The significance of brittle reaction layers in fusing of dental ceramics to titanium

This thesis comprises four intercomplementary parts that introduce new approaches to brittle reaction layers and mechanical compatibility of metalloceramic joints created when fusing dental ceramics to titanium. Several different methods including atomic layer deposition (ALD), sessile drop contact angle measurements, scanning acoustic microscopy (SAM), three-point bending (TPB, DIN 13 927 / ISO 9693), cross-section microscopy, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS) were employed. The first part investigates the effects of TiO2 layer structure and thickness on the joint strength of the titanium-metalloceramic system. Samples with all tested TiO2 thicknesses displayed good ceramics adhesion to Ti, and uniform TPB results. The fracture mode was independent of oxide layer thickness and structure. Cracking occurred deeper inside titanium, in the oxygen-rich Ti[O]x solid solution surface layer. During dental ceramics firing TiO2 layers dissociate and joints become brittle with increased dissolution of oxygen into metallic Ti and consequent reduction in the metal plasticity. To accomplish an ideal metalloceramic joint this needs to be resolved. The second part introduces photoinduced superhydrophilicity of TiO2. Test samples with ALD deposited anatase TiO2 films were produced. Samples were irradiated with UV light to induce superhydrophilicity of the surfaces through a cascade leading to increased amount of surface hydroxyl groups. Superhydrophilicity (contact angle ~0˚) was achieved within 2 minutes of UV radiation. Partial recovery of the contact angle was observed during the first 10 minutes after UV exposure. Total recovery was not observed within 24h storage. Photoinduced ultrahydrophilicity can be used to enhance wettability of titanium surfaces, an important factor in dental ceramics veneering processes. The third part addresses interlayers designed to restrain oxygen dissolution into Ti during dental ceramics fusing. The main requirements for an ideal interlayer material are proposed. Based on these criteria and systematic exclusion of possible interlayer materials silver (Ag) interlayers were chosen. TPB results were significantly better in when 5 μm Ag interlayers were used compared to only Al2O3-blasted samples. In samples with these Ag interlayers multiple cracks occurred inside dental ceramics, none inside Ti structure. Ag interlayers of 5 μm on Al2O3-blasted samples can be efficiently used to retard formation of the brittle oxygen-rich Ti[O]x layer, thus enhancing metalloceramic joint integrity. The most brittle component in metalloceramic joints with 5 μm Ag interlayers was bulk dental ceramics instead of Ti[O]x. The fourth part investigates the importance of mechanical interlocking. According to the results, the significance of mechanical interlocking achieved by conventional surface treatments can be questioned as long as the formation of the brittle layers (mainly oxygen-rich Ti[O]x) cannot be sufficiently controlled. In summary in contrast to former impressions of thick titanium oxide layers this thesis clearly demonstrates diffusion of oxygen from sintering atmosphere and SiO2 to Ti structures during dental ceramics firing and the following formation of brittle Ti[O]x solid solution as the most important factors predisposing joints between Ti and SiO2-based dental ceramics to low strength. This among other predisposing factors such as residual stresses created by the coefficient of thermal expansion mismatch between dental ceramics and Ti frameworks can be avoided with Ag interlayers.

Korkean lämpötilan vaikutus hiiren poskihampaan kiilteen kehitykseen in vitro

Tutkimuksen tarkoituksena oli selvittää kuumetta vastaavan elinviljelylämpötilan vaikutusta hiiren poskihampaiden kiilteen kehittymiseen. Tutkimus tehtiin in vitro ja siinä käytettiin E18- hiiriä, joiden hampaita kasvatettiin ´kuumeessa´ (39 °C) kolmannesta kasvatuspäivästä lähtien, osaa viisi ja osaa kolme päivää. Kontrollihampaita kasvatettiin 37 °C:ssa. Hampaita kasvatettiin yhteensä 11 päivää ja lopuksi ne kuvattiin. Stereomikroskooppikuvista mitattiin kiilteen korkeus ja kruunun korkeus ja laskettiin näiden suhde. Hampaat demineralisoitiin, valettiin parafiiniin, leikattiin leikkeiksi ja värjättiin HE-värjäyksellä. Leikkeistä mitattiin kiilteen paksuus ja kiilteen ja dentiinin yhteispaksuus ja laskettiin näiden suhde. Arvoja verrattiin kasvatusryhmien kesken. Tulokset analysoitiin Mann-Whitney-testillä. Kiilteen paksuus suhteessa kiilteen ja dentiinin yhteispaksuuteen oli pienempi ´kuumehampaissa´. Viisi tai kolme päivää ´kuumeessa´kasvatettujen hampaiden välillä ei ollut juurikaan eroja. Kiilteen korkeus suhteessa kruunun korkeuteen oli pienempi ´kuumehampaissa´ kuin kontrollihampaissa. Korkea lämpötila ei muutoin näyttänyt vaikuttavan hampaiden kehitykseen. Tutkimuksen perusteella voidaan sanoa, että kasvatuslämpötilan nosto kuumeen tasolle aiheuttaa hiiren molaarihampaan kiilteen kehityksen häiriintymistä. Tulos tukee kliinisiä havaintoja, joiden mukaan korkea kuume lapsella voi aiheuttaa kiilteen kehityshäiriöitä.

The effects of organic environmental toxicants on hard tissue formation in developing tooth : An in vitro study in mice

Dioxins are organic toxicants that are known to impair tooth development, especially dental hard tissue formation. The most toxic dioxin congener is 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Further, clinical studies suggest that maternal smoking during pregnancy can affect child s tooth development. One of the main components of tobacco smoke is the group of non-halogenated polycyclic aromatic hydrocarbons (PAHs), a representative of which is 7,12-dimethylbenz[a]anthracene (DMBA). Tributyltin (TBT), an organic tin compound, has been shown to impair bone mineralization in experimental animals. In addition to exposure to organic toxicants, a well-established cause for enamel hypomineralization is excess fluoride intake. The principal aim of this thesis project was to examine in vitro if, in addition to dioxins, other organic environmental toxicants, like PAHs and organic tin compounds, have adverse effects on tooth development, specifically on formation and mineralization of the major dental hard tissues, the dentin and the enamel. The second aim was to investigate in vitro if fluoride could intensify the manifestation of the detrimental developmental dental effects elicited by TCDD. The study was conducted by culturing mandibular first and second molar tooth germs of E18 NMRI mouse embryos in a Trowell-type organ culture and exposing them to DMBA, TBT, and sodium fluoride (NaF) and/or TCDD at various concentrations during the secretory and mineralization stages of development. Specific methods used were HE-staining for studying cell and tissue morphology, BrdU-staining for cell proliferation, TUNEL-staining for apoptosis, and QPCR, in situ hybridization and immunohistochemistry for the expressions of selected genes associated with mineralization. This thesis work showed that DMBA, TBT, TCDD and NaF interfere with dentin and enamel formation of embryonic mouse tooth in vitro, and that fluoride can potentiate the harmful effect of TCDD. The results suggested that adverse effects of TBT involve altered expression of genes associated with mineralization, and that DMBA and TBT as well as NaF and TCDD together primarily affect dentin mineralization. Since amelogenesis does not start until mineralization of dentin begins, impaired enamel matrix secretion could be a secondary effect. Dioxins, PAHs and organotins are all liposoluble and can be transferred to the infant by breast-feeding. Since doses are usually very low, developmental toxicity on most of the organs is difficult to indentify clinically. However, tooth may act as an indicator of exposure, since the major dental hard tissues, the dentin and the enamel, are not replaced once they have been formed. Thus, disturbed dental hard tissue formation raises the question of more extensive developmental toxicity.

Identification of collagenolytic MMP networks as potential biomarkers in progressive chronic periodontitis subjects and MMP-8 null allele model

Chronic periodontitis results from a complex aetiology, including the formation of a subgingival biofilm and the elicitation of the host s immune and inflammatory response. The hallmark of chronic periodontitis is alveolar bone loss and soft periodontal tissue destruction. Evidence supports that periodontitis progresses in dynamic states of exacerbation and remission or quiescence. The major clinical approach to identify disease progression is the tolerance method, based on sequential probing. Collagen degradation is one of the key events in periodontal destructive lesions. Matrix metalloproteinase (MMP)-8 and MMP-13 are the primary collagenolytic MMPs that are associated with the severity of periodontal inflammation and disease, either by a direct breakdown of the collagenised matrix or by the processing of non-matrix bioactive substrates. Despite the numerous host mediators that have been proposed as potential biomarkers for chronic periodontitis, they reflect inflammation rather than the loss of periodontal attachment. The aim of the present study was to determine the key molecular MMP-8 and -13 interactions in gingival crevicular fluid (GCF) and gingival tissue from progressive periodontitis lesions and MMP-8 null allele mouse model. In study (I), GCF and gingival biopsies from active and inactive sites of chronic periodontitis patients, which were determined clinically by the tolerance method, and healthy GCF were analysed for MMP-13 and tissue inhibitor of matrix metalloproteinases (TIMP)-1. Chronic periodontitis was characterised by increased MMP-13 levels and the active sites showed a tendency of decreased TIMP-1 levels associated with increments of MMP-13 and total protein concentration compared to inactive sites. In study (II), we investigated whether MMP-13 activity was associated with TIMP-1, bone collagen breakdown through ICTP levels, as well as the activation rate of MMP-9 in destructive lesions. The active sites demonstrated increased GCF ICTP levels as well as lowered TIMP-1 detection along with elevated MMP-13 activity. MMP-9 activation rate was enhanced by MMP-13 in diseased gingival tissue. In study (III), we analysed the potential association between the levels, molecular forms, isoenzyme distribution and degree of activation of MMP-8, MMP-14, MPO and the inhibitor TIMP-1 in GCF from periodontitis progressive patients at baseline and after periodontal therapy. A positive correlation was found for MPO/MMP-8 and their levels associated with progression episodes and treatment response. Because MMP-8 is activated by hypochlorous acid in vitro, our results suggested an interaction between the MPO oxidative pathway and MMP-8 activation in GCF. Finally, in study (IV), on the basis of the previous finding that MMP-8-deficient mice showed impaired neutrophil responses and severe alveolar bone loss, we aimed to characterise the detection patterns of LIX/CXCL5, SDF-1/CXCL12 and RANKL in P. gingivalis-induced experimental periodontitis and in the MMP-8-/- murine model. The detection of neutrophil-chemoattractant LIX/CXCL5 was restricted to the oral-periodontal interface and its levels were reduced in infected MMP-8 null mice vs. wild type mice, whereas the detection of SDF-1/CXCL12 and RANKL in periodontal tissues increased in experimentally-induced periodontitis, irrespectively from the genotype. Accordingly, MMP-8 might regulate LIX/CXCL5 levels by undetermined mechanisms, and SDF-1/CXCL12 and RANKL might promote the development and/or progression of periodontitis.

Renewable Energy and Climate Policies: Studies in the Forest and Energy Sector

‪This dissertation examines the impacts of energy and climate policies on the energy and forest sectors, focusing on the case of Finland. The thesis consists of an introduction article and four separate studies. The dissertation was motivated by the climate concern and the increasing demand of renewable energy. In particular, the renewable energy consumption and greenhouse gas emission reduction targets of the European Union were driving this work. In Finland, both forest and energy sectors are in key roles in achieving these targets. In fact, the separation between forest and energy sector is diminishing as the energy sector is utilizing increasing amounts of wood in energy production and as the forest sector is becoming more and more important energy producer.‬ ‪The objective of this dissertation is to find out and measure the impacts of climate and energy policies on the forest and energy sectors. In climate policy, the focus is on emissions trading, and in energy policy the dissertation focuses on the promotion of renewable forest-based energy use. The dissertation relies on empirical numerical models that are based on microeconomic theory. Numerical partial equilibrium mixed complementarity problem models were constructed to study the markets under scrutiny. The separate studies focus on co-firing of wood biomass and fossil fuels, liquid biofuel production in the pulp and paper industry, and the impacts of climate policy on the pulp and paper sector.‬ ‪The dissertation shows that the policies promoting wood-based energy may have have unexpected negative impacts. When feed-in tariff is imposed together with emissions trading, in some plants the production of renewable electricity might decrease as the emissions price increases. The dissertation also shows that in liquid biofuel production, investment subsidy may cause high direct policy costs and other negative impacts when compared to other policy instruments. The results of the dissertation also indicate that from the climate mitigation perspective, perfect competition is the favored wood market competition structure, at least if the emissions trading system is not global.‬ ‪In conclusion, this dissertation suggests that when promoting the use of wood biomass in energy production, the favored policy instruments are subsidies that promote directly the renewable energy production (i.e. production subsidy, renewables subsidy or feed-in premium). Also, the policy instrument should be designed to be dependent on the emissions price or on the substitute price. In addition, this dissertation shows that when planning policies to promote wood-based renewable energy, the goals of the policy scheme should be clear before decisions are made on the choice of the policy instruments.‬