2015
DOI: 10.1021/acs.nanolett.5b03829
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Kinetic Role of Carbon in Solid-State Synthesis of Zirconium Diboride using Nanolaminates: Nanocalorimetry Experiments and First-Principles Calculations

Abstract: Reactive nano-laminates afford a promising route for the low-temperature synthesis of zirconium diboride, an ultrahigh-temperature ceramic with metallic properties. Although the addition of carbon is known to facilitate sintering of ZrB 2 , its effect on the kinetics of the formation reaction has not been elucidated. We have employed a combined approach of nanocalorimetry and first-principles theoretical studies to investigate the kinetic role of carbon in the synthesis of ZrB 2 using B 4 C/Zr reactive nano-la… Show more

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Cited by 13 publications
(16 citation statements)
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“…This qualitative understanding explains the enhanced reactivity of Zr/B RNLs in the presence of C observed in nanocalorimetry experiments. 12,15 Our results suggest that any dopant atoms in the amorphous layers of the RNLs with a strong affinity for Zr and similar in size to B may enhance the amorphization of the Zr lattice and promote intermixing of the constituent layers. From the above results, one would expect N to have a stronger effect than C because the heat of mixing of the Zr−N bond is −233 kJ/mol, compared to −131 kJ/mol for Zr−C 26 (Figure 4b).…”
Section: Resultsmentioning
confidence: 80%
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“…This qualitative understanding explains the enhanced reactivity of Zr/B RNLs in the presence of C observed in nanocalorimetry experiments. 12,15 Our results suggest that any dopant atoms in the amorphous layers of the RNLs with a strong affinity for Zr and similar in size to B may enhance the amorphization of the Zr lattice and promote intermixing of the constituent layers. From the above results, one would expect N to have a stronger effect than C because the heat of mixing of the Zr−N bond is −233 kJ/mol, compared to −131 kJ/mol for Zr−C 26 (Figure 4b).…”
Section: Resultsmentioning
confidence: 80%
“…The accelerated B transport is then a consequence of the enhanced amorphization of the Zr lattice at the Zr/B 4 (C, N) interface, in good agreement with previous nanocalorimetry experiments. 12,14,15 We believe that the enhanced amorphization is caused by the stronger interaction between Zr and C or N than between Zr and B: C or N atoms at the interface distort the Zr lattice more effectively than B. The amorphous layer, in turn, enables faster B diffusion because of its larger free volume.…”
Section: Resultsmentioning
confidence: 99%
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“…All nanocalorimetry measurements were performed using an array of custom micromachined calorimetry sensors designed for combinatorial studies of composition spreads and heat treatments [22,23] (Fig. 1a,b).…”
Section: Nanocalorimetry Devicementioning
confidence: 99%