Effect of boron on the thermodynamic stability of amorphous polymer-derived Si-(B-)-CN ceramics

Amir H. Tavakoli, Jerzy A. Golczewski, Joachim Bill, Alexandra Navrotsky

Research output: Contribution to journalArticlepeer-review

31 Scopus citations


The reason for the higher thermal persistence of amorphous polymer-derived SiBCN ceramics (T ∼ 1700-2000 °C) compared to SiCN ones (T ∼ 1500 °C) has been a matter of debate for more than a decade. Despite recent experimental results which indicate a major kinetic effect of boron on the thermal persistence of the ceramics, no experimental investigation of the thermodynamic stability of the materials has been reported. In this work, we present measured energetics of a series of the amorphous ceramics with various boron contents (0-8.3 at.%) using high-temperature oxidative drop-solution calorimetry. Through measurement of the drop-solution enthalpies in molten sodium molybdate at 811 °C, the formation enthalpies of the amorphous ceramics from crystalline components (SiC, BN, Si 3N 4, C) at 25 °C were obtained and found to be between -1.4 and -26.6 kJ g-atom -1. The determined enthalpy data plus the estimated positive entropy of formation values point to the thermodynamic stability of the amorphous ceramics relative to the crystalline phases, but such stabilization diminishes with increasing boron content. In contrast, the higher boron content increases the temperature of Si 3N 4 crystallization despite less favorable energetics for the amorphous phase, implying more favorable energetics for crystallization. Thus the so-called "stability" of SiBCN ceramics in terms of persistence against Si 3N 4 crystallization appears to be controlled by kinetics rather than by thermodynamic stability.

Original languageEnglish (US)
Pages (from-to)4514-4522
Number of pages9
JournalActa Materialia
Issue number11
StatePublished - Jun 2012
Externally publishedYes


  • Amorphous polymer-derived Si(B)CN ceramics
  • Enthalpy of formation
  • Thermodynamic stability

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Polymers and Plastics
  • Metals and Alloys


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