Controlled radical polymerization (CRP) can be viewed as the middle ground between living anionic polymerization (LAP) and conventional free radical polymerization (FRP). It combines the precise control over polymer structure offered by LAP, under a tolerant reaction condition similar to FRP. One of the most studied CRP is atom transfer radical polymerization (ATRP), with over 10,000 papers published since its introduction in 1995. Despite the numerous studies, knowledge on its fundamental mechanism is still lacking, as evident from the lack of expression for full MWD and polydispersity that account for termination reaction. Since termination is unavoidable in ATRP, the existing expressions give inaccurate predictions as dead chains accumulate. In this study, we derived expressions for full MWD at low conversion and for polydispersity. These expressions allow us to quantify and gain better understanding on the contribution of termination. In addition, the resulting polydispersity expression shows better agreement than the existing equation when correlated with experiment data. In addition to the aforementioned questions, there are also controversies regarding the kinetics of surface-initiated ATRP, with researchers divided into two schools of theories. We evaluated the validity of these theories by comparing their predictions to experimental trends. Both theories were found to be inadequate in explaining all the experimental observations, thus triggering an investigation of the graft density. Graft density is an important determining property for polymer brushes, yet little is known about what affects its final value. Through simulations, we investigated the effect of experiment factors on the grafting density. A decrease in the amount of deactivator is found to decrease the grafting density, which could be explained by an increase in the number of monomers added per activation cycle. This knowledge allows us to explain the conflicting experiment observations regarding the growth trends of polymer layers reported in the literatures. / Thesis / Doctor of Philosophy (PhD) / Polymer materials are used almost everywhere in our daily life from clothing to water bottle. This wide range of applications owes to the nearly infinite possible properties that polymer can possess. Different polymerization processes to synthesize polymers have their own weaknesses and strengths. Herein we investigated the fundamental mechanism of one of the currently most attractive polymerization systems, atom transfer radical polymerization (ATRP). This process allows the synthesis of polymers with precisely tailored chain microstructures, making it possible to create polymer with sophisticated properties. Using modeling approaches, we derived explicit expressions for determining chain properties, allowing detailed investigation of how various factors affect these properties. Through these investigations, we obtained better understanding on the mechanism of ATRP in solution and on surface. This knowledge is crucial in providing insight and guiding experimental designs for better control over the material properties.

The presence of non-metallic inclusions (NMIs) have critical effects on both the mechanical properties and machinability of steels. In the present thesis, one focus is to study the characteristics of deformed sulfides (MnS) for a stainless steel (3R65) and a tool steel (42CrMo4). Three groups of MnS inclusions were detected in the samples taken after deformation of the steel: i) type RS (sulfides with a Rod-like geometry), ii) type PS (sulphides with a plate-like geometry) and iii) type OS (oxy-sulfides). Here, the elongated inclusions present in both stainless and tool steels were studied more in detail using SEM to determine the tendency for the inclusions to break.  The results showed that three types of elongated MnS inclusions could be identified, namely UU, UB and BB. Here, ‘U’ represents the unbroken edge(s) of inclusion and ‘B’ represents the broken edge(s) of an inclusion. The presence of these three types of inclusions in samples collected both before and after a heat treatment was studied and the results showed that the heat treatment had a very small effect on the morphologies of the elongated MnS inclusions for both stainless steels (containing <0.1 mass % C) and tool steels (containing 0.42 mass % C).  In the second part of the thesis, the characteristics of chips after machining of a 157REM Ce-treated steel and a 157C reference steel was studied. Furthermore, the effect of the NMIs on the chip breakability during machining was determined. The results show that a Ce modification of a 157C steel transforms the NMIs from large size elongated inclusions to small size inclusion with a spherical shape. This leads to an improved machinability of 157C steels. In addition, a newly developed weight distribution of chips (WDC) method, based on the chip weight measurements, was used to determine the tendencies for breaking of chips. The results of this investigation showed that the chips that were obtained from the machining of 157C and the 157REM steels could be classified into the following three types: i) type I chips (with a geometry containing one arc) and having a weight of less than 0.08 g, ii) type II chips (with a geometry containing two arcs) and having weights between 0.08 g and 0.15 g, and iii) type III chips (with a geometry containing three or more arcs) and having weights larger than 0.15 g. From industrial experience, it is known that a high amount of small type I chips will lead to a good chip breakability. The results from the machining test show that the fraction of type I chips from machining of the 157REM steel (65 %) is smaller than from machining of the 157C reference steel (80 %) when using a lower feed rate of 0.4 mm/rev. However, when using a higher feed rate of 0.5 mm/rev, 40 % of the chips belong to type I small chips for the 157REM steel and 14 % for the 157C steel. Based on the conditions used in this study and the obtained results, the following is clear in order to reach the best machinability: i) it is most advantageous to use the 157C steel when using a lower feed rate of 0.4 mm/rev and ii) it is most advantageous to use the 157REM steel when using a higher feed rate of 0.5 mm/rev. / Närvaron av icke-metalliska inneslutningar (NMIs) har en betydande påverkan både med avseende på mekaniska egenskaper såväl som skärbarhetsförmågan hos stål. I denna avhandling är ett fokus att studera deformerade sulfider (MnS)  i ett rostfritt stål (3R65) och ett verktygsstål (42CrMo4). Tre grupper av MnS inneslutningar återfanns i stålproverna, som togs efter deformation av stålet: i) RS (sulfider som har en cylindrisk geometri), ii) PS (sulfider som har en platt geometri) och iii) OS (oxy-sulfider). Dessutom så studerades utdragna inneslutningar mer i detalj med användande av SEM undersökningar i syfte att studera tendensen till att dessa inneslutningar bröts sönder. Resultaten visade att tre typer av utdragna inneslutningar kunde identifieras, nämligen UU, UB och BB. Här representerar ‘U’ en ände av en inneslutning som inte brutits sönder och ‘B’ representerar en ände av en inneslutning som brutits sönder. Närvaron av dessa tre typer av utdragna inneslutningar studerades i prover som togs både före och efter en värmebehandling, men resultaten visade att en värmebehandling hade en mycket liten påverkan på morfologin hos de utdragna MnS inneslutningarna för både rostfria stål (innehållande <0.1 mass % C) och verktygsstål (innehållande 0.42 mass % C).  I den andra delen av avhandlingen så studerades karakteristiken hos spånor som bildats efter skärande bearbetning av ett 157REM (Ce-behandlat) modifierat stål och ett 157C referensstål som inte modifierats. Dessutom så studerades inverkan av icke-metalliska inneslutningar på spånbrytningen under den skärande bearbetningen. Resultaten visar att en Ce-modifiering av stålet omvandlar inneslutningarna från stora och utdragna geometrier till små inneslutningar med en sfärisk geometri. Detta leder till en ökad skärbarhet hos 157C stål. Spånbrytbarheten bestämdes också med användande av en nyutvecklad metod (WDC metoden) som baseras sig på att bestämma vikten av spånor. Resultaten av denna utvärdering visade att spånorna som erhölls från bearbetning av 157C och 157REM stål kunde klassificeras enligt följande tre typer: i) typ I spånor (en geometri som består av en bågform) som har en vikt som är mindre än 0.08 g, ii) typ II spånor (en geometri som består av två bågformar) som har en mellan 0.08 g och 0.15 g och iii) typ III spånor (en geometri som består av tre eller fler bågformar) som har en vikt som är större än 0.15 g. Baserat på industriell erfarenhet så är det känt att en stor mängd av små typ I spånor är kopplad till en bra spånbrytbarhet. Resultaten från skärbarhetstesterna visar att andelen typ I spånor från bearbetning av ett 157REM stål (65 %) är mindre än vid bearbetning av ett 157C referens stål (80 %), när en lägre matningshastighet av 0.4 mm/rev används. Däremot så visar resultaten att om en högre matningshastighet av 0.5 mm/rev används vid bearbetning, så är andelen typ I spånor 40 % för 157REM stålet och 14 % för 157C referensstålet. I syfte att erhålla bästa möjliga skärbarhet så är det fördelaktigt att använda ett 157C referensstål för den lägre matningshastigheten av 0.4 mm/rev, men att använda ett 157REM stål för en högre matningshastighet av 0.5 mm/rev.