Today there are numerous methods to slow down a corrosion process of metallic materials. However, due to environmental effects and health risk issues, several traditional corrosion inhibitors have to be phased out. Hence, it is of great importance to develop new corrosion inhibitors that are “green”, safe, smart and multifunctional. In this essay, the focus is on mussel adhesive protein (MAP) and its possibility to reduce the rate of the corrosion process. The protein exhibit great adhesive strength and protective properties, allowing it to adhere to a multitude of different surfaces and is therefore of great interest of corrosion science. The protein Mefp-1, derived from the blue mussel´s foot, had been pre-adsorbed on the carbon steel surface and provided good corrosion inhibition in a basic chloride solution for a short exposure time. The protection was further improved with the assist of iron and ceria ions by formation of protein/ions complexes within the surface films and thus enhanced the corrosion protection for longer exposure time. Ceria nanoparticles were used in order to create a multi-layer composite film with an even higher corrosion protection. The results suggest a denser film compared to previous samples and a more uniform surface.

The global market for fluoropolymers, including polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), is growing rapidly due to their copious applications in the construction, automotive, medical, chemical, and electrical industries. Fluoropolymers owe their popularity partly to their excellent chemical and thermal stability and useful mechanical, piezoelectric, and ferroelectric properties. They are made into films or coatings that are used for corrosion protection or surface property enhancement. Electrophoretic deposition (EPD) has generated increasing interest in manufacturing advanced films for various applications due to its low cost, versatility, simple apparatus, and good film quality compared with other deposition techniques like dip coating, spin coating, electrospinning, or spay coating. Moreover, EPD facilitates uniform deposition on the substrates of complex shapes at a high deposition rate. The aim of this research is to develop novel biomimetic strategies for fabricating polymer films and their composite films with multifunctional particles through EPD. This method involves the electrophoresis of charged particles in a stable colloidal suspension towards an electrode, forming deposition. Fluoropolymers, however, are electrically neutral and chemically inert, and their EPD presents difficulties. Therefore, successful EPD depends on understanding how to modify the surface of polymer particles using advanced biosurfactants to impart charge and form a well dispersed, stable colloidal suspension. One strategy is to leverage the unique dispersing power of bile acids and salts as biosurfactants for EPD of PTFE and PVDF films and composite films. When doing so, it was found that the amphiphilic structure of bile salts such as sodium deoxycholate (DChNa) facilitated adsorption on the chemically inert, hydrophobic surfaces of PTFE, diamond, and carbon dots. In this strategy, DChNa acted as a charging, dispersing, film-forming agent for the co-deposition of PTFE composite films from an aqueous suspension. Water insoluble bile acids (BAs) were found to be biosurfactants for the EPD of PTFE and PVDF from organic solvents, in which lithocholic acid (LCA) was used as a co-dispersant for the fabrication of composite PTFE-diamond coatings and PTFE coatings provided corrosion protection for stainless steel in 3% NaCl solutions. The dispersing performance of four other bile acids, chenodeoxycholic acid (CDCA), deoxycholic acid (DCA), ursodeoxycholic acid (UDCA), and cholic acid (ChA), was analyzed and compared with LCA on the deposition performance of PVDF. It was found that the PVDF deposition yield obtained using different BAs increased in the order of LCA<CDCA<DCA<UDCA<ChA. This was attributed to the difference in number, position, and orientation of OH groups in the structures of the BAs. Another biomimetic strategy for the EPD of polymers and composites was inspired by the strong adsorption of mussel protein on rock surfaces in sea water. Catecholate-type molecules, caffeic acid (CA) and catechol violet (CV), were found to be biosurfactants for dispersing, charging, and depositing PVDF films and composites. Analyses of the deposition yield data, the chemical structure of the CA and CV, and the microstructure and composition of the films suggested that the aromatic rings on the CA and CV had hydrophobic interactions with the PVDF particles and that the phenolic groups formed bidentate chelating or bridging bonding to inorganic particle surfaces. The study demonstrated the feasibility of co-depositing PVDF with nanoparticles of TiO2, MnO2, and NiFe2O4. CA was also used for preparing PVDF-HFP particles and as a co-dispersant for the co-deposition of PVDF-HFP with NiFe2O4 and CuFe2O4 nanoparticles in order to make composite films that combine the ferrimagnetic properties of spinel ferrites with the multifunctional properties of ferroelectric polymers. / Dissertation / Doctor of Philosophy (PhD)

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<p> New electrophoretic deposition methods for the fabrication of advanced organic-inorganic composite coatings on metallic substrates for biomedical applications have been developed. In the proposed methods, chitosan was used as a matrix for the fabrication of multilayer and functional graded chitosan- hydroxyapatite (HA) coatings. The HA particles showed preferred orientation of c-axis parallel to the layer surface, which is similar to the bone structure. Electrochemical studies showed that the obtained coatings provided corrosion protection of the metallic substrates, such as stainless steel and Nitinol.</p> <p> The feasibility of co-deposition of chitosan and heparin has been demonstrated. Composite chitosan-heparin layers were used for the surface modification of chitosan-HA coatings. Obtained results paved the way for the electrophoretic fabrication of novel coatings for biomedical implants with improved blood compatibility.</p> <p> The feasibility of co-deposition of hyaluronic acid and HA has also been demonstrated. The co-deposition of hyaluronic acid and HA resulted in the fabrication of novel nanocomposite films by electrodeposition. The chemical composition, microstructure, corrosion protection, and other functional properties of the nanocomposites have been investigated. Co-deposition of hyaluronic acid and multiwalled carbon nanotubes has been studied by TGA/DT A and SEM studies.</p> <p> The feasibility of deposition of novel composites based on alginic acid has been demonstrated. New electrochemical strategies were used for the fabrication of alginic acid-HA, alginic acid-heparin and alginic acid -hyaluronic acid nanocomposites. The composition of these nanocomposite coatings can be varied by variation in bath composition for EPD.</p> <p> The electrochemical mechanisms for the fabrication of all these advanced organic-inorganic composite coatings have been developed.</p> / Thesis / Master of Applied Science (MASc)

Despite the high demand for press-hardenable steel (PHS) with coatings that provide sacrificial cathodic protection, Zn-based coatings have experienced limited use due to the significant challenges associated with avoiding liquid metal embrittlement (LME) while maintaining robust cathodic protection when using conventional PHS materials and processing techniques. The present research addresses these challenges by reducing the conventional direct hot press forming (DHPF) temperature to between 600–700 °C, such that forming and quenching occurs well below the Zn(Fe)liq → Г-Fe3Zn10 peritectic temperature of 782 °C, thereby removing the conditions necessary for LME to occur while allowing for formation of the cathodically-protective Г-Fe3Zn10 phase. The objective of this work was to define a process window for two galvanized prototype PHS alloys with compositions of 0.20C-2.01Mn-0.26Si-0.005B and 0.19C-2.5Mn-0.26Si-0.005B (wt%) that would result in fully martensitic microstructures, tensile strengths (TS) ≥ 1500 MPa, and robust cathodic protection, defined as attaining ≥ 15 vol% Г-Fe3Zn10 in the coating microstructure, while avoiding LME. Accomplishing this task involved characterizing both grades as a function of austenization time, stamping temperature, and strain imposed by the forming process in order to define process windows that resulted in parts that met the aforementioned property requirements. It was found that the approach of increasing the Mn content relative to conventional PHS grades was successful in improving the hardenability sufficiently to enable the formation of fully martensitic microstructures despite the lower effective cooling rates associated with the reduced DPHF temperatures. Microstructural imaging and tensile testing demonstrated that, for both prototype PHS grades, a process window exists for the production of parts that satisfy the targets of the formation of fully martensitic microstructures and TS ≥ 1500 MPa while exhibiting uniform elongation of about 0.05 followed by significant post-uniform elongation. The effect of DHPF temperature and strain imposed by the forming process on mechanical properties was found to be negligible. Tensile tests and fractography revealed that reducing the DHPF temperature to between 600–700 °C was successful in preventing LME, thereby allowing samples to fracture in a ductile manner. Micro-cracking in the coating of the DHPF part was observed; however, these cracks were arrested at the coating-substrate interface. For all tested conditions, the coating met the target of ≥ 15 vol% Г-Fe3Zn10, implying that robust cathodic protection is expected. Based on the results of these experiments, it was concluded that DHPF process windows that meet all of the property targets include austenization times and DHPF temperatures of 120–180 s and 600–700 °C, respectively, for the 2Mn grade, and 60–180 s and 600–700 °C, respectively, for the 2.5Mn grade. / Thesis / Master of Science (MSc)

Polyimides are frequently used as insulating layers in the microelectronics industry. These polymers are tough, have high thermal stability, and have favorable dielectric properties; consequently, polyimides are excellent materials for insulating layers in microelectronic devices. In this research, self-assembled monolayers are investigated for use as an adhesion promoter for metal substrates, and for corrosion protectors of the metal surface. Gold substrates modified by adsorption of 3- and 4-aminothiophenol monolayers, 3- and (4-mercaptophenyl) phthalimide (MPP) monolayers, and by reaction of the 3- and 4-aminothiophenol monolayers with the phthalic anhydride were studied using reflection absorption infrared spectroscopy, contact angle measurement, ellipsometry, and electrochemical measurements. Reactions on the monolayers are used to model the attachment of an insulating polyimide to the substrate. The covalent attachment of the anhydride is confirmed, and the efficiency of the reaction of the aminothiolphenol monolayers is investigated. The reactivity of the aminothiolphenol monolayers is found to depend on the position of the amino-group around the phenyl ring. Impedance spectroscopy is used to investigate the ionic insulating properties of these systems. The 4-mercaptophthalimide monolayer is found to have the highest monolayer resistance to ion transport. This result suggests that it forms the most densely packed monolayer. The monolayer resistance of the surfaces prepared by adsorption of the aminothiolphenol isomers followed by reaction with phthalic anhydride is much lower than the corresponding deposited mercaptophthalimide monolayers. These results suggest that the reaction efficiency is low. Impedance spectroscopy and polarization measurements suggests a higher protection efficiency for 3-mercaptophenylphthalimide. These results will be discussed in the context of the ability of the isomeric mercaptophthalimide monolayers to serve as protectors against substrate corrosion. / Ph. D.

The use of graphene and conductive polyaniline nanomaterials in the field of electrochemistry is increasing due to their excellent conductivity, rapid electron transfer and high specific surface area. However, these properties are strongly dependent on the preparation processes. To accelerate the development of advanced electrochemical sensors for the simultaneous detection of trace amounts of heavy metal ions, two facile and green methods are proposed to improve their performance in this thesis. The first one was dedicated to make graphene-carbon nanotube hybrid nanocomposites. The introduction of carbon nanotubes not only greatly enhances the conductivity of graphene but also suppresses, to some degree, the aggregation between graphene nanosheets. Another method proposed in this thesis work was to synthesize a phytic acid doped polyaniline nanofiber based nanocomposite. The synergistic contribution from polyaniline nanofibers and phytic acid enhances the accumulation efficiency and the charge transfer rate of metal ions during the differential pulse anodic stripping voltammetry analysis. The above-mentioned nanocomposite modified electrodes were all successfully applied to real samples for the simultaneous detection of Cd2+ and Pb2+ with good recovery rates. Meanwhile, corrosion protection is another important branch in the field of electrochemistry. In this direction, an active alkyd-polyaniline composite coating with self-healing functionality was prepared. The polyaniline used in this thesis was doped with p-toluene sulfonic acid, which was employed to increase the conductivity of polyaniline, and 1 wt.% of as-prepared polyaniline nanoparticles were found to offer an effective conductive network for anticorrosion. Finally, the reasons that such low loading levels of nanomaterials can result in significantly reinforced properties in nanocomposites were studied with combined atomic force microscopy (AFM) techniques. The results demonstrated that the interphase for a 40-nm-sized silica particle could extend to 55–70 nm in poly(ethyl methacrylate) (PEMA) and poly(isobutyl methacrylate) (PiBMA) polymer matrix, and the interphase exhibited a gradient distribution in surface nanomechanical properties. / <p>QC 20170315</p>

The combination of two cost-effective processes, i.e. casting and anodising, would be an interest for the aluminium component applications. However, there are some obstacles in the application of anodising on cast Al alloys. The challenges mostly relate to the alloying elements especially Si and the surface quality. With the development of casting process, cast aluminium alloys with low Si content can be casted, and a complex geometry component with reasonably good surface finish can be achieved. This study aims to identify the influence of Si on anodising and mechanical properties of Al-Si alloys. In this study, six Al-Si alloys with three different Si level and two different Sr level were investigated. Sr acts as a modifier to change the morphology of Si particles. The directional solidification technology was used to vary the microstructure coarseness by controlling the cooling rate to study the influence of Si level, Si particle morphology and cooling rate on mechanical properties, oxide layer formation and corrosion protection performance in cast Al-Si alloys. This study has observed that Si has a significant influence on anodising. During anodising, Si particles are anodised at a lower rate than the Al phase. The presence of Si particles in eutectic phase make the oxide layer locally thinner and more defected due to the low oxide growth rate in eutectic phase. This study observed the presence of residual metallic Al phase beneath or between Si particles. Due to their presence and their geometry, Al can be shielded by Si particles and prevented from oxidation. Si particles also act as a key role in the corrosion protection of oxide layer in Al-Si alloys. The corrosion attack propagates along Si particles as well as oxide defects to the Al substrate. It is found that the morphology of Si particles has a significant influence on the oxide layer formation and corrosion protection performance of the oxide layer on cast Al-Si alloys. A substantially improvement the corrosion resistance of anodised layer on Al-Si alloys is attributed to the morphology change from interconnected flakes to disconnected Si fibres when Sr is added, with less oxide defects and better oxide distribution. The Si level governs the mechanical properties of Al-Si based alloys. An increase of Si content in Al alloys improves the mechanical properties such as ultimate tensile and yield strength as well as hardness of the materials, but decreases the ductility. However, an increase of Si level in Al alloys decreases the thickness of oxide layer, and thereby, the corrosion protection of the oxide layer is deteriorated. / Kombinationen av två kostnadseffektiva processer, gjutning och anodisering, är av intresse för tillämpning på aluminiumkomponenter. Det finns dock hinder för tillämpning av anodisering på gjutna aluminiumlegeringar. Utmaningarna relaterar till effekten av legeringselement, i synnerhet Si, och komponentens ytkvalité. Med utvecklingen av gjutprocesser kan aluminiumlegeringar med lågt Si-innehåll gjutas, och komponenter med komplex geometri med förbättrad ytkvalité kan uppnås. Denna studie syftar till att identifiera påverkan av Si på anodisering och mekaniska egenskaper hos Al-Si-baserade legeringar. I denna studie undersöktes sex Al-Si-legeringar med tre nivåer av Si och två nivåer av Sr. Tillsatser av Sr leder till modifikation av morfologin hos Si-partiklar. Med hjälp av tekniken ”riktad stelning” varierades stelningshastigheten för att studera sambanden mellan halten och morfologin av Si, mikrostrukturens grovlek och dess inverkan på mekaniska egenskaper, samt oxidskiktets bildning och korrosionsbeständighet hos gjutna Al-Si-legeringar. Denna studie visar att Si har ett betydande inflytande på anodisering r. Under anodisering, anodiseras Si-partiklar i en lägre takt än Al-fasen. Närvaron av Si-partiklar i eutektisk fas bidrar till ett lokalt förtunnat oxidskikt med fler defekter på grund av den låga oxidtillväxthastigheten i eutektisk fas. Denna studie observerade förekomsten av kvarvarande metalliska Al fasen under eller mellan Si-partiklar. På grund av Si-partiklarnas närvaro och geometri, kan Al skärmas från oxidation. Si-partiklar har även en nyckelroll i korrosionsskydd av oxidskiktet i Al-Si-legeringar. Korrosionsangreppet propagerar längs Si-partiklar samt oxiddefekter till Al-substrat. Morfologin av Si-partiklar har funnits ha en betydande inverkan på oxidskiktets bildning och korrosionsskydd hos gjutna Al-Si-legeringar. En väsentlig förbättring av korrosionsbeständigheten i anodiserat skikt hos Al-Si-legeringar tillskrivs förändring av kiselns morfologi från sammankopplade flingor till osammanhängande fibrer när Sr tillsätts, med mindre oxiddefekter och bättre fördelning av oxid. Si halten påverkar de mekaniska egenskaperna hos Al-Si-baserade legeringar. En ökning av Si innehålleti Al-legeringar förbättrar de mekaniska egenskaperna såsom brott och sträckgräns samt hårdhet hos materialen, men minskar duktiliteten. En ökning med Si halt i Al-legeringar minskar dessvärre tjockleken hos oxidskiktet, och därigenom, försämrar oxidskiktets korrosionsskydd.