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Details of the carbothermic reduction/nitridation to synthesize hafnium nitride (HfN) and hafnium carbide (HfC) are scarce in the literature. Therefore, this current study was carried out to evaluate two pathways for synthesizing these two refractory materials: direct nitridation and carbothermic reduction/nitridation. Two mixtures of hafnium dioxide and carbon with C/ HfO2 molar ratios of 2.15 and 3.1 were nitridized directly using flowing nitrogen gas at elevated temperatures (1300−1700 °C). The 3.1 C/HfO2 molar ratio mixture was also carbothermically reduced under flowing argon gas to synthesize HfC, which was converted into HfN by introducing a nitridation step under both N2(g) and N2(g)-10% H2(g). X-ray diffraction results showed the formation of HfN at 1300 and 1400 °C and HfC1−yNy at ≥1400 °C under direct nitridation of samples using a C/HfO2 molar ratio of 2.15. These phase analysis data together with lower lattice strain and greater crystallite sizes of HfC1−yNy that formed at higher temperatures suggested that the HfC1−yNy phase is preferred over HfN at those temperatures. Carbothermic reduction of 3.1 C/HfO2 molar ratio samples under an inert atmosphere produced single-phased HfC with no significant levels of dissolved oxygen. Carbothermic reduction nitridation made two phases of different carbon levels (HfC1−yNy and HfC1−y′Ny′, where y′ < y), while direct nitridation produced a single HfC1−yNy phase under both N2 and N2-10% H2 cover gas environments.
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Molecular Structure and Environment Dependence of Shear-Driven Chemical Reactions: Tribopolymerization of Methylcyclopentane, Cyclohexane and Cyclohexene on Stainless Steel
Tribochemistry, which is another name for mechanochemistry driven by shear, deals with complex and dynamic interfacial processes that can lead to surface wear or formation of beneficial tribofilms. For better mechanistic understanding of these processes, we investigated the reactivity of tribopolymerization of organic molecules with different internal ring strain (methylcyclopentane, cyclohexane, and cyclohexene) on a stainless steel (SS) surface in inert (N2), oxidizing (O2), and reducing (H2) environments at room temperature. On the clean stainless steel surface, precursor molecules were found to physisorb with a broad range of molecular orientations. In inert and reducing environments, the strain-free cyclohexane showed the lowest tribochemical activity among the three molecules tested. Compared to the N2 environment, the tribochemical activity in H2 was suppressed. In the O2 environment, only cyclohexene produced tribofilms and methylcyclopentane while cyclohexane did not. When tribofilms were analyzed with Raman spectroscopy, the spectral features of diamond-like carbon (DLC) or amorphous carbon (a-C) were observed due to photochemical degradation of triboproducts. Based on infrared spectroscopy, tribofilms were found to be organic polymers containing oxygenated groups. Whenever polymeric tribrofilms were produced, wear volume was suppressed by orders of magnitudes but not completely to zero. These results support previously suggested mechanisms which involve surface oxygen as a reactant species in the tribopolymerization process.
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- PAR ID:
- 10475179
- Publisher / Repository:
- Springer
- Date Published:
- Journal Name:
- Tribology Letters
- Volume:
- 71
- Issue:
- 2
- ISSN:
- 1023-8883
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1007/s11249-023-01703-w
