50 resultados para SURFACE SEGREGATION


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Vätning av fasta ytor är ett viktigt fenomen i såväl naturen som i en lång rad av industriella tillämpningar. Det är allmänt känt att vätningen av en fast yta styrs av ytans kemi samt struktur. Målsättningen med avhandlingen var att studera hur kemisk heterogenitet och ytråhet på nanometernivå påverkar vätningsegenskaperna hos en fast yta. Ytorna som studerades var titandioxid-baserade kerama ytor som framställdes med hjälp av en sol-gel process. Vätningstudierna utfördes genom kontaktvinkelmätningar, vilket innebär att man mäter vinkeln som vätska/luft-gränsskiktet hos en vätskedroppe bildar mot en fast yta. Ytråheten hos materialen studerades främst genom atomkraftsmikroskopi (AFM). I AFM detekteras ytans struktur av en mycket skarp nål som skannar ytan. Resultaten i avhandlingen kunde framgångsrikt modelleras med existerande teorier för vätning av heterogena ytor.

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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.

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Offset printing is a popular printing method that is especially suitable for large and fast print jobs. Newspapers, magazines and books are typical examples of products printed with offset method. In high volume printing production high efficiency is essential. Offset printing uses tacky inks that cause serious stress to the paper surface. Dusting and linting are terms that describe how loose and weakly bonded particles are removed from the paper surface in the printing process. The removed particles accumulate in the process causing deteriorating print quality. This forces the printing operators to stop production for washing and cleaning. Time and money are lost. Dusting and linting tendency of paper can be decreased by improving the surface strength of paper. In the present work a method to increase the surface strength of paper was studied. In the literature part offset printing method and challenges related to offset printing are presented. A review of new methods for surface sizing of paper is also presented. The experimental part presents trials where an apparatus for improving paper surface strength was tested and developed in mill scale. Laboratory work supporting the actual mill scale operations is also presented. The acquired results provide a solid base of information to make decisions on how to proceed with research in the present field of study.

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Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

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Segregering eller segregation är ett fenomen som kan förekomma inom olika områden av samhället. Inom samhällsvetenskaperna kan segregering definieras som det rumsliga åtskiljandet av befolkningsgrupper på urval av ras eller etniskt ursprung, kön, social härkomst, religion, ålder, yrke, osv. Segregering av befolkningsgrupper sker ofta mer eller mindre frivilligt och är motsatsen till integration. Inom partikelteknologi definieras segregering oftast som det rumsliga åtskiljandet av beståndsdelarna i en blandning av olika partiklar. Segregering sker då på urval av bl.a. partiklarnas storlek, densitet, form, elektrostatiska eller mekaniska egenskaper, och kan beskrivas som motsatsen till blandning. Segregeringsmekanismer används för att förklara hur och varför en partikelblandning segregerar samt vad slutresultatet i form av den rumsliga fördelningen av partiklarna blir till följd av att blandningen utsetts för en viss behandling. I denna avhandling har segregering av partikelblandningar och speciellt torra mineralbaserade byggmaterial (t.ex. murbruk) till följd av lagring i siloer studerats. Vid industriell produktion av mineralbaserade byggmaterial används siloer för korttidslagring av slutprodukterna precis innan förpackning. Segregering leder till kraftiga variationer i sammansättningen för partikelströmmen ut ur silon, vilket gör att slutprodukterna inte uppfyller kvalitetskraven och kan därmed inte säljas till kunder. Detta leder till arbetsam och dyr bearbetning (återcirkulation) av produkterna med påföljder för produktionsekonomin samt hållbara utvecklingen. I avhandlingen identifierades de väsentligaste segregeringsmekanismerna för torra mineralbaserade byggmaterial i siloer. Dessutom klargjordes effekterna av materialegenskaper, processbetingelser och siloparametrar. Slutligen behandlas möjliga åtgärder för minskning av partikelsegregering i siloer samt tillämpning av matematiska metoder för simulering av partikelflöden med hjälp av datorer.

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Den viktigaste råvaran i papperstillverkning är pappersmassa. Massan innehåller (ved)fibrer men också finmaterial och andra typers (ved)celler, så som kärlceller. Hur dessa komponenter beter sig under arkformationen i pappersmaskinen eller hur de bidrar till egenskaperna hos det färdiga pappret avgörs till stor del av massakomponenternas ytkemiska sammansättning, fysiska struktur och mängden joniserbara grupper på ytan. I denna avhandling studerades ytegenskaperna hos fraktionerade kemiska massor och returfibermassor med avancerade analystekniker. Rester av avfärgningskemikalier identifierades på både returfibrer och på kärlceller. Dessa kan påverka arkformationen och arkstyrkan på returfiberpapper. Kärlcellernas cellväggsstruktur visade sig skilja sig från fibrernas. Resultaten kan främja utvecklingen av returfiberprosessen och användningen av kärlcellsrika lövvedsmassor.

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Kaikki kappaleet säteilevät sähkömagneettista energiaa. Radiometreillä voidaan mitata tätä säteilyä, ja mittausten avulla voidaan kaukokartoituksessa analysoida monia ilmakehään ja maan pintaan liittyviä ilmiöitä. Säteilyä kerätään useimmiten radiometriin kytketyn antennin avulla. Mikroaaltoalueella säteilystä saatava teho on verrannollinen kohteen kirkkauslämpötilaan. Kirkkauslämpötila on puolestaan verrannollinen kohteen fyysiseen lämpötilaan materiaalin emissiivisyyden kautta. Emissiivisyys voi vaihdella suuresti eri pintojen ja materiaalien välillä. Näin ollen mittaamalla kohteen kirkkauslämpötilaa saadaan tietoa sen ominaisuuksista. Mikroaaltoradiometrin avulla voidaan havaita öljyläikkä meren pinnalta, sekä määrittää öljyläikän paksuus. Öljy muodostaa ohuen kalvon meren pinnalla. Ohuen kalvon ylä- ja alapinnasta heijastuneet aallot kulkevat eri matkan, jonka seurauksena muodostuu interferenssikuvio. Interferenssi on joko konstruktiivinen tai destruktiivinen riippuen heijastusten vaihe-erosta. Pistetaajuudella tästä seuraa kalvon paksuudesta riippuva sinimuotoinen emissiivisyys. Mallintamalla tämä ilmiö riittävän tarkasti voidaan radiometrin mittaamaa kirkkauslämpötilaa verrata mallinnettuun arvoon ja täten määrittää öljykerroksen paksuus. Tässä työssä esitetään kahden radiometrin suunnittelu ja testaus. Työ rajoittuu radiometrien alustavaan testausvaiheeseen. Radiometrit on suunniteltu 36,5GHz sekä 89GHz taajuuksille. Työn suurin kontribuutio on radiometrien etupään suunnittelussa ja testauksessa, kalibraatiomenetelmien kehittämisessä sekä kylmäkuorman suunnittelussa. Lisäksi työssä esitetään radiometrien systeemisuunnittelu sekä siihen liittyvät simulaatiot.

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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.

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En djupare förståelse för växelverkan mellan partiklar i suspensioner är av betydelse för utvecklingen av en mängd olika industriella produkter och processer. Till exempel kan nämnas pigmentbaserade färger och bestrykning av papper. Genom att öka kontrollbarheten kan dessa lättare optimeras för att uppnå förbättrade produktegenskaper och/eller sänkta produktionskostnader. Av stor betydelse är även en förbättrad möjlighet att minska produktens miljöpåverkan. I avhandlingen studerades jonstyrkan och jonspecificiteten inverkan i olika akvatiska suspensioner innehållande olika elektrolyter. De partiklar som avhandlingen omfattade var metalloxider, leror samt latex. Jonstyrkan studerades från låga (c <10-3M) till och med höga (c> 10-1M) elektrolytkoncentrationer. Vid koncentrationer under 0.1 M var partikelladdningen styrd av pH och jonstyrkan. Vid högre elektrolytkoncentrationer påverkade även jonspecificiteten partikelladdningen. Jonspecificiteten arrangerades i fenomenologiska serier funna i litteraturen samt med Born modellen definierad i termodynamiken. Överraskande höga absoluta zeta-potential värden erhölls vid höga elektrolytkoncentrationer vilket visar att den elektrostatiska repulsionen har betydelse även vid dessa förhållanden. Vidare studerades titanoxidsuspensioners egenskaper i akvatiska, icke-akvatiska och blandade lösningssystem under varierande koncentration av oxal- och fosfatsyra. Vid lågt vatteninnehåll studerades även suspensioner med svavelsyra. Konduktiviteten i suspensioner med lågt vatteninnehåll ökade med tillsatt oxal- eller fosforsyra vilket är en omvänd effekt jämfört med svavelsyra eller akvatiska suspensioner. Den omvända effekten skiftade gradvis tillbaka med ökad vatteninnehåll. En analys av suspensionernas adsorption i höga etanolkoncentrationer gjordes med konduktiviteten, pH och zeta-potentialen. Viskositet studerades och applicerades framgångsrikt i viskositet/ytladdningsmodeller utvecklade för akvatiska suspensioner.

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This thesis presents an experimental study and numerical study, based on the discrete element method (DEM), of bell-less charging in the blast furnace. The numerical models are based on the microscopic interaction between the particles in the blast furnace charging process. The emphasis is put on model validation, investigating several phenomena in the charging process, and on finding factors that influence the results. The study considers and simulates size segregation in the hopper discharging process, particle flow and behavior on the chute, which is the key equipment in the charging system, using mono-size spherical particles, multi-size spheres and nonspherical particles. The behavior of the particles at the burden surface and pellet percolation into a coke layer is also studied. Small-scale experiments are used to validate the DEM models.

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This study investigated the surface hardening of steels via experimental tests using a multi-kilowatt fiber laser as the laser source. The influence of laser power and laser power density on the hardening effect was investigated. The microhardness analysis of various laser hardened steels was done. A thermodynamic model was developed to evaluate the thermal process of the surface treatment of a wide thin steel plate with a Gaussian laser beam. The effect of laser linear oscillation hardening (LLOS) of steel was examined. An as-rolled ferritic-pearlitic steel and a tempered martensitic steel with 0.37 wt% C content were hardened under various laser power levels and laser power densities. The optimum power density that produced the maximum hardness was found to be dependent on the laser power. The effect of laser power density on the produced hardness was revealed. The surface hardness, hardened depth and required laser power density were compared between the samples. Fiber laser was briefly compared with high power diode laser in hardening medium-carbon steel. Microhardness (HV0.01) test was done on seven different laser hardened steels, including rolled steel, quenched and tempered steel, soft annealed alloyed steel and conventionally through-hardened steel consisting of different carbon and alloy contents. The surface hardness and hardened depth were compared among the samples. The effect of grain size on surface hardness of ferritic-pearlitic steel and pearlitic-cementite steel was evaluated. In-grain indentation was done to measure the hardness of pearlitic and cementite structures. The macrohardness of the base material was found to be related to the microhardness of the softer phase structure. The measured microhardness values were compared with the conventional macrohardness (HV5) results. A thermodynamic model was developed to calculate the temperature cycle, Ac1 and Ac3 boundaries, homogenization time and cooling rate. The equations were numerically solved with an error of less than 10-8. The temperature distributions for various thicknesses were compared under different laser traverse speed. The lag of the was verified by experiments done on six different steels. The calculated thermal cycle and hardened depth were compared with measured data. Correction coefficients were applied to the model for AISI 4340 steel. AISI 4340 steel was hardened by laser linear oscillation hardening (LLOS). Equations were derived to calculate the overlapped width of adjacent tracks and the number of overlapped scans in the center of the scanned track. The effect of oscillation frequency on the hardened depth was investigated by microscopic evaluation and hardness measurement. The homogeneity of hardness and hardened depth with different processing parameters were investigated. The hardness profiles were compared with the results obtained with conventional single-track hardening. LLOS was proved to be well suitable for surface hardening in a relatively large rectangular area with considerable depth of hardening. Compared with conventional single-track scanning, LLOS produced notably smaller hardened depths while at 40 and 100 Hz LLOS resulted in higher hardness within a depth of about 0.6 mm.

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The understanding and engineering of bismuth (Bi) containing semiconductor surfaces are signi cant in the development of novel semiconductor materials for electronic and optoelectronic devices such as high-e ciency solar cells, lasers and light emitting diodes. For example, a Bi surface layer can be used as a surfactant which oats on a III-V compound-semiconductor surface during the epitaxial growth of IIIV lms. This Bi surfactant layer improves the lm-growth conditions if compared to the growth without the Bi layer. Therefore, detailed knowledge of the properties of the Bi/III-V surfaces is needed. In this thesis, well-de ned surface layers containing Bi have been produced on various III-V semiconductor substrates. The properties of these Bi-induced surfaces have been measured by low-energy electron di raction (LEED), scanning-tunneling microscopy and spectroscopy (STM), and synchrotron-radiation photoelectron spectroscopy. The experimental results have been compared with theoretically calculated results to resolve the atomic structures of the studied surfaces. The main ndings of this research concern the determination of the properties of an unusual Bi-containing (2×1) surface structure, the discovery and characterization of a uniform pattern of Bi nanolines, and the optimization of the preparation conditions for this Bi-nanoline pattern.

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Inorganic-organic sol-gel hybrid coatings can be used for improving and modifying properties of wood-based materials. By selecting a proper precursor, wood can be made water repellent, decay-, moisture- or UV-resistant. However, to control the barrier properties of sol-gel coatings on wood substrates against moisture uptake and weathering, an understanding of the surface morphology and chemistry of the deposited sol-gel coatings on wood substrates is needed. Mechanical pulp is used in production of wood-containing printing papers. The physical and chemical fiber surface characteristics, as created in the chosen mechanical pulp manufacturing process, play a key role in controlling the properties of the end-use product. A detailed understanding of how process parameters influence fiber surfaces can help improving cost-effectiveness of pulp and paper production. The current work focuses on physico-chemical characterization of modified wood-based materials with surface sensitive analytical tools. The overall objectives were, through advanced microscopy and chemical analysis techniques, (i) to collect versatile information about the surface structures of Norway spruce thermomechanical pulp fiber walls and understand how they are influenced by the selected chemical treatments, and (ii) to clarify the effect of various sol-gel coatings on surface structural and chemical properties of wood-based substrates. A special emphasis was on understanding the effect of sol-gel coatings on the water repellency of modified wood and paper surfaces. In the first part of the work, effects of chemical treatment on micro- and nano-scale surface structure of 1st stage TMP latewood fibers from Norway spruce were investigated. The chemicals applied were buffered sodium oxalate and hydrochloric acid. The outer and the inner fiber wall layers of the untreated and chemically treated fibers were separately analyzed by light microscopy, atomic force microscopy and field-emission scanning electron microscopy. The selected characterization methods enabled the demonstration of the effect of different treatments on the fiber surface structure, both visually and quantitatively. The outer fiber wall areas appeared as intact bands surrounding the fiber and they were clearly rougher than areas of exposed inner fiber wall. The roughness of the outer fiber wall areas increased most in the sodium oxalate treatment. The results indicated formation of more surface pores on the exposed inner fiber wall areas than on the corresponding outer fiber wall areas as a result of the chemical treatments. The hydrochloric acid treatment seemed to increase the surface porosity of the inner wall areas. In the second part of the work, three silane-based sol-gel hybrid coatings were selected in order to improve moisture resistance of wood and paper substrates. The coatings differed from each other in terms of having different alkyl (CH3–, CH3-(CH2)7–) and fluorocarbon (CF3–) chains attached to the trialkoxysilane sol-gel precursor. The sol-gel coatings were deposited by a wet coating method, i.e. spraying or spreading by brush. The effect of solgel coatings on surface structural and chemical properties of wood-based substrates was studied by using advanced surface analyzing tools: atomic force microscopy, X-ray photoelectron spectroscopy and time-of-flight secondary ion spectroscopy. The results show that the applied sol-gel coatings, deposited as thin films or particulate coatings, have different effects on surface characteristics of wood and wood-based materials. The coating which has a long hydrocarbon chain (CH3-(CH2)7–) attached to the silane backbone (octyltriethoxysilane) produced the highest hydrophobicity for wood and wood-based materials.

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This dissertation critically reviews the idea of meritocracy from both a theoretical and an empirical perspective. Based on a discussion of classical texts of social philosophy and sociology, it is argued that meritocracy as a concept for social stratification is best compatible with the sociological tradition of status attainment research: both frame social inequality in primarily individualistic terms, centring on the role of ascribed (e.g., gender, social background) and achieved (e.g., educational qualifications) characteristics for determining individuals’ socioeconomic rewards. This theoretical argument introduces the research problem at the core of this dissertation: to what extent can the individualistic conception of social stratification be maintained empirically? Fields of study and their interaction with educational attainment levels play a prominent role in the analysis of this question. Drawing on sociological versions of segmented labour market theory, it is assumed that fields of study may channel individuals into heterogeneous political-economic contexts on the labour market, which potentially modify the socioeconomic benefit individuals derive from their qualification levels. The focus on fields of study may also highlight economic differentials between men and women that derive from the persisting segregation of men’s and women’s occupational and educational specializations rather than direct gender discrimination on the labour market. The quantitative analyses in this dissertation consist of three research articles, which are based primarily on Finnish data, but occasionally extend the view to other European countries. The data sources include register-based macro- and microdata as well as survey data. Article I examines the extent and the patterns of gender segregation within the Finnish educational system between 1981 and 2005. The results show that differences between men’s and women’s field specializations have for the most part remained stable during this period, with particularly high levels of gender segregation observed at lower educational levels. The focus in Article II rests on the effects of gender-segregated fields of study on higher education graduates’ occupational status. It is shown that fields of study matter for accessing professional jobs and avoiding low-skilled positions in Finland: at the early career stage, particularly polytechnic graduates from female-dominated fields are less likely to work in professional positions. Finnish university graduates from male-dominated fields were more likely than their peers with different specializations to work as professionals, yet they also faced a greater risk of being sorted into lowskilled jobs if they failed to make use of this advantage. Article III proceeded to analyse the joint impact of educational qualification levels and fields of study on young adults’ median earnings in Finland between 1985 and 2005. The results show that qualification levels do not confer a consistent benefit in the process of earnings stratification. Advanced qualifications raise median earnings most clearly among individuals specializing in the same field of study. When comparing individuals with different field specializations, on the other hand, higher-level qualifications do not necessarily lead to higher median earnings. Overall, the findings of this dissertation reveal a heterogeneous effect of education for achieving social positions, which challenges individual-centred, meritocratic accounts of social stratification and underlines the problematic lack of structural and institutional dimensions in the dominant account of social status attainment.

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The aim of this thesis was to study the surface modification of reverse osmosis membranes by surfactants and the effect of modification on rejection and flux. The surfactants included anionic and nonionic surfactants. The purpose of membrane modification was to improve pure water permeability with increasing salt rejection. The literature part of the study deals with the basic principles of reverse osmosis technology and factors affecting the membrane performance. Also the membrane surface modification by surfactants and their influence on membrane’s surface properties and efficiency (permeability and salt rejection) were discussed. In the experimental part of the thesis two thin-film composite membranes, Desal AG and LE-4040, were modified on-line with three different surfactants. The effects of process parameters (pressure, pH, and surfactant concentration) on surface modification were also examined. The characteristics of the modified membranes were determined by measuring the membranes’ contact angle and zeta potentials. The zeta potential and contact angle measurements indicate that the surfactants were adsorbed onto the both membranes. However, the adsorption did not effect on membrane’s pure water permeability and salt rejection. Thereby, the surface modification of the Desal AG and LE-4040 membranes by surfactants was not able to improve the membrane’s performance.