of BFS. Compared with the other methods of determining the change of BFS, the SMM is more suitable for complex Brillouin spectrum profiles. More precise result and much faster processing speed have been verified in our simulation and experiments. The experimental results have shown that the measurement uncertainty of the BFS has been improved to 0.72 MHz by using the SMM, which is almost one-third of that by using the curve fitting method, and the speed of deriving the BFS change by the SMM is 120 times faster than that by the curve fitting method.

Improved data visualisation through multiple dissimilarity modelling

Popular dimension reduction and visualisation algorithms rely on the assumption that input dissimilarities are typically Euclidean, for instance Metric Multidimensional Scaling, t-distributed Stochastic Neighbour Embedding and the Gaussian Process Latent Variable Model. It is well known that this assumption does not hold for most datasets and often high-dimensional data sits upon a manifold of unknown global geometry. We present a method for improving the manifold charting process, coupled with Elastic MDS, such that we no longer assume that the manifold is Euclidean, or of any particular structure. We draw on the benefits of different dissimilarity measures allowing for the relative responsibilities, under a linear combination, to drive the visualisation process.

Improved estimation of postmortem interval with Cardiac Troponin T and improved analytical methods

Accurate knowledge of the time since death, or postmortem interval (PMI), has enormous legal, criminological, and psychological impact. In this study, an investigation was made to determine whether the relationship between the degradation of the human cardiac structure protein Cardiac Troponin T and PMI could be used as an indicator of time since death, thus providing a rapid, high resolution, sensitive, and automated methodology for the determination of PMI. ^ The use of Cardiac Troponin T (cTnT), a protein found in heart tissue, as a selective marker for cardiac muscle damage has shown great promise in the determination of PMI. An optimized conventional immunoassay method was developed to quantify intact and fragmented cTnT. A small sample of cardiac tissue, which is less affected than other tissues by external factors, was taken, homogenized, extracted with magnetic microparticles, separated by SDS-PAGE, and visualized with Western blot by probing with monoclonal antibody against cTnT. This step was followed by labeling and available scanners. This conventional immunoassay provides a proper detection and quantitation of cTnT protein in cardiac tissue as a complex matrix; however, this method does not provide the analyst with immediate results. Therefore, a competitive separation method using capillary electrophoresis with laser-induced fluorescence (CE-LIF) was developed to study the interaction between human cTnT protein and monoclonal anti-TroponinT antibody. ^ Analysis of the results revealed a linear relationship between the percent of degraded cTnT and the log of the PMI, indicating that intact cTnT could be detected in human heart tissue up to 10 days postmortem at room temperature and beyond two weeks at 4C. The data presented demonstrates that this technique can provide an extended time range during which PMI can be more accurately estimated as compared to currently used methods. The data demonstrates that this technique represents a major advance in time of death determination through a fast and reliable, semi-quantitative measurement of a biochemical marker from an organ protected from outside factors. ^

Lattice Boltzmann method for flow and heat transfer in microgeometries

Recent technological developments have made it possible to design various microdevices where fluid flow and heat transfer are involved. For the proper design of such systems, the governing physics needs to be investigated. Due to the difficulty to study complex geometries in micro scales using experimental techniques, computational tools are developed to analyze and simulate flow and heat transfer in microgeometries. However, conventional numerical methods using the Navier-Stokes equations fail to predict some aspects of microflows such as nonlinear pressure distribution, increase mass flow rate, slip flow and temperature jump at the solid boundaries. This necessitates the development of new computational methods which depend on the kinetic theory that are both accurate and computationally efficient. In this study, lattice Boltzmann method (LBM) was used to investigate the flow and heat transfer in micro sized geometries. The LBM depends on the Boltzmann equation which is valid in the whole rarefaction regime that can be observed in micro flows. Results were obtained for isothermal channel flows at Knudsen numbers higher than 0.01 at different pressure ratios. LBM solutions for micro-Couette and micro-Poiseuille flow were found to be in good agreement with the analytical solutions valid in the slip flow regime (0.01 < Kn < 0.1) and direct simulation Monte Carlo solutions that are valid in the transition regime (0.1 < Kn < 10) for pressure distribution and velocity field. The isothermal LBM was further extended to simulate flows including heat transfer. The method was first validated for continuum channel flows with and without constrictions by comparing the thermal LBM results against accurate solutions obtained from analytical equations and finite element method. Finally, the capability of thermal LBM was improved by adding the effect of rarefaction and the method was used to analyze the behavior of gas flow in microchannels. The major finding of this research is that, the newly developed particle-based method described here can be used as an alternative numerical tool in order to study non-continuum effects observed in micro-electro-mechanical-systems (MEMS).

An improved framework for dynamic origin-destination (O-D) matrix estimation

This dissertation aims to improve the performance of existing assignment-based dynamic origin-destination (O-D) matrix estimation models to successfully apply Intelligent Transportation Systems (ITS) strategies for the purposes of traffic congestion relief and dynamic traffic assignment (DTA) in transportation network modeling. The methodology framework has two advantages over the existing assignment-based dynamic O-D matrix estimation models. First, it combines an initial O-D estimation model into the estimation process to provide a high confidence level of initial input for the dynamic O-D estimation model, which has the potential to improve the final estimation results and reduce the associated computation time. Second, the proposed methodology framework can automatically convert traffic volume deviation to traffic density deviation in the objective function under congested traffic conditions. Traffic density is a better indicator for traffic demand than traffic volume under congested traffic condition, thus the conversion can contribute to improving the estimation performance. The proposed method indicates a better performance than a typical assignment-based estimation model (Zhou et al., 2003) in several case studies. In the case study for I-95 in Miami-Dade County, Florida, the proposed method produces a good result in seven iterations, with a root mean square percentage error (RMSPE) of 0.010 for traffic volume and a RMSPE of 0.283 for speed. In contrast, Zhou's model requires 50 iterations to obtain a RMSPE of 0.023 for volume and a RMSPE of 0.285 for speed. In the case study for Jacksonville, Florida, the proposed method reaches a convergent solution in 16 iterations with a RMSPE of 0.045 for volume and a RMSPE of 0.110 for speed, while Zhou's model needs 10 iterations to obtain the best solution, with a RMSPE of 0.168 for volume and a RMSPE of 0.179 for speed. The successful application of the proposed methodology framework to real road networks demonstrates its ability to provide results both with satisfactory accuracy and within a reasonable time, thus establishing its potential usefulness to support dynamic traffic assignment modeling, ITS systems, and other strategies.

Improved Annual Average Daily Traffic (AADT) estimation for local roads using parcel-level travel demand modeling

Annual Average Daily Traffic (AADT) is a critical input to many transportation analyses. By definition, AADT is the average 24-hour volume at a highway location over a full year. Traditionally, AADT is estimated using a mix of permanent and temporary traffic counts. Because field collection of traffic counts is expensive, it is usually done for only the major roads, thus leaving most of the local roads without any AADT information. However, AADTs are needed for local roads for many applications. For example, AADTs are used by state Departments of Transportation (DOTs) to calculate the crash rates of all local roads in order to identify the top five percent of hazardous locations for annual reporting to the U.S. DOT. ^ This dissertation develops a new method for estimating AADTs for local roads using travel demand modeling. A major component of the new method involves a parcel-level trip generation model that estimates the trips generated by each parcel. The model uses the tax parcel data together with the trip generation rates and equations provided by the ITE Trip Generation Report. The generated trips are then distributed to existing traffic count sites using a parcel-level trip distribution gravity model. The all-or-nothing assignment method is then used to assign the trips onto the roadway network to estimate the final AADTs. The entire process was implemented in the Cube demand modeling system with extensive spatial data processing using ArcGIS. ^ To evaluate the performance of the new method, data from several study areas in Broward County in Florida were used. The estimated AADTs were compared with those from two existing methods using actual traffic counts as the ground truths. The results show that the new method performs better than both existing methods. One limitation with the new method is that it relies on Cube which limits the number of zones to 32,000. Accordingly, a study area exceeding this limit must be partitioned into smaller areas. Because AADT estimates for roads near the boundary areas were found to be less accurate, further research could examine the best way to partition a study area to minimize the impact.^

A novel signal processing method for intraoperative neurophysiological monitoring in spinal surgeries

Intraoperative neurophysiologic monitoring is an integral part of spinal surgeries and involves the recording of somatosensory evoked potentials (SSEP). However, clinical application of IONM still requires anywhere between 200 to 2000 trials to obtain an SSEP signal, which is excessive and introduces a significant delay during surgery to detect a possible neurological damage. The aim of this study is to develop a means to obtain the SSEP using a much less, twelve number of recordings. The preliminary step involved was to distinguish the SSEP with the ongoing brain activity. We first establish that the brain activity is indeed quasi-stationary whereas an SSEP is expected to be identical every time a trial is recorded. An algorithm was developed using Chebychev time windowing for preconditioning of SSEP trials to retain the morphological characteristics of somatosensory evoked potentials (SSEP). This preconditioning was followed by the application of a principal component analysis (PCA)-based algorithm utilizing quasi-stationarity of EEG on 12 preconditioned trials. A unique Walsh transform operation was then used to identify the position of the SSEP event. An alarm is raised when there is a 10% time in latency deviation and/or 50% peak-to-peak amplitude deviation, as per the clinical requirements. The algorithm shows consistency in the results in monitoring SSEP in up to 6-hour surgical procedures even under this significantly reduced number of trials. In this study, the analysis was performed on the data recorded in 29 patients undergoing surgery during which the posterior tibial nerve was stimulated and SSEP response was recorded from scalp. This method is shown empirically to be more clinically viable than present day approaches. In all 29 cases, the algorithm takes 4sec to extract an SSEP signal, as compared to conventional methods, which take several minutes. The monitoring process using the algorithm was successful and proved conclusive under the clinical constraints throughout the different surgical procedures with an accuracy of 91.5%. Higher accuracy and faster execution time, observed in the present study, in determining the SSEP signals provide a much improved and effective neurophysiological monitoring process.

Lattice Boltzmann Method for Flow and Heat Transfer in Microgeometries

Recent technological developments have made it possible to design various microdevices where fluid flow and heat transfer are involved. For the proper design of such systems, the governing physics needs to be investigated. Due to the difficulty to study complex geometries in micro scales using experimental techniques, computational tools are developed to analyze and simulate flow and heat transfer in microgeometries. However, conventional numerical methods using the Navier-Stokes equations fail to predict some aspects of microflows such as nonlinear pressure distribution, increase mass flow rate, slip flow and temperature jump at the solid boundaries. This necessitates the development of new computational methods which depend on the kinetic theory that are both accurate and computationally efficient. In this study, lattice Boltzmann method (LBM) was used to investigate the flow and heat transfer in micro sized geometries. The LBM depends on the Boltzmann equation which is valid in the whole rarefaction regime that can be observed in micro flows. Results were obtained for isothermal channel flows at Knudsen numbers higher than 0.01 at different pressure ratios. LBM solutions for micro-Couette and micro-Poiseuille flow were found to be in good agreement with the analytical solutions valid in the slip flow regime (0.01 < Kn < 0.1) and direct simulation Monte Carlo solutions that are valid in the transition regime (0.1 < Kn < 10) for pressure distribution and velocity field. The isothermal LBM was further extended to simulate flows including heat transfer. The method was first validated for continuum channel flows with and without constrictions by comparing the thermal LBM results against accurate solutions obtained from analytical equations and finite element method. Finally, the capability of thermal LBM was improved by adding the effect of rarefaction and the method was used to analyze the behavior of gas flow in microchannels. The major finding of this research is that, the newly developed particle-based method described here can be used as an alternative numerical tool in order to study non-continuum effects observed in micro-electro-mechanical-systems (MEMS).

Determining polarization dependent diffraction coefficients from building edges using FDTD method

Electromagnetic waves in suburban environment encounter multiple obstructions that shadow the signal. These waves are scattered and random in polarization. They take multiple paths that add as vectors at the portable device. Buildings have vertical and horizontal edges. Diffraction from edges has polarization dependent characteristics. In practical case, a signal transmitted from a vertically polarized high antenna will result in a significant fraction of total power in the horizontal polarization at the street level. Signal reception can be improved whenever there is a probability of receiving the signal in at least two independent ways or branches. The Finite-Difference Time-Domain (FDTD) method was applied to obtain the two and three-dimensional dyadic diffraction coefficients (soft and hard) of right-angle perfect electric conductor (PEC) wedges illuminated by a plane wave. The FDTD results were in good agreement with the asymptotic solutions obtained using Uniform Theory of Diffraction (UTD). Further, a material wedge replaced the PEC wedge and the dyadic diffraction coefficient for the same was obtained.

Improved Accuracy in Optical Motion Capture Measurements Leads to Increased Sensitivity to Kinematic Changes

Clinical optical motion capture allows us to obtain kinematic and kinetic outcome measures that aid clinicians in diagnosing and treating different pathologies affecting healthy gait. The long term aim for gait centres is for subject-specific analyses that can predict, prevent, or reverse the effects of pathologies through gait retraining. To track the body, anatomical segment coordinate systems are commonly created by applying markers to the surface of the skin over specific, bony anatomy that is manually palpated. The location and placement of these markers is subjective and precision errors of up to 25mm have been reported [1]. Additionally, the selection of which anatomical landmarks to use in segment models can result in large angular differences; for example angular differences in the trunk can range up to 53o for the same motion depending on marker placement [2]. These errors can result in erroneous kinematic outcomes that either diminish or increase the apparent effects of a treatment or pathology compared to healthy data. Our goal was to improve the accuracy and precision of optical motion capture outcome measures. This thesis describes two separate studies. In the first study we aimed to establish an approach that would allow us to independently quantify the error among trunk models. Using this approach we determined if there was a best model to accurately track trunk motion. In the second study we designed a device to improve precision for test, re-test protocols that would also reduce the set-up time for motion capture experiments. Our method to compare a kinematically derived centre of mass velocity to one that was derived kinetically was successful in quantifying error among trunk models. Our findings indicate that models that use lateral shoulder markers as well as limit the translational degrees of freedom of the trunk through shared pelvic markers result in the least amount of error for the tasks we studied. We also successfully reduced intra- and inter-operator anatomical marker placement errors using a marker alignment device. The improved accuracy and precision resulting from the methods established in this thesis may lead to increased sensitivity to changes in kinematics, and ultimately result in more consistent treatment outcomes.

Implementing a structural continuity constraint and a halting method for the topology optimization of energy absorbers

This study investigates topology optimization of energy absorbing structures in which material damage is accounted for in the optimization process. The optimization objective is to design the lightest structures that are able to absorb the required mechanical energy. A structural continuity constraint check is introduced that is able to detect when no feasible load path remains in the finite element model, usually as a result of large scale fracture. This assures that designs do not fail when loaded under the conditions prescribed in the design requirements. This continuity constraint check is automated and requires no intervention from the analyst once the optimization process is initiated. Consequently, the optimization algorithm proceeds towards evolving an energy absorbing structure with the minimum structural mass that is not susceptible to global structural failure. A method is also introduced to determine when the optimization process should halt. The method identifies when the optimization method has plateaued and is no longer likely to provide improved designs if continued for further iterations. This provides the designer with a rational method to determine the necessary time to run the optimization and avoid wasting computational resources on unnecessary iterations. A case study is presented to demonstrate the use of this method.

Synthesis of Pr0.6Sr0.4FeO 3-δ -xCe0.9Pr0.1O 2-δ cobalt-free composite cathodes by a one-pot method for intermediate-temperature solid oxide fuel cells

Cobalt-free composite cathodes consisting of Pr_0.6Sr_0.4FeO _3-δ -xCe_0.9Pr_0.1O _2-δ (PSFO-xCPO, x = 0-50 wt%) have been synthesized using a one-pot method. X-ray diffraction, scanning electron microscopy, thermal expansion coefficient, conductivity, and polarization resistance (R _P ) have been used to characterize the PSFO-xCPO cathodes. Furthermore the discharge performance of the Ni-SSZ/SSZ/GDC/PSFO-xCPO cells has been measured. The experimental results indicate that the PSFO-xCPO composite materials fully consist of PSFO and CPO phases and posses a porous microstructure. The conductivity of PSFO-xCPO decreases with the increase of CPO content, but R _P of PSFO-40CPO shows the smallest value amongst all the samples. The power density of single cells with a PSFO-40CPO composite cathode is significantly improved compared with that of the PSFO cathode, exhibiting 0.43, 0.75, 1.08 and 1.30 W cm^-2 at 650, 700, 750 and 800 °C, respectively. In addition, single cells with the PSFO-40CPO composite cathode show a stable performance with no obvious degradation over 100 h when operating at 750 °C.

Phonic skills mediate improved literacy outcomes in at-risk primary school children: results from the Ready-to-Learn Programme

Background
Learning to read is a key goal during primary school: reading difficulties may curtail children’s learning trajectories. Controversy remains regarding what types of interventions are effective for children at risk for academic failure, such as children in disadvantaged areas. We present data from a complex intervention to test the hypothesis that phonic skills and word recognition abilities are a pivotal and specific causal mechanism for the development of reading skills in children at risk for poorer literacy outcomes.
Method
Over 500 pupils across 16 primary schools took part in a Cluster Randomised Controlled Trial from school year 1 to year 3. Schools were randomly allocated to the intervention or the control arm. The intervention involved a literacy-rich after-school programme. Children attending schools in the control arm of the study received the curriculum normally provided. Children in both arms completed batteries of language, phonic skills, and reading tests every year. We used multilevel mediation models to investigate mediating processes between intervention and outcomes.
Findings
Children who took part in the intervention displayed improvements in reading skills compared to those in the control arm. Results indicated a significant indirect effect of the intervention via phonics encoding.
Discussion
The results suggest that the intervention was effective in improving reading abilities of children at risk, and this effect was mediated by improving children’s phonic skills. This has relevance for designing interventions aimed at improving literacy skills of children exposed to socio-economic disadvantage. Results also highlight the importance of methods to investigate causal pathways from intervention to outcomes.