Fundamental Understanding and Functionality of Silicon Oxycarbide

Silicon oxycarbide (SiOC) is a unique polymer-derived ceramic (PDC) containing silicon, oxygen, and carbon atoms in the form of an amorphous network structure. The phase separation of SiOC is determined by polymeric precursors, pyrolysis temperatures, and atmosphere, which results in different compositions and microstructures. Because of its unique properties (high thermal stability, corrosion resistance, among others), SiOC has numerous applications in fields such as additive manufacturing, lithium-ion batteries, and advanced optics. In the SiOC system, SiO2 nanoclusters can be removed through the etching process, to create nanopores for increasing the surface area. By introducing the SiO2-forming filler (perhydropolysilazane) into SiOC, more SiO2 nanodomains with an average size of 1.72 nm were generated for an ultrahigh surface area of ~2100 m2/g material. Meanwhile, the distributions of domain wall thickness and pore distribution can be calculated by our modified model, to further understand the pore formation. The formation of porous SiOC ceramics with ultrahigh surface areas is greatly desired in numerous applications. Transition metal-containing SiOC composites have more functional properties over pure SiOC and receive more attention in different areas. High-temperature resistant TiC/SiOC was successfully synthesized by pyrolysis of polysiloxane (PSO) and titanium isopropoxide at 1200-1400 °C in argon. It had the first reported conductivity of >1000 S/m for TiC/SiOC ceramics. Nickel-containing SiOC magnetoceramics with soft ferromagnetism was fabricated from a base PSO with the addition of nickel 2,4‐pentanedionate. The effect of water vapor on the phase evolution of Ni/SiOC composites was studied at different pyrolysis temperatures, and the formation of nickel silicides was suppressed by the effect of water vapor during the pyrolysis. Our investigation showed the catalysts from transition metals induced the generation of metal silicides, silicon carbide, and turbostratic carbon with the catalytic activity corresponding to Fe > Co > Ni, which agrees with the activation energy calculation. Also, the phase separation of SiOC was proved to be predominant than local carbothermal reduction. In addition to these findings, a novel approach was developed through the Gibbs free energy minimization method to predict the phase content in PDCs with transition metal additives. And this work provides useful guidance to fabricate the transition metal-containing SiOCs with the desired phase content. Last, the state-of-the-art 4D-STEM technique, collaborated with Lawrence Berkeley National Laboratory, was applied to SiOC ceramics containing amorphous phase. The results showed that 4D-STEM is a valid approach to characterize the nanostructure of the amorphous phase as well as the crystallites. It solves the problem of analyzing SiOC materials at nanoscale due to the disordered atomic arrangement and properties.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Materials Science and Engineering

Department dc:contributor.department

Materials Science and Engineering

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2021

Author dc:creator

• Yang, Ni

Chair dc:contributor.committeechair

• Lu, Peizhen

Committee members dc:contributor.committeemember

• Pickrell, Gary R.
• Reynolds, William T. Jr.
• Bortner, Michael J.

• Polymer-derived ceramics
• silicon oxycarbide
• phase evolution
• high-temperature pyrolysis
• thermophysical property

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

vt_gsexam:28705

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/101789