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Surface modification is used to dramatically alter the thermal properties of a bulk metallic material. Thermal barrier coatings (TBCs) are typically applied using spray deposition or laser-based techniques to create a ceramic coating on a metal substrate. In this study, an effective TBC is created directly on a metallic substrate by inducing surface chemical reactions. Aluminum-zirconium (Al-Zr) substrates are used to induce surface-limited reactions that produce a 75-80% decrease in bulk thermal conductivity and diffusivity, respectively. The substrates are cylindrical disks 12.6 mm diameter and 2 mm thickness. Thermal properties are measured using laser flash analysis (LFA) at incrementally elevated temperatures. Focused ion beam (FIB) slicing of the substrate coupled with scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) show that the substrate oxidized only along the outer 20 μm of the bulk surface. The layer thickness is significantly less than typical TBCs that can range from 50 to 300 μm yet the 20 μm coating still achieves a dramatic reduction in thermal transport properties. Additionally, thermal analysis reveals a sequence of exothermic reactions starting at 439 °C that include both intermetallic (i.e., ZrAl3) and oxidation (i.e., Al2O3 and ZrO) reactions suggesting continuous surface bonding at the coating-metal interface. The onset of exothermic activity coincides with the transition in thermal properties measured using LFA. These results show that surface oxidation reactions could be used to dramatically alter the thermal transport properties of a metal substrate.