Pressure-induced Amorphization Research Articles

Origin of negative thermal expansion and pressure-induced amorphization in zirconium tungstate from a machine-learning potential

Understanding various macroscopic pressure-volume-temperature properties of materials on the atomistic level has always been an ambition for physicists and material scientists. Particularly, some materials such as zirconium tungstate (ZrW2O8), exhibit multiple exotic properties including negative thermal expansion (NTE) and pressure-induced amorphization (PIA). Here, using machine-learning based deep potential, we trace both of the phenomena in ZrW2O8 back to a common atomistic origin, where the nonbridging O atoms play a critical role. We demonstrate that the nonbridging O atoms confer great flexibility to vibration of polyhedrons, and kinetically drive volume shrinking on heating, or NTE. In addition, beyond a certain critical pressure, we find that the migration of nonbridging O atoms leads to additional bond formation that lowers the potential energy, suggesting that the PIA is a potential-driven first-order phase transition. Most importantly, we identify a second critical pressure beyond which the amorphous phase of ZrW2O8 undergoes a hidden phase transition from a reversible phase to an irreversible one.

Reticular chemistry for the rational design of mechanically robust mesoporous merged-net metal-organic frameworks

Reticular chemistry for the rational design of mechanically robust mesoporous merged-net metal-organic frameworks

Degenerate Lattice-Instability-Driven Amorphization under Compression in Metal Halide Perovskite CsPbI3.

Halide perovskites have been intensively investigated for photovoltaic applications because of their good optoelectronic properties and low cost. Various high-pressure experiments have shown that these materials generally undergo reversible phase transitions between different crystalline phases as well as between crystalline and amorphous phases under external pressure. Herein, using first-principles density functional theory (DFT) and ab initio molecular dynamics (AIMD) calculations, we investigate the origin of the pressure-induced amorphization in CsPbI3. We find that the amorphous-like structures obtained from AIMD calculations become more stable than the orthorhombic Pbnm phase above 6.66 GPa, in good agreement with the experimental value (4.44 GPa). We further find that an imaginary flat band appears in the phonon dispersion of the orthorhombic CsPbI3 phase across the Brillouin zone at 10 GPa, leading to degenerate lattice instabilities. These energetically degenerate phonon modes are related to PbI6 octahedral tilting modes and provide random local distortions, leading to amorphization.

Investigations on the intrinsic and template-dependent transformations of AlPO4-11 molecular sieve under high pressure

In this study, aluminophosphate molecular sieve AlPO4-11, with one-dimensional elliptical channels, was investigated under high pressure in non-penetrating silicone oil by X-ray powder diffraction, infrared spectroscopy and theoretical simulation, focusing on its intrinsic and template-modified mechanical behaviors. Two distinct compressible regimes were observed for both the calcined and as-synthesized AlPO4-11 frameworks before pressure-induced amorphization (PIA). The channel cross-section in the calcined AlPO4-11 framework showed an obvious increase in the ellipticity during this process. The framework structure began to lose crystallinity at approximately 2–3 GPa and underwent significant amorphization at 6.6 GPa. PIA was mainly induced via the destruction of the constructed species along the periodic crystallographic planes which are parallel to the channel axis. The bulk moduli showed that this empty framework was rather soft in these regimes. For the as-synthesized AlPO4-11 framework, the mechanical stability of the channels was markedly improved by the template molecules. A different elliptic deformation of the cross-section with a reduced contractility in the minor axis direction was presented. Discontinuous volume evolution occurs at 3–4 GPa and significant amorphization was postponed to 13.7 GPa. The as-synthesized AlPO4-11 was stiffer than calcined AlPO4-11 and showed a soft to hard transformation due to the strengthened host-guest interaction upon compression. Moreover, infrared spectra indirectly confirmed the structural collapses by detecting the vibrational characteristics of the embedded template molecules. The present results provided a comparative and basic knowledge of the intrinsic and extrinsic stability, compressibility, channel deformation and collapse of the AlPO4-11 framework under high pressure. This study emphasized the importance of guest molecules in modifying the mechanical behaviors of zeolites and resisting framework collapse.

Sol-gel processing of a covalent organic framework for the generation of hierarchically porous monolithic adsorbents

Sol-gel processing of a covalent organic framework for the generation of hierarchically porous monolithic adsorbents

Morphology Tuned Pressure Induced Amorphization in VO2(B) Nanobelts

Pressure-induced amorphization (PIA) has drawn great attention since it was first observed in ice. This process depends closely on the crystal structure, the size, the morphology and the correlated pressurization environments, among which the morphology-tuned PIA remains an open question on the widely concerned mesoscale. In this work, we report the synthesis and high-pressure research of VO2(B) nanobelts. XRD and TEM were performed to investigate the amorphization process. The amorphization pressure in VO2(B) nanobelts(~30 GPa) is much higher than that in previous reported 2D VO2(B) nanosheets(~21 GPa), the mechanism is the disruption of connectivity at particular relatively weaker bonds in the (010) plane. These results suggest a morphology-tuned pressure-induced amorphization, which could promote the fundamental understanding of PIA.

Providing evidence for two remarkably stable liquid states in water

Examining the second glass transition without pressure-induced ice amorphization via micron-sized water droplets

Coexistence of vitreous and crystalline phases of H2O at ambient temperature

Formation of vitreous ice during rapid compression of water at room temperature is important for biology and the study of biological systems. Here, we show that Raman spectra of rapidly compressed water at greater than 1 GPa at room temperature exhibits the signature of high-density amorphous ice, whereas the X-ray diffraction (XRD) pattern is dominated by crystalline ice VI. To resolve this apparent contradiction, we used molecular dynamics simulations to calculate full vibrational spectra and diffraction patterns of mixtures of vitreous ice and ice VI, including embedded interfaces between the two phases. We show quantitatively that Raman spectra, which probe the local polarizability with respect to atomic displacements, are dominated by the vitreous phase, whereas a small amount of the crystalline component is readily apparent by XRD. The results of our combined experimental and theoretical studies have implications for detecting vitreous phases of water, survival of biological systems under extreme conditions, and biological imaging. The results provide additional insight into the stable and metastable phases of H2O as a function of pressure and temperature, as well as of other materials undergoing pressure-induced amorphization and other metastable transitions.

Pressure-induced structural transformation of clathrate Ge136 via ultrafast recrystallization of an amorphous intermediate

We study the pressure-induced structural transformation of Ge$_{136}$ clathrate by ab initio molecular dynamics and metadynamics. The system under pressure first undergoes amorphization followed by an ultrafast recrystallization to the $\beta$-tin structure on the time scale of 30 ps. The initial pressure-induced amorphization of clathrate is triggered by high pressure while the subsequent fast recrystallization to $\beta$-tin is driven by low temperature. Interestingly, the amorphous intermediate is still diffusive even at room temperature, in spite of very strong undercooling, making the ultrafast recrystallization possible. The system provides an explicit example of structural transformation between two crystalline phases proceeding via non-crystalline intermediate. Upon fast decompression of the amorphous structure with incipient crystalline order the recrystallization is blocked and the system instead proceeds to the tetrahedral LDA amorphous phase.

Atomistic Models of Amorphous Metal–Organic Frameworks

There is an increasing interest in the amorphous states of metal-organic frameworks (MOFs) and porous coordination polymers, which can be produced by pressure-induced amorphization, temperature-induced amorphization, melt-quenching, ball-milling, irradiation, etc. They can exhibit useful physical and chemical properties, distinct from those achievable in the crystalline states, along with greater ease of processing, and intrinsic advantages over crystals and powders, such as high transparency and mechanical robustness. However, these amorphous states are particularly challenging to characterize, and the determination of their framework structure at the microscopic scale is difficult, with only indirect structural information available from diffraction experiments. In this Perspective, we review and compare the existing methodologies available for the determination of microscopic models of amorphous MOFs, based on both experimental data and simulation methods. In particular, we present the atomistic models that can be obtained using Reverse Monte Carlo (RMC) methods, Continuous Random Networks (CRN), classical and \emph{ab initio} molecular dynamics, reactive force fields, and simulated assembly/polymerization algorithms.

Anomalous density, sound velocity, and structure of pressure-induced amorphous quartz

The study of quartz and other silica systems under pressure is one of the most prolific domains of research over the past 50 years because of their applications in material science and fundamental relevance to planetary interiors. The characterization of the amorphous state is essential for the comprehension of pressure-induced amorphization of minerals, the metamorphism observed in shocked materials, and the study of melt structures under pressure. Here, we measured in situ, under static compression the density, sound velocities, and electronic structure of quartz as it passes through its pressure-induced amorphization transition. The transition pressure could be derived from the abrupt increase in density and sound velocity at 24 GPa, and from strong changes in the silicon ${L}_{2,3}$ edge and oxygen $K$ edge between 22 and 27 GPa observed in x-ray Raman scattering data, confirming previous results from x-ray diffraction. Above this pressure, our data show an anomalous behavior in density, sound velocity, and electronic fine structure compared to the cold compressed glass and other silica polymorphs. The pressure-induced amorphous quartz has a lower density relative to that of the compressed glass, consistent with the lower average coordination inferred from a different signature in the Si ${L}_{2,3}$ and O $K$ electronic absorption edges measured by x-ray Raman scattering spectroscopy. This behavior sheds light on the pressure limit of tetrahedral units in ${\mathrm{SiO}}_{2}$ components and the existence of polyamorphism in network-forming materials, and highlights the possibility to discriminate between different amorphous states with x-ray Raman scattering spectroscopy.

The phase transition of nicotinic acid under high pressure

By using Raman spectroscopic and diamond anvil cell (DAC) technique, the high-pressure Raman spectra of nicotinic acid have been conducted up to 17 GPa. According to the experimental results, nicotinic acid has undergone a possible structural phase transition at 2.5 GPa. At pressures higher than 17 GPa, all the Raman bands disappeared, suggesting a pressure-induced amorphization happens. After the pressure released to ambient condition, the Raman spectrum maintains the profile of that at 17 GPa, indicating that the amorphous state of nicotinic acid could be quenched to ambient.

Pressure-Induced Amorphization and Crystallization of Heterophase Pd Nanostructures.

Control of structural ordering in noble metals is very important for the exploration of their properties and applications, and thus it is highly desired to have an in-depth understanding of their structural transitions. Herein, through high-pressure treatment, the mutual transformations between crystalline and amorphous phases are achieved in Pd nanosheets (NSs) and nanoparticles (NPs). The amorphous domains in the amorphous/crystalline Pd NSs exhibit pressure-induced crystallization (PIC) phenomenon, which is considered as the preferred structural response of amorphous Pd under high pressure. On the contrary, in the spherical crystalline@amorphous core-shell Pd NPs, pressure-induced amorphization (PIA) is observed in the crystalline core, in which the amorphous-crystalline phase boundary acts as the initiation site for the collapse of crystalline structure. The distinct PIC and PIA phenomena in two different heterophase Pd nanostructures might originate from the different characteristics of Pd NSs and NPs, including morphology, amorphous-crystalline interface, and lattice parameter. This work not only provides insights into the phase transition mechanisms of amorphous/crystalline heterophase noble metal nanostructures, but also offers an alternative route for engineering noble metals with different phases.

Structural and optical properties evolution in pressure-induced amorphization of metal-organic framework ZIF-8

Structural and optical properties evolution in pressure-induced amorphization of metal-organic framework ZIF-8

Exploring High-Pressure Transformations in Low-Z (H2, Ne) Hydrates at Low Temperatures

The high pressure structural behavior of H2 and Ne clathrate hydrates with approximate composition H2/Ne·~4H2O and featuring cubic structure II (CS-II) was investigated by neutron powder diffraction using the deuterated analogues at ~95 K. CS-II hydrogen hydrate transforms gradually to isocompositional C1 phase (filled ice II) at around 1.1 GPa but may be metastably retained up to 2.2 GPa. Above 3 GPa a gradual decomposition into C2 phase (H2·H2O, filled ice Ic) and ice VIII’ takes place. Upon heating to 200 K the CS-II to C1 transition completes instantly whereas C1 decomposition appears sluggish also at 200 K. C1 was observed metastably up to 8 GPa. At 95 K C1 and C2 hydrogen hydrate can be retained below 1 GPa and yield ice II and ice Ic, respectively, upon complete release of pressure. In contrast, CS-II neon hydrate undergoes pressure-induced amorphization at 1.9 GPa, thus following the general trend for noble gas clathrate hydrates. Upon heating to 200 K amorphous Ne hydrate crystallizes as a mixture of previously unreported C2 hydrate and ice VIII’.

Experimental evidence for glass polymorphism in vitrified water droplets

The nature of amorphous ices has been debated for more than 35 years. In essence, the question is whether they are related to ice polymorphs or to liquids. The fact that amorphous ices are traditionally prepared from crystalline ice via pressure-induced amorphization has made a clear distinction tricky. In this work, we vitrify liquid droplets through cooling at ≥106 K ⋅ s-1 and pressurize the glassy deposit. We observe a first order-like densification upon pressurization and recover a high-density glass. The two glasses resemble low- and high-density amorphous ice in terms of both structure and thermal properties. Vitrified water shows all features that have been reported for amorphous ices made from crystalline ice. The only difference is that the hyperquenched and pressurized deposit shows slightly different crystallization kinetics to ice I upon heating at ambient pressure. This implies a thermodynamically continuous connection of amorphous ices with liquids, not crystals.

The microscopic transition process from high-density to low-density amorphous state of SnI4

A molecular crystalline SnI4 undergoes pressure-induced solid-state amorphization via molecular dissociation to the high-density amorphous (HDA) state, which we call Am-I. In the present study, we examine the reverse transition process from Am-I to the low-density amorphous (LDA) state, called Am-II. We first measure the structure factor on decompression from 30 GPa down to 1.1 GPa at room temperature, using in situ angle-dispersive synchrotron x-ray measurement and a diamond anvil cell. We then estimate the density, which exhibits an abrupt change between 3.3 and 3.0 GPa, indicating the HDA(Am-I)-to-LDA(Am-II) transition. We use the density and the molecular configuration generated from a molecular dynamics simulation as input to a reverse Monte Carlo fit. The fit vividly visualizes gradual molecular reassociation between 18 and 14 GPa within the Am-I region. The Am-I state can thus be divided into two states: the high-pressure Am-I state containing isolated Sn atoms and the low-pressure Am-I state consisting of deformed molecules connected by metallic I2 bonds. In the latter state, the molecular shape becomes C 3v -like just before the transition to Am-II, in which molecules recover the original T d symmetry. This local symmetry change has been detected on the liquid–liquid transition of SnI4, suggesting the strong coupling between the local symmetry and the global order parameter of density.

Pressure-Induced Emission toward Harvesting Cold White Light from Warm White Light.

The pressure-induced emission (PIE) behavior of halide perovskites has attracted widespread attention and has potential application in pressure sensing. However, high-pressure reversibility largely inhibits practical applications. Here, we describe the emission enhancement and non-doping control of the color temperature in two-dimensional perovskite (C6 H5 CH2 CH2 NH3 )2 PbCl4 ((PEA)2 PbCl4 ) nanocrystals (NCs) through high-pressure processing. A remarkable 5 times PIE was achieved at a mild pressure of 0.4 GPa, which was highly associated with the enhanced radiative recombination of self-trapped excitons. Of particular importance is the retention of the 1.6 times emission of dense (PEA)2 PbCl4 NCs upon the complete release of pressure, accompanied by a color change from "warm" (4403 K) to "cold" white light with 14295 K. The irreversible pressure-induced structural amorphization, which facilitates the remaining local distortion of inorganic Pb-Cl octahedra with respect to the steric hindrance of organic PEA+ cations, should be greatly responsible for the quenched high-efficiency photoluminescence.

Pressure-induced amorphization of noble gas clathrate hydrates

The high-pressure structural behavior of the noble gas (Ng) clathrate hydrates $\mathrm{Ar}\ifmmode\cdot\else\textperiodcentered\fi{}6.5\phantom{\rule{0.16em}{0ex}}{\mathrm{H}}_{2}\mathrm{O}$ and $\mathrm{Xe}\ifmmode\cdot\else\textperiodcentered\fi{}7.2\phantom{\rule{0.16em}{0ex}}{\mathrm{H}}_{2}\mathrm{O}$ featuring cubic structures II and I, respectively, was investigated by neutron powder diffraction (using the deuterated analogues) at 95 K. Both hydrates undergo pressure-induced amorphization (PIA), indicated by the disappearance of Bragg diffraction peaks, but at rather different pressures, at 1.4 and above 4.0 GPa, respectively. Amorphous Ar hydrate can be recovered to ambient pressure when annealed at $g1.5\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$ and 170 K and is thermally stable up to 120 K. In contrast, it was impossible to retain amorphous Xe hydrate at pressures below 3 GPa. Molecular dynamics (MD) simulations were used to obtain general insight into PIA of Ng hydrates, from Ne to Xe. Without a guest species, both cubic clathrate structures amorphize at 1.2 GPa, which is very similar to hexagonal ice. Filling of large-sized H cages does not provide stability toward amorphization for structure II, whereas filled small-sized dodecahedral D cages shift PIA successively to higher pressures with increasing size of the Ng guest. For structure I, filling of both kinds of cages, large-sized T and small-sized D, acts to stabilize in a cooperative fashion. Xe hydrate represents a special case. In MD, disordering of the guest hydration structure is already seen at around 2.5 GPa. However, the different coordination numbers of the two types of guests in the crystalline cage structure are preserved, and the state is shown to produce a Bragg diffraction pattern. The experimentally observed diffraction up to 4 GPa is attributed to this semicrystalline state.

Solvent-controlled elongation and mechanochemical strain in a metal-organic framework.

Under high pressure, crystals of [Zn(m-btcp)2(bpdc)2]·2DMF·H2O, referred to as DMOF are particularly sensitive to the type of pressure-transmitting media (PTM) employed: large PTM molecules seal the pores and DMOF is compressed as a closed system, whereas small PTM molecules are pushed into the pores, thereby altering the stoichiometry of DMOF. Compression in glycerol and Daphne 7474 leads to negative linear compressibility (NLC), while a mixture of methanol : ethanol : water 'hyperfills' the pores of the chiral framework, adjusting its 3-dimensional strain and resulting in pressure-induced amorphization around 1.2 GPa. The uptake of the small-molecule PTM strongly increases the dimensions of DMOF in the direction perpendicular to that of the NLC of the crystal.