The high-resolution powder diffractometer at the high flux isotope reactor

Neutron powder diffraction is increasingly recognized as one of the most powerful techniques for studying the structural and magnetic properties of advanced materials. Despite the growing demand to study an ever-increasing array of interesting materials, there is only a handful of neutron diffractometers available to serve the US neutron scattering community. This article describes the new high-resolution powder diffractometer that has recently been installed at the High Flux Isotope Reactor in Oak Ridge. The instrument is designed to provide an optimum balance between high neutron flux and high resolution. Due to its versatility the diffractometer can be employed for a large variety of experiments, but it is particularly adapted for refinements of structures with large interplanar spacings as well as of complex magnetic structures. In addition to traditional crystal and magnetic structural refinements, studies of phase transitions, thermal expansion, texture analysis, and ab initio structure solution from powder data can be undertaken.     

A neutron diffractometer with a linear position sensitive detector

A powder diffractometer with a linear position sensitive detector (PSD) has been designed and fabricated at BARC. The system is in operation at Dhruva reactor. The PSD has been tested for the position linearity and the uniformity of efficiency. The resolution Δd/d of the diffractometer has been found to be 1·3%. The data can be analyzed using profile refinement technique.     

Temperature variation of the Debye-Waller factors of Ba++ and F− ions in BaF2 powder by x-ray diffraction

The temperature variation of the Debye-Waller factors of Ba⁺⁺ and F⁻ ions in BaF₂ powder has been studied using x-ray powder diffraction over the temperature range 77°–298°K. A continuous flow cryostat has been specially fabricated for this purpose for the YPC 50 NM powder diffractometer available in the department. The Debye-Waller factors of Ba⁺⁺ and F⁻ between room temperature and 879°K have been measured using single crystal neutron diffraction by Cooperet al. Theoretical lattice dynamics shell model calculations using a 7-parameter model in a quasiharmonic approximation have been done over a temperature range 77° to 879°K. The theoretical values have been compared with the present x-ray measurements and the single crystal neutron diffraction values and the results are discussed.     

A twelve‐analyzer detector system for high‐resolution powder diffraction

A dedicated high‐resolution high‐throughput X‐ray powder diffraction beamline has been constructed at the Advanced Photon Source (APS). In order to achieve the goals of both high resolution and high throughput in a powder instrument, a multi‐analyzer detector system is required. The design and performance of the 12‐analyzer detector system installed on the powder diffractometer at the 11‐BM beamline of APS are presented.     

Pulsed neutron powder diffraction at high pressure by a capacity-increased sapphire anvil cell

A new design of opposed anvil cell for time-of-flight neutron powder diffraction was prepared for use at advanced pulsed sources. A couple of single-crystal sapphire sphere anvils and a gasket of fully hardened Ti–Zr null alloy were combined to compress 35 mm³ of sample volume to 1 GPa and 11 mm³ to 2 GPa of pressures, respectively. A very high-quality powder diffraction pattern was obtained at Japan Proton Accelerator Research Complex for a controversial high pressure phase of methane hydrate. The counting statistics, resolution, absolute accuracy and d-value range of the pattern were all improved to be best suitable for precise structure refinement. The sample is optically accessible to be measured by Raman and fluorescence spectroscopy during and after compression. The current cell will be an alternative choice to study hydrogenous materials of complex structures that are stable at the described pressure regime.     

Neutron diffraction study of quasi-one-dimensional spin-chain compounds Ca<Subscript>3</Subscript>Co<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>6</Subscript>

We report the results of the DC magnetization, neutron powder diffraction and neutron depolarization studies on the spin-chain compounds Ca₃Co_2–x Fe _x O₆ (x = 0, 0.1, 0.2 and 0.4). Rietveld refinement of neutron powder diffraction patterns at room temperature confirms the single-phase formation for all the compounds in rhombohedral structure with space group Rc. Rietveld refinement also confirms that Fe was doped at the trigonal prism site, 6a (0, 0, 1/4) of Co. The high temperature magnetic susceptibility obeys the Curie-Weiss law; the value of the paramagnetic Curie temperature (θ _p) decreases as the concentration of iron increases and it becomes negative for x = 0.4. No extra Bragg peak as well as no observable enhancement in the intensity of the fundamental (nuclear) Bragg peaks has been observed in the neutron diffraction patterns down to 30 K. No depolarization of neutron beam has been observed down to 3 K confirming the absence of ferro- or ferrimagnetic-like correlation.      

Design of a neutron polarizer using polarizing super mirrors for the TOF-SANS instrument at the J-PARC

Small-angle neutron scattering technique using polarized neutrons is powerful for studying structures in the range between nm and μm of magnetic materials. In addition, they have been used for the incident beam of focusing-geometry SANS instruments using a magnetic neutron lens, where a high polarization degree of about 99.9% is necessary because the imperfectness of the neutron polarization increases the background level. We are going to install such a magnetic focusing system on the new time-of-flight SANS (TOF-SANS) instrument at the J-PARC so as to make q_min smaller than 10⁻³ Å⁻¹ and improve the resolution of the conventional TOF-SANS at low q. As a polarizing device of the instrument, two V-shaped polarizing super mirrors arranged in crossed geometry to enhance the polarization degree has been considered. In this paper, we present the concept and the detailed design of this device and its performance estimated by Monte Carlo simulations.     

POLI-HEiDi: The new polarised neutron diffractometer at the hot source (SR9) at the FRM II—Project status

The project to upgrade the existing single-crystal diffractometer Heisses Einkristal Diffractometer (HEiDi) at FRM II with a polarised neutron option, enabling the investigation of magnetic ground states in single crystals has been ongoing since autumn 2004. After a detailed investigation of the possible options it has been decided to develop and rebuild the secondary spectrometer and keep the HEiDi monocromator. The new instrument has been named POLI-HEiDi as an abbreviation of Polarisation Investigator at HEiDi. Two different zero-field polarimeters will be made available for spherical neutron polarimetry, Cryoapad and MuPAD. Both, polarisation and analysis will be performed with polarised ³He spin filters. Several new and important components of the instrument have recently been commissioned. In this report we present these components and show how they fit with the design of the whole instrument.     

Structure and magnetic properties of colossal magnetoresistance compound Tb0.5Sr0.5CoO3

The structure and the magnetic properties of the doped rare earth cobaltite systems are of recent interest owing to the CMR phenomenon that occur in them. In this paper, we investigate the structure and magnetic properties of Tb_0.5Sr_0.5CoO₃ solid solution, for the first time, using neutron powder diffraction technique. The sample Tb_0.5Sr_0.5CoO₃ is found to crystallize in orthorhombic (Pbnm) symmetry. The unit cell volume and Co—O bond length reduce with temperature. The calculatede _g bandwidth obtained from structural parameters turns out to be 0.989 eV. Low temperature neutron diffraction profiles exhibit a magnetic contribution to the fundamental Bragg peaks indicating a ferromagnetic ordering belowT _c. The results are compared with Co—O—Co bond angles and Co—O bond length of La_0.5Sr_0.5CoO₃, highlighting the ionic size effects on substitution of Tb ion for La in the compound.     

Powder neutron diffraction of wüstite (Fe0.93O) to 12 GPa using large moissanite anvils

High-pressure powder neutron diffraction of wüstite-Fe_0.93O has been achieved to 12 GPa using a large gem-moissanite (SiC) anvil cell. The moissanite anvils are weakly absorbing and provide greater neutron fluxes to the sample than is possible with tungsten carbide anvils. There is minimal diffraction overlap from the single-crystal moissanite anvils compared to tungsten carbide or synthetic diamond anvils, providing cleaner background profiles. The required sample volume for high-pressure neutron diffraction is dramatically reduced to several cubic millimeters. High-quality powder diffraction patterns of wüstite were recorded at 90 min exposure times on the HIPPO diffractometer at LANSCE when the sample volume was in the range of ～10 mm³. This is about two orders of magnitude smaller than the necessary sample volume (～1.0 cm³) for the same kind of experiment with other high-pressure cells and nominal neutron fluxes.     

The neutron texture diffractometer at the China Advanced Research Reactor

The first neutron texture diffractometer in China has been built at the China Advanced Research Reactor,due to strong demand for texture measurement with neutrons from the domestic user community. This neutron texture diffractometer has high neutron intensity, moderate resolution and is mainly applied to study texture in commonly used industrial materials and engineering components. In this paper, the design and characteristics of this instrument are described. The results for calibration with neutrons and quantitative texture analysis of zirconium alloy plate are presented. The comparison of texture measurements with the results obtained in HIPPO at LANSCE and Kowari at ANSTO illustrates the reliability of the texture diffractometer.     

Structure refinement of sub-cubic-mm volume sample at high pressures by pulsed neutron powder diffraction: application to brucite in an opposed anvil cell

Neutron powder diffraction measurements of 0.9 mm³ of mixture of deuterated brucite and pressure medium were conducted at pressures to 2.8 GPa, using an opposed anvil cell and a medium-resolution diffractometer at Japan Proton Accelerator Research Complex pulsed neutron source. Spurious-free diffraction patterns were successfully obtained and refined to provide all structural parameters including Debye–Waller factors. Tilting of hydroxyl dipoles of brucite toward one of the three nearest-neighbor oxygen anions was confirmed to be substantial at pressure as low as 1.5 GPa. By this application, technical feasibility to analyze such a small sample has been newly established, which would be useful to extend the applications of neutron diffraction at high pressures.     

Low-temperature neutron diffraction study of La<Subscript>0.95</Subscript>Nd<Subscript>0.05</Subscript>CrO<Subscript>3</Subscript>

We have synthesized polycrystalline La_0.95Nd_0.05CrO₃ sample by doping the La-site of LaCrO₃ with Nd and its magnetic properties have been studied using DC magnetization and neutron diffraction techniques. DC magnetization study shows a paramagnetic to a weak ferromagnetic-like transition at ∼295 K followed by signatures of a spin reorientation phenomenon at 233 and 166 K and, finally a transition to an antiferromagnetic-like phase at ∼21 K. Low-temperature neutron diffraction measurements confirm a weak ferrimagnetic ordering of Cr³⁺ moments at all temperatures below 295 K.     

Magnetic studies of colossal magnetoresistance perovskites on macroscopic,mesoscopic and microscopic length scales

We have investigated magnetic correlations in various CMR manganites on macroscopic, mesoscopic and microscopic length scales by carrying out DC magnetization, neutron depolarization, and neutron diffraction measurements. We present here the effect of substituting Mn with Fe and La with Dy in the ferromagnetic La_0.7−xCa_xMnO₃ (x ∼ 0.3–0.33) compounds. Neutron diffraction has been used in order to characterize the long-range magnetic order and its gradual suppression by the substitution. Neutron depolarization study has been carried out in order to bridge the gap in our understanding regarding the nature of magnetic correlation obtained from the macroscopic and microscopic measurements. In particular, our study on La_0.67Ca_0.33Mn_0.9Fe_0.1O₃ has established the fact that a true double exchange mediated spin-glass is insulating. In another study of La-site ionic size effect and its disorder in (La_1−x Dy _x )_0.7Ca_0.3MnO₃, we have investigated the evolution of the length scale of magnetic ordering with a possible microscopic explanation and the results have been compared with that for the light rare earth substituted compounds.     

More about neutron–mirror neutron oscillation

It was pointed out recently that oscillation of the neutron n into a mirror neutron n′, a sterile twin of the neutron with exactly the same mass, could be a very fast process with baryon number violation, even faster than the neutron decay itself. This process is sensitive to magnetic fields and it could be observed by comparing the neutron loss rates in the UCN storage chambers for different magnetic backgrounds. We calculate the probability of the n−n′ oscillation in the case when a mirror magnetic field B′ is non-zero and show that in this case it can be suppressed or resonantly enhanced by applying the ordinary magnetic field B, depending on its strength and on its orientation with respect to B′. The recent experimental data, under this hypothesis, still allow for an n−n′ oscillation time of order 1 s or even smaller. Moreover, they indicate that the neutron losses are sensitive to the orientation of the magnetic field. If these hints will be confirmed in future experiments, this would point to the presence of a mirror magnetic field on the Earth of the order of 0.1 G, or some equivalent spin-dependent force of other origin that makes a difference between the neutron and mirror neutron states.     

Magnetic neutron diffraction under pressures up to 43 GPa. Study of the EuX and GdX compounds

We present some recent results on magnetic neutron studies at pressures above 40 GPa. We used diamond and sapphire anvil pressure cells for low temperature neutron studies and a powder diffractometer specialized for high pressure studies. Focusing systems and low-background conditions allowed us to study samples with volumes as small as 0.001 mm³ in a diamond anvil cell at a pressure of 50 GPa. This technical progress allowed us to obtain new results in studies of “textbook” magnetic insulators EuX (X = S, Se, Te) and GdX (X = As, Sb, Bi). We found new magnetic phases. In the Eu-chalcogenides we observed a strong anion-dependent increase of the ferromagnetic exchange with decreasing lattice constant. In contrast, in the GdX compounds the antiferromagnetic order remains stable up to a pressure of 43 GPa. We show the importance of our results to understand the origin of indirect exchange interactions in magnetic semiconductors with well localized magnetic shells. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural and magnetic phases of Bi<Subscript>1−x</Subscript>A<Subscript>x</Subscript>FeO<Subscript>3−</Subscript><Subscript>δ</Subscript> (A = Sr,Pb) perovskites

The Bi_1−xA_xFeO_{3− δ} (A = Sr, Pb) systems have been studied using the X-ray, neutron powder diffraction and magnetization measurements in a magnetic field up to 14 T. It was found that around x ∼ 0.06 the crystal symmetry changes from a rhombohedral (space group R3c) to pseudo-tetragonal. In the composition range 0.07 ≤ x ≤ 0.14 the phases with different symmetry of the unit cell coexist independent of synthesis conditions. The neutron powder diffraction shows that the iron ions have average oxidation state close to 3+. The magnetic structure for Bi_0.5Sr_0.5FeO_{3− δ} is found to be G-type antiferromagnetic with magnetic moment of about 3.8 μ_B/Fe³⁺. The weak ferromagnetic state due to magnetoelectric interactions was revealed in the lightly doped rhombohedrally distorted compositions. No evidence for a spontaneous magnetization was observed for the pseudo-tetragonal phases. These compositions show irreversible nonlinear magnetization vs. field behavior apparently due to small local deviations from the collinearity of the magnetic moments.     

Magnetic structure of (Fe0.97Cr0.03)2P

Magnetic behaviour of di-metal iron phosphide with a small substitution of iron by chromium, (Fe_0.97Cr_0.03)₂P, has been studied using SQUID magnetometry and powder neutron diffraction. It is paramagnetic at temperatures above ∼180 K with persisting short range ferromagnetic (FM) order. At lower temperatures three different regions of magnetic behaviour are identified. FM order evolves in the region 180 K-120 K but much more slowly and with much less magnetic moments than in Fe₂P. In the region 120 K-50 K negative exchange interactions gain some importance leading to a loss of FM order. Below 50 K FM interactions again dominate. Pinning centres influence the behaviour at low temperature up to ∼100 K.     

Crystal and magnetic structure of single-crystal La<Subscript>1-x</Subscript><Emphasis Type="Bold">Sr</Emphasis><Subscript>x</Subscript><Emphasis Type="Bold">MnO</Emphasis><Subscript>3</Subscript><Emphasis Type="Bold">(x ≈ 1/8)</Emphasis>

A neutron powder diffraction (NPD) study on the crystal and magnetic structure of a crushed La_1-xSr_xMnO₃ (x ≈ 1/8) single crystal has been performed. The sample belongs to orthorhombic (Pnma, O) above the Jahn-Teller (JT) transition temperature (T_JT) and monoclinic (P12₁/c1, M^′) in the JT regime. We have also refined the NPD data below the charge/orbital ordering (CO/OO) temperature (T_CO/OO) with a monoclinic (P12₁/c1, M^′′) model because the experimental resolution was insufficient to clearly identify a triclinic structure. The refined lattice parameters show an obvious breathing-mode distortion between T_CO/OO and T_JT, accompanied by a large deviation of the monoclinic angle β from 90°, signifying a very strong cooperative JT distortion. A ferromagnetic (FM) moment of 3.43(5)μ _B/Mn besides an A-type antiferromagnetic (A-AFM) moment of 0.54(2) μ _B/Mn is directed mainly along the b axis in P12₁/c1 symmetry at 5 K. With increasing temperature, the A-AFM domains transform into FM ones above ~100 K and the FM spin orientation turns from the b to the c axis in crystallographic b-c plane below T_c = 187(1) K. The magnetization measurements show typical anomalies around T_CO/OO and T_JT. The measured saturation moment of 3.9(1)μ _B/Mn at 70 kOe and 5 K is well consistent with the sum 3.97(5)μ _B/Mn of the refined FM and A-AFM moments at 5 K, implying the A-AFM spins are aligned in field direction at 70 kOe. The applied magnetic field can affect the paramagnetic insulating (PMI) state in the range of magnetic polarons. Based on the size of JT distortion and the bond-valence sums (BVS’s), the CO/OO phenomenon is being discussed.     

Studies on pore morphology of titanium and its oxide by small angle neutron scattering

Titanium metal bodies have been prepared from the sintered powder compacts of TiO₂ by a novel molten salt electrochemical approach, known as FFC Cambridge process. The phase and compositional characterizations of both Ti and TiO₂ have been carried out by X-ray diffraction. The pore morphologies of sintered TiO₂ pellet and the metallic Ti pellet, obtained after electrochemical reduction have been studied by SANS over a scattering wave vector q range of 0.003–3.5 nm⁻¹ using a double crystal diffractometer and a pin-hole collimated SANS instrument. In the case of reduced metal pellet, average pore size was found to be larger than that of the oxide pellet as the voids left behind after the oxygen atoms left the oxide matrix, could not coalesce.