Bottom-Up Synthesis and Mechanical Behavior of Refractory Coatings Made of Carbon Nanotube-Hafnium Diboride Composites

We use aligned carbon nanotube (CNT) forests as scaffolds to deposit hafnium diboride (HfB2) and fabricate millimeter-thick ultrahigh-temperature composite coating. HfB2 has a melting temperature of 3250 °C, which makes it an attractive candidate for applications requiring operation in extreme environments. Compared to typical refractory HfB2 processing, which requires temperatures exceeding 1500 °C, we use conformal HfB2 chemical vapor deposition (CVD) to coat CNT forests at a low temperature of 200 °C. During this process, nanometer-thin HfB2 films grow on the CNT surface and uniformly fill tall CNT forests, thus transforming nanometer film deposition to a scalable HfB2 coating technology. The conformal HfB2 coating process uses static (S-) CVD, where the precursor is fed into a closed system, enabling highly conformal coating and economically efficient utilization of the HfB2 precursor reaching 85%. The modulus and compressive strength of the composites are measured using flat-punch indentation of micropillars having various coating thickness. Filling the CNTs with HfB2 strengthens their node morphology and effectively enhances the mechanical properties. We study the nonlinear behavior of the material to extract a unique modulus value that describes the stress–strain response at any applied compression. At the highest HfB2 coating thickness of 45 nm, the solid fraction is increased from 2% for the bare CNTs to 36% for the composite; the modulus and strength reach 107 and 1.5 GPa, respectively. An analytical model is used to explain the mechanism of the measured structure–mechanical property scaling. Finally, the process is used to fabricate CNT-HfB2 films having 1.7 mm height, a centimeter square area, and only 5.8 × 10–6 nm/nm thickness gradient to demonstrate the potential for scalability.