Investigation of acrylic acid at high pressure using neutron diffraction.
Ontology highlight
ABSTRACT:
SUBMITTER: Johnston BF
PROVIDER: S-EPMC3994943 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Caprolactam, a precursor to nylon-6 has been investigated as part of our studies into the polymerization of materials at high pressure. Single-crystal X-ray and neutron powder diffraction data have been used to explore the high-pressure phase behavior of caprolactam; two new high pressure solid forms were observed. The transition between each of the forms requires a substantial rearrangement of the molecules and we observe that the kinetic barrier to the conversion can aid retention of phases beyond their region of stability. Form II of caprolactam shows a small pressure region of stability between 0.5 GPa and 0.9 GPa with Form III being stable from 0.9 GPa to 5.4 GPa. The two high-pressure forms have a catemeric hydrogen-bonding pattern compared with the dimer interaction observed in ambient pressure Form I. The interaction between the chains has a marked effect on the directions of maximal compressibility in the structure. Neither of the high-pressure forms can be recovered to ambient pressure and there is no evidence of any polymerization occurring.
| S-EPMC6600225 | biostudies-literature
Project description:The first high-pressure neutron diffraction study in a miniature diamond-anvil cell of a single crystal of size typical for X-ray diffraction is reported. This is made possible by modern Laue diffraction using a large solid-angle image-plate detector. An unexpected finding is that even reflections whose diffracted beams pass through the cell body are reliably observed, albeit with some attenuation. The cell body does limit the range of usable incident angles, but the crystallographic completeness for a high-symmetry unit cell is only slightly less than for a data collection without the cell. Data collections for two sizes of hexamine single crystals, with and without the pressure cell, and at 300 and 150 K, show that sample size and temperature are the most important factors that influence data quality. Despite the smaller crystal size and dominant parasitic scattering from the diamond-anvil cell, the data collected allow a full anisotropic refinement of hexamine with bond lengths and angles that agree with literature data within experimental error. This technique is shown to be suitable for low-symmetry crystals, and in these cases the transmission of diffracted beams through the cell body results in much higher completeness values than are possible with X-rays. The way is now open for joint X-ray and neutron studies on the same sample under identical conditions.
| S-EPMC4856139 | biostudies-literature
Project description:Above 2 GPa the phase diagram of water simplifies considerably and exhibits only two solid phases up to 60 GPa, ice VII and ice VIII. The two phases are related to each other by hydrogen ordering, with the oxygen sublattice being essentially the same. Here we present neutron diffraction data to 15 GPa which reveal that the rate of hydrogen ordering at the ice VII-VIII transition decreases strongly with pressure to reach timescales of minutes at 10 GPa. Surprisingly, the ordering process becomes more rapid again upon further compression. We show that such an unusual change in transition rate can be explained by a slowing down of the rotational dynamics of water molecules with a simultaneous increase of translational motion of hydrogen under pressure, as previously suspected. The observed cross-over in the hydrogen dynamics in ice is likely the origin of various hitherto unexplained anomalies of ice VII in the 10-15 GPa range reported by Raman spectroscopy, X-ray diffraction, and proton conductivity.
| S-EPMC7104228 | biostudies-literature
Project description:We report high-pressure neutron powder diffraction measurements of the most hydrated phase in the MgSO4–H2O system, magnesium sulfate undecahydrate, including an analysis of the elastic strain tensor and observations concerning phase changes that occur at high pressure. We have collected neutron powder diffraction data from MgSO4·11D2O (the deuterated analogue of meridianiite), a highly hydrated sulfate salt that is thought to be a candidate rock-forming mineral in some icy satellites of the outer solar system. Our measurements, made using the PEARL/HiPr and OSIRIS instruments at the ISIS neutron spallation source, covered the range 0.1 < P < 800?MPa and 150 < T < 280?K. The refined unit-cell volumes as a function of P and T are parameterized in the form of a Murnaghan integrated linear equation of state having a zero-pressure volume V0 = 706.23?(8)?Å3, zero-pressure bulk modulus K0 = 19.9?(4)?GPa and its first pressure derivative, K? = 9?(1). The structure’s compressibility is highly anisotropic, as expected, with the three principal directions of the unit-strain tensor having compressibilities of 9.6?×?10?3, 3.4?×?10?2 and 3.4?×?10?3 GPa?1, the most compressible direction being perpendicular to the long axis of a discrete hexadecameric water cluster, (D2O)16. At high pressure we observed two different phase transitions. First, warming of MgSO4·11D2O at 545?MPa resulted in a change in the diffraction pattern at 275?K consistent with partial (peritectic) melting; quasielastic neutron spectra collected simultaneously evince the onset of the reorientational motion of D2O molecules with characteristic time-scales of 20–30?ps, longer than those found in bulk liquid water at the same temperature and commensurate with the lifetime of solvent-separated ion pairs in aqueous MgSO4. Second, at ??0.9?GPa, 240?K, MgSO4·11D2O decomposed into high-pressure water ice phase VI and MgSO4·9D2O, a recently discovered phase that has hitherto only been formed at ambient pressure by quenching small droplets of MgSO4(aq) in liquid nitrogen. The fate of the high-pressure enneahydrate on further compression and warming is not clear from the neutron diffraction data, but its occurrence indicates that it may also be a rock-forming mineral in the deep mantles of large icy satellites.
| S-EPMC5289305 | biostudies-literature
Project description:Applications of neutron diffraction to microstructure evaluation of steel investigated by a project commissioned by the Innovative Structural Materials Association are summarized. The volume fraction of austenite (γ) for a 1.5Mn-1.5Si-0.2C steel was measured by various techniques including backscatter electron diffraction (EBSD) and X-ray diffraction. It is recommended to measure volume fraction and texture simultaneously using neutron diffraction. The γ reverse transformation was in situ monitored using dilatometry, EBSD, X-ray diffraction and neutron diffraction. The γ reversion kinetics showed excellent agreements between dilatometry and neutron diffraction, whereas the γ formation started at higher temperatures in EBSD and X-ray diffraction measurements. Such discrepancy is attributed to the change in chemical compositions at the specimen surface by heating; Mn and C concentrations were decreased with heating. Phase transformations from γ upon cooling were monitored, which enabled us to elucidate the changes in lattice parameters of ferrite (α) and γ affected by not only thermal contraction but also transformation strains, thermal misfit strains and carbon enrichment in γ in the above hypoeutectoid steel. Pearlitic transformation started after the carbon enrichment reached approximately 0.76 mass% and contributed to diffraction line broadening. Martensitic transformation with or without ausforming at 700°C was monitored for a medium carbon low alloyed steel. Dislocation density after ausforming was determined using the convolutional multiple whole profile fitting method for 10 s time-sliced data. The changes in γ and martensite lattice parameters upon quenching were tracked and new insights on internal stresses and the axial ratio of martensite were obtained.
| S-EPMC7008240 | biostudies-literature
Project description:In this work, the magnetic anisotropy in two iso-structural distorted tetrahedral Co(II) complexes, CoX 2tmtu2 [X = Cl(1) and Br(2), tmtu = tetra-methyl-thio-urea] is investigated, using a combination of polarized neutron diffraction (PND), very low-temperature high-resolution synchrotron X-ray diffraction and CASSCF/NEVPT2 ab initio calculations. Here, it was found consistently among all methods that the compounds have an easy axis of magnetization pointing nearly along the bis-ector of the compression angle, with minute deviations between PND and theory. Importantly, this work represents the first derivation of the atomic susceptibility tensor based on powder PND for a single-molecule magnet and the comparison thereof with ab initio calculations and high-resolution X-ray diffraction. Theoretical ab initio ligand field theory (AILFT) analysis finds the d xy orbital to be stabilized relative to the d xz and d yz orbitals, thus providing the intuitive explanation for the presence of a negative zero-field splitting parameter, D, from coupling and thus mixing of d xy and . Experimental d-orbital populations support this interpretation, showing in addition that the metal-ligand covalency is larger for Br-ligated 2 than for Cl-ligated 1.
| S-EPMC8420765 | biostudies-literature
Project description:Otoliths, calcium carbonate (CaCO3) ear bones, are among the most commonly used age and growth structures of fishes. Most fish otoliths are comprised of the most dense CaCO3 polymorph, aragonite. Sturgeon otoliths, in contrast, have been characterized as the rare and structurally enigmatic polymorph, vaterite-a metastable polymorph of CaCO3. Vaterite is an important material ranging from biomedical to personal care applications although its crystal structure is highly debated. We characterized the structure of Lake Sturgeon otoliths using thermal analysis and neutron powder diffraction, which is used non-destructively. We confirmed that while Lake Sturgeon otoliths are primarily composed of vaterite, they also contain the denser CaCO3 polymorph, calcite. For the vaterite fraction, neutron diffraction data provide enhanced discrimination of the carbonate group compared to x-ray diffraction data, owing to the different relative neutron scattering lengths, and thus offer the opportunity to uniquely test the more than one dozen crystal structural models that have been proposed for vaterite. Of those, space group P6522 model, a?=?7.1443(4)Å, c?=?25.350(4)Å, V?=?1121.5(2)Å3 provides the best fit to the neutron powder diffraction data, and allows for a structure refinement using rigid carbonate groups.
| S-EPMC5114672 | biostudies-literature
Project description:A hitherto unrecognized resolution effect in neutron Larmor diffraction (LD) is reported, resulting from small-angle neutron scattering (SANS) in the sample. Small distortions of the neutron trajectories by SANS give rise to a blurring of the Bragg angles of the order of a few hundredths of a degree, leading to a degradation of the momentum resolution. This effect is negligible for single crystals but may be significant for polycrystalline or powder samples. A procedure is presented to correct the LD data for the parasitic SANS. The latter is accurately determined by the SESANS technique (spin-echo small-angle neutron scattering), which is readily available on Larmor diffractometers. The analysis technique is demonstrated on LD and SESANS data from α-Fe2O3 powder samples. The resulting d-spacing range agrees with experimental data from high-resolution synchrotron radiation powder diffraction on the same sample.
| S-EPMC6998774 | biostudies-literature
Project description:Quasielastic neutron scattering (QENS) is an ideal technique for studying water transport and relaxation dynamics at pico- to nanosecond timescales and at length scales relevant to cellular dimensions. Studies of high pressure dynamic effects in live organisms are needed to understand Earth's deep biosphere and biotechnology applications. Here we applied QENS to study water transport in Shewanella oneidensis at ambient (0.1 MPa) and high (200 MPa) pressure using H/D isotopic contrast experiments for normal and perdeuterated bacteria and buffer solutions to distinguish intracellular and transmembrane processes. The results indicate that intracellular water dynamics are comparable with bulk diffusion rates in aqueous fluids at ambient conditions but a significant reduction occurs in high pressure mobility. We interpret this as due to enhanced interactions with macromolecules in the nanoconfined environment. Overall diffusion rates across the cell envelope also occur at similar rates but unexpected narrowing of the QENS signal appears between momentum transfer values Q = 0.7-1.1 Å(-1) corresponding to real space dimensions of 6-9 Å. The relaxation time increase can be explained by correlated dynamics of molecules passing through Aquaporin water transport complexes located within the inner or outer membrane structures.
| S-EPMC4703977 | biostudies-other
Project description:Fast charging (<15 min) of lithium-ion batteries (LIBs) for electrical vehicles (EVs) is widely seen as the key factor that will greatly stimulate the EV markets, and its realization is mainly hindered by the sluggish diffusion of Li+ . To have a mechanistic understanding of Li+ diffusion within LIBs, in this study, structural evolutions of electrodes for a Ni-rich LiNi0.6 Mn0.2 Co0.2 O2 (NMC622) || graphite cylindrical cell with high areal loading (2.78 mAh cm-2 ) are developed for operando neutron powder diffraction study at different charging rates. Via sequential Rietveld refinements, changes in structures of NMC622 and Lix C6 are obtained during moderate and fast charging (from 0.27 C to 4.4 C). NMC622 exhibits the same structural evolution regardless of C-rates. For phase transitions of Lix C6 , the stage I (LiC6 ) phase emerges earlier during the stepwise intercalation at a lower state of charge when charging rate is increased. It is also found that the stage II (LiC12 ) → stage I (LiC6 ) transition is the rate-limiting step during fast charging. The LiC12 → LiC6 transition mechanism is further analyzed using the Johnson-Mehl-Avrami-Kolmogorov model. It is concluded as a diffusion-controlled, 1D phase transition with decreasing nucleation kinetics under increasing chargingrates.
| S-EPMC8564430 | biostudies-literature