The crystal structure of the kaolinite: dimethylsulfoxide (DMSO) intercalate (P1, a = 5.187(2), b = 8.964(3), c = 11.838(4) Å, α = 91.53(1)°, β = 108.59(2), γ = 89.92(1)°) has been determined using spectroscopic and X-ray and neutron powder diffraction data. Both the X-ray and neutron powder diffraction patterns were refined. Solid-state 13C, 29Si, and 27Al nuclear magnetic resonance data and previously collected infrared spectroscopic data provided a useful starting model for structural refinement. Due to the extreme overlap of reflections of this low-symmetry unit cell, the Rietveld method proved inadequate, and quasi-single crystal methods were employed. Each DMSO molecule was found to be triply hydrogen bonded above the octahedral vacancy in the gibbsitic sheet of the kaolinite layer. One methyl group is keyed into the ditrigonal hole in the tetrahedral sheet with the other S-C bond parallel to the sheet. The DMSO molecules are accommodated by significant horizontal displacement of individual kaolinite layers to achieve almost perfect overlap of the octahedral vacancy by the adjacent ditrigonal hole.

On the basis of neutron diffraction studies, the two inner-hydroxyl ions in highly ordered kaolinite were recently shown to be differently oriented. One of the inner-hydroxyl ions points generally toward a hole in the octahedral sheet and the other toward a hole in the tetrahedral sheet. These orientations and the locations of the other atoms in the primitive triclinic unit cell have now been determined for a sample of Keokuk kaolinite with improved precision compared with that reported earlier. Rietveld structure refinement was carried out for the entire crystal structure simultaneously (99 atom positional and 17 other parameters) with each of two newly collected sets of high-resolution neutron powder diffraction data. The different orientations of the inner-hydroxyl ions are the most marked evidence that the unit cell is not C centered. The positions of the inner-surface hydrogen atoms provide further evidence in that all differ from a C-centered relationship by six to eight estimated standard deviations in their y coordinates. The cell is, therefore, not centered. The space group is P1.

The full structure of dickite from St. Claire, Pennsylvania, including hydrogen atoms, was refined in space group Cc using time-of-flight neutron powder diffraction data obtained at 12 K and Rietveld refinement/difference-Fourier methods (Rwp = 2.62%, reduced χ2 = 1.915, 113 variables, a = 5.1474(6)Å, b = 8.9386(10)Å, c = 14.390(2)Å, and ß = 96.483(1)°). The non-hydrogen structure is essentially identical to published structures for dickite, but the hydrogen positions are distinct. The inner hydroxyl group is approximately parallel to the (001) plane, inclined by 1.3° towards the tetrahedral sheet. Contrary to published low-temperature infrared (IR) spectra, there is no evidence that dickite possess lower symmetry at low temperatures although there is tentative evidence for statistical occupancy of H3 on more than one site. Low-temperature IR spectra of St. Claire and Wisconsin dickites do not show evidence for more than four hydroxyl groups and are consistent with the reported structure. Upon cooling from 300 to 15 K, the position of the OH3 stretching band increased from 3710 to 3731 cm−1. This large, positive shift in frequency was attributed to the increase in the internuclear O-H3 ⋯ O distance upon cooling. The frequency of the 3655 cm−1 band initially decreased by 2 cm−1 to 3653 cm−1 upon cooling from 300–125 K; however, the band increased in frequency by 1 cm−1 upon further cooling to 15 K. This unusual change in frequency upon cooling is consistent with the assignment of this band to OH2 and OH4. The position of the OH1 stretching band decreased from 3622 to 3620 cm−1 upon cooling, which was attributed, in part, to the observed increase in the Al-O(H1)-Al angle at low temperature.

The crystal structure of synthetic deuterated kaolinite was refined by Rietveld analysis using time-of-flight (TOF) neutron powder diffraction data. For non-hydrogen atoms, Cl symmetry was assumed. Starting models were tested in which only the direction of O-D vectors was varied. The constraints were introduced to all Al-O, Si-O and O-D bonds. The refinement adopting the former gives Pl(C1), a = 5.169(1) Å, b = 8.960(2) Å, c = 7.410(2) Å, α = 91.26(2)°, ß = 104.99(2)°, γ = 89.93(1)°, Rwp = 3.17%, R1 = 5.78% and S = 1.34 with constraints of l(Al-O)= 1.93 ± 0.05 Å, l(Si-O)= 1.62 ± 0.03 Å and l(D-O) = 0.95 ± 0.15 Å. The inner O-D vector points toward the tetrahedral sheet. All inner-surface O-D groups form H bonding with basal O atoms in the next kaolinite layers. The results agreed with those obtained from natural kaolinite.

The crystal structure of Keokuk kaolinite, including all H atoms, was refined in space group C1 using low-temperature (1.5 K) neutron powder diffraction data (λ = 1.9102 Å) and Rietveld refinement/difference-Fourier methods to Rwp = 1.78%, reduced χ2 = 3.32. Unit-cell parameters are: a = 5.1535(3) Å, b = 8.9419(5) Å, c = 7.3906(4) Å, α = 91.926(2)°, β = 105.046(2)°, γ = 89.797(2)°, and V = 328.70(5) Å3. Unit-cell parameters show that most of the thermal contraction occurred along the [001] direction, apparently due to a decrease in the interlayer distance. The non-H structure is very similar to published C1 structures, considering the low temperature of data collection, but the H atom positions are distinct. The inner OH group is essentially in the plane of the layers, and the inner-surface OH groups make angles of 60°–73° with the (001) plane. Difference-Fourier maps show minor anisotropy of the inner-OH group in the [001] direction, but the inner-surface OH groups appear to have their largest vibrational (or positional disorder) component parallel to the layers. Although no data indicate a split position of any of the H sites in kaolinite, there is support for limited random positional disorder of the H atoms. However, these data provided no support for a space group symmetry lower than C1.

Bentonite-bonded molding sand is one of the most common mold materials used in metal casting. The high casting temperatures cause dehydration and alteration of the molding sand, thereby degrading its reusability. Neutron radiography and neutron diffraction were applied to study these processes by using pure bentonite-quartz-water mixtures in simulation casting experiments. The aim of the experiments was to compare the dehydration behavior of raw and recycled mold material in order to assess possible causes of the limited reusability of molding sands in industrial application. Neutron radiography provided quantitative data for the local water concentrations within the mold material as a function of time and temperature. Dehydration zones, condensation zones, and areas of pristine hydrated molding sand could be established clearly. The kinematics of the zones was quantified. Within four cycles of de- and rehydration, no significant differences in water kinematics were detected. The data, therefore, suggest that the industrial handling (molding-sand additives and the presence of metal melt) may have greater effects on molding-sand reusability than the intrinsic properties of the pure bentonite–quartz–water system.

The crystal structure of biotite-1 M from Bancroft, Ontario, with the formula: $\left({\text{K}}_{1.96}{\text{Na}}_{0.13}{\text{Ca}}_{0.01}\right)\left({\text{Mg}}_{3.15}{\text{Fe}}_{2.59}^{2+}{\text{Ti}}_{0.17}{\text{Mn}}_{0.09}\right)\left({\text{Si}}_{5.98}{\text{Al}}_{1.92}{\text{Ti}}_{0.10}\right){\text{O}}_{20}\left[{\left(\text{OH}\right)}_{1.47}{\text{F}}_{1.98}\right]$, was determined by Rietveld refinement using high-resolution neutron powder diffraction at in situ temperatures ranging from 20 to 900°C. The room-temperature structure of the samples heated to between 400 and 900°C using an electric furnace in air was also refined. The crystal structures were refined to an RP of 2.98 — 5.06% and Rwp of 3.84–6.77%. For the in situ heating experiments in a vacuum, the unit-cell dimensions increased linearly to 600°C. The linear expansion coefficient for the c axis was 1.65 × 10−5°C−1, while those for the a and b dimensions were 4.44 × 10−6°C−1 and 5.21 × 10−6°C−1, respectively. Accordingly, the increase in the unit-cell volume up to 600 C occurred mainly along the c axis, resulting from the expansion in the K coordination sphere along that direction. Results for all K−O bonds were analyzed in terms of the lattice component and an inner component of the structural strain. The ditrigonal distortion decreased (3.76 at 20°C to 1.95 at 600°C) with temperature, because the shorter bonds expanded and the longer bonds contracted. The increase in the interlayer separation and the decrease in the interlayer octahedral flattening angle confirmed that the c-dominated expansion occurred in the interlayer region. In the case of the ex situ-heated samples, the cell dimensions decreased sharply at temperatures over 400 C. The octahedral sheet thickness and mean <M−O> distance decreased linearly due to oxidation of octahedral Fe. However, the interlayer separation and mean <K−O> distance decreased at temperatures over 400°C. At 400°C, dehydroxylation began to increase and interlayer regions became more constricted. The overall cell parameters decreased rapidly with increasing temperatures due to dehydroxylation. The large inner strain components in the K−O bonds also resulted in an increase in the considerable ditrigonal distortion (3.57° at 400°C to 6.15° at 900°C).

Magnesium hydroxyfluoride, Mg(OH)F, has been synthesized by a subcritical hydrothermal route from a 1:1 molar mixture of brucite, Mg(OH)2, and sellaite, MgF2 with a rutile type structure, in excess water. Using a combination of synchrotron X-ray and time-of-flight neutron powder diffraction, the structure of Mg(OH)F has been solved in the diaspore space group Pnma with a = 10.116(3), b = 4.6888(10) and c = 3.0794(7) Å at ambient conditions. The most intense diffraction lines are [dobs (hkl) Iobs]: 2.291 (211) 10, 4.253 (101) 7, 1.747 (212) 7, 2.229 (401) 6 and 1.480 (610) (4) Å, with the largest d-spacing at 5.058 Å. Sharp infrared stretching bands are located at 3679 and 3645 cm–1, with a broader band at 3535 cm–1. The topology of the structure is intermediate between that of the OH and F endmembers, being derived through notional shearing nearly normal to the sheets of octahedra of the CdI2/Mg(OH)2-type structure. Further similar shearing at an interval 1/2a would lead to a Cd(OH)F-type structure, which is also related to the rutile structure type. The observations and model presented here indicate a close correlation between the structural properties of the endmembers and Mg(OH)F.

The thermal expansion coefficients for natural troilite, FeS, Ni-rich pyrrhotite, Fe0.84Ni0.11S, and Ni-poor pyrrhotite, Fe0.87Ni0.02S, were measured during cooling by in situ neutron powder diffraction over the temperature range 873–373 K. Between 873 and 573 K, the mean thermal expansion coefficients for the three compositions are 7.4(3)×10−5 {FeS}, 8.0(4)×10−5 {Fe0.84Ni0.11S} and 8.5(4)×10−5 K−1 {Fe0.87Ni0.02S}. Below 573 down to 373 K, the first two increase considerably to 14.1(7)×10−5 {FeS} and 9.3(5)×10−5 {Fe0.84Ni0.11S} while the latter sample shows no significant variation, 8.4(5)×10−5 K−1. Below 573 K, the thermal expansion is highly anisotropic, with Δa/100 K−1 ranging from 0.89(9)% {FeS} to 0.48(12)% {Fe0.87Ni0.02S} while Δc/100 K−1 ranges from −0.39(11)% {FeS} to −0.13(2)% {Fe0.87Ni0.02S}.

Upon cooling through 573 K, troilite and pyrrhotite undergo a transition where the FeS6 octahedra distort and in the case of pyrrhotite, cation-vacancy clustering occurs. The thermal expansion coefficients are bigger for low cation-vacancy concentrations and decrease as the pyrrhotites become less stoichiometric. This indicates that the thermal expansion in these minerals is damped by vacancy ordering or clustering. The thermal expansion coefficients for troilite and pyrrhotite are amongst the largest reported for sulphide minerals and their role in the formation of ore textures is discussed briefly.

The high-temperature (HT) behaviour of kyanite (Al2SiO5) was investigated by in situ neutron powder diffraction up to 1200°C. Within the investigated T range, no phase transition was observed. The axial and volume thermal expansion coefficient (αj = lj-1(𝜕1j/𝜕T), αv = V-1 (𝜕V/𝜕T)), calculated by weighted linear regression through the data points, are: αa = 5.5(2) x 10-5, αb= 5.9(2) x 10-5, αc = 5.18(8) xl0-5, αv = 7.4(1) x 10-3 “C-1, with αa:αb:αc = 1.06:1.14:1. All three angles of the kyanite lattice show a slight decrease with T, with 𝜕α/𝜕T = -2(2) x 10-5, 𝜕β/𝜕T = -4(1) x 10-5, 𝜕γ/𝜕T = –10(2) x 10-5%C. The magnitudes of the principal Lagrangian unit-strain coefficients (ε1,ε2, ε3) and the orientations of the thermal strain-ellipsoids, between the ambient temperature and each measured T, were calculated. The magnitude and the orientation of all the three unit-strain coefficients are almost maintained constant with T. At T-To = 1177°C , ε^a = 76(2)°, ε^b = 70(2)°, ε^c = 38(3)°, ε2^a = 49(3)°, ε2^b = 66(3)°, ε2^c = 127(4)°, ε3^a = 135(3)°, ε3^b = 31(3)°, ε3^c = 91(2)° with ε1:ε2:ε3 = 1.57:1.29:1. The structural refinements, performed at 23, 600, 650, 700, 750, 800, 900, 950, 1050 and 1200°C allowed the description of the structural evolution and the main T-induced deformation mechanisms, which are mainly represented by the polyhedral distortions of the AlO6 octahedra.

Phengite 3T (Dora-Maira massif, Italian western Alps), with chemical composition K0.96Na0.01Al1.44Mg0.56(Si3.59 Al0.41)O10(OH)2 has been investigated using powder neutron diffraction, at the ILL (Institut Laue-Langevin) Facility, on the D2B diffractometer. Data sets were collected at 293 and 873 K, and the present results are compared with those obtained previously using the time-of-flight (TOF) technique, on the same compound. In the octahedral sheet, Al tends to order into the M2 site, in accordance with the measurements mentioned above, whereas the Al/Si tetrahedral ordering we observe (i.e. Si fully into T1 site) is at variance with that determined previously. These discrepancies are ascribed to the presence of talc impurities in the sample used previously (∼6 wt.%), which affected the results obtained.

Analysis of in situ neutron powder diffraction data collected for the porous framework material Zn(hba) during gas adsorption reveals a two-stage response of the host lattice to increasing CO2 guest concentration, suggesting progressive occupation of multiple CO2 adsorption sites with different binding strengths. The response of the lattice to moderate CH4 guest concentrations is virtually indistinguishable from the response to CO2, demonstrating that the influence of host–guest interactions on the Zn(hba) framework is defined more strongly by the concentration than by the identity of the guests.

The program FAULTS has been used to simulate the X-ray powder diffraction (XRD), neutron powder diffraction (NPD), and electron diffraction (ED) patterns of several structural models for LiNi1/3Mn1/3Co1/3O2, including different types of ordering of the transition metal (TM) cations in the TM slabs, different amounts of Li+/NiII+ cation mixing and different amounts of stacking faults. The results demonstrate the relevance of the structural information provided by NPD and ED data as compared with XRD to characterize the microstructure of NMC (LiNi1−y-zMnyCozO2) compounds.

The yttrium-based metal–organic framework, Y(btc) (btc = 1,3,5-benzenetricarboxylate), shows moderate uptake of methane (0.623 mmol g−1) and molecular oxygen (0.183 mmol g−1) at 1 bar and 308 K. Neutron powder-diffraction data for the guest-free, CD4-, and O2-loaded framework reveal multiple adsorption sites for each gas. Both molecular guests exhibit interactions with the host framework characterised by distances between the framework and guest atoms that range from 2.83 to 4.81 Å, with these distances identifying interaction most commonly between the guest molecule and the carboxylate functional groups of the benzenetricarboxylate bridging ligand of the host.

Rietveld neutron powder profile analysis of the (Na1−xKx)0.5Bi0.5TiO3 (NKBT) series (x=0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) is reported over the temperature range 293–993 K. A detailed characterization of the structures and phase transitions occurring across this series as a function of temperature has been made. Room-temperature refinements have revealed a rhombohedral phase, space group R3c for x=0, 0.2, and 0.4, which exhibits an antiphase, a−a−a− oxygen tilt system with parallel cation displacements along [111]p. An intermediate zero-tilt rhombohedral phase, space group R3m possessing cation displacements along [111]p, has been established for x=0.5 and 0.6. At the potassium-rich end of the series at x=0.8 and 1.0, a tetragonal phase, space group P4mm is observed possessing cation displacements along [001]. At the sodium-rich end of the series for x=0.2, the unusual tetragonal structure with space group P4bm is seen for Na0.5Bi0.5TiO3 which possesses a combination of in-phase a0a0c+ tilts and antiparallel cation displacements along the polar axis. Temperature-induced phase transitions are reported and structural modifications are discussed.

Transformation behaviors of the technologically important polycrystalline Ti50.75Ni47.75Fe1.50 shape memory alloy were investigated using differential scanning calorimeter (DSC) and powder diffraction techniques. DSC revealed that there are two-stage (i.e., cubic→trigonal→monoclinic) martensitic phase transformations on cooling and a one-step transformation (monoclinic→cubic) on heating. In situ structural refinement of cubic→trigonal→monoclinic on cooling was carried out using the D1A high-resolution neutron powder diffractometer at the Institut Laue-Langevin Neutrons for Science in Grenoble, France. Results showed that the phases involved during the phase transition are consistent with the differential scanning calorimeter cooling curve, and the refined crystal structure parameters obtained from Rietveld refinements with the generalized spherical harmonic description agreed reasonably well with X-ray single-crystal data. Subsequently, a combined neutron and synchrotron structural refinement for each phase was conducted because the trial refinements initially using only the synchrotron data of trigonal phase yielded a false minimum with a somewhat high goodness-of-fit χ2. Results obtained from the combined neutron and synchrotron data of the cubic, trigonal, and monoclinic phases show that the same minimum goodness-of-fit indices were always obtained.

Crystal structure and phase transformation behaviors in two Ni-Mn-Ga ferromagnetic shape memory alloys (FSMAs) with compositions of Ni48Mn30Ga22 and Ni53Mn25Ga22 (at. %) as a function of temperature were investigated by in situ neutron diffraction experiments. Neutron diffraction technique proves to be highly efficient in characterizing structural transformation in Ni-Mn-Ga FSMAs, which consist of nearby elements in the periodic table. Our neutron results show that Ni48Mn30Ga22 has a cubic, L21 Heusler structure from 373 to 293 K. Its crystal structure changes into a seven-layered orthorhombic martensitic structure when cooled to 243 K, and no further transformation is observed upon cooling to 19 K. Neutron diffraction results also show that Ni53Mn25Ga22 has a tetragonal I4/mmm martensitic structure from 20 to 403 K. A pre-transformation around room temperature is observed from an abrupt jump in unit-cell volume of Ni53Mn25Ga22, which corresponds with an endothermic peak detected in a heated DSC curve.

The structural models of three synthetic Al-substituted goethite specimens have been refined from the neutron data, including crystallographic determinations of the Al levels and H positions. The d-I data were calculated for the final models. A relationship between the c unit cell parameter and Al content has been extended to the entire goethite-diaspore solid-solution system, which makes the regression equation procedure simpler and more accurate. A second prospective H site could not be confirmed because of the quality of existing neutron data. However, it is hoped that a further neutron powder diffraction study of a synthetic, fully deuterated goethite material may allow the existence of the site to be demonstrated.

Phase transformation temperatures of a polycrystalline Ni-rich Ti49.86Ni50.14 shape memory alloy were investigated using a differential scanning calorimeter. In situ structural and texture analyses of the monoclinic Ti49.86Ni50.14 were investigated using neutron powder diffractometer technique. Differential scanning calorimeter results showed that this Ni-rich alloy has a one-step cubic to monoclinic martensitic phase transformation on cooling and a one-step monoclinic to cubic transformation on heating. In situ high-resolution neutron powder diffraction data of the monoclinic phase from low temperatures to room temperature on heating are consistent with the differential scanning calorimeter’s heating results. In addition, the refined monoclinic crystal structure parameters for all neutron diffraction data sets agree satisfactorily with single-crystal X-ray diffraction results. The multiple-data-set capabilities of the GSAS Rietveld refinement program, with a generalized spherical-harmonics description was used successfully to extract the texture description directly from a simultaneous refinement using 52 time-of-flight monoclinic neutron diffraction patterns, taken from a polycrystalline sample held in 13 orientations inside the diffractometer.

Preferred orientation or texture is a common feature of experimental powder patterns. The mathematics of two commonly used models for preferred orientation—the March-Dollase and the generalized spherical-harmonic models—is reviewed. Both models were applied individually to neutron powder data from uniaxially pressed molybdite (MoO3) and calcite (CaCO3) powders in Rietveld analyses, as well as the as-received powders. The structural refinement results are compared to single-crystal structures. The results indicate that reasonable refinement of crystal structures can be obtained using either the March model or generalized spherical-harmonic description. However, the generalized spherical-harmonic description provided better Rietveld fits than the March model for the molybdite and calcite. Therefore, the generalized spherical-harmonic description is recommended for correction of preferred orientation in neutron diffraction analysis for both crystal structure refinement and phase composition analysis. Subsequently, the generalized spherical-harmonic description is extended to crystal structure refinement of annealed and the aged polycrystalline Ni-rich Ni50.7Ti49.30 shape memory alloys.