917 resultados para Metal in the architecture
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The present work aimed at identifying the Symphyla species diversity and abundance in various land-use systems under different degrees of intensification in western Amazonia. This is the first inventory of Symphyla in primary and secondary forest, crops, agroforestry systems and pastures which was carried out in Benjamin Constant municipality, in the region of the Upper Solimões River, Brazil. Samples (n = 101) were collected using a metal corer, and the symphylan extraction was carried out using Berlese-Tullgren funnels. Two genera and three species of symphylans were encountered. Considering the diversity encountered in Amazonian inventories, with only four genera and five known species overall, the three species found in the present study are considered a reasonable representation of the regional diversity. Two of the Hanseniella species found have been known to cause plant damage.
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ABSTRACT Adult neuronal plasticity is a term that corresponds to a set of biological mechanisms allowing a neuronal circuit to respond and adapt to modifications of the received inputs. Mystacial whiskers of the mouse are the starting point of a major sensory pathway that provides the animal with information from its immediate environment. Through whisking, information is gathered that allows the animal to orientate itself and to recognize objects. This sensory system is crucial for nocturnal behaviour during which vision is not of much use. Sensory information of the whiskers are sent via brainstem and thalamus to the primary somatosensory area (S1) of the cerebral cortex in a strictly topological manner. Cell bodies in the layer N of S 1 are arranged in ring forming structures called barrels. As such, each barrel corresponds to the cortical representation in layer IV of a single whisker follicle. This histological feature allows to identify with uttermost precision the part of the cortex devoted to a given whisker and to study modifications induced by different experimental conditions. The condition used in the studies of my thesis is the passive stimulation of one whisker in the adult mouse for a period of 24 hours. It is performed by glueing a piece of metal on one whisker and placing the awake animal in a cage surrounded by an electromagnetic coil that generates magnetic field burst inducing whisker movement at a given frequency during 24 hours. I analysed the ultrastructure of the barrel corresponding the stimulated whisker using serial sections electron microscopy and computer-based three-dimensional reconstructions; analysis of neighbouring, unstimulated barrels as well as those from unstimulated mice served as control. The following elements were structurally analyzed: the spiny dendrites, the axons of excitatory as well as inhibitory cells, their connections via synapses and the astrocytic processes. The density of synapses and spines is upregulated in a barrel corresponding to a stimulated whisker. This upregulation is absent in the BDNF heterozygote mice, indicating that a certain level of activity-dependent released BDNF is required for synaptogenesis in the adult cerebral cortex. Synpaptogenesis is correlated with a modification of the astrocytes that place themselves in closer vicinity of the excitatory synapses on spines. Biochemical analysis revealed that the astrocytes upregulate the expression of transporters by which they internalise glutamate, the neurotransmitter responsible for the excitatory response of cortical neurons. In the final part of my thesis, I show that synaptogenesis in the stimulated barrel is due to the increase in the size of excitatory axonal boutons that become more frequently multisynaptic, whereas the inhibitory axons do not change their morphology but form more synapses with spines apposed to them. Taken together, my thesis demonstrates that all the cellular elements present in the neuronal tissue of the adult brain contribute to activity-dependent cortical plasticity and form part of a mechanism by which the animal responds to a modified sensory experience. Throughout life, the neuronal circuit keeps the faculty to adapt its function. These adaptations are partially transitory but some aspects remain and could be the structural basis of a memory trace in the cortical circuit. RESUME La plasticité neuronale chez l'adulte désigne un ensemble de mécanismes biologiques qui permettent aux circuits neuronaux de répondre et de s'adapter aux modifications des stimulations reçues. Les vibrisses des souris sont un système crucial fournissant des informations sensorielles au sujet de l'environnement de l'animal. L'information sensorielle collectée par les vibrisses est envoyée via le tronc cérébral et le thalamus à l'aire sensorielle primaire (S 1) du cortex cérébral en respectant strictement la somatotopie. Les corps cellulaires dans la couche IV de S 1 sont organisés en anneaux délimitant des structures nommées tonneaux. Chaque tonneau reçoit l'information d'une seule vibrisse et l'arrangement des tonneaux dans le cortex correspond à l'arrangement des vibrisses sur le museau de la souris. Cette particularité histologique permet de sélectionner avec certitude la partie du cortex dévolue à une vibrisse et de l'étudier dans diverses conditions. Le paradigme expérimental utilisé dans cette thèse est la stimulation passive d'une seule vibrisse durant 24 heures. Pour ce faire, un petit morceau de métal est collé sur une vibrisse et la souris est placée dans une cage entourée d'une bobine électromagnétique générant un champ qui fait vibrer le morceau de métal durant 24 heures. Nous analysons l'ultrastructure du cortex cérébral à l'aide de la microscopie électronique et des coupes sériées permettant la reconstruction tridimensionnelle à l'aide de logiciels informatiques. Nous observons les modifications des structures présentes : les dendrites épineuses, les axones des cellules excitatrices et inhibitrices, leurs connections par des synapses et les astrocytes. Le nombre de synapses et d'épines est augmenté dans un tonneau correspondant à une vibrisse stimulée 24 heures. Basé sur cela, nous montrons dans ces travaux que cette réponse n'est pas observée dans des souris hétérozygotes BDNF+/-. Cette neurotrophine sécrétée en fonction de l'activité neuronale est donc nécessaire pour la synaptogenèse. La synaptogenèse est accompagnée d'une modification des astrocytes qui se rapprochent des synapses excitatrices au niveau des épines dendritiques. Ils expriment également plus de transporteurs chargés d'internaliser le glutamate, le neurotransmetteur responsable de la réponse excitatrice des neurones. Nous montrons aussi que les axones excitateurs deviennent plus larges et forment plus de boutons multi-synaptiques à la suite de la stimulation tandis que les axones inhibiteurs ne changent pas de morphologie mais forment plus de synapses avec des épines apposées à leur membrane. Tous les éléments analysés dans le cerveau adulte ont maintenu la capacité de réagir aux modifications de l'activité neuronale et répondent aux modifications de l'activité permettant une constante adaptation à de nouveaux environnements durant la vie. Les circuits neuronaux gardent la capacité de créer de nouvelles synapses. Ces adaptations peuvent être des réponses transitoires aux stimuli mais peuvent aussi laisser une trace mnésique dans les circuits.
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Mice deficient in CCR7 signals show severe defects in lymphoid tissue architecture and immune response. These defects are due to impaired attraction of CCR7+ DC and CCR7+ T cells into the T zones of secondary lymphoid organs and altered DC maturation. It is currently unclear which CCR7 ligand mediates these processes in vivo as CCL19 and CCL21 show an overlapping expression pattern and blocking experiments have given contradictory results. In this study, we addressed this question using CCL19-deficient mice expressing various levels of CCL21. Complete deficiency of CCL19 and CCL21 but not CCL19 alone was found to be associated with abnormal frequencies and localization of DC in naïve LN. Similarly, CCL19 was not required for DC migration from the skin, full DC maturation and efficient T-cell priming. Our findings suggest that CCL21 is the critical CCR7 ligand regulating DC homeostasis and function in vivo with CCL19 being redundant for these processes.
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ABSTRACTThe pollution of air, soil and water by heavy metals through anthropogenic activities is an object of numerous environmental studies since long times. A number of natural processes, such as volcanic activity, hydrothermal fluid circulation and weathering of metal-rich deposits may lead to an additional and potentially important input and accumulation of heavy metals in the environment. In the Swiss and French Jura Mountains, anomalous high cadmium (Cd) concentrations (up to 16 ppm) in certain soils are related to the presence of underlying Cd-enriched (up to 21 ppm) carbonate rocks of Middle to Late Jurassic age. The aim of this study is to understand the processes controlling Cd incorporation into carbonate rocks of Middle and Late Jurassic age and to reconstruct the sedimentary and environmental conditions, which have led to Cd enrichments in these sedimentary rocks.Cd concentrations in studied hemipelagic sections in France vary between 0.1 and 0.5 ppm (mean 0.15 ppm). Trace-element behavior and high Mn concentrations suggest that sediment accumulation occurred in a well-oxygenated environment. Increases in Cd contents in the bulk-rock carbonate sediments may be related to increases in surface-water productivity under oxic conditions and important remineralization of organic matter within the water column. In platform settings preserved in the Swiss Jura Mountains, no correlation is observed between Cd contents and evolution of environmental conditions. Cd concentrations in these platform sections are often below the detection limit, with isolated peaks of up to 21 ppm. These important Cd enrichments are associated with peaks in Zn concentrations and are present in carbonate rocks independently of facies and age. The high Cd contents in these shallow-water carbonate rocks are partly related to the presence of disseminated, Cd-rich (up to 1.8%), sphalerite (ZnS) mineralization. The basement rocks are considered to be the source of metals for sulfide mineralization in the overlying Jurassic strata, as the sphalerite Pb isotope pattern is comparable to that of granite rocks from the nearby southern Black Forest crystalline massif. The Rb-Sr ages of sphalerite samples indicate that a main phase of sphalerite formation occurred near the boundary between the late Middle and early Late Jurassic, at around 162 Ma, as a result of enhanced tectonic and hydrothermal activity in Europe, related to the opening of the Central Atlantic and to the tectonic/thermal subsidence during spreading of the Alpine Tethys. I therefore propose to use unusually high Cd concentrations in carbonates as a tracer of tectonic activity in the Jura Mountains area, especially in the case when important enrichments in Zn co-occur. Paleoproductivity reconstructions based on records of authigenic Cd may be compromised not only by post-depositional redistribution, but also by incorporation of additional Cd from hydrothermal solutions circulating in the rock.The circulation of metal-rich hydrothermal fluids through the sediment sequence, in addition to specific environmental conditions during sedimentation, contributes to the incorporation of Cd into the carbonate rocks. However, only hydrothermal activity has led to the unusually high concentrations of Cd in carbonate rocks of Bajocian-Oxfordian age, through the formation of sphalerite mineralization.
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Diplomityön tarkoituksena oli löytää keino korkean mangaanipitoisuuden hallintaan ECF-valkaisussa. Kirjallisuusosassa käsiteltiin eri metallien ja kuidun vuorovaikutuksia sekä niiden vaikutuksia prosessiin. Lisäksi käytiin läpi sellunvalmituksen yleisimpiä metallienhallintamenetelmiä. Työn kokeellisessa osassa tehtiin esikokeina laboratoriokokeita, jotta löydettiin oikeat kelatointistrategiat tehdasmittakaavan koeajoille. Laboratoriovalkaisut suoritettiin kuudella eri kemikaalilla käyttäen DD3-pesurin jälkeistä massaa ja samanlaisia parametrejä kuin tehdasvalkaisussa. Kolmesta eri valkaisusekvenssistä paras tulos saavutettiin D0-QEP-sekvenssillä. Tehdasmittakaavan koeajojen tavoitteena oli saavuttaa alle 1 mg/kg jäännösmangaanipitoisuus valkaistussa massassa ja korkeampi vaaleus EOP-vaiheessa pienemmällä klooridioksidin kulutuksella. Koeajoissa käytettiinDTPA:ta ja EDTA:ta kahdeksassa eri koepisteessä. Pienimpiin jäännöspitoisuuksiin päästiin koepisteissä, joissa kelatointiaine annosteltiin ennen valkaisun viimeistä pesuvaihetta tai sen jälkeen. Samanlaisia tuloksia saavutettiin koepisteissä, joissa kelatointiaine lisättiin suoraan EOP-vaiheeseen. Tällöin kelatointiaineen käyttö johti myös korkeampaan vaaleuteen EOP-vaiheessa pienemmällä kappakertoimella kuin referenssissä. Säästöt klooridioksidin kulutuksessa eivät olleet kuitenkaan tarpeeksi suuret kattaakseen kelatointiaineiden käytön kustannuksia. Kustannustehokkain tapa kontrolloida jäännösmangaanipitoisuutta oli EDTA:n annostelu D2 DD-pesurin jälkeen. Haittapuolena tälläisessä kelatoinnissa oli metallikompleksien palautuminen valkaisuun kuivauskoneen kiertoveden mukana. Tärkeimmät onnistuneeseen kelatointiin vaikuttavat parametrit olivat lajittelussa käytetyn rikkihapon annos, D0-vaiheen pH ja D0 DD-pesurin pesutehokkuus.
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The imperial cult area of Tarraco was built in the 1st century AD in the highest part of the city and presided over the seat of the Concilium Prouinciae Hispaniae Citerioris. It was a temenos with a similar layout to that of the Forum Pacis and architectural decoration imitating that of the Forum Augustum in Rome, where the use of marble was a fundamental part of the architectural and sculptural decorative programme. An extensive assemblage of marble was recovered during the excavations carried out under the Tarragona Cathedral Master Plan. It reflects the use of imperial quarries in the decorative programme and has been analyzed at the Unitat d’Estudis Arqueomètrics (ICAC) facilities. This assemblage reflects the wide panorama of marmora imported and used in the decoration of the temenos. Local varieties of marmora have been identified in Tarraco, plus a series of foreign marmora from quarries all over the Roman Empire (Greece, Turkey, Egypt and North Africa). All this shows the involvement of the imperial power in the monumental architecture of the capital of the prouincia Hispania Citerior.
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Diplomityöntavoitteena on tutkia, kuinka nimiketiedon hallinnalla voidaan parantaa kustannustehokkuutta projektiohjautuvassa toimitusketjussa. Työn kohdeyritys on Konecranes Oyj:n tytäryhtiö Konecranes Heavy Lifting Oy. Nimiketiedon hallinta liittyy läheisesti tuotetiedon hallintaan. Teoriaosassa käsitellään toimitusketjuympäristön tekijöitä, modulaarisuuden ja asiakaskohtaisuuden ongelmallisuutta sekä informaatiovirran vaikutuksia eri toiminnoissa. Yritysosassa vertaillaan konsernitason kahta liiketoiminta-aluetta strategiavalintojen, tuotteiden modulaarisuuden sekä tilaus-toimitusprosessissa liikkuvan nimikeinformaation perusteella. Diplomityön tuloksena annetaan suuntaviivat; nimikemassan eheytykseen, strategisten nimikkeiden tunnistamiseen ja määrittämiseen, nimikkeiden hallintaan sekä master-datan sijoittamiseen tietojärjestelmäympäristöön.
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The widespread implementation of GIS-based 3D topographical models has been a great aid in the development and testing of archaeological hypotheses. In this paper, a topographical reconstruction of the ancient city of Tarraco, the Roman capital of the Tarraconensis province, is presented. This model is based on topographical data obtained through archaeological excavations, old photographic documentation, georeferenced archive maps depicting the pre-modern city topography, modern detailed topographical maps and differential GPS measurements. The addition of the Roman urban architectural features to the model offers the possibility to test hypotheses concerning the ideological background manifested in the city shape. This is accomplished mainly through the use of 3D views from the main city accesses. These techniques ultimately demonstrate the ‘theatre-shaped’ layout of the city (to quote Vitrubius) as well as its southwest oriented architecture, whose monumental character was conceived to present a striking aspect to visitors, particularly those arriving from the sea.
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The depositional stratigraphy of within-channel deposits in sandy braided rivers is dominated by a variety of barforms (both singular `unit' bars and complex `compound' bars), as well as the infill of individual channels (herein termed `channel fills'). The deposits of bars and channel fills define the key components of facies models for braided rivers and their within-channel heterogeneity, knowledge of which is important for reservoir characterization. However, few studies have sought to address the question of whether the deposits of bars and channel fills can be readily differentiated from each other. This paper presents the first quantitative study to achieve this aim, using aerial images of an evolving modern sandy braided river and geophysical imaging of its subsurface deposits. Aerial photographs taken between 2000 and 2004 document the abandonment and fill of a 1 3 km long, 80 m wide anabranch channel in the sandy braided South Saskatchewan River, Canada. Upstream river regulation traps the majority of very fine sediment and there is little clay (<1%) in the bed sediments. Channel abandonment was initiated by a series of unit bars that stalled and progressively blocked the anabranch entrance, together with dune deposition and stacking at the anabranch entrance and exit. Complete channel abandonment and subsequent fill of up to 3 m of sediment took approximately two years. Thirteen kilometres of ground-penetrating radar surveys, coupled with 18 cores, were obtained over the channel fill and an adjacent 750 m long, 400 m wide, compound bar, enabling a quantitative analysis of the channel and bar deposits. Results show that, in terms of grain-size trends, facies proportions and scale of deposits, there are only subtle differences between the channel fill and bar deposits which, therefore, renders them indistinguishable. Thus, it may be inappropriate to assign different geometric and sedimentological attributes to channel fill and bar facies in object-based models of sandy braided river alluvial architecture.
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Environmentally harmful consequences of fossil fuel utilisation andthe landfilling of wastes have increased the interest among the energy producers to consider the use of alternative fuels like wood fuels and Refuse-Derived Fuels, RDFs. The fluidised bed technology that allows the flexible use of a variety of different fuels is commonly used at small- and medium-sized power plants ofmunicipalities and industry in Finland. Since there is only one mass-burn plantcurrently in operation in the country and no intention to build new ones, the co-firing of pre-processed wastes in fluidised bed boilers has become the most generally applied waste-to-energy concept in Finland. The recently validated EU Directive on Incineration of Wastes aims to mitigate environmentally harmful pollutants of waste incineration and co-incineration of wastes with conventional fuels. Apart from gaseous flue gas pollutants and dust, the emissions of toxic tracemetals are limited. The implementation of the Directive's restrictions in the Finnish legislation is assumed to limit the co-firing of waste fuels, due to the insufficient reduction of the regulated air pollutants in the existing flue gas cleaning devices. Trace metals emission formation and reduction in the ESP, the condensing wet scrubber, the fabric filter, and the humidification reactor were studied, experimentally, in full- and pilot-scale combustors utilising the bubbling fluidised bed technology, and, theoretically, by means of reactor model calculations. The core of the model is a thermodynamic equilibrium analysis. The experiments were carried out with wood chips, sawdust, and peat, and their refuse-derived fuel, RDF, blends. In all, ten different fuels or fuel blends were tested. Relatively high concentrations of trace metals in RDFs compared to the concentrations of these metals in wood fuels increased the trace metal concentrations in the flue gas after the boiler ten- to hundred-folds, when RDF was co-fired with sawdust in a full-scale BFB boiler. In the case of peat, lesser increase in trace metal concentrations was observed, due to the higher initial trace metal concentrations of peat compared to sawdust. Despite the high removal rate of most of the trace metals in the ESP, the Directive emission limits for trace metals were exceeded in each of the RDF co-firing tests. The dominat trace metals in fluegas after the ESP were Cu, Pb and Mn. In the condensing wet scrubber, the flue gas trace metal emissions were reduced below the Directive emission limits, whenRDF pellet was used as a co-firing fuel together with sawdust and peat. High chlorine content of the RDFs enhanced the mercuric chloride formation and hence the mercury removal in the ESP and scrubber. Mercury emissions were lower than theDirective emission limit for total Hg, 0.05 mg/Nm3, in all full-scale co-firingtests already in the flue gas after the ESP. The pilot-scale experiments with aBFB combustor equipped with a fabric filter revealed that the fabric filter alone is able to reduce the trace metal concentrations, including mercury, in the flue gas during the RDF co-firing approximately to the same level as they are during the wood chip firing. Lower trace metal emissions than the Directive limits were easily reached even with a 40% thermal share of RDF co-firing with sawdust.Enrichment of trace metals in the submicron fly ash particle fraction because of RDF co-firing was not observed in the test runs where sawdust was used as the main fuel. The combustion of RDF pellets with peat caused an enrichment of As, Cd, Co, Pb, Sb, and V in the submicron particle mode. Accumulation and release oftrace metals in the bed material was examined by means of a bed material analysis, mass balance calculations and a reactor model. Lead, zinc and copper were found to have a tendency to be accumulated in the bed material but also to have a tendency to be released from the bed material into the combustion gases, if the combustion conditions were changed. The concentration of the trace metal in the combustion gases of the bubbling fluidised bed boiler was found to be a summary of trace metal fluxes from three main sources. They were (1) the trace metal flux from the burning fuel particle (2) the trace metal flux from the ash in the bed, and (3) the trace metal flux from the active alkali metal layer on the sand (and ash) particles in the bed. The amount of chlorine in the system, the combustion temperature, the fuel ash composition and the saturation state of the bed material in regard to trace metals were discovered to be key factors affecting therelease process. During the co-firing of waste fuels with variable amounts of e.g. ash and chlorine, it is extremely important to consider the possible ongoingaccumulation and/or release of the trace metals in the bed, when determining the flue gas trace metal emissions. If the state of the combustion process in regard to trace metals accumulation and/or release in the bed material is not known,it may happen that emissions from the bed material rather than the combustion of the fuel in question are measured and reported.
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Semantic Web technology is able to provide the required computational semantics for interoperability of learning resources across different Learning Management Systems (LMS) and Learning Object Repositories (LOR). The EU research project LUISA (Learning Content Management System Using Innovative Semantic Web Services Architecture) addresses the development of a reference semantic architecture for the major challenges in the search, interchange and delivery of learning objects in a service-oriented context. One of the key issues, highlighted in this paper, is Digital Rights Management (DRM) interoperability. A Semantic Web approach to copyright management has been followed, which places a Copyright Ontology as the key component for interoperability among existing DRM systems and other licensing schemes like Creative Commons. Moreover, Semantic Web tools like reasoners, rule engines and semantic queries facilitate the implementation of an interoperable copyright management component in the LUISA architecture.
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BACKGROUND: There are limited data on the composition and smoke emissions of 'herbal' shisha products and the air quality of establishments where they are smoked. METHODS: Three studies of 'herbal' shisha were conducted: (1) samples of 'herbal' shisha products were chemically analysed; (2) 'herbal' and tobacco shisha were burned in a waterpipe smoking machine and main and sidestream smoke analysed by standard methods and (3) the air quality of six waterpipe cafes was assessed by measurement of CO, particulate and nicotine vapour content. RESULTS: We found considerable variation in heavy metal content between the three products sampled, one being particularly high in lead, chromium, nickel and arsenic. A similar pattern emerged for polycyclic aromatic hydrocarbons. Smoke emission analyses indicated that toxic byproducts produced by the combustion of 'herbal' shisha were equivalent or greater than those produced by tobacco shisha. The results of our air quality assessment demonstrated that mean PM2.5 levels and CO content were significantly higher in waterpipe establishments compared to a casino where cigarette smoking was permitted. Nicotine vapour was detected in one of the waterpipe cafes. CONCLUSIONS: 'Herbal' shisha products tested contained toxic trace metals and PAHs levels equivalent to, or in excess of, that found in cigarettes. Their mainstream and sidestream smoke emissions contained carcinogens equivalent to, or in excess of, those of tobacco products. The content of the air in the waterpipe cafes tested was potentially hazardous. These data, in aggregate, suggest that smoking 'herbal' shisha may well be dangerous to health.
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Neljännen sukupolven mobiiliverkot yhdistävät saumattomasti televerkot, Internetin ja niiden palvelut. Alkuperin Internetiä käytettiin vain paikallaan pysyviltä tietokoneilta perinteisten televerkkojen tarjotessa puhelin- ja datapalveluita. Neljännen sukupolven mobiiliverkkojen käyttäjät voivat käyttää sekä Internetiin perustuvia että perinteisten televerkkojen palveluita liikkuessaankin. Tämä diplomityö esittelee neljännen sukupolven mobiiliverkon yleisen arkkitehtuurin. Arkkitehtuurin perusosat kuvaillaan ja arkkitehtuuria verrataan toisen ja kolmannen sukupolven mobiiliverkkoihin. Aiheeseen liittyvät Internet-standardit esitellään ja niiden soveltuvuutta mobiiliverkkoihin pohditaan. Langattomia, lyhyen kantaman nopeita liitäntäverkkotekniikoita esitellään. Neljännen sukupolven mobiiliverkoissa tarvittavia päätelaitteiden ja käyttäjien liikkuvuuden hallintamenetelmiä esitellään. Esitelty arkkitehtuuri perustuu langattomiin, lyhyen kantaman nopeisiin liitäntäverkkotekniikoihin ja Internet-standardeihin. Arkkitehtuuri mahdollistaa yhteydet toisiin käyttäjiin ilman tietoa heidän senhetkisestä päätelaitteesta tai sijainnista. Internetin palveluitavoidaan käyttää missä tahansa neljännen sukupolven mobiiliverkon alueella. Yleiskäytöistä liikkuvuuden hallintamenetelmää yhden verkon alueelle ehdotetaan. Menetelmää voidaan käyttää yhdessä esitellyn arkkitehtuurin kanssa.
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Ankle fractures in adults are usually managed by open reduction internal fixation. In elderly patients the surgical dilemma relates to bone quality. Osteoporosis is the enemy of internal fixation, and secure purchase of screws in osteopenic bone may be difficult to achieve. Insufficient screw purchase may lead to loss of reduction, wound breakdown, and infection. Postoperative management after osteosynthesis usually requires an extended period of restricted weight bearing. However, this is not feasible in older patients as a result of their lack of strength in the upper extremities and frequent comorbidities. Therefore, augmen- ted methods of internal fixation and specific surgical techniques have been developed using metal and bone cement. This permits this fragile population to begin early full weight bearing in a removable brace.
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Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.