MAX phases are layered hexagonal early transition metal carbides, sometimes nitrides, where M is an early transition metal, A is an A group element, most prominently groups 13 or 14, and X is either carbon or nitrogen.1 They are gaining a lot of attention because of their unusual properties. Particularly, their hardness, chemical stability at room temperature, and high melting points. These properties provide a material that is viable for a wide range of demanding applications.2,3 MAX phases display a combination of both ceramic and metallic characteristics. Furthermore, they also serve as a precursor for two-dimensional MXenes.4,5<br/>Generally, bulk synthesis of MAX phases is done through traditional solid state synthesis techniques. For example, three solid state synthesis techniques include solid state method, hot pressing and arc melting and annealing. During solid state method, the powder precursors are preheated between 350 and 400°C, allowing for decomposition of starting reagents and removal of volatile products leaving only the oxides. At this point the germination phase has completed, and the crystal growth phase begins. Under the effect of a concentration gradient and very high temperatures, cations migrate, forming well-ordered layers. Slow cooling rates are used in order to ensure crystallinity of the product.6 The second method, hot pressing, involves the mixing of powder precursors thoroughly and then cold pressed into a green body – a ceramic body powder pre-sintering. They are then heated under vacuum and often high pressure in order to form the product. Two variants of hot-pressing exits: reactive hot pressing, where the pressure during the reaction will vary throughout the reaction, and isostatic hot pressing, where the pressure is held constant throughout the entire reaction.7 Another solid-state technique is arc melting and annealing. During arc melting, alternating current is applied to the electrode inside an inert reactor, which is arranged as to generate an arc discharge. The heat produced by arcing causes rapid melting of the samples.8 While these methods are most common, they are not always viable due to the specialized equipment required in order to achieve the high temperature and pressure conditions. Furthermore, these specific techniques don’t allow for high control over particle size and morphology. <br/>Because of this, alternative, non-conventional synthesis techniques have been developed involving more readily available tube furnaces and microwaves, which lack the extreme pressures instead opting for ambient conditions.9 Sol-gel techniques have been developed by the group of Christina Birkel, and have successfully produced MAX phases through calcination of homogeneous citric acid-based gel-precursors. Some advantages of using these gel-precursors include shorter diffusion paths, and faster mass transport, thus, resulting in lower reaction temperatures and shorter reaction times. Ultimately, this allows for control over particle morphology and size.10<br/>The focus of this work is to discover optimal synthesis conditions to create spherical Cr2GaC. Spherical MAX phases have been briefly explored in existing literature using polymer-based hollow microsphere templates.10 These polymer microspheres have been used to synthesize spherical metal oxides. This is achieved by heating the metal oxide precursors which adhere to the spheres, then by thermal treatment, the template is then removed.11 <br/>Two different microsphere templates will be explored to study the advantages and disadvantages of different size distributions and surface conditions of the spheres. Furthermore, reaction temperature, reaction time, citric acid equivalents, and gel to microsphere ratio will be altered to determine optimal synthesis parameters for depositing Cr2GaC onto spherical templates. Cr2GaC serves as a model compound because it has been successfully synthesized through sol-gel chemistry in the past.10 This phase will be prepared through non-conventional sol-gel chemistry, with various heating profiles, both furnace and microwave, and will be characterized through X-ray diffraction (XRD), and Rietveld refinement. Further, the morphology and atomic composition will be analyzed through scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS).
This project aimed to understand the effects of composition and phase distribution on the corrosion behavior of magnesium-aluminum (Mg-Al) alloys in an ionic liquid electrolyte. The purpose of studying corrosion in nonaqueous ILs is to determine the anodic dissolution behaviors of the alloy phases without the interference of side reactions that occur in aqueous electrolytes, such as di-oxygen or water reduction. Three commercial Mg-Al alloys were studied: AZ91D (9% Al), AM60 (6% Al), and AZ31B (3% Al). An annealed alloy containing solid-solution α-phase Mg-Al with 5 at% aluminum content (Mg5Al) was also used. The ionic liquid chosen for this project was 1:2 molar ratio choline-chloride:urea (cc-urea), a deep eutectic solvent. After potentiostatic corrosion in cc-urea, the magnesium alloys were found to form a high surface area porous morphology as corrosion duration increased. This morphology consists of aluminum-rich ridges formed by Al nanowires surrounding an aluminum-poor base area, but with an overall increase in surface Al composition, indicating selective dealloying of the Mg in cc-urea and redistribution of the Al on the surface. Further work will focus on the development of hydrophobic coatings using ionic liquids.
Everything seemed poised against any proposed physical and experimental stability of a structure like graphene. “Thermodynamically impossible”– a not uncommon shutdown to proposed novel physical or chemical concepts– was once used to describe the entire field of proposed two-dimensional crystals functioning separately from a three-dimensional base or crystalline structure. Rudolf Peierls and Lev Davoidovich Landau, both very accomplished physicists respectively known for the Manhattan Project and for developing a mathematical theory of helium superfluidity, rejected the possibility of isolated monolayer to few-layered crystal lattices. Their reasoning was that diverging thermodynamic-based crystal lattice fluctuations would render the material unstable regardless of controlled temperature. This logic is flawed, but not necessarily inaccurate– diamond, for instance, is thermodynamically metastable at room temperature and pressure in that there exists a slow (i.e. slow on the scale of millions of years) but continuous transformation to graphite. However, this logic was used to support an explanation of thermodynamic impossibility that was provided for graphene’s lack of isolation as late as 1979 by Cornell solid-state physicist Nathaniel David Mermin. These physicists’ claims had clear and consistent grounding in experimental data: as thin films become thinner, there exists a trend of a decreasing melting temperature and increasing instability that renders the films into islands at somewhere around ten to twenty atomic layers. This is driven by the thermodynamically-favorable minimization of surface energy.