Intermediate Crystalline Research Articles

Phase transformation and structural development in mechano-synthesized calcium-copper-titanate electroceramics

This research focuses on the mechano-synthesis of synthesizing calcium-copper-titanate (CCTO) powder through mechanical alloying of the respective oxides aiming to optimize the production of nanoscale electroceramics with high dielectric properties. Structural characterization was carried out using X-ray diffraction with Rietveld refinement (phase identification and quantification), while transmission electron microscopy was employed to observe particle size changes including the reduction of particle size to nanometric scales (10–35 nm). The mechano-synthesis process involving CaO, CuO, and TiO2 resulted in the creation of perovskite CCTO, with minimal contamination observed from the milling process. Significant particle size reduction, nanostructure formation, and a high level of amorphization, alongside polymorphic transitions in TiO2 during milling that played a critical role in achieving full amorphization, which was essential for the formation of high-purity CCTO. The study demonstrates that after 256 h of milling, 88 wt% of the powder consisted of crystalline CCTO, highlighting the potential for enhanced performance in dielectric and microelectronic applications. There was no detection of either stoichiometric CCTO or any non-stoichiometric phases prior to the complete amorphization of the powders. Therefore, results revealing significant advancements in particle size reduction, nanostructure formation, and amorphization, which influence enhanced material performance. Nucleating and growing the CCTO phase directly from an amorphous state without the formation of intermediate crystalline phases clears the potential for optimizing CCTO production processes.

Nanoscale View of Alignment and Domain Growth in a Hexagonal Columnar Liquid Crystal.

Highly ordered liquid crystalline (LC) phases have important potential for organic electronics. We studied the molecular alignment and domain structure in a columnar LC thin film with nanometer resolution during in situ heating using four-dimensional scanning transmission electron microscopy (4D STEM). The initial disordered vapor-deposited LC glass thin film rapidly ordered at its glass transition temperature into a hexagonal columnar phase with small (<10 nm), well-aligned, planar domains (columns oriented parallel to the surface). Upon further heating, the domains coarsen via bulk diffusion, then the film crystallizes, then finally transforms back to an LC phase at an even higher temperature. The LC phase at high temperature shows straight columns of molecules, which we attribute to structure inherited from the intermediate crystalline phase. Nanoscale 4D STEM offers direct insight into the mechanisms of domain reorganization, and intermediate crystallization is a potential approach to manipulate orientational order and texture at the nano- to mesoscale in LC thin films.

Operando electron spin probes for the study of battery processes

Operando electron spin probes, namely magnetometry and electron paramagnetic resonance (EPR), provide real-time insights into the electrochemical processes occurring in battery materials and devices. In this work, we describe the design criteria and outline the development of operando magnetometry and EPR electrochemical cells. Notably, we show that a clamping mechanism, or springs, are needed to achieve sufficient compression of the battery stack and an electrochemical performance on par with that of a standard Swagelok-type cell. The tandem use of operando EPR and magnetometry allows us to identify five distinct and reversible redox processes taking place on charge and discharge of the intercalation-type LiNi0.5Mn0.5O2 Li-ion cathode. While redox processes in conversion-type electrodes are notoriously difficult to investigate using standard characterization methods (e.g. X-ray based) and/or post mortem analysis, due to the formation of poorly crystalline and metastable reaction intermediates and products during cycling, we show that operando magnetometry provides unique insight into the kinetics and reversibility of Fe nanoparticle formation in the Na3FeF6 electrode for Na-based batteries. Step increases in the cell magnetization upon extended cycling indicate the build-up of Fe nanoparticles in the system, hinting at only partially reversible charge–discharge processes. The broad applicability of the tools developed herein to a range of electrode chemistries and structures, from intercalation to conversion electrodes, and from crystalline to amorphous systems, makes them particularly promising for the development of electrochemical energy storage technologies and beyond.

Provenance and Paleoclimate of the Triassic to Middle Jurassic Adigrat Sandstone, Blue Nile Basin, Central Ethiopia

AbstractMineralogical and geochemical studies have been undertaken on the Triassic to Lower Jurassic Adigrat Sandstone of the Blue Nile Basin of central Ethiopia to infer its source rock type, paleoweathering, and paleoclimatic history. The Adigrat Sandstone occurs at the basal section of the Mesozoic sedimentary formation and unconformably overlays the Neoproterozoic–Paleozoic crystalline rocks, or locally, the Karroo sediments in the northern Blue Nile Basin. A mineralogical study reveals that quartz (Q), feldspars (F), and lithic fragments (L) are the framework grains of the sandstone. On the QFL diagram, the plot of the modal composition of the sandstone mainly falls within the feldspathic arenite and quartzose arenite fields. The geochemical data of the lower section of the sandstone mainly falls within the arkose and subarkose fields, whereas the upper section data falls within the quartzose and sublithic arenite fields. Mineralogical and geochemical weathering indices indicate that the provenances of the Adigrat Sandstone were exposed to pronounced weathering intensity, where the lower part of the sandstone was controlled by arid to semi‐arid conditions, whereas the upper section was linked to humid to semi‐humid (tropical to subtropical) climatic conditions. Mineralogical and geochemical data also indicate that mafic to intermediate basement rocks were the primary source rocks of the sediment. Perhaps the sediment was assumed to have been reworked by multi‐cyclic sedimentary processes. The discriminant function diagram, the REE pattern, La/Th vs. La/Yb, and the Th–Hf–Co plot are consistent. A comparison of provenance studies for the Adigrat Sandstone in the Blue Nile Basin and the Mekele outlier of northern Ethiopia indicates that the sediment of the former is highly sorted, experienced higher weathering intensity, and compositionally derived from mafic to intermediate crystalline rocks. On the other hand, the sediment of the latter is essentially a weathering product of felsic rocks.

Radiographic description phase composition of lithium niobate crystals with anomal growth of domains during soft proton exchange

The formation of periodically polarized waveguide structures in lithium niobate crystals for nonlinear optical transformations of laser radiation in the telecommunications wavelength range is an important applied problem. One of the options for forming waveguides with low switching fields can be waveguides obtained by soft proton exchange. In this work, using X-ray diffraction analysis, it is shown that anomalously low polarization switching thresholds occur in layers with so-called intermediate κ-phases when varying the time of soft proton exchange, and when varying the concentration of lithium benzoate, a transition from the metastable β-phase to the intermediate κ-phase is revealed. The results obtained support the hypothesis that the proton concentration gradient leads to a decrease in the threshold field for polarization switching. However, high-concentration metastable and intermediate crystalline phases lead to an increase in optical losses and temperature instability of waveguides.

Interactions and reactivity in crystalline intermediates of mechanochemical cyclorhodation reactions.

There is experimental evidence that solid mixtures of the rhodium dimer [Cp*RhCl2]2 and benzo[h] quinoline (BHQ) produce two different polymorphic molecular cocrystals called 4α and 4β under ball milling conditions. The addition of NaOAc to the mixture leads to the formation of the rhodacycle [Cp*Rh-(BHQ)Cl], where the central Rh atom retains its tetracoordinate character. Isolate 4β reacts with NaOAc leading to the same rhodacycle while isolate 4α does not under the same conditions. We show that the puzzling difference in reactivity between the two cocrystals can be traced back to fundamental aspects of the intermolecular interactions between the BHQ and [Cp*RhCl2]2 fragments in the crystalline environment. To support this view, we report a number of descriptors of the nature and strength of chemical bonds and intermolecular interactions in the extended solids and in a cluster model. We calculate formal quantum mechanical descriptors based on electronic structure, electron density, and binding and interaction energies including an energy decomposition analysis. Without exception, all descriptors point to 4β being a transient structure higher in energy than 4α with larger local and global electrophilic and nucleophilic powers, a more favorable spatial and energetic distribution of the frontier orbitals, and a more fragile crystal structure.

Modulation of Phase Behavior and Microscopic Dynamics in Cationic Vesicles by 1-Decyl-3-methylimidazolium Bromide.

Synthetic cationic lipids have garnered significant attention as promising candidates for gene/DNA transfection in therapeutic applications. The phase behavior of the vesicles formed by these lipids is intriguing, revealing intricate connections to the structure and dynamics of the membrane. These phenomena emerge from the complex interplay between hydrophobic and electrostatic interactions of the lipids. In this study, we explore the impact of an ionic liquid-based surfactant, 1-decyl-3-methylimidazolium bromide (DMIM[Br]), on the structural, dynamical, and phase behavior of cationic dihexadecyldimethylammonium bromide (DHDAB) vesicles. Our investigations indicate that the addition of DMIM[Br] increases the vesicle size while thinning the membrane. Further, DMIM[Br] also induces substantial changes in the membrane phase behavior. At 10 and 25 mol %, DMIM[Br] eliminates the pre-transition from coagel to intermediate crystalline (IC) phase and decreases the onset temperature of the main phase transition to the fluid phase. In the cooling cycle, the addition of DMIM[Br] further induces the formation of an intermediate gel phase. This behavior is reminiscent of the non-synchronous ordering observed in the DODAB membrane, a longer-chain counterpart of DHDAB. Interestingly, at 40 mol % of DMIM[Br], the formation of the intermediate gel phase is largely suppressed. Neutron scattering data provide evidence that the addition of DMIM[Br] enhances lipid mobility in coagel and fluid phases, suggesting that DMIM[Br] acts as a plasticizer, enhancing membrane fluidity across all of the phases. Our findings infer that DMIM[Br] modulates the membrane's phase behavior and fluidity, two essential ingredients for the efficient transport of cargo, by controlling the balance of electrostatic and hydrophobic interactions.

Nonclassical Nucleation and Crystallization of LiNbO3 Nanoparticles from the Aqueous Solvothermal Alkoxide Route.

The exact molecular reaction pathway and crystallization mechanisms of LiNbO3 nanoparticles under solvothermal conditions are derived through extensive time- and temperature-resolved experiments allowing to track all the transient molecular and solid species. Starting with a simple mixing of Li/Nb ethoxides, water addition is used to promote condensation after ligand exchange with different co-solvents including alcohols and glycols of variable carbon-chain length. A nonclassical nucleation scheme is first demonstrated after the identification of new octanuclear complexes with a {Li4Nb4O10} core whose solvophobic interactions mediate their aggregation, thus, resulting in a colloidal gel at room-temperature. Upon heating, a more or less frustrated aggregation-mediated crystallization process is then evidenced leading to LiNbO3 nanocrystals of adjustable mean size between 20 and 100nm. Such a fine control can be attributed to the variable Nb-OR (R = alkoxy/glycoxy ligand) binding interactions at the surface of crystalline intermediates. Demonstration of such a nonclassical nucleation process and crystallization mechanism for LiNbO3 not only sheds light on the entire growth process of multifunctional nanomaterials with non-perovskite crystalline structures, but also opens new avenues for the identification of novel bimetallic oxoclusters involved in the formation of several mixed oxides from the aqueous alkoxide route.

High-Entropy Oxides in the Mullite-Type Structure.

High-entropy materials (HEMs) represent a new class of solid solutions containing at least five different elements. Their compositional diversity makes them promising as platforms for the development of functional materials. We synthesized new HEMs in a mullite-type structure and present five compounds, i.e., Bi2(Al0.25Ga0.25Fe0.25Mn0.25)4O9 and A2Mn4O10 with variations of A = Nd, Sm, Y, Er, Eu, Ce, and Bi, demonstrating the vast accessible composition space. By combining scattering, microscopy, and spectroscopy techniques, we show that our materials are mixed solid solutions. Remarkably, when following their crystallization in situ using X-ray diffraction and X-ray absorption spectroscopy, we find that the HEMs form through a metastable amorphous phase without the formation of any crystalline intermediates. We expect that our synthesis is excellently suited to synthesizing diverse HEMs and therefore will have a significant impact on their future exploration.

Amorphous Solid Forms of Ranolazine and Tryptophan and Their Relaxation to Metastable Polymorphs.

Different methods were explored for the amorphization of ranolazine, a sparingly soluble anti-anginal drug, such as mechanochemistry, quench-cooling, and solvent evaporation from solutions. Amorphous phases, with Tg values lower than room temperature, were obtained by cryo-milling and quench-cooling. New forms of ranolazine, named II and III, were identified from the relaxation of the ranolazine amorphous phase produced by cryo-milling, which takes place within several hours after grinding. At room temperature, these metastable polymorphs relax to the lower energy polymorph I, whose crystal structure was solved in this work for the first time. A binary co-amorphous mixture of ranolazine and tryptophan was produced, with three important advantages: higher glass transition temperature, increased kinetic stability preventing relaxation of the amorphous to crystalline phases for at least two months, and improved aqueous solubility. Concomitantly, the thermal behavior of amorphous tryptophan obtained by cryo-milling was studied by DSC. Depending on experimental conditions, it was possible to observe relaxation directly to the lower energy form or by an intermediate metastable crystalline phase and the serendipitous production of the neutral form of this amino acid in the pure solid phase.

The Role of Crystalline Intermediates in Mechanochemical Cyclorhodation Reactions Elucidated by in-Situ X-ray Powder Diffraction and Computation.

The occurrence of crystalline intermediates in mechanochemical reactions might be more widespread than previously assumed. For example, a recent study involving the acetate-assisted C-H activation of N-Heterocycles with [Cp*RhCl2 ]2 by ball milling revealed the formation of transient cocrystals between the reagents prior to the C-H activation step. However, such crystalline intermediates were only observed through stepwise intervallic ex-situ analysis, and their exact role in the C-H activation process remained unclear. In this study, we monitored the formation of discrete, stoichiometric cocrystals between benzo[h]quinoline and [Cp*RhCl2 ]2 by ball milling using in-situ synchrotron X-ray powder diffraction. This continuous analysis revealed an initial cocrystal that transformed into a second crystalline form. Computational studies showed that differences in noncovalent interactions made the [Cp*RhCl2 ]2 unit in the later-appearing cocrystal more reactive towards NaOAc. This demonstrated the advantage of cocrystal formation before the acetate-assisted metalation-deprotonation step, and how the net cooperative action of weak interactions between the reagents in mechanochemical experiments can lead to stable supramolecular assemblies, which can enhance substrate activation under ball-milling conditions. This could explain the superiority of some mechanochemical reactions, such as acetate-assisted C-H activation, compared to their solution-based counterparts.

Transition Mechanism from the Metastable Two-Dimensional Gel to the Stable Three-Dimensional Crystal of Imidazolium-Based Ionic Liquids.

One important quest for making high quality materials with amphiphiles is to understand how a disordered self-assembly changes to a stable crystalline state. Herein, we addressed the basic question by investigating the phase transition mechanism of imidazolium-based ionic liquid (IL) [C16mim]Br, using time-resolved small- and wide-angle X-ray scattering (SAXS-WAXS), differential scanning calorimetry, and Fourier transform infrared spectroscopy techniques. Totally, a hexagonal phase, two lamellar-gel phases, and three lamellar-crystalline phases were observed, showing the special polymorphism of the system. It was demonstrated that at low concentrations the two-dimensional gel phase (Lβ1) transforms into the most stable lamellar-crystal phase (Lc3) through two intermediate crystalline phases Lc1 and Lc2. At high concentrations, the Lβ1 phase changes to a condensed lamellar gel phase (Lβ2) before changing to Lc2 and eventually to Lc3. Comparative studies using [C16mim]Cl and [C16mim]NO3 unveiled that the interactions between the counterions and the headgroups of the IL, as well as the dehydration process, govern the nucleation process of Lc3 and thus the formation of the crystal. The in-depth investigation on the transition mechanism and the phase polymorphism in the present work advances our understanding of the crystallization of amphiphilic ionic liquids in dispersions and would promote future applications.

Enhanced Methanol Oxidation in Alkaline Media on Electrodeposited Ni Electrodes by Morphological and Crystallographic Evolution

This research aims at exploiting the electrocatalytic behaviour of nano-crystalline nickel electrodes electrodeposited by different techniques including direct current (DC), pulse current (PC), or pulse reversal current (PRC) for methanol electrooxidation in alkaline solutions. We understand that PC electrodeposition forms pyramidal shaped grains with a preferential Bragg diffraction peak of (111), whereas PRC produced refined spherical grain morphology with a strong (200) diffraction peak. However, DC electrodeposition exhibits an intermediate morphology and crystalline structure. Cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) show that PRC electrodeposition develops Ni electrodes with better electrocatalytic activity for methanol electrooxidation than other two nickel electrodes. Based on the CV curve, the current density for Ni prepared by PRC electrodeposition methods is about 75.26 mA.cm−2, which is higher than those of DC and PC methods. This higher activity of PRC electrodeposited nickel is attributed to the low charge transfer resistance confirmed by Nyquist plots. We attributed this behavior to the (200)-oriented crystallographic texture, spherical grain morphology, and consequently the high electrochemical active surface area of this nickel electrode. This work reveals the importance of surface morphology and crystallography on the electrocatalytic behaviour of nickel electrodes for electrochemical energy devices.

Dehydration of Niclosamide Monohydrate Polymorphs: Different Mechanistic Pathways to the Same Product.

Many active pharmaceutical ingredients (APIs) can crystallize as hydrates or anhydrates, the relative stability of which depends on their internal structures as well as the external environment. Hydrates may dehydrate unexpectedly or intentionally, though the molecular-level mechanisms by which such transformations occur are difficult to predict a priori. Niclosamide is an anthelmintic drug on the World Health Organization's "List of Essential Medicines" that crystallizes in two monohydrate forms: HA and HB. Through complementary time-resolved synchrotron powder X-ray diffraction and thermogravimetric kinetic studies, we demonstrate that the two monohydrates dehydrate via distinctly different solid state pathways yet yield the same final anhydrate phase. Water loss from HA via diffusion yields an isomorphous desolvate intermediate which can rearrange to at least two different polymorphs, only one of which exhibits long-term stability. In contrast, dehydration of HB proceeds via a surface nucleation process where simultaneous water loss and product formation occur with no detectable crystalline intermediates. Comparative analysis of the two systems serves to highlight the complex relationship between lattice structure and solid state dehydration processes.

Modernist materials synthesis: Finding thermodynamic shortcuts with hyperdimensional chemistry

Synthesis remains a challenge for advancing materials science. A key focus of this challenge is how to enable selective synthesis, particularly as it pertains to metastable materials. This perspective addresses the question: how can “spectator” elements, such as those found in double ion exchange (metathesis) reactions, enable selective materials synthesis? By observing reaction pathways as they happen (in situ) and calculating their energetics using modern computational thermodynamics, we observe transient, crystalline intermediates that suggest that many reactions attain a local thermodynamic equilibrium dictated by local chemical potentials far before achieving a global equilibrium set by the average composition. Using this knowledge, one can thermodynamically “shortcut” unfavorable intermediates by including additional elements beyond those of the desired target, providing access to a greater number of intermediates with advantageous energetics and selective phase nucleation. Ultimately, data-driven modeling that unites first-principles approaches with experimental insights will refine the accuracy of emerging predictive retrosynthetic models for complex materials synthesis. TOC Diagram: Schematic representation of the energy bandgaps, photogenerated charge separation, and photocatalytic activities improvement mechanism over g-C3N4/SmFeO3 nanosheets Z-scheme based nanocomposites

Effects of Biliary Phospholipids on Cholesterol Crystallization and Growth in Gallstone Formation.

The prevalence of cholesterol gallstone disease is increasing, primarily due to the global epidemic of obesity associated with insulin resistance, and this trend leads to a considerable healthcare, financial, and social burden worldwide. Although phospholipids play an essential role in maintaining cholesterol solubility in bile through both mixed micelles and vesicles, little attention has been paid to the impact of biliary phospholipids on the pathogenesis of cholesterol gallstone formation. A reduction or deficiency of biliary phospholipids results in a distinctly abnormal metastable physical-chemical state of bile predisposing to supersaturation with cholesterol. Changes in biliary phospholipid concentrations influence cholesterol crystallization by yielding both liquid crystalline and "anhydrous" crystalline metastable intermediates, evolving into classical parallelogram-shaped cholesterol monohydrate crystals in supersaturated bile. As a result, five distinct crystallization pathways, A-E, have been defined, mainly based on the prime habits of liquid and solid crystals in the physiological or pathophysiological cholesterol saturation of gallbladder and hepatic bile. This review concisely summarizes the chemical structures and physical-chemical properties of biliary phospholipids and their physiological functions in bile formation and cholesterol solubility in bile, as well as comprehensively discusses the latest advances in the role of biliary phospholipids in cholesterol crystallization and growth in gallstone formation, largely based on the findings from clinical and animal studies and in vitro experiments. The insights gleaned from uncovering the cholelithogenic mechanisms are expected to form a fundamental framework for investigating the hitherto elusive events in the earliest stage of cholesterol nucleation and crystallization. This may help to identify better measures for early diagnosis and prevention in susceptible subjects and effective treatment of patients with gallstones.

Supramolecular intermediates in thermo-mechanochemical direct amidations.

We present a solvent-free thermo-mechanochemical approach for the direct coupling of carboxylic acids and amines, which avoids activators and additives. Detailed analysis of the reactions by ex situ and in situ monitoring methods led to the observation, isolation, and characterisation of multicomponent crystalline intermediates that precede the formation of amides. We applied our methodology for the quantitative synthesis of the active pharmaceutical ingredient moclobemide.

TEM Investigation of Asymmetric Deposition-Driven Crystalline-to-Amorphous Transition in Silicon Nanowires.

Controlling the shape and internal strain of nanowires (NWs) is critical for their safe and reliable use and for the exploration of novel functionalities of nanodevices. In this work, transmission electron microscopy was employed to examine bent Si NWs prepared by asymmetric electron-beam evaporation. The asymmetric deposition of Cr caused the formation of nanosized amorphous-Si domains; the non-crystallinity of the Si NWs was controlled by the bending radius. No other intermediate crystalline phase was present during the crystalline-to-amorphous transition, indicating a direct phase transition from the original crystalline phase to the amorphous phase. Moreover, amorphous microstructures caused by compressive stress, such as amorphous Cr domains and boxes, were also observed in the asymmetric Cr layer used to induce bending, and the local non-crystallinity of Cr was lower than that of Si under the same bending radius.

Impact of urea-based deep eutectic solvents on Mg-MOF-74 morphology and sorption properties

Deep eutectic solvents (DES) based on different urea derivatives have been demonstrated to be efficient green alternatives for the ionothermal synthesis of the prototypical Mg-MOF-74 with a strong impact on the morphology and sorption properties of the material. While the synthesis of the material is rather straightforward in the reline (choline chloride:urea 1:2) DES, higher temperatures and longer reaction times are necessary in the e-urea (2-imidazolidinone, ethylene-urea) based analogous system. Interestingly, in the latter, a variety of intermediate crystalline phases could be observed and characterized by single-crystal X-ray diffraction. In these compounds, coordination of the DES components – the chloride anion and e-urea derivative – to the Mg(II) cation was found to compete with the carboxylate linker. It was rationalized that the difference in the synthesis conditions and in the isolation of intermediate systems originate from the varying decomposition kinetics of the DES and hence from the basicity of the solvent. Although the same material is obtained as ascertained by powder X-ray diffraction and elemental analysis, the final morphology characterized by SEM and TEM is dependent on the nature of the solvent. Whereas the classical rod-like shape is observed in reline, an unusual morphology showing slices perpendicular to the main growth axis is present in the e-urea based DES. For the material featuring this unusual morphology, a higher specific surface area and CO2 uptake were found, which were associated with a higher degree of microporosity.

Amorphization-induced energy loss of amorphous Si anodes for Li-ion batteries

The thermodynamic stability and energy loss (kinetic overpotential) of amorphous Si (a-Si) anodes during electrochemical cycling are investigated by intensive free energy analysis based on molecular dynamics simulations. We first demonstrate the trade-off between energy loss and specific capacity that the enhancement of maximum Li concentration (specific capacity) is compensated with the increase of kinetic overpotential. The effects of external pressure and reaction rate on the formation enthalpy and kinetic overpotential of a-Si anodes are also explored. We find that both effects destabilize amorphous Li-Si (a-LixSi) phases with raised formation enthalpies, and result in the increased kinetic overpotential of a-Si anodes during electrochemical cycling. Our thermodynamic analysis predicts the constant value of overpotential, due to the neglect of ohmic contribution and possible formation of intermediate crystalline LixSi phases. These computational results provide a better understanding of the amorphization effect on the energy loss of alloying-type anodes.