In this study a new method is introduced to produce bimodal grain structures in low carbon steels. This method is based on cold rolling of dual phase structures and appropriate annealing treatments. The difference in the recrystallization behaviour of ferrite and martensite yields a heterogeneous microstructure with a distribution of coarse and fine grains. These types of microstructures are of interest for optimizing the balance of strength and uniform elongation in ultra-fine grained low carbon steels.

No description available.

The separation of natural and anthropogenically caused climatic changes is an important task of contemporary climate research. For this purpose, a detailed knowledge of the natural variability of the climate during warm stages is a necessary prerequisite. Beside model simulations and historical documents, this knowledge is mostly derived from analyses of so-called climatic proxy data like tree rings or sediment as well as ice cores. In order to be able to appropriately interpret such sources of palaeoclimatic information, suitable approaches of statistical modelling as well as methods of time series analysis are necessary, which are applicable to short, noisy, and non-stationary uni- and multivariate data sets. Correlations between different climatic proxy data within one or more climatological archives contain significant information about the climatic change on longer time scales. Based on an appropriate statistical decomposition of such multivariate time series, one may estimate dimensions in terms of the number of significant, linear independent components of the considered data set. In the presented work, a corresponding approach is introduced, critically discussed, and extended with respect to the analysis of palaeoclimatic time series. Temporal variations of the resulting measures allow to derive information about climatic changes. For an example of trace element abundances and grain-size distributions obtained near the Cape Roberts (Eastern Antarctica), it is shown that the variability of the dimensions of the investigated data sets clearly correlates with the Oligocene/Miocene transition about 24 million years before present as well as regional deglaciation events. Grain-size distributions in sediments give information about the predominance of different transportation as well as deposition mechanisms. Finite mixture models may be used to approximate the corresponding distribution functions appropriately. In order to give a complete description of the statistical uncertainty of the parameter estimates in such models, the concept of asymptotic uncertainty distributions is introduced. The relationship with the mutual component overlap as well as with the information missing due to grouping and truncation of the measured data is discussed for a particular geological example. An analysis of a sequence of grain-size distributions obtained in Lake Baikal reveals that there are certain problems accompanying the application of finite mixture models, which cause an extended climatological interpretation of the results to fail. As an appropriate alternative, a linear principal component analysis is used to decompose the data set into suitable fractions whose temporal variability correlates well with the variations of the average solar insolation on millenial to multi-millenial time scales. The abundance of coarse-grained material is obviously related to the annual snow cover, whereas a significant fraction of fine-grained sediments is likely transported from the Taklamakan desert via dust storms in the spring season. / Die Separation natürlicher und anthropogen verursachter Klimaänderungen ist eine bedeutende Aufgabe der heutigen Klimaforschung. Hierzu ist eine detaillierte Kenntnis der natürlichen Klimavariabilität während Warmzeiten unerlässlich. Neben Modellsimulationen und historischen Aufzeichnungen spielt hierfür die Analyse von sogenannten Klima-Stellvertreterdaten eine besondere Rolle, die anhand von Archiven wie Baumringen oder Sediment- und Eisbohrkernen erhoben werden. Um solche Quellen paläoklimatischer Informationen vernünftig interpretieren zu können, werden geeignete statistische Modellierungsansätze sowie Methoden der Zeitreihenanalyse benötigt, die insbesondere auf kurze, verrauschte und instationäre uni- und multivariate Datensätze anwendbar sind. Korrelationen zwischen verschiedenen Stellvertreterdaten eines oder mehrerer klimatologischer Archive enthalten wesentliche Informationen über den Klimawandel auf großen Zeitskalen. Auf der Basis einer geeigneten Zerlegung solcher multivariater Zeitreihen lassen sich Dimensionen schätzen als die Zahl der signifikanten, linear unabhängigen Komponenten des Datensatzes. Ein entsprechender Ansatz wird in der vorliegenden Arbeit vorgestellt, kritisch diskutiert und im Hinblick auf die Analyse von paläoklimatischen Zeitreihen weiterentwickelt. Zeitliche Variationen der entsprechenden Maße erlauben Rückschlüsse auf klimatische Veränderungen. Am Beispiel von Elementhäufigkeiten und Korngrößenverteilungen des Cape-Roberts-Gebietes in der Ostantarktis wird gezeigt, dass die Variabilität der Dimension der untersuchten Datensätze klar mit dem Übergang vom Oligozän zum Miozän vor etwa 24 Millionen Jahren sowie regionalen Abschmelzereignissen korreliert. Korngrößenverteilungen in Sedimenten erlauben Rückschlüsse auf die Dominanz verschiedenen Transport- und Ablagerungsmechanismen. Mit Hilfe von Finite-Mixture-Modellen lassen sich gemessene Verteilungsfunktionen geeignet approximieren. Um die statistische Unsicherheit der Parameterschätzung in solchen Modellen umfassend zu beschreiben, wird das Konzept der asymptotischen Unsicherheitsverteilungen eingeführt. Der Zusammenhang mit dem Überlapp der einzelnen Komponenten und aufgrund des Abschneidens und Binnens der gemessenen Daten verloren gehenden Informationen wird anhand eines geologischen Beispiels diskutiert. Die Analyse einer Sequenz von Korngrößenverteilungen aus dem Baikalsee zeigt, dass bei der Anwendung von Finite-Mixture-Modellen bestimmte Probleme auftreten, die eine umfassende klimatische Interpretation der Ergebnisse verhindern. Stattdessen wird eine lineare Hauptkomponentenanalyse verwendet, um den Datensatz in geeignete Fraktionen zu zerlegen, deren zeitliche Variabilität stark mit den Schwankungen der mittleren Sonneneinstrahlung auf der Zeitskala von Jahrtausenden bis Jahrzehntausenden korreliert. Die Häufigkeit von grobkörnigem Material hängt offenbar mit der jährlichen Schneebedeckung zusammen, während feinkörniges Material möglicherweise zu einem bestimmten Anteil durch Frühjahrsstürme aus der Taklamakan-Wüste herantransportiert wird.

In order to improve understanding of diesel soot oxidation, an experimental rig was designed and set up, in which the soot oxidation conditions, such as temperature, oxygen partial pressure, and CO2 partial pressure, could be varied independently of each other. The oxidizing gas flow in the oxidizer was under laminar condition. This test rig comprised a naturally-aspirated single cylinder engine which acted as the soot generator, and a separate premixed oxidation burner system in which soot extracted from the engine was oxidized under controlled conditions. Diesel soot was extracted from the engine exhaust pipe and from the engine pre-combustion chamber, and the soot-laden gas was then conveyed to the burner where it was oxidized. The burner was positioned vertically and it had a flat flame whose thickness was only a few millimetres. The hot gases from the flame flew upwards through a quartz transparent tube which acted as the soot oxidation duct. The soot-laden gas from the engine was premixed with the feedgas (itself a premixed mixture of methane, air, oxygen, and nitrogen) to the burner. The soot particles passed vertically through the flame front and continued burning in the post-flame gas flowing through the quartz tube oxidation duct. The oxygen concentration and temperature of the post-flame soot oxidation gas were controllable by adjusting the flowrate and composition of the burner feedgas. Diesel soot particles were sampled at different heights along the centreline of the quartz tube above the burner. Profiles of oxygen concentration, temperature, and soot particle velocity in the oxidation zone were thus measured. Morphology and size distributions of the sampled diesel soot particles were analyzed by means of Transmission Electron Microscopy (TEM) and a computer software called ImagePro Plus. Subsequently, the specific surface oxidation rates of the soot particles were worked out based on soot particle size distributions. The TEM micrographs obtained in this study showed that the diesel soot agglomerates existed in forms of clusters and chains, each containing between a small number and thousands of individual, mostly spherical tiny particles. Of order 97% of the individual spherical particles (spherules) had a size range from 10 to 80 nm. Occasionally, individual spherules of about 150 nm in diameter could be observed. The diesel soot particles sampled from the pre-chamber of the engine had different size distributions from those sampled from the exhaust of the engine, indicating that the soot underwent an oxidation process in the combustion chamber. Soot oxidation experiments were performed in the burner post-flame gas under oxygen partial pressures ranging from 0.010 to 0.050 atm and temperatures from 1520 to 1820 K. The test results showed that the oxidation rates of the diesel soot extracted from the diesel engine were generally lower than those predicted by the well-known Nagle and Strickland-Constable formula; however, the measured oxidation rates were higher than the predictions made with another well-known formula - the Lee formula. The soot extracted from the engine pre-chamber appeared not to oxidize as fast as the soot extracted from the exhaust of the engine. CO2 gas injection to the post-flame oxidation gas at constant oxygen partial pressure and oxidation temperature seemed to have accelerated the diesel soot oxidation rate. Based on the experimental results of this study and the results of other researchers, modifications to the Nagle and Strickland-Constable formula and to the Lee formula were accomplished. Also, an empirical expression, as an alternative to semi-empirical formulae, was worked out and presented in the thesis.

For disperse system drug formulations, meaningful particle size distribution (PSD) comparators are essential in determining pharmaceutical equivalency and predicting biopharmaceutical equivalence in terms of the effect of particle size on the rate and extent of drug input. In formulation development and licensure, particle size characterization has been applied to establish relationships for bioequivalence of generic pharmaceutical drug products. The current approaches recommended by the US-FDA using median and span are not adequate to predict drug product performances or account for multi-modal PSD performance properties. The use of PSD similarity metric and the development and incorporation of drug release predictions based on PSD properties into PBPK models for various drug administration routes may provide a holistic approach for evaluating the effect of PSD differences on in vitro release of disperse systems and the resulting pharmacokinetic impact on drug product performance. The objectives of this study are to provide a rational approach for PSD comparisons by 1) developing similarity computations for PSD comparisons and 2) using PBPK-models to specifically account for PSD effects on drug input rates via a subcutaneous (SQ) administration route. Two techniques for measuring PSDs of reference (reference-listed drug product) and test (generic) drug products were investigated: OVL and PROB, as well as the current standard measurements of median and span. In addition, release rate profiles of each product pair simulated from modified Bikhazi and Higuchi’s model were used to compute release rate comparators such as similarity factor (f2) and fractional time ratios. A subcutaneous input PBPK model was developed and used to simulate blood concentration-time profiles of reference and test drug products. Pharmacokinetic responses such as AUC, Cmax, and Tmax were compared using standard bioequivalence criteria. PSD comparators, release rate comparators, and bioequivalence metrics were related to determine their relationships and identify the appropriate approach for bioequivalence waiver. OVL showed better predictions for bioequivalence compared to PROB, median, and span. For release profile comparisons, the f2 method was the best for bioequivalence prediction. The use of both release rate (e.g., f2) and PSD (e.g., OVL) comparison metrics significantly improved bioequivalence prediction to about 90%.

This thesis is a part of a collaboration between Höganäs AB and Luleå University of Technology, aiming at replacing fossil process coal with bio-coal in their sponge iron process. The difference in gasification reactivity, i.e. reaction rate, between fossil coals and bio-coals is the major challenge in the endeavor to decrease the climate impact of the existing process. The goal of this thesis is to develop a model of reaction rate for bio-coals in relation to particle size distribution. Different particle size distributions were combined and tested to see how that affects the effective reaction rate. Within the scope of this work, gasification reactivities of different materials, including coal, cokes, and bio-coals, were determined. Three bio-coals were selected to study the effect of particle size distribution on reactivity. Kinetic parameters were determined by using thermogravimetric analysis in the temperature range of 770-850 °C while varying CO2 partial pressure between 0.1-0.4 atm. The effect of particle size on the reaction rate was investigated by using particles with diameter between 0.18 and 6.3 mm. The effect of particle size distribution on the reactivity of bio-coal in a packed bed was carried out in a macro thermogravimetric reactor with a constant bed volume of 6.5 cm3 at 980 °C and 40% (vol.) of CO2. The experimental investigation in three different rate-limiting steps was done for one bio-coal sample, i.e. Cortus Bark bio-coal. The activation energy of the bio-coal was 187 kJ mol-1, and the reaction order was 0.365. For the internal diffusion control regime, an increase in particle size resulted in low reaction rate. The effective diffusivity calculated from the Thiele modulus model was 1.41*10-5 m2 s-1. For the external diffusion control regime, an increase in particle size increased the reaction rate up to a certain point where it plateaued at >1 mm. By choosing two discrete particle size distributions, where a smaller average distribution can fit into a larger average distribution the reaction rate was lowered by 30% compared to only using a single narrow particle size distribution. This solution decreased the difference of apparent reaction rate in a packed bed between the bio-coal and anthracite from 6.5 times to 4.5 times. At the moment the model is not generalized for all bio-coals. However, the developed methodology can be routinely applied to assess the different bio-coal samples. One possible error can be that pyrolysis influences the gasification rate for bio-coal that is pyrolyzed below the temperature of the gasification test. There is a clear correlation between particle size distributions, bulk density, and apparent reactivity. By mixing two distributions the reaction rate of Cortus Bark was reduced from 6.5 times the reaction rate of anthracite to 4.5.

Particle breakage can be significant in stirred vessels such as crystallizers. During crystallization, particle breakage can occur due to particle contact with other particles, the impeller, the suspension fluid, and/or the vessel. Such breakage produces fines and can cause filter plugging downstream. Although research has been conducted with respect to particle breakage, a comprehensive study is still needed to quantify the breakage occurring in stirred vessels. The overall goal of this research is to model the particle breakage occurring in a stirred vessel by analyzing the particle size and shape distributions that result from breakage. Breakage experiments are based on collision influences that affect the two dominant collisions types, crystal-to-crystal and crystal-to-impeller collisions. Results showed that the quantity of fines produced are affected by the solids concentration or magma density and suspension fluid utilized. Additionally, aqueous saturated solutions produced particle size distributions that differ from those obtained using a nonsolvent. Similar particle size distributions for two different materials (NaCl and KCl) are achieved in the same nonsolvent (acetonitrile) by adjusting the agitation rate using the Zwietering correlation to account for property differences; moreover, the same agitation rate adjustment produced similar distributions for KCl in acetone and acetonitrile which were both nonsolvents. However, modifications to the Zwietering correlation, such as changing the significance of the initial particle size, are proposed before this method of adjustment is deemed accurate. Number-based population modeling of particle breakage is achieved within 1-5% error for NaCl at each agitation rate investigated. Breakage modeling using a discretized population balance equation with Austin's equation for attrition and the power law form of the product function for fragmentation is a viable approach; however, more work is needed to increase the accuracy of this model.

No description available.

One of the most important factors that influences a stream's hydraulic and ecological health is the streambed's sediment size distribution. This distribution affects streambed stability, sediment transport rates, and flood levels by defining the roughness of the stream channel. Adverse effects on water quality and wildlife can be expected when excessive fine sediments enter a stream. Many chemicals and toxic materials are transported through streams by binding to fine sediments. Increases in fine sediments also seriously impact the survival of fish species present in the stream. Fine sediments fill tiny spaces between larger particles thereby denying fish embryos the necessary fresh water to survive. Reforestation, constructed wetlands, and slope stabilization are a few management practices typically utilized to reduce the amount of sediment entering a stream. To effectively gauge the success of these techniques, the sediment size distribution of the stream must be monitored. Gravel bed streams are typically stratified vertically, in terms of particle size, in three layers, with each layer having its own distinct grain size distribution. The top two layers of the stream bed, the pavement and subpavement, are the most significant in determining the characteristics of the stream. These top two layers are only as thick as the largest particle size contained within each layer. This vertical stratification by particle size makes it difficult to characterize the grain size distribution of the surface layer. The traditional bulk or volume sampling procedure removes a specified volume of material from the stream bed. However, if the bed exhibits vertical stratification, the volume sample will mix different populations, resulting in inaccurate sample results. To obtain accurate results for the pavement size distribution, a surface oriented sampling technique must be employed. The most common types of surface oriented sampling are grid and areal sampling. Due to limitations in the sampling techniques, grid samples typically truncate the sample at the finer grain sizes, while areal samples typically truncate the sample at the coarser grain sizes. When combined with an analysis technique, either frequency-by-number or frequency-by-weight, the sample results can be represented in terms of a cumulative grain size distribution. However, the results of different sampling and analysis procedures can lead to biased results, which are not equivalent to traditional volume sampling results. Different conversions, dependent on both the sampling and analysis technique, are employed to remove the bias from surface sample results. The topic of the present study is to determine the accuracy of sediment samples obtained by the different sampling techniques. Knowing the accuracy of a sample is imperative if the sample results are to be meaningful. Different methods are discussed for placing confidence intervals on grid sample results based on statistical distributions. The binomial distribution and its approximation with the normal distribution have been suggested for these confidence intervals in previous studies. In this study, the use of the multinomial distribution for these confidence intervals is also explored. The multinomial distribution seems to best represent the grid sampling process. Based on analyses of the different distributions, recommendations are made. Additionally, figures are given to estimate the grid sample size necessary to achieve a required accuracy for each distribution. This type of sample size determination figure is extremely useful when preparing for grid sampling in the field. Accuracy and sample size determination for areal and volume samples present difficulties not encountered with grid sampling. The variability in number of particles contained in the sample coupled with the wide range of particle sizes present make direct statistical analysis impossible. Limited studies have been reported on the necessary volume to sample for gravel deposits. The majority of these studies make recommendations based on empirical results that may not be applicable to different size distributions. Even fewer studies have been published that address the issue of areal sample size. However, using grid sample results as a basis, a technique is presented to estimate the necessary sizes for areal and volume samples. These areal and volume sample sizes are designed to match the accuracy of the original grid sample for a specified grain size percentile of interest. Obtaining grid and areal results with the same accuracy can be useful when considering hybrid samples. A hybrid sample represents a combination of grid and areal sample results that give a final grain size distribution curve that is not truncated. Laboratory experiments were performed on synthetic stream beds to test these theories. The synthetic stream beds were created using both glass beads and natural sediments. Reducing sampling errors and obtaining accurate samples in the field are also briefly discussed. Additionally, recommendations are also made for using the most efficient sampling technique to achieve the required accuracy. / Master of Science

Spot core from the San Andreas Fault Observatory at Depth (SAFOD) borehole provides the opportunity to characterize and quantify damage and mineral alteration of siliciclastics within an active, large-displacement plate-boundary fault zone. Deformed arkosic, coarse-grained, pebbly sandstone, and fine-grained sandstone and siltstone retrieved from 2.55 km depth represent the western damaged zone of the San Andreas Fault, approximately 130 m west of the Southwest Deforming Zone (SDZ). The sandstone is cut by numerous subsidiary faults that display extensive evidence of repeating episodes of compaction, shear, dilation, and cementation. The subsidiary faults are grouped into three size classes: 1) small faults, 1 to 2 mm thick, that record an early stage of fault development, 2) intermediate-size faults, 2 to 3 mm thick, that show cataclastic grain size reduction and flow, extensive cementation, and alteration of host particles, and 3) large subsidiary faults that have cemented cataclastic zones up to 10 mm thick. The cataclasites contain fractured host-rock particles of quartz, oligoclase, and orthoclase, in addition to albite and laumontite produced by syn-deformation alteration reactions. Five structural units are distinguished in the subsidiary fault zones: fractured sandstones, brecciated sandstones, microbreccias, microbreccias within distinct shear zones, and principal slip surfaces. We have quantified the particle size distributions and the particle shape of the host rock mineral phases and the volume fraction of the alteration products for these representative structural units. Shape characteristics vary as a function of shear strain and grain size, with smooth, more circular particles evolving as a result of increasing shear strain. Overall, the particle sizes are consistent with a power law distribution over the particle size range investigated (0.3 µm < d < 400 µm). The exponent (fractal dimension, D) is found to increase with shear strain and volume fraction of laumontite. This overall increase in D and evolution of shape with increasing shear strain reflects a general transition from constrained comminution, active at low shear strains to abrasion processes that dominate at high shear strains.