Towards lightweight nanocomposite coatings for corrosion inhibition: Graphene, carbon nanotubes, and nanostructured magnesium as case studies
Dennis, Robert Vincent, III
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The field of nanocomposites is a burgeoning area of research due to the interest in the remarkable properties which can be achieved through their use in a variety of applications, including corrosion resistant coatings. Lightweighting is of increasing importance in the world today due to the ever growing push towards energy efficiency and the green movement and in recent years there has been a vast amount of research performed in the area of developing lightweight nanocomposites for corrosion inhibition. Many new composite materials have been developed through the use of newly developed nanomaterials (including carbonaceous and metallic constituents) and their specialized incorporation in the coating matrix materials. We start with a general review on the development of hybrid nanostructured composites for corrosion protection of base metals from a sustainability perspective in Chapter 1. This review demonstrates the ever swelling requirements for a paradigm shift in the way that we protect metals against corrosion due to the costs and environmental concerns that exist with currently used technology. In Chapter 2, we delve into the much required understanding of graphene oxide and reduced graphene oxide through near-edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements to elucidate information about the electronic structure upon incorporation of nitrogen within the structure. For successful integration of the carbonaceous nanomaterials into a composite coating, a full swath of knowledge is necessary. Within this work we have shown that upon chemical defunctionalization of graphene oxide to reduced graphene oxide by means of hydrazine treatment, nitrogen is incorporated into the structure in the form of a pyrazole ring. In Chapter 3, we demonstrate that by way of in situ polymerization, graphene and multiwalled carbon nanotubes can be incorporated within a polymer (polyetherimide, PEI) matrix. Two systems have been developed including graphene and multiwalled carbon nanotubes that act synergistically at a concentration of 2 wt.% each along with graphene at 20 wt.%. The in situ polymerization technique allows for well dispersed carbon nanomaterials within the polymer matrix, which is always a necessary requirement for success as a multifunctional composite coating. After testing in harsh corrosive brine environments these coatings outperformed the polymer by itself and even Zn galvanized steel, lowering the estimated corrosion rate by several orders of magnitude. Chapter 4 displays the possible uses of functionalized carbon nanomaterials in the design of a nanocomposite for corrosion resistance. In this work we establish a method of crosslinking and curing of the polymer matrix using the carbon nanofiller materials as a curing agent through the knowledge partially developed from work outlined in Chapter 2. Here we have used the native functional groups (hydroxyls and carboxylic acids) on graphene oxide and oxidized multiwalled carbon nanotubes to initiate the curing reaction with a well-known commercially available and commonly used epoxy resin. This technology allows for the chemical integration of the nanofiller within the polymer matrix, ensuring excellent dispersion, and also removing the need for often toxic curing agents. The nanocomposites created here have also been tested for their corrosion resistant properties. Concluding with Chapter 5, we exploit some of our previous work on the development of nanostructured magnesium for use in corrosion resistant coatings based on Mg-rich primer technology. It was shown that Mg nanoplatelets allow for a much increased surface area for interaction with the polymer matrix, leading to excellent property enhancement at a significantly reduced pigment volume concentration and coating thickness. These enhancements lead to less material being used, lighter/thinner coatings, and improved performance. These nano Mg-rich primer formulations were shown to protect the underlying steel substrates from corrosion upon breakdown, in the form of a scratch to the metal surface, of the coating; preferentially oxidizing before the iron in steel. The coatings also were found to reduce the corrosion rate by up to 4 orders of magnitude.