Late Transition Metal and Aluminum Complexes for the Polymerization of Ethene and Acrylates

Polyethene, polyacrylates and polymethyl acrylates are versatile materials that find wide variety of applications in several areas. Therefore, polymerization of ethene, acrylates and methacrylates has achieved a lot attention during past years. Numbers of metal catalysts have been introduced in order to control the polymerization and to produce tailored polymer structures. Herein an overview on the possible polymerization pathways for ethene, acrylates and methacrylates is presented. In this thesis iron(II) and cobalt(II) complexes bearing tri- and tetradentate nitrogen ligands were synthesized and studied in the polymerization of tertbutyl acrylate (tBA) and methyl methacrylate (MMA). Complexes are activated with methylaluminoxane (MAO) before they form active combinations for polymerization reactions. The effect of reaction conditions, i.e. monomer concentration, reaction time, temperature, MAO to metal ratio, on activity and polymer properties were investigated. The described polymerization system enables mild reaction conditions, the possibility to tailor molar mass of the produced polymers and provides good control over the polymerization. Moreover, the polymerization of MMA in the presence of iron(II) complex with tetradentate nitrogen ligands under conditions of atom transfer radical polymerization (ATRP) was studied. Several manganese(II) complexes were studied in the ethene polymerization with combinatorial methods and new active catalysts were found. These complexes were also studied in acrylate and methacrylate polymerizations after MAO activation and converted into the corresponding alkyl (methyl or benzyl) derivatives. Combinatorial methods were introduced to discover aluminum alkyl complexes for the polymerization of acrylates and methacrylates. Various combinations of aluminum alkyls and ligands, including phosphines, salicylaldimines and nitrogen donor ligands, were prepared in situ and utilized to initiate the polymerization of tBA. Phosphine ligands were found to be the most active and the polymerization MMA was studied with these active combinations. In addition, a plausible polymerization mechanism for MMA based on ESI-MS, 1H and 13C NMR is proposed.

Copper Diffusion Barrier Deposition on Integrated Circuit Devices by Atomic Layer Deposition Technique

Transfer from aluminum to copper metallization and decreasing feature size of integrated circuit devices generated a need for new diffusion barrier process. Copper metallization comprised entirely new process flow with new materials such as low-k insulators and etch stoppers, which made the diffusion barrier integration demanding. Atomic Layer Deposition technique was seen as one of the most promising techniques to deposit copper diffusion barrier for future devices. Atomic Layer Deposition technique was utilized to deposit titanium nitride, tungsten nitride, and tungsten nitride carbide diffusion barriers. Titanium nitride was deposited with a conventional process, and also with new in situ reduction process where titanium metal was used as a reducing agent. Tungsten nitride was deposited with a well-known process from tungsten hexafluoride and ammonia, but tungsten nitride carbide as a new material required a new process chemistry. In addition to material properties, the process integration for the copper metallization was studied making compatibility experiments on different surface materials. Based on these studies, titanium nitride and tungsten nitride processes were found to be incompatible with copper metal. However, tungsten nitride carbide film was compatible with copper and exhibited the most promising properties to be integrated for the copper metallization scheme. The process scale-up on 300 mm wafer comprised extensive film uniformity studies, which improved understanding of non-uniformity sources of the ALD growth and the process-specific requirements for the ALD reactor design. Based on these studies, it was discovered that the TiN process from titanium tetrachloride and ammonia required the reactor design of perpendicular flow for successful scale-up. The copper metallization scheme also includes process steps of the copper oxide reduction prior to the barrier deposition and the copper seed deposition prior to the copper metal deposition. Easy and simple copper oxide reduction process was developed, where the substrate was exposed gaseous reducing agent under vacuum and at elevated temperature. Because the reduction was observed efficient enough to reduce thick copper oxide film, the process was considered also as an alternative method to make the copper seed film via copper oxide reduction.

Theory and Analysis of Classic Heavy Metal Harmony

This thesis explores melodic and harmonic features of heavy metal, and while doing so, explores various methods of music analysis; their applicability and limitations regarding the study of heavy metal music. The study is built on three general hypotheses according to which 1) acoustic characteristics play a significant role for chord constructing in heavy metal, 2) heavy metal has strong ties and similarities with other Western musical styles, and 3) theories and analytical methods of Western art music may be applied to heavy metal. It seems evident that in heavy metal some chord structures appear far more frequently than others. It is suggested here that the fundamental reason for this is the use of guitar distortion effect. Subsequently, theories as to how and under what principles heavy metal is constructed need to be put under discussion; analytical models regarding the classification of consonance and dissonance and chord categorization are here revised to meet the common practices of this music. It is evident that heavy metal is not an isolated style of music; it is seen here as a cultural fusion of various musical styles. Moreover, it is suggested that the theoretical background to the construction of Western music and its analysis can offer invaluable insights to heavy metal. However, the analytical methods need to be reformed to some extent to meet the characteristics of the music. This reformation includes an accommodation of linear and functional theories that has been found rather rarely in music theory and musicology.

Mikä yliopisto-opiskelijaa kiihdyttää? : Opiskeluympäristöjen tutkimusta CASS-kokemusotantamenetelmällä flow-teoriaa ja ydintunneteorioita soveltaen

Flow experience is often defined either as an experience of high concentration and enjoyment or as a situation, where high challenges are matched with high skills. According to core-emotion theories, the experience of any emotion contains two core emotions: valence and arousal. Through an accurate mathematical model, the present study investigated, whether the experience of concentration and enjoyment is related to situations where both challenge and skills are high and in balance. Further, it was investigated what sort of core emotions are related to differing relationships between challenge and skills. Finally, university students’ experiences of their natural study environments were described in terms of core emotions and in terms of relationships between challenge and skills. Participants were 55 university students who participated two weeks research period. Altogether 3367 questionnaire answers were collected with the CASS experience-sampling method, operating in 3G-mobile phones. The relationship between challenge and skills (competence) was defined in an exact way in polar coordinates. An enjoyable and concentrated flow experience was defined as a sum variable of absorption, interest and enthusiasm. Core emotions were calculated with factor analysis from nine emotion variables. As expected, an experience of concentration and enjoyment was, on average, related to the situations where both challenge and skills were high and in balance. This was not, however, the case in every situation. Thus, it should be taken into consideration how flow experience is operationalised in experience sampling studies. When flow experience was defined as a situation of high challenge and high skills, it was often related to high valence and arousal emotions such as excitement or enthusiasm. A happier or a more tranquil enjoyment was related to situations of moderate challenge and high skills. Experiences differed clearly between various natural study environments. At lectures students were often bored or mentally absent, and did not experience challenges. In a small group students were often excited or enthusiastic, and showed optimal balance between challenge and skills. At library students felt satisfied and were engaged in highly challenging work.

Pelaamiskokemukset ja pelaamisen yksilöllisten merkitysten yhteys flow n kokemiseen

The main goal of this study was to explore experiences induced by playing digital games (i.e. meaning of playing). In addition, the study aimed at structuring the larger entities of gaming experience. This was done by using theory-driven and data grounded approaches. Previously gaming experiences have not been explored as a whole. The consideration of gaming experiences on the basis of psychological theories and studies has also been rare. The secondary goal of this study was to clarify, whether the individual meanings of playing are connected with flow experience in an occasional gaming situation. Flow is an enjoyable experience and usually activities that induce flow are gladly repeated. Previously, flow has been proved to be an essential concept in the context of playing, but the relations between meanings of playing and flow have not been studied. The relations between gender and gaming experiences were examined throughout the study, as well as the relationship between gaming frequency and experiences. The study was divided into two sections, of which the first was composed according to the main goals. Its data was gathered by using an Internet questionnaire. The other section covered the themes that were formulated on the basis of the secondary aims. In that section, the participants played a driving game for 40 minutes and then filled in a questionnaire, which measured flow related experiences. In both sections, the participants were mainly young Finnish adults. All the participants in the second section (n = 60) had already participated in the first section (n = 267). Both qualitative and quantitative research techniques were used in the study. In the first section, freely described gaming experiences were classified according to the grounded theory. After that, the most common categories were further classified into the basic structures of gaming experience, some according to the existing theories of experience structure and some according to the data (i.e. grounded theory). In the other section flow constructs were measured and used as grouping variables in a cluster analysis. Three meaningful groups were compared regarding the meanings of gaming that were explored in the first section. The descriptions of gaming experiences were classified into four main categories, which were conceptions of the gaming process, emotions, motivations and focused attention. All the theory-driven categories were found in the data. This frame of reference can be utilized in future when reliability and validity of already existing methods for measuring gaming experiences are considered or new methods will be developed. The connection between the individual relevance of gaming and flow was minor. However, as the scope was specified to relations between primary meanings of playing and flow, it was noticed that attributing enjoyment to gaming did not lead to the strongest flow-experiences. This implies that the issue should be studied more in future. As a whole this study proves that gamer-related research from numerous vantage points can benefit from concentrating on gaming experiences.

Psychophysiology of flow experience : An explorative study

This study explored the possibilities the psychophysiological methodology offer to flow research. Facial electromyography has often been used to index valence, and electrodermal activity to index arousal, the two basic dimensions of emotion. It was hypothesized that these measures can also be used to examine enjoyment, a basic component of flow experiment. A digital game was used to induce flow, and physiological activity of 32 subjects was measured continuously. Flow State Scale was used to assess flow. Activity of corrugator supercilii muscle, an index of negative valence, was negatively correlated with flow reports, as hypothesized. Contrary to hypothesis, skin conductance level, an index of arousal, was unrelated to self-reported flow. The results for association between flow and zygomaticus major and orbicularis oculi muscle activities, indices of positive valence, were inconclusive, possibly due to experimental design where only tonic measures were available. Psychophysiological methods are recommended for future studies of flow. Specifically, the time series approach may be particularly viable in examining the temporal aspects of flow, an area currently unexplored. Furthermore, it is suggested that digital game research would benefit from psychophysiological study of game-related flow.