Research and development of III-V semiconductor surfaces for improved device interfaces

This thesis is devoted to understanding and improving technologically important III-V compound semiconductor (e.g. GaAs, InAs, and InSb) surfaces and interfaces for devices. The surfaces and interfaces of crystalline III-V materials have a crucial role in the operation of field-effect-transistors (FET) and highefficiency solar-cells, for instance. However, the surfaces are also the most defective part of the semiconductor material and it is essential to decrease the amount of harmful surface or interface defects for the next-generation III-V semiconductor device applications. Any improvement in the crystal ordering at the semiconductor surface reduces the amount of defects and increases the material homogeneity. This is becoming more and more important when the semiconductor device structures decrease to atomic-scale dimensions. Toward that target, the effects of different adsorbates (i.e., Sn, In, and O) on the III-V surface structures and properties have been investigated in this work. Furthermore, novel thin-films have been synthesized, which show beneficial properties regarding the passivation of the reactive III-V surfaces. The work comprises ultra-high-vacuum (UHV) environment for the controlled fabrication of atomically ordered III-V(100) surfaces. The surface sensitive experimental methods [low energy electron diffraction (LEED), scanning tunneling microscopy/spectroscopy (STM/STS), and synchrotron radiation photoelectron spectroscopy (SRPES)] and computational density-functionaltheory (DFT) calculations are utilized for elucidating the atomic and electronic properties of the crucial III-V surfaces. The basic research results are also transferred to actual device tests by fabricating metal-oxide-semiconductor capacitors and utilizing the interface sensitive measurement techniques [capacitance voltage (CV) profiling, and photoluminescence (PL) spectroscopy] for the characterization. This part of the thesis includes the instrumentation of home-made UHV-compatible atomic-layer-deposition (ALD) reactor for growing good quality insulator layers. The results of this thesis elucidate the atomic structures of technologically promising Sn- and In-stabilized III-V compound semiconductor surfaces. It is shown that the Sn adsorbate induces an atomic structure with (1×2)/(1×4) surface symmetry which is characterized by Sn-group III dimers. Furthermore, the stability of peculiar ζa structure is demonstrated for the GaAs(100)-In surface. The beneficial effects of these surface structures regarding the crucial III-V oxide interface are demonstrated. Namely, it is found that it is possible to passivate the III-V surface by a careful atomic-scale engineering of the III-V surface prior to the gate-dielectric deposition. The thin (1×2)/(1×4)-Sn layer is found to catalyze the removal of harmful amorphous III-V oxides. Also, novel crystalline III-V-oxide structures are synthesized and it is shown that these structures improve the device characteristics. The finding of crystalline oxide structures is exploited by solving the atomic structure of InSb(100)(1×2) and elucidating the electronic structure of oxidized InSb(100) for the first time.

Machine vision methods for process measurements in pulping

The papermaking industry has been continuously developing intelligent solutions to characterize the raw materials it uses, to control the manufacturing process in a robust way, and to guarantee the desired quality of the end product. Based on the much improved imaging techniques and image-based analysis methods, it has become possible to look inside the manufacturing pipeline and propose more effective alternatives to human expertise. This study is focused on the development of image analyses methods for the pulping process of papermaking. Pulping starts with wood disintegration and forming the fiber suspension that is subsequently bleached, mixed with additives and chemicals, and finally dried and shipped to the papermaking mills. At each stage of the process it is important to analyze the properties of the raw material to guarantee the product quality. In order to evaluate properties of fibers, the main component of the pulp suspension, a framework for fiber characterization based on microscopic images is proposed in this thesis as the first contribution. The framework allows computation of fiber length and curl index correlating well with the ground truth values. The bubble detection method, the second contribution, was developed in order to estimate the gas volume at the delignification stage of the pulping process based on high-resolution in-line imaging. The gas volume was estimated accurately and the solution enabled just-in-time process termination whereas the accurate estimation of bubble size categories still remained challenging. As the third contribution of the study, optical flow computation was studied and the methods were successfully applied to pulp flow velocity estimation based on double-exposed images. Finally, a framework for classifying dirt particles in dried pulp sheets, including the semisynthetic ground truth generation, feature selection, and performance comparison of the state-of-the-art classification techniques, was proposed as the fourth contribution. The framework was successfully tested on the semisynthetic and real-world pulp sheet images. These four contributions assist in developing an integrated factory-level vision-based process control.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Characterization Of Process Efficiency Improvement In Laser Additive Manufacturing

Laser additive manufacturing (LAM), known also as 3D printing, has gained a lot of interest in past recent years within various industries, such as medical and aerospace industries. LAM enables fabrication of complex 3D geometries by melting metal powder layer by layer with laser beam. Research in laser additive manufacturing has been focused in development of new materials and new applications in past 10 years. Since this technology is on cutting edge, efficiency of manufacturing process is in center role of research of this industry. Aim of this thesis is to characterize methods for process efficiency improvements in laser additive manufacturing. The aim is also to clarify the effect of process parameters to the stability of the process and in microstructure of manufactured pieces. Experimental tests of this thesis were made with various process parameters and their effect on build pieces has been studied, when additive manufacturing was performed with a modified research machine representing EOSINT M-series and with EOS EOSINT M280. Material used was stainless steel 17-4 PH. Also, some of the methods for process efficiency improvements were tested. Literature review of this thesis presents basics of laser additive manufacturing, methods for improve the process efficiency and laser beam – material- interaction. It was observed that there are only few public studies about process efficiency of laser additive manufacturing of stainless steel. According to literature, it is possible to improve process efficiency with higher power lasers and thicker layer thicknesses. The process efficiency improvement is possible if the effect of process parameter changes in manufactured pieces is known. According to experiments carried out in this thesis, it was concluded that process parameters have major role in single track formation in laser additive manufacturing. Rough estimation equations were created to describe the effect of input parameters to output parameters. The experimental results showed that the WDA (width-depth-area of cross-sections of single track) is correlating exponentially with energy density input. The energy density input is combination of the input parameters of laser power, laser beam spot diameter and scan speed. The use of skin-core technique enables improvement of process efficiency as the core of the part is manufactured with higher laser power and thicker layer thickness and the skin with lower laser power and thinner layer thickness in order to maintain high resolution. In this technique the interface between skin and core must have overlapping in order to achieve full dense parts. It was also noticed in this thesis that keyhole can be formed in LAM process. It was noticed that the threshold intensity value of 106 W/cm2 was exceeded during the tests. This means that in these tests the keyhole formation was possible.

Transient current technique simulation of semiconductor detectors

Nowadays advanced simulation technologies of semiconductor devices occupies an important place in microelectronics production process. Simulation helps to understand devices internal processes physics, detect new effects and find directions for optimization. Computer calculation reduces manufacturing costs and time. Modern simulation suits such as Silcaco TCAD allow simulating not only individual semiconductor structures, but also these structures in the circuit. For that purpose TCAD include MixedMode tool. That tool can simulate circuits using compact circuit models including semiconductor structures with their physical models. In this work, MixedMode is used for simulating transient current technique setup, which include detector and supporting electrical circuit. This technique was developed by RD39 collaboration project for investigation radiation detectors radiation hard properties.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Susteinable steelmaking by process integration

Environmental issues, including global warming, have been serious challenges realized worldwide, and they have become particularly important for the iron and steel manufacturers during the last decades. Many sites has been shut down in developed countries due to environmental regulation and pollution prevention while a large number of production plants have been established in developing countries which has changed the economy of this business. Sustainable development is a concept, which today affects economic growth, environmental protection, and social progress in setting up the basis for future ecosystem. A sustainable headway may attempt to preserve natural resources, recycle and reuse materials, prevent pollution, enhance yield and increase profitability. To achieve these objectives numerous alternatives should be examined in the sustainable process design. Conventional engineering work cannot address all of these substitutes effectively and efficiently to find an optimal route of processing. A systematic framework is needed as a tool to guide designers to make decisions based on overall concepts of the system, identifying the key bottlenecks and opportunities, which lead to an optimal design and operation of the systems. Since the 1980s, researchers have made big efforts to develop tools for what today is referred to as Process Integration. Advanced mathematics has been used in simulation models to evaluate various available alternatives considering physical, economic and environmental constraints. Improvements on feed material and operation, competitive energy market, environmental restrictions and the role of Nordic steelworks as energy supplier (electricity and district heat) make a great motivation behind integration among industries toward more sustainable operation, which could increase the overall energy efficiency and decrease environmental impacts. In this study, through different steps a model is developed for primary steelmaking, with the Finnish steel sector as a reference, to evaluate future operation concepts of a steelmaking site regarding sustainability. The research started by potential study on increasing energy efficiency and carbon dioxide reduction due to integration of steelworks with chemical plants for possible utilization of available off-gases in the system as chemical products. These off-gases from blast furnace, basic oxygen furnace and coke oven furnace are mainly contained of carbon monoxide, carbon dioxide, hydrogen, nitrogen and partially methane (in coke oven gas) and have proportionally low heating value but are currently used as fuel within these industries. Nonlinear optimization technique is used to assess integration with methanol plant under novel blast furnace technologies and (partially) substitution of coal with other reducing agents and fuels such as heavy oil, natural gas and biomass in the system. Technical aspect of integration and its effect on blast furnace operation regardless of capital expenditure of new operational units are studied to evaluate feasibility of the idea behind the research. Later on the concept of polygeneration system added and a superstructure generated with alternative routes for off-gases pretreatment and further utilization on a polygeneration system producing electricity, district heat and methanol. (Vacuum) pressure swing adsorption, membrane technology and chemical absorption for gas separation; partial oxidation, carbon dioxide and steam methane reforming for methane gasification; gas and liquid phase methanol synthesis are the main alternative process units considered in the superstructure. Due to high degree of integration in process synthesis, and optimization techniques, equation oriented modeling is chosen as an alternative and effective strategy to previous sequential modelling for process analysis to investigate suggested superstructure. A mixed integer nonlinear programming is developed to study behavior of the integrated system under different economic and environmental scenarios. Net present value and specific carbon dioxide emission is taken to compare economic and environmental aspects of integrated system respectively for different fuel systems, alternative blast furnace reductants, implementation of new blast furnace technologies, and carbon dioxide emission penalties. Sensitivity analysis, carbon distribution and the effect of external seasonal energy demand is investigated with different optimization techniques. This tool can provide useful information concerning techno-environmental and economic aspects for decision-making and estimate optimal operational condition of current and future primary steelmaking under alternative scenarios. The results of the work have demonstrated that it is possible in the future to develop steelmaking towards more sustainable operation.

Enhancing the Usability of Drug Materials by Electrostatic Atomisation

Electrospraying or electrostatic atomisation is a process of liquid disruption by electrostatic forces. When liquid is brought into an electric field, charge is induced to its surface. Once the repulsive electrostatic force exceeds the liquid surface tension, the liquid disrupts into small highly charged droplets. The size of the electrosprayed droplets can range from hundreds of micrometers down to a few tens of nanometers. Electrospraying can be used not only to produce droplets, but also solid particles. The research presented in this thesis concentrates on producing drug particles by this method. In the experiments, a drug powder was dissolved in a convenient solvent and the solution was atomised. The solvent was then evaporated from the formed droplets in a drying medium and inside each droplet, a dense cluster of the dissolved drug remained. From the pharmaceutical point of view, the most important characteristics of the produced particles are size distribution, porosity, crystal form and degree of crystallinity. These properties affect the dissolution behaviour and ultimately the drug bioavailability in the body. The effects of electrostatic atomization on the aforementioned characteristics are generally not well understood. The research focused on studying these particle properties and finding possible correlations with the spraying parameters. The produced droplets were dried either under atmospheric or reduced pressure, the latter in order to improve the drying process. Special emphasis was put on implementing the spraying under reduced pressure, and the effects of the drying pressure on particle properties. Based on the results, the possibilities to enhance the dissolution of poorly soluble drugs by this method were estimated. In the course of experiments, it was also discovered that electrospraying may have a profound effect on the polymorphic form of the produced drug particles. In the light of the obtained results, it was concluded that electrospraying may offer a valuable tool to overcome some of the challenges met in modern drug development and formulation.

Weld joint characteristics by nano-materials addition

The need for industries to remain competitive in the welding business, has created necessity to develop innovative processes that can exceed customer’s demand. Significant development in improving weld efficiency, during the past decades, still have their drawbacks, specifically in the weld strength properties. The recent innovative technologies have created smallest possible solid material known as nanomaterial and their introduction in welding production has improved the weld strength properties and to overcome unstable microstructures in the weld. This study utilizes a qualitative research method, to elaborate the methods of introducing nanomaterial to the weldments and the characteristic of the welds produced by different welding processes. The study mainly focuses on changes in the microstructural formation and strength properties on the welded joint and also discusses those factors influencing such improvements, due to the addition of nanomaterials. The effect of nanomaterial addition in welding process modifies the physics of joining region, thereby, resulting in significant improvement in the strength properties, with stable microstructure in the weld. The addition of nanomaterials in the welding processes are, through coating on base metal, addition in filler metal and utilizing nanostructured base metal. However, due to its insignificant size, the addition of nanomaterials directly to the weld, would poses complications. The factors having major influence on the joint integrity are dispersion of nanomaterials, characteristics of the nanomaterials, quantity of nanomaterials and selection of nanomaterials. The addition of nanomaterials does not affect the fundamental properties and characteristics of base metals and the filler metal. However, in some cases, the addition of nanomaterials lead to the deterioration of the joint properties by unstable microstructural formations. Still research are ongoing to achieve high joint integrity, in various materials through different welding processes and also on other factors that influence the joint strength.

Modification of Photocatalyst with Enhanced Photocatalytic Activity for Water

Increasing demand and shortage of energy resources and clean water due to the rapid development of industry, population growth and long term droughts have become an issue worldwide. As a result, global warming, long term droughts and pollution-related diseases are becoming more and more serious. The traditional technologies, such as precipitation, neutralization, sedimentation, filtration and waste immobilization, cannot prevent the pollution but restrict the waste chemicals only after the pollution emission. Meanwhile, most of these treatments cannot thoroughly degrade the contaminants and may generate toxic secondary pollutants into ecosystem. Heterogeneous photocatalysis as the innovative wastewater technology attracts many attention, because it is able to generate highly reactive transitory species for total degradation of organic compounds, water pathogens and disinfection by-products. Semiconductor as photocatalysts have demonstrated their efficiency in degrading a wide range of organics into readily biodegradable compounds, and eventually mineralized them to innocuous carbon dioxide and water. But, the efficiency of photocatalysis is limited, and hence, it is crucial issue to modify photocatalyst to enhance photocatalytic activity. In this thesis, first of all, two literature views are conducted. A survey of materials for photocatalysis has been carried out in order to summarize the properties and the applications of photocatalysts that have been developed in this field. Meanwhile, the strategy for the improvement of photocatalytic activity have been explicit discussed. Furthermore, all the raw material and chemicals used in this work have been listed as well as a specific experimental process and characterization method has been described. The synthesize methods of different photocatalysts have been depicted step by step. Among these cases, different modification strategies have been used to enhance the efficiency of photocatalyst on degradation of organic compounds (Methylene Blue or Phenol). For each case, photocatalytic experiments have been done to exhibit their photocatalytic activity.The photocatalytic experiments have been designed and its process have been explained and illustrated in detailed. Moreover, the experimental results have been shown and discussion. All the findings have been demonstrated in detail and discussed case by case. Eventually, the mechanisms on the improvement of photocatalytic activities have been clarified by characterization of samples and analysis of results. As a conclusion, the photocatalytic activities of selected semiconductors have been successfully enhanced via choosing appropriate strategy for the modification of photocatalysts.

SEPARATION OF SATURED AND UNSATURATED FATTY ACIDS FROM PALM FATTY ACIDS DISTILLATES IN CONTINUOUS MULTISTAGE COUNTERCURRENT COLUMNS WITH SUPERCRITICAL CARBON DIOXIDE AS SOLVENT: A PROCESS DESIGN METHODOLOGY

In this work the separation of multicomponent mixtures in counter-current columns with supercritical carbon dioxide has been investigated using a process design methodology. First the separation task must be defined, then phase equilibria experiments are carried out, and the data obtained are correlated with thermodynamic models or empirical functions. Mutual solubilities, Ki-values, and separation factors aij are determined. Based on this data possible operating conditions for further extraction experiments can be determined. Separation analysis using graphical methods are performed to optimize the process parameters. Hydrodynamic experiments are carried out to determine the flow capacity diagram. Extraction experiments in laboratory scale are planned and carried out in order to determine HETP values, to validate the simulation results, and to provide new materials for additional phase equilibria experiments, needed to determine the dependence of separation factors on concetration. Numerical simulation of the separation process and auxiliary systems is carried out to optimize the number of stages, solvent-to-feed ratio, product purity, yield, and energy consumption. Scale-up and cost analysis close the process design. The separation of palmitic acid and (oleic+linoleic) acids from PFAD-Palm Fatty Acids Distillates was used as a case study.

Characterization of new sources of derivative starches as wall materials of essential oil by spray drying

Starch derivatives of taro (Colocasia esculenta L. Schott) and rice were characterized as wall materials of orange oil (d-limonene) by spray drying. Native starches were initially hydrolyzed with HCl and then esterified. Succinylated starches were modified using a conventional method in a slurry and were extruded; whereas, the phosphorylated starches were modified using the extrusion process. Viscosity and solubility of starches reduced after acid hydrolysis, derivatization, and extrusion. The particle size of the wall materials ranged between 20.05 and 31.81 µm. The encapsulation efficiency of the phosphorylated taro, rice, and waxy corn starches was 96.9, 96.8 and 97.1% respectively, and 98.6, 98.1, and 98.8% for succynilated taro, rice, and waxy corn starches, respectively. Starch derivatives of taro and rice could potentially be used as wall materials of orange oil d-limonene.

Pulssitettu laserablaatio mikrofluidisten kanavistojen sarjatuotantomenetelmänä

Puolijohteiden yleistyttyä vuodesta 1948 alkaen, ovat elektroniset laitteet pienentyneet jatkuvasti tehojen kuitenkin kasvaessa. Kasvaneet tehotiheydet kuitenkin vaikeuttavat laitesuunnittelua, sillä puoljohdekomponenttien suorituskyvylle ja eliniälle on oleellista lämpötilojen ja lämpötilavaihteluiden minimointi. Perinteisen ilmajäähdytyksen lähestyessä rajojaan niin kokonaistehon kuin järkevän energiatehokkuudenkin suhteen, on parhaaksi seuraavaksi teknologiaksi ennustettu kaksifaasijäähdytystä, jonka suorituskyky ja energiatehokkuus ovat vaaditulla tasolla. Kaksifaasijäähdytyksen optimaaliselle toiminnalle tärkeää on hyvin suunniteltu ja tarkasti valmistettu lämmönsiirtopinta, jota kutsutaan mikrokanavistoksi. Pulssitettu laserkaiverrus on edistynyt valmistustekniikka, jonka tarkkuus ja luotettavuus sopisivat mikrokanavistojen valmistamiseen. Laserkaiverruksella saavutettavat lopputulokset vaihtelevat kuitenkin materiaalista riippuen ja kupari – jota käytetään yleisesti lämmönjohteena – on eräs huonoimmin lasertyöstöön reagoivista materiaaleista ja siksi on oleellista selvittää laser-kaiverruksen toimivuutta kuparisten mikrokanavistojen valmistuksessa. Pulssitetun laser-kaiverruksen eri variaatioista nanosekunti-luokan pulssinpituuksilla toimivat laitteet ovat jatkuvan tuotannon kannalta paras vaihtoehto niiden hyvän tuottavuuden, saatavuuden sekä kohtuullisen alkuinvestoinnin vuoksi. Käytännön kaiverruskokeiden perusteella selvisi, että menetelmä on laatunsa ja tarkkuutensa puolesta sopiva varsinaiseen tuotantoon. Kaiverruksen tehokkuus kuparia työstettäessä on kuitenkin ennakoituakin heikompi ja niin valmistus- kuin suunnitelu-prosessikin vaativat vielä jatkotutkimusta ja -kehitystä.

Real-time adaptive control of ultra-fast laser scribing process with spectrometer online monitoring

There exist several researches and applications about laser welding monitoring and parameter control but not a single one have been created for controlling of laser scribing processes. Laser scribing is considered to be very fast and accurate process and thus it would be necessary to develop accurate turning and monitoring system for such a process. This research focuses on finding out whether it would be possible to develop real-time adaptive control for ultra-fast laser scribing processes utilizing spectrometer online monitoring. The thesis accurately presents how control code for laser parameter tuning is developed using National Instrument's LabVIEW and how spectrometer is being utilized in online monitoring. Results are based on behavior of the control code and accuracy of the spectrometer monitoring when scribing different steel materials. Finally control code success is being evaluated and possible development ideas for future are presented.

Metal oxides prepared through the nanocasting approach-mechanistic study, surface interactions and applications in separation

Mesoporous metal oxides are nowadays widely used in various technological applications, for instance in catalysis, biomolecular separations and drug delivery. A popular technique used to synthesize mesoporous metal oxides is the nanocasting process. Mesoporous metal oxide replicas are obtained from the impregnation of a porous template with a metal oxide precursor followed by thermal treatment and removal of the template by etching in NaOH or HF solutions. In a similar manner to the traditional casting wherein the product inherits the features of the mold, the metal oxide replicas are supposed to have an inverse structure of the starting porous template. This is however not the case, as broken or deformed particles and other structural defects have all been experienced during nanocasting experiments. Although the nanocasting technique is widely used, not all the processing steps are well understood. Questions over the fidelity of replication and morphology control are yet to be adequately answered. This work therefore attempts to answer some of these questions by elucidating the nanocasting process, pin pointing the crucial steps involved and how to harness this knowledge in making wholesome replicas which are a true replication of the starting templates. The rich surface chemistry of mesoporous metal oxides is an important reason why they are widely used in applications such as catalysis, biomolecular separation, etc. At times the surface is modified or functionalized with organic species for stability or for a particular application. In this work, nanocast metal oxides (TiO2, ZrO2 and SnO2) and SiO2 were modified with amino-containing molecules using four different approaches, namely (a) covalent bonding of 3-aminopropyltriethoxysilane (APTES), (b) adsorption of 2-aminoethyl dihydrogen phosphate (AEDP), (c) surface polymerization of aziridine and (d) adsorption of poly(ethylenimine) (PEI) through electrostatic interactions. Afterwards, the hydrolytic stability of each functionalization was investigated at pH 2 and 10 by zeta potential measurements. The modifications were successful except for the AEDP approach which was unable to produce efficient amino-modification on any of the metal oxides used. The APTES, aziridine and PEI amino-modifications were fairly stable at pH 10 for all the metal oxides tested while only AZ and PEI modified-SnO2 were stable at pH 2 after 40 h. Furthermore, the functionalized metal oxides (SiO2, Mn2O3, ZrO2 and SnO2) were packed into columns for capillary liquid chromatography (CLC) and capillary electrochromatography (CEC). Among the functionalized metal oxides, aziridinefunctionalized SiO2, (SiO2-AZ) showed good chemical stability, and was the most useful packing material in both CLC and CEC. Lastly, nanocast metal oxides were synthesized for phosphopeptide enrichment which is a technique used to enrich phosphorylated proteins in biological samples prior to mass spectrometry analysis. By using the nanocasting technique to prepare the metal oxides, the surface area was controlled within a range of 42-75 m2/g thereby enabling an objective comparison of the metal oxides. The binding characteristics of these metal oxides were compared by using samples with different levels of complexity such as synthetic peptides and cell lysates. The results show that nanocast TiO2, ZrO2, Fe2O3 and In2O3 have comparable binding characteristics. Furthermore, In2O3 which is a novel material in phosphopeptide enrichment applications performed comparably with standard TiO2 which is the benchmark for such phosphopeptide enrichment procedures. The performance of the metal oxides was explained by ranking the metal oxides according to their isoelectric points and acidity. Overall, the clarification of the nanocasting process provided in this work will aid the synthesis of metal oxides with true fidelity of replication. Also, the different applications of the metal oxides based on their surface interactions and binding characteristics show the versatility of metal oxide materials. Some of these results can form the basis from which further applications and protocols can be developed.