Replacing solventborne coating with waterborne can reduce emission of VOC from paint shops, and decrease the amount of CO2 released from after-burners. The chemistry of 2K WB urethane coatings includes complex kinetics, with a selectivity which is highly dependent on application and curing conditions. To be able to design a coating process producing stable high quality coatings, it is important to know what factors affect the material properties. In this project, the effect of variations in temperature during curing of 2K WB and 2K SB topcoats have been evaluated in order to determine if there are any measurable effects on the material. The significance of these difference have also been evaluated to substantiate the need for thorough design of the curing process. After evaluation of visual, mechanical and chemical properties, as well as the durability of the cured topcoats, it was found that the effect of curing temperature on the level of gloss on 2K WB topcoats could be seen with the naked eye. Effects on colour, hardness, flexibility, adhesion and durability could also be measured, and revealed apparent changes in the material. Increased curing temperature had effects on both cross-linking density and isocyanate conversion. The heightened temperature contributed to the formation of topcoats with significantly decreased level of gloss and reduced stone-chip resistance, but also increased hardness and chemical resistance to an extent that was deemed significant. Varied curing temperature was found to give variations in durability, which with time may give different ageing properties of parts coated under different conditions. Before implementation of this type of waterborne topcoat, it is recommended that several properties be further evaluated, such as the effect of humidity and wet paint viscosity on the material properties. / Genom att ersätta lösningsmedelsburna ytbehandlingar med vattenburna kan man kraftigt reducera utsläppen av VOC från lackeringsverkstäder och minska mängden CO2som frigörs från efterbrännare. Kemin för 2K WB uretanlacker innefattar komplex kinetik med selektivitet som är starkt beroende av applicerings- och härdningsbetingelser. För att kunna konstruera en ytbehandlingsprocess som producerar stabila högkvalitativa ytbehandlingar är det viktigt att känna till vilka faktorer påverkar materialegenskaperna. I detta projekt har effekten av variationer i temperatur under härdning av 2K WB och 2K SB topplack utvärderats för att fastställa om det resulterar i mätbara effekter på den färdiga topplacken. Även signifikansen av dessa skillnader har utvärderats för att bedöma behovet av noggrann utformning av härdningsprocessen. Efter utvärdering av visuella, mekaniska och kemiska egenskaper samt hållbarheten hos de härdade lackerna, fanns det att effekten av härdningstemperaturen på nivån av glans för 2K WB topplacker kunde ses med blotta ögat. Effekter på färg, hårdhet, flexibilitet, vidhäftning och hållbarhet visades också mätbara, och visade på tydliga förändringar i materialet. Förhöjd härdningstemperatur visade sig ha effekter på både tvärbindningsdensiteten och omsättning av isocyanater hos härdaren. En förhöjd härdningstemperatur påvisades även bidra till bildandet av en topplack med avsevärt minskad glansnivå och visst minskad stenskottsbeständighet, men även ökad hårdhet och kemikalietålighet i en omfattning som fanns signifikant. Varierad härdningstemperatur visade sig ge variationer i hållfasthet, som med tiden riskerar att ge olika åldringsegenskaper hos komponenter belagda under olika förhållanden. Innan denna typ av vattenburen täckfärg implementeras i produktion rekommenderas att ytterligare egenskaper utvärderas, såsom inverkan av fukt och våtfärgsviskositet på ytbehandlingens slutegenskaper

Thermally expandable microspheres are spherical particles around 5-­‐40 µm in size, consisting of a polymeric shell in which a blowing agent has been encapsulated. The microspheres are expanded upon heating, resulting in a particularly low density. Microspheres are therefore suitable to use as light weight filler or as foaming agent. AkzoNobel is world leading in the production of expandable microspheres, which are commercialised under the name Expancel. Sustainability is a great focus at AkzoNobel and two issues that AkzoNobel works with today is to develop products free from chlorine and Me1. The aim with this thesis has been to investigate whether it is possible to produce microspheres free from these chemicals and to see if they can be a more sustainable alternative to one of the existing Expancel grades. In this study, the microspheres have been produced through free radical suspension polymerisation and analysed by measuring mainly the particle size and expansion properties. The polymeric shell was composed of the monomers acrylonitrile, methacrylonitrile, and methyl acrylate. The main focus has been to evaluate the silica-­‐based stabilisation system, which stabilise the monomer droplets during the suspension polymerisation. The stabilisation is possible due to the formation of silica flocs that is adsorbed on the surface of the droplets. It has been investigating how different parameters, e.g. amount of stabiliser or mixing procedure, affects the formation of silica flocs and the stabilisation of monomer droplets. For the silica-­‐based system, it was found that the mixing order, stirring rate, and amount of stabilisers affect the formation of flocs. It was also seen that the amount of stabiliser affect the stabilisation of droplets, and that some stabilisers is more significant than others. Microspheres without chlorine and Me1 have successfully been produced in laboratory scale (50 mL and 1 L). The expansion and size of the microspheres produced in this study was relatively similar to one of the existing Expancel grades. However, the reproducibility of polymerisations in 1 litre reactors has been poor. / Termiskt expanderbara mikrosfärer är sfäriska partiklar, ca 5-­‐40 µm i diameter, som består av ett polymerskal som innesluter en drivgas. Mikrosfärerna expanderar när de utsätts för värme och erhåller då en mycket låg densitet. De är därför lämpliga att använda som fyllmedel då låg vikt är önskvärt eller som skummedel. AkzoNobel är världsledande inom produktion av expanderbara mikrosfärer, som marknadsförs under namnet Expancel. Hållbar utveckling är en viktig fråga för AkzoNobel och två problem som de står inför idag är att utveckla produkter fria från klor och Me1. Målet med detta examensarbete har varit att undersöka om det är möjligt att framställa mikrosfärer fria från dessa kemikalier och om de framtagna mikrosfärerna skulle kunna vare ett hållbarare alternativ till en av de befintliga Expancel-­‐ produkterna. I den här studien har mikrosfärerna framställts genom suspensionspolymerisation som initierats av fria radikaler och de har analyserats främst genom att mäta partikelstorlek och expansionsegenskaper. Polymerskalet bestod av monomererna akrylnitril, metakrylnitril och metylakrylat. I det här arbetet har det viktigaste varit att utvärdera det silikabaserade stabiliseringssystemet som stabiliserar monomerdropparna vid polymerisationen. Stabiliseringen är möjlig eftersom silika bildar flockar som adsorberar på ytan av monomerdropparna. Olika parametrar, exempelvis mängd stabiliseringsmedel och satsningsförfarande, har därför varierats för att undersöka vilken effekt det får på flockningen av silika och stabiliseringen av monomerdroppar. Satsningsordning och omrörningshastiget för stabiliseringssystemet samt mängd stabiliseringsmedel är några av de faktorer som påverkar bildningen av flockar. Det konstaterades även att mängd stabiliseringsmedel påverkar stabiliseringen utav monomerdropparna. Fulländade mikrosfärer utan klor och Me1 har framställts i laboratorieskala (50 mL och 1 L) och partikelstorleken samt expansionsegenskaper är jämförbara med en av Expancels nuvarande produkter. Dock har reproducerbarheten i 1 litersskala varit otillfredsställande.

Möjligheten att syntetisera UV-härdande bindemedel från enbart förnyelsebara startmaterial (syra A och alkohol A) eller från kombinationer av dessa med konventionella monomerer (syra B, C och D; alkohol B, C, D, E samt cyklisk ester A) utvärderades. Effekten av två katalysatorer, tenn(II)oktanoat och butyltenn, på direkt förestring och på ringöppning utvärderades. Totalt framställdes 22 polyestrar som analyserades med avseende på syratal, medelmolekylvikt (SEC), kulörindex (Gardner), och strukturell sammansättning (NMR). Bindemedlen formulerades med UV-initiator och härdades med UV-ljus. De torra filmerna utvärderades med avseende på hårdhet (pendelhårdhet), flexibilitet och kemisk resistens.   Det var möjligt att framställa polyestrar baserade på ovan nämnda monomerer. Några monomer gav bäst egenskaper med avseende på pendelhårdhet och flexibilitet medan andra byggstenar resulterade i bättre kemisk resistens.

This study focus on trying to understand what factors regarding bumper materials and coatings affect the radar transparency at 77 GHz. Dielectric spectroscopy was done at 25 unique samples, consisting of various plastic substrates, primers, basecoats and clearcoats with the Free-spaced method in the 60-90 GHz region. The plastic substrate consisted of Polypropylene-blend with different fillers such as talc, carbon black and metal flakes. The basecoats analyzed were 2 solid factory coatings (one black and one white), 5 factory coating containing different effect pigments such as metal flakes, Xiralic, and Mica, 1 factory PVD coating and 2 aftermarket basecoats. All samples were provided by a Volvo Cars’ supplier, however, some samples were repainted with the aftermarket coatings. The complex permittivites were calculated for each PP-blend and coating from the curve fitting of the measured S-parameters from the Free-spaced method. Material analysis such as thickness measurements of the plastic substrate and coatings, ATR-FTIR spectroscopy, TGA and DSC were done at all plastic substrates. The plastic substrates and the coating were also observed in optical microscope and in SEM. The calculated permittivities were compared with the results from the material analysis and correlations between increased metal content in the basecoat and higher real permittivity were found. Some relationship between the size of the metal flakes and the radar transparency could also be observed. Further, correlations between higher real permittivity with higher concentration of talc and carbon black were detected. MATLAB was used to provide an example for optimization of the plastic thickness for a given basecoat in order to have minimal reflection at 77 GHz.

This thesis describes a sequence of experiments which have been performed with the intention to produce synthetic nacre. Synthetic nacre is a biomimetic material based on nacre, a material which can be found in mollusc shells. Nacre is a nanocomposite which has improved mechanical properties compared to the principal component aragonite (95% wt%). The improved properties of nacre are derived from the polymeric components in the composite which allows from redistribution of forces under load. Carbonates sequester CO2 in the geological CO2-cycle. If precursor are sourced correctly, the CaCO3 in synthetic nacre can temporarily sequester CO2. Crystals with the intended pseudohexagonal morphology have been synthesised. However, subsequent quantitative analysis could not support these findings in a follow-up experiment. This discrepancy might have been caused by differences in the method. Moist nanopaper was found to be mineralisable while maintaining a layered structure.

PLA nanofibers were successively produced by thermo-responsive transformation of PLA particles in water. The morphological structure of the nanofibers could be optimized by the heat treatment as well as the incorporation of GO to the fiber surface. PLA/GO fiber demonstrated a more stable morphology and GO provided good compatibility between PLA and starch. Both PLA and PLA/GO fibers incorporated in starch films resulted in increased thermal stability and mechanical properties. However, the most favorable properties were assigned starch films containing high concentration of PLA/GO fibers. These films with completely green components could possibly be utilized in biodegradable packaging applications.

Biodiesel and hydrotreated vegetable oil (HVO) are currently viewed by the transportation sector as the most viable alternative fuels to replace petroleum-based fuels. The use of biodiesel has, however, been limited by the deteriorative effect of biodiesel on rubber parts in automobile fuel systems. This work therefore aimed at investigating the degradation of acrylonitrile butadiene rubber (NBR) and fluoroelastomers (FKM) on exposure to biodiesel and HVO at different temperatures and oxygen concentrations in an automated ageing equipment and a high-pressure autoclave. The oxidation of biodiesel at 80 °C was promoted by an increase in the oxygen partial pressure, resulting in the formation of larger amounts of hydroperoxides and acids in the fuel. The fatty acid methyl esters of the biodiesel oxidized less at 150 °C on autoclave aging, because the termination reactions between alkyl and alkylperoxyl radicals dominated over the initiation reactions. HVO consists of saturated hydrocarbons, and remained intact during the exposure. The NBR absorbed a large amount of biodiesel due to fuel-driven internal cavitation in the rubber, and the uptake increased with increasing oxygen partial pressure due to the increase in concentration of oxidation products of the biodiesel. The absence of a tan δ peak (dynamical mechanical measurements) of the bound rubber and the appearance of carbon black particles devoid of rubber suggested that the cavitation was caused by the detachment of bound rubber from particle surfaces. A significant decrease in the strain-at-break and in the Payne-effect amplitude of NBR exposed to biodiesel was explained as being due to the damage caused by biodiesel to the rubber-carbon-black network. During the high-temperature autoclave ageing, the NBR swelled less in biodiesel, and showed a small decrease in the strain-at-break due to the cleavage of rubber chains. The degradation of NBR in the absence of carbon black was due only to biodiesel-promoted oxidative crosslinking. The zinc cations released by the dissolution of zinc oxide particles in biodiesel promoted reduction reactions in the acrylonitrile part of the NBR. Heat-treated star-shaped ZnO particles dissolved more slowly in biodiesel than the commercial ZnO nanoparticles due to the elimination of inter-particle porosity by heat treatment. The fuel sorption was hindered in HVO-exposed NBR by the steric constraints of the bulky HVO molecules. The extensibility of NBR decreased only slightly after exposure to HVO, due to the migration of plasticizer from the rubber. The bisphenol-cured FKM co- and terpolymer swelled more than the peroxide-cured GFLT-type FKM in biodiesel due to the chain cleavage caused by the attack of biodiesel on the double bonds formed during the bisphenol curing. The FKM rubbers absorbed biodiesel faster, and to a greater extent, with increasing oxygen concentration. It is suggested that the extensive biodiesel uptake and the decrease in the strain-at-break and Young’s modulus of the FKM terpolymer was due to dehydrofluorination of the rubber by the coordination complexes of biodiesel and magnesium oxide and calcium hydroxide particles. An increase in the CH2-concentration of the extracted FKM rubbers suggested that biodiesel was grafted onto the FKM at the unsaturated sites resulting from dehydrofluorination. / <p>QC 20170227</p>

Cellulose nanofibrils are a biobased and renewable material with potential to be used in many different applications. Such applications include air filtration, absorption of liquids, and thermal insulation.  To be used for these applications the cellulose nanofibrils must form a porous and dry material. However, maintaining some degree of porosity after drying is difficult, since the fibrils are extracted in liquid and tend to collapse into a dense material upon drying. Certain methods have proven effective for making a dry porous material from cellulose nanofibrils, but these are often expensive and not suitable for large scale production. The aim of this project is to test possible methods for making a highly porous cellulose nanofibril-based material. These methods must be environmentally sustainable and suitable for large scale production. An extensive screening has been conducted with the aim of identifying methods resulting in materials with high porosity. The obtained materials have been analysed further to give a more thorough understanding of the porosity as well as other characteristics. The results indicate that cross-links in the material strengthen the structure, and that drying samples from water always results in complete collapse or very dense materials while drying samples from certain solvents other than water results in more porous materials. The analysed materials had very different porosities, some of which were relatively high. The most porous material analysed by Brunauer-Emmett-Teller gas adsorption had a surface area of 9.5 m2/g. This project gives insight into how cross-linking chemistries and treatment with different solvents and pH affect the resulting cellulose nanofibril-based material, as well as knowledge about which methods can be used to successfully produce dry porous cellulose nanofibril-based materials.

A key trend in the PVC market is to replace or decrease the amount of phthalate plasticisers used due to increasing health concerns. Therefore, the demand for non-phthalate based plasticisers is growing rapidly. Mineral oils are used in a variety of rubber and polymer applications as plasticisers; however, due to the lower polarity their applicability in PVC compounds is limited. Therefore, these materials are typically used as secondary plasticiser along with a primary for the purpose of improved properties and cost reduction. Some of the non-phthalate based solutions are fast fusing plasticisers, which act like solvents and have too rapid and too high plasticizing effect. This makes the compounding difficult and could cause problems in production. These substances have good compatibility with mineral oils, and using them together in PVC compounds can help the compounding issue by reducing the solvent power and increasing the fusion time to a level where the production parameters are similar to compounding with phthalates.   The aim of this study was to evaluate the use of mineral oils as a secondary plasticiser in a non-phthalate system for PVC. Four different grades of mineral oil and three non-phthalate plasticisers were used in compounding and compression moulding of PVC sample films. Mechanical, physical and chemical testing were done to assess the properties in a comparative study with phthalate plasticized PVC.   Tensile testing and hardness measurements showed that the mineral oils did not contribute with any plasticizing effect for the non-phthalate plasticisers tested in the study. The hardness was instead slightly increased for all the sample films that contained mineral oil. This indicates that the mineral oil either is less efficient than the primary plasticiser or that it affects the primary plasticisers intramolecular shielding between the PVC chains.       The shrinkage test showed that the migration of mineral oil was acceptable, especially the thicker grades of mineral oils had low migration. Colour stability test showed that the thicker mineral oil grades had some problems with discolouration. The discolouration is probably related to content of polyaromatics and oxidation stability.

Emulsion polymerizations of vinyl acetate (VAc) were performed by fully or partially replacing poly(vinyl alcohol) (PVA) with renewable materials as protective colloids or by adding renewable materials, as additives or fillers, to the emulsions during or after polymerization. The purpose of the study was to increase the amount of renewable materials in the emulsion. A total of 19 emulsions were synthesized. Different recipes were used for the synthesis. The following renewable materials were studied; hydroxyethyl cellulose (HEC) with different molecular weights, starch and proteins. HEC and starch were used as protective colloids. Proteins were used as additives or fillers. Cross-linking agent A and Cross-linking agent B were used as cross-linking agents. A total of 26 formulations were pressed, either cold or hot. The synthesized emulsions were evaluated with respect to pH, solids content, viscosity, minimum film formation temperature (MFFT), glass transition temperature (Tg), particle size and molecular weight (Mw). The tensile shear strengths of the emulsions were evaluated according to EN 204 and WATT 91. It was possible to fully, or partially, replace PVA as protective colloid with renewable materials. It was also possible to use renewable materials as additives or fillers in the emulsions. The emulsions obtained properties that differed from the reference. Generally, emulsions with HEC as protective colloid showed lower viscosity and slightly higher MFFT, Tg and molecular weight than emulsions with PVA as protective colloid. Larger particle sizes than the reference were obtained for emulsions containing PVA combined with renewable materials. The emulsion with starch as protective colloid exhibited the largest particle size. 10 formulations passed the criteria for D2. The emulsions where PVA was fully or partially replaced with HEC or starch showed a water resistance similar to the reference (around D2). The addition of protein did not decrease the water and heat resistance compared to the reference. Addition of protein after polymerization increased the water resistance (D2) compared to addition during polymerization. Addition of cross-linking agents did not increase the water resistance further. Two formulations passed the criteria for D3. The emulsion in the first formulation had PVA as protective colloid and protein B was added during polymerization. The emulsion in the second formulation had HEC as protective colloid. To both of these emulsions, protein A was added after polymerization, as a filler, combined with Cross-linking agent B as cross-linking agent before hot pressing. The first formulation also showed a good heat resistance (passed the criteria for WATT 91).