Hydrogen bonding in glassy trehalose-water system: Insights from density functional theory and molecular dynamics simulations.

We report a detailed density functional theory and molecular dynamics study of hydrogen bonding between trehalose and water, with a special emphasis on interactions in the amorphous solid state. For comparison, water-water interactions in water dimers and tetramers are evaluated using quantum calculations. The results show that the hydrogen bonding energy is dependent not only on the geometry (bond length and angle) but also on the local environment of the hydrogen bond. This is seen in quantum calculations of complexes in vacuum as well as in amorphous solid states with periodic boundary conditions. The temperature-induced glass transition in the trehalose-water system was studied using molecular dynamics simulations with varying cooling and heating rates. The obtained parameters of the glass transition are in good agreement with the experiments. Moreover, the dehydration of trehalose in the glassy state was investigated through a gradual dehydration with multiple small steps under isothermal conditions. From these simulations, the values of water sorption energy at different temperatures were obtained. The partial molar enthalpy of mixing of water value of -18 kJ/mol found in calorimetric experiments was accurately reproduced in these simulations. These findings are discussed in light of the hydrogen bonding data in the system. We conclude that the observed exothermic effect is due to different responses of liquid and glassy matrices to perturbations associated with the addition or removal of water molecules.

Grain Size-Dependent Thermal Expansion of Nanocrystalline Metals.

In the present work, we have used classical molecular dynamics and quantum mechanical density functional theory modeling to investigate the grain size-dependent thermal expansion coefficient (CTE) of nanocrystalline Cu. We find that the CTE increases by up to 20% with a gradually decreasing grain size. This behavior emerges as a result of the increased population of occupied anti-bonding states and bond order variation in the grain boundary regions, which contribute to the reduced resistance against thermally-induced bond stretching and dictate the thermal expansion behavior in the small grain size limit. As a part of the present work, we have established a procedure to produce ab initio thermal expansion maps that can be used for the prediction of the grain size-dependent CTE. This can serve as a modeling tool, e.g., to explore the impact of grain boundary impurity segregation on the CTE.

Kinetically Limited Phase Formation of Pt-Ir Based Compositionally Complex Thin Films.

The phase formation of PtIrCuAuX (X = Ag, Pd) compositionally complex thin films is investigated to critically appraise the criteria employed to predict the formation of high entropy alloys. The formation of a single-phase high entropy alloy is predicted if the following requirements are fulfilled: 12 J∙K-1 mol-1 ≤ configurational entropy ≤ 17.5 J∙K-1 mol-1, -10 kJ∙mol-1 ≤ enthalpy of mixing ≤ 5 kJ∙mol-1 and atomic size difference ≤ 5%. Equiatomic PtIrCuAuX (X = Ag, Pd) fulfill all of these requirements. Based on X-ray diffraction and energy-dispersive X-ray spectroscopy data, near-equiatomic Pt22Ir23Cu18Au18Pd19 thin films form a single-phase solid solution while near-equiatomic Pt22Ir23Cu20Au17Ag18 thin films exhibit the formation of two phases. The latter observation is clearly in conflict with the design rules for high entropy alloys. However, the observed phase formation can be rationalized by considering bond strengths and differences in activation energy barriers for surface diffusion. Integrated crystal orbital Hamilton population values per bond imply a decrease in bond strength for all the interactions when Pd is substituted by Ag in PtIrCuAuX which lowers the surface diffusion activation energy barrier by 35% on average for each constituent. This enables the surface diffusion-mediated formation of two phases, one rich in Au and Ag and a second phase enriched in Pt and Cu. Hence, phase formation in these systems appears to be governed by the complex interplay between energetics and kinetic limitations rather than by configurational entropy.

Molecular Coverage Determines Sliding Wear Behavior of n-Octadecylphosphonic Acid Functionalized Cu-O Coated Steel Disks against Aluminum.

The sliding wear behavior of Cu-O coated steel disks functionalized with n-octadecyl-phosphonic acids was evaluated against aluminum in ball-on-disk tribometer experiments. After 5 m of sliding the friction coefficient of the functionalized sample with maximum molecular coverage is ≤0.3 ± 0.1. Surfaces with lower coverage mitigate friction and wear as well exhibiting initially similar low friction coefficients but reveal the breakdown of lubrication for sliding distances <5 m. The length of the low friction sliding distance before breakdown scales with the coverage of n-octadecylphosphonic acids on the Cu-O surface. Coverage hence determines the tribological behavior of the functionalized surface against sliding aluminum. As the coverage is increased, detrimental asperity contacts between the rubbing surfaces are reduced.

Effect of chemical composition, defect structure, and stress state on the elastic properties of (V1-x Al x )1-y N y .

For (V1-x Al x )1-y N y  an extensive and theoretically unexplained spread in experimentally obtained elastic moduli ranging from 254 to 599 GPa is reported in literature. To identify its origin, the effect of chemical composition (0 ⩽ x ⩽ 0.75), non-metal to metal ratio (N/M-ratio: 0.48 ⩽ y  ⩽ 0.52), and stress state (-6 ⩽ σ ⩽ 2 GPa) on the elastic modulus at room temperature is studied sytematically by density functional theory employing the Debye-Grüneisen model. As the Al concentration is increased from x = 0 to x = 0.75, strong Al-N sp3d2 hybridization causes an increase in elastic modulus of 26%. The effect of the N/M-ratio on the elastic properties is also Al content dependent. As y  is increased from y  = 0.50 to y  = 0.52, decreasing bond distance upon vacancy formation causes an anomalous increase in the elastic modulus of 6% for V1-y N y , while a decrease in elastic modulus of up to 5% occurs for (V1-x Al x )1-y N y . A stress state variation from +2 to -6 GPa increases the elastic modulus e.g. for (V0.5Al0.5)0.5N0.5 by 70 GPa and hence 13% due to shifts in density of states towards lower energies implying bond strengthening. Thus, it is suggested that the extensive spread of 58% in reported elastic moduli for (V1-x Al x )1-y N y  can at least in part be rationalized based on variations in chemical composition, off-stoichiometry induced point defects, and stress state.

First Principles Investigation of Anomalous Pressure-Dependent Thermal Conductivity of Chalcopyrites.

The effect of compression on the thermal conductivity of CuGaS2, CuInS2, CuInTe2, and AgInTe2 chalcopyrites (space group I-42d) was studied at 300 K using phonon Boltzmann transport equation (BTE) calculations. The thermal conductivity was evaluated by solving the BTE with harmonic and third-order interatomic force constants. The thermal conductivity of CuGaS2 increases with pressure, which is a common behavior. Striking differences occur for the other three compounds. CuInTe2 and AgInTe2 exhibit a drop in the thermal conductivity upon increasing pressure, which is anomalous. AgInTe2 reaches a very low thermal conductivity of 0.2 W·m-1·K-1 at 2.6 GPa, being beneficial for many energy devices, such as thermoelectrics. CuInS2 is an intermediate case. Based on the phonon dispersion data, the phonon frequencies of the acoustic modes for CuInTe2 and AgInTe2 decrease with increasing pressure, thereby driving the anomaly, while there is no significant pressure effect for CuGaS2. This leads to the negative Grüneisen parameter for CuInTe2 and AgInTe2, a decreased phonon relaxation time, and a decreased thermal conductivity. This softening of the acoustic modes upon compression is suggested to be due to a rotational motion of the chalcopyrite building blocks rather than a compressive oscillation. The negative Grüneisen parameters and the anomalous phonon behavior yield a negative thermal expansion coefficient at lower temperatures, based on the Grüneisen vibrational theory.

Synthesis of Intermetallic (Mg1-x,Alx)2Ca by Combinatorial Sputtering.

The synthesis-composition-structure relationship in the Mg-Ca-Al system is studied using combinatorial magnetron sputtering. With increasing deposition temperature, a drastic decrease in Mg concentration is obtained. This behavior can be understood based on density functional theory calculations yielding a desorption energy of 1.9 eV/atom for Mg from a hexagonal Mg nanocluster which is far below the desorption energy of Mg from a Mg2Ca nanocluster (3.4 eV/atom) implying desorption of excess Mg during thin film growth at elevated temperatures. Correlative structural and chemical analysis of binary Mg-Ca thin films suggests the formation of hexagonal Mg2Ca (C14 Laves phase) in a wide Mg/Ca range from 1.7 to 2.2, expanding the to date reported stoichiometry range. Pronounced thermally-induced desorption of Mg is utilized to synthesize stoichiometric (Mg1-x,Alx)2Ca thin films by additional co-sputtering of elemental Al, exhibiting a higher desorption energy (6.7 eV/atom) compared to Mg (3.4 eV/atom) from Mg2Ca, which governs its preferred incorporation during synthesis. X-ray diffraction investigations along the chemical gradient suggest the formation of intermetallic C14 (Mg1-x,Alx)2Ca with a critical aluminum concentration of up to 23 at.%. The introduced synthesis strategy, based on the thermally-induced desorption of weakly bonded species, and the preferential incorporation of strongly bonded species, may also be useful for solubility studies of other phases within this ternary system as well as for other intermetallics with weakly bonded alloying constituents.

From qualitative to quantitative description of the anomalous thermoelastic behavior of V, Nb, Ta, Pd and Pt.

To study the anomalous thermoelastic behavior of bcc V, Nb, Ta as well as fcc Pd and Pt a density functional theory (DFT) based model is used, which allows for the calculation of the elastic constant [Formula: see text] and [Formula: see text] as a function of temperature. Available experimental [Formula: see text] trends are correctly reproduced indicating that the electronic structure mechanisms enabling anomalous behavior are captured by the model. A DFT based correlative investigation between V, Nb, Ta, Pd and Pt with anomalous thermoelastic properties and Mo and Cu with ordinary behavior reveals a high density of states (DOS) at the Fermi level to be a necessary but not sufficient condition for an anomalous thermoelastic behavior. In addition, anomalous metals in contrast to ordinary metals reallocate electronic states in the vicinity of the Fermi level upon lattice distortion, causing an increase in bond strength as identified by crystal orbital Hamilton population (COHP) analysis. Hence, we have identified the combination of high DOS and electronic reallocation upon lattice distortion to be the physical origin for anomalous thermoelastic behavior in metals. The absence of an anomaly for [Formula: see text]-type distortion in V, Nb, Ta, Pd and Pt is suggested to be due to the less pronounced reallocation of states compared to [Formula: see text]-type distortion.

Tuneable thermal expansion of poly (3,4-ethylenedioxythiophene) polystyrene sulfonate.

Linear coefficient of thermal expansion is calculated for a mixture of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT:PSS) using density functional theory and the Debye-Grüneisen model. The linear coefficient of thermal expansion is a key factor in thermal management (thermal conductivity, thermal stress and thermal fatigue) of microelectronic and energy devices, being common applications of the conjugated polymeric PEDOT:PSS system. The obtained value of 53 × 10-6 K-1 at room temperature can be rationalised based on the electronic structure analysis. The PEDOT and PSS units are bonded by a dipole-dipole interaction between S in PEDOT and H in PSS. A C-C bond in a benzene ring (PSS) or thiophene (PEDOT) is up to 13 times stronger than the S-H bond. By adjusting the population of the S-H bonds by deprotonating PSS, the linear coefficient of thermal expansion can be enhanced by 57%. This allows for tuning the thermal properties of PEDOT:PSS in cutting-edge devices.

Crystallite size-dependent metastable phase formation of TiAlN coatings.

It is well known that surface energy differences thermodynamically stabilize nanocrystalline γ-Al2O3 over α-Al2O3. Here, through correlative ab initio calculations and advanced material characterization at the nanometer scale, we demonstrate that the metastable phase formation of nanocrystalline TiAlN, an industrial benchmark coating material, is crystallite size-dependent. By relating calculated surface and volume energy contributions to the total energy, we predict the chemical composition-dependent phase boundary between the two metastable solid solution phases of cubic and wurzite Ti1-xAlxN. This phase boundary is characterized by the critical crystallite size d critical . Crystallite size-dependent phase stability predictions are in very good agreement with experimental phase formation data where x was varied by utilizing combinatorial vapor phase condensation. The wide range of critical Al solubilities for metastable cubic Ti1-xAlxN from x max = 0.4 to 0.9 reported in literature and the sobering disagreement thereof with DFT predictions can at least in part be rationalized based on the here identified crystallite size-dependent metastable phase formation. Furthermore, it is evident that predictions of critical Al solubilities in metastable cubic TiAlN are flawed, if the previously overlooked surface energy contribution to the total energy is not considered.

On atomic mechanisms governing the oxidation of Bi2Te3.

Oxidation of Bi2Te3 (space group R [Formula: see text] m) has been investigated using experimental and theoretical means. Based on calorimetry, x-ray photoelectron spectroscopy and thermodynamic modelling, Bi2Te3 is at equilibrium with Bi2O3 and TeO2, whereby the most stable compound is Bi2Te3, followed by Bi2O3. The reactivity of Bi towards oxygen is expected to be higher than that of Te. This notion is supported by density functional theory. The strongest bond is formed between Bi and Te, followed by Bi-O. This gives rise to unanticipated atomic processes. Dissociatively adsorbed oxygen diffuses through Bi and Te basal planes of Bi2Te3(0 0 0 1) and preferably interacts with Bi. The Te termination considerably retards this process. These findings may clarify conflicting literature data. Any basal plane off-cut or Bi terminations trigger oxidation, but a perfect basal cleavage, where only Te terminations are exposed to air, may be stable for a longer period of time. These results are of relevance for applications in which surfaces are of key importance, such as nanostructured Bi2Te3 thermoelectric devices.

Thermal expansion of Pd-based metallic glasses by ab initio methods and high energy X-ray diffraction.

Metallic glasses are promising structural materials due to their unique properties. For structural applications and processing the coefficient of thermal expansion is an important design parameter. Here we demonstrate that predictions of the coefficient of thermal expansion for metallic glasses by density functional theory based ab initio calculations are efficient both with respect to time and resources. The coefficient of thermal expansion is predicted by an ab initio based method utilising the Debye-Grüneisen model for a Pd-based metallic glass, which exhibits a pronounced medium range order. The predictions are critically appraised by in situ synchrotron X-ray diffraction and excellent agreement is observed. Through this combined theoretical and experimental research strategy, we show the feasibility to predict the coefficient of thermal expansion from the ground state structure of a metallic glass until the onset of structural changes. Thereby, we provide a method to efficiently probe a potentially vast number of metallic glass alloying combinations regarding thermal expansion.

Deformation behavior of Re alloyed Mo thin films on flexible substrates: In situ fragmentation analysis supported by first-principles calculations.

A major obstacle in the utilization of Mo thin films in flexible electronics is their brittle fracture behavior. Within this study, alloying with Re is explored as a potential strategy to improve the resistance to fracture. The sputter-deposited Mo1-xRex films (with 0 ≤ x ≤ 0.31) were characterized in terms of structural and mechanical properties, residual stresses as well as electrical resistivity. Their deformation behavior was assessed by straining 50 nm thin films on polyimide substrates in uniaxial tension, while monitoring crack initiation and propagation in situ by optical microscopy and electrical resistance measurements. A significant toughness enhancement occurs with increasing Re content for all body-centered cubic solid solution films (x ≤ 0.23). However, at higher Re concentrations (x > 0.23) the positive effect of Re is inhibited due to the formation of dual-phase films with the additional close packed A15 Mo3Re phase. The mechanisms responsible for the observed toughness behavior are discussed based on experimental observations and electronic structure calculations. Re gives rise to both increased plasticity and bond strengthening in these Mo-Re solid solutions.

Ultra-stiff metallic glasses through bond energy density design.

The elastic properties of crystalline metals scale with their valence electron density. Similar observations have been made for metallic glasses. However, for metallic glasses where covalent bonding predominates, such as metalloid metallic glasses, this relationship appears to break down. At present, the reasons for this are not understood. Using high energy x-ray diffraction analysis of melt spun and thin film metallic glasses combined with density functional theory based molecular dynamics simulations, we show that the physical origin of the ultrahigh stiffness in both metalloid and non-metalloid metallic glasses is best understood in terms of the bond energy density. Using the bond energy density as novel materials design criterion for ultra-stiff metallic glasses, we are able to predict a Co33.0Ta3.5B63.5 short range ordered material by density functional theory based molecular dynamics simulations with a high bond energy density of 0.94 eV Å-3 and a bulk modulus of 263 GPa, which is 17% greater than the stiffest Co-B based metallic glasses reported in literature.

Topology and electronic structure of flexible (Nb,Ru)O2 thermoelectrics.

Using combinatorial reactive sputtering, we have synthesised Nb-Ru-O thin films on Kapton (polyimide) with the Ru/Nb ratio from 0.5 to 1.1 in a dioxide type of environment. Based on correlative analysis, including synchrotron diffraction experiments and density functional theory, the topology of these amorphous samples is characterised by short metal-oxygen bonds and very pronounced metal-metal interactions within the second coordination shell. We suggest that the role of Nb is within bond length reduction and promotion of quantum confinement, giving rise to an increase in the Seebeck coefficient. Furthermore, these Nb-Ru-O thin films are mechanically flexible as there are no crack formation and delamination upon bending or rolling. This may be rationalised as follows. Nb-Ru-O appears ductile due to low topological connectivity and forms strong bonds with Kapton.

Elastic properties of amorphous T 0.75Y0.75B14 (T = Sc, Ti, V, Y, Zr, Nb) and the effect of O incorporation on bonding, density and elasticity (T' = Ti, Zr).

We have systematically studied the effect of transition metal valence electron concentration (VEC) of amorphous T 0.75Y0.75B14 (a-T 0.75Y0.75B14, T = Sc, Ti, V, Y, Zr, Nb) on the elastic properties, bonding, density and electronic structure using ab initio molecular dynamics. As the transition metal VEC is increased in both periods, the bulk modulus increases linearly with molar- and mass density. This trend can be understood by a concomitant decrease in cohesive energy. T' = Ti and Zr were selected to validate the predicted data experimentally. A-Ti0.74Y0.80B14 and a-Zr0.75Y0.75B14 thin films were synthesized by high power pulsed magnetron sputtering. Chemical composition analysis revealed the presence of up to 5 at.% impurities, with O being the largest fraction. The measured Young's modulus values for a-Ti0.74Y0.80B14 (301 ± 8 GPa) and a-Zr0.75Y0.75B14 (306 ± 9 GPa) are more than 20% smaller than the predicted ones. The influence of O incorporation on the elastic properties for these selected systems was theoretically studied, exemplarily in a-Ti0.75Y0.75B12.75O1.25. Based on ab initio data, we suggest that a-Ti0.75Y0.75B14 exhibits a very dense B network, which is partly severed in a-Ti0.75Y0.75B12.75O1.25. Upon O incorporation, the average coordination number of B and the molar density decrease by 9% and 8%, respectively. Based on these data the more than 20% reduced Young's modulus obtained experimentally for films containing impurities compared to the calculated Young's modulus for a-Ti0.75Y0.75B14 (without incorporated oxygen) can be rationalized. The presence of oxygen impurities disrupts the strong B network causing a concomitant decrease in molar density and Young's modulus. Very good agreement between the measured and calculated Young's modulus values is obtained if the presence of impurities is considered in the calculations. The implications of these findings are that prediction efforts regarding the elastic properties of amorphous borides containing oxygen impurities on the at.% level are flawed without taking the presence of impurities into account.

Electronic hybridisation implications for the damage-tolerance of thin film metallic glasses.

A paramount challenge in materials science is to design damage-tolerant glasses. Poisson's ratio is commonly used as a criterion to gauge the brittle-ductile transition in glasses. However, our data, as well as results in the literature, are in conflict with the concept of Poisson's ratio serving as a universal parameter for fracture energy. Here, we identify the electronic structure fingerprint associated with damage tolerance in thin film metallic glasses. Our correlative theoretical and experimental data reveal that the fraction of bonds stemming from hybridised states compared to the overall bonding can be associated with damage tolerance in thin film metallic glasses.

Modeling of metastable phase formation diagrams for sputtered thin films.

A method to model the metastable phase formation in the Cu-W system based on the critical surface diffusion distance has been developed. The driver for the formation of a second phase is the critical diffusion distance which is dependent on the solubility of W in Cu and on the solubility of Cu in W. Based on comparative theoretical and experimental data, we can describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation. Metastable phase formation diagrams for Cu-W and Cu-V thin films are predicted and validated by combinatorial magnetron sputtering experiments. The correlative experimental and theoretical research strategy adopted here enables us to efficiently describe the relationship between the solubilities and the critical diffusion distances in order to model the metastable phase formation during magnetron sputtering.

Theoretical study of phase stability and elastic properties of T 0.75Y0.75B14 (T = Sc, Ti, V, Y, Zr, Nb, Si).

In this study the phase stability, elastic properties, and plastic behaviour of icosahedral transition metal borides T 0.75Y0.75B14 (T = Sc, Ti, V, Y, Zr, Nb, Si) have been investigated using density functional theory. Phase stability critically depends on the charge transferred by T and Y to the B icosahedra. For the metal sublattice occupancy investigated here, the minimum energy of formation is identified at an effective B icosahedra charge of - 1.8 ± 0.1. This charge corridor encompasses the highest phase stability among all the reported icosahedral transition metal boride systems so far. This data provides guidance for future experimental efforts: from a wear-resistance point of view, Sc0.75Y0.75B14, Ti0.75Y0.75B14, and Zr0.75Y0.75B14 exhibit a rather unique and attractive combination of large Young's modulus values ranging from 488 to 514 GPa with the highest phase stability for icosahedral transition metals borides reported so far.

Vacancy filling effect in thermoelectric NbO.

Using density functional theory, we have systematically explored the 1a and 1b vacancy filling in NbO (space group Pm-3m) with Nb and N, respectively, to design compounds with large Seebeck coefficients. The most dominating effect was identified for filling of 1b Wyckoff sites with N giving rise to a fivefold increase in the Seebeck coefficient. This may be understood based on the electronic structure. Nb d-nonmetal p hybridization induces quantum confinement and hence enables the enhancement of the Seebeck coefficient. This was validated by measuring the Seebeck coefficient of reactively sputtered thin films. At 800 °C these electrically conductive oxynitrides exhibit the Seebeck coefficient of -70 µV K(-1), which is the largest absolute value ever reported for these compounds.