Oxygen adsorption on Cu(510)

Tässä työssä on tutkittu kuparin (510)-askelpinnan reaktiivisuutta käyttäen apuna kvanttimekaanisia ab initio laskentamenetelmiä. Tutkimus on toteutettu laskemalla happiatomin adsorptioenergia ja tilatiheys erilaisissa potentiaalisissa adsorptiopaikoissa pinnalla. Myös happimolekyylin adsorptiota ja hajoamista ontarkasteltu laskemalla pintaa lähestyvälle molekyylille potentiaalienergiapintoja. Energiapintojen tuloksia on myös täydennetty kvanttimekaanisilla molekyylidynamiikkalaskuilla. Metallisia askelpintoja pidetään yleisesti sileitä pintoja reaktiivisempina happea kohtaan, johtuen askeleen reunan pienentävästä vaikutuksesta molekyylin hajoamisen tiellä olevaan energiavaliin. On kuitenkin olemassa myös tuloksia, jotka osoittavat hapen tarttumisprosessin olevan hallitseva juuri terassialueella, askeleen reunan sijasta. Tässä työssä on todettu hapen adsorboituvan Cu(510)-pinnalla tehokkaimmin juuri terassilla olevaan hollow-paikkaan. Myös adsorptioenergiat ovat tällä pinnalla pienempiä kuin sileällä (100)-pinnalla. Potentiaalienergiapintojen perusteella Cu(510)-pinnan todetaan myös olevan vähemmän reaktiivinen kuin askelpintojen yleisesti odotetaan olevan, vaikka askeleen reunan todetaankin pienentävän happiatominhajoamisen esteenä olevaa energiavallia.

The role of van der Waals interactions in the case of H2 adsorption on ruthenium (0001) surface

Computational material science with the Density Functional Theory (DFT) has recently gained a method for describing, for the first time the non local bonding i.e., van der Waals (vdW) bonding. The newly proposed van der Waals-Density Functional (vdW-DF) is employed here to address the role of non local interactions in the case of H2 adsorption on Ru(0001) surface. The later vdW-DF2 implementation with the DFT code VASP (Vienna Ab-initio Simulation Package) is used in this study. The motivation for studying H2 adsorption on ruthenium surface arose from the interest to hydrogenation processes. Potential energy surface (PES) plots are created for adsorption sites top, bridge, fcc and hcp, employing the vdW-DF2 functional. The vdW-DF yields 0.1 eV - 0.2 eV higher barriers for the dissociation of the H2 molecule; the vdW-DF seems to bind the H2 molecule more tightly together. Furthermore, at the top site, which is found to be the most reactive, the vdW functional suggests no entrance barrier or in any case smaller than 0.05 eV, whereas the corresponding calculation without the vdW-DF does. Ruthenium and H2 are found to have the opposite behaviors with the vdW-DF; Ru lattice constants are overestimated while H2 bond length is shorter. Also evaluation of the CPU time demand of the vdW-DF2 is done from the PES data. From top to fcc sites the vdW-DF computational time demand is larger by 4.77 % to 20.09 %, while at the hcp site it is slightly smaller. Also the behavior of a few exchange correlation functionals is investigated along addressing the role of vdW-DF. Behavior of the different functionals is not consistent between the Ru lattice constants and H2 bond lengths. It is thus difficult to determine the quality of a particular exchange correlation functional by comparing equilibrium separations of the different elements. By comparing PESs it would be computationally highly consuming.

0 AND 02 ADSORPTION ON Ag/Cu[100]

In this work the adsorption mechanisms of atomic and molecular oxygen on Cu(100) surface are studied using ab initio simulation methods. Through the atomistic scale under-standing of the elementary oxidation processes we can further understand the large-scale oxidation. Copper is a material widely used in industry which makes it an interesting subject, and also understanding the oxidation of copper helps us understand the oxidation mechanism of other metals. First we have a look on some theory on surface alloys in general and behaviour of Ag on Cu(100) surface. After that the physical background there is behind the methods of density functional calculations are discussed, and some methods, namely potential energy surfaces and molecular dynamics, are introduced. Then there is a brief look on the numerical details used in the calculations, and after that, the results of the simulations are exhibited.

Oxygen adsorption on Cu(211) and structurally and chemically modified Cu(100)

Kuparipinnan hapettuminen on viimevuosina ollut suosittu tutkimuskohde materiaalitieteissä kuparin laajan teollisuuskäytön vuoksi. Teollisuussovellusten, kuten suojaavien pintaoksidien kehittäminen vaatii kuitenkin syvällistä tuntemusta hapettumisprosessista ja toisaalta myös normaaliolosuhteissa materiaalissa esiintyvien hilavirheiden vaikutuksesta siihen. Tässä työssä keskitytäänkin tutkimaan juuri niitä mekanismeja, joilla erilaiset pintavirheet ja porrastettu pintarakenne vaikuttavathapen adsorptioprosessiin kuparipinnalla. Tutkimus on tehty käyttämällä laskennallisia menetelmiä sekä VASP- ja SIESTA-ohjelmistoja. Työssätutkittiin kemiallisia ja rakenteellisia virheitä Cu(100)-pinnalla, joka on reaktiivisin matalanMillerin indeksin pinta ja porrastetun pinnan tutkimuksessa käytettiin Cu(211)-pintaa, joka puolestaan on yksinkertainen, stabiili ja aiemmissa tutkimuksissa usein käytetty pintarakenne. Työssä tutkitut hilavirheet, adatomit, vähentävät molekyylin dissosiaatiota kuparipinnalla, kun taas vakanssit toimivat dissosiaation keskuksina. Kemiallisena epäpuhtautena käytetty hopeakerros ei estä kuparin hapettumista, sillä happi aiheuttaa mielenkiintoisen segregaatioilmiön, jossa hopeatyöntyy syvemmälle pinnassa jättäen kuparipinnan suojaamattomaksi. Porrastetulla pinnalla (100)-hollow on todennäköisin paikka molekyylin dissosiaatiolle, kun taas portaan bridge-paikka on suotuisin molekulaariselle adsorptiolle. Lisäksi kuparin steppipinnan todettiin olevan reaktiivisempi kuin tasaiset kuparipinnat.

R&D Performance Analysis: Case Studies on the Challenges and Promotion of the Evaluation and Measurement of R&D

Due to the intense international competition, demanding, and sophisticated customers, and diverse transforming technological change, organizations need to renew their products and services by allocating resources on research and development (R&D). Managing R&D is complex, but vital for many organizations to survive in the dynamic, turbulent environment. Thus, the increased interest among decision-makers towards finding the right performance measures for R&D is understandable. The measures or evaluation methods of R&D performance can be utilized for multiple purposes; for strategic control, for justifying the existence of R&D, for providing information and improving activities, as well as for the purposes of motivating and benchmarking. The earlier research in the field of R&D performance analysis has generally focused on either the activities and considerable factors and dimensions - e.g. strategic perspectives, purposes of measurement, levels of analysis, types of R&D or phases of R&D process - prior to the selection of R&Dperformance measures, or on proposed principles or actual implementation of theselection or design processes of R&D performance measures or measurement systems. This study aims at integrating the consideration of essential factors anddimensions of R&D performance analysis to developed selection processes of R&D measures, which have been applied in real-world organizations. The earlier models for corporate performance measurement that can be found in the literature, are to some extent adaptable also to the development of measurement systemsand selecting the measures in R&D activities. However, it is necessary to emphasize the special aspects related to the measurement of R&D performance in a way that make the development of new approaches for especially R&D performance measure selection necessary: First, the special characteristics of R&D - such as the long time lag between the inputs and outcomes, as well as the overall complexity and difficult coordination of activities - influence the R&D performance analysis problems, such as the need for more systematic, objective, balanced and multi-dimensional approaches for R&D measure selection, as well as the incompatibility of R&D measurement systems to other corporate measurement systems and vice versa. Secondly, the above-mentioned characteristics and challenges bring forth the significance of the influencing factors and dimensions that need to be recognized in order to derive the selection criteria for measures and choose the right R&D metrics, which is the most crucial step in the measurement system development process. The main purpose of this study is to support the management and control of the research and development activities of organizations by increasing the understanding of R&D performance analysis, clarifying the main factors related to the selection of R&D measures and by providing novel types of approaches and methods for systematizing the whole strategy- and business-based selection and development process of R&D indicators.The final aim of the research is to support the management in their decision making of R&D with suitable, systematically chosen measures or evaluation methods of R&D performance. Thus, the emphasis in most sub-areas of the present research has been on the promotion of the selection and development process of R&D indicators with the help of the different tools and decision support systems, i.e. the research has normative features through providing guidelines by novel types of approaches. The gathering of data and conducting case studies in metal and electronic industry companies, in the information and communications technology (ICT) sector, and in non-profit organizations helped us to formulate a comprehensive picture of the main challenges of R&D performance analysis in different organizations, which is essential, as recognition of the most importantproblem areas is a very crucial element in the constructive research approach utilized in this study. Multiple practical benefits regarding the defined problemareas could be found in the various constructed approaches presented in this dissertation: 1) the selection of R&D measures became more systematic when compared to the empirical analysis, as it was common that there were no systematic approaches utilized in the studied organizations earlier; 2) the evaluation methods or measures of R&D chosen with the help of the developed approaches can be more directly utilized in the decision-making, because of the thorough consideration of the purpose of measurement, as well as other dimensions of measurement; 3) more balance to the set of R&D measures was desired and gained throughthe holistic approaches to the selection processes; and 4) more objectivity wasgained through organizing the selection processes, as the earlier systems were considered subjective in many organizations. Scientifically, this dissertation aims to make a contribution to the present body of knowledge of R&D performance analysis by facilitating dealing with the versatility and challenges of R&D performance analysis, as well as the factors and dimensions influencing the selection of R&D performance measures, and by integrating these aspects to the developed novel types of approaches, methods and tools in the selection processes of R&D measures, applied in real-world organizations. In the whole research, facilitation of dealing with the versatility and challenges in R&D performance analysis, as well as the factors and dimensions influencing the R&D performance measure selection are strongly integrated with the constructed approaches. Thus, the research meets the above-mentioned purposes and objectives of the dissertation from the scientific as well as from the practical point of view.

Oxygen adsorption on clean and oxygen precovered Cu(100)

Kuparipinnan hapettumisen alkuvaiheet ovat vielä nykyisin tutkijoille epäselviä. Kuitenkin, jotta hapettumisprosessia voitaisiin säädellä, on sangen tärkeää ymmärtää mistä varsinainen hapettuminen lähtee liikkeelle ja mitkä ovat hapettumisen seuraavat vaiheet. Tähän kysymykseen haetaan vastauksia tässä työssä käyttäen puhtaasti teoreettisia menetelmiä pinnan käsittelyssä. Aikaisempien teoreettisten ja kokeellisten tutkimusten välillä on pieni ristiriita liittyen hapen tarttumistodennäköisyyteen. Teoreettisten tutkimusten mukaan happi ei puhtaalle pinnalle tullessaan näe potentiaalivallia, mutta kokeelliset tutkimukset osoittavat sellaisen kuitenkin olevan. Tuohon ristiriitaan pureudutaan käyttäen aikaisemmista laskuista poikkeavaa kvanttimekaaniseen molekyylidynamiikkaan perustuvaa lähestymistapaa. Työssä havaitaan, että aikaisemmin yleisesti käytetty menetelmä hukkaa huomattavan määrän tietoa ja siten tutkijat eivät voi ainoastaan tyytyä tarkastelemaan kyseisellä menetelmällä saatuja tuloksia. Kuparipinnalle havaittiin, että korkeilla molekyylin kineettisen energian arvolla aikaisemmin suoritetut laskut hajottavista trajektoreista pitävät paikkansa, mutta matalilla kineettisen energian arvoilla molekyyli kohtaa erittäin voimakkaan ``steering'' vaikutuksen ja trajektorit joiden piti olla hajottavia johtavatkin molekulaariseen adsorptioon. Kun hapen konsentraatio pinnalla on suurempi kuin 0.5 ML, pinta rekonstruoituu. Myös rekonstruktion jälkeistä pintaa on tutkittu samanlaisilla menetelmillä kuin puhdasta pintaa. Rekonstruoituneelle pinnalle ei löydetty hajottavia trajektoreita ja havaittiin, että hapelle annetun kineettisen energian matalilla arvoilla myös tässä tapauksessa on erittäin voimakas ``steering'' vaikutus.

Convergence and divergence in global economy and social development : global perspectives on the contents of economic and soical development policy and its effects on rich and poor countries

The study of convergence and divergence in global economy and social development utilises comparative indicators to investigate the contents of economic and social development policy and their effects on the global samples that represent the rich industrial, semi-industrial and the poor developing nations. The study searchesfor answers to questions such as "what are the objectives of economic growth policies in globalisation under the imperatives of convergence and divergence, and how do these affect human well-being in consideration to the objectives of social policy in various nations?" The empirical verification of data utilises the concepts of the `logic of industrialism´ for comparative analysis that focuses mainly on identifying the levels of well-being in world nations after the Second World War. The perspectives of convergence and divergence in global economy and social development critically examine the stages of early development processes in global economy, distinguish the differences between economy and social development, illustrate the contents of economic and social development policies, their effects on rich and poor countries, and the nature of convergence and divergence in propelling economic growth and unequal social development in world nations. The measurement of convergence and divergence in global economy and social development utilised both economic and social data that were combined into an index that measures the precise levels of the effects of economic and social development policies on human well-being in the rich and poor nations. The task of finding policy solutions to resolve the controversies are reviewed through empirical investigations and the analyses of trends indicated within economic and social indicators and data. These revealed how the adoption of social policy measures in translating the gains from economic growth, towards promoting education, public health, and equity, generate social progress and longer life expectancy, higher economic growth, and sustain more stable macro economy for the nations. Social policy is concerned with the translation of benefits from objectives of global economic growth policies, to objectives of social development policy in nation states. Social policy, therefore, represents an open door whereby benefits of economic growth policies are linked with the broader objectives of social development policy, thereby enhancing the possibility of extending benefits from economic growth to all human being in every nation.

Effects of the partial removal of wood hemicelluloses on the properties of kraft pulp

The objective of this work was to study the effects of partial removal of wood hemicelluloses on the properties of kraft pulp.The work was conducted by extracting hemicelluloses (1) by a softwood chip pretreatment process prior to kraft pulping, (2) by alkaline extraction from bleached birch kraft pulp, and (3) by enzymatic treatment, xylanase treatment in particular, of bleached birch kraft pulp. The qualitative and quantitative changes in fibers and paper properties were evaluated. In addition, the applicability of the extraction concepts and hemicellulose-extracted birch kraft pulp as a raw material in papermaking was evaluated in a pilot-scale papermaking environment. The results showed that each examined hemicellulose extraction method has its characteristic effects on fiber properties, seen as differences in both the physical and chemical nature of the fibers. A prehydrolysis process prior to the kraft pulping process offered reductions in cooking time, bleaching chemical consumption and produced fibers with low hemicellulose content that are more susceptible to mechanically induced damages and dislocations. Softwood chip pretreatment for hemicellulose recovery prior to cooking, whether acidic or alkaline, had an impact on the physical properties of the non-refined and refined pulp. In addition, all the pretreated pulps exhibited slower beating response than the unhydrolyzed reference pulp. Both alkaline extraction and enzymatic (xylanase) treatment of bleached birch kraft pulp fibers indicated very selective hemicellulose removal, particularly xylan removal. Furthermore, these two hemicellulose-extracted birch kraft pulps were utilized in a pilot-scale papermaking environment in order to evaluate the upscalability of the extraction concepts. Investigations made using pilot paper machine trials revealed that some amount of alkalineextracted birch kraft pulp, with a 24.9% reduction in the total amount of xylan, could be used in the papermaking stock as a mixture with non-extracted pulp when producing 75 g/m2 paper. For xylanase-treated fibers there were no reductions in the mechanical properties of the 180 g/m2 paper produced compared to paper made from the control pulp, although there was a 14.2% reduction in the total amount of xylan in the xylanase-treated pulp compared to the control birch kraft pulp. This work emphasized the importance of the hemicellulose extraction method in providing new solutions to create functional fibers and in providing a valuable hemicellulose co-product stream. The hemicellulose removal concept therefore plays an important role in the integrated forest biorefinery scenario, where the target is to the co-production of hemicellulose-extracted pulp and hemicellulose-based chemicals or fuels.

A multimethod examination of contributors to successful on-the-job learning for vocational students

Rapid changes in working life and competence requirements of different professions have increased interest in workplace learning. It is considered an effective way to learn and update professional skills by performing daily tasks in an authentic environment. Especially, ensuring a supply of skilled future workers is a crucial issue for firms facing tight competition and a shortage of competent employees due to the retirement of current professionals. In order to develop and make the most of workplace learning, it is important to focus on workplace learning environments and the individual characteristics of those participating in workplace learning. The literature has suggested various factors that influence adults' and professionals’ workplace learning of profession-related skills, but lacks empirical studies on contextual and individual-related factors that positively affect students' workplace learning. Workers with vocational education form a large group in modern firms. Therefore, elements of vocational students’ successful workplace learning during their studies, before starting their career paths, need to be examined. To fill this gap in the literature, this dissertation examines contributors to vocational students’ workplace learning in Finland, where students’ workplace learning is included in the vocational education and training system. The study is divided into two parts: the introduction, comprised of the overview of the relevant literature and the conclusion of the entire study, and five separate articles. Three of the articles utilize quantitative methods and two use qualitative methods to examine factors that contribute to vocational students’ workplace learning. The results show that, from the students’ perspective, attitudinal, motivational, and organizationrelated factors enhance the student’s development of professionalism during the on-the-job learning period. Specifically, the organization-related factors such as innovative climate, guidance, and interactions with seniors have a strong positive impact on the students’ perceived development of professional skills because, for example, the seniors’ guidance and provision of new viewpoints for the tasks helps the vocational students to gain autonomy at work performance. A multilevel analysis shows that of those factors enhancing workplace learning from the student perspective, innovative climate, knowledge transfer accuracy, and the students’ performance orientation were significantly related to the workplace instructors’ assessment regarding the students’ professional performance. Furthermore, support from senior colleagues and the students’ self-efficacy were both significantly associated with the formal grades measuring how well the students managed to learn necessary professional skills. In addition, the results suggest that the students’ on-the-job learning can be divided into three main phases, of which two require efforts from both the student and the on-the-job learning organization. The first phase includes the student’s application of basic professional skills, demonstration of potential in performing daily tasks, and orientation provided by the organization at the beginning of the on-the-job learning period. In the second phase, the student actively develops profession-related skills by performing daily tasks, thus learning a fluent working style while observing the seniors’ performance. The organization offers relevant tasks and follows the student’s development. The third level indicates a student who has reached the professional level described as a full occupation. The results suggest that constructing the vocational students’ successful on-the-job learning period requires feedback from seniors, opportunities to learn to manage entire work processes, self-efficacy on the part of the students, proactive behavior, and initiative in learning. The study contributes to research on workplace learning in three ways: firstly, it identifies the key individual- and organization-based factors that influence the vocational students’ successful on-the-job learning from their perspective and examines mutual relationships between these factors. Second, the study provides knowledge of how the factors related to the students’ view of successful workplace learning are associated with the workplace instructors’ perspective and the formal grades. Third, the present study finds elements needed to construct a successful on-the-job learning for the students.

Incentivising Innovation? The competition law approach to the new challenge clauses in the competition rules for technology licensing agreements of the EU

Tutkielman aiheena on EU:n kilpailuoikeudellinen lähestymistapa challenge-lausekkeisiin teknologinsiirtosopimuksia koskevassa ryhmäpoikkeusasetuksessa. Teknologian lisensoinnin katsotaan olevan tärkeä väline teknologian kehityksen levittämisessä ja innovaation edistämisessä. Joissakin tapauksissa lisenssisopimus voi sisältää kilpailua rajoittavia lausekkeita, joiden voidaan kuitenkin nähdä hyödyttävän kilpailua kokonaisuutta arvostellen. Tällaisia lausekkeita ovat niin sanotut ”no-challenge” – lauseke, eli sopimusehto, jonka nojalla lisenssinsaaja sitoutuu olemaan haastamatta lisensoidun immateriaalioikeuden pätevyyttä ja ”termination-on-challenge” – lauseke, joka antaa lisensoijalle haastettaessa oikeuden päättää lisenssisopimus. Tutkielmassa perehdytään challenge -lausekkeiden hyväksyttävyyden arviointiin Euroopan unionin kilpailuoikeuden näkökulmasta uuden 1.5.2014 voimaan tulleen ryhmäpoikkeusasetuksen valossa. Muissa kuin yksinoikeuksia luovissa teknologiansiirtosopimuksissa olevat termination-on-challenge – lausekkeita tulee uusimmassa ryhmäpoikkeusetuksessa aina perustua yritysten itse suorittamaan tapauskohtaiseen arviointiin. No-challenge – lausekkeet ovat jatkossakin aiemman käytännön mukaisesti ryhmäpoikkeuksen soveltamisalan ulkopuolella. Komission on perustellut challenge - lausekkeiden jättämistä asetuksen ulkopuolelle julkisella intressillä, joka on päästä eroon mitättömistä immateriaalioikeuksista. Komission on katsonut, että challenge – lausekkeiden kilpailua rajoittava ominaisuus on mitättömien immateriaalioikeuksien esiintyminen markkinoilla, mikä osaltaan vääristää kilpailua ja hidastaa toimijoiden markkinoille pääsyä. Toisaalta lausekkeiden voidaan sanoa edistävän kilpailua, sillä ne usein tarjoavat immateriaalioikeuden haltijalle riittävän oikeussuojan ja kannustimen lisensoida teknologia, mikä lisää kilpailua, keksijöiden kannustimia panostaa innovaatioihin sekä vähentää transaktiokustannuksia. Tutkielman keskeinen tulos on ennen kaikkea challenge-lausekkeiden kilpailuvaikutusten tunnistamisessa ja komission perusteluiden kriittisessä arvioinnissa. Komission linjauksen perustelut eivät saa riittävää tukea ottaen huomioon vaikutustenarvioinnin, EU:n tuomioistuinkäytännön sekä taloustieteellisen lähestymistavan. Tutkielman tulosten pohjalta ja tukeutuen eri oikeuslähteisiin, taloustieteellisiin argumentteihin ja oikeusvertailevaan tutkimukseen, on mahdollista tehdä johtopäätöksiä niistä seikoista ja argumenteista, joilla on merkitystä uuden politiikkalinjauksen kilpailuvaikutuksiin.