Kinetic isotope effects of proton transfer reaction for amines by ultrasonic relaxation methods: Unexpected evidence from the results in ethylamine solutions

Ultrasonic absorption coefficients for ethylamine in heavy water (D2O) and in light water (H2O) have been measured in the frequency range from 0.8 to 220 MHz at 25 degrees C. A single relaxational process has been observed in these two kinds of solutions. From the concentration dependence of the ultrasonic relaxation parameters, and following the reaction mechanism proposed by Eigen et al. for ethylamine in H2O, the causes of the relaxations have been attributed to a perturbation of an equilibrium associated with a deuteron or proton transfer reaction. The rate and equilibrium constants have been estimated from deuterioxide or hydroxide ion concentration dependence of the relaxation frequency, and the kinetic isotope effects have been determined. In addition, the standard volume changes of the reactions have been calculated from the concentration dependence of the maximum absorption per wavelength, and the adiabatic compressibility has also been determined from the density and sound velocity for ethylamine in D2O and in H2O, respectively. These results are compared with those for propylamine and butylamine and are discussed in relation to the different kinetic properties between D2O and H2O, the reaction radii derived by Debye theory, and the structural properties of the reaction intermediate.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

叠前地震数据规则化、重建及噪音压制

I address of reconstruction of spatial irregular sampling seismic data to regular grids. Spatial irregular sampling data impairs results of prestack migration, multiple attenuations, spectra estimation. Prestack 5-D volumes are often divided into sub-sections for further processing. Shot gathers are easy to obtain from irregular sampling volumes. My strategy for reconstruction is as follows: I resort irregular sampling gathers into a form of easy to bin and perform bin regularization, then utilize F-K inversion to reconstruct seismic data. In consideration of poor ability of F-K regularization to fill in large gaps, I sort regular sampling gathers to CMP and proposed high-resolution parabolic Radon transform to interpolate data and extrapolate offsets. To strong interfering noise--multiples, I use hybrid-domain high-resolution parabolic Radon transform to attenuate it. F-K regularization demand ultimately for lower computing costs. I proposed several methods to further improve efficiency of F-K inversion: first I introduce 1D and 2D NFFT algorithm for a rapid calculation of DFT operators; then develop fast 1D and 2D CG method to solve least-square equations, and utilize preconditioner to accelerate convergence of CG iterations; what’s more, I use Delaunay triangulation for weight calculation and use bandlimit frequency and varying bandwidth technique for competitive computation. Numerical 2D and 3D examples are offered to verify reasonable results and more efficiency. F-K regularization has poor ability to fill in large gaps, so I rearrange data as CMP gathers and develop hybrid-domain high-resolution parabolic Radon transforms which be used ether to interpolate null traces and extrapolate near and far offsets or suppress a strong interfere noise: multiples. I use it to attenuate multiples to verify performances of our algorithm and proposed routines for industrial application. Numerical examples and field data examples show a nice performance of our method.

砂泥岩薄互层储层预测方法与应用研究

With the deeply development of exploration and development in petroleum in China, new increasing reserves are found in old oil fields and the verge of the old ones through re-study of geological property. It is more and more important to discovery and develop thin layer or thin inter-bedded layers reservoirs. All of the targets are thin sand-shale inter-bedded reservoirs and the core technology is reservoir predictions between wells in thin sand-shale inter-bedded layers. The continuity of the thin sand-shale inter-bedded layers in space or separating and heterogeneity is the key of reservoir geology research. The seismic reflection, high resolution analysis method and inversion method to thin sand-shale inter-bedded layers are thorough discussed and deeply studied in this paper to try to find the methods and resolutions of reservoir geology research. The below is followed. 1. Based on the pre-research of other people, five models are created: the sand sphenoid body, interlay sandstone and interlay shale of the equal thickness, interlay sandstone of the equal thickness and interlay shale of the unequal thickness, interlay sandstone of the unequal thickness and interlay shale of the unequal thickness, interlay sandstone of the changing thickness in sequence and interlay shale of the changing thickness in sequence. Then the study of the forward modeling are conducted on the thin layer and thin inter-bedded layers geological characters and seismic reflections including amplitude, frequency, phase, wave shape and time-frequency responding in the domains of time and frequency. The affect of petro-physics difference of layers, single thin layer thickness, thickness of inter-bedded, layer number of inter-bedded, incident wavelet domain frequency and types, sample interval to seismic reflection characters, frequency spectrum and time-frequency respond of reflectivity is theoretically discussed. 2. Qualitatively analyzing the sedimentary rhythm of the thin inter-bedded layers in vertical orientation and computing the single layer thickness or the average thickness with the method of generalized S transform. Identifying the reflecting interface or lithology interface using the amplitude value of amplitude spectrum domain frequency. 3. Based on the seismic respond of thin sand-shale inter-bedded layers, bring out the high resolution analysis method of seismic data in thin sand-shale inter-bedded layers using wavelet analysis and the idea of affecting low and high frequency with middle frequency. Then analyzing the effect to the method and testing some wavelets in the method. This method is applied to the theoretical models and the field data. 4. Bring forward one improved very fast simulated annealing method (IVFSA) to resolve the problem nonlinearity and multi-parameters of the inversion in thin inter-bedded layers. And IVFSA is more productive and higher precision than general ways. 5. New target constrained function is used in the inversion based on the property of the inversion in thin inter-bedded layers. 6. Making the full use of geological and logging information, IVFSA and the new function are applied in the non-linear inversion to improve reservoir prediction and evaluation in thin inter-bedded formations combined with the idea of logging and seismic inversion. This method was applied to the field data and got good results.

小波域地震资料的处理方法（WSSP）研究

The modeling formula based on seismic wavelet can well simulate zero - phase wavelet and hybrid-phase wavelet, and approximate maximal - phase and minimal - phase wavelet in a certain sense. The modeling wavelet can be used as wavelet function after suitable modification item added to meet some conditions. On the basis of the modified Morlet wavelet, the derivative wavelet function has been derived. As a basic wavelet, it can be sued for high resolution frequency - division processing and instantaneous feature extraction, in acoordance with the signal expanding characters in time and scale domains by each wavelet structured. Finally, an application example proves the effectiveness and reasonability of the method. Based on the analysis of SVD (Singular Value Decomposition) filter, by taking wavelet as basic wavelet and combining SVD filter and wavelet transform, a new de - noising method, which is Based on multi - dimension and multi-space de - noising method, is proposed. The implementation of this method is discussed the detail. Theoretical analysis and modeling show that the method has strong capacity of de - noising and keeping attributes of effective wave. It is a good tool for de - noising when the S/N ratio is poor. To give prominence to high frequency information of reflection event of important layer and to take account of other frequency information under processing seismic data, it is difficult for deconvolution filter to realize this goal. A filter from Fourier Transform has some problems for realizing the goal. In this paper, a new method is put forward, that is a method of processing seismic data in frequency division from wavelet transform and reconstruction. In ordinary seismic processing methods for resolution improvement, deconvolution operator has poor part characteristics, thus influencing the operator frequency. In wavelet transform, wavelet function has very good part characteristics. Frequency - division data processing in wavelet transform also brings quite good high resolution data, but it needs more time than deconvolution method does. On the basis of frequency - division processing method in wavelet domain, a new technique is put forward, which involves 1) designing filter operators equivalent to deconvolution operator in time and frequency domains in wavelet transform, 2) obtaining derivative wavelet function that is suitable to high - resolution seismic data processing, and 3) processing high resolution seismic data by deconvolution method in time domain. In the method of producing some instantaneous characteristic signals by using Hilbert transform, Hilbert transform is very sensitive to high - frequency random noise. As a result, even though there exist weak high - frequency noises in seismic signals, the obtained instantaneous characteristics of seismic signals may be still submerged by the noises. One method for having instantaneous characteristics of seismic signals in wavelet domain is put forward, which obtains directly the instantaneous characteristics of seismic signals by taking the characteristics of both the real part (real signals, namely seismic signals) and the imaginary part (the Hilbert transfom of real signals) of wavelet transform. The method has the functions of frequency division and noise removal. What is more, the weak wave whose frequency is lower than that of high - frequency random noise is retained in the obtained instantaneous characteristics of seismic signals, and the weak wave may be seen in instantaneous characteristic sections (such as instantaneous frequency, instantaneous phase and instantaneous amplitude). Impedance inversion is one of tools in the description of oil reservoir. one of methods in impedance inversion is Generalized Linear Inversion. This method has higher precision of inversion. But, this method is sensitive to noise of seismic data, so that error results are got. The description of oil reservoir in researching important geological layer, in order to give prominence to geological characteristics of the important layer, not only high frequency impedance to research thin sand layer, but other frequency impedance are needed. It is difficult for some impedance inversion method to realize the goal. Wavelet transform is very good in denoising and processing in frequency division. Therefore, in the paper, a method of impedance inversion is put forward based on wavelet transform, that is impedance inversion in frequency division from wavelet transform and reconstruction. in this paper, based on wavelet transform, methods of time - frequency analysis is given. Fanally, methods above are in application on real oil field - Sansan oil field.

地震波场模拟及叠前深度偏移的李群方法

The processes of seismic wave propagation in phase space and one way wave extrapolation in frequency-space domain, if without dissipation, are essentially transformation under the action of one parameter Lie groups. Consequently, the numerical calculation methods of the propagation ought to be Lie group transformation too, which is known as Lie group method. After a fruitful study on the fast methods in matrix inversion, some of the Lie group methods in seismic numerical modeling and depth migration are presented here. Firstly the Lie group description and method of seismic wave propagation in phase space is proposed, which is, in other words, symplectic group description and method for seismic wave propagation, since symplectic group is a Lie subgroup and symplectic method is a special Lie group method. Under the frame of Hamiltonian, the propagation of seismic wave is a symplectic group transformation with one parameter and consequently, the numerical calculation methods of the propagation ought to be symplectic method. After discrete the wave field in time and phase space, many explicit, implicit and leap-frog symplectic schemes are deduced for numerical modeling. Compared to symplectic schemes, Finite difference (FD) method is an approximate of symplectic method. Consequently, explicit, implicit and leap-frog symplectic schemes and FD method are applied in the same conditions to get a wave field in constant velocity model, a synthetic model and Marmousi model. The result illustrates the potential power of the symplectic methods. As an application, symplectic method is employed to give synthetic seismic record of Qinghai foothills model. Another application is the development of Ray+symplectic reverse-time migration method. To make a reasonable balance between the computational efficiency and accuracy, we combine the multi-valued wave field & Green function algorithm with symplectic reverse time migration and thus develop a new ray+wave equation prestack depth migration method. Marmousi model data and Qinghai foothills model data are processed here. The result shows that our method is a better alternative to ray migration for complex structure imaging. Similarly, the extrapolation of one way wave in frequency-space domain is a Lie group transformation with one parameter Z and consequently, the numerical calculation methods of the extrapolation ought to be Lie group methods. After discrete the wave field in depth and space, the Lie group transformation has the form of matrix exponential and each approximation of it gives a Lie group algorithm. Though Pade symmetrical series approximation of matrix exponential gives a extrapolation method which is traditionally regarded as implicit FD migration, it benefits the theoretic and applying study of seismic imaging for it represent the depth extrapolation and migration method in a entirely different way. While, the technique of coordinates of second kind for the approximation of the matrix exponential begins a new way to develop migration operator. The inversion of matrix plays a vital role in the numerical migration method given by Pade symmetrical series approximation. The matrix has a Toepelitz structure with a helical boundary condition and is easy to inverse with LU decomposition. A efficient LU decomposition method is spectral factorization. That is, after the minimum phase correlative function of each array of matrix had be given by a spectral factorization method, all of the functions are arranged in a position according to its former location to get a lower triangular matrix. The major merit of LU decomposition with spectral factorization (SF Decomposition) is its efficiency in dealing with a large number of matrixes. After the setup of a table of the spectral factorization results of each array of matrix, the SF decomposition can give the lower triangular matrix by reading the table. However, the relationship among arrays is ignored in this method, which brings errors in decomposition method. Especially for numerical calculation in complex model, the errors is fatal. Direct elimination method can give the exact LU decomposition But even it is simplified in our case, the large number of decomposition cost unendurable computer time. A hybrid method is proposed here, which combines spectral factorization with direct elimination. Its decomposition errors is 10 times little than that of spectral factorization, and its decomposition speed is quite faster than that of direct elimination, especially in dealing with a large number of matrix. With the hybrid method, the 3D implicit migration can be expected to apply on real seismic data. Finally, the impulse response of 3D implicit migration operator is presented.

各向异性介质中的地震面波和S波分裂

Surface wave propagation in the anisotropic media and S-wave splitting in China mainland are focused in this M.S. dissertation. We firstly introduced Anderson parameters in the research of surface wave propagation in the anisotropic media were deduced, respectively. By applying the given initial model to the forward calculation of Love wave, we compared dispersion curves of Love wave in the anisotropic media with the one in the isotropic media. the results show that, although the two kind of results are similar with each other, the effect of anisotropy can not be neglected. Furthermore, the variation of anisotropy factors will result in the variation of dispersion curves, especially for high-mode one. The method of grid dispersion inversion was then described for further tectonic inversion. We also deduced inversion equation on the condition that the layered media is anisotropic, and calculated the phase-velocity partial derivatives with respect to the model parameters, P- and S-wave velocities, density, anisotropic parameters for Rayleigh wave and Love wave. Having analyzed the results of phase-velocity partial derivatives, we concluded that the derivatives within each period decreased with the depth increasing, the phase-velocity of surface wave is sensitive to the S-wave velocities and anisotropic factors and is not sensitive to the densities of layers. Dispersion data of Love wave from the events occurred during the period from 1991 to 1998 around the Qinghai and Tibet Plateau, which magnitudes are more than 5.5, have been used in the grid dispersion inversion. Those data have been preprocessed and analyzed in the F-T domain. Then the results of 1°*1° grid dispersion inversion, the pure path dispersion data, in the area of Qianghai and Tibet Plateau were obtained. As an example, dispersion data have been input for the tectonic inversion in the anisotropic media, and the results of anisotropic factors under the region of Qianghai and Tibet Plateau were initially discussed. As for the other part of this dissertation. We first introduced the phenomena of S-wave splitting and the methods for calculation the splitting parameters. Then, We applied Butterworth band-pass filter to S-wave data recorded at 8 stations in China mainland, and analyzed S-wave splitting at different frequency bands. The results show the delay time and the fast polarization directions of S-wave splitting depend upon the frequency bands. There is an absence of S-wave splitting at the station of Wulumuqi (WMQ) for the band of 0.1-0.2Hz. With the frequency band broaden, the delay time of S-wave splitting decreases at the stations of Beijing (BJI), Enshi (ENH), Kunming (KMI) and Mudanjiang (MDJ); the fast polarization direction at Enshi (ENH) changes from westward to eastward, and eastward to westward at Hailaer (HIA). The variations of delay time with bands at Lanzhou (LZH) and qiongzhong (QIZ) are similar, and there is a coherent trend of fast polarization directions at BJI, KMI and MDJ respectively. Initial interpretations to the results of frequency band-dependence of S-wave splitting were also presented.

井间地震技术研究和应用

Cross well seismic technique is a new type of geophysical method, which observes the seismic wave of the geologic body by placing both the source and receiver in the wells. By applying this method, it averted the absorption to high-frequency component of seismic signal caused by low weathering layers, thus, an extremely high-resolution seismic signal can be acquired. And extremely fine image of cross well formations, structure, and reservoir can be achieved as well. An integrated research is conducted to the high-frequency S-wave and P-wave data and some other data to determine the small faults, small structure and resolving the issues concerning the thin bed and reservoir's connectivity, fluid distribution, steam injection and fracture. This method connects the high-resolution surface seismic, logging and reservoir engineering. In this paper, based on the E & P situation in the oilfield and the theory of geophysical exploration, a research is conducted on cross well seismic technology in general and its important issues in cross well seismic technology in particular. A technological series of integrated field acquisition, data processing and interpretation and its integrated application research were developed and this new method can be applied to oilfield development and optimizing oilfield development scheme. The contents and results in this paper are as listed follows: An overview was given on the status quo and development of the cross well seismic method and problems concerning the cross well seismic technology and the difference in cross well seismic technology between China and international levels; And an analysis and comparison are given on foreign-made field data acquisition systems for cross-well seismic and pointed out the pros and cons of the field systems manufactured by these two foreign companies and this is highly valuable to import foreign-made cross well seismic field acquisition system for China. After analyses were conducted to the geometry design and field data for the cross well seismic method, a common wave field time-depth curve equation was derived and three types of pipe waves were discovered for the first time. Then, a research was conducted on the mechanism for its generation. Based on the wave field separation theory for cross well seismic method, we believe that different type of wave fields in different gather domain has different attributes characteristics, multiple methods (for instance, F-K filtering and median filtering) were applied in eliminating and suppressing the cross well disturbances and successfully separated the upgoing and downgoing waves and a satisfactory result has been achieved. In the area of wave field numerical simulation for cross well seismic method, a analysis was conducted on conventional ray tracing method and its shortcomings and proposed a minimum travel time ray tracing method based on Feraiat theory in this paper. This method is not only has high-speed calculation, but also with no rays enter into "dead end" or "blinded spot" after numerous iterations and it is become more adequate for complex velocity model. This is first time that the travel time interpolation has been brought into consideration, a dynamic ray tracing method with shortest possible path has been developed for the first arrivals of any complex mediums, such as transmission, diffraction and refraction, etc and eliminated the limitation for only traveling from one node to another node and increases the calculation accuracy for minimum travel time and ray tracing path and derives solution and corresponding edge conditions to the fourth-order differential sonic wave equation. The final step is to calculate cross well seismic synthetics for given source and receivers from multiple geological bodies. Thus, real cross-well seismic wave field can be recognized through scientific means and provides important foundation to guide the cross well seismic field geometry designing. A velocity tomographic inversion of the least square conjugated gradient method was developed for cross well seismic velocity tomopgraphic inversion and a modification has been made to object function of the old high frequency ray tracing method and put forward a thin bed oriented model for finite frequency velocity tomographic inversion method. As the theory model and results demonstrates that the method is simple and effective and is very important in seismic ray tomographic imaging for the complex geological body. Based on the characteristics of the cross well seismic algorithm, a processing flow for cross well seismic data processing has been built and optimized and applied to the production, a good section of velocity tomopgrphic inversion and cross well reflection imaging has been acquired. The cross well seismic data is acquired from the depth domain and how to interprets the depth domain data and retrieve the attributes is a brand new subject. After research was conducted on synthetics and trace integration from depth domain for the cross well seismic data interpretation, first of all, a research was conducted on logging constraint wave impedance of cross well seismic data and initially set up cross well seismic data interpretation flows. After it applied and interpreted to the cross well seismic data and a good geological results has been achieved in velocity tomographic inversion and reflection depth imaging and a lot of difficult problems for oilfield development has been resolved. This powerful, new method is good for oilfield development scheme optimization and increasing EOR. Based on conventional reservoir geological model building from logging data, a new method is also discussed on constraining the accuracy of reservoir geological model by applying the high resolution cross well seismic data and it has applied to Fan 124 project and a good results has been achieved which it presents a bight future for the cross well seismic technology.

Inspection Methods in Programming

The work reported here lies in the area of overlap between artificial intelligence software engineering. As research in artificial intelligence, it is a step towards a model of problem solving in the domain of programming. In particular, this work focuses on the routine aspects of programming which involve the application of previous experience with similar programs. I call this programming by inspection. Programming is viewed here as a kind of engineering activity. Analysis and synthesis by inspection area prominent part of expert problem solving in many other engineering disciplines, such as electrical and mechanical engineering. The notion of inspections methods in programming developed in this work is motivated by similar notions in other areas of engineering. This work is also motivated by current practical concerns in the area of software engineering. The inadequacy of current programming technology is universally recognized. Part of the solution to this problem will be to increase the level of automation in programming. I believe that the next major step in the evolution of more automated programming will be interactive systems which provide a mixture of partially automated program analysis, synthesis and verification. One such system being developed at MIT, called the programmer's apprentice, is the immediate intended application of this work. This report concentrates on the knowledge are of the programmer's apprentice, which is the form of a taxonomy of commonly used algorithms and data structures. To the extent that a programmer is able to construct and manipulate programs in terms of the forms in such a taxonomy, he may relieve himself of many details and generally raise the conceptual level of his interaction with the system, as compared with present day programming environments. Also, since it is practical to expand a great deal of effort pre-analyzing the entries in a library, the difficulty of verifying the correctness of programs constructed this way is correspondingly reduced. The feasibility of this approach is demonstrated by the design of an initial library of common techniques for manipulating symbolic data. This document also reports on the further development of a formalism called the plan calculus for specifying computations in a programming language independent manner. This formalism combines both data and control abstraction in a uniform framework that has facilities for representing multiple points of view and side effects.

The Geometry of Frequency Squares

Mavron, Vassili; Jungnickel, D.; McDonough, T.P., (2001) 'The Geometry of Frequency Squares', Journal of Combinatorial Theory, Series A 96, pp.376-387 RAE2008

Human papillomavirus detection in women with and without human immunodeficiency virus infection in Colombia

Background: HIV infection leads to a decreasing immune response, thereby facilitating the appearance of other infections, one of the most important ones being HPV. However, studies are needed for determining associations between immunodeficiency caused by HIV and/or the presence of HPV during the course of cervical lesions and their degree of malignancy. This study describes the cytological findings revealed by the Papanicolaou test, laboratory characteristics and HPV molecular profile in women with and without HIV infection. Methods: A total of 216 HIV-positive and 1,159 HIV-negative women were invited to participate in the study; PCR was used for the molecular detection of HPV in cervical samples. Statistical analysis (such as percentages, Chi-square test and Fisher's exact test when applicable) determined human papillomavirus (HPV) infection frequency (single and multiple) and the distribution of six types of high-risk-HPV in women with and without HIV infection. Likewise, a logistic regression model was run to evaluate the relationship between HIV-HPV infection and different risk factors. Results: An association was found between the frequency of HPV infection and infection involving 2 or more HPV types (also known as multiple HPV infection) in HIV-positive women (69.0% and 54.2%, respectively); such frequency was greater than that found in HIV-negative women (44.3% and 22.7%, respectively). Statistically significant differences were observed between both groups (p = 0.001) regarding HPV presence (both in infection and multiple HPV infection). HPV-16 was the most prevalent type in the population being studied (p = 0.001); other viral types had variable distribution in both groups (HIV-positive and HIV-negative). HPV detection was associated with <500 cell/mm(3) CD4-count (p = 0.004) and higher HIV-viral-load (p = 0.001). HPV-DNA detection, <200 cell/mm(3) CD4-count (p = 0.001), and higher HIV-viral-load (p = 0.001) were associated with abnormal cytological findings. Conclusions: The HIV-1 positive population in this study had high multiple HPV infection prevalence. The results for this population group also suggested a greater association between HPV-DNA presence and cytological findings. HPV detection, together with low CD4 count, could represent useful tools for identifying HIV-positive women at risk of developing cervical lesions.

Evaluation of Speaker Normalization Methods for Vowel Recognition Using Fuzzy ARTMAP and K-NN

A procedure that uses fuzzy ARTMAP and K-Nearest Neighbor (K-NN) categorizers to evaluate intrinsic and extrinsic speaker normalization methods is described. Each classifier is trained on preprocessed, or normalized, vowel tokens from about 30% of the speakers of the Peterson-Barney database, then tested on data from the remaining speakers. Intrinsic normalization methods included one nonscaled, four psychophysical scales (bark, bark with end-correction, mel, ERB), and three log scales, each tested on four different combinations of the fundamental (Fo) and the formants (F1 , F2, F3). For each scale and frequency combination, four extrinsic speaker adaptation schemes were tested: centroid subtraction across all frequencies (CS), centroid subtraction for each frequency (CSi), linear scale (LS), and linear transformation (LT). A total of 32 intrinsic and 128 extrinsic methods were thus compared. Fuzzy ARTMAP and K-NN showed similar trends, with K-NN performing somewhat better and fuzzy ARTMAP requiring about 1/10 as much memory. The optimal intrinsic normalization method was bark scale, or bark with end-correction, using the differences between all frequencies (Diff All). The order of performance for the extrinsic methods was LT, CSi, LS, and CS, with fuzzy AHTMAP performing best using bark scale with Diff All; and K-NN choosing psychophysical measures for all except CSi.

Speaker Normalization Methods for Vowel Cognition: Comparative Analysis Using Neural Network and Nearest Neighbor Classifiers

Intrinsic and extrinsic speaker normalization methods are systematically compared using a neural network (fuzzy ARTMAP) and L1 and L2 K-Nearest Neighbor (K-NN) categorizers trained and tested on disjoint sets of speakers of the Peterson-Barney vowel database. Intrinsic methods include one nonscaled, four psychophysical scales (bark, bark with endcorrection, mel, ERB), and three log scales, each tested on four combinations of F0 , F1, F2, F3. Extrinsic methods include four speaker adaptation schemes, each combined with the 32 intrinsic methods: centroid subtraction across all frequencies (CS), centroid subtraction for each frequency (CSi), linear scale (LS), and linear transformation (LT). ARTMAP and KNN show similar trends, with K-NN performing better, but requiring about ten times as much memory. The optimal intrinsic normalization method is bark scale, or bark with endcorrection, using the differences between all frequencies (Diff All). The order of performance for the extrinsic methods is LT, CSi, LS, and CS, with fuzzy ARTMAP performing best using bark scale with Diff All; and K-NN choosing psychophysical measures for all except CSi.

Development of large-scale colloidal crystallisation methods for the production of photonic crystals

Colloidal photonic crystals have potential light manipulation applications including; fabrication of efficient lasers and LEDs, improved optical sensors and interconnects, and improving photovoltaic efficiencies. One road-block of colloidal selfassembly is their inherent defects; however, they can be manufactured cost effectively into large area films compared to micro-fabrication methods. This thesis investigates production of ‘large-area’ colloidal photonic crystals by sonication, under oil co-crystallization and controlled evaporation, with a view to reducing cracking and other defects. A simple monotonic Stöber particle synthesis method was developed producing silica particles in the range of 80 to 600nm in a single step. An analytical method assesses the quality of surface particle ordering in a semiquantitative manner was developed. Using fast Fourier transform (FFT) spot intensities, a grey scale symmetry area method, has been used to quantify the FFT profiles. Adding ultrasonic vibrations during film formation demonstrated large areas could be assembled rapidly, however film ordering suffered as a result. Under oil cocrystallisation results in the particles being bound together during film formation. While having potential to form large areas, it requires further refinement to be established as a production technique. Achieving high quality photonic crystals bonded with low concentrations (<5%) of polymeric adhesives while maintaining refractive index contrast, proved difficult and degraded the film’s uniformity. A controlled evaporation method, using a mixed solvent suspension, represents the most promising method to produce high quality films over large areas, 75mm x 25mm. During this mixed solvent approach, the film is kept in the wet state longer, thus reducing cracks developing during the drying stage. These films are crack-free up to a critical thickness, and show very large domains, which are visible in low magnification SEM images as Moiré fringe patterns. Higher magnification reveals separation between alternate fringe patterns are domain boundaries between individual crystalline growth fronts.

Voltage properties of optically injected long wavelength VCSELs: Theory and experiment

Future high speed communications networks will transmit data predominantly over optical fibres. As consumer and enterprise computing will remain the domain of electronics, the electro-optical conversion will get pushed further downstream towards the end user. Consequently, efficient tools are needed for this conversion and due to many potential advantages, including low cost and high output powers, long wavelength Vertical Cavity Surface Emitting Lasers (VCSELs) are a viable option. Drawbacks, such as broader linewidths than competing options, can be mitigated through the use of additional techniques such as Optical Injection Locking (OIL) which can require significant expertise and expensive equipment. This thesis addresses these issues by removing some of the experimental barriers to achieving performance increases via remote OIL. Firstly, numerical simulations of the phase and the photon and carrier numbers of an OIL semiconductor laser allowed the classification of the stable locking phase limits into three distinct groups. The frequency detuning of constant phase values (ø) was considered, in particular ø = 0 where the modulation response parameters were shown to be independent of the linewidth enhancement factor, α. A new method to estimate α and the coupling rate in a single experiment was formulated. Secondly, a novel technique to remotely determine the locked state of a VCSEL based on voltage variations of 2mV−30mV during detuned injection has been developed which can identify oscillatory and locked states. 2D & 3D maps of voltage, optical and electrical spectra illustrate corresponding behaviours. Finally, the use of directly modulated VCSELs as light sources for passive optical networks was investigated by successful transmission of data at 10 Gbit/s over 40km of single mode fibre (SMF) using cost effective electronic dispersion compensation to mitigate errors due to wavelength chirp. A widely tuneable MEMS-VCSEL was established as a good candidate for an externally modulated colourless source after a record error free transmission at 10 Gbit/s over 50km of SMF across a 30nm single mode tuning range. The ability to remotely set the emission wavelength using the novel methods developed in this thesis was demonstrated.