834 resultados para Behavior-based safety
Resumo:
The question of the trainability of executive functions and the impact of such training on related cognitive skills has stirred considerable research interest. Despite a number of studies investigating this, the question has not yet been solved. The general aim of this thesis was to investigate two very different types of training of executive functions: laboratory-based computerized training (Studies I-III) and realworld training through bilingualism (Studies IV-V). Bilingualism as a kind of training of executive functions is based on the idea that managing two languages requires executive resources, and previous studies have suggested a bilingual advantage in executive functions. Three executive functions were studied in the present thesis: updating of working memory (WM) contents, inhibition of irrelevant information, and shifting between tasks and mental sets. Studies I-III investigated the effects of computer-based training of WM updating (Study I), inhibition (Study II), and set shifting (Study III) in healthy young adults. All studies showed increased performance on the trained task. More importantly, improvement on an untrained task tapping the trained executive function (near transfer) was seen in Study I and II. None of the three studies showed improvement on untrained tasks tapping some other cognitive function (far transfer) as a result of training. Study I also used PET to investigate the effects of WM updating training on a neurotransmitter closely linked to WM, namely dopamine. The PET results revealed increased striatal dopamine release during WM updating performance as a result of training. Study IV investigated the ability to inhibit task-irrelevant stimuli in bilinguals and monolinguals by using a dichotic listening task. The results showed that the bilinguals exceeded the monolinguals in inhibiting task-irrelevant information. Study V introduced a new, complementary research approach to study the bilingual executive advantage and its underlying mechanisms. To circumvent the methodological problems related to natural groups design, this approach focuses only on bilinguals and examines whether individual differences in bilingual behavior correlate with executive task performances. Using measures that tap the three above-entioned executive functions, the results suggested that more frequent language switching was associated with better set shifting skills, and earlier acquisition of the second language was related to better inhibition skills. In conclusion, the present behavioral results showed that computer-based training of executive functions can improve performance on the trained task and on closely related tasks, but does not yield a more general improvement of cognitive skills. Moreover, the functional neuroimaging results reveal that WM training modulates striatal dopaminergic function, speaking for training-induced neural plasticity in this important neurotransmitter system. With regard to bilingualism, the results provide further support to the idea that bilingualism can enhance executive functions. In addition, the new complementary research approach proposed here provides some clues as to which aspects of everyday bilingual behavior may be related to the advantage in executive functions in bilingual individuals.
Resumo:
In order to encourage children and adolescents to defend and support their victimized peers, it is important to identify factors that either maximize or minimize the probability that students will engage in such behaviors. This thesis is composed of four studies designed to elucidate how a variety of factors work in conjunction to explain why some children defend their victimized classmates, whereas others remain passive or reinforce the bully. The conceptual framework of this thesis is drawn from several theoretical considerations, including social cognitive learning theory, the expectancy-value framework as well as the literature emphasizing the importance of empathy in motivating behaviors. Also the child-by-environment perspective and the socialecological perspective influenced this research. Accordingly, several intra- and interpersonal characteristics (e.g., social cognitions, empathy, and social status) as well as group-level factors (e.g., norms) that may either enhance or reduce the probability that students defend their victimized peers are investigated. In Studies I and II, the focus is on social cognitions, and special attention is paid to take into account the domain-specificity of cognition-behavior processes. Self-efficacy for defending is still an interest of study III, but the role of affective empathy on defending is also investigated. Also social status variables (preference and perceived popularity) are evaluated as possible moderators of links between intrapersonal factors and defending. In Study IV, the focus is expanded further by concentrating on characteristics of children’s proximal environments (i.e., classroom). Bullying norms and collective perceptions (i.e., connectedness among the students and the teachers’ ability to deal with bullying situations) are examined. Data are drawn from two research projects: the Kaarina Cohort Study (consisting of fourth and eighth graders) and the randomized controlled trial (RCT) evaluating the effects of the KiVa antibullying program (consisting of third to fifth graders). The results of the thesis suggest that defending the victims of bullying is influenced by a variety of individual level motivational characteristics, such as social cognitions and affective empathy. Also, both perceived popularity and social preference play a role in defending, and the findings support the conceptualization that behavior results from the interplay between the characteristics of an individual child and their social-relational environment. Classroom context further influences students’ defending behavior. Thus, antibullying efforts targeting peer bystanders should aim to influence intra- and interpersonal characteristics of children and adolescents as well as their social environment.
Resumo:
Value-based selling is a salesperson behavioral mode which concentrates on generating superior customer value. Although service dominant logic emphasizes customer value as a central tenet for achieving strategic objectives, sales management literature has predominantly circumvented the subject matter of customer value. The purpose of this thesis is to demonstrate the distinctiveness and positive sales performance outcomes of value-based selling. Additionally, performance outcomes of value-based selling are contrasted with other key sales behaviors, selling skills and motivational orientations. As a part of this thesis, large-scale survey of 730 respondents was collected. The survey was tailored for the needs of a value-based selling research group led by Ph.D. Harri Terho. The research group used convenience sampling to select the salespeople of 25 medium- and large-scale companies in Finland which currently either practice value-based selling or consider developing these activities. This thesis contains three key findings: value-based selling is established as a distinct sales behavior, it relates directly and positively to salesperson performance and it explains the link between customer-oriented selling and salesperson performance. Value-based selling relates to salesperson performance especially in the following GICS-sectors: energy, industrials and materials. However, relationship selling relates to performance strongest in the energy sector and adaptive selling in industrials sector. In sum, it is evident that actively crafting customer value is a successful sales behavior in many business-to-business marketing environments while other sales behaviors, excluding customer-oriented selling, still uphold their significance.
Resumo:
Currently, there is a growing interest in medicinal plants, because of an increased demand for alternate therapies. In this study, the antimicrobial activity and toxicity of the essential oil of Lippia origanoides (L. origanoides) were investigated. The essential oil of L. origanoides was extracted by steam-dragging distillation and its constituents were identified by chromatography coupled with mass spectrometry. Among the 15 compounds identified, the most abundant were carvacrol (29.00%), o-cymene (25.57%), and thymol methyl ether (11.50%). The essential oil was studied in antimicrobial assays to determine the MIC and MBC. The results indicated that a concentration of 120μL/mL of oil was sufficient to inhibit the growth of the following microorganisms: Escherichia coli (ATCC 25922), Staphylococcus aureus (ATCC 25923) and Salmonella cholerasuis (ATCC 10708). Acute and chronic toxic effects of orally administered oil were investigated in Wistar rats by using standard methods. Doses of 30, 60 and 120mg/kg of the essential oil did not induce significant changes in weight, behavior or hematological and biochemical parameters in the animals. There were no signs of any histopathological changes to the liver, kidneys or heart of the treated rats, suggesting that Lippia origanoides oil is non-toxic after oral administration in acute or chronic toxicity studies. The results obtained in this study show that the essential oil of L. origanoides has a high safety margin, with no detectable toxic effects in rats treated with doses to 120mg/kg. In addition, L. origanoides oil demonstrated potent antimicrobial activity against S. aureus, E. coli and S. cholerasuis. Based on these findings, this essential oil may have practical application as a veterinary antimicrobial.
Resumo:
This thesis presents a set of methods and models for estimation of iron and slag flows in the blast furnace hearth and taphole. The main focus was put on predicting taphole flow patterns and estimating the effects of various taphole conditions on the drainage behavior of the blast furnace hearth. All models were based on a general understanding of the typical tap cycle of an industrial blast furnace. Some of the models were evaluated on short-term process data from the reference furnace. A computational fluid dynamics (CFD) model was built and applied to simulate the complicated hearth flows and thus to predict the regions of the hearth exerted to erosion under various operating conditions. Key boundary variables of the CFD model were provided by a simplified drainage model based on the first principles. By examining the evolutions of liquid outflow rates measured from the furnace studied, the drainage model was improved to include the effects of taphole diameter and length. The estimated slag delays showed good agreement with the observed ones. The liquid flows in the taphole were further studied using two different models and the results of both models indicated that it is more likely that separated flow of iron and slag occurs in the taphole when the liquid outflow rates are comparable during tapping. The drainage process was simulated with an integrated model based on an overall balance analysis: The high in-furnace overpressure can compensate for the resistances induced by the liquid flows in the hearth and through the taphole. Finally, a recently developed multiphase CFD model including interfacial forces between immiscible liquids was developed and both the actual iron-slag system and a water-oil system in laboratory scale were simulated. The model was demonstrated to be a useful tool for simulating hearth flows for gaining understanding of the complex phenomena in the drainage of the blast furnace.
Resumo:
Pulse Response Based Control (PRBC) is a recently developed minimum time control method for flexible structures. The flexible behavior of the structure is represented through a set of discrete time sequences, which are the responses of the structure due to rectangular force pulses. The rectangular force pulses are given by the actuators that control the structure. The set of pulse responses, desired outputs, and force bounds form a numerical optimization problem. The solution of the optimization problem is a minimum time piecewise constant control sequence for driving the system to a desired final state. The method was developed for driving positive semi-definite systems. In case the system is positive definite, some final states of the system may not be reachable. Necessary conditions for reachability of the final states are derived for systems with a finite number of degrees of freedom. Numerical results are presented that confirm the derived analytical conditions. Numerical simulations of maneuvers of distributed parameter systems have shown a relationship between the error in the estimated minimum control time and sampling interval
Resumo:
Maritime safety is an issue that has gained a lot of attention in the Baltic Sea area due to the dense maritime traffic and transportation of oil in the area. Lots of effort has been paid to enhance maritime safety in the area. The risk exists that excessive legislation and other requirements mean more costs for limited benefit. In order to utilize both public and private resources efficiently, awareness is required of what kind of costs maritime safety policy instruments cause and whether the costs are in relation to benefits. The aim of this report is to present an overview of the cost-effectiveness of maritime safety policy instruments focusing on the cost aspect: what kind of costs maritime safety policy causes, to whom, what affects the cost-effectiveness and how cost-effectiveness is studied. The study is based on a literature review and on the interviews of Finnish maritime experts. The results of this study imply that cost-effectiveness is a complicated issue to evaluate. There are no uniform practices for which costs and benefits should be included in the evaluation and how they should be valued. One of the challenges is how to measure costs and benefits during the course of a longer time period. Often a lack of data erodes the reliability of evaluation. In the prevention of maritime accidents, costs typically include investments in ship structures or equipment, as well as maintenance and labor costs. Also large investments may be justifiable if they respectively provide significant improvements to maritime safety. Measures are cost-effective only if they are implemented properly. Costeffectiveness is decreased if a measure causes overlapping or repetitious work. Costeffectiveness is also decreased if the technology isn’t user-friendly or if it is soon replaced with a new technology or another new appliance. In future studies on the cost-effectiveness of maritime safety policy, it is important to acknowledge the dependency between different policy instruments and the uncertainty of the factors affecting cost-effectiveness. The costs of a single measure are rarely relatively significant and the effect of each measure on safety tends to be positive. The challenge is to rank the measures and to find the most effective combination of different policy instruments. The greatest potential offered for the analysis of cost-effectiveness of individual measures is their implementation in clearly defined risk situations, in which different measures are truly alternative to each other. Overall, maritime safety measures do not seem to be considered burdening for the shipping industry in Finland at the moment. Generally actors in the Finnish shipping industry seem to find maintaining a high safety level important and act accordingly.
Resumo:
Growing traffic is believed to increase the risk of an accident in the Gulf of Finland. As the consequences of a large oil accident would be devastating in the vulnerable sea area, accident prevention is performed at the international, regional and national levels. Activities of shipping companies are governed with maritime safety policy instruments, which can be categorised into regulatory, economic and information instruments. The maritime regulatory system has been criticised for being inefficient because it has not been able to eliminate the violations that enable accidents. This report aims to discover how maritime governance systems or maritime safety policy instruments could be made more efficient in the future, in order to improve the maritime safety level. The results of the research are based on a literature review and nine expert interviews, with participants from shipping companies, interest groups and authorities. Based on the literature and the interviews, a suggestion can be made that in the future, instead of implementing new policy instruments, maritime safety risks should be eliminated by making the existing system more efficient and by influencing shipping companies’ safety culture and seafarers’ safety related attitudes. Based on this research, it can be stated that the development of maritime safety policy instruments should concentrate on harmonisation, automation and increasing national and cross-border cooperation. These three tasks could be primarily accomplished by developing the existing technology. Human error plays a role in a significant number of maritime accidents. Because of this, improving companies’ safety culture and voluntary activities that go beyond laws are acknowledged as potential ways of improving maritime safety. In the future, maritime regulatory system should be developed into a direction where the private sector has better possibilities to take part in decision-making.
Resumo:
A web service is a software system that provides a machine-processable interface to the other machines over the network using different Internet protocols. They are being increasingly used in the industry in order to automate different tasks and offer services to a wider audience. The REST architectural style aims at producing scalable and extensible web services using technologies that play well with the existing tools and infrastructure of the web. It provides a uniform set of operation that can be used to invoke a CRUD interface (create, retrieve, update and delete) of a web service. The stateless behavior of the service interface requires that every request to a resource is independent of the previous ones facilitating scalability. Automated systems, e.g., hotel reservation systems, provide advanced scenarios for stateful services that require a certain sequence of requests that must be followed in order to fulfill the service goals. Designing and developing such services for advanced scenarios with REST constraints require rigorous approaches that are capable of creating web services that can be trusted for their behavior. Systems that can be trusted for their behavior can be termed as dependable systems. This thesis presents an integrated design, analysis and validation approach that facilitates the service developer to create dependable and stateful REST web services. The main contribution of this thesis is that we provide a novel model-driven methodology to design behavioral REST web service interfaces and their compositions. The behavioral interfaces provide information on what methods can be invoked on a service and the pre- and post-conditions of these methods. The methodology uses Unified Modeling Language (UML), as the modeling language, which has a wide user base and has mature tools that are continuously evolving. We have used UML class diagram and UML state machine diagram with additional design constraints to provide resource and behavioral models, respectively, for designing REST web service interfaces. These service design models serve as a specification document and the information presented in them have manifold applications. The service design models also contain information about the time and domain requirements of the service that can help in requirement traceability which is an important part of our approach. Requirement traceability helps in capturing faults in the design models and other elements of software development environment by tracing back and forth the unfulfilled requirements of the service. The information about service actors is also included in the design models which is required for authenticating the service requests by authorized actors since not all types of users have access to all the resources. In addition, following our design approach, the service developer can ensure that the designed web service interfaces will be REST compliant. The second contribution of this thesis is consistency analysis of the behavioral REST interfaces. To overcome the inconsistency problem and design errors in our service models, we have used semantic technologies. The REST interfaces are represented in web ontology language, OWL2, that can be part of the semantic web. These interfaces are used with OWL 2 reasoners to check unsatisfiable concepts which result in implementations that fail. This work is fully automated thanks to the implemented translation tool and the existing OWL 2 reasoners. The third contribution of this thesis is the verification and validation of REST web services. We have used model checking techniques with UPPAAL model checker for this purpose. The timed automata of UML based service design models are generated with our transformation tool that are verified for their basic characteristics like deadlock freedom, liveness, reachability and safety. The implementation of a web service is tested using a black-box testing approach. Test cases are generated from the UPPAAL timed automata and using the online testing tool, UPPAAL TRON, the service implementation is validated at runtime against its specifications. Requirement traceability is also addressed in our validation approach with which we can see what service goals are met and trace back the unfulfilled service goals to detect the faults in the design models. A final contribution of the thesis is an implementation of behavioral REST interfaces and service monitors from the service design models. The partial code generation tool creates code skeletons of REST web services with method pre and post-conditions. The preconditions of methods constrain the user to invoke the stateful REST service under the right conditions and the post condition constraint the service developer to implement the right functionality. The details of the methods can be manually inserted by the developer as required. We do not target complete automation because we focus only on the interface aspects of the web service. The applicability of the approach is demonstrated with a pedagogical example of a hotel room booking service and a relatively complex worked example of holiday booking service taken from the industrial context. The former example presents a simple explanation of the approach and the later worked example shows how stateful and timed web services offering complex scenarios and involving other web services can be constructed using our approach.
Resumo:
The overall goal of the study was to describe nurses’ acceptance of an Internet-based support system in the care of adolescents with depression. The data were collected in four phases during the period 2006 – 2010 from nurses working in adolescent psychiatric outpatient clinics and from professionals working with adolescents in basic public services. In the first phase, the nurses’ anticipated perceptions of the usefulness of the Internet-based support system before its implementation was explored. In the second phase, the nurses’ perceived ease of computer and Internet use and attitudes toward it were explored. In the third phase, the features of the support system and its implementation process were described. In the fourth phase, the nurses’ experiences of behavioural intention and actual system use of the Internet-based support were described in psychiatric out-patient care after one year use. The Technology Acceptance Model (TAM) was used to structure the various research phases. Several benefits were identified from the nurses’ perspective in using the Internet-based support system in the care of adolescents with depression. The nurses’ technology skills were good and their attitudes towards computer use were positive. The support system was developed in various phases to meet the adolescents’ needs. Before the implementation of the information technology (IT)-based support system, it is important to pay attention to the nurses’ IT-training, technology support, resources, and safety as well as ethical issues related to the support system. After one year of using the system, the nurses perceived the Internet-based support system to be useful in the care of adolescents with depression. The adolescents’ independent work with the support system at home and the program’s systematic character were experienced as conducive from the point of view of the treatment. However, the Internet-based support system was integrated only partly into the nurseadolescent interaction even though the nurses’ perceptions of it were positive. The use of the IT-based system as part of the adolescents’ depression care was seen positively and its benefits were recognized. This serves as a good basis for future IT-based techniques. Successful implementations of IT-based support systems need a systematic implementation plan and commitment from the part of the organization and its managers. Supporting and evaluating the implementation of an IT-based system should pay attention to changing the nurses’ work styles. Health care organizations should be offered more flexible opportunities to utilize IT-based systems in direct patient care in the future.
Influence of surface functionalization on the behavior of silica nanoparticles in biological systems
Resumo:
Personalized nanomedicine has been shown to provide advantages over traditional clinical imaging, diagnosis, and conventional medical treatment. Using nanoparticles can enhance and clarify the clinical targeting and imaging, and lead them exactly to the place in the body that is the goal of treatment. At the same time, one can reduce the side effects that usually occur in the parts of the body that are not targets for treatment. Nanoparticles are of a size that can penetrate into cells. Their surface functionalization offers a way to increase their sensitivity when detecting target molecules. In addition, it increases the potential for flexibility in particle design, their therapeutic function, and variation possibilities in diagnostics. Mesoporous nanoparticles of amorphous silica have attractive physical and chemical characteristics such as particle morphology, controllable pore size, and high surface area and pore volume. Additionally, the surface functionalization of silica nanoparticles is relatively straightforward, which enables optimization of the interaction between the particles and the biological system. The main goal of this study was to prepare traceable and targetable silica nanoparticles for medical applications with a special focus on particle dispersion stability, biocompatibility, and targeting capabilities. Nanoparticle properties are highly particle-size dependent and a good dispersion stability is a prerequisite for active therapeutic and diagnostic agents. In the study it was shown that traceable streptavidin-conjugated silica nanoparticles which exhibit a good dispersibility could be obtained by the suitable choice of a proper surface functionalization route. Theranostic nanoparticles should exhibit sufficient hydrolytic stability to effectively carry the medicine to the target cells after which they should disintegrate and dissolve. Furthermore, the surface groups should stay at the particle surface until the particle has been internalized by the cell in order to optimize cell specificity. Model particles with fluorescently-labeled regions were tested in vitro using light microscopy and image processing technology, which allowed a detailed study of the disintegration and dissolution process. The study showed that nanoparticles degrade more slowly outside, as compared to inside the cell. The main advantage of theranostic agents is their successful targeting in vitro and in vivo. Non-porous nanoparticles using monoclonal antibodies as guiding ligands were tested in vitro in order to follow their targeting ability and internalization. In addition to the targeting that was found successful, a specific internalization route for the particles could be detected. In the last part of the study, the objective was to clarify the feasibility of traceable mesoporous silica nanoparticles, loaded with a hydrophobic cancer drug, being applied for targeted drug delivery in vitro and in vivo. Particles were provided with a small molecular targeting ligand. In the study a significantly higher therapeutic effect could be achieved with nanoparticles compared to free drug. The nanoparticles were biocompatible and stayed in the tumor for a longer time than a free medicine did, before being eliminated by renal excretion. Overall, the results showed that mesoporous silica nanoparticles are biocompatible, biodegradable drug carriers and that cell specificity can be achieved both in vitro and in vivo.
Resumo:
Retaining players and re-attracting switching players has long been a central topic for SNG providers with regard to the post-adoption stage of playing an online game. However, there has not been much research which has explored players’ post-adoption behavior by incorporating the continuance intention and the switching intention. In addition, traditional IS continuance theories were mainly developed to investigate users’ continued use of utilitarian IS, and thus they may fall short when trying to explain the continued use of hedonic IS. Furthermore, compared to the richer literature on IS continuance, far too little attention has been paid to IS switching, leading to a dearth of knowledge on the subject, despite the increased incidence of the switching phenomenon in the IS field. By addressing the limitations of prior literature, this study seeks to examine the determinants of SNG players’ two different post-adoption behaviors, including the continuance intention and the switching intention. This study takes a positivist approach and uses survey research method to test five proposed research models based on Unified Theory of Acceptance and Use of Technology 2; Use and Gratification Theory; Push-Pull-Mooring model; Cognitive Dissonance Theory; and a self-developed model respectively with empirical data collected from the SNG players of one of the biggest SNG providers in China. A total of 3919 valid responses and 541 valid responses were used to examine the continuance intention and the switching intention, respectively. SEM is utilized as the data analysis method. The proposed research models are supported by the empirical data. The continuance intention is determined by enjoyment, fantasy, escapism, social interaction, social presence, social influence, achievement and habit. The switching intention is determined by enjoyment, satisfaction, subjective norms, descriptive norms, alternative attractiveness, the need for variety, change experience, and adaptation cost. This study contributes to IS theories in three important ways. Firstly, it shows IS switching should be included in IS post-adoption research together with IS continuance. Secondly, a modern IS is usually multi-functional and SNG players have multiple reasons for using a SNG, thus a player’s beliefs about the hedonic, social and utilitarian perceptions of their continued use of the SNG exert significant effects on the continuance intention. Thirdly, the determinants of the switch ing intention mainly exert push, pull, and mooring effects. Players’ beliefs about their current SNG and the available alternatives, as well as their individual characteristics are all significant determinants of the switching intention. SNG players combine these effects in order to formulate the switching intention. Finally, this study presents limitations and suggestions for future research.
Resumo:
Paper-based analytical technologies enable quantitative and rapid analysis of analytes from various application areas including healthcare, environmental monitoring and food safety. Because paper is a planar, flexible and light weight substrate, the devices can be transported and disposed easily. Diagnostic devices are especially valuable in resourcelimited environments where diagnosis as well as monitoring of therapy can be made even without electricity by using e.g. colorimetric assays. On the other hand, platforms including printed electrodes can be coupled with hand-held readers. They enable electrochemical detection with improved reliability, sensitivity and selectivity compared with colorimetric assays. In this thesis, different roll-to-roll compatible printing technologies were utilized for the fabrication of low-cost paper-based sensor platforms. The platforms intended for colorimetric assays and microfluidics were fabricated by patterning the paper substrates with hydrophobic vinyl substituted polydimethylsiloxane (PDMS) -based ink. Depending on the barrier properties of the substrate, the ink either penetrates into the paper structure creating e.g. microfluidic channel structures or remains on the surface creating a 2D analog of a microplate. The printed PDMS can be cured by a roll-ro-roll compatible infrared (IR) sintering method. The performance of these platforms was studied by printing glucose oxidase-based ink on the PDMS-free reaction areas. The subsequent application of the glucose analyte changed the colour of the white reaction area to purple with the colour density and intensity depending on the concentration of the glucose solution. Printed electrochemical cell platforms were fabricated on paper substrates with appropriate barrier properties by inkjet-printing metal nanoparticle based inks and by IR sintering them into conducting electrodes. Printed PDMS arrays were used for directing the liquid analyte onto the predetermined spots on the electrodes. Various electrochemical measurements were carried out both with the bare electrodes and electrodes functionalized with e.g. self assembled monolayers. Electrochemical glucose sensor was selected as a proof-of-concept device to demonstrate the potential of the printed electronic platforms.
Resumo:
In this thesis, two negatively valenced emotions are approached as reflecting children’s self-consciousness, namely guilt and shame. Despite the notable role of emotions in the psychological research, empirical research findings on the links between guilt, shame, and children’s social behavior – and particularly aggression – have been modest, inconsistent, and sometimes contradictory. This thesis contains four studies on the associations of guilt, shame, emotion regulation, and social cognitions with children’s social behavior. The longitudinal material of the thesis was collected as a survey among a relatively large amount of Finnish preadolescents. In Study I, the distinctiveness of guilt and shame in children’s social behavior were investigated. The more specific links of emotions and aggressive behavior were explored in Study II, in which emotion regulation and negative emotionality were treated as the moderators between guilt, shame, and children’s aggressive behavior. The role of emotion management was further evaluated in Study III, in which effortful control and anger were treated as the moderators between domain-specific aggressive cognitions and children’s aggressive behavior. In the light of the results from the Studies II and III, it seems that for children with poor emotion management the effects of emotions and social cognitions on aggressive behavior are straight-forward, whereas effective emotion management allows for reframing the situation. Finally, in Study IV, context effects on children’s anticipated emotions were evaluated, such that children were presented a series of hypothetical vignettes, in which the child was acting as the aggressor. Furthermore, the identity of the witnesses and victim’s reactions were systematically manipulated. Children anticipated the most shame in situations, in which all of the class was witnessing the aggressive act, whereas both guilt and shame were anticipated the most in the situations, in which the victim was reacting with sadness. Girls and low-aggressive children were more sensitive to contextual cues than boys and high-aggressive children. Overall, the results of this thesis suggest that the influences of guilt, shame, and social cognition on preadolescents’ aggressive behavior depend significantly on the nature of individual emotion regulation, as well as situational contexts. Both theoretical and practical implications of this study highlight a need to acknowledge effective emotion management as enabling the justification of one’s own immoral behavior.
Resumo:
The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.