Bio-ethanol valorization towards C4s including 1-butanol over metal modified alumina and zeolite catalysts

Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations.

PDM system functions and utilizations analysis to improve efficiency of sheet metal product design and manufacturing

This study will concentrate on Product Data Management (PDM) systems, and sheet metal design features and classification. In this thesis, PDM is seen as an individual system which handles all product-related data and information. The meaning of relevant data is to take the manufacturing process further with fewer errors. The features of sheet metals are giving more information and value to the designed models. The possibility of implementing PDM and sheet metal features recognition are the core of this study. Their integration should make the design process faster and manufacturing-friendly products easier to design. The triangulation method is the basis for this research. The sections of this triangle are: scientific literature review, interview using the Delphi method and the author’s experience and observations. The main key findings of this study are: (1) the area of focus in triangle (the triangle of three different point of views: business, information exchange and technical) depends on the person’s background and their role in the company, (2) the classification in the PDM system (and also in the CAD system) should be done using the materials, tools and machines that are in use in the company and (3) the design process has to be more effective because of the increase of industrial production, sheet metal blank production and the designer’s time spent on actual design and (4) because Design For Manufacture (DFM) integration can be done with CAD-programs, DFM integration with the PDM system should also be possible.

Reducing contact resistance in graphene devices

In this thesis, the contact resistance of graphene devices was investigated because high contact resistance is detrimental to the performance of graphene field-effect transistors (GFET). Method for increasing so-called edge-contact area was applied in device fabrication process, as few nanometers thick Ni layer was used as a catalytic etchant during the annealing process. Finally, Ni was also used as a metal for contact. GFETs were fabricated using electron beam lithography using graphene fabricated by chemical vapor deposition (CVD). Critical part of the fabrication process was to preserve the high quality of the graphene channel while etching the graphene at contact areas with Ni during the annealing. This was achieved by optimizing the combination of temperature and gas flows. The structural properties of graphene were studied using scanning electron microscopy, scanning confocal μ-Raman spectroscopy and optical microscopy. Evaluation of electric transport properties including contact resistance was carried out by transmission line method and four-probe method. The lowest contact resistance found was about at 350 Ωμm. In addition, different methods to transfer CVD graphene synthesized on copper were studied. Typical method using PMMA as a supporting layer leaves some residues after its removal, thus effecting on the performance of a graphene devices. In a metal assisted transfer method, metal is used as an interfacial layer between PMMA and graphene. This allows more effective removal of PMMA. However, Raman spectra of graphene transferred by metal assisted method showed somewhat lower quality than the PMMA assisted method

Application of cerium oxide thin films grown by atomic layer deposition for soot removal

The objective of the thesis is to study cerium oxide thin films grown by the atomic layer deposition (ALD) for soot removal. Cerium oxide is one of the most important heterogeneous catalysts and can be used in particulate filters and sensors in a diesel exhaust pipe. Its redox/oxidation properties are a key factor in soot oxidation. Thus, the cerium oxide coating can help to keep particulate filters and sensors clean permanently. The literature part of the thesis focuses on the soot removal, introducing the origin and structure of soot, reviewing emissions standards for diesel particulate matter, and presenting methods and catalysts for soot removal. In the experimental part the optimal ALD conditions for cerium oxide were found, the structural properties of cerium oxide thin films were analyzed, and the catalytic activity of the cerium oxide for soot oxidation was investigated. Studying ALD growth conditions of cerium oxide films and determining their critical thickness range are important to maximize the catalytic performance operating at comparatively low temperature. It was found that the cerium oxide film deposited at 300 °C with 2000 ALD cycles had the highest catalytic activity. Although the activity was still moderate and did not decrease the soot oxidation temperature enough for a real-life application. The cerium oxide thin film deposited at 300 °C has a different crystal structure, surface morphology and elemental composition with a higher Ce3+ concentration compared to the films deposited at lower temperatures. The different properties of the cerium oxide thin film deposited at 300 °C increase the catalytic activity most likely due to higher surface area and addition of the oxygen vacancies.

Artificial Ribonucleases: Oligonucleotides Conjugated with Metal Ion Chelates of Azacrowns

Ribonucleic acid (RNA) has many biological roles in cells: it takes part in coding, decoding, regulating and expressing of the genes as well as has the capacity to work as a catalyst in numerous biological reactions. These qualities make RNA an interesting object of various studies. Development of useful tools with which to investigate RNA is a prerequisite for more advanced research in the field. One of such tools may be the artificial ribonucleases, which are oligonucleotide conjugates that sequence-selectively cleave complementary RNA targets. This thesis is aimed at developing new efficient metal-ion-based artificial ribonucleases. On one hand, to solve the challenges related to solid-supported synthesis of metal-ion-binding conjugates of oligonucleotides, and on the other hand, to quantify their ability to cleave various oligoribonucleotide targets in a pre-designed sequence selective manner. In this study several artificial ribonucleases based on cleaving capability of metal ion chelated azacrown moiety were designed and synthesized successfully. The most efficient ribonucleases were the ones with two azacrowns close to the 3´- end of the oligonucleotide strand. Different transition metal ions were introduced into the azacrown moiety and among them, the Zn2+ ion was found to be better than Cu2+ and Ni2+ ions.

An account of a copy from the 15th century of a map of the world engraved on metal, which is preserved in cardinal Stephan Borgia's museum at Velletri

Erip.: Ymer 1891.

Welding of additively manufactured stainless steel parts: Comparative study between sheet metal and selective laser melted parts

Additive manufacturing is a fast growing manufacturing technology capable of producing complex objects without the need for conventional manufacturing process planning. During the process the work piece is built by adding material one layer at a time according to a digital 3D CAD model. At first additive manufacturing was mainly used to make prototypes but the development of the technology has made it possible to also make final products. Welding is the most common joining method for metallic materials. As the maximum part size of additive manufacturing is often limited, it may sometimes be required to join two or more additively manufactured parts together. However there has been almost no research on the welding of additively manufactured parts so far, which means that there has been very little information available on the possible differences compared to the welding of sheet metal parts. The aim of this study was to compare the weld joint properties of additively manufactured parts to those of sheet metal parts. The welding process that was used was TIG welding and the test material was 316L austenitic stainless steel. Weld joint properties were studied by making tensile, bend and hardness tests and by studying the weld microstructures with a microscope. Results show that there are certain characteristics in the welds of additively manufactured parts. The building direction of the test pieces has some impact on the mechanical properties of the weld. Nevertheless all the welds exhibited higher yield strength than the sheet metal welds but at the same time elongation at break was lower. It was concluded that TIG welding is a feasible process for welding additively manufactured parts.

Een eenfalligh Kennedoom af nödtorftelighe articklar vthdraghne aff then Helga schrifft / Laurentius Olai Gestricius. (Coll. 762, Aholansaari Foundation's deposition)

Quire structure: 9xIV⁷² + (IV–1)⁷⁹. Text in one column, on (mostly) 26–33 lines, not ruled. Catchwords frequently used at the foot of each page to indicate the next word when a sentence continues on the next page. Not foliated. Gothic Cursive in one saec. XVI² hand. The first initial of the book has been touched with what looks like red pencil. This may be a later addition, as also the green tint to the outer edges of the block. Titles and rubrics distinguished, if at all, through layout only. A note fol. [47]v (see also the main text on fol. [31]v) indicates that the text was copied in 1580. The Anti-Papist poem mentions the Jesuit Antonio Possevino, active in Sweden in 1577–1580 (Kiiskinen ed. 2010, 25, 27). The texts appear to be copies of printed works, with the possible exception of the Anti-Papist poem. The publication of Eric Falck’s Een Tröstbook is known, but apparently no printed copies survive; Laurentius Olai Gestricius’ catechism is otherwise unknown. He was a teacher in Gävle from 1557 or 1558, then curate of Västerås from 1561 and of Stockholm in 1562, where he died in 1565 (Kiiskinen ed. 2010, 15, 349; Collijn ed. 1927–1938, vol. 2, 324).

Metal additive manufacturing of internal flow channels with powder bed fusion processes

This thesis studies the advantages, disadvantages and possibilities of additive manufacturing in making components with internal flow channels. These include hydraulic components, components with cooling channels and heat exchangers. Processes studied in this work are selective laser sintering and selective laser melting of metallic materials. The basic principles of processes and parameters involved in the process are presented and different possibilities of internal channel manufacturing and flow improvement are introduced

Emission, kinetic and magnetic phenomena in rare-earth and transition metal doped ZnSe single crystals

In this work emission, optical, electrical and magnetic properties of the d- and f- elements doped zinc selenide crystals were investigated within a wide temperature range. Doping was performed in various technological processes: during the growth by chemical vapor transport method; by thermal diffusion from the Bi or Zn melt. Concentration of the doping impurity in the crystals was controlled by amount of the dopant in the source material or by its concentration in the doping media. Special interest in the work was paid to the influence of the different concentrations of Cr and Yb impurities on ZnSe crystals’ properties, correlations between observed effects and similarities with the Ni, Mn and Gd dopants are analysed. Possibility of formation of the excitons bound to the doping d-ions was shown. In contrast to this, it was observed that f-elements do not bound excitons, but prevent formation of excitons bound to some uncontrolled impurities. A mechanism of Cr doping impurity interaction with background impurities and zinc selenide structural defects was proposed based on experimental data. An assumption about resonant energy transfer between double charged chromium ions and complexes based on crystals’ vacancy defects was made. A correlation between emission and magnetic properties of the d- ions doped samples was established. Based on this correlation a mechanism explaining the concentration quench of the emission was proposed. It was found that f-ions bind electrically active shallow and deep donor and acceptor states of background impurity to electrically neutral complexes. This may be observed as “purification” of ZnSe crystals by doping with the rare-earth elements, resulting i tendency of the properties of f-ion doped crystals to the properties of intrinsic crystals, but with smaller concentration of uncontrolled native and impurity defects. A possible interpretation of this effect was proposed. It was shown that selenium substituting impurities decrease efficiency of the Yb doping. Based on this experimental results an attempt to determine ytterbium ion surroundings in the crystal lattice was made. It was shown that co-doping of zinc selenide crystals with the d- and f- ions leads to the combination of the impurities influence on the material’s properties. On the basis of obtained data an interaction mechanism of the d- and f-elements co-dopants was proposed. Guided by the model of the ytterbium ion incorporation in the selenide sublattice of the ZnSe crystals, an assumption about stabilization of single charged chromium ions in the zinc sublattice crystal nodes, by means of formation of the local charge compensating clusters, was made.

Green welding in practice

Efficient production and consumption of energy has become the top priority of national and international policies around the world. Manufacturing industries have to address the requirements of the government in relation to energy saving and ecologically sustainable products. These industries are also concerned with energy and material usage due to their rising costs. Therefore industries have to find solutions that can support environmental preservation yet maintain competitiveness in the market. Welding, a major manufacturing process, consumes a great deal of material and energy. It is a crucial process in improving a product’s life-cycle cost, strength, quality and reliability. Factors which lead to weld related inefficiencies have to be effectively managed, if industries are to meet their quality requirements and fulfil a high-volume production demand. Therefore it is important to consider some practical strategies in welding process for optimization of energy and material consumption. The main objective of this thesis is to explore the methods of minimizing the ecological footprint of the welding process and methods to effectively manage its material and energy usage in the welding process. The author has performed a critical review of the factors including improved weld power source efficiency, efficient weld techniques, newly developed weld materials, intelligent welding systems, weld safety measures and personnel training. The study lends strong support to the fact that the use of eco-friendly welding units and the quality weld joints obtained with minimum possible consumption of energy and materials should be the main directions of improvement in welding systems. The study concludes that, gradually implementing the practical strategies mentioned in this thesis would help the manufacturing industries to achieve on the following - reduced power consumption, enhanced power control and manipulation, increased deposition rate, reduced cycle time, reduced joint preparation time, reduced heat affected zones, reduced repair rates, improved joint properties, reduced post-weld operations, improved automation, improved sensing and control, avoiding hazardous conditions and reduced exposure of welder to potential hazards. These improvement can help in promotion of welding as a green manufacturing process.

Roll-to-roll atomic layer deposition process for flexible electronics applications

Atomic Layer Deposition (ALD) is the technology of choice where very thin and highquality films are required. Its advantage is its ability to deposit dense and pinhole-free coatings in a controllable manner. It has already shown promising results in a range of applications, e.g. diffusion barrier coatings for OLED displays, surface passivation layers for solar panels. Spatial Atomic Layer Deposition (SALD) is a concept that allows a dramatic increase in ALD throughput. During the SALD process, the substrate moves between spatially separated zones filled with the respective precursor gases and reagents in such a manner that the exposure sequence replicates the conventional ALD cycle. The present work describes the development of a high-throughput ALD process. Preliminary process studies were made using an SALD reactor designed especially for this purpose. The basic properties of the ALD process were demonstrated using the wellstudied Al2O3 trimethyl aluminium (TMA)+H2O process. It was shown that the SALD reactor is able to deposit uniform films in true ALD mode. The ALD nature of the process was proven by demonstrating self-limiting behaviour and linear film growth. The process behaviour and properties of synthesized films were in good agreement with previous ALD studies. Issues related to anomalous deposition at low temperatures were addressed as well. The quality of the coatings was demonstrated by applying 20 nm of the Al2O3 on to polymer substrate and measuring its moisture barrier properties. The results of tests confirmed the superior properties of the coatings and their suitability for flexible electronics encapsulation. Successful results led to the development of a pilot scale roll-to-roll coating system. It was demonstrated that the system is able to deposit superior quality films with a water transmission rate of 5x10-6 g/m2day at a web speed of 0.25 m/min. That is equivalent to a production rate of 180 m2/day and can be potentially increased by using wider webs. State-of-art film quality, high production rates and repeatable results make SALD the technology of choice for manufacturing ultra-high barrier coatings for flexible electronics.

Weldability of powder bed fusion fabricated stainless steel 316L sheets to cold rolled sheet metal

Weldability of powder bed fusion (PBF) fabricated components has come to discussion in past two years due to resent developments in the PBF technology and limited size of the machines used in the fabrication process. This study concentrated on effects of energy input of welding on mechanical properties and microstructural features of welds between PBF fabricated stainless steel 316L sheets and cold rolled sheet metal of same composition by the means of destructive testing and microscopic analysis. Optical fiber diameter, laser power and welding speed were varied during the experiments that were executed following one variable at a time (OVAT) method. One of the problems of welded PBF fabricated components has been lower elongations at break comparing to conventionally manufactured components. Decreasing energy input of the laser keyhole welding decreased elongations at break of the welded specimens. Ultimate tensile strengths were not affected significantly by the energy input of the welding, but fracturing of the specimens welded using high energy input occurred from the weld metal. Fracturing of the lower energy input welds occurred from the PBF fabricated base metal. Energy input was found to be critical factor for mechanical properties of the welds. Multioriented grain growth and formation of neck at fusion zone boundary on the cold rolled side of the weld was detected and suspected to be result from weld pool flows caused by differences in molten weld pool behaviour between the PBF fabricated and cold rolled sides of the welds.

The role of metal ions in selective and sustainable processes

Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.