Refractory Materials, Volume 7: Transition Metal Carbides and Nitrides discusses the developments in transition metal carbide and nitride research. This volume is organized into nine chapters that emphasize the mechanical and superconducting properties of these compounds. The introductory chapters deal with the general properties, preparation techniques, characterization, crystal chemistry, phase relationships, and thermodynamics of transition metal carbides and nitrides. The following chapter highlights the mechanical properties of these compounds, such as elastic and plastic deformation, fracture, strengthening mechanisms, and hardness. The discussion then shifts to specific electrical and magnetic properties, including electrical resistivity, Hall coefficient, and magnetic susceptibility. A separate chapter is devoted to carbides and nitrides as superconductors. The concluding chapters explore certain theories that explain the mechanisms of band structure and bonding in carbides and nitrides. This volume is of great value to research workers in metallurgy, ceramics, physics, chemistry, and related fields, as well as to advanced students investigating problems concerning high temperature materials or interstitial compounds.
Carbides, nitrides and borides are families of related refractory materials. Traditionally they have been employed in applications associated with engineering ceramics where either high temperature strength or stability is of primary importance. In recent years there has been a growing awareness of the interesting electrical, thermal and optical properties exhibited by these materials, and the fact that many can be prepared as monolithic ceramics, single crystals and thin films. In practical terms carbides, nitrides and borides offer the prospect of a new generation of semiconductor materials, for example, which can function at very high temperatures in severe environmental conditions. However, as yet, we have only a limited understanding of the detailed physics and chemistry of the materials and how the preparation techniques influence the properties. Under the auspices of the NATO Science Committee an Advanced Research Workshop (ARW) was held on the Physics and Chemistry of Carbides, Nitrides and Borides (University of Manchester, 18-22 September, 1989) in order to assess progress to date and identify the most promising themes and materials for future research. An international group of 38 scientists considered developments in 5 main areas: The preparation of powders, monolithic ceramics, single crystals and thin films; Phase transformations, microstructure, defect structure and mass transport; Materials stability; Theoretical studies; Electrical, thermal and optical properties of bulk materials and thin films.
This book describes the rapidly expanding field of two-dimensional (2D) transition metal carbides and nitrides (MXenes). It covers fundamental knowledge on synthesis, structure, and properties of these new materials, and a description of their processing, scale-up and emerging applications. The ways in which the quickly expanding family of MXenes can outperform other novel nanomaterials in a variety of applications, spanning from energy storage and conversion to electronics; from water science to transportation; and in defense and medical applications, are discussed in detail.
Nanostructured materials with tailored properties are regarded as a fundamental element in the development of future science and technology. Research is still ongoing into the nanosized construction elements required to create functional solids. The recently developed technique, nanocasting, has great advantage over others in terms of the synthesis of special nanostructured materials by the careful choice of suitable elements and nanoengineering steps. This new book summarizes the recent developments in nanocasting, including the principles of nanocasting, syntheses of novel nanostructured materials, characterization methods, detailed synthetic recipes and further possible development in this area. The book focuses on the synthesis of porous solids from the viewpoint of methodology and introduces the science of nanocasting from fundamental principles to their use in synthesis of various materials. It starts by outlining the principles of nanocasting, requirements to the templates and precursors and the tools needed to probe matter at the nanoscale level. It describes how to synthesize nano structured porous solids with defined characteristics and finally discusses the functionalization and application of porous solids. Special attention is given to new developments in this field and future perspectives. A useful appendix covering the detailed synthetic recipes of various templates including porous silica, porous carbon and colloidal spheres is included which will be invaluable to researchers wanting to follow and reproduce nanocast materials. Topics covered in the book include: * inorganic chemistry * organic chemistry * solution chemistry * sol-gel and interface science * acid-base equilibria * electrochemistry * biochemistry * confined synthesis The book gives readers not only an overview of nanocasting technology, but also sufficient information and knowledge for those wanting to prepare various nanostructured materials without needing to search the available literature.
Since the isolation and characterization of graphene, there has been a growing interest in 2D materials owing to their unique properties compared to their 3D counterparts. Recently, a family of 2D materials of early transition metal carbides and nitrides, labelled MXenes, has been discovered (Ti2CTz, Ti3C2Tz, Mo2TiC2Tz, Ti3CNTz, Ta4C3Tz, Ti4N3Tz among many others), where T stands for surface-terminating groups (O, OH, and F). MXenes are mostly produced by selectively etching A layers (where A stands for group A elements, mostly groups 13 and 14) from the MAX phases. The latter are a family of layered ternary carbides and/or nitrides and have a general formula of Mn+1AXn (n = 1-3), where M is a transition metal and X is carbon and/or nitrogen. The produced MXenes have a conductive carbide core and a non-conductive O-, OH- and/or F-terminated surface, which allows them to work as electrodes for energy storage applications, such as Li-ion batteries and supercapacitors. Prior to this work, MXenes were produced in the form of flakes of lateral dimension of about 1 to 2 microns; such dimensions and form are not suitable for electronic characterization and applications. I have synthesized various MXenes (Ti3C2Tz, Ti2CTz and Nb2CTz) as epitaxial thin films, a more suitable form for electronic and photonic applications. These films were produced by HF, NH4HF2 or LiF + HCl etching of magnetron sputtered epitaxial Ti3AlC2, Ti2AlC, and Nb2AlC thin films. For transport properties of the Ti-based MXenes, Ti2CTz and Ti3C2Tz, changing n from 1 to 2 resulted in an increase in conductivity but had no effect on the transport mechanism (i.e. both Ti3C2Tx and Ti2CTx were metallic). In order to examine whether the electronic properties of MXenes differ when going from a few layers to a single flake, similar to graphene, the electrical characterization of a single Ti3C2Tz flake with a lateral size of about 10 μm was performed. These measurements, the first for MXene, demonstrated its metallic nature, along with determining the nature of the charge carriers and their mobility. This indicates that Ti3C2Tz is inherently of 2D nature independent of the number of stacked layers, unlike graphene, where the electronic properties change based on the number of stacked layers. Changing the transition metal from Ti to Nb, viz. comparing Ti2CTz and Nb2CTz thin films, the electronic properties and electronic conduction mechanism differ. Ti2CTz showed metallic-like behavior (resistivity increases with increasing temperature) unlike Nb2CTz where the conduction occurs via variable range hopping mechanism (VRH) - where resistivity decreases with increasing temperature. Furthermore, these studies show the synthesis of pure Mo2CTz in the form of single flakes and freestanding films made by filtering Mo2CTz colloidal suspensions. Electronic characterization of free-standing films made from delaminated Mo2CTz flakes was investigated, showing that a VRH mechanism prevails at low temperatures (7 to ≈ 60 K). Upon vacuum annealing, the room temperature, RT, conductivity of Mo2CTx increased by two orders of magnitude. The conduction mechanism was concluded to be VRH most likely dominated by hopping within each flake. Other Mo-based MXenes, Mo2TiC2Tz and Mo2Ti2C3Tz, showed VRH mechanism at low temperature. However, at higher temperatures up to RT, the transport mechanism was not clearly understood. Therefore, a part of this thesis was dedicated to further investigating the transport properties of Mo-based MXenes. This includes Mo2CTz, out-of-plane ordered Mo2TiC2Tz and Mo2Ti2C3Tz, and vacancy ordered Mo1.33CTz. Magneto-transport of free-standing thin films of the Mo-based MXenes were studied, showing that all Mo-based MXenes have two transport regimes: a VRH mechanism at lower temperatures and a thermally activated process at higher temperatures. All Mo-based MXenes except Mo1.33CTz show that the electrical transport is dominated by inter-flake transfer. As for Mo1.33CTz, the primary electrical transport mechanism is more likely to be intra-flake. The synthesis of vacancy ordered MXenes (Mo1.33CTz and W1.33CTz) raised the question of possible introduction of vacancies in all MXenes. Vacancy ordered MXenes are produced by selective etching of Al and (Sc or Y) atoms from the parent 3D MAX phases, such as (Mo2/3Sc1/3)2AlC, with in-plane chemical ordering of Mo and Sc. However, not all quaternary parent MAX phases form the in-plane chemical ordering of the two M metals; thus the synthesis of the vacancy-ordered MXenes is restricted to a very limited number of MAX phases. I present a new method to obtain MXene flakes with disordered vacancies that may be generalized to all quaternary MAX phases. As proof of concept, I chose Nb-C MXene, as this 2D material has shown promise in several applications, including energy storage, photothermal cell ablation and photocatalysts for hydrogen evolution. Starting from synthetizing (Nb2/3Sc1/3)2AlC quaternary solid solution and etching both the Sc and Al atoms resulted in Nb1.33C material with a large number of vacancies and vacancy clusters. This method may be applicable to other quaternary or higher MAX phases wherein one of the transition metals is more reactive than the other, and it could be of vital importance in applications such as catalysis and energy storage.
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