Elemental analysis of wood materials by external millibeam thick target PIXE

PIXE (Particle Induce X-ray Emission spectrometry) was used for analysing stem bark and stem wood of Scots pine, Norway spruce and Silver birch. Thick samples were irradiated, in laboratory atmosphere, with 3 MeV protons and the beam current was measured indirectly using a photo multiplicator (PM) tube. Both point scans and bulk analyses were performed with the 1 mm diameter proton beam. In bulk analyses, whole bark and sectors of discs of the stem wood were dry ashed at 550 ˚C. The ashes were homogenised by shaking and prepared to target pellets for PIXE analyses. This procedure generated representative samples to be analysed, but the enrichment also enabled quantification of some additional trace elements. The ash contents obtained as a product of the sample preparation procedure also showed to be of great importance in the evaluation of results in environmental studies. Spot scans from the pith of pine wood outwards, showed clearly highest concentrations of manganese, calcium and zinc in the first spot irradiated, or 2-3 times higher than in the surrounding wood. For stem wood from the crown part of a pine this higher concentration level was found in the first four spots/mms, including the pith and the two following growth rings. Zinc showed increasing concentrations outwards in sapwood of the pine stem, with the over-all lowest concentrations in the inner half of the sapwood. This could indicate emigration of this element from sapwood being under transformation to heartwood. Point scans across sapwood of pine and spruce showed more distinct variations in concentrations relative to hearth wood. Higher concentrations of e.g. zinc, calcium and manganese were found in earlywood than in denser latewood. Very high concentrations of iron and copper were also seen for some earlywood increments. The ash content of stem bark is up to and order higher than for the stem wood. However, when the elemental concentration in ashes of bark and wood of the same disc were compared, these are very similar – this when trees are growing at spots with no anthropogenic contamination from the atmosphere. The largest difference was obtained for calcium which appeared at two times high concentrations in ashes of bark than in ashes of the wood (ratio of 2). Pine bark is often used in monitoring of atmospheric pollution, where concentrations in bark samples are compared. Here an alternative approach is suggested: Bark and the underlying stem wood of a pine trees are dry ashed and analysed. The elemental concentration in the bark ash is then compared to the concentration of the same element in the wood ash. Comparing bark to wood includes a normalisation for the varying availability of an element from the soil at different sites. When this comparison is done for the ashes of the materials, a normalisation is also obtained for the general and locally different enrichment of inorganic elements from wood to bark. Already a ratio >2 between the concentration in the bark ash and the concentration in the wood ash could indicate atmospheric pollution. For monitoring where bark is used, this way of “inwards” comparison is suggested - instead of comparing to results from analyses of bark from other trees (read reference areas), growing at sites with different soil and, locally, different climate conditions. This approach also enables evaluation of atmospheric pollution from sampling of only relative few individual trees –preferable during forest felling.

The history of Lapland : containing a geographical description, and a natural history of that country; with an account of the inhabitants, their original, religion, customs, habits, marriages, conjurations, employments, &c. Written by John Scheffer, ... Translated from the last edition in Latin, and illustrated with many curious copper-cutts. To which are added, the travels of the King of Sweden's mathematicians into Lapland: the history of Livonia, and the wars there: also a journey into Lapland, Finland, &c. Written by Dr. Olof Rudbeck in the year 1701

Added engraved title page: The history of Lapland.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Improving the competitiveness of electrolytic Zinc process by chemical reaction engineering approach

This doctoral thesis describes the development work performed on the leachand purification sections in the electrolytic zinc plant in Kokkola to increase the efficiency in these two stages, and thus the competitiveness of the plant. Since metallic zinc is a typical bulk product, the improvement of the competitiveness of a plant was mostly an issue of decreasing unit costs. The problems in the leaching were low recovery of valuable metals from raw materials, and that the available technology offered complicated and expensive processes to overcome this problem. In the purification, the main problem was consumption of zinc powder - up to four to six times the stoichiometric demand. This reduced the capacity of the plant as this zinc is re-circulated through the electrolysis, which is the absolute bottleneck in a zinc plant. Low selectivity gave low-grade and low-value precipitates for further processing to metallic copper, cadmium, cobalt and nickel. Knowledge of the underlying chemistry was poor and process interruptions causing losses of zinc production were frequent. Studies on leaching comprised the kinetics of ferrite leaching and jarosite precipitation, as well as the stability of jarosite in acidic plant solutions. A breakthrough came with the finding that jarosite could precipitate under conditions where ferrite would leach satisfactorily. Based on this discovery, a one-step process for the treatment of ferrite was developed. In the plant, the new process almost doubled the recovery of zinc from ferrite in the same equipment as the two-step jarosite process was operated in at that time. In a later expansion of the plant, investment savings were substantial compared to other technologies available. In the solution purification, the key finding was that Co, Ni, and Cu formed specific arsenides in the “hot arsenic zinc dust” step. This was utilized for the development of a three-step purification stage based on fluidized bed technology in all three steps, i.e. removal of Cu, Co and Cd. Both precipitation rates and selectivity increased, which strongly decreased the zinc powder consumption through a substantially suppressed hydrogen gas evolution. Better selectivity improved the value of the precipitates: cadmium, which caused environmental problems in the copper smelter, was reduced from 1-3% reported normally down to 0.05 %, and a cobalt cake with 15 % Co was easily produced in laboratory experiments in the cobalt removal. The zinc powder consumption in the plant for a solution containing Cu, Co, Ni and Cd (1000, 25, 30 and 350 mg/l, respectively), was around 1.8 g/l; i.e. only 1.4 times the stoichiometric demand – or, about 60% saving in powder consumption. Two processes for direct leaching of the concentrate under atmospheric conditions were developed, one of which was implemented in the Kokkola zinc plant. Compared to the existing pressure leach technology, savings were obtained mostly in investment. The scientific basis for the most important processes and process improvements is given in the doctoral thesis. This includes mathematical modeling and thermodynamic evaluation of experimental results and hypotheses developed. Five of the processes developed in this research and development program were implemented in the plant and are still operated. Even though these processes were developed with the focus on the plant in Kokkola, they can also be implemented at low cost in most of the zinc plants globally, and have thus a great significance in the development of the electrolytic zinc process in general.

HIMALDOC: A Tool for a Regional Open Repository on Sustainable Mountain Development Issues in the Hindu Kush Himalaya

Poster at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

The dominions of the Czar of Russia Alba or Great Duke of Moscovia in which are the Dukedoms of Moscow, Wolodimer, Rezan, Worotin, Novogorod-Sewierski, Czernihow, Smolensko, Reschow, Twer, Novogorod-Weliki, Biele Jezora, Wologda, .. /

1 kartta :, käsinvär. ;, 57 x 88 cm, lehti 62,5 x 92,5 cm

The expedition of Alexander the Great, first king of Persia : according to Quintus Curtius, Arrian, and others

Julkaisussa: Geographia classica : the geography of the ancients

A map of Marco Polo's voyages & travels in the 13th century through a great part of Asia, all Tartary, the East India islands & part of Africa

Nimeketiedot nimiönkehyksissä

Replacing Copper with New Carbon Nanomaterials in Electrical Machine Windings

Electrical machines have significant improvement potential. Nevertheless, the field is characterized by incremental innovations. Admittedly, steady improvement has been achieved, but no breakthrough development. Radical development in the field would require the introduction of new elements, such that may change the whole electrical machine industry system. Recent technological advancements in nanomaterials have opened up new horizons for the macroscopic application of carbon nanotube (CNT) fibres. With values of 100 MS/m measured on individual CNTs, CNT fibre materials hold promise for conductivities far beyond those of metals. Highly conductive, lightweight and strong CNT yarn is finally within reach; it could replace copper as a potentially better winding material. Although not yet providing low resistivity, the newest CNT yarn offers attractive perspectives for accelerated efficiency improvement of electrical machines. In this article, the potential for using new CNT materials to replace copper in machine windings is introduced. It does so, firstly, by describing the environment for a change that could revolutionize the industry and, secondly, by presenting the breakthrough results of a prototype construction. In the test motor, which is to our knowledge the first in its kind, the presently most electrically conductive carbon nanotube yarn replaces usual copper in the windings.

Digital Humanities For Everyone’s Benefit?: interplay in social media with the great audience, high-esteemed researcher and self-conscious library

The National Library of Finland realizes the Digitization Project of Kindred Languages in 2012–15. The project is financially supported by the Kone Foundation. During this project the National Library of Finland has digitized and made available approximately 1200 monograph and more than 100 newspaper titles in several Uralic languages. The materials are available to both researchers and citizens in the National Library’s Fenno-Ugrica collection. The project will produce digitized materials in the Uralic languages as well as their development tools to support linguistic research and citizen science. The resulting materials will constitute the largest resource for the Uralic languages in the world. Through this project, researchers will gain access to corpora which they have not been able to study before and to which all users will have open access regardless of their place of residence. In my presentation, I will discuss 1) how we utilized the social media (Facebook, Twitter, VKontakte etc) to gain audience for our collection and 2) how the needs of researchers and laymen were met in crowdsourcing.

Hiilinanojohteiden makroskooppinen johtavuus

Hiilinanojohteet ovat sähkönjohteita, joiden valmistuksessa on käytetty hiilinanoputkia, eli yhden atomikerroksen paksuisesta hiiliatomiverkosta koostuvia rakenteita. Hiilinanoputket ovat viime vuosina keränneet suurta mielenkiintoa erinomaisten fysikaalisten ominaisuuksiensa ansiosta. Tämän työn tavoitteena on selvittää, voitaisiinko hiilinanojohteiden sähkönjohtavuus saada riittävälle tasolle, jotta niillä saatettaisiin korvata nykyisiä kuparista valmistettuja johteita. Vaikka kuparilla on erinomainen johtavuus, sen käytöllä on omat heikkoutensa, kuten korkea hinta, virran ahtautuminen, suuri tiheys ja heikko mekaaninen kestävyys. Hiilinanojohteet voisivat olla yksi osa-alue kehitettäessä uusia energiatehokkaita ja ympäristöystävällisiä laitteita nyky-yhteiskunnan tarpeisiin. Työn tulosten perusteella voidaan todeta, että nykyisten hiilinanojohteiden sähkönjohtavuus on yhä liian pieni laajamittaiseen käyttöön. Johtavuus on kuitenkin lisääntynyt jatkuvasti viime vuosina. Kehitystyön avulla hiilimateriaalin potentiaalia saadaan hyödynnettyä koko ajan enemmän, ja ajan myötä hiilijohteista voi tulla varteenotettava kilpailija perinteisille johdemateriaaleille. Hiilinanojohteet tulevat luultavasti aluksi yleistymään käyttökohteissa, joissa niiden muut ominaisuudet täydentävät hyvin sähkönjohtavuutta.

Development and characterization of thin printed films for gas sensing applications

The monitoring and control of hydrogen sulfide (H2S) level is of great interest for a wide range of application areas including food quality control, defense and antiterrorist applications and air quality monitoring e.g. in mines. H2S is a very poisonous and flammable gas. Exposure to low concentrations of H2S can result in eye irritation, a sore throat and cough, shortness of breath, and fluid retention in the lungs. These symptoms usually disappear in a few weeks. Long-term, low-level exposure may result in fatigue, loss of appetite, headache, irritability, poor memory, and dizziness. Higher concentrations of 700 - 800 ppm tend to be fatal. H2S has a characteristic smell of rotten egg. However, because of temporary paralysis of olfactory nerves, the smelling capability at concentrations higher than 100 ppm is severely compromised. In addition, volatile H2S is one of the main products during the spoilage of poultry meat in anaerobic conditions. Currently, no commercial H2S sensor is available which can operate under anaerobic conditions and can be easily integrated in the food packaging. This thesis presents a step-wise progress in the development of printed H2S gas sensors. Efforts were made in the formulation, characterization and optimization of functional printable inks and coating pastes based on composites of a polymer and a metal salt as well as a composite of a metal salt and an organic acid. Different processing techniques including inkjet printing, flexographic printing, screen printing and spray coating were utilized in the fabrication of H2S sensors. The dispersions were characterized by measuring turbidity, surface tension, viscosity and particle size. The sensing films were characterized using X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy and an electrical multimeter. Thin and thick printed or coated films were developed for gas sensing applications with the aim of monitoring the H2S concentrations in real life applications. Initially, a H2S gas sensor based on a composite of polyaniline and metal salt was developed. Both aqueous and solvent-based dispersions were developed and characterized. These dispersions were then utilized in the fabrication of roll-to-roll printed H2S gas sensors. However, the humidity background, long term instability and comparatively lower detection limit made these sensors less favourable for real practical applications. To overcome these problems, copper acetate based sensors were developed for H2S gas sensing. Stable inks with excellent printability were developed by tuning the surface tension, viscosity and particle size. This enabled the formation of inkjet-printed high quality copper acetate films with excellent sensitivity towards H2S. Furthermore, these sensors showed negligible humidity effects and improved selectivity, response time, lower limit of detection and coefficient of variation. The lower limit of detection of copper acetate based sensors was further improved to sub-ppm level by incorporation of catalytic gold nano-particles and subsequent plasma treatment of the sensing film. These sensors were further integrated in an inexpensive wirelessly readable RLC-circuit (where R is resistor, L is inductor and C is capacitor). The performance of these sensors towards biogenic H2S produced during the spoilage of poultry meat in the modified atmosphere package was also demonstrated in this thesis. This serves as a proof of concept that these sensors can be utilized in real life applications.

VAP-1 as drug target in inflammation : structural features determining ligand interactions

Vascular adhesion protein-1 (VAP-1), which belongs to the copper amine oxidases (CAOs), is a validated drug target in inflammatory diseases. Inhibition of VAP-1 blocks the leukocyte trafficking to sites of inflammation and alleviates inflammatory reactions. In this study, a novel set of potent pyridazinone inhibitors is presented together with their X-ray structure complexes with VAP-1. The crystal structure of serum VAP-1 (sVAP-1) revealed an imidazole binding site in the active site channel and, analogously, the pyridazinone inhibitors were designed to bind into the channel. This is the first time human VAP-1 has been crystallized with a reversible inhibitor and the structures reveal detailed information of the binding mode on the atomic level. Similarly to some earlier studied inhibitors of human VAP-1, the designed pyridazinone inhibitors bind rodent VAP-1 with a lower affinity than human VAP-1. Therefore, we made homology models of rodent VAP-1 and compared human and rodent enzymes to determine differences that might affect the inhibitor binding. The comparison of the crystal structures of the human VAP-1 and the mouse VAP-1 homology model revealed key differences important for the species specific binding properties. In general, the channel in mouse VAP-1 is more narrow and polar than the channel in human VAP-1, which is wider and more hydrophobic. The differences are located in the channel leading to the active site, as well as, in the entrance to the active site channel. The information obtained from these studies is of great importance for the development and design of drugs blocking the activity of human VAP-1, as rodents are often used for in vivo testing of candidate drugs. In order to gain more insight into the selective binding properties of the different CAOs in one species a comprehensive evolutionary study of mammalian CAOs was performed. We found that CAOs can be classified into sub-families according to the residues X1 and X2 of the Thr/Ser-X1-X2-Asn-Tyr-Asp active site motif. In the phylogenetic tree, CAOs group into diamine oxidase, retina specific amine oxidase and VAP-1/serum amine oxidase clades based on the residue in the position X2. We also found that VAP-1 and SAO can be further differentiated based on the residue in the position X1. This is the first large-scale comparison of CAO sequences, which explains some of the reasons for the unique substrate specificities within the CAO family.