Solid Transition Research Articles

Towards poured earth construction mimicking cement solidification: demonstration of feasibility via a biosourced polymer

The feasibility of building with earth in the same and simple way as cement-based concrete has been demonstrated as an environmental-friendly alternative. Sodium alginate, a bio-sourced polymer, is used to induce a liquid–solid transition to a clay based suspension, similar to hydraulic binders. The polymer gelation occurs via calcium ions released from the binding phase through a gentle acidification of the mix. It leads to a substantial solidification of the wet material, theoretically sufficient to remove the formwork of an earth wall within 24 h without waiting for drying. Working time is adjusted using a chelator which forms complexes with calcium ions.

From the Atomistic to the Mesoscopic Scale Modeling of Phase Transition in Solids

The phase-field method is a very powerful tool to model the phase transformation and microstructural evolution of solids at mesoscopic scale. However, several important phenomena, like defect formation, grain boundary motion, or reconstructive phase transitions require an atomic scale study. Recently an approach called the quasi-particle approach, based on the Atomic Density Function theory was developed to incorporate the atomic-level crystalline structures into standard continuum theory for pure and multicomponent systems. This review focuses on the description of different computational methods used to model microstructural evolution and self-assembly phenomena at mesoscopic and atomistic scales. Various application examples of these methods are also presented.

Universal scaling of the stress-strain curve in amorphous solids.

The yielding transition of amorphous solids is a phase transition with a special type of universality. Critical exponents and scaling relations have been defined and proposed near the yield stress. We show here that, even in the initial stage of shear far below the yield stress, the stress-strain curve of amorphous solids also shows critical scaling with universal exponents. The key point is to remove the elastic part of the strain, and the shear stress exhibits a sublinear scaling with the plastic strain. We show how this critical scaling is related to the finite size effect of the minimum strain to trigger the first plastic avalanche after a quench. We point out that this sublinear scaling between the stress and the plastic strain implies the divergence of a high-order shear modulus. A scaling relation is derived between two exponents characterizing the stress-strain curve and the density distribution of the local stabilities, respectively. We test the critical scaling of the stress-strain curve using both mesoscopic and atomistic simulations and get satisfying agreement in two and three dimensions.

Rare-earth elements in aqueous chloride systems: Thermodynamic modeling of binary and multicomponent systems in wide concentration ranges

A model has been developed for calculating thermodynamic properties and phase equilibria in binary and multicomponent aqueous systems containing rare earth element chlorides. Here, the rare earth elements encompass the lanthanides except promethium plus yttrium. The model is based on a comprehensive database of solid-liquid equilibria, osmotic and activity coefficients, enthalpies of dilution and heat capacities of solutions. The computational framework relies on the previously developed Mixed-Solvent Electrolyte (MSE) model. The model accurately reproduces the properties of binary rare earth chloride – water systems and of ternary mixtures that additionally include HCl, NaCl, or CaCl2. Solid-liquid phase diagrams have been obtained to provide a convenient summary of the solubility of stable and metastable hydrated solid phases. Analysis of the stability of solid hydrates reveals systematic trends within the rare earth series. At ambient and elevated temperatures, the calculations show an increase in the stability range of rare earth chloride hexahydrates with decreasing cation radius, accompanied by a gradual disappearance of the heptahydrate. At low temperatures, the stable solid phases transition from the decahydrate at higher cation radii to octahydrate in an intermediate range and a combination of pentadeca- and nonahydrates at lower radii. The calculated standard-state enthalpies of formation of the hydrates agree with independently obtained values from calorimetric measurements, thus verifying the internal consistency of the model.

Analysis of photon emission induced by light and heavy ions in time-of-flight medium energy ion scattering

Abstract We present a systematic analysis of the photon emission observed due to impact of pulsed keV ion beams in time-of-flight medium energy ion scattering (ToF-MEIS) experiments. Hereby, hydrogen, helium and neon ions served as projectiles and thin gold and titanium nitride films on different substrates were employed as target materials. The present experimental evidence indicates that a significant fraction of the photons has energies of around 10 eV, i.e. on the order of typical valence and conduction band transitions in solids. Furthermore, the scaling properties of the photon emission with respect to several experimental parameters were studied. A dependence of the photon yield on the projectile velocity was observed in all experiments. The photon yield exhibits a dependence on the film thickness and the scattering angle, which can be explained by photon production along the path of the incident ion through the material. Additionally, a strong dependence on the projectile type was found with the photon emission being higher for heavier projectiles. This difference is larger than the respective difference in electronic stopping cross section. The photon yield shows a strong material dependence, and according to a comparison of SiO2 and Si seems to be subject to matrix effects.

Multiwalled carbon nanotubes reinforced poly (ether‐ketone) nanocomposites: Assessment of rheological, mechanical, and electromagnetic shielding properties

This study investigates the effect of multiwalled carbon nanotubes (MWCNTs) content on rheological, mechanical, and EMI shielding properties in Ka band (26.5‐40 GHz) of poly (ether‐ketone) [PEK] prepared by melt compounding using twin screw extruder. Transmission electron microscopy (TEM) and field emission gun scanning electron microscopy (FEG‐SEM) studies were adopted to identify dispersion of nanotubes in PEK matrix. TEM and SEM images showed uniform dispersion of MWCNTs in PEK/MWCNT composites even at loading of 5 wt%. The rheological studies showed that the material experiences viscous (fluid) to elastic (solid) transition at 1 wt% loading beyond which nanotubes form continuous network throughout the matrix which in turn promotes reinforcement. Additionally, Van‐Gurp Palmen plot (phase angle vs complex modulus) and values of damping factor further confirm that the material undergoes viscous to elastic transition at 1 wt% loading. This reinforcement effect of nanotubes is reflected in enhanced mechanical properties (flexural strength and flexural modulus). Flexural strength and flexural modulus of PEK showed an increment of 17% upon incorporation of 5 wt% of MWCNTs. Total shielding effectiveness (SET) of −38 dB with very high shielding effectiveness due to absorption (SEA ~ −34 dB) was observed at 5 wt% loading of MWCNTs in PEK matrix in the frequency range of 26.5‐40 GHz (Ka band).

The solidification and precipitation behaviors of AE42 magnesium alloy

The solidification and precipitation behaviors of AE42 magnesium at different quenching temperatures were studied. The results showed that the liquid–solid transition temperature range of AE42 alloy was from 630[Formula: see text]C to 590[Formula: see text]C. Precipitation of two kinds of rare earth compounds during solidification had been found. One was Al2RE phase at 616[Formula: see text]C. The other was Al[Formula: see text]RE3 phase at 604[Formula: see text]C. The solidification path of AE42 alloy was L [Formula: see text] [Formula: see text]-Mg [Formula: see text] [Formula: see text]-Mg+Al2RE [Formula: see text] Al2RE+[Formula: see text]-Mg+Al[Formula: see text]RE3.

Invariant electrical resistivity of Co along the melting boundary

The Earth's core is comprised mainly of Fe and Ni with some light alloying element(s) and the electrical resistivity behavior of these elements is an important property for characterizing geodynamo action, determining energy sources, and for understanding core thermal evolution. Knowledge of the electrical resistivity of solid and liquid transition metals with electronic structures similar to Fe reinforces our understanding of core properties. The electrical resistivity of high purity Co has been measured at pressures up to 5 GPa in a large volume press and at temperatures up to 100 K above the melting temperature. The results demonstrate that resistivity of Co is invariant along the melting boundary. This is interpreted in terms of the antagonistic effects of P-induced reduction in the amplitude of lattice vibrations tending to decrease resistivity, and the P-induced shift of the Fermi level closer to the d-resonance which tends to increase resistivity. We calculated the electronic thermal conductivity of Co using the Wiedemann–Franz law and show that it increases with pressure both in the solid and liquid states and decreases with temperature in the solid and increases in the liquid state. The pressure dependences of electrical resistivity and electronic thermal conductivity calculated from equations involving bulk modulus and the Gruneisen parameter are in reasonable agreement with values measured in this study. The constant resistivity of Co along its melting boundary found in our study portends similar behavior for its electronic structural analog, Fe. This prediction suggests that the electronic thermal conductivity of Fe at Earth's inner core boundary could be similar to its 1 atm value at the melting point. Using this value of thermal conductivity for the inner core boundary would admit thermal convection as an energy source for the geodynamo prior to the birth of the inner core.

Efficient chemical potential evaluation with kinetic Monte Carlo method and non-uniform external potential: Lennard-Jones fluid, liquid, and solid.

The aim of this paper is to present a method of a direct evaluation of the chemical potential of fluid, liquid, and solid with kinetic Monte Carlo simulation. The method is illustrated with the 12-6 Lennard-Jones (LJ) system over a wide range of density and temperature. A distinctive feature of the methodology used in the present study is imposing an external potential on the elongated simulation box to split the system into two equilibrium phases, one of which is substantially diluted. This technique provides a reliable direct evaluation of the chemical potential of the whole non-uniform system (including that of the uniformly distributed dense phase in the central zone of the box), which, for example, is impossible in simulation of the uniform crystalline phase. The parameters of the vapor-liquid, liquid-solid, and fluid-solid transitions have been reliably determined. The chemical potential and the pressure are defined as thermodynamically consistent functions of density and temperature separately for the liquid and the solid (FCC) phases. It has been shown that in two-phase systems separated by a flat interface, the crystal melting always occurs at equilibrium conditions. It is also proved that in the limit of zero temperature, the specific heat capacity of an LJ crystal at constant volume is exactly 3Rg (where Rg is the gas constant) without resorting to harmonic oscillators.

Solid State Transition from γ to α-Al2O3 Induced by SPEX Mechanical Milling

Solid State Transition from γ to α-Al₂O₃ Induced by SPEX Mechanical Milling

Solid ion transition route to 3D S–N-codoped hollow carbon nanosphere/graphene aerogel as a metal-free handheld nanocatalyst for organic reactions

A novel metal-free bulk nanocatalyst, S–N-codoped hollow carbon nanosphere/graphene aerogel (SNC-GA-1000), has been successfully fabricated using a facile and clean solid ion transition route. In this method, ZnS is used as the hard template and S source, while polydopamine acts as a reducing agent and carbon source. At a high annealing temperature, Zn metal is reduced and evaporates, leaving only free S vapor to diffuse into the carbon layer. Interestingly, the as-obtained SNC-GA-1000 exhibits much higher catalytic activity in an organic reduction reaction than unloaded bare S–N-codoped carbon nanospheres. Hydrothermal reduction of the graphene oxide sheets loaded with ZnS@polydopamine core–shell nanospheres (ZnS@PDA) affords a three-dimensional bulk graphene aerogel. Although nanosized catalysts exhibit high catalytic activities, their subsequent separation is not always satisfactory, making post-treatment difficult. This approach achieves a trade-off between activity and separability. More importantly, due to the 3D structural nature, such bulk and handheld nanocatalysts can be easily separated and recycled.

Excess vibrational modes of a crystal in an external non-affine field

Thermal displacement fluctuations in a crystal may be classified as either “affine” or “non-affine”. While the former couples to external stress with familiar consequences, the response of a crystal when non-affine displacements are enhanced using the thermodynamically conjugate field, is relatively less studied. We examine this using a simple model of a crystal in two dimensions for which analytical calculations are possible. Enhancing non-affine fluctuations destabilises the crystal. The population of small frequency phonon modes increases, with the phonon density of states shifting, as a whole, towards zero frequency. Even though the crystal is free of disorder, we observe growing length and time scales. Our results, which may have implications for the glass transition and structural phase transitions in solids, are compared to molecular dynamics simulations. Possibility of experimental verification of these results is also discussed. We show that it is possible to enhance non-affine displacement fluctuations in a crystal using an external field. Although transient, these fluctuations can shift the phonon density of states to low frequencies and cause “Boson peak” like phenomenon in an otherwise perfect crystal without quenched disorder.

Thermal properties of iopamidol

Three crystal forms of iopamidol, an iodinated contrast media used in radiology, have been so far elucidated: an anhydrous, a monohydrate and a pentahydrate form (labeled hereafter as W0, W1 and W5, respectively), which showed the occurrence of different conformations, atropisomeric in nature. Specifically, the anhydrous and monohydrate forms contain iopamidol with a “syn” conformation of the two symmetric sidearms, while an “anti” conformation was found in the pentahydrate, making it a conformational (pseudo)-polymorph of the first two. The three crystal forms have been here investigated by means of DSC, variable temperature X-ray powder diffraction and Raman spectroscopy. This study enabled us to highlight the thermal-induced transformations, leading to the discovery of new crystal forms, for a total of four hydrated and four distinct anhydrous phases. In particular, the DSC curve of W0 revealed only a reversible solid–solid transition at around 180 °C before melting, with subsequent degradation above 300 °C. W1, after the loss of lattice water around 100 °C, shows a characteristic split peak at about 250 °C, which is attributed to melting. Below 150 °C, powder diffraction of W1 suffers of minor changes, with a smooth variation of the lattice parameters, in agreement with a progressive loss of water in a reversible event, monitored also by DSC. At variance, W5 evidenced an irreversible loss of water in three distinct steps, for three, one and one H2O molecules each, respectively; subsequent transitions occur at 140 and 180 °C, before melting at 240 °C. Three clearly visible transformations were also detected by variable temperature powder diffraction measurements, where the loss of three molecules of water in a single step, generating a bis-hydrated species (W2), is followed by a second dehydration process leading, above 75 °C, to a new monohydrate phase W1′, different from the known W1 form. The Raman spectra of the three crystal forms, measured upon heating up to 160 °C, evidenced changes in spectral regions of amides that, according to our simulations of the vibrational properties, can be attributed to changes of the hydration properties and, more significantly, in terms of the “syn” and “anti” conformations.

Deconfined quantum criticality in SU(3) antiferromagnets on the triangular lattice

We propose field theories for a deconfined quantum critical point in SU(3) antiferromagnets on the triangular lattice. In particular we consider the continuous transition between a magnetic, three-sublattice color-ordered phase and a trimerized SU(3) singlet phase. Starting from the magnetically ordered state we derive a critical theory in terms of fractional bosonic degrees of freedom, in close analogy to the well-developed description of the SU(2) N\'eel---valence bond solid (VBS) transition on the square lattice. Our critical theory consists of three coupled $C{P}^{2}$ models and we study its fixed point structure using a functional renormalization group approach in a suitable large $N$ limit. We find a stable critical fixed point and estimate its critical exponents, thereby providing an example of deconfined criticality beyond the universality class of the $C{P}^{N}$ model. In addition we present a complementary route towards the critical field theory by studying topological defects of the trimerized SU(3) singlet phase.

Diffusive and martensitic nucleation kinetics in solid-solid transitions of colloidal crystals

Solid–solid transitions between crystals follow diffusive nucleation, or various diffusionless transitions, but these kinetics are difficult to predict and observe. Here we observed the rich kinetics of transitions from square lattices to triangular lattices in tunable colloidal thin films with single-particle dynamics by video microscopy. Applying a small pressure gradient in defect-free regions or near dislocations markedly transform the diffusive nucleation with an intermediate-stage liquid into a martensitic generation and oscillation of dislocation pairs followed by a diffusive nucleus growth. This transformation is neither purely diffusive nor purely martensitic as conventionally assumed but a combination thereof, and thus presents new challenges to both theory and the empirical criterion of martensitic transformations. We studied how pressure, density, grain boundary, triple junction and interface coherency affect the nucleus growth, shape and kinetic pathways. These novel microscopic kinetics cast new light on control solid–solid transitions and microstructural evolutions in polycrystals.

Surface-Induced Frustration in Solid State Polymorphic Transition of Native Cellulose Nanocrystals.

The presence of an interface generally influences crystallization of polymers from melt or from solution. Here, by contrast, we explore the effect of surface immobilization in a direct solid state polymorphic transition on individual cellulose nanocrystals (CNCs), extracted from a plant-based origin. The conversion from native cellulose I to cellulose III crystal occurred via a host-guest inclusion of ethylene diamine inside the crystal. A 60% reduction in CNC width (height) in atomic force microscopy images suggested that when immobilized on a flat modified silica surface, the stresses caused by the inclusion or the subsequent regeneration resulted in exfoliation, hypothetically, between the van der Waals bonded sheets within the crystal. Virtually no changes in dimensions were visible when the polymorphic transition was performed to nonimmobilized CNCs in bulk dispersion. With reservations and by acknowledging the obvious dissimilarities, the exfoliation of cellulose crystal sheets can be viewed as analogous to exfoliation of 2D structures like graphene from a van der Waals stacked solid. Here, the detachment is triggered by an inclusion of a guest molecule inside a host cellulose crystal and the stresses caused by the firm attachment of the CNC on a solid substrate, leading to detachment of molecular sheets or stacks of sheets.

Shape-driven solid–solid transitions in colloids

Solid-solid phase transitions are the most ubiquitous in nature, and many technologies rely on them. However, studying them in detail is difficult because of the extreme conditions (high pressure/temperature) under which many such transitions occur and the high-resolution equipment needed to capture the intermediate states of the transformations. These difficulties mean that basic questions remain unanswered, such as whether so-called diffusionless solid-solid transitions, which have only local particle rearrangement, require thermal activation. Here, we introduce a family of minimal model systems that exhibits solid-solid phase transitions that are driven by changes in the shape of colloidal particles. By using particle shape as the control variable, we entropically reshape the coordination polyhedra of the particles in the system, a change that occurs indirectly in atomic solid-solid phase transitions via changes in temperature, pressure, or density. We carry out a detailed investigation of the thermodynamics of a series of isochoric, diffusionless solid-solid phase transitions within a single shape family and find both transitions that require thermal activation or are "discontinuous" and transitions that occur without thermal activation or are "continuous." In the discontinuous case, we find that sufficiently large shape changes can drive reconfiguration on timescales comparable with those for self-assembly and without an intermediate fluid phase, and in the continuous case, solid-solid reconfiguration happens on shorter timescales than self-assembly, providing guidance for developing means of generating reconfigurable colloidal materials.

New Intermediate Polymorph of 1-Fluoro-adamantane and Its Second-Order-like Transition toward the Low Temperature Phase

Phase transitions of 1-fluoro-adamantane have been thoroughly investigated by temperature-resolved second harmonic generation (TR-SHG) and X-ray powder diffraction (XRPD). A new polymorph—an intermediate centrosymmetric phase (MT)—between the known orientationally disordered high temperature phase (HT, Fm3m, Z = 4) and the low temperature phase (LT, P421c, Z = 2) was unveiled by TR-SHG. The crystal structure of MT was resolved by XRPD in the P42/nmc (Z = 2) space group, and it is related to the LT phase in a group–subgroup relation. No evidence of any solid–solid transition between these two phases by differential scanning calorimetry (DSC) or cold-stage microscopy could be obtained. Therefore, combing TR-SHG, XRPD, DSC, and cold-stage microscopy results, a second-order transition mechanism is proposed for the MT ↔ LT transition. Moreover, the critical exponent (β) of the order parameter was calculated by fitting TR-SHG data to a critical power law. The obtained β value (0.26) is close to the value from...

Particle-Scale Study of Structural Transition of Solid Phase in Gas-Fluidized Beds

Bed structure is important to heat and mass transfer in fluidization. This study investigates solid structural transition for cohesive particles by the combined approach of computational fluid dynamics and discrete element method, supported by Voronoi tessellation. Macroscopic behaviors of fluidized beds are first discussed in connection with microscopic structural transitions. Then, the properties of Voronoi polyhedra are analyzed at both bed and particle scales. In addition, the correlation of coordination number and porosity is examined at a particle scale, and their combined probability distribution is analyzed to identify dominant structure of particles in different flow regimes. Finally, an index is proposed as the ratio of coordination number and porosity to differentiate microscopic states of a particle. These findings should be useful for the study of flow, heat, and mass transfer in fluidized beds and for the understanding of solid-like to fluid-like transition of granular materials.

Microscopic evidence of stishovite generated in low‐pressure shock experiments on porous sandstone: Constraints on its genesis

AbstractIt has been almost exactly half a century since the first synthesis of stishovite in shock experiments on quartz was reported, but its formation conditions during shock is still under debate. Here, we present direct transmission electron microscopic observation of stishovite within material recovered from high‐explosive shock experiments on porous sandstone shocked at 7.5 and 12.5 GPa. Our observations allow for new conclusions on the genesis of stishovite in a close‐to‐nature environment. The formation of stishovite in short‐time shock experiments proves that its crystallization is ultrafast (<1 μs). Crystals were found only embedded in amorphous veins indicating homogeneous nucleation. Crystallization from melt rather than from glass can be concluded from the observation of roundish, defect‐free crystals up to 150 nm in diameter embedded in nondensified glass. The formation of stishovite at 7.5 GPa is in accordance with the phase diagram of silica, if rapid undercooling is present that becomes only possible by the existence of small hot spots in an otherwise cold material, which is supported by transient heat calculation. The absence of coesite at 7.5 GPa suggests kinetic hindrance of its crystallization from melt and, thus, smaller critical cooling rates compared to stishovite where critical cooling rates are estimated to be as large as 1011 K s−1. While the amorphous veins containing stishovite represent unambiguously hot spots, no associated pressure amplification could be verified within these veins. The rapid liquidus crystallization of stishovite only in hot spots generated in porous material is an alternative formation mechanism to the widely accepted theory of solid–solid transition from quartz to stishovite and might represent the more general mechanism occurring in nature for low shock pressure events.