Preparation of titanium oxycarbide from various titanium raw materials:Part I.Carbothermal reduction

Carbothermal reduction was performed at temperatures up to 1600°C for vanadium-bearing titanomagnetite,ilmenite concentrate,and high titania slag.The possibility of selective carbothermal reduction was discussed in detail from the viewpoint of thermodynamics,and also tested.The products were analyzed by X-ray diffraction,scanning electron microscopy,and chemical analysis.The results show that it is possible to reduce all iron oxide to metallic iron,and titania to oxycarbide（TiCxOy）,without the reduction of other oxides like silica and magnesia.

Thermodynamic and thermoelectric properties of titanium oxycarbide with metal vacancy

Normal titanium oxycarbide exhibits an excellent electrical conductivity and a high carrier concentration of approximately 10^(21) cm^(-3);however,the low Seebeck coefficient limits the thermoelectric application.In this study,first-principle calculations demonstrate that the metal vacancy of titanium oxycarbide weakens the density of state passing through the valence band at the Fermi level,impairing the carrier concentration and enhancing carrier mobility.Thermodynamic analysis justifies the formation of titanium oxycarbide with metal vacancy through solid-state reaction.Transmission electron microscopic images demonstrate the segregation of metal vacancy based on the observation of the defect-rich and single-crystal face-centered cubic regions.Metal vacancy triggers the formation of vacancy-rich and single-crystal face-centered cubic regions.The aggregation of metal vacancy leads to the formation of the vacancy-rich region and other regions with a semi-coherent interface,suppressing the carrier concentration from 1.71×10^(21) to 4.5×10^(20) cm^(-3) and resulting in the Seebeck coefficient from -11μV/K of TiC_(0.5)O_(0.5) to -64μV/K at 1073 K.Meanwhile,vacancies accelerate electron migration from 1.65 to 4.22 cm^(-2)·V^(-1)·s^(-1),maintaining high conductivity.The figure of merit(ZT)increases more than five orders of magnitude via the introduction of metal vacancy,with the maximum figure of 2.11×10^(-2) at 1073 K.These results indicate the potential thermoelectric application of metal-oxycarbide materials through vacancy engineering.

Nb-and Ta-doped(Hf,Zr,Ti)C multicomponent carbides with enhanced oxidation resistance at 2500℃

Enhancing oxidation resistance of multicomponent carbides above 2000℃is critical for their thermal protection applications.For this purpose,novel Nb-and Ta-doped(Hf,Zr,Ti)C multicomponent carbides were designed to improve their oxidation resistance at 2500℃.The results demonstrated that Nb and Ta doping reduced the oxidation rate constant by 16.67%and 25.17%,respectively,thereby significantly improving the oxidation resistance of(Hf,Zr,Ti)C.This enhancement was attributed to the changes in oxycarbide composition and distribution within the oxide layer by adding Nb and Ta.Owing to the different oxidation tendencies of the constituent elements,a distinctive structure was formed in which(Hf,Zr)O_(2)served as a skeleton,and various oxycarbides were dispersed throughout the oxide layer.The doped Nb and Ta were retained within oxycarbides,retarding the diffusion of oxygen into the lattice.More importantly,the addition of Nb and Ta reduced the size of oxycarbides,decreasing both size and quantity of the pores in the oxide layer and facilitating the formation of a more effective oxygen barrier.

Processing and characterization of polymer precursor derived silicon oxycarbide ceramic foams and compacts

This work focused on the fabrication of silicon oxycarbide ceramic(SiOC)foams as well as dense compacts using poly(hydridomethylsiloxane)(PHMS)as a polymer precursor.The room-temperature cross-linking of PHMS was achieved by the addition of 1,4-diazabicyclo[2.2.2]octane(DABCO)with the release of hydrogen gas as a by-product.This resulted in self-blowing of the polymer precursor at room temperature and thereby offered the possibility of producing SiOC foams without the need of any external blowing agents.We also reported the fabrication of crack-free silicon oxycarbide compacts by cold compaction and pyrolysis route using polyvinyl alcohol(PVA)as a processing additive.Cylindrical-shaped pellets were pyrolysed at 1300℃in argon atmosphere with a ceramic yield of approximately 85%.Increased resistance to phase separation and crystallization up to 1400℃was attributed to the presence of large volume fraction of free carbon in the material which was confirmed by Raman spectroscopy.

A HfC nanowire point electron source with oxycarbide surface of lower work function for high-brightness and stable field-emission

Electric field-induced point electron source is highly demanded for microscopy,spectroscopy,lithography,X-ray tubes,microwave devices,and data displays.However,the instability in emission current and requirement of ultrahigh vacuum have often limited its extensive applications.Herewith we report a single-crystalline HfC nanowire with oxycarbide emission surface for stable electron emission at 50 nA with fluctuations less than 1%in a vacuum of 4×10^−7 Pa.The emitter has a low work function of 2.5 eV measured by the field emission Fowler-Nordheim curve and it is in good agreement with density functional theory(DFT)calculations.The energy spread is in a range of 0.21–0.26 eV with a corresponding reduced brightness 1.95×10^11−3.81×10^11 A·m^−2·sr^−1·V^−1.The HfC nanowire with oxycarbide emission surface is a qualified candidate for the next-generation electron source with high brightness,large current,and low energy spread.