High-density Phase Research Articles

Microscopic phase identification of cement-stabilized clay by nanoindentation and statistical analytics

The mechanical properties of cement-stabilized clay (CSC), are significantly inferior to that of concrete and mortar due to the presence of clay minerals. To reveal the interaction between clinker's functional constituent and clay minerals within the CSC matrix to promote the performance of stabilized clay, large data sets cross-scale nanoindentation coupled with thermogravimetric analyses were involved. Two commercially available clays (i.e., kaolin and bentonite, whose dominant clay minerals are kaolinite and montmorillonite, respectively) stabilized by two key functional constituents of cement clinker, i.e., tricalcium silicate (C3S) and tricalcium aluminate (C3A), were investigated to unravel the primary hydration of the cement clinker, pozzolanic reactions with clay minerals, and the microstructure's evolution. Large data sets of elastic modulus and hardness derived from the nanoindentation tests were statistically investigated by two deconvolution methods: probability density function and cumulative distribution function. The results indicated that calcium silicate hydrates (C-S-H) and calcium aluminate hydrates (C-A-H) were the major reaction products for C3S-stabilized and C3A-stabilized clays. However, during the secondary pozzolanic reaction process, the dissolved colloids from the clay minerals and the hydrated products would react and accumulate at the interface between the primary cementitious paste and clay particles to form a new soft, porous phase. The deconvolution and thermogravimetric analysis also indicate that more pozzolanic products and high-density (HD) porous phases were detected in bentonite than in kaolin, suggesting that the pozzolanic reaction in montmorillonite is much more pronounced than that in kaolinite. This understanding can clarify the interaction between clay minerals, hydration products, and distinct CSC for traditional cementitious materials.

Condensation driven by a quantum phase transition

The grand canonical thermodynamics of a bosonic system is studied in order to identify the footprint of its own high-density quantum phase transition. The phases displayed by the system at zero temperature establish recognizable patterns at finite temperature that emerged in the proximity of the boundary of the equilibrium diagram. The gapped phase underlines a state of collectivism/condensation at finite temperature in which particles coalesce into the ground state in spite of interacting attractively. The work establishes a framework that allows to study the phenomenon of condensation under the effect of attraction.

Signatures of sluggish dynamics and local structural ordering during ice nucleation.

We investigate the microscopic pathway of spontaneous crystallization in the ST2 model of water under deeply supercooled conditions via unbiased classical molecular dynamics simulations. After quenching below the liquid-liquid critical point, the ST2 model spontaneously separates into low-density liquid (LDL) and high-density liquid phases, respectively. The LDL phase, which is characterized by lower molecular mobility and enhanced structural order, fosters the formation of a sub-critical ice nucleus that, after a stabilization time, develops into the critical nucleus and grows. Polymorphic selection coincides with the development of the sub-critical nucleus and favors the formation of cubic (Ic) over hexagonal (Ih) ice. We rationalize polymorphic selection in terms of geometric arguments based on differences in the symmetry of second neighbor shells of ice Ic and Ih, which are posited to favor formation of the former. The rapidly growing critical nucleus absorbs both Ic and Ih crystallites dispersed in the liquid phase, a crystal with stacking faults. Our results are consistent with, and expand upon, recent observations of non-classical nucleation pathways in several systems.

CO adsorption on Co(0001) revisited: High-coverage CO superstructures on the close-packed surface of cobalt

The adsorbate overlayer structures formed by CO on highly covered Co(0001) were investigated using temperature programmed desorption, low energy electron diffraction, reflection absorption infrared spectroscopy and synchrotron-based x-ray photoemission spectroscopy, with the purpose to clarify some recent confusion on CO adsorption at high coverages. TPD shows that the coverage of the (2√3 × 2√3)R30o structure (abbreviated as 2√3 structure) is 7/12 (0.583) ML. Its unit cell contains one COtop and six CObridge species that form three ‘bridge dicarbonyls’ in which two CObridge adsorbates share the same cobalt surface atom. Between 0.58 and 0.63 ML the 2√3 structure breaks up into small 2D domains separated by antiphase domain boundaries that consist of ‘double bridge dicarbonyls’ in which three CObridge adsorbates share two cobalt surface atoms. A phase transition that occurs around 0.63 ML creates previously unknown c(8 × 2) and c(12 × 2) domain boundary structures which consist of high density strips with a (2 × 2)–3CO structure and top/hollow site occupation which are separated by antiphase domain boundaries with a lower local coverage. Up to 0.63 ML the structures found at low temperature in UHV are very similar to those observed by others using in-situ STM at 300 K under CO pressure. This changes above 0.63 ML, where STM shows that moiré structures form instead of the c(n × 2) domain boundary structures. We propose that the moiré and c(n × 2) structures have a very similar enthalpy of formation so that small variations of temperature and CO chemical potential can lead to different structures for the same CO coverage. We show that these high-density phases that exist above 0.5 ML do not form at the typical pressures and temperatures used in applied FTS, but they do need to be considered when CO adsorption at room temperature is used as a diagnostic tool to characterize the catalyst surface.

Phase transition from nematic to high-density disordered phase in a system of hard rods on a lattice

A system of hard rigid rods of length k on hypercubic lattices is known to undergo two phase transitions when chemical potential is increased: from a low density isotropic phase to an intermediate density nematic phase, and on further increase to a high-density phase with no orientational order. In this paper, we argue that, for large k, the second phase transition is a first-order transition with a discontinuity in density in all dimensions greater than 1. We show that the chemical potential at the transition is ≈kln[k/lnk] for large k, and that the density of uncovered sites drops from a value ≈(lnk)/k^{2} to a value of order exp(-ak), where a is some constant, across the transition. We conjecture that these results are asymptotically exact, in all dimensions d≥2. We also present evidence of coexistence of nematic and disordered phases from Monte Carlo simulations for rods of length 9 on the square lattice.

Microstructure and mechanical properties of medium-entropy alloys with a high-density η-D024 phase

Medium-entropy alloys (MEAs) have attracted considerable research attention because of their excellent mechanical properties. In these, the γ’ phase has been utilized as a strengthening phase. However, the η phase has not been widely investigated. Herein, we explain the precipitation behavior of the η phase in a non-equimolar CoCrNiTi MEA. The MEA adopts a face-centered cubic (FCC) matrix upon Ni3Ti η phase precipitation. Various characterization techniques were used to analyze the microstructure, phase structure, and phase composition of the as-prepared MEA. The grain size and volume fraction of the η phase were ~ 70 nm and ~ 35%, respectively. The FCC-η interface exhibited semi-coherence, adopting an interplanar angle of 23°. Upon precipitation strengthening, the MEA exhibited a yield strength of ~1.7 GPa, an ultimate tensile strength of ~2 GPa, and an elongation of ~2.87%. This work facilitates a novel approach to ultrahigh-strength alloy production.

Atomistic structure and anomalous heat capacity of low-density liquid carbon: Molecular dynamics study with machine learning potential

Liquid carbon remains the source of several unsolved questions related to its structure and region of thermodynamic stability. Experiments demonstrate a drastic decrease in the density for liquid carbon along the graphite melting line in the pressure range P = 1–3 GPa and the nature of this phenomenon is unclear. A recent experimental study [A.M. Kondratyev and A.D. Rakhel, PRL (2019)] revealed another peculiar and still unexplained feature of the liquid carbon – its excessive heat capacity. Using classical molecular dynamics with machine learning potential GAP-20, we study the structural properties of liquid carbon and demonstrate that at P < 1–2 GPa it resembles a net of sp-hybridized chains, rather than a typical covalent liquid, with nanoscale porosity of this phase being responsible for the density decrease. We also show that excessive heat capacity could be a direct manifestation of a smooth transition from a high-density sp2-hybridized phase into a low-density sp-hybridized.

Optimizing strength and electrical conductivity of Cu-Cr-Zr alloy by two-stage aging treatment

Cu-Cr-Zr alloy can be strengthened by modulating the aging process. In this work, the effect of two-stage aging on the properties of Cu-Cr-Zr solid solution was studied. Hardness, tensile properties and electrical properties were tested, and the microstructures were examined by transmission electron microscope. The results show that pre-aging can facilitate the formation of GP zones in the matrix, and thus accelerate the precipitation of high-density nano-sized phase in a shorter time as compared to that in the one-stage aging process. The two-stage aging route harmonizes the strength, ductility and electrical conductivity of the alloy, and provides an accessible strategy to ameliorate the comprehensive properties of the Cu-Cr-Zr alloy.

Ultrafast Nanoscopy of High-Density Exciton Phases in WSe2.

The density-driven transition of an exciton gas into an electron-hole plasma remains a compelling question in condensed matter physics. In two-dimensional transition metal dichalcogenides, strongly bound excitons can undergo this phase change after transient injection of electron-hole pairs. Unfortunately, unavoidable nanoscale inhomogeneity in these materials has impeded quantitative investigation into this elusive transition. Here, we demonstrate how ultrafast polarization nanoscopy can capture the Mott transition through the density-dependent recombination dynamics of electron-hole pairs within a WSe2 homobilayer. For increasing carrier density, an initial monomolecular recombination of optically dark excitons transitions continuously into a bimolecular recombination of an unbound electron-hole plasma above 7 × 1012 cm-2. We resolve how the Mott transition modulates over nanometer length scales, directly evidencing the strong inhomogeneity in stacked monolayers. Our results demonstrate how ultrafast polarization nanoscopy could unveil the interplay of strong electronic correlations and interlayer coupling within a diverse range of stacked and twisted two-dimensional materials.

Special point "trains" in the M-R diagram of hybrid stars

We present a systematic investigation of the possible locations for the special point (SP), a unique feature of hybrid neutron stars in the massradius diagram. The study is performed within the two-phase approach where the high-density (quark matter) phase is described by the covariant nonlocal Nambu–Jona-Lasinio (nlNJL) model equation of state (EOS) which is shown to be equivalent to a constant-sound-speed (CSS) EOS. For the nuclear matter phase around saturation density different relativistic density functional EOSs are used: DD2p00, its excluded-volume modification DD2p40 and the hypernuclear EOS DD2Y-T. In the present contribution we apply the Maxwell construction scheme for the deconfinement transition and demonstrate that a simultaneous variation of the vector and diquark coupling constants results in the occurrence of SP "trains" which are invariant against changing the nuclear matter EOS. We propose that the SP train corresponding to a variation of the diquark coupling at constant vector coupling is special since it serves as a lower bound for the line of maximum masses and accessible radii of massive hybrid stars.

Quasi-water layer sandwiched between hexagonal ice and wall and its influences on the ice tensile stress.

The presence of a quasi-water/premelting layer at the interface between wall and ice when the temperature (T) is below the melting point was extensively observed in experiments. In this work, molecular dynamics simulations are performed to analyze the underlying physics of the quasi-water layer and the effects of the layer on the ice tensile stress. The results indicate that each molecule and its four nearest neighbours in the quasi-water layer representing an equilibrium structure gradually form a tetrahedral ice-like arrangement from an unstructured liquid-like structure along the direction away from the wall. The average density of the quasi-water layer is equal to or higher than the bulk density of water at T ≥ 240 K or T ≤ 240 K respectively, and reaches 1.155 g cm-3 at T = 210 K, suggesting a structural correlation with the high-density liquid phase of water. Depending on the temperature and wall wettability, the thickness of the quasi-water layer (Hq) ranges from ∼2 Å to ∼25 Å. For prescribed hydrophilic walls, Hq increases monotonically with temperature, and is almost proportional to(Tm - T)-1/3, where Tm is the melting temperature of ice. Hq keeps an almost constant value (2 Å) as the temperature increases and rises sharply after passing a threshold temperature of T ≈ 250 K. In the joint effects of the wall wettability and quasi-water layer's thickness, the ice tensile stress decreasing monotonically at a larger temperature shows an upward trend and then reduces to almost a constant value as the wall changes from a hydrophobic to a hydrophilic one. The results reveal the potential development of anti-icing/de-icing techniques by heating the wall or modifying its surface to increase Hq.

The Suppressed High Density Phase in Three-Lane Asymmetric Exclusion Processes with Narrow Entrances

The Suppressed High Density Phase in Three-Lane Asymmetric Exclusion Processes with Narrow Entrances

Dynamic tensile mechanisms and constitutive relationship in CrFeNi medium entropy alloys at room and cryogenic temperatures

Harsh service conditions in aerospace, defense and military, and other fields are calling for materials with excellent mechanical properties to undergo extreme deformation (such as elevated and cryogenic temperatures and high strain rates) without sustaining damage while retaining high strength. Outstanding mechanical properties of high or medium entropy alloys (MEAs) render them potential candidates. In this paper, as the temperature decreases, a breakthrough of the strength-ductility tradeoff is achieved in a CrFeNi MEA with partially recrystallized face-centered cubic phases, together with body-centered cubic (BCC) precipitates. At a strain rate of $3000\phantom{\rule{0.16em}{0ex}}{\mathrm{s}}^{\ensuremath{-}1}$, the yield strength (YS) is increased from 920 MPa at 298 K to 1320 MPa at 77 K, while the uniform elongation (UE) increases by 28.5%. This phenomenon also occurs at quasistatic tension. Under low-temperature loading, nanotwins are popularly activated due to the decreased stacking fault energy with decreasing temperatures. A positive strain-rate dependent YS arises owing to the contributions from the short-range dislocation obstacles, BCC phases, and refined grains. High-density dislocations and BCC phases result in the degeneration of UE, especially with the increase of strain rates. Strain-rate- and temperature-dependent constitutive models were successfully established to predict the deformation behaviors of CrFeNi MEAs under such a wide range of strain rates at room and cryogenic temperatures.

Structural transformation and dynamical heterogeneity in Germania melt under compression: molecular dynamic simulation

The structural transformation and dynamical heterogeneity in Germania (GeO2) are investigated via molecular dynamics (MD) simulation. The MD model with 5499 atoms was constructed under pressure up to 150 GPa and at a temperature of 3500 K. The structural transformation mechanism has been studied by observing domain structures and boundary oxygen atoms. The simulation result reveals that GeO2 consists of separate domains and boundaries in its melt structure. Under compression, the structure of GeO2 changes gradually and represents many types of structures. The melt structure exhibits many structural domains Dx, and polymorphism appears at pressures of 12 and 20 GPa. The change of tetrahedral structure to octahedral structure in germanium coordination occurred in parallel with the process of merging and splitting of domain structure. Moreover, the existence of high- and low-density phases in GeO2 melt is indicated. The high-density phase is D6 domain and boundary oxygen while the low-density phase is D4 and D5 domain. The compression mechanism in GeO2 melt mainly is a reduction of average Voronoi volume of oxygen and Voronoi volume of D6, boundary atoms oxygen. Furthermore, we find the dynamical heterogeneity at ambient pressure. The separate “fast” regions and “slow” regions in GeO2 are detected via link-cluster function.

A strain-driven thermotropic phase boundary in BaTiO3 at room temperature by cycling compression

In BaTiO3 single crystals, we observed a strain-driven phase transition from the tetragonal phase to the tetragonal-orthorhombic phase boundary which can be introduced by slow cycling compressions (a loading of up to 0.5 GPa, strain rate of 10−4 s−1, and 100 cycles) at room temperature. Different from the well-known tetragonal to cubic phase transition under stress (∼2 GPa), it only takes place locally around bent 90° domain walls. The inhomogeneous local stress and electrical fields as well as the mobile point defect pinning effect contribute to the phase re-entrance. Through comparison experiments by in situ synchrotron x-ray diffraction, Raman scattering, and (scanning) transmission electron microscopy, we explored the phase transition mechanism. Based on that, we developed a mechanical method to obtain well-stabilized high-density thermotropic phase boundary structures (with tetragonal, orthorhombic, and bridging monoclinic phases) in BaTiO3 for potential applications.

Emulsifying properties of lentil protein preparations obtained by dry fractionation

Dry fractionated legume protein ingredients are gaining attention as alternatives to conventional solvent extracted legume proteins, being more resource efficient and often exhibiting novel functional properties. However, lack of knowledge about the relationship between composition and functionality limit a more wide-spread use of dry-fractionated legume protein in applications. In this study, lentil fractions of different degrees of refinement were prepared using air classification having protein and starch contents of 16–59% and 4–64%, respectively. The dry fractionated lentil fractions could emulsify and stabilize 10 wt% oil-in-water emulsions, while a conventional lentil protein isolate used for comparison was not able to form stable emulsions. The latter had significantly larger mean droplet diameters (around 20 µm) due to droplet flocculation than emulsions made with the different lentil fractions ranging between 0.3 and 5.5 µm. Similar surface charges (between −22 and −31 mV) indicated that the discrepancy could be ascribed to differences in steric repulsion and mechanical strength of the interfacial layers between conventionally and dry fractionated lentil. Storage stability tests of emulsions stabilized with dry fractionated samples resulted in separation into a low and higher density phase with the individual droplets being stable against coalescence in both phases. The phase separation was attributed to gravimetrical sedimentation of larger insoluble components accumulating in the denser phase, which was impacted by the degree of refinement by air classification. The results highlight the potential of dry fractionation for the production of sustainable ingredients with unique composition and functionality.

Influence of α-Al2O3 Template and Process Parameters on Atomic Layer Deposition and Properties of Thin Films Containing High-Density TiO2 Phases

High-density phases of TiO2, such as rutile and high-pressure TiO2-II, have attracted interest as materials with high dielectric constant and refractive index values, while combinations of TiO2-II with anatase and rutile have been considered promising materials for catalytic applications. In this work, the atomic layer deposition of TiO2 on α-Al2O3 (0 0 0 1) (c-sapphire) was used to grow thin films containing different combinations of TiO2-II, anatase, and rutile, and to investigate the properties of the films. The results obtained demonstrate that in a temperature range of 300–400 °C, where transition from anatase to TiO2-II and rutile growth occurs in the films deposited on c-sapphire, the phase composition and other properties of a film depend significantly on the film thickness and ALD process time parameters. The changes in the phase composition, related to formation of the TiO2-II phase, caused an increase in the density and refractive index, minor narrowing of the optical bandgap, and an increase in the hardness of the films deposited on c-sapphire at TG ≥ 400 °C. These properties, together with high catalytic efficiency of mixed TiO2-II and anatase phases, as reported earlier, make the films promising for application in various functional coatings.

Dynein-Inspired Multilane Exclusion Process with Open Boundary Conditions.

Motivated by the sidewise motions of dynein motors shown in experiments, we use a variant of the exclusion process to model the multistep dynamics of dyneins on a cylinder with open ends. Due to the varied step sizes of the particles in a quasi-two-dimensional topology, we observe the emergence of a novel phase diagram depending on the various load conditions. Under high-load conditions, our numerical findings yield results similar to the TASEP model with the presence of all three standard TASEP phases, namely the low-density (LD), high-density (HD), and maximal-current (MC) phases. However, for medium- to low-load conditions, for all chosen influx and outflux rates, we only observe the LD and HD phases, and the maximal-current phase disappears. Further, we also measure the dynamics for a single dynein particle which is logarithmically slower than a TASEP particle with a shorter waiting time. Our results also confirm experimental observations of the dwell time distribution: The dwell time distribution for dyneins is exponential in less crowded conditions, whereas a double exponential emerges under overcrowded conditions.

Influences of pre-rolling deformation on aging precipitates and mechanical properties for a novel Al–Cu–Li alloy

Pre-rolling deformation is a preferable procedure in practice, compared to pre-stretching, to improve the performances of the rolled Al–Cu–Li plates. In the present work, the different strains of pre-rolling were applied to a rolled Al–Cu–Li alloys before aging. The influence of pre-rolling on mechanical properties and precipitates during 200 °C aging was carefully investigated through hardness test, tensile test, and microstructure characterization. It was found that the aging precipitation behavior was rather complicated for the not pre-rolled samples, various abnormal precipitates were precipitated along with the large diameter and low-density of T1 (Al2CuLi) phase after a period of aging. After pre-rolling, the nucleation of T1 phase was greatly promoted while the formation of other phases was inhibited, resulting in the precipitation behavior became dominated by the high density and tiny T1 phase. Furthermore, the precipitation kinetics of the T1 phase was continually accelerated by increasing the pre-stain, which facilitated the more rapid aging response, higher T1 phase density and continuous improvement of mechanical properties. The strain of pre-rolling could be increased to 20% to obtain the optimal properties, and the tensile strength of the 20% pre-rolled samples increased to ∼520 MPa in peak aged state, compared to ∼360 MPa of the samples only T6 tempered.

Asymmetric exclusion processes with fixed resources: Reservoir crowding and steady states.

We study the reservoir crowding effect by considering the nonequilibrium steady states of an asymmetric exclusion process (TASEP) coupled to a reservoir with fixed available resources and dynamically coupled entry and exit rate. We elucidate how the steady states are controlled by the interplay between the coupled entry and exit rates, both being dynamically controlled by the reservoir population, and the fixed total particle number in the system. The TASEP can be in the low-density, high-density, maximal current, and shock phases. We show that such a TASEP is different from an open TASEP for all values of available resources: here the TASEP can support only localized domain walls for any (finite) amount of resources that do not tend to delocalize even for large resources, a feature attributed to the form of the dynamic coupling between the entry and exit rates. Furthermore, in the limit of infinite resources, in contrast to an open TASEP, the TASEP can be found in its high-density phase only for any finite values of the control parameters, again as a consequence of the coupling between the entry and exit rates.