Single crystal diffraction with X-rays and neutrons: High quality at high pressure?

Abstract

Single crystal X-ray and neutron diffraction is essential for determining occupancies, positional as well as static and dynamic displacement parameters in crystalline matter by measuring Bragg, satellite or diffuse reflections. In our contribution a new low-temperature high pressure cell for neutron single crystal diffraction will be presented. It is designed to operate from a few K to ambient temperature in “orange” cryostats at pressures up to at least 3 GPa. We will present first neutron diffraction results obtained at E4/HMI Berlin and discuss the quality of the data and the significance of the results. A software package has been written (as a part of the PROMETHEUS system), which deals with the data reduction for both X-ray and neutron high pressure cell single crystal data. Likewise a data collection program has been developed for single crystal data collection on four-circle diffractometers using Merrill-Bassett cells. A series of single crystal experiments on H₂O and D₂O ice VI and KDP (KH₂PO₄) show that results of very high quality can be obtained routinely including even higher order terms in the atomic displacement parameters.     

High pressure neutron diffraction studies using the Paris-Edinburgh cell

Abstract

Neutron diffraction was until recently confined to pressures below ～ 3 GPa. This restricted range has limited the high-pressure structural information that is available for a wide range of phenomena for which neutron diffraction is the technique of choice. But now the recently-developed Paris-Edinburgh cell can achieve pressures up to ～ 30 GPa with a sample volume large enough to allow accurate structural studies with neutrons. After a period of development of the neutron scattering techniques needed to obtain the best possible results using the cell, a variety of successful structural studies have been performed. These illustrate the value of neutron diffraction in important areas such as locating hydrogen and other low-Z atoms in structures, the measurement of accurate structural pressure dependence and the examination of the changes in atomic thermal motion with pressure.     

High pressure neutron diffraction using the paris-edinburgh cell: Experimental possibilities and future prospects

Abstract

High pressure neutron diffraction using the Paris-Edinburgh cell has attracted considerable interest ever since it has been shown that full structural data can be obtained at pressures up to 10 GPa. In this paper we will focus on the current state of this technique. Specifically, we report on new experimental possibilities concerning: i) access to “ultrahigh” pressures beyond 20 GPa, ii) experiments at variable temperatures down to 100 K, and iii) experiments on single crystals in inelastic neutron scattering. Current attempts to increase the pressure and temperature range are discussed.     

Modified Bridgman anvils for high pressure synthesis and neutron scattering

ABSTRACT

A simple modified Bridgman design for large volume pressure anvils usable in the Paris-Edinburgh (PE) press has been demonstrated at Oak Ridge National Laboratory Spallation Neutron Source. The design shows advantages over the toroidal anvils typically used in the PE press, mainly rapid compression/decompression rates, complete absence of blow-outs upon drastic phase transitions, simplified cooling, high reliability, and relative low loads (～40 tons) corresponding to relatively high pressures (～20?GPa). It also shows advantages over existing large-volume diamond cells as sample volumes of ～2–3?mm³ can be easily and rapidly synthesized. The anvils thus allow sample sizes sufficient for in situ neutron diffraction as well as rapid synthesis of adequate amounts of new materials for ex situ analysis via total neutron scattering and neutron spectroscopy.     

Developments of nano-polycrystalline diamond anvil cells for neutron diffraction experiments

ABSTRACT

A new high pressure cell for neutron diffraction experiments using nano-polycrystalline anvils is presented. The cell design, off-line pressure generation tests and a gas-loading procedure for this cell are described. The performance is illustrated by powder neutron diffraction patterns of ice VII to ～82?GPa. We also demonstrate the feasibility of single crystal neutron diffraction experiments of Fe₃O₄ at ambient conditions using this cell and discuss the current limitation and future developments.     

Neutron Diffraction Study of the p - T Phase Diagram for Erbium

Electrical resistivity measurements performed on a single crystal of erbium as a function of temperature and hydrostatic pressure have provided a preliminary p - T phase diagram. The results have been interpreted in terms of a model for the magnetic structures of Er deduced from neutron diffraction studies at ambient pressure. This model predicted the existence of a magnetic structure with a wave vector of Q =2/7 c * at 4.2 K, when the applied pressure is larger than 3 kbar. This paper reports a neutron diffraction study of erbium made in the temperature range of 4 to 100 K, at pressures between 0.5 and 6 kbar. We have observed the predicted suppression of the low temperature conical ferromagnetic phase and the emergence of a new phase with Q =8/33 c *. The neutron diffraction measurements has enabled us to identify the various phases that develop from the cycloidal phases previously observed at atmospheric pressure.     

Rietveld analysis of high pressure powder diffraction data

Abstract

X-ray and neutron powder diffraction data obtained from samples contained within high pressure cells are generally of lower quality than data collected from samples at ambient conditions. The far smaller sample size as well as possible contamination of the pattern by the pressure cell means that Rietveld refinement techniques must be adapted to extract the maximum useful information from the data. These problems become paramount as larger structures at high pressure are attempted. Techniques such as “leBail extraction”, “soft restraints” and “rigid body refinement” will be discussed with application to analysis of high pressure neutron powder diffraction data.     

A new high P-T cell for neutron diffraction up to 7 GPa and 2000 K with measurement of temperature by neutron radiography

Abstract

This paper reports developments to enable neutron diffraction at simultaneous high temperatures and pressures using the Paris-Edinburgh cell. These include a new design of a cell assembly with internal heating. One of the novel features of our system is the use of neutron radiographic methods for measurement of temperature. Fully refinable neutron diffraction patterns obtained by time of flight technique with our apparatus are found to be of comparable quality to previous high-pressure studies at ambient temperatures. In this paper we describe the procedures for the generation and measurement of pressure and temperature and illustrate the quality of the data which can be obtained. The present system may be used on a routine basis for experiments up to 7 GPa and temperature approaching 2000 K. Current attempts are discussed for extending these measurements to a wider domain of pressures and temperatures.     

Structural study of ND4I at high pressures and low temperatures

Abstract

Structure, positional, and thermal parameters of ND₄I were studied at high pressures up to 90 kbar and low temperatures down to 10 K using time-of-flight neutron diffraction. The phase transition from a disordered CsCI-type cubic phase ND₄I(II) into a recently discovered high pressure phase ND₄I(V) was observed at P = 80(5) kbar. Surprisingly, the structure of the high pressure phase V was found to bear a strong resemblance to that of the ambient pressure, low-temperature phase III - tetragonal structure with an antiparallel ordering of ammonium ions, space group P4/nmm. The critical value of the deuterium positional parameter corresponding to the II-V transition is close to the one for the phase transition between the disordered and ordered CsCl-type cubic phases II and IV in other ammonium halides.     

Investigation of Nd2CuO4 crystal structure at high pressure by neutron diffraction

Abstract

The crystal structure of Nd₂CuO₄ has been studied by neutron diffraction at pressure up to 5 Gpa. The volume compressibility value was determined as 5·6·10^?3/Gpa. The decrease of positional parameter of neodymium at high pressure has been observed. This structural change is explained by pressure induced neodymium ions charge increase.     

Angle-dispersive powder diffraction at high pressure using an image-plate area detector

Abstract

An imaging-plate system designed for the full Rietveld refinement of crystal structures at high pressure is described. Emphasis is given to techniques that have been developed to obtain data free from contaminating diffraction peaks and to a general method of processing the diffraction data. The advantages of using pressure cells that allow full diffraction patterns to be collected are also described.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’, Daresbury Laboratory 20-21 July 1991     

A structural comparison of supercooled water and intermediate density amorphous ices

New data are presented on neutron diffraction in ultrapure bulk supercooled heavy water measured down to 262?K. The data are analysed in terms of the trends observed in the first sharp diffraction peak (FSDP) parameters, the feature which dominates the measured neutron spectra. The neutron FSDP position, height and width are compared to literature data for supercooled water, water under pressure and to the same parameters obtained for recently discovered intermediate density amorphous ices. It is found that the FSDP parameters in supercooled water and the amorphous ices generally exhibit a similar behaviour, suggesting a new structural regime may occur in deeply supercooled water below Q ₀?～?1.83?Å^?1 (T?～?251?K) associated with increased intermediate range ordering. It is argued that this structural regime may be linked to a similar trend in the density which appears when the density is plotted as a function of FSDP position. A detailed comparison of the neutron and X-ray structure factors for supercooled water and intermediate density amorphous ices with the same FSDP positions is also made. The diffraction data show that although the overall general structures are qualitatively very similar, the amorphous ice correlations are considerably sharper and extend to much higher radial distances.     

Neutron scattering studies of the D-O and D-12 cyclohexane under high pressure

Abstract

Preliminary results of neutron diffraction and inelastic neutron scattering studies under high pressure of normal (D-O) and deuterated (D-12) cyclohexane are presented.     

High pressure neutron diffraction to beyond 20 GPa and below 1.8 K using Paris-Edinburgh load frames

We describe a method for collecting neutron diffraction patterns simultaneously at high pressure (>22?GPa) and low temperature (<1.8?K). The system uses ～5–10?mm³ samples compressed by double-toroidal sintered diamond anvils, with the required forces generated by a Paris-Edinburgh press of 30?kg mass. Technical details are given and diffraction data of ε-iron at 22.6?GPa and 1.79?K are presented.     

Two-dimensional ordering in 1-propanol-graphite-oxide intercalates: isotopic effects

ABSTRACT

Intercalation of fully deuterated 1-propyl alcohol into graphite oxide is studied by means of the unique capabilities offered by the NIMROD neutron diffractometer. We develop methods to estimate the amount of intercalant present within the neutron irradiated volume using for the purpose of the set of constraints implicit in the outputs of the Gudrun diffraction data treatment software. The results are compared to those from our previous study on of fully hydrogenated 1-propanol intercalation [C. Cabrillo, F. Barroso-Bujans, R. Fernandez-Perea, F. Fernandez-Alonso, D. Bowron and F.J. Bermejo, Carbon 100, 546 (2016)] where a two-dimensional ordering transition under slow heating from 100?K was discovered. The rearrangement of the 1-propanol molecular pillars did allow for the formation of bilayer intercalation. In contrast, sample deuteration leads to remarkable differences in both the intercalation kinetics and intercalate thermal response, avoiding the two-dimensional transition which would lead to bilayer formation. Finally, neutron diffraction results have enabled us to disentangle the highly anomalous behaviour exhibited by hitherto unpublished broad band dielectric spectroscopy studies which are now understood on the basis of the two-dimensional transition just referred to.     

High pressure cell for neutron diffraction investigations

Abstract

The design of a titanium-zirconium clamped cylinder-piston type pressure cell for neutron diffraction investigations under hydrostatic pressure up to 10 kbars without supports is described. It is the first time that Freon-11 has been used as a hydrostatic pressure transmitting medium. The following results carried out at the room temperature are presented: the discovery of the transition from I to 111 phase in a LiKSO₄ single crystal and the results of the investigation on the influence of pressure upon the structure of the YBaCuO HTSC obtained by means of the powder diffraction method.     

Structural study of ND4Br at high pressure

Abstract

A structure of ND₄Br has been studied at pressures up to 9 GPa by means of time-of-flight neutron diffraction. A phase transition to the high pressure phase V was observed at P=8·2(5)GPa. It was found that the phase V has a tetragonal structure with an antiparallel ordering of ammonium ions, space group P4/nmm which is in strong resemblance with low temperature modification ND₄Br(III). Deuterium positional parameter as a function of pressure was obtained.     

A new belt-type apparatus for neutron-based rheological measurements at gigapascal pressures

We have developed a new solid-media apparatus for performing rheological investigations at multi-gigapascal pressures. The pressure cell consists of a simple belt design and fits in a modified 250 tonne Paris–Edinburgh press. Elastic strains are measured by neutron diffraction, on the ENGIN-X experimental station at ISIS. Stresses are estimated from the measured strains in combination with published values of the elastic moduli. As an exemplair of the method, we present data from initial deformation experiments on pyrope garnet at 1.5 GPa and 873 K. Data collection times are as short as 60 min and the elastic strain resolution is better than 10^?4. We anticipate, however, that by interrupted testing, strain rates as low as 10^?9/s, or lower, will be measurable.     

Double-Q magnetic structures and strong planar anisotropy in tetragonal ErRu2Ge2and ErRu2Si2

Single crystal magnetization measurements and powder neutron diffraction on tetragonal ErRu₂Ge₂ as well as anisotropy of the paramagnetic susceptibility and specific heat measurements on ErRu₂Si₂ are presented. Besides the huge crystal field contribution to the uniaxial anisotropy, which favors the basal plane, a strong in-plane anisotropy is evidenced. From these features and neutron diffraction experiments it is shown that magnetic structures of these materials are double-Q and accordingly non-colinear below their Néel temperature (5.2 and 6.0 K for Ge and Si based compounds, respectively). The magnetic structures induced during the metamagnetic processes are discussed. Received 24 December 1999