Pressure Phase Transformation Research Articles

ТЕРМОДИНАМИЧЕСКИЙ АНАЛИЗ ПРОЦЕССА ФОРМИРОВАНИЯ НАНОСТРУКТУРНОГО ПОЛИКРИСТАЛЛИЧЕСКОГО МАТЕРИАЛА НА ОСНОВЕ НАНОАЛМАЗОВ, МОДИФИЦИРОВАННЫХ НЕАЛМАЗНЫМ УГЛЕРОДОМ (ЧАСТЬ 1)

The influence of the size of carbon particles on the parameters of the graphite–diamond phase transformation is considered. It is shown that the surface energy of carbon nanoparticles of various shapes (spherical, columnar) makes a significant contribution to their total thermodynamic potential, which leads to a shift in the diamond–graphite equilibrium curve to the low pressure region and an expansion of the diamond phase stability region. At the same time, the change in the chemical potential (Gibbs free energy) during the direct (not catalytic) transition of thin-film graphite-like nanostructures into diamond will be higher than for “massive” graphite, which leads to an increase in the pressure of phase transformation into diamond. To reduce the parameters of diamond formation and obtain nanostructured diamond polycrystals, it is proposed to use nanodiamond particles with a nanometer surface layer of non-diamond (graphitelike) carbon as the starting material. In this case, the nanodiamond surface will influence the transition of a nanometer layer of graphite (graphite-like carbon) into diamond under more favorable thermodynamic parameters.

Analysis of transformation of a thin graphite-like carbon layer on the detonation nanodiamond surface into diamond

The article considers the process of obtaining nanostructured diamond materials due to phase transformation of thin films based on carbon non-diamond forms on the nanodiamond surface into diamond. For the synthesis of nanostructured diamond polycrystalline superhard material, various variants of the initial mixture based on nanodiamond with non-diamond carbon on the surface are proposed (surface-graphitized nanodiamond, surface-graphitized nanodiamond with addition of purified nanodiamond, detonation diamond-containing charge with a surface layer of “amorphous” carbon, including purified nanodiamond additives). The influence of the structure of a thin non-diamond layer on the parameters of graphite to diamond transition is revealed. For a carbon film with a disordered structure (the so-called “amorphous” carbon), the transition pressure to diamond will be about 10–15 GPa, which is significantly higher than the phase transformation pressure for thin graphite films in this temperature range. It is shown that the increase in the pressure of transformation of a thin layer of “amorphous” carbon is caused by its lower surface energy compared to the surface energy of graphite. It has been established that the region of transformation of a thin graphite-like film with a thickness of about 1 nm, formed on the 2–10 nm nanodiamond surface into diamond will be below the graphite-diamond equilibrium line in the temperature range of 1000– 2500 °C. Additional introduction of purified nanodiamond particles leads to a decrease in the pressure of transformation of thin layers of non-diamond carbon into a diamond structure from 10–15 to 2–7 GPa, which is due to the effect of the surface of catalytically active diamond nanoparticles on the thermodynamic stimulus of phase transformation.

High pressure effects on ferroelectric tetragonal phase in BaTi1−xFexO3 (x=1%)

The pressure-driven phase transformation in polycrystalline BaTi[Formula: see text]FexO3 ([Formula: see text]%), synthesized by a solid-state reaction method, was investigated using synchrotron X-ray diffraction and Raman spectroscopy. All measurements were performed at room temperature within a large pressure range up to 36.5 GPa. The results clearly demonstrate a phase transformation from the ferroelectric tetragonal structure of P4mm symmetry to the paraelectric cubic structure of Pm-3m symmetry in the studied sample at the pressure of about 18 GPa. This phase transformation pressure is much higher than those previously reported for BaTiO3-based systems, indicating the stabilization of the ferroelectric phase by doping 1% Fe into BaTiO3. Feature modes of the tetragonal phase still persist while some new modes appear in the Raman spectra at pressures above 18 GPa. This is probably due to accumulated stress and/or local microscopic disorders in the sample, which are associated with the displacement of the Ti atoms along unit-cell diagonals.

Recent <i>In Situ</i> Experimental and Theoretical Advances in Severe Plastic Deformations, Strain-Induced Phase Transformations, and Microstructure Evolution under High Pressure

Severe plastic deformations (SPD) under high pressure, mostly by high-pressure torsion, are employed for producing nanostructured materials and stable or metastable high-pressure phases. However, they were studied postmortem after pressure release. Here, we review recent in situ experimental and theoretical studies of coupled SPD, strain-induced phase transformations (PTs), and microstructure evolution under high pressure obtained under compression in diamond anvil cell or compression and torsion in rotational diamond anvil cell. The utilization of x-ray diffraction with synchrotron radiation allows one to determine the radial distribution of volume fraction of phases, pressure, dislocation density, and crystallite size in each phase and find the main laws of their evolution and interaction. Coupling with the finite element simulations of the sample behavior allows the determination of fields of all components of the stress and plastic strain tensors and volume fraction of high-pressure phase and provides a better understanding of ways to control occurring processes. Atomistic, nanoscale and scale-free phase-field simulations allow elucidation of the main physical mechanisms of the plastic strain-induced drastic reduction in phase transformation pressure (by one to two orders of magnitude), the appearance of new phases, and strain-controlled PT kinetics in comparison with hydrostatic loading. Combining in situ experiments with multiscale theory potentially leads to the formulation of methods to control strain-induced PT and microstructure evolution and designing economic synthetic paths for the defect-induced synthesis of desired high-pressure phases, nanostructures, and nanocomposites.

In situ nanoelectromechanical characterization of phase transformation in Si phononic crystal during nanoindentation

The size dependence of Young’s modulus and the critical pressure for phase transformation from the diamond structure at ambient pressure to a metallic β-Sn structure at high pressure was studied in a Si phononic crystal. We used dynamic mechanical analysis and in situ electrical characterization with an electrically conducting diamond nanoindentation tip. Experiments on several phononic periodic sizes enabled us to establish that the Young’s modulus and critical phase-transformation pressure decreased as the neck width (periodic structure) of the phononic crystal shrank. The finding enables us to understand the reduction in the thermal conductivity of the Si phononic crystal at the local neck between the nanoholes.

Elastic-plastic deformation behavior of sapphire M-plane under static loading using nano-indentation

Elastic-plastic response of M-plane single crystal sapphire was explored via a nano-indenter with a Berkovich tip. Elastic-plastic transition was observed with eight different points (ranging from 0.30 to 0.55 mN) subject to respective peak load. Mechanical properties i.e., Oliver-Pharr hardness and elastic modulus were also determined in the onset elastic and elastic-plastic regions. Stable value of elastic modulus estimated from Oliver-Pharr nanoindentation experiments was around 430 ± 15.0 GPa. However, Oliver-Pharr hardness in purely elastic and elastic–plastic (ISE) regions was approximately 2.19 and 2.0 times greater than the non-ISE hardness values respectively. Values of hardness in the non-ISE region were also in compliance with the depth independent hardness calculated through Nix-Gao and proportional specimen resistance models. Additionally, principal stresses and maximum shear stress were estimated on pop-in burst using Hertzian contact theory. Values of the critical resolved shear stress (CRSS) and maximum possible shear strength were also calculated at the first pop-in burst. Moreover, plastic zone size enhanced 1.36 times by shifting of critical load from 0.30 to 0.55 mN. Multiplication of Schmid factor and interplanar spacing indicated two slip systems i.e., prism {011‾1‾} <101‾1‾> and pyramidal {112‾0} <1‾100>, which are verified in the Transmission electron microscopy (TEM) images. Estimated values of maximum contact pressures at respective critical loads were much lower in comparison to phase transformation pressure of sapphire. Maximum tensile stress was also calculated using Hertzian contact theory relations. Obtained value of maximum tensile strength was 3.58 times lower than cleavage fracture stress at the first pop-in.

Heat Capacities of Nanostructured Wurtzite and Rock Salt ZnO: Challenges of ZnO Nano-Phase Diagram

Low-temperature heat capacities (Cp) of nanostructured rock salt (rs-ZnO) and wurtzite (w-ZnO) polymorphs of zinc oxide were measured in the 2–315 K temperature range. No significant influence of nanostructuring on Cp of w-ZnO has been observed. The measured Cp of rock salt ZnO is lower than that of wurtzite ZnO below 100 K and is higher above this temperature. Using available thermodynamic data, we established that the equilibrium pressure between nanocrystalline w-ZnO and rs-ZnO is close to 4.6 GPa at 300 K (half as much as the onset pressure of direct phase transformation) and slightly changes with temperature up to 1000 K.

Analysis of Micro-Segregation of Solute Elements on the Central Cracking of Continuously Cast Bloom

On the basis of the Brody–Flemings model and modified Voller–Beckermann model, an analytical model of micro-segregation is established by considering the actual solidification cooling conditions of bloom. According to the developed model, the interdendritic solute distribution at the origin of the cracking gap is obtained. It is found that both phosphorus and sulfur have quite severe segregation, but both carbon and manganese have slight segregation; these results agree well with the semiquantitative analysis results of the scanning electron microscope (SEM). At the same time, the interdendritic segregation leads to an enhanced increase in the temperature range of crack formation; correspondingly, the possibility of cracking significantly increases and, thus, element segregation is the internal cause of crack formation. On the other hand, taking into account heat transfer, phase transformation, and metallurgical pressure, the strain of the solid shell is revealed through finite element software. When the solid shell thickness is equal to the distance of 90 mm between the opening point of the crack and the inner arc side, the tensile strain of the solid front is much bigger than the critical strain, which meets the external cause of crack formation; therefore, reasons for the cracking of blooms are successfully found.

Effect of doping on nanoindentation induced incipient plasticity in InP crystal

This article is concerned with incipient plasticity in an InP crystal studied by nanoindentation experiments and ab initio simulations. We consider dislocation-nucleation phenomena and pressure-induced phase transformation to be the alternative mechanisms that govern the elastic-plastic transition displayed by the InP crystal. The ab initio calculations have shown that S- and Zn-doping of the low-pressure zinc blende structure of InP decreases the pressure of phase transformation of the rock-salt structure. The nanoindentation examination of undoped as well as S- and Zn-doped crystals of (001) and (111) orientation revealed an increase in contact pressure at the onset of plastic behavior (pop-in) for doped specimens. As they are contrary to the outcomes of the ab initio simulations, the results of nanoindentation experiments point toward dislocation nucleation as an origin of InP incipient plasticity. Additional investigations were performed on an undoped as well as Si-doped GaAs crystal, which showed that the contact pressure at the pop-in event takes a lower value for the Si-doped sample than the undoped sample. This result is in contrast to the case of the InP crystal displaying phase transformation-steered incipient plasticity of GaAs. Our investigations exhibit the complexity of the semiconductor’s nanodeformation simultaneously providing a convenient way to identify its incipient plasticity mechanism.

Understanding controversies in the \u03b1-\u03c9 and \u03c9-\u03b2 phase transformations of zirconium from nonhydrostatic thermodynamics

Significant debate has been noted in the α-ω and ω-β phase transformations of zirconium. The initial pressure of the α-to-ω transformation at room temperature has been reported to vary from 0.25 to 7.0 GPa, while the hydrostatic transformation is believed to occur at approximately 2.2 GPa. Shear stress is commonly considered as a key factor leading to the discrepancy. However, the principal mechanisms previously proposed concluded that the phase transformation pressure would be decreased in the presence of shear stress. The experimental results of the α-ω transformation in zirconium are contrary to this conclusion. In the ω-β phase diagram of zirconium, the dT/dP along the phase boundary near the α-ω-β triple-point was reported to be either positive or negative, but no theoretical explanation, especially a quantitative one, has been proposed. This article aimed to quantitatively investigate and explain the controversies reported in the α-ω and ω-β phase transformations of zirconium by applying a new nonhydrostatic thermodynamic formalism for solid medium, which has recently been proposed and is capable of quantitatively estimating the impact of shear stress on phase transformations in solids.

Structure Evolution, Elastic and Electronic Properties of Pt‐Doped Ti Alloy under Pressure

The hexagonal closest packed (hcp) to face‐centered cube (fcc) phase transformation of Ti(Pt) alloy with phase transformation pressure of ≈36.8 GPa at 0 K is found using the first‐principle method. The relatively low phase transformation pressure of hcp to fcc structure for Ti(Pt) alloy may be caused by the foregoing tetragonal isostructural transition of fcc Ti(Pt) alloy at ≈32 GPa. Accompanied with the tetragonal isostructural transition, the unit‐cell parameters (a, c) and volume of fcc Ti(Pt) alloy are discontinuous. The axial ratio (c/a) changes from ≈0.471 to ≈0.338; a axis has anomalously negative compressibility, c axis has positive compressibility. Anomalous elastic properties between 32 and 40 GPa, such as the extremely irregular elastic stability factor F and elastic anisotropy index AU, indicate the weak mechanical stability of fcc Ti(Pt) alloy in the phase transformation region. The total density of states, Mulliken population analysis, and difference of charge density indicate that the Pt–Ti interatomic interactions weaken with increasing pressure.

Coupled nonlinear elasticity, plastic slip, twinning, and phase transformation in single crystal titanium for plate impact loading

High purity single crystal titanium (Ti) under shockwave loading in plate impact experiment is modeled and simulated, with help of the finite element. A thermodynamically consistent system of equations is formulated in the frame of large deformation to consider material anisotropy, rate dependence, and multi-physics including nonlinear elasticity, dislocation based plastic slip, deformation twinning, and phase transformation. A novel kinematics is proposed to consider phase transformation in the α twin variants and also to consider the dislocation based slip in all of components of parent material, primary twins and the ω phase. The thermodynamically consistent driving forces for plastic slip, twinning, and phase transformation are developed based upon the second law of thermodynamics. For nonlinear elasticity, the stiffness matrix is dependent on the volume fractions of all components, and the volumetric part of Cauchy stress is obtained from the nonlinear equation of state. Dislocation based plastic slip in multi-variant and multiphase heterogeneous materials is developed and interactions of dislocations among all slip modes are taken into account. A mechanism for dislocation density evolution during twinning and phase transformation is proposed. The shock loading along the [0001] and [101¯1] directions of single crystal high purity Ti is investigated computationally. Very good correspondence between simulation and experiment is obtained, which includes pole figures, volume fractions of components, free surface velocity, peak pressure, and phase transformation pressure. Multiple experimental phenomena are interpreted based upon the progression of dislocation slip, deformation twinning, and phase transformation. In compression with the [101¯1] crystal, a higher volume fraction in the primary twins but a lower secondary twin volume fraction in the [0001] crystal in experiment was observed. The higher propensity for phase transformation occurs in the [0001] crystal is reproduced. In addition to material texture, distributions of temperature, stresses, and plastic strains dependent on the impact loading directions are revealed.

Imaging the Hydrogen Absorption Dynamics of Individual Grains in Polycrystalline Palladium Thin Films in 3D.

Defects such as dislocations and grain boundaries often control the properties of polycrystalline materials. In nanocrystalline materials, investigating this structure-function relationship while preserving the sample remains challenging because of the short length scales and buried interfaces involved. Here we use Bragg coherent diffractive imaging to investigate the role of structural inhomogeneity on the hydriding phase transformation dynamics of individual Pd grains in polycrystalline films in three-dimensional detail. In contrast to previous reports on single- and polycrystalline nanoparticles, we observe no evidence of a hydrogen-rich surface layer and consequently no size dependence in the hydriding phase transformation pressure over a 125-325 nm size range. We do observe interesting grain boundary dynamics, including reversible rotations of grain lattices while the material remains in the hydrogen-poor phase. The mobility of the grain boundaries, combined with the lack of a hydrogen-rich surface layer, suggests that the grain boundaries are acting as fast diffusion sites for the hydrogen atoms. Such hydrogen-enhanced plasticity in the hydrogen-poor phase provides insight into the switch from the size-dependent behavior of single-crystal nanoparticles to the lower transformation pressures of polycrystalline materials and may play a role in hydrogen embrittlement.

The α → ω phase transformation in zirconium followed with ms-scale time-resolved X-ray absorption spectroscopy

ABSTRACTThe conditions of the pressure-induced phase transformation in zirconium have been reported to be influenced by the sample purity, the pressurizing conditions, and the deformation rate. Here, we study this transformation using a dynamic diamond-anvil cell compression setup and ms-scale time-resolved X-ray absorption spectroscopy. The sample pressure is also monitored at the same timescale using the ruby luminescence method. For the samples used in this study (polycrystal of 99.9+ purity, hydrostatically compressed in neon pressure transmitting medium), the phase transformation pressure is very close in static (11 GPa) and in dynamic (12±1 GPa) compression and the transformation is achieved in less than a few ms at 12 GPa. Comparison with literature studies suggest that the kinetics and the mechanism of this martensitic phase transformation are different under hydrostatic and non-hydrostatic compression.

Compression and shear on lead in a rotational diamond anvil cell

ABSTRACTBy application of large plastic shear on a lead sample in a rotational diamond anvil cell, we studied the pressure self-multiplication and the stress deviation phenomena, along with the consequential effects on a phase transformation of lead. It is indicated that pressure can be promoted by the gradual addition of shear. The stress deviation in the sample along different Chi angles is minimal and within the systematic error range. It is thus specified that a quasi-hydrostatic condition is generated in the sample chamber. Moreover surprisingly, under such shear-controlled pressure elevation, the lead fcc-to-hcp phase transformation pressure is found to initiate and complete, respectively, at 12.8 and 18.5 GPa, which is identical to those observed in hydrostatic compressions. The phenomena of the so-launched quasi-hydrostatic pressure, the self-multiplication, along with the consequential effects on the phase transformation properties by shear at pressures are expected to lead to further understanding of materials as well as to potential new technologies at extremes.

Pressure, temperature, and electric field dependence of phase transformations in niobium modified 95/5 lead zirconate titanate

Ceramic niobium modified 95/5 lead zirconate-lead titanate (PZT) undergoes a pressure induced ferroelectric to antiferroelectric phase transformation accompanied by an elimination of polarization and a volume reduction. Electric field and temperature drive the reverse transformation from the antiferroelectric to ferroelectric phase. The phase transformation was monitored under pressure, temperature, and electric field loading. Pressures and temperatures were varied in discrete steps from 0 MPa to 500 MPa and 25 °C to 125 °C, respectively. Cyclic bipolar electric fields were applied with peak amplitudes of up to 6 MV m−1 at each pressure and temperature combination. The resulting electric displacement–electric field hysteresis loops were open “D” shaped at low pressure, characteristic of soft ferroelectric PZT. Just below the phase transformation pressure, the hysteresis loops took on an “S” shape, which split into a double hysteresis loop just above the phase transformation pressure. Far above the phase transformation pressure, when the applied electric field is insufficient to drive an antiferroelectric to ferroelectric phase transformation, the hysteresis loops collapse to linear dielectric behavior. Phase stability maps were generated from the experimental data at each of the temperature steps and used to form a three dimensional pressure–temperature–electric field phase diagram.

Enhanced densification under shock compression in porous silicon

Under shock compression, most porous materials exhibit lower densities for a given pressure than that of a full-dense sample of the same material. However, some porous materials exhibit an anomalous, or enhanced, densification under shock compression. The mechanism driving this behavior was not completely determined. We present evidence from atomistic simulation that pure silicon belongs to this anomalous class of materials and demonstrate the associated mechanisms responsible for the effect in porous silicon. Atomistic response indicates that local shear strain in the neighborhood of collapsing pores catalyzes a local solid-solid phase transformation even when bulk pressures are below the thermodynamic phase transformation pressure. This metastable, local, and partial, solid-solid phase transformation, which accounts for the enhanced densification in silicon, is driven by the local stress state near the void, not equilibrium thermodynamics. This mechanism may also explain the phenomenon in other covalently bonded materials.

Strain-induced phase transformation under compression in a diamond anvil cell: Simulations of a sample and gasket

Combined high pressure phase transformations (PTs) and plastic flow in a sample within a gasket compressed in diamond anvil cell (DAC) are studied for the first time using finite element method. The key point is that phase transformations are modelled as strain-induced, which involves a completely different kinetic description than for traditional pressure-induced PTs. The model takes into account, contact sliding with Coulomb and plastic friction at the boundaries between the sample, gasket, and anvil. A comprehensive computational study of the effects of the kinetic parameter, ratio of the yield strengths of high and low-pressure phases and the gasket, sample radius, and initial thickness on the PTs and plastic flow is performed. A new sliding mechanism at the contact line between the sample, gasket, and anvil called extrusion-based pseudoslip is revealed, which plays an important part in producing high pressure. Strain-controlled kinetics explains why experimentally determined phase transformation pressure and kinetics (concentration of high pressure phase vs. pressure) differ for different geometries and properties of the gasket and the sample: they provide different plastic strain, which was not measured. Utilization of the gasket changes radial plastic flow toward the center of a sample, which leads to high quasi-homogeneous pressure for some geometries. For transformation to a stronger high pressure phase, plastic strain and concentration of a high-pressure phase are also quasi-homogeneous. This allowed us to suggest a method of determining strain-controlled kinetics from experimentation, which is not possible for weaker and equal-strength high-pressure phases and cases without a gasket. Some experimental phenomena are reproduced and interpreted. Developed methods and obtained results represent essential progress toward the understanding of PTs under compression in the DAC. This will allow one optimal design of experiments and conditions for synthesis of new high pressure phases.

Phase transformations in nanograin materials under high pressure and plastic shear: nanoscale mechanisms

There are two main challenges in the discovery of new high pressure phases (HPPs) and transforming this discovery into technologies: finding conditions to synthesize new HPPs and finding ways to reduce the phase transformation (PT) pressure to an economically reasonable level. Based on the results of pressure-shear experiments in the rotational diamond anvil cell (RDAC), superposition of plastic shear on high pressure is a promising way to resolve these problems. However, physical mechanisms behind these phenomena are not yet understood. Here, we elucidate generic mechanisms of coupled nucleation and evolution of dislocation and HPP structures in the nanograin material under pressure and shear utilizing the developed advanced phase field approach (PFA). Dislocations are generated at the grain boundaries and are densely piled up near them, creating a strong concentrator of the stress tensor. Averaged shear stress is essentially larger in the nanograin material due to grain boundary strengthening. This leads to the increase in the local thermodynamic driving force for PT, which allows one to significantly reduce the applied pressure. For all cases, the applied pressure is 3-20 times lower than the PT pressure and 2-12.5 times smaller than the phase equilibrium pressure. Interaction between nuclei leads sometimes to their coalescence and growth of the HPP away from stress concentrators. Plasticity plays a dual role: in addition to creating stress concentrators, it may relax stresses at other concentrators, thus competing with PT. Some ways to optimize the loading parameters have been found that lead to methods for controlling PT. Since such a local stress tensor with high shear stress component cannot be created without plastic deformations, this may lead to new transformation paths and phases, which are hidden during pressure induced PTs.

The sound velocity measurement in diacylglycerol oil under high pressure

In this article, the influence of high pressure on sound velocity at 293 K has been presented. The investigated diacylglycerol oil (DAG – [D82T18]AG) was composed of 82% DAGs and 18% triacylglycerols. The variation of sound velocity with hydrostatic pressure for DAG was evaluated up to 400 MPa. The phase transformation in DAG has been observed as a discontinuity of the dependence of sound velocity on pressure. The sound velocity during the phase transition has shown distinct increment. Also the volume changes have been measured. It has shown the rapid drop of the volume at the phase transformation pressure due to the possible crystallization of DAG oil.