Bonding of Composite Resin to Alumina and Zirconia Ceramics with Special Emphasis on Surface Conditioning and Use of Coupling Agents

Dental oxide ceramics have been inspired by their biocompability and mechanical properties which have made durable all-ceramic structures possible. Clinical longevity of the prosthetic structures is dependent on effective bonding with luting cements. As the initial shear bond strength values can be comparable with several materials and procedures, long-term durability is affected by ageing. Aims of the current study were: to measure the shear bond strength of resin composite-to-ceramics and to evaluate the longevity of the bond; to analyze factors affecting the bond, with special emphasis on: the form of silicatization of the ceramic surface; form of silanization; type of resin primer and the effect of the type of the resin composite luting cement; the effect of ageing in water was studied regarding its effect to the endurance of the bond. Ceramic substrates were alumina and yttrium stabilized zirconia. Ceramic conditioning methods included tribochemical silicatization and use of two silane couplings agents. A commercial silane primer was used as a control silane. Various combinations of conditioning methods, primers and resin cements were tested. Bond strengths were measured by shear bond strength method. The longevity of the bond was generally studied by thermocycling the materials in water. Additionally, in one of the studies thermal cycling was compared with long-term water storaging. Results were analysed statistically with ANOVA and Weibull analysis. Tribochemical treatment utilizing air pressure of 150 kPa resulted shear bond strengths of 11.2 MPa to 18.4 MPa and air pressure of 450 kPa 18.2 MPa to 30.5 MPa, respectively. Thermocycling of 8000 cycles or four years water storaging both decreased shear bond strength values to a range of 3.8 MPa to 7.2 MPa whereas initial situation varied from 16.8. Mpa to 23.0 MPa. The silane used in studies had no statistical significance. The use of primers without 10-MDP resulted spontaneous debonding during thermocycling or shear bond strengths below 5 MPa. As conclusion, the results showed superior long-term bonding with primers containing 10-MDP. Silicatization with silanizing showed improved initial shear bond strength values which considerably decreased with ageing in water. Thermal cycling and water storing for up to four years played the major role in reduction of bond strength, which could be due to thermal fatigue of the bonding interface and hydrolytic degradation of the silane coupled interface.

Spectrometrical Monitoring of Laser Sintering Process of Ceramic Material

This thesis is done as a part of project called FuncMama that is a project between Technical Research Centre of Finland (VTT), Oulu University (OY), Lappeenranta University of Technology (LUT) and Finnish industrial partners. Main goal of the project is to manufacture electric and mechanical components from mixed materials using laser sintering. Aim of this study was to create laser sintered pieces from ceramic material and monitor the sintering event by using spectrometer. Spectrometer is a device which is capable to record intensity of different wavelengths in relation with time. In this study the monitoring of laser sintering was captured with the equipment which consists of Ocean Optics spectrometer, optical fiber and optical lens (detector head). Light from the sintering process hit first to the lens system which guides the light in to the optical fibre. Optical fibre transmits the light from the sintering process to the spectrometer where wavelengths intensity level information is detected. The optical lens of the spectrometer was rigidly set and did not move along with the laser beam. Data which was collected with spectrometer from the laser sintering process was converted with Excel spreadsheet program for result’s evaluation. Laser equipment used was IPG Photonics pulse fibre laser. Laser parameters were kept mainly constant during experimental part and only sintering speed was changed. That way it was possible to find differences in the monitoring results without fear of too many parameters mixing together and affecting to the conclusions. Parts which were sintered had one layer and size of 5 x 5 mm. Material was CT2000 – tape manufactured by Heraeus which was later on post processed to powder. Monitoring of different sintering speeds was tested by using CT2000 reference powder. Moreover tests how different materials effect to the process monitoring were done by adding foreign powder Du Pont 951 which had suffered in re-grinding and which was more reactive than CT2000. By adding foreign material it simulates situation where two materials are accidently mixed together and it was studied if that can be seen with the spectrometer. It was concluded in this study that with the spectrometer it is possible to detect changes between different laser sintering speeds. When the sintering speed is lowered the intensity level of light is higher from the process. This is a result of higher temperature at the sintering spot and that can be noticed with the spectrometer. That indicates it could be possible to use spectrometer as a tool for process observation and support the idea of having system that can help setting up the process parameter window. Also important conclusion was how well the adding of foreign material could be seen with the spectrometer. When second material was added a significant intensity level raise could be noticed in that part where foreign material was mixed. That indicates it is possible to see if there are any variations in the material or if there are more materials mixed together. Spectrometric monitoring of laser sintering could be useful tool for process window observation and temperature controlling of the sintering process. For example if the process window for specific material is experimentally determined to get wanted properties and satisfying sintering speed. It is possible if the data is constantly recorded that the results can show faults in the part texture between layers. Changes between the monitoring data and the experimentally determined values can then indicate changes in the material being generated by material faults or by wrong process parameters. The results of this study show that spectrometer could be one possible tool for monitoring. But to get in that point where this all can be made possible much more researching is needed.

Optimization of the procedure for removing iron deposits on ceramic filter media

In this thesis, cleaning of ceramic filter media was studied. Mechanisms of fouling and dissolution of iron compounds, as well as methods for cleaning ceramic membranes fouled by iron deposits were studied in the literature part. Cleaning agents and different methods were closer examined in the experimental part of the thesis. Pyrite is found in the geologic strata. It is oxidized to form ferrous ions Fe(II) and ferric ions Fe(III). Fe(III) is further oxidized in the hydrolysis to form ferric hydroxide. Hematite and goethite, for instance, are naturally occurring iron oxidesand hydroxides. In contact with filter media, they can cause severe fouling, which common cleaning techniques competent enough to remove. Mechanisms for the dissolution of iron oxides include the ligand-promoted pathway and the proton-promoted pathway. The dissolution can also be reductive or non-reductive. The most efficient mechanism is the ligand-promoted reductive mechanism that comprises two stages: the induction period and the autocatalytic dissolution.Reducing agents(such as hydroquinone and hydroxylamine hydrochloride), chelating agents (such as EDTA) and organic acids are used for the removal of iron compounds. Oxalic acid is the most effective known cleaning agent for iron deposits. Since formulations are often more effective than organic acids, reducing agents or chelating agents alone, the citrate¿bicarbonate¿dithionite system among others is well studied in the literature. The cleaning is also enhanced with ultrasound and backpulsing.In the experimental part, oxalic acid and nitric acid were studied alone andin combinations. Also citric acid and ascorbic acid among other chemicals were tested. Soaking experiments, experiments with ultrasound and experiments for alternative methods to apply the cleaning solution on the filter samples were carried out. Permeability and ISO Brightness measurements were performed to examine the influence of the cleaning methods on the samples. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis of the solutions was carried out to determine the dissolved metals.

Development of a Ceramic Membrane Filtration Equipment and Its Applicability for Different Wastewaters

In this thesis the membrane filtration equipment for plate type ceramic membranes was developed based on filtration results achieved with different kinds of wastewaters. The experiments were mainly made with pulp and board mill wastewaters, but some experiments were also made with a bore well water and a stone cutting mine wastewater. The ceramicmembranes used were alpha-alumina membranes with a pore size of 100 nm. Some ofthe membranes were coated with a gamma-alumina layer to reduce the membrane pore size to 10 nm, and some of them were modified with different metal oxides in order to change the surface properties of the membranes. The effects of operationparameters, such as cross-flow velocity, filtration pressure and backflushing on filtration performance were studied. The measured parameters were the permeateflux, the quality of the permeate, as well as the fouling tendency of the membrane. A dynamic membrane or a cake layer forming on top of the membrane was observed to decrease the flux and increase separa-tion of certain substances, especially at low cross-flow velocities. When the cross-flow velocities were increased the membrane properties became more important. Backflushing could also be used to decrease the thickness of the cake layer and thus it improved the permeate flux. However, backflushing can lead to a reduction of retentions in cases where the cake layer is improving them. The wastewater quality was important for the thickness of the dynamic membrane and the membrane pore size influenced the permeate flux. In general, the optimization of operation conditions is very important for the successful operation of a membrane filtration system. The filtration equipment with a reasonable range of operational conditions is necessary, especiallywhen different kinds of wastewaters are treated. This should be taken into account already in the development stage of a filtration equipment.

Keraamisten teräpalojen käyttö niukkaseosteisten terästen lastuamiseen normaaleissa toimitustiloissa

Tämän tutkimuksen tavoitteena oli tutkia keraamisten kääntöterien soveltuvuus niukkaseosteräksille ja M-käsittelyn vaikutus teränkestoaikoihin. Lisäksi tavoitteena oli tutkia keraamiseosten erityisominaisuudet ja muodostaa käsitys keraamisilla kääntöterillä sorvaamisen erityisvaatimuksista. Kirjallisuusosassa selvitettiin tutkimushetkellä saatavissa olleet keraamiset teräaineseokset ja niiden ominaisuudet sekä selvitettiin keraamisten kääntöterien viimeaikaiset kehitystrendit. Lastuamistutkimus toteutettiin standardin ISO 3685:1993 mukaisesti, minkä lisäksi mitattiin lastuamisvoimat ja tehtiin kokeessa käytetyille terille lastunmurtokoe. Koemateriaalit olivat Imatra Steelin GreenCut, Hydax 25, M-käsittelemätön 42CrMo4 ja M-käsitelty MoC410M. Kokeissa käytetyt kääntöterät olivat eri valmistajien alumiinioksiditeriä, titaanikarbidiseostettuja alumiinioksiditeriä, kuituvahvisteisia ja yksi puhdas titaanikarbidiseosteinen terä. Koetulosten perusteella hyvän teränkestoajan saavuttamiseksi on tärkeää valita oikea keraamiseos ja sille soveltuvat parametrit. Oikein valituilla parametreilla M-terästä sorvattaessa tulokset ylittävät kovametalleilla saavutettavissa olevat arvot. Tulosten perusteella niukkaseostettujen terästen sorvaus onnistuu hyvin keraamisilla kääntöterillä, mutta kovametallisorvaukseen verrattuna syöttöä on laskettava ja lastuamisnopeutta lisättävä. Tämän työn tuloksia voidaan soveltaa sopivissa olosuhteissa toteutettavassa kappaletavaratuotannossa. Sovelluksen onnistuminen vaatii tukevat työstöolosuhteet ja riittävien lastuamisnopeuksien saavuttamisen.

Kaasutuskaasun puhdistus

Tässä diplomityössä on selvitetty hiilestä, jätteestä tai biopolttoaineesta kaasutetun kaasun märkä- ja kuivapuhdistusta. Kaasutuskaasun puhdistuksella voidaan likainen ja jopa ongelmallinen aines muuttaa tai puhdistaa sellaiseksi ympäristökelpoiseksi polttoaineeksi, että sitä voidaan käyttää nykyisissä kulutuskohteissa ongelmitta. Lisäkannustusta kaasutuskaasun puhdistus saa uusista EU-direktiiveistä, jotka tulevat rajoittamaan jätteiden läjittämistä kaatopaikoille. Loppusijoitukseen meneviä jätevirtoja voidaan energiakäytöllä pienentää huomattavasti.Työ on tehty PVO-Engineering Oy:n voimalaitostekniikan osastolle kevään 2001 aikana. Työn tavoitteena oli kasvattaa yrityksen tietomäärää kaasutuskaasun puhdistuksen osalta. Lisäksi pyrittiin selvittämään uuden keraamisen pussisuodatinmateriaalin käyttöä kaasutuskaasun kuumakuivasuodatuksessa. Työn ensimmäisessä osassa esitetään kaasutuskaasun koostumuksen ja syntymisen lisäksi tämän työn lähtökohdat ja tavoitteet. Toisessa osassa selvitetään kaasulle asetettavia vaatimuksia eri käyttötapojen mukaan. Kolmannessa ja neljännessä osassa selvitetään puhdistettavien komponenttien käyttäytymistä ja sopivia puhdistusmenetelmiä.Kaasutuskaasun puhdistustekniikka vaihtelee paljonkin riippuen kaasun käyttökohteesta. Eroja syntyy käyttökohteen asetettamista vaatimuksista polttoaineelle, kaasutettavan polttoaineen koostumuksesta ja laadun vaihtelusta. Puhdistuksessa keskitytään kloori -, rikki -, typpi - ja metalliyhdisteiden poistamiseen kaasuvirrasta. Erotuskyvyllä arvioituna eri puhdistusmenetelmistä tehokkaimpia ovat pesurisähkösuodatinyhdistelmät. Niiden suuret jätemäärät ovat kuitenkin iso ongelma. Kuumakuivapuhdistuksessa pyritään kehittämään menetelmä, jossa syntyvät jätemäärät ovat pieniä ja puhdistustulos on riittävä. Puhdistuksen apukeinona käytetään usein erilaisia katalyyttejä. Tunnetuimpia ovat erilaiset kalsiumpohjaiset materiaalit ja mineraalit. Katalyyteillä voidaan tehostaa tarpeellisia kemiallisia reaktioita puhdistusprosessissa. Kaikki puhdistukseen liittyvät ongelmat ovat kooltaan niin suuria, että niiden ratkaisemiseksi on tulevaisuudessa tehtävä lujasti töitä. Markkinanäkymät toimivalle puhdistustekniikalle ovat nykymaailmassa hyvät. Niinpä tuotekehitykseen laitetut panokset voivat tulevaisuudessa olla yritykselle kullan arvoisia.

The Pursuit of Efficient Copyright Licensing : How Some Rights Reserved Attempts to Solve the Problems of All Rights Reserved

This dissertation analyses the growing pool of copyrighted works, which are offered to the public using Creative Commons licensing. The study consist of analysis of the novel licensing system, the licensors, and the changes of the "all rights reserved" —paradigm of copyright law. Copyright law reserves all rights to the creator until seventy years have passed since her demise. Many claim that this endangers communal interests. Quite often the creators are willing to release some rights. This, however, is very difficult to do and needs help of specialized lawyers. The study finds that the innovative Creative Commons licensing scheme is well suited for low value - high volume licensing. It helps to reduce transaction costs on several le¬vels. However, CC licensing is not a "silver bullet". Privacy, moral rights, the problems of license interpretation and license compatibility with other open licenses and collecting societies remain unsolved. The study consists of seven chapters. The first chapter introduces the research topic and research questions. The second and third chapters inspect the Creative Commons licensing scheme's technical, economic and legal aspects. The fourth and fifth chapters examine the incentives of the licensors who use open licenses and describe certain open business models. The sixth chapter studies the role of collecting societies and whether two institutions, Creative Commons and collecting societies can coexist. The final chapter summarizes the findings. The dissertation contributes to the existing literature in several ways. There is a wide range of prior research on open source licensing. However, there is an urgent need for an extensive study of the Creative Commons licensing and its actual and potential impact on the creative ecosystem.

Cleaning of ceramic filter plates

In this thesis, cleaning of ceramic filter plates clogged by iron oxides was studied. Oxalic acid is considered as the most effective cleaning agent for the plates fouled by iron oxides, but when using oxalic acid, sparingly soluble calcium oxalate may be formed and it can blind the filter media. Suitability of another chemical for cleaning the plates clogged by iron oxides was studied in this thesis. The literature part was mostly about the properties of the chemical, about its reactions, industrial uses, safety issues etc. In the experimental part, the efficiency of the chemical for cleaning of the ceramic plates clogged by iron oxides was studied. Two kinds of plates were used in the experiments; the others were clogged by hematite and the others by magnetite. Both soaking and flow-through experiments were done. A suitable concentration, pH and temperature were tried to find in the experiments. Also the effect of ultrasound was studied. The efficiency of the cleaning was examined by measuring the permeability of the plates during the experiments. ICP-OES analysis was performed for determining the amount of dissolved iron in the washing solution. Some experiments were also done with oxalic acid. The results from the oxalic acid experiments were compared to the results from the experiments with the other chemical. In the experiments with the other chemical, the permeability increased more and the amounts of dissolved iron were larger. According to the results from the experiments, the method of application of the washing solutions had an impact on the washing results.

Building the map of innovation for membrane materials (Ceramic membranes)

This work proposes a method of visualizing the trend of research in the field of ceramic membranes from 1999 to 2006. The presented approach involves identifying problems encountered during research in the field of ceramic membranes. Patents from US patent database and articles from Science Direct(& by ELSEVIER was analyzed for this work. The identification of problems was achieved with software Knowledgist which focuses on the semantic nature of a sentence to generate series of subject action object structures. The identified problems are classified into major research issues. This classification was used for the visualization of the intensity of research. The image produced gives the relation between the number of patents, with time and the major research issues. The identification of the most cited papers which strongly influence the research of the previously identified major issues in the given field was also carried out. The relations between these papers are presented using the metaphor of social network. The final result of this work are two figures, a diagram showing the change in the studied problems a specified period of time and a figure showing the relations between the major papers and groups of the problems