High-resolution Synchrotron X-ray Research Articles

The Development and Atomic Structure of Zinc Oxide Crystals Grown within Polymers from Vapor Phase Precursors.

Sequential infiltration synthesis (SIS), also known as vapor phase infiltration (VPI), is a quickly expanding technique that allows growth of inorganic materials within polymers from vapor phase precursors. With an increasing materials library, which encompasses numerous organometallic precursors and polymer chemistries, and an expanding application space, the importance of understanding the mechanisms that govern SIS growth is ever increasing. In this work, we studied the growth of polycrystalline ZnO clusters and particles in three representative polymers: poly(methyl methacrylate), SU-8, and polymethacrolein using vapor phase diethyl zinc and water. Utilizing two atomic resolution methods, high-resolution scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, we probed the evolution of ZnO nanocrystals size and crystallinity level inside the polymers with advancing cycles─from early nucleation and growth after a single cycle, through the formation of nanometric particles within the films, and to the coalescence of the particles upon polymer removal and thermal treatment. Through in situ Fourier transform infrared spectroscopy and microgravimetry, we highlight the important role of water molecules throughout the process and the polymers' hygroscopic level that leads to the observed differences in growth patterns between the polymers, in terms of particle size, dispersity, and the evolution of crystalline order. These insights expand our understanding of crystalline materials growth within polymers and enable rational design of hybrid materials and polymer-templated inorganic nanostructures.

Temperature-dependent synchrotron XRD study and electrical properties of the (1-x)BZT-(x)BCT lead-free piezoceramics

In recent years, researchers have shown the feasibility of the BZT-xBCT lead-free piezoelectric ceramics for using in various applications such as actuator, energy harvester, high-frequency ultrasonic transducer, etc. However, little evidence of temperature-dependent electrical properties of the BZT-xBCT ceramic was found. Moreover, some researchers have utilized Raman spectroscopy to observe the phase transition of the BZT-xBCT ceramic, but the Raman spectra of ferroelectric polymorphic phases are almost identical and hard to distinguish. In contrast, synchrotron radiation exhibits a high degree of monochromatization and collimation with smaller wavelength than x-ray tubes, resulting in the improvement of resolution for identifying the overlapping peaks. Therefore, this work aims to determine phase coexistence of the BZT-xBCT ceramic near phase boundary region by using high-resolution synchrotron x-ray powder diffraction in comparison with the temperature-dependent electrical properties. This work found that the occurrence of thermally-induced polymorphic phase transformations for the BZT-xBCT ceramics plays a significant role in the observed temperature-dependent electrical properties. Moreover, this work observed a trace of surface damaged layer (the presence of low-angle shoulder in the synchrotron XRD profiles) from mechanical grinding during sample preparation for XRD measurement, which has not previously been found in the BZT-xBCT ceramics. These finding will help to better understand the temperature-dependent functional properties of the BZT-xBCT ceramic for transferring into practical applications.

Pressure/temperature-assisted crystallographic engineering–A strategy for developing the infrared phosphors

Light-emitting diodes utilizing the near-infrared (NIR), harnessed through the doping of Cr ion with structural engineering to tune the luminescent properties, provide a compelling avenue for cutting-edge high-tech industries. Overcoming the challenge of altering the local coordination surrounding the activators is crucial for advancing novel NIR phosphors. Here, we propose a pressure-assisted crystallographic engineering strategy to design the new Cr-doped phosphors. Implementing this approach at high temperature and pressure facilitates the phase transition from β-LiGaO2:Cr to α-LiGaO2:Cr, enabling the LiGaO2:Cr material to emit the NIR light, which was initially unattainable. Additionally, we demonstrate the in-situ monitoring of the reverse phase transition from α-LiGaO2:Cr to β-LiGaO2:Cr, validated by in-situ temperature-dependent high-resolution synchrotron X-ray diffraction. Furthermore, α-LiGaO2:Cr and β-LiGaO2:Cr exhibit unexpected optical properties characterized through synchrotron X-ray absorption, photoluminescence, temperature-dependent, and pressure-dependent analyses. Moreover, the α-LiGaO2:Cr shows strong mechanoluminescence and persistent luminescence. This research paves the way for developing novel NIR phosphors and sheds light on the analyses of pressure-assisted research.

The lattice contraction of UO2 from Cr doping as determined via high resolution synchrotron X-ray powder diffraction

High resolution synchrotron powder X-ray diffraction analysis of Cr-doped UO2 samples with additions of Cr2O3 as 0, 500, 1000, 1500, 2500 to 3500 ppm prepared under sintering conditions of -420 kJ/mol and 1700 °C is reported. The lattice dependence from Cr doping is established through the Rietveld refinement method where the rate of linear lattice parameter contraction from Cr doping, Δacr, was found to be considerably smaller and more subtle than previously described. This investigation highlights the need for high resolution and precise specimen preparation when measuring and interpreting subtle changes to nuclear material crystal structures due to trace doping.

Multiscale Length Structural Investigation and Thermoelectric Performance of Double-Filled Sr0.2Yb0.2Co4Sb12: An Exceptional Thermal Conductivity Reduction by Filler Segregation to the Grain Boundaries.

Among thermoelectric materials, skutterudites are the most prominent candidates in the mid-temperature range applications. In the multiple-filled Sr0.2Yb0.2Co4Sb12 skutterudite, with Sr and Yb as fillers, we have enhanced the thermoelectric performance of CoSb3 through the reduction of lattice thermal conductivity and the optimization of carrier concentration and electrical conductivity. The high-pressure synthesis of the double-filled derivative promotes filling fraction fluctuation. This is observed by high angular resolution synchrotron X-ray diffraction, showing a phase segregation that corresponds to an inhomogeneous distribution of the filler atoms, located at the 2a positions of the cubic space group Im3̅. In addition, scanning transmission electron microscopy (STEM) combined with EELS spectroscopy clearly shows a segregation of Sr atoms from the surface of the grains, which is compatible with the synchrotron X-ray powder diffraction results. Mean square displacement parameters analysis results in Einstein temperatures of ∼94 and ∼67 K for Sr and Yb, respectively, and a Debye temperature of ∼250 K. The strong effect on resonant and disorder scattering yields a significantly lower lattice thermal conductivity of 2.5 W m-1 K-1 at 773 K. Still, good weighed-mobility values were obtained, with high filling fraction of the Yb and Sr elements. This drives a reduced electrical resistivity of 2.1 × 10-5 Ω m, which leads to a peak zT of 0.26 at 773 K. The analysis and results performed for the synthesized (Sr,Yb)-double filled CoSb3, shed light on skutterudites for potential waste-heat recovery applications.

Ex-situ characterization and simulation of density fluctuations evolution during sintering of binder jetted 316L

Efficient density evolution during sintering of the as-printed component is vital to reach full densification and required properties of binder jet (BJT) components. However, due to the high porosity and brittle nature of the green compact, analysis of the microstructure development during sintering is very difficult, resulting in lack of understanding of the densification process. Density development from green state (57 ± 1.6 %) up to full density (99 ± 0.3 %) was characterized by high-resolution synchrotron X-Ray computed tomography (SXCT) on BJT 316L samples from ex-situ interrupted sintering tests. Periodicity of density fluctuations along the building direction was revealed for the first time and was related to the layer thickness of ∼ 42 µm during printing that decreased down to ∼ 33 µm during sintering. Sintering simulations, utilizing a continuum sintering model developed for BJT, allowed to replicate the density evolution during sintering with a mean error of 2 % and its fluctuation evolution from green (1.66 %) to sintered (0.56 %) state. Additionally, simulation of extreme particle size segregation (1 µm to 130 µm) suggested that non-optimized printing could lead to undesirable density fluctuation amplitude rapid increase (∼10 %) during sintering. This might trigger the nucleation of defects (e.g., layer delamination, cracking, or excessive residual porosity) during the sintering process.

An uneven distribution of strontium in the coccolithophore Scyphosphaera apsteinii revealed by nanoscale X-ray fluorescence tomography.

Coccolithophores are biogeochemically and ecologically important phytoplankton that produce a composite calcium carbonate-based exoskeleton - the coccosphere - comprised of individual platelets, known as coccoliths. Coccoliths are stunning examples of biomineralization; their formation featuring exceptional control over both biomineral chemistry and shape. Understanding how coccoliths are formed requires information about minor element distribution and chemical environment. Here, the first high-resolution 3D synchrotron X-ray fluorescence (XRF) mapping of a coccolith is presented, showing that the lopadoliths of Scyphosphaera apsteinii display stripes of different Sr concentration. The presence of Sr stripes is unaffected by elevated Sr in the culture medium, macro-nutrient concentration, and light intensity, indicating that the observed stripiness is an expression of the fundamental coccolith formation process in this species. Current Sr fractionation models, by contrast, predict an even Sr distribution and will have to be modified to account for this stripiness. Additionally, nano-XANES analyses show that Sr resides in a Ca site in the calcite lattice in both high and low Sr stripes, confirming a central assumption of current Sr fractionation models.

Resilience of the Aurivillius structure upon La and Cr doping in a Bi5Ti3FeO15 multiferroic.

Combining the experimental techniques of high-resolution X-ray diffraction, magnetometry, specific heat measurement, and X-ray photoelectron, Raman and dielectric spectroscopy techniques, we have studied the influence of La and Cr doping on the crystal structure and magnetism of the room temperature Aurivillius multiferroic Bi5Ti3FeO15 by investigating the physical properties of (Bi4La)Ti3FeO15 and Bi5Ti3 (Fe0.5Cr0.5)O15. The parent (Bi5Ti3FeO15) and the doped ((Bi4La)Ti3FeO15 and Bi5Ti3(Fe0.5Cr0.5)O15) compounds crystallize in the A21am space group, which is confirmed through our analysis of high-resolution synchrotron X-ray diffraction data obtained on phase-pure polycrystalline powders. We determined the oxidation states of the metal atoms in the studied compounds as Fe3+, Ti4+, Cr3+, and La3+ through the analysis of X-ray photoelectron spectroscopy data. The magnetic susceptibilities of the three compounds are marked by the absence of a long-range ordered ground state, but dominated by superparamagnetic clusters with dominant antiferromagnetic interactions. This signature of short-range magnetism is also seen in specific heat as a low temperature enhancement which is suppressed upon the application of external magnetic fields up to 8 T. Our dielectric spectroscopy experiments showed that the three studied compounds display similar features in the dielectric constant measured as a function of frequency. However, upon doping La at the Bi site, the width of the ferroelectric hysteresis loop increases for (Bi4La)Ti3FeO15 compared to that of the parent compound Bi5Ti3FeO15, and with Cr doping, Bi5Ti3(Fe0.5Cr0.5)O15 becomes a leaky dielectric. The resilience of the Aurivillius crystal structure towards doping of La at the Bi site and Cr at the Fe site is clearly seen in the bulk properties of magnetic susceptibility, specific heat and the average crystal structure. The relevance of changes in the local structure is evident from our Raman spectroscopy and X-ray pair distribution function studies.

Anisotropic thermo-mechanical response of layered hexagonal boron nitride and black phosphorus: application as a simultaneous pressure and temperature sensor.

Hexagonal boron nitride (hBN) and black phosphorus (bP) are crystalline materials that can be seen as ordered stackings of two-dimensional layers, which lead to outstanding anisotropic physical properties. Knowledge of the thermal equations of state of hBN and bP is of great interest in the field of 2D materials for a better understanding of their anisotropic thermo-mechanical properties and exfoliation mechanism towards the preparation of important single-layer materials like hexagonal boron nitride nanosheets and phosphorene. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the thermoelastic parameters of hBN and bP. Here, we report accurate thermal expansion and compressibility measurements along the individual crystallographic axes, using in situ high-temperature and high-pressure high-resolution synchrotron X-ray diffraction. In particular, we have quantitatively determined the subtle variations of the in-plane and volumetric thermal expansion coefficients and compressibility parameters by subjecting these materials to hydrostatic conditions and by collecting a large number of data points in small pressure and temperature increments. In addition, based on the anisotropic behavior of bP, we propose the use of this material as a sensor for the simultaneous determination of pressure and temperature in the range of 0-5 GPa and 298-1700 K, respectively.

Effects of applied pressure and residual heat quenching on the mechanical and thermal properties of cast Al–Mg–Zn–Mn–Fe alloys

In this study, the effects of applied pressure (AP) and residual heat quenching (RQ) on the mechanical properties and thermal conductivities of Al-4.6Mg-3.6Zn-0.86Mn-0.48Fe alloys were investigated based on intensively microstructure analysis by scanning electron microscope (SEM), high resolution transmission electron microscopy (HRTEM) and synchrotron X-ray tomography (SXT). The results indicated that AP and RQ did not change the type of intermetallic; instead, they reduced the length and quantity of lath-like Al6(Fe,Mn) and significantly refined the grain by increasing the cooling rate. Moreover, η′ precipitation particles were enriched near the grain boundaries, which was beneficial for the yield strength of the alloy; the AP + RQ sample exhibited the best mechanical properties of the ultimate tensile strength, yield strength and elongation of 269 MPa, 164 MPa and 11.4 %, respectively, which were 19 %, 17 %, and 83.8 % higher than those of the gravity cast (GC) sample. Moreover, the thermal conductivity of the AP + RQ sample did not show significant changes, which were attributed to the reduction in solid solute caused by the increased volume fraction of η′ precipitates, thus improving the thermal conductivity; however, the formation of numerous semi-coherent interfaces between η′ and the matrix led to increased lattice distortion, resulting in electron scattering.

Semi-Quantitative Analyses of Ferromanganese Nodules from the Pacific Ocean Using Synchrotron X-ray Powder Diffraction

The geochemistry and mineralogy of Mn nodules offer crucial insights into the origins, environmental changes, and distribution of abyssal resources. However, the conventional laboratory X-ray diffractometer, usually employed for semi-quantitative analysis of mineral composition in Mn nodules, often fails to sufficiently detect minor phases due to beam flux limitations and high background signals. In this study, we investigated differences in manganate composition, even when comprising around 1% of the phase fraction, in two manganese nodules (KC-8 and KODOS-10) using high-resolution synchrotron X-ray diffraction. The Mn/Fe ratios of KC-8 and KODOS-10 were 1.32 and 6.24, respectively, indicating that KC-8 and KODOS-10 were predominantly formed in hydrogenetic and diagenetic environments. Both samples contained quartz, vernadite, buserite, and feldspar. Todorokite and illite were exclusively observed in KODOS-10. In KC-8, the phase fractions of vernadite and buserite among manganates ranged from 94(5)%–100(4)% and 6(1)%–0%, respectively. However, in KODOS-10, the fractions of vernadite, buserite, and todorokite ranged from 47(1)%–56(2)%, 33.6(4)%–40.1(3)%, and 10(3)%–16.3(8)%, respectively.

Anomalous excitonic phase diagram in band-gap-tuned Ta2Ni(Se,S)5

During a band-gap-tuned semimetal-to-semiconductor transition, Coulomb attraction between electrons and holes can cause spontaneously formed excitons near the zero-band-gap point, or the Lifshitz transition point. This has become an important route to realize bulk excitonic insulators – an insulating ground state distinct from single-particle band insulators. How this route manifests from weak to strong coupling is not clear. In this work, using angle-resolved photoemission spectroscopy (ARPES) and high-resolution synchrotron x-ray diffraction (XRD), we investigate the broken symmetry state across the semimetal-to-semiconductor transition in a leading bulk excitonic insulator candidate system Ta2Ni(Se,S)5. A broken symmetry phase is found to be continuously suppressed from the semimetal side to the semiconductor side, contradicting the anticipated maximal excitonic instability around the Lifshitz transition. Bolstered by first-principles and model calculations, we find strong interband electron-phonon coupling to play a crucial role in the enhanced symmetry breaking on the semimetal side of the phase diagram. Our results not only provide insight into the longstanding debate of the nature of intertwined orders in Ta2NiSe5, but also establish a basis for exploring band-gap-tuned structural and electronic instabilities in strongly coupled systems.

Impact of nano-scale cavities on hydrogen storage and retention in yttrium hydride

In situ synchrotron high-energy x-ray diffraction experiments and detailed transmission electron microscopy (TEM) characterization were conducted on as-fabricated and neutron-irradiated yttrium hydrides. The high-resolution synchrotron x-ray diffraction revealed minor α yttrium and major δ yttrium hydride phases in all specimens. Specimens were subject to heat treatments (heating-cooling cycles), and the intensity of α yttrium partially and completely disappeared in as-fabricated and neutron-irradiated specimens, respectively. The disappearance of α yttrium was unforeseen because hydrogen was expected to leave δ phase, causing an increase in α yttrium diffraction peak intensity. This observation indicated a surplus of hydrogen in the specimens where it was odd for hydride-forming early transition metal elements. The subsequent through-focus TEM characterization discovered nanometric cavities in both as-fabricated and neutron-irradiated yttrium hydride specimens for the first time. Two types of cavities were identified as fabrication-caused and irradiation-induced. The fabrication-caused cavities were associated with regions having linear deformation features, interfaces, and inclusions. The irradiation-induced cavities were observed as being formed isolated in the yttrium hydride phase. The presence of such nanometric cavities was considered as potential hydrogen storage pockets where the overall hydrogen storing capacity of yttrium hydride would be enhanced.

Hidden Hexavalent Chromium Ions with Subtle Structural Evolution in Near-Infrared Phosphors.

Cr-doped inorganic materials are pivotal in developing near-infrared optical materials; however, multivalent Cr ions and their respective distribution in the materials remain ambiguous. Herein, a series of Li(Sc1-xInx)O2:Cr phosphors containing both Cr3+/Cr6+ ions are prepared. High-resolution synchrotron X-ray diffraction (XRD) reveals two similar phases in Li(Sc1-xInx)O2. Raman spectra further confirm distinct scattering patterns for the two end-member compositions, corroborating the findings from the synchrotron XRD analysis. Cr K-edge X-ray absorption near-edge structure and extended X-ray absorption fine structure demonstrate that most Cr ions in the as-prepared samples are Cr6+, while Cr3+ becomes dominant after washing with water. Moreover, the source and distribution of Cr3+ and Cr6+ ions in the as-prepared and washed samples are revealed through X-ray fluorescence and X-ray excited optical luminescence techniques, which indicate that Cr6+ ions aggregate within the sample, while Cr3+ ions are evenly distributed. Photoluminescence, decay curves, and line shape analyses are implemented to resolve the electron-lattice interactions, and the corresponding mechanisms are provided to explain the asymmetry between photoluminescence and photoluminescence excitation spectra. Overall, this study provides valuable insights into the distribution of low-concentration multivalence ions in solid-state materials and offers a deeper understanding of the approaches to precisely resolve the subtle changes in the crystal structure.

Quantifying weak interactions in ferroelectric and paraelectric phases of phenazine and chloroanilic acid co-crystal using experimental and theoretical electron densities.

The co-crystal of phenazine and chloroanilic acid is known to display paraelectric properties at room temperature. It shows a paraelectric to ferroelectric phase transition at 253 K and has an incommensurately modulated ferroelectric phase below 137 K. High-resolution synchrotron X-ray data were collected at 160 K to model the experimental electron-density distributions, and derived topological properties from the electron density were used to quantify the weak interactions responsible for the origin of the ferroelectric phase. The structure and non-covalent interactions are analysed using Hirshfeld surfaces and energy frameworks. The topological properties, energies, atomic charges and molecular electrostatic potential surfaces are determined from the experimental data, further supported by theoretical calculations. The results from the ferroelectric phase are compared with the paraelectric phase. Although the structural descriptions indicate neutral phenazine and chloroanilic acid molecules in the ferroelectric phase, the topological properties of the electron density indicate a considerable amount of proton transfer in the O-H...O hydrogen bond. Indeed, the displaced H atom in the O-H...O hydrogen bond suggests a mixed covalent/polar nature of chemical bonding. Subtle changes in the chemical bonding and proton-transfer pathways could be detected from the high-resolution electron-density studies.

Multiple unconventional charge density wave transitions in LaPt2Si2 superconductor clarified with high-energy X-ray diffraction

The quasi-2D platinum-based rare earth intermetallic LaPt2Si2 has attracted attention as it exhibits strong interplay between charge density wave order and superconductivity. However, most of the results reported on this material come from theoretical calculations, preliminary bulk investigations and powder samples, which makes it difficult to uniquely determine the temperature evolution of its crystal structure and, consequently, of its charge density wave transition. Therefore, the published literature around LaPt2Si2 is often controversial. Here, by means of high-resolution synchrotron X-ray diffraction data, we clarify some of the poorly or partially understood aspects of the physics of LaPt2Si2. In particular, we resolve the complex evolution of its crystal structure and superstructures, identifying the temperature dependence of multiple density wave transitions in good quality LaPt2Si2 single crystals. According to our findings, on cooling from room temperature LaPt2Si2 undergoes a series of subtle structural transitions which can be summarised as follows: second order commensurate tetragonal (P4/nmm)-to-incommensurate structure followed by a first order incommensurate-to-commensurate orthorhombic (Pmmn) transition and then a first order commensurate orthorhombic (Pmmn)-to-commensurate tetragonal (P4/nmm). The structural transitions are accompanied by both incommensurate and commensurate superstructural distortions of the lattice. The observed behavior is compatible with discommensuration of the CDW in this material.

Multimodal and multiscale characterization reveals how tendon structure and mechanical response are altered by reduced loading.

Tendons are collagen-based connective tissues where the composition, structure and mechanics respond and adapt to the local mechanical environment. Adaptation to prolonged inactivity can result in stiffer tendons that are more prone to injury. However, the complex relation between reduced loading, structure, and mechanical performance is still not fully understood. This study combines mechanical testing with high-resolution synchrotron X-ray imaging, scattering techniques and histology to elucidate how reduced loading affects the structural properties and mechanical response of rat Achilles tendons on multiple length scales. The results show that reduced in vivo loading leads to more crimped and less organized fibers and this structural inhomogeneity could be the reason for the altered mechanical response. Unloading also seems to change the fibril response, possibly by altering the strain partitioning between hierarchical levels, and to reduce cell density. This study elucidates the relation between in vivo loading, the Achilles tendon nano-, meso‑structure and mechanical response. The results provide fundamental insights into the mechanoregulatory mechanisms guiding the intricate biomechanics, tissue structural organization, and performance of complex collagen-based tissues. STATEMENT OF SIGNIFICANCE: Achilles tendon properties allow a dynamic interaction between muscles and tendon and influence force transmission during locomotion. Lack of physiological loading can have dramatic effects on tendon structure and mechanical properties. We have combined the use of cutting-edge high-resolution synchrotron techniques with mechanical testing to show how reduced loading affects the tendon on multiple hierarchical levels (from nanoscale up to whole organ) clarifying the relation between structural changes and mechanical performance. Our findings set the first step to address a significant healthcare challenge, such as the design of tailored rehabilitations that take into consideration structural changes after tendon immobilization.

Multi-scale and multi-modal imaging study of mantle xenoliths and petrological implications

Abstract The accurate textural characterization of mantle xenoliths is one of the fundamental steps to understanding the main processes occurring in the upper mantle, such as sub-solidus recrystallization, magmatic crystallization, and metasomatism. Texture, composition, and mineralogy reflect the temperature, pressure, stress conditions, melting, and/or contamination events undergone before and during the entrapment in the host magma. For these reasons, characterizing the three-dimensional (3D) texture of silicate, oxide, sulfide, and glass phases has great importance in the study of mantle xenoliths. We performed a multi-scale and multi-modal 3D textural analysis based on X-ray computed microtomography (µ-CT) data of three mantle xenoliths from different geodynamic settings (i.e., mobile belt zone, pericraton, oceanic hotspot). The samples were selected to represent different, variably complex internal structures composed of grains of different phases, fractures, voids, and fluid inclusions of different sizes. We used an approach structured in increasing steps of spatial and contrast resolution, starting with in-house X-ray µ-CT imaging (spatial resolution from 30 µm down to 6.25 µm) and moving to high-resolution synchrotron X-ray µ-CT at the micrometer scale. We performed a 3D characterization of mantle xenoliths, comparing the results with the analysis of conventional 2D images (thin sections) obtained by optical microscopy and simulating the random sectioning of several thin sections to estimate the probability of correct modal classification. The 3D models allow the extraction of textural information that cannot be quantified solely from thin sections: spinel layering, distribution of silicic glass, and related vesicles. Moreover, high-density volumes identified as sulfides were detected in two xenoliths, showing no relation with the spinel layering in one case and a preferential concentration along fractures in the other. Given the variety of textures and mineral assemblages of mantle xenoliths worldwide, the results are used to suggest experimental and analytical protocols for the characterization of these materials.

In situ X-ray tomography study on internal damage evolution of solid propellant for carrier rockets

Nitrate Ester Plasticized Polyether (NEPE) propellant has been widely used for carrier rockets. However, the propellant is usually subjected to complex loads, changing the microstructures, which eventually affects its structural integrity. To elucidate the damage mechanism of the propellant, an in situ tensile testing rig with a maximum strain rate of 0.1 s−1 was developed with high-resolution synchrotron X-ray tomography. The internal microstructure and the resultant damage evolution have been characterized quantitatively. The mechanical behaviour of sampled propellant was extracted from the dynamic mechanical analysis. In addition, numerical simulation in terms of the spatial geometry of filler particles was performed in the framework of the micromechanical approach. To visualize the debonding process, a cohesive-zone model was employed to trace the debonding at the filler/matrix interface and then the damage evolution was characterized according to the cohesive behaviour. The results can assist in correlating the cohesive behaviour due to local heterogeneity with the macroscopic mechanical response for the NEPE propellant.

Induced-Fit-Identification in a Rigid Metal-Organic Framework for ppm-Level CO2 Removal and Ultra-Pure CO Enrichment.

Removing CO2 from crude syngas via physical adsorption is an effective method to yield eligible syngas. However, the bottleneck in trapping ppm-level CO2 and improving CO purity at higher working temperatures are major challenges. Here we report a thermoresponsive metal-organic framework (1a-apz), assembled by rigid Mg2(dobdc) (1a) and aminopyrazine (apz), which not only affords an ultra-high CO2 capacity (145.0/197.6 cm3 g-1 (0.01/0.1 bar) at 298 K) but also produces ultra-pure CO (purity ≥ 99.99%) at a practical ambient temperature (TA). Several characterization results, including variable-temperature tests, in-situ high-resolution synchrotron X-ray diffraction (HR-SXRD), and simulations, explicitly unravel that the excellent property is attributed to the induced-fit-identification in 1a-apz that comprises self-adaption of apz, multiple binding sites, and complementary electrostatic potential (ESP). Breakthrough tests suggest that 1a-apz can remove CO2 from 1/99 CO2/CO mixtures at practical 348 K, yielding 70.5 L kg-1 of CO with ultra-high purity of ≥ 99.99%. The excellent separation performance is also revealed by separating crude syngas that contains quinary mixtures of H2/N2/CH4/CO/CO2 (46/18.3/2.4/32.3/1, v/v/v/v/v).