Persistent Link:
http://hdl.handle.net/10150/228496
Title:
Processing of Ultra High Temperature Ceramics
Author:
Walker, Luke Sky
Issue Date:
2012
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Embargo:
Release after 04-May-2013
Abstract:
For hypersonic flight to enable rapid global transport and allow routine space access thermal protection systems must be developed that can survive the extreme aerothermal heating and oxidation for extended periods of time. Ultra high temperature ceramics (UHTCs) are the only potential materials capable of surviving the extreme hypersonic environment however extensive research in processing science and their oxidation properties are required before engineering systems can be developed for flight vehicles. Investigating the role of oxides during processing of ultra high temperature ceramics shows they play a critical role in both synthesis of ceramic powders and during densification. During spark plasma sintering of UHTCs the oxides can result in the formation of vapor filled pores that limit densification. A low temperature heat treatment can remove the oxides responsible for forming the vapor pores and also results in a significant improvement of the densification through a particle surface physical modification. The surface modification breaks up the native continuous surface oxide increasing the surface energy of the powder and removing the oxide as a barrier to diffusion that must be overcome before densification can begin. During synthesis of UHTCs from sol-gel the B₂O₃ phase acts as the main structure of the gel limiting the transition metal oxide network. While heat treating to form diborides the transition metal oxide undergoes preferential reduction forming carbides that reduce B₂O₃ while at high temperature encourage particle growth and localized extreme coarsening. To form phase pure borides B₂O₃ is required in excessive quantities to limit residual carbides, however carbide reduction and grain growth are connected. When the UHTC systems of ZrB₂-SiC are exposed to oxidation, either as dense ceramics or coatings on Carbon-Carbon composites, at high temperatures they undergo a complex oxidation mechanism with simultaneous material transport, precipitation and evaporation of oxide species that forms a glass ceramic protective oxygen barrier on the surface. The composite effect observed between the oxides of ZrB₂-SiC enables them to survive extreme oxidizing environments where traditional SiC oxidation barrier coatings fail.
Type:
text; Electronic Dissertation
Keywords:
Oxidation Resistance; Powder Processing; Sol-Gel; UHTC; Materials Science & Engineering; Carbon-Carbon; Cermics
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Materials Science & Engineering
Degree Grantor:
University of Arizona
Advisor:
Corral, Erica L.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleProcessing of Ultra High Temperature Ceramicsen_US
dc.creatorWalker, Luke Skyen_US
dc.contributor.authorWalker, Luke Skyen_US
dc.date.issued2012-
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.releaseRelease after 04-May-2013en_US
dc.description.abstractFor hypersonic flight to enable rapid global transport and allow routine space access thermal protection systems must be developed that can survive the extreme aerothermal heating and oxidation for extended periods of time. Ultra high temperature ceramics (UHTCs) are the only potential materials capable of surviving the extreme hypersonic environment however extensive research in processing science and their oxidation properties are required before engineering systems can be developed for flight vehicles. Investigating the role of oxides during processing of ultra high temperature ceramics shows they play a critical role in both synthesis of ceramic powders and during densification. During spark plasma sintering of UHTCs the oxides can result in the formation of vapor filled pores that limit densification. A low temperature heat treatment can remove the oxides responsible for forming the vapor pores and also results in a significant improvement of the densification through a particle surface physical modification. The surface modification breaks up the native continuous surface oxide increasing the surface energy of the powder and removing the oxide as a barrier to diffusion that must be overcome before densification can begin. During synthesis of UHTCs from sol-gel the B₂O₃ phase acts as the main structure of the gel limiting the transition metal oxide network. While heat treating to form diborides the transition metal oxide undergoes preferential reduction forming carbides that reduce B₂O₃ while at high temperature encourage particle growth and localized extreme coarsening. To form phase pure borides B₂O₃ is required in excessive quantities to limit residual carbides, however carbide reduction and grain growth are connected. When the UHTC systems of ZrB₂-SiC are exposed to oxidation, either as dense ceramics or coatings on Carbon-Carbon composites, at high temperatures they undergo a complex oxidation mechanism with simultaneous material transport, precipitation and evaporation of oxide species that forms a glass ceramic protective oxygen barrier on the surface. The composite effect observed between the oxides of ZrB₂-SiC enables them to survive extreme oxidizing environments where traditional SiC oxidation barrier coatings fail.en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
dc.subjectOxidation Resistanceen_US
dc.subjectPowder Processingen_US
dc.subjectSol-Gelen_US
dc.subjectUHTCen_US
dc.subjectMaterials Science & Engineeringen_US
dc.subjectCarbon-Carbonen_US
dc.subjectCermicsen_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineMaterials Science & Engineeringen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorCorral, Erica L.en_US
dc.contributor.committeememberPotter, Barrett G., Jr.en_US
dc.contributor.committeememberLoy, Douglas A.en_US
dc.contributor.committeememberMuralidharan, Krishnaen_US
dc.contributor.committeememberCorral, Erica L.en_US
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