Abstract Hafnium carbide (HfC) is an ultrahigh‐temperature ceramic with high melting point, chemical stability, hardness, and wear resistance. However, its low fracture toughness and poor thermal shock resistance limit its structural applications in extreme environments. In this study, co‐curing of liquid precursors was carried out prior to complete pyrolysis of individual polymeric precursors. First, HfC preceramic polymer precursor was cured, followed by silicon carbonitride (SiCN) precursor curing on a 2D carbon fiber (CF) cloth using the drop‐coating process. The infiltrated CFs were pyrolyzed at 800°C to achieve CF/HfC‐SiCN ceramic mini‐composites. The cross‐linked precursor‐to‐ceramic yield was observed to be as high as 65% when the procedure was carried out in an inert environment. Although stable up to 1200°C, CF/HfC‐SiCN samples demonstrated susceptibility to oxidation at 1500°C in ambient air. The oxidation of HfC in the presence of SiC leads to the formation of a hafnium‐containing silicate (HfxSiyOz) along with hafnia (HfO2). This compound of silicate and hafnia limits oxygen diffusion better than SiO2and HfO2individually. The incorporation of SiCN in HfC ceramic led to improved phase stability compared to a neat HfC system. The results of this study also show that the use of liquid‐phase precursors for HfC and SiCN in the polymer‐infiltrated pyrolysis method is a promising approach to fabricating high‐temperature structural ceramic matrix composites with good oxidation resistance.
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Porous SiOC/SiC ceramics via an active-filler-catalyzed polymer-derived method
In this study, bulk and porous SiOC materials were synthesized via a polymer-derived ceramic (PDC) method from a base polysiloxane (PSO) precursor and an iron (Fe) catalyst under an inert pyrolytic atmosphere. Fe catalyzes not only the formation and nucleation of β-SiC at lower temperatures but also promotes phase separation of the amorphous SiO x C y phase, compared to PDCs without the Fe catalyst. Samples with Fe pyrolyzed at 1100 °C have an appreciable β-SiC content compared to a negligible/unobservable β-SiC content in the corresponding Fe-less samples. Selective etching of the SiO 2 phase shows that Fe also induces segregation of the amorphous SiO x C y phase, yielding larger specific surface areas and gas sorption capability below 1300 °C. At 1500 °C, the pore structure changes to form interconnected networks due to the highly phase separated SiO 2 and β-SiC microstructure. A Gibbs free energy minimization method was used to determine the relative phase content of the pyrolyzed samples, with the effect of Fe quantified with simplified vapor–liquid–solid (VLS), solid–liquid–solid (SLS), and classical nucleation theories.
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- Award ID(s):
- 2024546
- PAR ID:
- 10293442
- Date Published:
- Journal Name:
- Materials Chemistry Frontiers
- Volume:
- 5
- Issue:
- 17
- ISSN:
- 2052-1537
- Page Range / eLocation ID:
- 6530 to 6545
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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