Effect of Substitutional Oxygen on Properties of Ti3 C2 Tx MXene Produced Using Recycled TiO2 Source.

MXenes are an emerging class of 2D materials with unique properties including metallic conductivity, mechanical flexibility, and surface tunability, which ensure their utility for diverse applications. However, the synthesis of MXenes with high crystallinity and atomic stoichiometry in a low-cost process is still challenging because of the difficulty in controlling the oxygen substitute in the precursors and final products of MXenes, which limits their academic understanding and practical applications. Here, a novel cost-effective method is reported to synthesize a highly crystalline and stoichiometric Ti3 C2 Tx MXene with minimum substitutional oxygen impurities by controlling the amount of excess carbon and time of high-energy milling in carbothermal reduction of recycled TiO2 source. The highest used content (2 wt%) of excess-carbon yields TiC with the highest carbon content and minimal oxygen substitutes, which leads to the Ti3 AlC2 MAX phase with improved crystallinity and atomic stoichiometry, and finally Ti3 C2 Tx MXene with the highest electrical conductivity (11738 S cm-1 ) and superior electromagnetic shielding effectiveness. Additionally, the effects of carbon content and substitutional oxygen on the physical properties of TiC and Ti3 AlC2 are elucidated by density-functional-theory calculations. This inexpensive TiO2 -based method of synthesizing high-quality Ti3 C2 Tx MXene can facilitate large-scale production and thus accelerate global research on MXenes.

Role of Oxygen in the Ti3AlC2 MAX Phase in the Oxide Formation and Conductivity of Ti3C2-Based MXene Nanosheets.

Ti3C2Tx MXene, a two-dimensional transition metal carbide, has attracted substantial interest due to its unique physical properties and a wide range of potential applications. Although the properties of devices using MXene have been substantially enhanced in recent years, it is not fully understood how the oxygen concentration in Ti3AlC2 MAX affects oxide formation in Ti3C2-based MXene nanosheets and their fundamental properties. To this end, we compared two types of MAX phases: MAX with low oxygen content (LO-MAX) and MAX synthesized by a conventional process. Since the conventional MAX synthesis employs metal (Ti) as a primary material, it is referred to as metal-based MAX (MB-MAX) from here. The oxygen content of the LO-MAX was only 0.56 wt %, which was about 20% compared to that of MAX synthesized using conventional methods. We compared the properties of MXene nanosheets prepared from the LO-MAX with MXene nanosheets obtained from the MB-MAX. Microscopic and chemical analyses revealed smooth and wrinkle-free morphology and small amounts of oxygen in MXene nanosheets prepared from LO-MAX (LO-MXene). The LO-MXene nanosheet film exhibited an exceptionally high conductivity of 10,540 S/cm and an ultralow surface roughness of 1.7 nm, which originated from inhibited surface oxide formation. Moreover, the inhibition of oxide formation strengthened the function of -O or -OH groups on the surface of MXene, thereby facilitating strong hydrogen bonding to the polymer with hydroxyl groups. To clearly reveal these properties, we prepared a pressure sensor by coating these MXene nanosheets on nylon/polyester fibers. The fabricated sensor exhibited a high sensitivity of up to 85.6/kPa and excellent stretch stability and reliability. These results clearly revealed that lowering the oxygen content in MAX can make a decisive contribution to improving the fundamental properties of MXene nanosheets prepared therefrom.

Solid solution cermet: (Ti,Nb)(CN)-Ni cermet.

Solid solution powders without W, (Ti,Nb)(CN) powders with a B1 structure (NaCl like), were synthesized by high energy milling and carbothermal reduction in nitrogen. The range of molar ratios of Ti/Nb for forming complete (Ti,Nb)(CN) phase was broader than that of Ti/W for the (Ti,W)(CN) phase because carbide or carbonitride of Nb had a B1 crystal structure identical to Ti(CN) while WC had a hexagonal crystal structure. The results revealed that the hardness of (Ti,Nb)(CN)-Ni cermets was higher than that of (Ti,W)(CN)-Ni cermets. The lower density of the (Ti,Nb)(CN) powder contributed to the higher hardness compared to (Ti,W)(CN) because the volumetric ratio of (Ti,Nb)(CN) in the (Ti,Nb)(CN)-Ni cermets was higher than that of (Ti,Nb)(CN) in the (Ti,W)(CN)-Ni cermets at the same weight ratio of Ni. Additionally, it was assumed that intrinsic the properties of (Ti,Nb)(CN) could also be the cause for the high hardness of the (Ti,Nb)(CN)-Ni cermets.

Solid-solution nanocrystallite formation by high-energy milling.

Solid-solution nanocrystalline powders were prepared by the high-energy milling of Ti alloys with graphite. The B1 structure (NaCl-like structure) phases, (Ti, Cr)C and (Ti, Al)C, were formed during the milling process of Ti-Cr + graphite and Ti-Al + graphite, and the synthetic procedures were investigated in terms of the phase evolution from XRD data. The (Ti, Al)C phase was obtained after milling for 20 hr at BPR = 40:1 (under a more severe condition), while the (Ti, Cr)C phase formed after milling for 20 hr at BPR = 20:1 (a relatively soft condition). The difference in the tendency to create a solid solution with Ti in the B1 structure caused a difference in the synthetic behavior of (Ti, Al)C and (Ti, Cr)C. In other words, (Ti, Cr)C is formed earlier than (Ti, Al)C during milling because the atomic size of Cr (0.166 nm) is similar to that of Ti (0.176 nm), which leads to the straightforward formation of the solid-solution (Ti, Cr)C as compared to when (Ti, Al)C is used. As a result, the crystallite size of the (Ti, Al)C phase (2-3 nm) synthesized at a later stage becomes smaller than that of the (Ti, Cr)C phase (5 10 nm) formed at an earlier stage during milling.

A new method for the identification and quantification of magnetite-maghemite mixture using conventional X-ray diffraction technique.

The electrical explosion of Fe wire in air produced nanoparticles containing the binary mixture of magnetite (Fe(3)O(4)) and maghemite (γ-Fe(2)O(3)). The phase identification of magnetite and maghemite by the conventional X-ray diffraction method is not a simple matter because both have the same cubic structure and their lattice parameters are almost identical. Here, we propose a convenient method to assess the presence of magnetite-maghemite mixture and to further quantify its phase composition using the conventional peak deconvolution technique. A careful step scan around the high-angle peaks as (511) and (440) revealed the clear doublets indicative of the mixture phases. The quantitative analysis of the mixture phase was carried out by constructing a calibration curve using the pure magnetite and maghemite powders commercially available. The correlation coefficients, R(2), for magnetite-maghemite mixture was 0.9941. According to the method, the iron oxide nanoparticles prepared by the wire explosion in this study was calculated to contain 55.8 wt.% maghemite and 44.2 wt.% magnetite. We believe that the proposed method would be a convenient tool for the study of the magnetite-maghemite mixture which otherwise requires highly sophisticated equipments and techniques.