Mosaic Crystals Research Articles

Generation of terahertz radiation with a specified spectral profile from a mosaic combined organic crystal.

We present a method for the generation of terahertz (THz) pulses with a high optical-to-THz conversion efficiency and a smooth spectrum. The method is based on the optical rectification of near-infrared femtosecond laser pulses with a wavelength of 1240 nm in a mosaic combined crystal, consisting of two pieces of nonlinear organic crystals, OH1 and DSTMS. The mosaic combined crystal produces a relatively smooth spectrum in the 0.3-4.5 THz range with no pronounced absorption dips and with a maximum in a spectral amplitude at about 2 THz. The peak field strength is 9.6 MV/cm for an effective crystal diameter of 4.3 mm.

Effects of mosaic crystal instrument functions on x-ray Thomson scattering diagnostics

Mosaic crystals, with their high integrated reflectivities, are widely employed in spectrometers used to diagnose high energy density systems. X-ray Thomson scattering (XRTS) has emerged as a powerful diagnostic tool of these systems, providing in principle direct access to important properties such as the temperature via detailed balance. However, the measured XRTS spectrum is broadened by the spectrometer instrument function (IF), and without careful consideration of the IF one risks misdiagnosing system conditions. Here, we consider in detail the IF of 40 and 100 μm mosaic Highly Annealed Pyrolytic Graphite crystals, and how the broadening varies across the spectrometer in an energy range of 6.7–8.6 keV. Notably, we find a strong asymmetry in the shape of the IF toward higher energies. As an example, we consider the effect of the asymmetry in the IF on the temperature inferred via XRTS for simulated 80 eV CH plasmas and find that the temperature can be overestimated if an approximate symmetric IF is used. We, therefore, expect a detailed consideration of the full IF will have an important impact on system properties inferred via XRTS in both forward modeling and model-free approaches.

Dolomite formation in the Miocene Kardiva platform, Maldives archipelago: a tale of closed-system and open-system dolomitization by current pumping of seawater

Dolomites from two IODP Expedition 359 sites on the northeastern margin of the Miocene Kardiva platform, Maldives archipelago, were examined to explore the question of open versus closed system dolomitization in a drowned carbonate platform. The uppermost approx. 130 m of platform margin carbonate at site U1465 contains less than or equal to 12% dolomite except for five, meters-thick intervals with up to 65% dolomite. All U1465 dolomites consists of decimicron-sized euhedral cement crystals and mimetically replaced peloids and coralline red algal clasts. The abundance and the petrographic features of these dolomites are similar to periplatform and slope dolomite in many other settings that have been interpreted as the product of hydrologically closed-system diagenesis. In contrast, the recovered platform margin deposits at site U1469 are greater than 99% dolomite. Those dolomites are partially fabric retentive with fine-to-medium crystalline, planar subhedral to euhedral crystal mosaics of replacive dolomite and dolomite cement, all with Sr contents that average 256 ppm. Their characteristics are comparable to Neogene platform carbonates universally interpreted to signify hydrologically open-system dolomitization. Sr-isotope ages indicate Miocene dolomitization at both sites after platform drowning, and 18Odolomite values are compatible with dolomitization by cold (10⁰ to 15⁰ C) seawater when the platform margin was, on average, approx..400 m below sea level (mbsl). A current pumping mechanism for the advection of seawater into the top of the platform at site U1469 is proposed and tested with a computational fluid-flow simulation. Current pumping occurs when strong ocean bottom currents flow over sedimentary bedforms and generate lateral pressure differences along the sediment-water interface. The pressure differentials drive seawater through the underlying sediments. The flow simulation shows that the ocean currents that swept large sediment sand waves over and off the drowned Kardiva platform for many millions of years could have vigorously pumped Miocene seawater to sub-seafloor depths of many tens of meters . Mass balance considerations suggest complete dolomitization of the upper 20 m of the platform within 500 Ky or less. The current pumping mechanism could drive dolomitization and mineralogical stabilization below hiatal surfaces, or very slowly accumulating sediments, in any marine setting characterized by strong bottom currents. The greater acidity of Mioc ene seawater relative to younger seawater possibly made the pumping, by any means, of Miocene seawater of normal salinity an effective dolomitizing agent at site U1469 and in undrowned Miocene platforms globally.

Interfacial Engineering for Controlled Crystal Mosaicity in Single-Crystalline Perovskite Films.

Organic-inorganic hybrid perovskites have attracted significant attention for optoelectronic applications due to their efficient photoconversion properties. However, grain boundaries and irregular crystal orientations in polycrystalline films remain issues. This study presents a method for producing crystalline-orientation-controlled perovskite single-crystal films using retarded solvent evaporation. It is shown that single-crystal films, grown via inverse temperature crystallizationwithin a confined space, exhibit enhanced optoelectronic property. Using interfacial polymer layer, this method produces high-quality perovskite single-crystalline films with varying crystal orientations. Density functional theory calculations confirm favorable adsorption energies for (110) surfaces with methylammonium iodide and PbI2 terminations on poly(3-hexylthiophene), and stronger adsorption for (224) surfaces with I and methylammonium terminations on polystyrene, influenced by repulsive forces between the thiophene group and the perovskite surface. The correlation between charge transport characteristics and perovskite single-crystalline properties highlights potential advancements in perovskite optoelectronics, improving device performance and reliability.

Indexing neutron transmission spectra of a rotating crystal.

Neutron time-of-flight transmission spectra of mosaic crystals contain Bragg dips, i.e., minima at wavelengths corresponding to diffraction reflections. The positions of the dips are used for investigating crystal lattices. By rotating the sample around a fixed axis and recording a spectrum at each rotation step, the intensity of the transmitted beam is obtained as a function of the rotation angle and wavelength. The questions addressed in this article concern the determination of lattice parameters and orientations of centrosymmetric crystals from such data. It is shown that if the axis of sample rotation is inclined to the beam direction, the reflection positions unambiguously determine reciprocal-lattice vectors, which is not the case when the axis is perpendicular to the beam. Having a set of such vectors, one can compute the crystal orientation or lattice parameters using existing indexing software. The considerations are applicable to arbitrary Laue symmetry. The work contributes to the automation of the analysis of diffraction data obtained in the neutron imaging mode.

Relevance of Platinum Underlayer Crystal Quality for the Microstructure and Magnetic Properties of the Heterostructures YbFeO3/Pt/YSZ(111).

The hexagonal ferrite h-YbFeO3 grown on YSZ(111) by pulsed laser deposition is foreseen as a promising single multiferroic candidate where ferroelectricity and antiferromagnetism coexist for future applications at low temperatures. We studied in detail the microstructure as well as the temperature dependence of the magnetic properties of the devices by comparing the heterostructures grown directly on YSZ(111) (i.e., YbPt_Th0nm) with h-YbFeO3 films deposited on substrates buffered with platinum Pt/YSZ(111) and in dependence on the Pt underlayer film thickness (i.e., YbPt_Th10nm, YbPt_Th40nm, YbPt_Th55nm, and YbPt_Th70nm). The goal was to deeply understand the importance of the crystal quality and morphology of the Pt underlayer for the h-YbFeO3 layer crystal quality, surface morphology, and the resulting physical properties. We demonstrate the relevance of homogeneity, continuity, and hillock formation of the Pt layer for the h-YbFeO3 microstructure in terms of crystal structure, mosaicity, grain boundaries, and defect distribution. The findings of transmission electron microscopy and X-ray diffraction reciprocal space mapping characterization enable us to conclude that an optimum film thickness for the Pt bottom electrode is ThPt = 70 nm, which improves the crystal quality of h-YbFeO3 films grown on Pt-buffered YSZ(111) in comparison with h-YbFeO3 films grown on YSZ(111) (i.e., YbPt_Th0nm). The latter shows a disturbance in the crystal structure, in the up-and-down atomic arrangement of the ferroelectric domains, as well as in the Yb-Fe exchange interactions. Therefore, an enhancement in the remanent and in the total magnetization was obtained at low temperatures below 50 K for h-YbFeO3 films deposited on Pt-buffered substrates Pt/YSZ(111) when the Pt underlayer reached ThPt = 70 nm.

High-Spatial-Resolution Benchtop X-ray Fluorescence Imaging through Bragg-Diffraction-Based Focusing with Bent Mosaic Graphite Crystals: A Simulation Study.

X-ray fluorescence imaging (XFI) can localize diagnostic or theranostic entities utilizing nanoparticle (NP)-based probes at high resolution in vivo, in vitro, and ex vivo. However, small-animal benchtop XFI systems demonstrating high spatial resolution (variable from sub-millimeter to millimeter range) in vivo are still limited to lighter elements (i.e., atomic number Z≤45). This study investigates the feasibility of focusing hard X-rays from solid-target tubes using ellipsoidal lens systems composed of mosaic graphite crystals with the aim of enabling high-resolution in vivo XFI applications with mid-Z (42≤Z≤64) elements. Monte Carlo simulations are performed to characterize the proposed focusing-optics concept and provide quantitative predictions of the XFI sensitivity, in silico tumor-bearing mice models loaded with palladium (Pd) and barium (Ba) NPs. Based on simulation results, the minimum detectable total mass of PdNPs per scan position is expected to be on the order of a few hundred nanograms under in vivo conform conditions. PdNP masses as low as 150 ng to 50 ng could be detectable with a resolution of 600 μm when imaging abdominal tumor lesions across a range of low-dose (0.8 μGy) to high-dose (8 μGy) exposure scenarios. The proposed focusing-optics concept presents a potential step toward realizing XFI with conventional X-ray tubes for high-resolution applications involving interesting NP formulations.

Guinea fowl eggshell structural analysis at different scales reveals how organic matrix induces microstructural shifts that enhance its mechanical properties

Guinea fowl eggshells have an unusual structural arrangement that is different from that of most birds, consisting of two distinct layers with different microstructures. This bilayered organization, and distinct microstructural characteristics, provides it with exceptional mechanical properties. The inner layer, constituting about one third of the eggshell thickness, contains columnar calcite crystal units arranged vertically as in most bird shells. However, the thicker outer layer has a more complex microstructural arrangement formed by a switch to smaller calcite domains with diffuse/interlocking boundaries, partly resembling the interfaces seen in mollusk shell nacre. The switching process that leads to this remarkable second-layer microstructure is unknown. Our results indicate that the microstructural switching is triggered by changes in the inter- and intracrystalline organic matrix. During production of the outer microcrystalline layer in the later stages of eggshell formation, the interactions of organic matter with mineral induce an accumulation of defects that increase crystal mosaicity, instill anisotropic lattice distortions in the calcite structure, interrupt epitaxial growth, reduce crystallite size, and induce nucleation events which increase crystal misorientation. These structural changes, together with the transition between the layers and each layer having different microstructures, enhance the overall mechanical strength of the Guinea fowl eggshell. Additionally, our findings provide new insights into how biogenic calcite growth may be regulated to impart unique functional properties. Statement of significanceAvian eggshells are mineralized to protect the embryo and to provide calcium for embryonic chick skeletal development. Their thickness, structure and mechanical properties have evolved to resist external forces throughout brooding, yet ultimately allow them to crack open during chick hatching. One particular eggshell, that of the Guinea fowl, has structural features very different from other galliform birds – it is bilayered, with an inner columnar mineral structure (like in most birds), but it also has an outer layer with a complex microstructure which contributes to its superior mechanical properties. This work provides novel and new fundamental information about the processes and mechanisms that control and change crystal growth during the switch to microcrystalline domains when the second outer layer forms.

Solidification of Tilted-Lamellar Eutectic Grains with a Crystal Mosaicity: A Numerical Simulation Approach

Solidification of Tilted-Lamellar Eutectic Grains with a Crystal Mosaicity: A Numerical Simulation Approach

A study of the complex dynamics of dendrite solidification coupled to structural mechanics.

The impact of structural mechanics is often overlooked when modelling the solidification of dendritic microstructures, despite experimental observations that the interaction between these processes can be a factor leading to the development of crystal mosaicity throughout the microstructure which can itself lead to more serious defects. When considered at all, the structural mechanical behaviour of columnar dendrites is often considered as being analogous to a cantilever beam both in interpretations of experimental results and in existing numerical modelling. While this is not an unreasonable assumption when considering a dendrite in isolation, this is a scenario that infrequently occurs. In this paper a parametric study is presented using a Cellular Automata solidification solver coupled to a Finite Volume Structural Mechanics solver. These results highlight the complex non-linear behaviour that arises when considering dendrite interaction, demonstrating the significantly different microstructures that can be obtained by varying only the force experienced by the system.

A von Hamos full-cylindrical spectrometer based on striped Si/Ge crystal for advanced x-ray spectroscopy.

High-energy resolution core-level spectroscopies, including a group of different techniques to obtain element-specific information of the electronic structure around an absorption site, have become powerful tools for studying the chemical state, local geometric structure, and the nature of chemical bonding. High-resolution x-ray absorption and x-ray emission spectroscopies are well-established experimental techniques but have always been limited by the number of emitted photons and the limited acceptance of solid angles, as well as requiring high energy stability and repeatability for the whole experimental setup. A full-cylindrical x-ray spectrometer based on flexible HAPG (highly annealed pyrolitic graphite) mosaic crystals is an effective solution for the above issues. However, large-area HAPG remains expensive and is often not easy to access. Here, we present an alternative approach by using segmented single crystals (Si and Ge) with different orientations instead of the HAPG as a dispersive element. The proposed method drastically improved the energy resolution up to 0.2-2eV in the range of 2-10keV. High-pressure x-ray emission and resonant x-ray emission spectra are presented to demonstrate the capabilities of the instrument. The new design is particularly suitable for high-resolution spectroscopy applications at fourth-generation synchrotron radiation sources or free-electron lasers.

Early dolomitization and subsequent hydrothermal modification of the middle Permian Qixia Formation carbonate in the northwest Sichuan Basin

High-quality dolomite reservoir are widely developed in Permian Qixia Formation in northwest Sichuan Basin. Understanding the genesis of dolomite is significant to predicting high-quality reservoir distribution. Based on the petrographical and geochemical characteristics, three types of dolomites and one type of dolomite cement were identified in the Qixia Formation in northwest Sichuan Basin: micritic to fine-crystalline dolomites (D1), medium-crystalline dolomite (D2), medium-to coarse-crystalline dolomite (D3) and saddle dolomite cement.Type D1 dolomites are characterized by micritic to fine-sized crystals, lamellar structure, generally dull to no luminescence, and relatively high strontium (Sr) concentrations. These characteristics suggest that type D1 dolomites were initially formed during the penecontemporaneous phase. The wide range of depleted δ18O values, slightly higher 87Sr/86Sr ratios and slightly positive europium (Eu) anomalies indicate that type-D1 dolomites were subsequently subjected to hydrothermal modification. Type D2 dolomite is characterized by unimodal middle-sized crystals and crystal texture dominated by nonplanar crystals. It usually occurs as thin or thick layers in the study area. The δ18O and δ13C values of type D2 dolomite generally fall within the estimated Middle Permian marine dolomite and show a significantly positive offset compared to those of coeval seawater. The 87Sr/86Sr ratios of type D2 dolomite are slightly higher than the coeval seawater. These features combined with the flat rare earth element (REE) profile and relatively high Sr concentrations (both are similar to the host limestone) indicate that type D2 dolomites first precipitated in the slightly evaporated Middle Permian seawater during the near-surface to shallow burial phase. Type D3 dolomites are mainly characterized by interlocking mosaic crystals with crystal sizes varying from 300 μm to 900 μm. It mainly occurs as patches in type D2 dolomites or as a thick layer sandwiched by type D2 dolomites. These features combined with its high 87Sr/86Sr ratios, δ18O depletion and positive Eu anomalies (which are very similar to those of the saddle dolomites) demonstrate that it is formed by hydrothermal recrystallization upon type D2 dolomites. Saddle dolomite generally occurs as the filling cement of pores, vugs, and fractures and is usually combined with matrix dolomite to form zebra dolomite and hydrothermal dolomite breccia. It has a curve crystal face, demonstrates wavy extinction under cross-polarization and red luminescence under a cathodoluminescence microscope. These features, together with the highest Th, most negative δ18O value and highest 87Sr/86Sr ratio compared to those of all types of dolomites in the study area as well as the positive Eu anomalies suggest that it should have been formed by hydrothermal fluid precipitation.Type D1 and type D3 dolomites are volumetrically minor and the pores are poorly developed. Saddle dolomite cemented and filled the pores and vugs of matrix dolomite, resulting in reservoir damage. Type D2 dolomites constitute the main body of high-quality reservoir in Qixia Formation. It precipitated in the slightly evaporated penesaline Middle Permian seawater during the near-surface to shallow burial phase. Potential high-quality reservoirs may occur in the shoal around the limited inter-shoal sea.

Mosaic of Anodic Alumina Inherited from Anodizing of Polycrystalline Substrate in Oxalic Acid.

The anodizing of aluminium under oscillating conditions is a versatile and reproducible method for the preparation of one-dimensional photonic crystals (PhCs). Many anodizing parameters have been optimised to improve the optical properties of anodic aluminium oxide (AAO) PhCs. However, the influence of the crystallographic orientation of an Al substrate on the characteristics of AAO PhCs has not been considered yet. Here, the effect of Al substrate crystallography on the properties of AAO PhCs is investigated. It is experimentally demonstrated that the cyclic anodizing of coarse-grained aluminium foils produces a mosaic of photonic crystals. The crystallographic orientation of Al grains affects the electrochemical oxidation rate of Al, the growth rate of AAO, and the wavelength position of the photonic band gap.

Brillouin light scattering spectroscopy as a versatile probe of hypersound in diverse materials systems

An overview of the inelastic laser light scattering technique of Brillouin spectroscopy and its application to the study of hypersound in a diverse set of materials systems will be presented. In particular, results obtained from recent Brillouin scattering experiments on natural gastropod mucus, layered high temperature superconductor Bi2Sr2CaCu2O8+δ, biotite micas, and satellite tobacco mosaic virus crystals will be highlighted. Collectively, these results demonstrate the utility of Brillouin light scattering spectroscopy as a sensitive non-destructive probe of hypersound velocity and attenuation in the vicinity of structural phase transitions, the influence of chemical composition and incommensurate structure on material elasticity, and of phonon dynamics in challenging materials classes.

Origin of Dolomite in Lacustrine Organic-Rich Shale: A Case Study in the Shahejie Formation of the Dongying Sag, Bohai Bay Basin

In most organic-rich shale reservoirs, dolomite is widely distributed and has different types and crystal sizes. However, the characteristics and formation mechanism of the dolomites in organic-rich shale are still poorly understood. Petrographic and geochemical analyses were performed to interpret the formation of dolomite in the lacustrine organic-rich shale of the Shahejie Formation, Dongying Sag, Bohai Bay Basin. Four types of dolomites, which represent episodic recrystallization, were classified based on crystal size and shape: 1) micritic dolomite (Dol-1), 2) sub-to euhedral (cloudy cores with clear rims) dolomite (planar-e) (Dol-2), 3) anhedral dolomite (coarse planar-s to nonplanar crystals) in phosphatic particles (Dol-3), and 4) fracture-filling anhedral dolomite (Dol-4). Dol-1 has nonplanar mosaic micritic crystals with irregular intercrystalline boundaries and dull cathodoluminescence (CL), suggesting dolomitization during the early burial stage. Dol-1 tends to occur under high paleosalinity and warm conditions. Furthermore, the syngenetic relationship, with abundant framboidal pyrite and gypsum, suggests that bacterial sulfate reduction (BSR) may influence the formation of Dol-1. The high content of Sr and low content of Mn/Sr also indicate less influence on burial. The Dol-2 crystals show cloudy cores with clear rims attributed to progressive dolomitization during burial. Dol-2 is always associated with the organic matter within the organic matter-rich lamina. The anhedral crystals and undulate (sweeping) extinction of Dol-3, which is usually encased by phosphatic particles in the organic-rich lamina, reflect the recrystallization affected by bacteria and the subsequent thermal evolution of organic matter. Dol-4 fulfills the abnormal pressure fractures crosscutting the earlier phases (Dol-1 and Dol-2) with undulate (sweeping) extinction and different rare earth element (REE) patterns. Dol-4 may be affected by hydrothermal fluids, which are influenced by the thermal evolution of organic matter. The 87Sr/86Sr values of the four types of dolomites similarly demonstrate the same dolomitizing fluids. Dol-1 to Dol-3 have similar REE patterns but are different from Dol-4, suggesting that Dol-4 likely resulted from circulation through basinal sediments instead of different fluids. Focusing on the origin of dolomite has been instrumental in understanding the diagenetic evolution, fluid flow, and organic-inorganic interactions in organic-rich shale and, hence, the reservoir formation of shale oil.

DEVELOPMENT OF FIBROUS CALCITE VEINS RELATED TO HYDROCARBON GENERATION AND OVERPRESSURING IN ORGANIC‐RICH SHALE SOURCE ROCKS: THE VACA MUERTA FORMATION, NEUQUÉN BASIN, ARGENTINA

Fibrous calcite bed‐parallel veins (BPVs) are a typical feature of the Upper Jurassic – Lower Cretaceous Vaca Muerta Formation in the subsurface of the Neuquén Basin (Argentina). The formation is considered to be the main source rock in the basin as well as an important unconventional play. This study examines the growth of BPVs through an analysis of core from three wells located along a transect extending for some 150 km from the NE Platform near the basin margin in the east to the Agrio fold‐and‐thrust belt at the Andean deformation front in the west. The main objective is to integrate fluid inclusion data with the palaeothermal and palaeopresure evolution obtained from a regional‐scale 2D basin and petroleum systems model to examine the timing of fracture development and its relationship with hydrocarbon generation in the Vaca Muerta Formation through time.The apertures of BPVs were measured in more than 360 m of core from three wells (wells A, D and E). This data was combined with optical petrography to investigate the number of calcite cementation events, and the temperature of cement precipitation based on fluid inclusion data. The organic geochemical and mineralogical characteristics of the Vaca Muerta source rock were also analysed. The integrated results were incorporated into a poro‐elastic basin model to investigate the impact of horizontal shortening due to Andean compression on pore pressure development and fracturing in the Vaca Muerta Formation. This framework allowed the timing of BPV formation to be determined together with possible mechanisms governing overpressure conditions through time.Near the Andean deformation front in the west of the modelled section where the Vaca Muerta Formation is in the wet gas window (well D) and dry gas window (well A), BPVs are characterized by two or more generations of calcite fibres indicating multiple growth phases. Calcite which precipitated during cementation event 1 (E1) in the internal zones of BPVs consists of crystals oriented perpendicular to fracture walls, indicating perpendicular vein opening. Calcite precipitated during cementation event 2 (E2) in the outer zones of BPVs includes curved and oblique crystals. During this phase, shear occurred between the opening vein walls as a result of horizontal shortening. Cementation event 3 (E3) is characterized by an equant mosaic of calcite crystals which preserve intracrystalline porosity. E1cements formed between 110 and 90 Ma with trapping temperatures of ∼112 °C (upper Vaca Muerta, well A) and ∼125 °C (lower Vaca Muerta, well D). Fracturing resulted from disequilibrium compaction and from volumetric expansion due to primary cracking of kerogen within the oil window. E2 cements record a trapping temperature of ∼159 °C and formed between 70 and 55 Ma (lower Vaca Muerta, well D) during maximum burial of the Vaca Muerta Formation, synchronous with the secondary cracking of retained liquid hydrocarbons and the beginning of Andean compression. E3 cements (upper Vaca Muerta, well A) have a trapping temperature of ∼162 °C, and formed between 65 Ma and 53 Ma synchronous with the generation of thermogenic gas.By contrast, in the east of the modelled section in the less deformed foreland area of the Neuquén Basin where the Vaca Muerta Formation is in the early oil window (well E), BPVs are composed of a single generation of calcite fibres (E1)with a trapping temperature of ∼118 °C. The E1 cement is characterized by calcite crystals which are oriented perpendicular to fracture walls with no evidence of shearing. According to model simulations, cementation here occurred between 64 Ma and 53 Ma during maximum burial and was related to overpressures which resulted from both disequilibrium compaction and primary transformation of kerogen into oil.The data presented suggests that in some intervals of the Vaca Muerta Formation, a slight increase in TOC content is accompanied by an increase in vein thickness, with the highest number of cementation events occurring towards the Andean deformation front in the west of the study area compared to the foreland in the east.

Magnesium Ions Direct the Solid‐State Transformation of Amorphous Calcium Carbonate Thin Films to Aragonite, Magnesium‐Calcite, or Dolomite

AbstractAmorphous calcium carbonate (ACC) is a common precursor to crystalline calcium carbonate, and is of particular importance in biomineralization, where its crystallization in privileged environments ensures a pseudomorphic transformation. While organisms regulate this process using organic molecules and magnesium ions to selectively form calcite or aragonite, it has proven highly challenging to replicate this polymorph selectivity synthetically. Here, it is demonstrated that remarkable control can be achieved over the chemical composition and structure of crystalline calcium carbonate by using heat to drive a pseudomorphic transformation of ACC thin films. The crystal polymorph can be tuned from low magnesium‐calcite to pure aragonite, high magnesium‐calcite, and ultimately dolomite according to the magnesium content of the ACC, and mosaics of large single crystals are generated at elevated temperatures rather than the spherulitic structures formed at room temperature. This methodology also enables an in situ investigation of the ACC crystallization mechanism using transmission electron microscopy. Finally, the approach can be combined with templating methods to generate arrays of large aragonite single crystals with preselected morphologies. These results demonstrate that exceptional control can be achieved through the solid‐state transformation of Mg‐ACC, which has relevance to both synthetic and biological systems.

Optimization of highly oriented pyrolytic graphite applied to neutron crystal optics

The neutron diffraction properties of highly oriented pyrolytic graphite (HOPG) are reviewed using experimental results that have been obtained by diffraction of high-energy gamma rays, X-rays and neutrons. The interpretation of the empirical data based on diffraction theory leads to generic diagrams that display the performance of HOPG as a function of crystal thickness, mosaic spread and neutron wavelength. The analysis of the relation between the defect structure and diffraction properties demonstrates the usefulness of a detailed X-ray diffraction study to maximize the efficiency of composite neutron monochromators and analyzers. The optimization procedure is illustrated by the configuration of a double-focusing monochromator.

Creating Tunable Mesoporosity by Temperature‐Driven Localized Crystallite Agglomeration (Small 7/2022)

Tunable Mesoporosity In article number 2107006, Chae Un Kim, Ja-Hyoung Ryu, Myoung Soo Lah, and co-workers synthesize a tunable mesoporous metal-organic framework that can be used for enzymatic immobilization through heat treatment of highly mosaic crystals with low-density crystallites through localized agglomeration of volume-reduced crystallites.

Order and Disorder in Layered Double Hydroxides: Lessons Learned from the Green Rust Sulfate─Nikischerite Series

Layered double hydroxides (LDHs) occur naturally and are synthesized for catalysis, drug delivery, and contaminant remediation. They consist of Me(II)–Me(III) hydroxide sheets separated by hydrated interlayers and weakly held anions. Often, LDHs are nanocrystalline, and sheet stacking and Me(II)–Me(III) arrangement can be disordered, which influences the reactivity and complicates structural characterization. We have used pair distribution function (PDF) analysis to provide detailed information about local and medium range order (≤9 nm) and to determine the structure of synthetic Fe(II)–Fe(III)/Al(III) LDH. The data are consistent with ordered Me(II) and Me(III) in hydroxide sheets, where structural coherence along the c axis decreases with increasing Al content. The PDF for Fe(II)–Al(III) LDH (nikischerite) is best matched by a pattern for a single metal hydroxide sheet. Parallel to decreased structural coherence between layers, coherence within layers decreased to ∼6 nm for synthetic nikischerite. Thus, the length scale of atomic ordering decreased within and between the sheets, resulting in mosaic crystals with coherent scattering domains decreasing in all directions. The high density of grain boundary terminations would affect reactivity. Based on classical nucleation theory and the Kossel crystal growth model, we propose that loss of structural coherence stems from increased supersaturation and the presence of Al-hydroxides during the formation of the Al-rich LDH.