A physical interpretation of softening of pressure-sensitive and anisotropic materials

Several new dynamic models are proposed to explain the mechanical behaviour of softening of pressure-sensitive and anisotropic materials at a macroscopic level. If a pressure-sensitive material is loaded by a force and a variable pressure or an anisotropic material is subjected to a load with a changeable loading direction relative to the material frame, their stress–strain relationships become more complicated. Mechanical behaviours of these stress–strain relationships have to cover the feature concerning the change of pressure or loading direction, i.e. mechanical properties of pressure-sensitive material corresponding to different pressure state or anisotropic material relating to different loading direction will play an important role in deciding their stress–strain relationships. Such shift of material properties due to the variable pressure or loading history may significantly expand the traditional concept of the stability of material deformation, and the second order of plastic work being negative may be a response of stable plastic deformation, which is commonly called softening.     

Ab initio studies on ammonium iodine under high pressure

Ammonium iodine(NH_4I) as an important member of hydrogen-rich compounds has attracted a great deal of attention owing to its interesting structural changes triggered by the relative orientations of adjacent ammonium ions. Previous studies of ammonium iodide have remained in the low pressure range experimentally, which we first extended to so high pressure(250 GPa). We have investigated the structures of ammonium iodine under high pressure through ab initio evolutionary algorithm and total energy calculations based on density functional theory. The static enthalpy calculations show that phase V is stable until 85 GPa where a new phase Ibam is identified. Calculations of phonon spectra show that the Ibam phase is stable between 85 GPa and 101 GPa and the Cm phase is stable up to 130 GPa. In addition, ammonium iodine dissociates into NH_3, H_2, and I_2 at 74 GPa. Subsequently, we analyzed phonon spectra and electronic band structures, finding that phonon softening is not the reason of dissociation and NH_4I is always a semiconductor within the pressure range.     

Revealing the Pressure-Induced Softening/Weakening Mechanism in Representative Covalent Materials

Diamond, cubic boron nitride(c-BN), silicon(Si), and germanium(Ge), as examples of typical strong covalent materials, have been extensively investigated in recent decades, owing to their fundamental importance in material science and industry. However, an in-depth analysis of the character of these materials' mechanical behaviors under harsh service environments, such as high pressure, has yet to be conducted. Based on several mechanical criteria, the effect of pressure on the mechanical properties of these materials is comprehensively investigated.It is demonstrated that, with respect to their intrinsic brittleness/ductile nature, all these materials exhibit ubiquitous pressure-enhanced ductility. By analyzing the strength variation under uniform deformation, together with the corresponding electronic structures, we reveal for the first time that the pressure-induced mechanical softening/weakening exhibits distinct characteristics between diamond and c-BN, owing to the differences in their abnormal charge-depletion evolution under applied strain, whereas a monotonous weakening phenomenon is observed in Si and Ge. Further investigation into dislocation-mediated plastic resistance indicates that the pressure-induced shuffle-set plane softening in diamond(c-BN), and weakening in Si(Ge), can be attributed to the reduction of antibonding states below the Fermi level, and an enhanced metallization, corresponding to the weakening of the bonds around the slipped plane with increasing pressure, respectively. These findings not only reveal the physical mechanism of pressure-induced softening/weakening in covalent materials, but also highlights the necessity of exploring strain-tunable electronic structures to emphasize the mechanical response in such covalent materials.     

有机材料(EDT-DSDTFVO)FeCl_4和(EDT-DSDTFVO)GaCl_4的输送现象

通过对有机材料(EDT-DSDTFVO)2FeCl4和(EDT-DSDTFVO)2GaCl4的输送测定,对其电阻率的温度依赖性以及压力效果进行了系统的比较,虽然两类盐的电阻率随着温度的变化行为十分相似,但是其压力效果尤其在高压时表现出明显的差异性。认为这种差异性和π-d相互作用密切相关。在这里,用EDT-DSDTFVO表示ethylenedithiodiselenadithiafulvalenothioquinone-1,3-dithiole methide。     

高压下TiN等结构相变的第一性原理研究

 利用基于密度泛函理论的赝势平面波方法和线性响应理论,研究了TiN的物态方程、电子能带结构和声子色散曲线随压强的变化关系。结果表明：TiN 的电子能带结构并未随着压强的增加而出现反常,没有出现电子的拓扑结构相变;零压下出现软化的声子模式并没有随着压强的增加而继续软化。因此可以认为在0～12 GPa 压强范围内,TiN 发生等结构相变的原因不是由于电子的拓扑形貌发生变化和声子软化引起的。     

Salt crystallization as damage mechanism in porous building materials--a nuclear magnetic resonance study

Salts can damage building materials by chemical reactions or crystallization, which is a serious threat to cultural heritage. In order to develop better conservation techniques, more knowledge of the crystallization processes is needed. In a porous material, the size of a salt crystal is limited by the sizes of the pores. It has been predicted that as a consequence, the solubility of a salt increases with decreasing pore size. This increase seems to be related to an increase of the stress generated by a crystal on the pore wall. It has been suggested that the resulting stress could become high enough to induce failure. We have studied the crystallization of salts in porous materials with well-defined pore sizes. Samples were saturated at 40 degrees C with saturated Na2SO4 and Na2CO3 solutions. Next we have cooled the samples to 0 degrees C and waited for nucleation. After nucleation occurred, the solubility in the porous material was measured with nuclear magnetic resonance (NMR) as a function of the temperature. The measurements on Na2CO3 indeed show an increase in solubility with a decrease in pore size. For Na2SO4, we did not observe a pore size-dependent solubility. However, we have to remark that these results show a metastable crystal phase. The results can be used to calculate the actual pressure exerted by the crystals onto the pore wall.     

Numerical irreversibility in self-gravitating small N-body systems, II: Influence of instability affected by softening parameters

We investigate the fundamental characteristics of numerical irreversibility appearing in self-gravitating small N-body systems by means of a molecular dynamics method from the viewpoint of time-reversible dynamics. We reconsider a closed spherical system consisting of 250 point-particles interacting through the Plummer softened potential. To investigate the characteristics of numerical irreversibility, we examine the influence of the instability affected by the softening parameter for the softened potential (the instability considered here is the instability of a dynamical system in chaos theory, e.g., a separation rate of the distance between two nearby trajectories in phase space or speed space). To this end, under the restriction of constant initial energy, the softening parameter for the Plummer softened potential is varied from 0.005R to 0.050R, where R is the radius of the spherical container. We first confirm that the size of the softening parameter, i.e., the deviation of the potential from a pure gravitational potential, influences the virial ratio, the density, the pressure on the spherical container, etc., during an early stage of the relaxation process. Through a time-reversible simulation based on a velocity inversion technique, we demonstrate that numerical irreversibility due to round-off errors appears more rapidly with decreasing softening parameter. This means that the higher the instability of the system or the higher the separation rate of the distance between two nearby trajectories, the earlier the memory of the initial conditions is lost. We show that the memory loss time , when the simulated trajectory completely forgets its initial conditions, increases approximately linearly with the timescale of the chaotic system, i.e., the Lyapunov time t_λ. In a small self-gravitating system, propagation of numerical irreversibility or loss of reversibility depends on both the energy state of the system and the instability affected by the softening parameter.     

Enhancement of the superconducting transition temperature of MgB2 by a strain-induced bond-stretching mode softening

We report a systematic increase of the superconducting transition temperature T(c) with a biaxial tensile strain in MgB2 films to well beyond the bulk value. The tensile strain increases with the MgB2 film thickness, caused primarily by the coalescence of initially nucleated discrete islands (the Volmer-Weber growth mode.) The T(c) increase was observed in epitaxial films on SiC and sapphire substrates, although the T(c) values were different for the two substrates due to different lattice parameters and thermal expansion coefficients. We identified, by first-principles calculations, the underlying mechanism for the T(c) increase to be the softening of the bond-stretching E(2g) phonon mode, and we confirmed this conclusion by Raman scattering measurements. The result suggests that the E(2g) phonon softening is a possible avenue to achieve even higher T(c) in MgB2-related material systems.     

Origin of negative thermal expansion in cubic ZrW2O8 revealed by high pressure inelastic neutron scattering

Isotropic negative thermal expansion has been reported in cubic ZrW2O8 over a wide range of temperatures (0-1050 K). Here we report the direct experimental determination of the Grüneisen parameters of phonon modes as a function of their energy, averaged over the whole Brillouin zone, by means of high pressure inelastic neutron scattering measurements. We observe a pronounced softening of the phonon spectrum at P = 1.7 kbar compared to that at ambient pressure by about 0.1-0.2 meV for phonons of energy below 8 meV. This unusual phonon softening on compression, corresponding to large negative Grüneisen parameters, is able to account for the observed large negative thermal expansion.     

Microscopic origins of the anomalous melting behavior of sodium under high pressure

X-ray diffraction experiments have shown that sodium exhibits a dramatic pressure-induced drop in melting temperature, which extends from 1000 K at ~30 GPa to as low as room temperature at ~120 GPa. Despite significant theoretical effort to understand the anomalous melting, its origins are still debated. In this work, we reconstruct the sodium phase diagram by using an ab initio quality neural-network potential. Furthermore, we demonstrate that the reentrant behavior results from the screening of interionic interactions by conduction electrons, which at high pressure induces a softening in the short-range repulsion.     

Analysis of the crystal lattice instability for cage–cluster systems using the superatom model

We have investigated the lattice dynamics for a number of rare-earth hexaborides based on the superatom model within which the boron octahedron is substituted by one superatom with a mass equal to the mass of six boron atoms. Phenomenological models have been constructed for the acoustic and lowenergy optical phonon modes in RB₆ (R = La, Gd, Tb, Dy) compounds. Using DyB₆ as an example, we have studied the anomalous softening of longitudinal acoustic phonons in several crystallographic directions, an effect that is also typical of GdB₆ and TbB₆. The softening of the acoustic branches is shown to be achieved through the introduction of negative interatomic force constants between rare-earth ions. We discuss the structural instability of hexaborides based on 4f elements, the role of valence instability in the lattice dynamics, and the influence of the number of f electrons on the degree of softening of phonon modes.     

Vibrational properties of RbNd(WO4)2: high pressure Raman study, structural and phonon calculations

RbNd(WO(4))(2) was investigated by high pressure Raman spectroscopy in the 0.1-12.3 GPa pressure interval. The assignment of modes was made based on lattice dynamics calculations and the results of these calculations helped us to also discuss the high pressure behavior of phonon spectra in this material. Our results show that a double oxygen bridge plays a fundamental role in the vibrational properties of this system. A density functional theory (DFT) calculation of hydrostatic pressure effects on RbNd(WO(4))(2) was performed in order to understand the effect of internal bond changes on the vibrational properties of RbNd(WO(4))(2). No pressure induced structural phase transition was observed in the Raman study at room temperature, and the DFT calculation (T = 0 K) is consistent with this result. The anomalous softening of the bridge stretching mode at 770 cm(-1) was attributed to the decrease of W-O1-W bond angle with increasing pressure.     

Theoretical study of the transverse acoustic phonons of GaSb at high pressure

We have investigated the phonon dispersion curves and one-phonon density of states up to the pressure of 8 GPa using a theoretical model, namely the rigid ion model. The transverse acoustic phonons as a function of pressure have been compared with the recently measured inelastic neutron scattering data which show a strong softening near the zone boundaries. The calculated one-phonon density of states show pronounced shift in the peak positions with the increase in pressure.     

Structural, Electronic Properties and Chemical Bonding of Borate Li4CaB2O6 under High Pressure： an Ab Initio Investigation

We calculate structural, electronic properties and chemical bonding of borate Li4CaB2O6 under high pressure by means of the local density-functional pseudopotential approach. The equilibrium lattice constants, density of states, Mulliken population, bond lengths, bond angles as well as the pressure dependence of the band gap are presented. Analysis of the simulated high pressure band structure suggests that borate Li4CaB2O6 can be used as the semi-conductor optical material. Based on the Mulliken population analysis, it is found that the electron transfer of the Li atom is very different from that of other atoms in the studied range of high pressures. The charge populations of the Li atom decrease with the pressure up to 60 GPa, then increase with the pressure.     

Softening induced instability of a stretched cohesive granular layer

We report on a cellular pattern which spontaneously forms at the surface of a thin layer of a cohesive granular material submitted to in-plane stretching. We present a simple model in which the mechanism responsible of the instability is the "strain softening" exhibited by humid granular materials above a typical strain. Our analysis indicates that such a type of instability should be observed in any system presenting a negative stress sensitivity to strain perturbations.     

High pressure investigations of melamine

We have performed mid- and far-infrared (IR), Raman, and angular dispersive X-ray diffraction studies on melamine at high pressure up to 36 GPa. We have confirmed the presence of three phase transitions; the first between 1 and 2 GPa, the second between 7 and 9 GPa, and the third near 16 GPa. We observed a softening of the N–H symmetric and antisymmetric vibrations with pressure, suggesting that intermolecular hydrogen bonding increases as the intermolecular distance decreases similarly to what was observed in triamino-trinitrobenzene. The molecular decompression data from core intramolecular peaks of mid-IR and Raman indicate that melamine did not chemically decompose up to the highest investigated pressures but the sample suffered some irreversible amorphization. We have further clarified the lack of observation of any phase transitions in prior Raman and IR studies by examining the pressure dependence of other uninvestigated modes of vibration.     

Pressure-induced structural phase transition in ReO3

We have investigated the pressure-induced structural phase transition in ReO₃ by neutron diffraction on a single crystal. We collected neutron diffraction intensities from the ambient and high pressure phases at P=7 kbar and refined the crystal structures. We have determined the stability of the high pressure phase as a function temperature down to T=2 K and have constructed the (P-T) phase diagram. The critical pressure is P_c=5.2 kbar at T=300 K and decreases almost linearly with decreasing temperature to become P_c=2.5 kbar at T=50 K. The phase transition is driven by the softening of the M₃ phonon mode. The high pressure phase is formed by the rigid rotation of almost undistorted ReO₆ octahedra and the Re-O-Re angle deviates from 180°. We do not see any evidence for the existence of the tetragonal (P4/mbm) intermediate pressure phase reported earlier.     

Structural evolution and bandgap modulation of layered β-GeSe2 single crystal under high pressure

Germanium diselenide (GeSe₂) is a promising candidate for electronic devices because of its unique crystal structure and optoelectronic properties. However, the evolution of lattice and electronic structure of $β$-GeSe₂ at high pressure is still uncertain. Here we prepared high-quality $β$-GeSe₂ single crystals by chemical vapor transfer (CVT) technique and performed systematic experimental studies on the evolution of lattice structure and bandgap of $β$-GeSe₂ under pressure. High-precision high-pressure ultra low frequency (ULF) Raman scattering and synchrotron angle-dispersive x-ray diffraction (ADXRD) measurements support that no structural phase transition exists under high pressure up to 13.80 GPa, but the structure of $β$-GeSe₂ turns into a disordered state near 6.91 GPa and gradually becomes amorphous forming an irreversibly amorphous crystal at 13.80 GPa. Two Raman modes keep softening abnormally upon pressure. The bandgap of $β$-GeSe₂ reduced linearly from 2.59 eV to 1.65 eV under pressure with a detectable narrowing of 36.5%, and the sample under pressure performs the piezochromism phenomenon. The bandgap after decompression is smaller than that in the atmospheric pressure environment, which is caused by incomplete recrystallization. These results enrich the insight into the structural and optical properties of $β$-GeSe₂ and demonstrate the potential of pressure in modulating the material properties of two-dimensional (2D) Ge-based binary material.     

Force networks and elasticity in granular silos

We have made experimental observations of the force networks within a two-dimensional granular silo similar to the classical system of Janssen. Models like that of Janssen predict that pressure within a silo saturates with depth as the result of vertical forces being redirected to the walls of the silo where they can then be carried by friction. We use photoelastic particles to obtain information not available in previous silo experiments --the internal force structure. We directly compare various predictions with the results obtained by averaging ensembles of experimentally obtained force networks. We identify several differences between the mean behavior in our system and that predicted by Janssen-like models: We find that the redirection parameter describing how the force network transfers vertical forces to the walls varies with depth. We find that changes in the preparation of the material can cause the pressure within the silo to either saturate or to continue building with depth. Most strikingly, we observe a nonlinear response to overloads applied to the top of the material in the silo. For larger overloads we observe the previously reported “giant overshoot” effect where overload pressure decays only after an initial increase (G. Ovarlez et al., Phys. Rev. E 67, 060302(R) (2003)). For smaller overloads we find that additional pressure propagates to great depth. Analysis of the differences between the inter-grain contact and force networks suggests that, for our system, when the load and the particle weight are comparable, particle elasticity acts to stabilize the force network, allowing deep propagation. For larger loads, the force network rearranges, resulting in the expected, Janssen-like behavior. Thus, a meso-scale network phenomenon results in an observable nonlinearity in the mean pressure profile.     

钍基碳化物ThC的高压结构稳定性研究

钍基碳化物ThC是重要的核材料,基于第一性原理计算,我们研究了ThC的结构稳定性及相变.声子色散曲线表明基态结构的晶格能够稳定到42 GPa附近,当压力继续升高时虚频的出现表明了动力学的不稳定.经比较基态Fm-3m及高压相Pnma结构的自由能,发现零温下,相变压力为22.4 GPa,符合声子色散曲线的结果,同时预测了两种结构的相变边界.