High-resolution Electron Microscopy Observations Research Articles

Macropinocytic cups function as signal platforms for the mTORC2-AKT pathway to modulate LPS-induced cytokine expression in macrophages.

Macropinocytosis is a large-scale endocytosis process that is primarily observed in phagocytes as part of their cellular function to ingest antigens. Once phagocytes encounter gram-negative bacteria, the receptor proteins identify lipopolysaccharides (LPSs), which trigger radical membrane ruffles that gradually change to cup-like structures. The open area of the cups closes to generate vesicles called macropinosomes. The target bacteria are isolated by the cups and engulfed by the cells as the cups close. In addition to its ingestion function, macropinocytosis also regulates the AKT pathway in macrophages. In the current study, we report that macropinocytic cups are critical for LPS-induced AKT phosphorylation (pAKT) and cytokine expression in macrophages. High-resolution scanning electron microscope (SEM) observations detailed the macropinocytic cup structures induced by LPS stimulation. Confocal microscopy revealed that AKT and the kinase molecule mTORC2 were localized in the cups. The biochemical analysis showed that macropinocytosis inhibition blocked LPS-induced pAKT. RNA-Seq, qPCR, and ELISA analyses revealed that the inhibition of macropinocytosis or the AKT pathway causes a decrease in the expression of pro-inflammatory cytokines IL-6 and IL-1α. Moreover, activation of the transcription factor NF-κB, which regulates the cytokine expression downstream of the AKT/IκB pathway, was hindered when macropinocytosis or AKT were inhibited. These results indicate that LPS-induced macropinocytic cups function as signal platforms for the AKT pathway to regulate the cytokine expression by modulating NF-κB activity in LPS-stimulated macrophages. Based on these findings, we propose that macropinocytosis may be a good therapeutic target for controlling cytokine expression.

Chemical and topological disordering in M23C6 due to irradiation: An atomic-scale observation

To clarify the stability of M23C6 precipitate in steels under irradiation, the chemical and topological disordering behaviors in M23C6 subjected to ion irradiation at elevated temperatures were investigated with the combined application of high-resolution electron microscopy (HREM) and electron energy-loss spectroscopy (EELS). Results show that the duplex structured M23C6 which is the core-crystalline and shell-amorphous was observed in the specimen irradiated at 623 K, nevertheless, no amorphous phase was observed in the specimen irradiated at 673 K. HREM observation confirmed the occurrence of the chemical disordering in irradiated M23C6, and the disordering of W atoms in the M23C6 unit cell was clarified by the peak intensity profile of the atomic column from the HREM image. EELS analyses indicate that no obvious chemical shift was observed by the core-loss spectrum, however, the change in the electron mean free path (λ) due to irradiation was confirmed by the low-loss spectrum, which is related to the formation of both irradiation defects and amorphous phase. It is proposed that the decreased material density upon irradiation is ascribed to the formation of W-vacancy-dominated defect clusters. An obvious change in interatomic distance was not observed in the irradiated M23C6 based on the radical distribution function analysis by extended energy-loss fine structure spectrum. However, the peak intensity decreased by irradiation, confirming the occurrence of chemical and topological disordering, regardless of the carbide being crystalline or amorphous.

Towards building a unified adsorption model for goethite based on direct measurements of crystal face compositions: I. Acidity behavior and As(V) adsorption

We have determined the proton, electrolyte (NaNO3) and arsenate affinity constants on the corresponding surface sites of goethite. An empirical optimization approach was applied using the Charge Distribution Multisite Complexation (CD-MUSIC) model, initially, by simulating an extensive proton adsorption data set obtained from four goethites of specific surface areas (SSAs) spanning from 43 to 89 m2/g. Each goethite showed different crystal face compositions, which were measured previously from independent high resolution electron microscopy observations. Only the capacitance value was left as an additional optimizing parameter. For arsenate adsorption, with the above optimized values fixed, the contributing surface arsenate complexes and their respective affinity constants and charge distributions (CD) were also optimized. A unified set of affinity and CD parameters was obtained, where the only resulting variables among goethites were the capacitance 1, the specific surface area and the crystal face contributions (and thus their reactive surface site densities).It was found that the site density parameter is decisive when data show adsorption maxima, such as in the arsenate adsorption isotherms. The self-consistent modeling approach yielded pKa values of singly-coordinated sites of 8.82, and of triply-coordinated sites of 9.65. Three surface arsenate complexes bound only to singly-coordinated sites were found to describe all experimental data, although only two of them were predominant across the pH and As(V) concentration ranges investigated: a bidentate non protonated (BD) complex, and a protonated monodentate (HMD) one. Charge distribution of surface arsenate complexes was found to significantly influence the optimizations, but increased values of optimized capacitance 1 were found to compensate for previously underestimated surface site density values, to yield almost identical surface affinity and CD parameters.Finally, correlations found between surface site density and capacitance-1 parameters with SSA expanded the applicability of the modeling approach presented, to other goethites with different SSAs than the ones investigated here.

Effect of High-Temperature Annealing on Raman Characteristics of Silicon Nanowire Arrays

We demonstrate two distinct experimental processes involving the large-area growth of ordered and disordered silicon nanowire arrays (SiNWs) on a p-type silicon substrate using the metal-assisted chemical etching method. The two processes are based on the etching of monocrystalline silicon wafers by randomly distributed Ag films and ultra-thin Au films with ordered nano-mesh arrays, respectively, wherein the growth of SiNWs is implemented using a specific proportion of a HF-containing solution at room temperature. In this study, the microstructural change mechanisms for the two morphologically different arrays before and after annealing were investigated using Raman spectra. The effects of various mechanisms on the observed Raman scattering peak’s deviation from symmetry, redshift and broadening were analyzed. The evolution of the unstable amorphous structures of nanoscale materials during the high-temperature annealing process was observed via high-resolution scanning electron microscope (SEM) observations. The scattering peak parameters determined from the Raman spectra led to conclusions concerning the various mechanisms by which high-temperature annealing influences the microstructures of the two morphologically different SiNWs fabricated on the p-type silicon substrate. Therefore, the deviation of SiNWs from the monocrystalline silicon scattering peak at 520.05 cm−1 when changing the diameter of the nanowire columns was calculated to further analyze the effect of thermal annealing on Raman characteristics.

Calcitic shells in the aragonite sea of the earliest Cambrian

Abstract The initial acquisition of calcium carbonate polymorphs (aragonite and calcite) at the onset of skeletal biomineralization by disparate metazoans across the Ediacaran-Cambrian transition is thought to be directly influenced by Earth's seawater chemistry. It has been presumed that animal clades that first acquired mineralized skeletons during the so-called “aragonite sea” of the latest Ediacaran and earliest Cambrian (Terreneuvian) possessed aragonite or high-Mg calcite skeletons, while clades that arose in the subsequent “calcite sea” of Cambrian Series 2 acquired low-Mg calcite skeletons. Here, contrary to previous expectations, we document shells of one of the earliest helcionelloid molluscs from the basal Cambrian of southwestern Mongolia that are composed entirely of low-Mg calcite and formed during the Terreneuvian aragonite sea. The extraordinarily well-preserved Postacanthella shells have a simple prismatic microstructure identical to that of their modern low-Mg calcite molluscan relatives. High-resolution scanning electron microscope observations show that calcitic crystallites were originally encased within an intra- and interprismatic organic matrix scaffold preserved by aggregates of apatite during early diagenesis. This indicates that not all molluscan taxa during the early Cambrian produced aragonitic shells, weakening the direct link between carbonate skeletal mineralogy and ambient seawater chemistry during the early evolution of the phylum. Rather, our study suggests that skeletal mineralogy in Postacanthella was biologically controlled, possibly exerted by the associated prismatic organic matrix. The presence of calcite or aragonite mineralogy in different early Cambrian molluscan taxa indicates that the construction of calcium carbonate polymorphs at the time when skeletons first emerged may have been species dependent.

Deformation mechanisms of a NiTi alloy under high cycle fatigue

In this paper, high-cycle fatigue mechanisms of a pseudoelastic NiTi shape memory alloy (SMA) under different mean strains are investigated. The uni-axial cyclic tensile tests with small amplitude of 0.25% are operated at three different states, i.e. austenite/elastic region, austenite and martensite coexisted region and martensite/elastic region with a pre-strain. Mechanical results indicate that the cyclic deformation strain is mainly in the inhomogeneous deformation band when the sample cycling in the B2 + B19′ phase coexist status. Cyclic deformation in the B2 + B19’ phase showed cyclic hardening effect. With increasing of the mean strain, the saturation stress is decreased, and saturation rate is reduced. The mean strain effect on the high-cycle fatigue life of NiTi is attributed to the inhomogeneous transformation of martensite. High resolution electron microscopy (HREM) observations and atomic simulations showed that partial dislocations with the Burgers vectors of 1/2<110> are induced on (001)M twin planes, the interaction of dislocations and edge dislocations in martensite results in cyclic hardening in martensite. While cyclic softening in martensite at the upper plateau of stress–strain (S–S) curve is attributed to the grain reorientation/rotation phenomenon. It suggests that newly generated stress-induced martensite at the interface of martensite and austenite could increase the high-cycle fatigue of NiTi SMA.

Damage-Free Femtosecond X-Ray Laser Snapshot Imaging of Catalyst Layer Nano-Structures of Polymer Electrolyte Fuel Cells

The realization of the hydrogen society, where hydrogen is used as clean and renewable energy, is desired to reduce carbon dioxide emissions and achieve sustainable development. The polymer electrolyte fuel cell (PEFC) is a key technology for automobiles in the hydrogen society as an alternative to conventional internal combustion engines. However, further improvements in PEFC performances are required for the full-scale spread of fuel cell vehicles. This study aims to image the nanostructures of the catalyst layer, which is particularly important in determining the performance of PEFCs, and correlate the observed structures with mass transfer in the catalyst layer. The catalyst layer contains catalyst-loaded carbon supports thinly covered with an ionomer responsible for proton conduction. We are especially interested in observing the support structure and ionomer coverage.We performed coherent X-ray imaging studies on the catalyst particles of PEFCs using an X-ray free-electron laser (XFEL) facility: SACLA (SPring-8 Angstrom Compact free electron LAser). Femtosecond XFEL allows us to capture radiation-damage-free snapshot images by outrunning major radiation damage processes. Damage-free imaging is of great value because radiation damage often causes a problem in high-resolution electron microscopy observation of ionomers. We used the coherent diffractive imaging (CDI) technique to observe catalyst particles of PEFCs. In CDI, sample images are reconstructed from measured coherent diffraction patterns using phase-retrieval calculation instead of objective lenses. CDI enables quantitative phase imaging and allows high-contrast imaging of the catalyst particles, which are almost transparent to X-rays.The measurement was carried out for catalyst particles in the dried condition and in solution. Our study showed that the image contrast can be adjusted by changing the electron density of the volume surrounding the sample1). The dried sample was prepared by dropping catalyst ink onto a silicon nitride membrane and air-dried. The solution sample was enclosed in micro-liquid enclosure arrays2,3) developed at Hokkaido University. The coherent diffraction patterns were measured by irradiating the sample catalyst particles with the 100-nm-focused XFEL beam with a photon energy of 4 keV using MAXIC-S (Multiple Application X-ray Imaging Chamber-S)4). The phase-retrieval calculation reconstructed the sample images. Fig. 1 shows a reconstructed image of a catalyst particle in water. The reconstructed image shows many white spots, which can be interpreted as platinum-cobalt catalysts. The pixel size of the reconstructed image is 1.3 nm, demonstrating among the highest spatial resolution in X-ray imaging. We will continue our study to observe the support structures and their ionomer coverage to understand the mass transfer in the catalyst layer.This work was supported by the FC-Platform of NEDO (New Energy and Industrial Technology Development Organization). The XFEL experiments were performed at SACLA with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal Nos. 2020A8106, 2021A8010, and 2021B8019).

Effects of manual washing with three alkaline sterilizing agent solutions on egg quality during storage

This study aimed to investigate the abundance of microorganisms and quality of eggs washed with different washings (tap water, 0.03% calcium hypochlorite solution, 0.25% hydrogen peroxide solution, or 1% sodium percarbonate solution) and unwashed for 28-day storage. The results showed that the washing significantly decreased the abundance of microorganisms in all cases. Washing with one of the three alkaline sterilizing agent solutions significantly inhibited the deterioration of egg quality (evidenced by lower weight loss, air cell depth, albumen pH, yolk pH, and total volatile base nitrogen, but higher Haugh unit and yolk index) during storage, while washing with tap water showed opposite effects. The texture profile analysis and high-resolution scanning electron microscopy observation showed that all washings had slight negative effects on eggshell quality (eggshell breaking strength and microstructure), and washing with the alkaline sterilizing agent solution had no additional effects. The results might be attractive to egg preservation industry.

Contribution of clay on storage and adsorption capacities of the Middle Permian marls, South China

A significant gas show appeared in JY66-1 well when it was drilled into the Middle Permian limestone-marl alternation interval, high-resolution scanning electron microscopic (SEM) observation shows that clay-related pores were developed extensively. There have been a lot of comprehensive studies on the origin of organic-matter pores and their pore size distribution, but few studies on the scales of clay-related pores and their contributions to the total pore volume and surface area. In this paper, we conducted thin section and SEM observation, mercury intrusion, low pressure N2 adsorption and high-pressure CH4 adsorption experiments, to characterize the pore volume and surface area of Mg-clay-bearing samples. The result suggests that the pore volume of clay-related pores mainly derives from the Intra-aggregate pores of 5–100 nm pore size, while the absolute and relative contributions of Interlayer pores (smaller than 2 nm) and Intra-tactoid pores (2–5 nm) to the total pore volume are small. Based on TOC contents and inorganic mineral compositions, a multiple regression analysis was carried out on the contributions of organic-matter and clay-related pores to pore volume in the pore-diameter ranges of smaller than 2 nm, 2–5 nm, 5–100 nm and larger than 100 nm. Although the contribution of clay-related pores (including inter-aggregate pores, Intra-aggregate pores, Intra-tactoid pores, Interlayer pores) to the total pore volume is comparable to that of organic-matter pores, the latter still contributes most of the pore surface area and CH4 adsorption site. It can be interpreted by the fact that the specific surface area of the dominant Intra-aggregate pores is significantly smaller than that of organic-matter pores. The conclusion of this study can be applied for the analyses of storage and adsorption capacity in all gas shales containing both organic and clay minerals.

Radiation-induced amorphization of M23C6 in F82H steel: An atomic-scale observation

The purpose of the present study is to clarify the instability behavior of M23C6 under irradiation, specifically the occurrence of radiation-induced amorphization (RIA). Ion irradiation of 10.5 MeV-Fe3+ at elevated temperatures from 573 to 623 K was conducted into the reduced activation ferritic/martensitic steels (F82H) and its model alloy (Fe-8Cr-0.1C). A bilayer contrast of the particle consisting of an amorphous-rim phase and inner crystalline core of M23C6 was observed in the irradiated F82H specimen, but not in the model alloy. From the high-resolution electron microscope observation, the preferential occupation site of W into M23C6 lattice was identified as 8c-site prior to irradiation in F82H specimen, which shifted to other sites due to chemical disordering upon irradiation. Evaluation of the intensity ratio between 8c and another site of M23C6, 8c/4a, then revealed that the extent of chemical disordering of W was mitigated at the amorphous-crystal interface region in comparison with the central of the particle. The hypothesis for the formation mechanism of an amorphous-rim in M23C6 was presumed as the deviation from the stoichiometric composition at the local interface due to the irradiation-enhanced diffusion and/or ballistic mixing under the current circumstances, although the efforts from experimental and/or simulation studies are still necessary to achieve a further understanding of the RIA behavior in M23C6.

In-situ high-resolution scanning electron microscopy observation of electrodeposition and stripping of lead in an electrochemical cell

A compact electrochemical cell capped with a silicon nitride (SiN) film of 50 nm thick as an electron window was developed for a side-entry holder of a high-resolution scanning electron microscope (SEM). Electrodeposition and stripping of lead (Pb) were examined on a gold electrode formed on the SiN film, which was faced inside the cell filled with an aqueous solution of lead nitrite. The SEM images of growth and dissociation of Pb were recorded simultaneously with cyclic voltammograms, controlled with a two-terminal potentiostat. Particulate growth of Pb at the edge of a gold (Au) electrode was observed at the underpotential deposition of Pb, followed by dendrite growth of Pb at higher deposition potentials. The growth mode changed depending on the edge morphology of the Au electrode. This indicated that in-situ microscopic observation was invaluable for understanding the phenomena of electrodeposition in electrochemistry.

The rock-fabric/petrophysical characteristics and classification of the micropores hosted between the calcite and dolomite crystals

For the substantial hydrocarbon potential and academic significance, focus of interest has been directed towards the microporous carbonate. Compared with the documented shallow burial microporous carbonate, carbonate with a depth deeper than 6000 m present, of course, different characteristics due to the long-term influences of the strong cementation and compaction. With the deepening of exploration, it is therefore essential to improve the understanding about the deep burial microporous carbonate. In this paper, an integrated petrographic and petrophysical approach, which combines thin section, high-resolution field emission scanning electron microscopy (FESEM) observations, and nuclear magnetic resonance (NMR) measurements, is chosen to study the deep to ultradeep carbonate in the Shunnan area, Tarim Basin, NW China.Results show that all the studied carbonate samples consist entirely of micropores with a radius less than 10 μm, belonging to the strictly microporous carbonate. These micropores exist between the calcite and dolomite microcrystals. To reliably calculate the permeability based on NMR data, a newly introduced factor P aiming to adjust the T2 cut-off value derived from the relaxation curve is applied to enhance the Coates model. Values of P are found to correlate well with the FFI (free fluid index) of the bioclastic and bioclasts-free detrital limestones through different quantitative relationships, respectively. Permeabilities calculated from the modified Coates model are in good agreements with those measured by the pulse-decay method (R2 = 0.93, 0.67). Considering the existing classifications of pore systems are not applicable to the peculiar intercrystalline micropores within the deep burial microporous carbonate, a noval classification scheme is thus explored by integrating the rock-fabric and petrophysical properties. Micropores hosted within the subhedral to anhedral microcrystals with distinct boundaries are the main reserving space of the microbial lime-/dolostone, which lead to relatively higher porosities (averaging 3.41%) than the detrital limestone (1.99%) and dolostone (2.47%), and an identical right-skewed trimodal NMR T2 distribution. Micropores related with the coalescent polyhedral to anhedral microcrystals, that are always glued together to form fusing boundaries, are mainly located within the micrite matrix and allochem of the detrital limestone. Certain relationships among porosity, permeability and FFI/BVI also exist for the bioclastic and bioclasts-free detrital limestones, respectively. Micropores within the dolostone exist between the rhombic dolomite crystals. This proposed classification of micropores comprehensively reflects the depositional, diagenetic textures and physical properties of the deep burial microporous carbonate. The particularity of microbial lime-/dolostone is highlighted.

Fracture, Dissolution, and Cementation Events in Ordovician Carbonate Reservoirs, Tarim Basin, NW China

Ordovician carbonate rocks of the Yijianfang Formation in the Tabei Uplift, Tarim Basin, contain deeply buried (&gt;6000 m), highly productive oil and gas reservoirs associated with large cavities (&gt;10 m). Previous workers inferred that large cavities are paleocaves (paleokarst) formed near the surface and subsequently buried. Alternately, caves may have formed by dissolution at depth along faults. Using 227 samples from 16 cores, we document textures and cement compositions bearing on cavity histories with petrographic, high-resolution scanning electron microscopy (SEM), isotopic, and fluid inclusion microthermometric observations. Results show that dissolution occurred at depth and was caused by (1) acidic fluids derived from Middle-Late Silurian and/or Devonian-Permian hydrocarbon generation and maturation, (2) high-temperature fluids, of which some were associated with Late Permian igneous activity, and (3) Mg-rich fluids that accompanied Jurassic-Cretaceous deformation and the formation of partially open fractures and stylobreccias (fault breccias). The relative paragenetic sequence of the structure-related diagenesis suggests seven stages of fracturing, dissolution, and cementation. Mottle fabrics in the Yijianfang Formation contain argillaceous carbonate-rich silt and are bioturbation features formed within the marine environment. Those mottled fabrics differ from clearly karstic features in the overlying Lianglitage Formation, which formed by near-surface dissolution and subsequent infilling of cavities by allochthonous sediment. Mottle fabrics are crosscut by compacted fractures filled with phreatic-vadose marine cements and followed by subsequent generations of cement-filled fractures and vugs indicating that some fractures and vugs became cement filled prior to later dissolution events. Calcite cements in fractures and vugs show progressively depleted values of δ18O documenting cement precipitation within the shallow (~220 m), intermediate (~625 m), and deep (~2000 m) diagenetic environments. Deep (mesogenetic) dissolution associated with fractures is therefore the principal source of the high porosity-permeability in the reservoir, consistent with other pieces of evidence for cavities localized near faults.

Interconnected 3D Framework of CeO2 with High Oxygen Storage Capacity: High-Resolution Scanning Electron Microscopic Observation

CeO2 nanocasting in a mesoporous hard template provides a three-dimensionally (3D) interconnected skeleton framework consisting of CeO2 nanoparticles with particles smaller than 7 nm. Low-voltage high-resolution scanning electron microscopy with Ar-ion-beam cross-sectional polishing revealed numerous CeO2 (∼250 nm) clusters distributed in the SBA-15 mesochannels. Each CeO2 framework consists of CeO2 primary nanocrystals that are mutually and coherently connected. The mesochannel walls of the mesoporous silica might confine the growth of the CeO2 nanocrystals, resulting in a high oxygen storage capacity of the material. A series of cross-sectional images obtained by using damage-free Ar-ion-beam polishing revealed the mechanism of pore filling and CeO2 structuring process: that from the nucleation and growth of the CeO2 in the mesopores to the self-organization of nanocrystals that form multiple nanowires along the mesochannels. Furthermore, self-organized nanowires were arranged periodically and were mutually connected finally to form a negative replica of the ordered mesoporous SBA-15 silica.

LiCoO2 with double porous structure obtained by electrospray deposition and its evaluation as an electrode for lithium-ion batteries

An in-situ temperature-controlled Raman spectroscopy aided unique electrode fabrication technique has been developed for Li-ion battery applications, ensuring superior electrochemical quality of the multi-porous LiCoO2 films with higher stoichiometric purity of high temperature (HT)-LiCoO2 phase, by observing the structural changes during the fabrication process and thus confirming the transformation from the low temperature (LT)-LiCoO2 phase. This much desired simple process is not only free of any sort of binders or carbon additives but also works at atmospheric pressure, leading to a very simple deposition technique using a homemade and inexpensive set-up. Also, the time of depositions were varied and resultant films we investigated for their electrochemical performance. The high-resolution scanning electron microscope (SEM) observation has revealed not only a μm-size porous structure but also three-dimensional cross-link with 10 nm-level pores of the material, which ensured the much-desired porosity for high-performance cathodes.

Strain-Induced Metastable Phase Stabilization in Ga2O3 Thin Films.

It is well known that metastable and transient structures in bulk can be stabilized in thin films via epitaxial strain (heteroepitaxy) and appropriate growth conditions that are often far from equilibrium. However, the mechanism of heteroepitaxy, particularly how the nominally unstable or metastable phase gets stabilized, remains largely unclear. This is especially intriguing for thin-film Ga2O3, where multiple crystal phases may exist under varied growth conditions with spatial and dimensional constraints. Herein, the development and distribution of epitaxial strain at the Ga2O3/Al2O3 film-substrate interfaces is revealed down to the atomic resolution along different orientations, with an aberration-corrected scanning transmission electron microscope. Just a few layers of metastable α-Ga2O3 structure were found to accommodate the misfit strain in direct contact with the substrate. Following an epitaxial α-Ga2O3 structure of about couple unit cells, several layers (4-5) of transient phase appear as the intermediate structure to release the misfit strain. Subsequent to this transient crystal phase, the nominally unstable κ-Ga2O3 phase is stabilized as the major thin-film phase form. We show that the epitaxial strain is gracefully accommodated by rearrangement of the oxygen polyhedra. When the structure is under large compressive strain, Ga3+ ions occupy only the oxygen octahedral sites to form a dense structure. With gradual release of the compressive strain, more and more Ga3+ ions occupy the oxygen tetrahedral sites, leading to volumetric expansion and the phase transformation. The structure of the transition phase is identified by high-resolution electron microscopy observation, complemented by the density functional theory calculations. This study provides insights from the atomic scale and their implications for the design of functional thin-film materials using epitaxial engineering.

Effect of One-Step and Two-Step Aging Treatments on Microstructure and Properties of an Al-9.0Zn-2.0Mg-2.0Cu Alloy

Aging treatments of an Al-9.0Zn-2.0Mg-2.0Cu alloy, which belongs to high strength aluminum alloy widely used in aerospace industry, are investigated by various techniques, including hardness, electrical conductivity, mechanical properties, transmission electron microscopy (TEM) and high-resolution electron microscopy (HREM). The result shows that hardness and conductivity for one-step aging treatment increase with aging time prolongs while those for two-step aging treatment exhibit increment and decrement, respectively. Besides, the ultimate tensile strength (UTS) and yield strength (YS) for one-step and two-step aging treatments show slow increase and obvious decrease, respectively. Based on these, typical T6 and T76 aging regimes are extracted for microstructure observation. The matrix precipitates for the T6 alloy have small size and dispersive distribution while that for the T76 alloy has big size and sparse distribution. The grain boundary precipitates for both exhibit discontinuous distribution and the T76 alloy has larger size and broader precipitate free zones. The selected area diffraction patterns and HREM observations reveal that main precipitates for the T6 alloy are GPI zone, GPII zone and η' phase while for the T76 alloy are η' phase and η phase.

An experimental study of organic matter, minerals and porosity evolution in shales within high-temperature and high-pressure constraints

Abstract The development and evolution of porosity in organic-rich shales (ORSs) is critical to the commercial exploitation of shale oil and gas resources. In this paper, we present the results of high-temperature and high-pressure experiments on typical marine and lacustrine shales to investigate porosity changes. The samples were taken from the Proterozoic Xiamaling Formation in the North China Platform, the Permian Lucaogou Formation in the Junggar Basin, the Triassic Chang 7 member in the Ordos Basin, and the Silurian Longmaxi Formation in the Sichuan Basin, all in China. We found that the key factors influencing porosity evolution include the extent of compaction, abundance of organic matter, degree of thermal evolution, and organic matter–inorganic mineral framework. The effects of thermal evolution on the pore structure of high-mature shales are more obvious than those on low-mature shales. Although the porosity evolution is positively correlated with maturity, we found evidence for different porosity evolution in ORSs in the oil window. High-resolution scanning electron microscopy observations of experimental and actual core samples indicate that liquid hydrocarbon is adsorbed and dissolved in organic matter in the oil window, leading to swelling of the organic material. This explains why there are few organic matter pores in lacustrine shales in China. The pore structure evolution is similar for marine and lacustrine shales, suggesting that kerogen has a stronger influence on the porosity evolution of shale than does the depositional environment. The lower limit of vitrinite reflectance values (Ro) at which abundant organic pores develop is 1.5%–2.5%, and the degree of pore development in ORSs is highest when Ro values are 2.5%–3.0%. These results have important implications for shale oil and gas exploration.

Atomic scale analyses of {\bb Z}-module defects in an NiZr alloy.

Some specific structures of intermetallic alloys, like approximants of quasicrystals, have their unit cells and most of their atoms located on a periodic fraction of the nodes of a unique {\bb Z}-module [a set of the irrational projections of the nodes of a (N > 3-dimensional) lattice]. Those hidden internal symmetries generate possible new kinds of defects like coherent twins, translation defects and so-called module dislocations that have already been discussed elsewhere [Quiquandon et al. (2016). Acta Cryst. A72, 55-61; Sirindil et al. (2017). Acta Cryst. A73, 427-437]. Presented here are electron microscopy observations of the orthorhombic phase NiZr - and its low-temperature monoclinic variant - which reveal the existence of such defects based on the underlying {\bb Z}-module generated by the five vertices of the regular pentagon. New high-resolution electron microscopy (HREM) and scanning transmission electron microscopy high-angle annular dark-field (STEM-HAADF) observations demonstrate the agreement between the geometrical description of the structure in five dimensions and the experimental observations of fivefold twins and translation defects.

How Short-Lived Ikaite Affects Calcite Crystallization

The pathways of CaCO3 crystallization are manifold, often involving one or several metastable amorphous or nanocrystalline intermediate phases. The presence of such intermediates is often overlooked, because they are short-lived and/or occur at small molar fractions. However, their occurrence does not just impact the mechanisms and pathways of formation of the final stable CaCO3 phase, but also affects their crystal size, shape, and structure. Here we document the presence of a short-lived intermediate through in situ and time-resolved small and wide-angle X-ray scattering combined with high resolution electron microscope observations. When ikaite forms concomitant with the dissolution of amorphous calcium carbonate (ACC) but prior to calcite formation, fairly large glendonite-type calcite crystals grow despite the presence of citrate ligands that usually reduce crystal size. These were ideal seeding crystals for further crystallization from supersaturated ions in solution. In contrast, in the absence of ikaite the crystallization of calcite proceeds through transformation from ACC, resulting in fine-grained spherulitic calcite with sizes ∼8 times smaller than when ikaite was present. Noteworthy is that the formation of the intermediate ikaite, although it consumes less than 3 mol % of the total precipitated CaCO3, still clearly affected the calcite formation mechanism.