Effects of Zr on the precursor architecture and high-temperature nanostructure evolution of SiOC polymer-derived ceramics

Liu, Chen; Pan, Ruiqun; Hong, Changqing; Zhang, Xinghong; Han, Wenbo; Han, Jiecai; Du, Shiyu

doi:10.1016/j.jeurceramsoc.2015.09.009

Cited by 49 publications

(38 citation statements)

References 38 publications

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“…Their growth is also limited by low diffusion. These results are in good agreement with previous reported SiOC PDC . In the CS pattern, the peak detected at 26.6° is attributed to the (002) reflection of graphitic carbon (JCPDS Card No.…”

Section: Resultssupporting

confidence: 93%

“…This band is composed of two transverse optical (TO) resonant modes, an intense one attributed to TO1 Si–O–Si stretching mode at 1090 cm −1 , and a shoulder identified as TO2 Si–O–Si stretching mode around 1200 cm −1 . The absorption band of Si–C is observed between 747 and 855 cm −1 . The Si–C stretching observed is quite weak for S1200 and begins to increase at temperature above 1450°C, owing to the beginning of carbothermal reduction.…”

Section: Resultsmentioning

confidence: 99%

“…Raman spectroscopy was performed to analyze structural evolution of the free carbon phase (Figure ). The Raman spectrum exhibits two major bands attributed to the D band (~1355 cm −1 ) and G band (~1608 cm −1 ) of the free carbon phase, which are assigned to the disordered carbon (turbostratic carbon layers or nanographitic domains) and graphitized carbon (in‐plane displacement of carbon atoms in hexagonal carbon sheets), respectively . These bands can vary in intensity, position, and width depending on the structural ordering of carbon, and the relative parameters are listed in Table .…”

Section: Resultsmentioning

confidence: 99%

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Structure and energetics of SiOC and SiOC‐modified carbon‐bonded carbon fiber composites

et al. 2017

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The incorporation of SiOC polymer-derived ceramics into porous carbon materials could provide tailored shapeable, mechanical, electrical, and oxidation-resistant properties for high-temperature applications. Understanding the thermodynamic and kinetic stability of such materials is crucial for their practical application. We report here the dependence of structures and energetics of SiOC and SiOC-modified carbon-bonded carbon fiber composites (CBCFs) on the pyrolysis temperature using spectroscopic methods and high-temperature oxide melt solution calorimetry. The results indicate that a SiOC ceramic pyrolyzed at 1200°C and 1600°C is energetically stable with respect to an isocompositional mixture of cristobalite, silicon carbide, and graphite by 4.9 and 10.3 kJ/mol, respectively, and more energetically stable than that pyrolyzed at 1450°C. Their thermodynamic stability is related to their structural evolution. SiOC-modified CBCFs become energetically less stable with increasing preparation temperature and concomitant increase in excess carbon content. K E Y W O R D S silicon oxycarbide, structure, thermodynamics

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Section: Resultssupporting

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Structure and energetics of SiOC and SiOC‐modified carbon‐bonded carbon fiber composites

et al. 2017

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“…The first paper describing the modification of Si-H functional siloxane copolymer with zirconium alkoxides has recently been published. [21] Zirconium-containing polysiloxane gel was prepared by sol-gel method involving the hydrolysis of methyltriethoxysilane and methyldiethoxysilane in a water/ethanol solvent followed by reaction with zirconium tetrapropoxide at 80 °C. The FTIR spectrum of this product showed complete conversion of Si-H functional groups.…”

Section: Doi: 101002/marc202000601mentioning

confidence: 99%

“…The broad ZrOCH 2 -signal is consistent with a high ligand exchange rate. [23] We expected that the reaction of Zr(O n Pr) 4 with a polysiloxane containing SiH groups would lead to the generation of alkoxy-and siloxy-zirconate groups on the copolymer as a result of its hydride substitution [21] as well as possible chain scission. The zirconium contained in the reaction system promotes the hydrolytic condensation of the formed groups, leading to crosslinking of the prepolymer and the formation of a composite with uniformly incorporated zirconium atoms.…”

Section: Doi: 101002/marc202000601mentioning

confidence: 99%

Reactions of Zirconium (IV) n‐Propoxide with SiH‐Functional Polysiloxanes as a Route to Siloxane–Zirconium Hybrid Materials with Enhanced Refractive Index

Rubinsztajn

Chojnowski

Mizerska

et al. 2020

Macromol. Rapid Commun.

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The reaction of poly(hydromethylsiloxane‐co‐methylphenylsiloxane) with zirconium (IV) n‐propoxide in dry toluene leads to extensive scission of the siloxane chain and conversion of Si‐H groups. These processes produce oligomeric siloxanes and organosilanes containing moisture sensitive propoxy and siloxy‐zirconate groups. The obtained post‐reaction solution of zirconium containing heterosiloxane oligomers is stable under anhydrous conditions for several weeks. However, its exposure to moisture initiates the hydrolytic condensation of the reactive groups leading to cross‐linking and the formation of a siloxane–zirconium composite. Spin coating of the siloxane–zirconium prepolymer followed by exposure to moisture produces thin films with excellent light transparency and increased refractive index. The final coatings are characterized by ellipsometry, UV–Vis, IR, and 29Si MAS NMR spectroscopies.

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SiCO Ceramics as Storage Materials for Alkali Metals/Ions: Insights on Structure Moieties from Solid‐State NMR and DFT Calculations

et al. 2023

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Polymer‐derived silicon oxycarbide ceramics (SiCO) have been considered as potential anode materials for lithium‐ and sodium‐ion batteries. To understand their electrochemical storage behavior, detailed insights into structural sites present in SiCO are required. In this work, the study of local structures in SiCO ceramics containing different amounts of carbon is presented. 13C and 29Si solid‐state MAS NMR spectroscopy combined with DFT calculations, atomistic modeling, and EPR investigations, suggest significant changes in the local structures of SiCO ceramics even by small changes in the material composition. The provided findings on SiCO structures will contribute to the research field of polymer‐derived ceramics, especially to understand electrochemical storage processes of alkali metal/ions such as Na/Na+ inside such networks in the future.

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Effects of Zr on the precursor architecture and high-temperature nanostructure evolution of SiOC polymer-derived ceramics

Cited by 49 publications

References 38 publications

Structure and energetics of SiOC and SiOC‐modified carbon‐bonded carbon fiber composites

Structure and energetics of SiOC and SiOC‐modified carbon‐bonded carbon fiber composites

Reactions of Zirconium (IV) n‐Propoxide with SiH‐Functional Polysiloxanes as a Route to Siloxane–Zirconium Hybrid Materials with Enhanced Refractive Index

SiCO Ceramics as Storage Materials for Alkali Metals/Ions: Insights on Structure Moieties from Solid‐State NMR and DFT Calculations

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