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Item Surface Property Modification of Coatings via Self-Stratification(North Dakota State University, 2010) Pieper, Robert JosephBiological fouling occurs everywhere in the marine environment and is a significant problem for marine vessels. Anti-fouling coatings have been used effectively to prevent fouling; however, these coatings harm non-targeted sea-life. Fouling-release coatings (FRC) appear to be an alternative way to combat fouling. FRC do not necessarily prevent the settlement of marine organisms but rather allow their easy removal with application of shear to the coatings surface. These coatings must be non-toxic, non-leaching, have low surface energy, low modulus, and durability to provide easy removal of marine organisms. Here the goal is to develop FRC based on thermosetting siloxane-polyurethane, amphiphilic polyurethane, and zwitterionic/amphiphilic polyurethane systems. A combinatorial high-throughput approach has been taken in order to explore the variables that may affect the performance of the final coatings. Libraries of acrylic polyols were synthesized using combinatorial high-throughput techniques by either batch or semi-batch processes. The design of the experiments for the batch and semi-batch processes were done combinatorially to explore a range of compositions and various reaction process variables that cannot be accomplished or are not suitable for single reaction experiments. Characterization of Rapid-GPC, high-throughput DSC, and gravimetrically calculated percent solids verified the effects of different reaction conditions on the MW, glass transition temperatures, and percent conversion of the different compositions of acrylic polyols. Coatings were characterized for their surface energy, pseudobarnacle pull-off adhesion, and were subjected to bioassays including marine bacteria, algae, and barnacles. From the performance properties results the acrylic polyol containing 20% hydroxyethyl acrylate and 80% butyl acrylate was selected for further siloxane-polyurethane formulations and were subjected to the same physical, mechanical, and performance testing. Amiphiphilic copolymers based on PDMS molecular weight and the addition of PEG based polymer blocks on the properties of acrylic-polyurethane coatings were explored. The key properties screened were surface energy, determined by contact angle measurements using water and methylene iodide, dynamic water contact angle, and pseudobarnacle adhesion properties. The data from all of the biological assays indicates that the novel coatings were able to resist fouling and have low fouling adhesion for the broad variety of fouling organisms tested.Item Surface Optimization of Siloxane-Polyurethane Marine Coatings for Improved Fouling-Release Properties(North Dakota State University, 2016) Galhenage, Teluka PasanBiofouling has been an economically and environmentally costly problem to mankind ever since they set sail. Biofouling causes frictional drag leading to slow vessel speeds, and increased fuel costs. Antifouling (AF) coatings containing biocides have been used for decades, however, since some biocides have shown undesired effects towards the environment, a non-toxic solution to combat fouling is desired. Subsequently, fouling release (FR) coatings quickly gained acceptance as a non-toxic approach to contend with biofouling. Unlike AF coatings, FR coatings not necessarily prevent settlement of organisms, they permit weak adhesion which is easily released by water shear or light grooming. The siloxane-polyurethane (SiPU) coatings based on the concept of self-stratification is a non-toxic and durable approach to prepare FR coatings. In this work, several approaches were considered to optimize surface properties of SiPU coatings. Incorporation of phenyl-methyl silicone oils led to improved FR properties towards several marine organisms in laboratory assays and in ocean field immersion. Enhancement in FR properties may be attributed to slowly exuding silicone oil providing surface lubricity, weakening the adhesion of marine organisms. Addition of diphenyldimethyl siloxane in to SiPU coatings at different ratios resulted in micro-scale surface topographical features which negatively affected microfouling-release while several coatings displayed good FR performance towards macrofouling organisms. In another study, decreasing the acid group content helped to improve FR performance towards barnacles, but FR performance towards diatoms were compromised. Novel amphiphilic siloxane-polyurethane (AmSiPU) coatings from polyisocyanate pre-polymers modified with polydimethyl siloxane and polyethylene glycol displayed excellent FR properties towards several marine organisms during laboratory assays. These AmSiPU coatings show promise as contenders to commercial FR standards. Initial development of SiPU coatings with hydrophilic surfaces showed promise, as the coatings showed rapidly rearranging surfaces with comparable FR performance to commercial standards which claim hydrophilic surface properties. During freshwater field immersion trials, SiPU coatings displayed excellent mussel FR performance up to 3 years. Surface analysis suggested that solvent content affected self-stratification and morphology of SiPU coatings. The SiPU coating system is a highly tunable, tough, environmentally friendly, and practical FR solution which can evolve along with non-toxic commercial marine coatings.Item Magnesium Alloy Particulates used as Pigments in Metal-Rich Primer System for AA2024 T3 Corrosion Protection(North Dakota State University, 2011) Xu, HongAs an alternative to the present toxic chromate-based coating system now in use, the Mg-rich primer technology has been designed to protect Al alloys (in particular Al 2024 T3) and developed in analogy to Zn-rich primers for steel substrate. As an expansion of this concept, metal-rich primer systems based on Mg alloy particles as pigments were studied. Five different Mg alloy pigments, AM60, AZ91B, LNR91, AM503 and AZG, were characterized by using the same epoxy-polyamide polymer as binder, a same dispersion additive and the same solvent. Different Mg alloy-rich primers were formulated by varying the Mg alloy particles and their pigment volume concentrations (PVC). The electrochemical performance of each Mg alloy-rich primer after the cyclic exposure in Prohesion chamber was investigated by electrochemical impedance Spectroscopy (EIS). The results indicated that all the Mg alloy-rich primers could provide cathodic protection for AA 2024 T3 substrates. However, the Mg alloys as pigments in metal-rich primers seemed to exhibit the different anti-corrosion protection performances, such as the barrier properties, due to the different properties of these pigments. In these investigations, multiple samples of each system were studied and statistical methods were used in analyzing the EIS data. From these results, the recommendation for improved EIS data analysis was made. CPVC studies were carried out on the Mg alloy-rich primers by using three Mg alloy pigments, AM60, AZ91B and LNR91. A modified model for predicting CPVC is proposed, and the results showed much better agreement between the CPVC values obtained from the experimental and mathematical methods. Using the data from the AM60 alloy pigment system, an estimate of experimental coarseness was done on a coating system, the first time such an estimate has been performed. By combining various surface analysis techniques, such as scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and confocal Raman microscopy, the oxidation products formed after exposure were identified. It was found that variation of Al content in Mg alloy could significantly affect the pH of the microenvironment in the primer films and result in the formation of various oxidation products.Item Surface Modifying Amphiphilic Additives for the Improvement of Fouling-Release Properties of Siloxane-Polyurethane Coatings(North Dakota State University, 2022) Benda, JacksonSince mankind has navigated the world’s oceans, marine biofouling has been a persistent problem with several negative economic and environmental consequences. In modern times, the buildup of biofouling causes a significant reduction in vessel speed, leading to increased power consumption, higher costs of operation, and an increase in greenhouse gas emissions. Two of the most widely used protection strategies to combat this highly complex and dynamic phenomenon include the application of biocide containing anti-fouling (AF), or more environmentally friendly non-toxic fouling-release (FR) coatings. Traditional FR coatings utilize low surface energy components such as polydimethylsiloxane (PDMS), but often suffer mechanical failure and poor adhesion to the substrate. Recently, the development of a self-stratifying siloxane-polyurethane (SiPU) FR coating combined the desirable FR properties of PDMS containing materials, with the mechanically durable and tough attributes of a polyurethane. Several methods to improve on the FR properties of these coating systems involved the incorporation of hydrophilic moieties like polyethylene glycol (PEG), zwitterionic polymers, or carboxylic acid containing groups into the SiPU network, producing a heterogenous, amphiphilic surface. These types of amphiphilic surfaces have great potential to become a major component of the next generation of highly performing FR coatings. In this work, the use of non-reactive surface modifying amphiphilic additives (SMAAs) consisting of PDMS and PEG was explored as a viable method for further improvement of FR properties of SiPU coatings, while also maintaining coating integrity in marine environments. Additives with varying amounts of PDMS and PEG content were incorporated at several concentrations in both hydrophobic, and inherently amphiphilic SiPU FR coating systems. It was shown that these additives significantly alter the surface properties and morphology, producing surfaces that improve AF/FR performance against several model marine fouling organisms. The methodologies used for these types of coatings were also applied to a non-FR, polyurethane coating. This allowed for a more fundamental investigation into how these SMAAs are distributed throughout a coating system, and how FR properties arise. Lastly, commonly used FR coatings, including SiPUs, were applied to oil boom fabrics to observe their effect on FR properties and cleanability.Item Highly Functionalized Thermosets from Renewables for Composites and Coatings Applications(North Dakota State University, 2017) Yu, ArvinRenewable sources have attracted attention due to their affordable cost and wide availability. Vegetable oils are renewable sources that have been extensively studied as potential replacement for petroleum derived chemicals. However, vegetable oils tend to produce soft materials with modest properties due to their chemical structure. Consequently, their modifications have been studied to develop high performance materials with improved properties. One of the modifications involves substituting the glycerol core with sucrose to increase the functionality per molecule. Another approach is converting the less reactive internal carbon-carbon double bonds with the more reactive epoxy groups, which permits access to a variety of crosslinking pathways. Epoxidized sucrose soyate (ESS) is a sucrose ester fatty acid (SEFA), which was epoxidized via the Prilezhaev reaction. ESS has a rigid sucrose core and epoxy functionalized fatty acid side chains. The high functionality of ESS was exploited and it was converted to methacrylated and carbonated resins. The methacrylated resins were applied in producing themosets by free-radical polymerizations while the carbonated resins were studied in step-growth polymerizations. Several studies were done to exploit the high functionality of the methacrylated resins: reduction of the viscosity while increasing crosslinkable moieties, introduction of ductility, structure-property relationships, and investigation of resin versatility in photocurable systems. Meanwhile, the carbonated resins were used to form non-isocyanate polyurethane (NIPU) coatings via cyclic carbonate-amine reactions. Overall, the highly functionalized bio-based thermosets showed very promising properties for composites and coatings applications.Item Investigation of Novel Approaches for Improved Amphiphilic Fouling-Release Coatings(North Dakota State University, 2020) Rahimi, AlirezaMarine biofouling has troubled mankind, both environmentally and economically, since they set sail, resulting in many undesired consequences such as increased drag, reduced maneuverability, increased fuel consumption and greenhouse gas emissions, and heightened maintenance costs. This problem is highly complex as it involves more than 4000 marine organisms with varying modes of adhesion and surface preferences as well as many aquatic environments. The common state-of-the-art approaches to contend with marine biofouling on the submerged surfaces of ships in seawater has antifouling (AF) and fouling-release (FR) surfaces. As AF coating systems utilize biocides which are often toxic to the environment to prevent settlement of biofoulants, the endeavors have been shifted towards non-toxic FR marine system. Many FR systems take advantage of low surface energy and modulus polydimethylsiloxane (PDMS) on their surface, while the recent attempts explored the simultaneous effect of PDMS and hydrophilic moieties (i.e. polyethylene glycol (PEG) or zwitterionic polymers) on an FR surface, known as amphiphilic surfaces. Thus, the work in this dissertation focused on attaining amphiphilic surfaces with desirable FR performance. The studies in this dissertation were investigated to deliver two goals: 1) Enhancing the (FR) fouling-release performance of previously developed coating systems; 2) Introducing novel fouling-release marine coatings with set criteria. To address the former, a series of amphiphilic additives containing PDMS and hydrophilic polymers (zwitterionic-based or PEG) were prepared in chapters two-five. These additives were incorporated in several previously developed FR coating systems in order to modify their surfaces and enhance their FR performance. To address the latter, two amphiphilic marine coating systems were explored for accessing durable, non-toxic, and effective FR surfaces using epoxy-amine crosslinking chemistry. Overall, the studies in this dissertation not only demonstrated viable FR surfaces with desirable performance against several representative marine organisms such as N. incerta, U. linza, C. lytica, barnacles, and mussels but also contributed a deeper understanding about the effect of amphiphilicity concentration/balance on surface and FR properties.Item Modification of Diglycidyl Ether of Bisphenol-A Epoxy Primer for Multi-Substrate Application(North Dakota State University, 2022) Chea, GwendorleneTraditional vehicles and aircraft have consisted primarily of steel and aluminum alloys which due to their density, has resulted in various logistic problems including transportation, maneuverability, fuel efficiency. These hindrances have led to a major increase in the incorporation of composites material into this equipment. As the use of these composite increases, multi-substrate coating systems that can provide adequate corrosion protection to metal components, as well as superior adhesion and flexibility to the composites, are needed. The goal of this work is the modification of diglycidyl ether of bisphenol-A epoxy coating systems for improved flexibility and adhesion for the development of multi-substrate primer. For this purpose, commercial additives of various chemistry (liquid rubber, polysulfide, novolac phenolic resins, silane coupling agents, and polyethers) were incorporated into a model epoxy-polyamine coating and their effect on flexibility and adhesion was investigated. Based on their performance, the top-performing additives were incorporated into a fully pigmented modified primer. Overall, the studies in this dissertation not only demonstrated improved flexibility and adhesion to metal and composites but also improved overall corrosion protection compared to an unmodified primer.Item Embedded Reference Electrodes for Corrosion Potential Monitoring, Electrochemical Characterization, and Controlled-Potential Cathodic Protection(North Dakota State University, 2012) Merten, Bobbi Jo ElizabethA thin wire Ag/AgCl reference electrode was prepared using 50 μm Ag wire in dilute FeCl3. The wire was embedded beneath the polyurethane topcoat of two sacrificial coating systems to monitor their corrosion potential. This is the first report of a reference electrode embedded between organic coating layers to monitor substrate health. The embedded reference electrode (ERE) successfully monitored the corrosion potential of Mg primer on AA 2024-T3 for 800 days of constant immersion in dilute Harrison’s solution. Zn primer on steel had low accuracy in comparison. This is in part due to short circuiting by Zn oxidation products, which are much more conductive than Mg corrosion products. Data interpretation was improved through statistical analysis. On average, ERE corrosion potentials are 0.1 to 0.2 V and 0.2 to 0.3 V more positive than a saturated calomel electrode (SCE) in solution for AA 2024-T3 and steel coating systems, respectively. Further research may confirm that ERE obtains corrosion potential information not possible by an exterior, conventional reference electrode. The ERE is stable under polarization. AA 2024-T3 was polarized to -0.95 V vs ERE to emulate controlled potential cathodic protection (CPCP) applications. Polarizations of -0.75 V vs ERE are recommended for future experiments to minimize cathodic delamination. The ERE was utilized to analyze coating mixtures of lithium carbonate, magnesium nitrate, and Mg metal on AA2024-T3. Corrosion potential, low frequency impedance by electrochemical impedance spectroscopy (EIS), and noise resistance by electrochemical noise method (ENM) were reported. Coating performance ranking is consistent with standard electrochemical characterization and visual analyses. The results suggest anti-corrosion resistance superior to a standard Mg primer following 1600 hours of B117 salt spray. Both lithium carbonate and magnesium nitrate are necessary to achieve corrosion protection. Unique corrosion protective coatings for aluminum could be designed through continued mixture optimization. The Ag wire ERE has been utilized for the characterization and ranking of experimental coatings on metal substrates. Structural health monitoring and corrosion potential feedback of cathodic protection systems are additional uses. There is some indication that CPCP may be applied by ERE to control the substrate polarization for an organic coating system.Item Synthesis, Characterization, and Applications of Electroactive Polymeric Nanostructures for Organic Coatings(North Dakota State University, 2015) Suryawanshi, Abhijit JagnnathElectroactive polymers (EAP) such as polypyrrole (PPy) and polyaniline (PANI) are being explored intensively in the scientific community. Nanostructures of EAPs have low dimensions and high surface area enabling them to be considered for various useful applications. These applications are in several fields including corrosion inhibition, capacitors, artificial muscles, solar cells, polymer light emitting diodes, and energy storage devices. Nanostructures of EAPs have been synthesized in different morphologies such as nanowires, nanorods, nanotubes, nanospheres, and nanocapsules. This variety in morphology is traditionally achieved using soft templates, such as surfactant micelles, or hard templates, such as anodized aluminum oxide (AAO). Templates provide stability and groundwork from which the polymer can grow, but the templates add undesirable expense to the process and can change the properties of the nanoparticles by integrating its own properties. In this study a template free method is introduced to synthesize EAP nanostructures of PPy and PANI utilizing ozone oxidation. The simple techniques involve ozone exposure to the monomer solution to produce aqueous dispersions of EAP nanostructures. The synthesized nanostructures exhibit uniform morphology, low particle size distribution, and stability against agglomeration. Ozone oxidation is further explored for the synthesis of silver-PPy (Ag-PPy) core-shell nanospheres (CSNs). Coatings containing PPy nanospheres were formulated to study the corrosion inhibition efficiency of PPy nanospheres. Investigation of the coatings using electrochemical techniques revealed that the PPy nanospheres may provide corrosion inhibition against filiform corrosion by oxygen scavenging mechanism. Finally, organic corrosion inhibitors were incorporated in PPy to develop efficient corrosion inhibiting systems, by using the synergistic effects from PPy and organic corrosion inhibitors.Item Development of Novel Kraft Lignin Resin for Use in Thermoset Materials(North Dakota State University, 2019) Krall, EricVideo summarizing a Ph.D. dissertation for a non-specialist audience.