Search

Low-index surfaces and morphologies of cobalt spinel (Co 3 O 4 ) are studied using density functional theory calculations. For each of the surfaces (100), (110), and (111), a set of terminations with different surface compositions and atomic structures are assessed to study their thermodynamic stability under different environmental conditions. Surface energies are calculated as functions of oxygen's chemical potential, which in turn is a function of temperature and partial pressure. We select seven typical shapes of cobalt oxide nanoparticles and compute their free energies of formation using the surface energies of all the surrounding facets. The results show that the shapes of octahedron and cuboctahedron have the lowest Gibbs free energies among the seven shapes for all the environmental conditions being explored. [ABSTRACT FROM AUTHOR]

Hydrogen atmosphere can significantly change the tribological behavior at diamond and diamondlike carbon (DLC) surfaces and the friction-reducing effect depends on the partial pressure of hydrogen. We combined density functional theory modeling and thermodynamic quantities to predict the equilibrium partial pressures of hydrogen at temperature T, PH2 (T), for a fully atomic hydrogen passivated diamond surface. Above the equilibrium PH2 (T), ultralow friction can be achieved at diamond and DLC surfaces. The calculation agrees well with friction tests at various testing conditions. We also show that PH2 (T) increases with temperature; therefore, the temperature effect observed in friction tests should first be treated as an equilibrium factor rather than a kinetic factor. [ABSTRACT FROM AUTHOR]

Niobium‑chromium (Nb Cr) carbide coatings were deposited on graphite using the thermo-reactive deposition and diffusion (TRD) technique. The microstructure, hardness, and coefficient of thermal expansion were characterized to search for the optimal treatment parameters for hard and adherent coatings on graphite. The growth rate increased with treatment temperature for fixed treatment duration and remained constant at a constant temperature for about 6 h. The coatings were found to consist of alternating Nb and Cr layers, and this interesting multilayer structure might be explained by the thermodynamics of oxide reduction and carbide formation reactions. Compared to the single-carbides layer, the hardness of the complex coatings increased from about 2500 HV to above 3000 HV, and displayed a smaller gradient of the depth-dependent hardness from the coating to the substrate. The variation of coefficient of thermal expansion of the samples with temperature was similar to that of the graphite substrate at temperatures from 40 to 450 °C. These results showed the effectiveness of the TRD method for synthesizing hard and adherent carbide coatings on graphite, and for other coating/substrate systems with sharply dissimilar mechanical properties. [Display omitted] • Nb Cr complex carbide layers were formed on graphite materials by the TRD technique for the first time. • The maximum coating thicknesses can reach up to 20 μm, positively correlate with the TRD treatment temperature/time. • The elements distributions and unique alternating Nb Cr multilayer structure in the coatings were reported and discussed. • The coatings showed excellent hardness performance (>2500 HV) with good adhesions to the graphite substrates. [ABSTRACT FROM AUTHOR]

Abstract: The elastic and thermodynamic properties of NiB, Ni2B, Ni3B, orthorhombic Ni4B3(O–Ni4B3), monoclinic Ni4B3(M–Ni4B3), and Ni23B6, are calculated via first-principles method for the Ni–B system. The ground state energies, the full sets of elastic constants and the associated macroscopic elastic parameters of these Ni–B alloys are computed for the first time. Taking contributions from lattice vibrations and thermally excited electrons into account, thermodynamic properties at finite temperatures are then predicted. In addition, we measure the molar heat capacity at constant pressure for NiB and compare the results with the theoretical predictions. Various calculations demonstrate that the first-principles calculation can be used to clarify the diverse experimental data, and provide reliable thermodynamic data. [Copyright &y& Elsevier]

Graphite may store lithium or potassium, but not sodium, in its interlayer space under ambient conditions. It is, however, unclear whether binary alkali alloys of Li-Na, Li-K, and Na-K may substitute pure Li or K to form binary alkali alloy-graphite intercalation compounds. We investigate thermodynamics of the binary alloy-graphite intercalation compounds using density functional theory with van der Waals density functionals. We find Li-rich co-intercalation compounds and K-rich ones are associated with negative formation energies, and the Na-K alloy has the broadest domain of co-intercalation (approximately up to 36% Na). Because of convexity of the formation-energy functions, these compounds are metastable and tend to decompose even when formation energies are negative. Na metal is among the decomposition products. Binary Li-K alloys in graphite form segregated phases of LiC6 and KC8, and this allows one to fabricate Li-K mixed-ion batteries using graphite anodes, whereas Li-Na and Na-K alloys are thermodynamically unfavorable. The study highlights the importance of convexity of formation-energy functions in thermodynamics of alloy-graphite intercalation compounds. [ABSTRACT FROM AUTHOR]

Devices based on AlN generally require adherent and strong interfaces between AlN and other materials, whereas most metals are known to be nonwetting to AlN and form relatively weak interfaces with AlN. In this study, we selected four representative metals (Al, Cu, Ti, and Zr) to study the adhesion strength of the AlN/metal interfaces. Mathematical models were constructed between the adhesion strength and enthalpy of formation of Al–metal solid solutions, the surface energies of the metals, and the lattice mismatch between the metals and AlN, based on thermodynamic parameters calculated using density functional theory. It appears that the adhesion strength is mainly determined by the lattice mismatch, and is in no linear correlation with either the Al–metal solution's formation enthalpies or the metals’ surface energies. We also investigated the nucleation thermodynamics of the four metals on AlN substrates. It was found that Ti forms the strongest interface with AlN, and has the largest driving force for nucleation on AlN substrates among the four metals. [ABSTRACT FROM AUTHOR]

• Multiple terminations of surfaces (10 1 ¯ 0) , (10 1 ¯ 1) , (11 2 ¯ 0) , and (0001) of Y(OH) 3 are established. • Effects of temperature and partial pressure of water and oxygen are included through first-principles thermodynamics. • The equilibrium morphology is of elongated hexagonal bipyramid enclosed by stoichiometric surfaces. Yttrium hydroxide Y(OH) 3 is an important precursor for yttrium oxides, and its morphologies are inherited by the yttrium oxides, thus affecting the products' properties and performance. Hydrothermally synthesized Y(OH) 3 particles are typically elongated hexagonal bipyramid, but thermodynamic parameters are inadequate for quantitative modeling of the morphology. We calculate surface energies and surface stresses of low-index orientations using density functional theory, and present a thermodynamic morphology model based on these parameters. We find that the thermodynamically stable surface terminations are always stoichiometric, and the surface energies are in the order of γ (10 1 ¯ 0) < γ (10 1 ¯ 1) < γ (11 2 ¯ 0) < γ (0001). The equilibrium morphology is of hexagonal prism capped by hexagonal pyramid enclosed by (10 1 ¯ 1) and (10 1 ¯ 0) surfaces. Because these terminations are stoichiometric, varying temperature or pressure is ineffective for modifying Y(OH) 3 particles' morphology, whereas surfactants should be used for this purpose in hydrothermal synthesis. Image, graphical abstract [ABSTRACT FROM AUTHOR]